Worked solutions for ‘Applied Colloid & Surface Chemistry’ by RM. Fashley and ME. Karaman (J:Wiley, 2004) Chapter 2 1. Answer: Us Laplee ation inthe fron 28): 4 272082 Gives presure of 2 bars. Addition of sarin will reduce the jntrfucial teason and hence the pressure, The use of yrophobie porous materials to prevent water Now is used in clothing and in concentatg orange juice. 2: soa he La in or ie P= ae ‘aeulate the pressure ditkrence between each bubble andthe atmosphere and therefore ‘betwen the bubbles, The pressure differance betwen the two bubbles ean then be used in the Laplace equation te obtain the radi (1.Sem) of the (spotica) Soap Sts formed boroon the bubbles ‘Ammer: Use the cailany rise equation (2.9). Make sure that you convert the parameters to St unis, Te calculated surface tension value is: 0.62Nm". 4, Ansver: Apply the fll Laplace equation to calculate the pressure diflvence across the ‘water interface, relative atmospheric pressure. The diffrence in these two pressures ust cqul the hydos ference of 4.1mm, esse diference inthe water Ge hp). This gives a hoight4 Answer: Us the oat he Laplaepesusequton or apis (ap = 202282 ). The Laplace pressure for stable meniscus is LS bars (convert to ST) and hence the capillary radius mast be 033 micros (given that we know tha he contact angle of water on Toons 1105. 6, Answers The patie of snd ean beheld getter by the Laplace pressure generated ina meniscus (se diagram below) of wetting water. By comparison, for full immersion ‘complete drying 0 menisus ean form. 7. Angwer: Most powdered building materils (eg sand and clay) are sufficiently yaoi (ee diagram below), for water to wet and form » meniscus which will hold the particles together 18, Answers Fist wes realze that wo frees act onthe lower patel do tothe ‘merisots, Both ofthese att old the particles together. These are the pressure peered bythe Lape pressure and he surface tension forces ating along the vee Phar ine. (Ale, itshould be assumed that th weight ofthe ower particle negligible Featve tothe meniscus forces) ‘The Laplace pressre aces the curved interface can be dvely calculated using the own radi Ry and R, Cat, however, because the radi ae diferent directions, ha is ris positive (athe seme ofconbuting and atractivo presse between the patil) snd Res negative (it acto push the pails par). Ths the Laplace presses ‘horeore given by the equation: P= 7 5. This pressure acts old the mR patcls together and es ove an ates af 8? Hence the total fore, de tothe Laplace pressure, sting onthe prtcle can be ealulated, “The second tem i site tension force etng slong the TPL ofthe lower patil. “This erfae tension sets inthe diction ofthe interface atthe pint of contact with the particle. Simple geomety tells us that the angle the droplet surface attaches wo the droplet, Feltve tothe vsti! destion given by e040 ~ 0.1 Gob ~ 66) Than tho vertical ‘component ofthe fore ting along the TPL onthe lowe pail canbe easily caleuated as: Fy, =O8*7 #244 R, Combining these wo Forces gives a ttl force ating onthe lower particle of @.18mN,9. Annver This problem flows the tne pis sth previo queso, thats we incite tsb fares dow apace resend te vera component fh ses nnn resting slo the thse par ine (TPL). Once Sean the vo pina al fhe ered menus arin opposte det nd ‘therefore their signs are different. Thus the Laplace pressure is given by: A =7h-—-2), wrt pesue at ars the ana! Yo hold the patil to the suas The Lape presste em ont binding fre of 5.6 ‘The secon term is gvenby the vertical component af he surface tension around the TPL: Fy, = Sng y*2"x*R, . This gives contribution of2,1SE-ON, Somming ose 60 Toros gives the minimum fre F (a S8uN) roquiodto detach the patie Chapter 3 1. Answer: First fal itshould te realized tha rom the Gibbs" adsorption isotherm the ‘maximum adsorption dest (Je minimum are pr adsorbed molecule) occurs at he ‘maximum slope onthe zh i ia bath eases tha iste linea slope othe rap) Further, it shoold te realzed that fora 3:1 eleoeoyte (ie CoRCI) 4 molecular species dso at the arsrer surface per surfactant molec. Alo, fr measurement ‘concentrated salt (150M NaC) the bulk concentration of only one species (he ionized ‘uratant monomer eanging With surfaetnt concentration. Take eave With the Unis. ‘The Gibbs adsorption iste appropriate fr analysis oF the wae isotherms hal 5202) necase 4 molecular species adsorb. It shouldbe razed hatin aera ‘btsining data fom the graph we donot nod te convert molarity concentration units to SI Gemolesim because inc 2) and hence the units ence. Using the water daa on the nae region ofthe graph the adsorption density i eaeulted as 1.2 males This vale can then be converted tothe coresponding ea por molecule: [CAE-ISmmolccule ora minim molecular are of I The form fhe Gs gun fr the lower raph in high tyes aa alainc ence inne i chenialpotei) as thesia concentaton sincresd, Using ) sn ony ne pce anger blk onsation Gesthis equation the graph gives a maximum adsomtion desiy of 18 ols? which coesponds toa minimum area of 0S ‘These results are intresting because the show that the Gibbs model gives reasonsle ress, even in this complex system, The aren pr molec shoul decrease with Increased electrolyte asthe ionic head-groups become serened and ean pack closer togeter 2 Answer: ‘A: The horizontal line conesponds to 20 adsorption B: The curved region conespending to increasing adsorption densities, occurring over a funy narrow eancenratia ange (C:The liner region coresponds to constant adsorption density. Not thatthe inerfai tension sil alsin hi ron. D: The horizontal epion ere does not correspond to ero adsorption buts cansed by the surfactant concentration raining conta, asl the added molecules se asemble nto ‘aggregates such as micelles. This occurs at Concentration above the eral mille ‘eoesntation me) val Chapter 4 3. Answer: Bquation 48 sve the sanded fre energy of transfer of surfactant ‘molents from an aqusous environmen, as fee monomers to molecules in a iil ‘funetion ofits ems vale. Thus, the dilerece in fee energy of tanafer between surfactants with the same ead group but different chain lengths must be ue tothe fre ‘nergy associated wit he transfer of the exta methylene groupe fom aqueous to liquid ‘nydoeaibon environment inte contr ofa micelle, Thus, th average fice energy of leansfr 25-215 or abut 0 6KT per grou.Chapter: 1. Answer: Using the Debye length equation 6.11 we obtain the values for NSC: 30hm, Snm and nm, For MgSO, the comesponding valves ate 1Snm, 1S and Sm. 2. Answers Use citer the approximate equation forthe deay in potential next ta fat surface (eqn 6.14) or the exact equation (oqn 613) to calle the potentials and then a several pins ws the Bolumsnn distribution function (eqn 66) to calculate the individu on conesntations. 44 Answer: Use equation 47: [Ig =2e,De2yo?expld), whith gives the sweling pressure using the superposition pinciple- Fist caeulte the Debye length (") of the Solution, which s7.88nm. The penmitivty of free space, e, sequal fo 88S4E-12 (Cay andthe diiceticeonsan of waters 80. Subsituton into the equation gives a swelling presse of 3250Nm", 'S Answer: The hyostae pressureon a colunn of water lem high is given by the fundamental equation of hyostais: P= hpg, Hence the hydrostatic suction pressure ‘ting odin the weting fim i 98 Nav. Ifthe itr intrfae as no hag this ‘means tha the film canbe considered us one hal of to lat surfaces with -60mV' on «cach surface but separated by toe the thickness ofthe film. (Since £ 0 atthemid- plane, which therefore has 0 chat, fiom equation 6.16). Equation 647: [Tp =26j>atyg2eap(nd, ein hen Be sed cele the answer, tho parameters are known, Noe thats twice the thickness of the wate ln td hat we must assume atthe Debye lng af water is (ypicall) about Stam, ‘Tse values ea to cae fil thickness of 75nm.6 Answer: The chemical ie energy of adsorption (8) must be ual othe letrostatc work dono (+) in binging single change fot bulk soon to the hanged surfice, Thus: Av... = =z), s where 2, isthe charge onthe ion, Which means tat the chemical potential of adsorption i 1.2820 J pe ono about 3K | 6 Aver: sige pin pine an bin tte tea a themida an ten uh Bolan dit eal Na on Ths hn pte en by: vg <2¥un “24e-x2), whim i esis opal -24a Laut ‘The consipningBolzmann disibuen etn Cx)-C(B) ex] - 2942] hich cones: Ci Lee) wher fy, ithe posve valu of ho ic ce ee) leith pov va lovtrone charge, This gives a Na+ on concentration athe mid-plane of 2SuiM, 9. Answer: The electrostatic decay away from a Mt, charged surfice given ‘spprosmately by the equation: w(x) = yp exp(xx) «Since th Debye length in this case |s30nm, ithe potential Sum away is 10m the sufae potential must be 11.8, ‘The Boltzmann equation gives the concentration ofeach on from the exation aves] core. 2 re "Note that in using his equation the signs of, and (3) Ste wn eet 2 bn ome tov: Tore} cl -20] cpus 45a? mn nena nit nettChapter 7 2 Answer: The magnitde of the refractive index measured at visible frequencies is & ‘measure ofthe strength fits van der Waals interaction or Hamaker constant becuse & high value corresponds t significant UV absorption ~ the main contributor to the vw interaction, ‘The three possible interactions are: 1:1, 13:2 and 2:32. In the Fist case (3:1) we will have the stongest attraction cass the paticles have oll correlated frequencies (since the materials are the sate) aid « strong UV contribution, {i the second case (1:33) the aw interaction with the solvent wil be trong and the replacement of solvent with an approsching particle will kad to a weaker vw interaction. Hence in this case the vw free willbe repulsive and will wt to separate particles 1 and 2. Inthe final case (2:3:2) te correlation between the same materials i 2 will dominete ‘over the interaction wit he solvent an the vw force wil be 3. Answer: ‘The interaction wil be the same. The Hamaker constants forthe cases Avs are equal 0 ‘hose for Ay fo all atria, 4, Answer: The rapid copulation canton shown above is useful because unde these conditions both Vs ~ 0 and dV = 0 forthe same separation distance = H¥, 3 expt = 2, 7 Thus: 2aaeyDy} expl-xtl) = 4 w, a, 29 (-n)me,by expat)» ha, re =O (anes extn »‘where on dzectsubstiuson iti found thatthe spacial distance H* = «(le the Debye eng). The extial surface potential can than be ditty obtained by subitton of nto citer eqution above, The erica coagulation vale is thea found tobe 29V. 5. Answer: The inersetion energy for close separation distances for iguids which only ave va intersetons mst be equa othe work done to erate two new srives pe unit sea, e 2, wheres thesurfae tension ofthe iui, This, 27-=Fiy and therefore y= SS?