ee SURPACE CHEMISTRY as SURFACE CHEMISTRY Eaten Chemistry is that branch of chemistry whieh stutly ofthe phenomena occurring at the surface or ve, ve, atthe Boundary separating two bulk phases lutions The two bull n be pure compe od by putting a hyp between the te bulk phases involved, e, solid-tiquid oF soli Tigi. No inert comple The anerface is slash 1 enists between gases as they are interface, €-8.. dissolution, erystallisation, corrosion, alysis, electrode processes, ete Cea 2.1 Definition 1g and retaining the molecules The phenomenon of attract ‘ofa substance on the surface of a liquid ot solid result to higher concentration oF the molecules on the surface is adsorption. Adsorption of gases at metal surface is called osclusion Ta Achorhateand Advorbent The substance which gets adsorbed on any surf adsorbate for example, if gas gets adsorbed on to the surface ofa solic, then the gas is tertaed as the adsorbate, The substance on the surface of which adsorption takes place ts called adsorbent Adsorbent may be a solid oF 2 liquid. Metal powders, powdered charcoal, animal charcoal siiea powder ete, are ccommanly used as adsorbents, PX Adsorbate JW \y (oes0r ( colt salt) ery Adsorbent and adsorbate 23_Devorption The removal of the ads tesorption. This can be done b} the pressure of the system. ee : Absorption ce are uniformly distributed When the molec throughout the body of entid ne Howit ‘sealed absorption 73 Sorption “The phenomenon in which adsorption and absorption occu simultancously is sie(@inin) sare absorbed as well absorbed in cotton fibA Adsorption is instantaneous i.e. @ fast process while absorption is a slow process. aa EE seasons oe ouied Sorption ference between Adsorption and Absorption Main points of difference berween adsorption and absorption are given below.RETW SURFACE CHEMISTRY ENADSORPTION AND ABSORPTION Advorpii I. Miya surface pheno In At, the substanc fom the su Sony retained ace and doe: the butk oF inte: Sn HOF OF the solid ar Tiguid, x , & |i it the eonccntation of the adsoubed molecules is always greater at the free phase BEA [eis rapid in the begining and stows Water vapours are adsorbed by acl, Gi) NH, is adsorbed by charcoal, () Decolourisation of sugar solution by activated or animal charcoal, (vi) _ Ink is adsorbed by blotting paper. Absorption _| x Wimphes that a subst stance 1s uniformly | istrnbuted, though the body af the solid or liquid BE Init the coneenuatian is tow. es. Woceus atthe unitorm vate (2) Water vapours are absorbed by anhydrous sic wet (i) NEI, is uber toed in water forming NUON 2.7 Mechanism of adsorption (b) Molecules at the surface experiencing a net inward foree of attraction in case of (a) liquid (0) solid (e) metal with free valencies active role of Only the surface atoms of an adsorbent play an in adsorption, These atoms possess unbalanced for al's forces and chemical various types such as, Vander Ws bond forces (free valencies) Thus, due to residual or unbalanced iny Jancies at the surface, liquicls and solids fain the n.lecules of a yard forces of attraction or free va have the property to attract and ret gas or a dissolved substance on to their surface. 2.8 Charactersties gil Adsorption refers to the existence of a higher ‘concentration of any particular component at the surface of aliquid oF a solid phase ag 28.2 Adsorption is invariably accompanied by evolution of beat, ets an exothermie process. In other words (AHL af 2.8.3 When a gas is adsorbed, the freedom of movement of its molecules becomes restricted. On account of it, decrease in the entropy of the gas after adsorption, Le. AS ismegative. Adsorption is thus accompanied by decrease in enthalpy we AG as well as decrease in entropy of the system and h also decreases nthe AG. 2.8.4 Adsorption is accompanied by dectease (fice energy charge) ofthe system when 4G = 0 {adsorption equilibrium és said (0 be established.) 2.8.5 For a process to be spontaneous, the thermodynamic requirement is that AG must be negative, ic. there is decrease. in free energy. On the basis of Gibb's Helmholtz equation, TAS}. AG can be negative if AH has [AG = ant sulliciently high negative value and TAS has positive value. ty z 4, 4 ati yOj SURFACE CHEMISTRY Ad \lsorptionea be classitied into two categories as deseribved below 2.9.1 Physical adsorption :Hthe forces of atrastion existing between adsorbate andl adsorbent are Vander Waa’ frees, sal adsorption, This type ot niplion salsa known as physisweprion or Vander Waal adsorption, tt can be easily reversed by heating & orces of attraction 2. Chemical adsorpti es and adsorbent are existing bewween adsorbate particles a ‘ eT ath as chemical bonds, the almost of the same stre ical adsorption, This type of das chemisorption or adsorptia : adsorption is also calle Langmuir adsorption. This type of adsorption cannot ji Lan} be easily reversed COMPARISON BETWEEN PHYSISORPTION AND CHEMISORPTION E Chemisorpti Phy sisorp a «Nader Waal's adsorption) (Langmuir adsorption) r 2 igh hem of adsorption in dhe range of Low heat of adsorpion usta in range 1 High het * ed20-0ktina 50400kI nel i 2 Force ofattaction are Vander Waat's forces. | 2 Fotees of attraction are Chietmes vviny wases itiste 3 Misineversble 44 Trasually takes place at low 4. Itakes place at high temperature tcmperatte and decreases with increasing lemperature S$ nas related wo the case of liqueication 5 Wisnotretared ofthe 6 Iefonmsmulumoleeuar layers 6 Itforms monomolecular layers. 7 does wot require any aetwation 7. Mvequires high activation energy X High pressure is favourable. Decrease 8. High pressure is favourable, Decrease of pressure causes desorption. Of pressure does not cause desorption 9 Wis nat very specific 9. Mis highly specific. Note FE ue 19 formation of mutilayers physical adsorption decreases after some times F Chemisorption and physisonption bath are exothermic. 2.10 Factors which affect the extent of adsorption solid surface The following are th 9 on solid surface. 0.1 Nature of the adsorbate (gas) and adsorbent (solid) ie factors which affect the adsorption of Porous and finely powdered solid e.g, charcoal, fullers carth, adsorb more as compared to the hard non-porous ‘materials. Due to this property powdered charcoal is used in gas masks used in coal mines. Gases with high eritical te higher extent as comp: temperatures. perature are adsorbed at wared to gases with lower criti Wrlumes of gases at N.T.P., adsorbed by 1g of charcoal at 288 i Hy Ny co cH, Het NH, so, iorbed (ml) | 47 80. 93 162 R 181 380 Critical temp (k) 3B 324 406 430 7 =) Ad Isorpt10.2 Surface area of the solid adsorbent : The extent of Isomption dep! adsorbent, 1.¢, ta rface area of the ids directly upon the surface area of the surface area of the adsorbent, greater is the extent of adsorption 2.10.3 Effect of pressure on the adsorbate gas : eave in the pressure of the adsorbate gas increases, the extent of adsorptio © AL Tow temperature, the extent of adsorption incr rapidly with pressure. * At low pressure, the extent of adsorption is found to be directly proportional to the pressure. At high pressure (closer to the saturation vapour pressure of the yas), the adsorption tends to achieve a limiting value N, ADSORNED 1 oo Wem oflig + 2.10.4 Effect of temperature As adsorptionis accompanied by evolution of heat, so according to the Le- Chatelier’s principle, he magnitude of adsorption should decrease with rise in temperature The amount of heat when one mole of the gas is onthe adsorbent is called the heat of adsorption. 1 Adsorption Isotherms ‘A mathemat adsorbed cal equation which describes the relationship between pressure (p) of the gaseous adsorbate and the extent of adsorption at any fixed temperature is called adsorption isotherms, Thus, if g of an adsorbate is adsorbed on m g of the adsorbent, then Extent of adsorption = m SURFACE CHEMIS + Freundtigy PLS Where lar laver on the surf where, x is the weight of the gas adsorbed by m gm of the adsorbent at a pressure P. thus x/m represents the amount of gas adsorbed by the adsorbent per gm (unit mass). K and are constant at a particular temperature and for a partieu| adsorbent and adsorbate (gas), nis always greater than one indicating that the amount of the gas adsorbed does not increase as rapidly as the pressure At low pressure, the extent of adsorption varies linearly Xp with pressure = & P' th pressure At high pressure, it becomes independent of pressure Xx pe m At moderate pressure ~~ depends upon pressure raised to powers =u. Pe m rn: pt ae, 2 Adsorption Isobar A graph drawn between the amount ofthe gas adsorbed per gram of the adsorbent (x/m) and temperature equilibrium pressure of adsorbate g; isobar. ata constant as is known as adsorption alm ee alm Temperature = Temperature = Physical adsorption Chemical adsorption"he physical adsorption isobar shows a decrease in x Uwoughout with ris he chemisorption isobar shows an initial inerease with temperature and then the expected decrease, The in th ial increase Is because of the fact at the Heat supplied acts a required in Solid surfaces can also adsorb solutes from solutions. A few examples are When litmus solution is shaken with charcoal, it becomes colo less b suse the dye ofthe litmus solution is adsorbed by chareol * Whenthe cotourleys Mg( OI), is precipitated in the presence ‘of magneson reayent (a blue coloured dye). it nequires blue colour because the dye is adsorbed on the solid precipitate The extent of adsorption fiom solution depends upon the concentration of the solute he solution, and can be Freundlich isotherm. The Freundlich expressed by the ausorptign isotherm for the adsorption from, solution is, 2 = ke* where x isthe mass ofthe solute adsorbed, ms of the solid adsorbent, © is the equilibrium concentration of the solute in the solution, # is a constant having value greater than one. k is the proportionality ‘constant, (The value of & depends upon the nature of solid, Hts particle size, temperature, and the nature of solute and solvent ete.) The plot of /or against e is similar to that Freundlich adsorption isotherm, The above equations may tne following form, log * = logk +1 tog m n ‘where e isthe equilibrium conc ion ofthe solute in the solution from solution ‘udsorption from solutions by solid adsorbents is found ‘depend upon the following factors 2.14.1 Nature of the adsorbate and the adsorbent 2.14.2 The «lsorption decreases with temperature. 2.14.3 Greater the surface area of the adsorbe the a nt wreater is ‘sorption In case of adsorption by solids from the solutions, mostly surface of the solid adsorbent so that concentration of solute on the surface of the adsrobent is greater than inthe bulk. However in some eases. the solvent from the solution may be adsorbed by the xlsorbent so that the concentration of the solution increases as compared to initial concentration. When the concentration of the adsorbate is more on the surface of the adsorbent than in the bulk, it is called positive adsorption. Ifthe concentration of the adsorbate increases in the bulk after adsorption, itis called negative adsorption. Blood solution + Cone, KCI solution -> Positive adsorption BlogffSdlution + dilute KCI solution > Negative adsorption plications of Adsorption ‘The phenomenon of adsorption finds a number of applications. Important applications are given as follows. 2.16.1 Produetion of high vacuum : A bulk of charcoal cooled in liquid air is connected to a vessel which has already been exhausted as for as possible by a vacuum pump. The remaining traces of air are adsorbed by the charcoal to produce a very high vacuum. j 2.16.2 In Gas masks : It isa device which consists of activated charcoal ora mixture of adsorbents, This apparatus is used to adsorb poisonous gases (¢.g. Cl, , CO, oxide of sulphur etc.) _ and thus purify the air for breathing is coal mines, 2.16.3 For desiccation or dehumidification ; Certain. substances have a strong tendency to absorb water such silica and alumina (Al,O,). These substances can be used reduce/remove water vapours or moisture present in the ai Silica gel is also used for dehumidification in electroni equipment 2.16.5 Meterogeneous cat ‘sis : Mostly heterogeneoy Mle Feuclions proceed through the adsorption #ascous reactants on solid catalyst. For ex mple,1 is used for the hydrogenall + Finely powdered nicke oils, «Finely divided vanadium pemtaoniste (V,0,) is used in the contact process for the manufacture of sulphune acd as catalyst © 7%, Pa are wsed in many industrial processes © Manufacture of ammonia using iron asa catalyst : Due to the difference i 2.16.6 Se degree of adsorption of gases by charcoal, a mixture of inert aves can be separated by adsorption on coconut charcoat at different low temperatures. Chard water: © The hard water is made to pass through a column packed with zeolite (sodium aluminium silicate) 2.16.8 De-ionisation of water : + For softening water ean be de-ionised by removing all dissolved salts with the help of cation and anion-exchanger resin, 2.16.9 In curing diseases : A number of drugs are adsorbed on the germs and kill them or these are adsorbed on the tissues and heat them. 2.16.10 Cleaning agents : Soap and detergents get adsorbed on the interface and thus reduce the surface tension between dirt and cloth, subsequently the dirt is removed from the. cloth. 2.16.11 Froth floatation process : * A low grade sulphide ore is concentrated by separating it from silica and other earthy matter by this method. * The finely divided ore is added to water containing pine oil and foaming agent * The air is bubbled through the mixture. The foam formed rises to the surface on which mineral particles wetted with oil are adsorbed while earthy matter settle down at the bottom, 2.16.12 In adsorption indicators : Surface of certain precipitates such as silver halide, have the property of adsorbing some dyes like eosin, fluorescein etc, In this case of precipitation titrations (for example AgNO, Versus NaC) the indicator is adsorbed al the end point producing 4 characteristic colour on the precipitate, SURFACE CHEMISTRY ysis : The phenomenon of 3.16.13 Chromatographic ana The p aiven an exeetient techn aoa aphic analysis. The technique known as chromatog and industral ts number of 2PP Me Tchmique as based on differential Chromatographic tec Sys muinre Jitferent constituent gusorption of ditle cs yes get adsorbed on the cle 2.16.14 In dyeing : Many 6 von speeds down a these wy ig known as catalysts the reaction and the phenomeno! Types of be broaaly divided into the following types Catalytic reactions ants and the 4.1.1 Homogencous catalysis : When the reactants and ¢ catalyst are in the same phase (i. catalysis is said to be Aomogencous. The following are some solid, liquid or gas). The of the examples of homogenco' ysis. Oxidation of sulphur dioxide into sulphur triowide with oxygen in the presence of oxides of nitrogen as the catalyst in the lead chamber process. 250, (g)+ (gy) 2+ 250 (x) The reactants, products and talyst all are in gaseaus state i.e, same phase. Hydrolysis of methyl acetate is eatall by hydrochloric acid CH,COOCH, (/}+H,0(/) Ys ced by 1° ions furnished CH,COOH(/)+ CH,ON(/) Hydrolysis of sugar is catalysed by H" ions furnished by sulphuric acid, Cy3Hy,0, (1) + H,0(/) ES, {Scere stn) CHO, (1) +CH,,0, (1) 3.1.2 Heterogencous catalysis : The catalytic process in which the reactants and the catalyst are in different phases isknown as heterogeneous catalysi Some ofthe examples of heterogeneous catalysis are given below. Oxidation of sulphur dioxide into sulphur trioxide in the Presence of platinum metal or vanadium pentaoxide as catalyst in the contact process for the manufacture of sulphuric acid. The reactants are in gaseous state while the catalyst is in solid state.250 (g)+ ,(¢) “4 250 ,Combination bet ination Between nitroycin and hydiogen v0 form Shona n the presence of finely divided iron in Haber process, N 5 2NH Ce) + 3H e). Oxidation of ammonia into nitric oxide in the presence of platinum gauze as iyst in Ostwald process, + OH Ox) Hydrogenation of vegetable ols in the py ance of finely divided nickel as catalyst » Vegetable Ghee (x) When the rate of the reaction accelerated by the foreign substance, it sid to bs posit catalyst and phenomenon as positive catalysis, Some examples of positive catalysis are given below, Decomposition ot Hy yin presence of colloidal platinum, 2H, (O—*42H, (D+ j(g) 1A Negative ulded to the here are certain, substance which, wh tion mixture, retard the reaction rate instead of increasing it. These are called negative catalyst oF inhibitory and the phenomenon is known as nega catalysis. Some examples are as follows, * The oxidation of chloroform by airis retarded ifsome aleohol is added to i ICHCI + 4g) #5 2COCT(@) + HCI) 3.1.5 Auto-catalysis: Incertain rea ions, one of the product ats as a cat {nthe initial stages the reaction is slow but as soon as the products come into existence the reaction rate increases. This type of phenomenon is known as aufo- catalysis, Some examples are as follows, The rate of oxidation of oxalic acid by acidified potassium permanganate increases as the reaction progresses, This acecleration is due to the presence of Mn?" ions which are formed during reaction. Thus Mn? “ions act as SH.C,O, + 2KMnO, +3H,S0, —> 2MnSO, +K,SO, +10CO, +8H,0 i! is poured on copper. the reaction is very inning, gradually the reaction becomes f id during the reaction duet the formation of nitrous which acts as an auto-eatalyst © Intydrolysis of ethyl acetate, acetic acid and ethyl alcohol ae formed The reaction is initially very slow but gradually eases. This is due to formation of acetic acid its rate whieh acts as an auto-catalyst in this reaction, on influences the 3.1.6 Induced cat i ' Iysis : When one react te of other reaction, whieh does not occur under ordinary conditions, the phenomenon is known as induced catalysis. Some examplesare as follows, ‘The reduction of yercurie chloride (IIgCI,) with oxalic acid is very slow, but potassium permanganat reduced readily with oxalic acid. If, however, oxalic acid is added toa mixture of potassium permanganate and MgCl, both are reduced simultaneously, The reduction of potassium permanganate, thus, induces the reduetion of mereusie chloride. 3.1.7 Acid-base catalysis : ecording to the Arrhenius and Oswald H* or OH ions actas catalysts. For example, Hydrolysis ofan ester, CH,COOC,H,()+H,0() Ho ES CH,COOH (1) + C,11,0H () Inversion of cane sugar, Cote WOH, SoC (OFC Ha 6D Conversion of acetone into diacetone alcohol, CH,COCH, (1) +CH,COCH, () OH", CH,COCH,.C(CH,),OH () Decomposition of nitramide, NH,NO, (I) OH" _, NO(g) +H,0() The following are the characteristics which are common to most of catalytic reactions. 3.2.1 A catalyst remains unchanged in mass and chemical composition at the end of the reaction, 3.2.2 The catalyst can not initiate the reaction: The function Of the catalyst is to alter the sp eed of the reaction rather than to start it 3.2.3 The catalyst is generally specific in nature A substance, which acts as a catalyst for a particular reaction,SURFACE CHEM ISTRY " Theories of C3 fails to catalyse the other reaction , different eatalysts 0 Theory of Homogeneous Catatyai, 1 Cullision Theory ‘he same reactant may for different proslucts aa. oflsion theory, a reaction occur og, S24 The catalyst can not change the position of |. outing wo the payee iena(cersetel neta ' and count of effective ce : equilibrium: The catalyst catalyse both forward and account of a ‘packard reactions to the same extent ina reversible reaction molecules. For € aeoe a nuatenw te area alecuiles must possess a mi and thus have no effect on the equilibria constant molecules mst Saad 8 ytic promoters : Substances which themselves, ns aetain energy) Ae he colision mele na are not catalysts, but when mixed an small quantities with an activated complex whic the catalysts ides a new pathway involving we theit efficiency are called as promoters molecules. ‘The catalyst provid p or activators, lower amount of activation energy. Thus, 32.6 Ca ytie poisons : Substances which destroy the T activity of the eatalyst by their presence are knme ne f a catalytic poisons, wn | | ll vl 32 Change oftemperature alters the rate at eatalytie wee] oo reaction at does for the same reaction in absence of catalyst : By inereasing the temp. falue, there is an increase in the catalytic power of a catalyst but certai 2 Adsorption theory of Heterogeneous Catalysis + after a temperature its power begins to decrease. A catalyst has thus, a particular temperature catalytic mt k e at which its activity is maximum, This temperature is termed aS optimum temperature, Heterogeneous catalytic reactions generally proceed via A positive catalyst lowers the activation eneray Pane ae y s ' adsorption of reactants on the surface of the catalyst reoeises Mechanism of such surface reactions may be explained in . ‘ems ofdifusion theory of eatalysis. Thisthcory postulates 8 keer, ‘ {he following sequence for gascous reactions on 9 solid z we = /Cotclysecs surface. 3 f emir E f Step: (i) Ditfusion of the reactants to the surface : Step: (ii) Adsorption of the reactant molecules onto the £ surface. Se, - ‘Step: (ii) Actual chemical reaction on the sur © ‘met Megas acy + (Ht) Actual chemical reaction on the surfac & = t Step: (iv) Desorption of the Products from the surface, Fioot store Products (C+D) ‘Step: (v) Difhusion oF the produets away from the g Reaction sequence euenee In generally, Step (iit) determine, Step (ii) and (iv) may be rate d Oo D ~tuy gy ~ q Boog +a =Aurface Rewetion the rate of reaction, Hi letermining neatalysed reaction face catalysed fue) reaction 4. Desorption op ‘ther sctiong Pronluctotevnte Dahon SPexrptionofome the surface product mules Mechunisins or the surface ryAE GR 3.3.3 Advantages 33 Advantages ot modern adsorption theaty :Thistheory canexplain the following Stall quantity of the catalyst is sttficient because the Catalyst iy regenerated agamn and again * The catalyst takes poet in the reaction bal 3s produced back: ‘changed in mays and chemical composition at the end the reaction, ually adsorbed on Catalytic poisons, it present c preter the catalyst surfitce, thereby hindering the aclsorption of tant molecules, Hence, they slow down the activity oF the catalyst ‘hus theory, however, cannot explain satisfactorily the aetion ‘of eatalytic promoters 3d Eneyme catalysis Fueymes are complex nitvagenous substances secreted by. tables & organisms. Enzyt protein molecules of higher molecular mass. ( 15,000 1,000,000 gymol) Enzymes for colloidal solutions, very effective catalysts, They catalyse wected with natural in water ane numerous reactions, espectally those © ctions occur in the bodies of processes, Numerous re: sand plants (@ maintain the life process, These reactions are catalysed by enzymes, The enzymes are thus, ered ay bio-chemical catalysts and the phenomenon is known as biochemical catalysis. x, Nitrogenase is an enzyme present in bacte nodules of leguminous plants such as pe: catalyses the conversion of atmospheric N, to NI, Inthe human body, the enzyme carbonic anhydrase catalyses the reaction of CO, with HO, CO, fa) +10 = Hag) + HCO, faq) The forward reaction accurs wh blood takes up CO, in the tissues, andl the reverse reaction occurs when the blood releases CO, tu eve fe .|_. (Peseta) complex {ctiows take place int two steps Thus, the enzymic catalysed as Follows yine-substrate complex (hast and Reversible) Step f. Formation af e us F Ssubte hoes Enzyine Substrate comple sbstrate complex to form the Step 2. Diswiciation of ensyme: ts [00] , Product ssociation p (Slow and Rate determining, ) ‘The lity ofeatalysts to accelerate of acceleration can be as 3.5.1 Activity : Activity is the: sions. The d reactions. For example reaction high as jg! times in cert between Mand O, to form F/O in presence of platinum 1es place with explosive violence. \d O, can be stored ind 3.5.2 Selectivity : Is the ability of catalysts to dire to yield particular products (excluding other) cu, reaction (iy cHycHecH, BME tI >CH, = CHCH lumino- silicates of the general f [W10,],(Si0,), 14,0, where, M maybe simple mula, M, tionlike Na’, Kor Ca*’ <1 is the charge on the simple cation, m is the number of molecules of water of crystallization, They have Honey comb like structure called § cage, The re catalyzed by zeolites depend upon the Feactant clions shape and size of the ‘und product molecules, That is why these types of, reactions are called sha ape selective-catalysis,SURFACE CHEMISTR: ’ Y ely used as cata Zeolites are being very widely i petrochemical industries for cracking of hydrocarbons ang isomerization, An important 2 olite catalyst used in i petroleum industry is ZSM-S*** (Zeolite Sieve of Molecular “i/ I Porosity 5). It converts aleohols directly into wasolin “tal < (petrol) by fast dehydrating them so that a musture « ee) hydrocarbons is formed {9) The sodatite (or 1) cage, (9) zeolte-A Alcohols —,,25¥-5 peat» Hydrocarbons zeolite: of hard water Fe used as “ion-exchangers’ in se 4.7 Catalysis used in Industries -(€) Faujasite SOME INDUSTRIALCATALYTIC PROCESSES, Process Reactions with catalyst and other conditions Haber's process for the N.{g) + 3 Hy(g) —! manufacture of ammonia Se 20H, Ostwald's process for the 4 NH,(g) +50, (g) aeretcaya> 4 NO(g) + 6 H,0 (g) manufacture of nitric acid 2NO (g) + 0, (g) 225_, 2 No, (g) 4 NO; (g) + 2 H,0 (l) + 0, (g) > 4 HNO, (1) Contact process for the 280, (g) + O, (g) SSE 2.50, (g) manufacture of sulphuric ” acid SO,(g) + H,SO, (0) —S73-723K 5,9) —_-H#200_ 2H,S0, (aq) Oleum Bosch’'s process for the CO =H, + H,Olg) —Ep Se _ CO, (g) - 2 H, (g) manufacture of hydrogen. Wacres T-87K Deacon's process for the 4 HCl (g) +O, (g) S82 5 2H,0 (+2 Cl, (g) manufacture of chlorine CO (g) + 2H, (g) + CH,OH (I) ynthesis of methanol Hydrogenation of Oil (t) ~ H, (g) Sg > Vanaspati ghee (8) vegetable oils=e oreo COLLOIDAL STATE The colloidal state dep uls on the particle size. ste as mtermedliate state between tr In true solutions the size of the particles af salute is very solution andl suspension coatons] Relation sina an sh, thee cae nat he deed bY any optics | ECan pew r means and freely diffuse through membranes. It is a orm homogenous system om tome | > mogenous syst 10m 2 0° 20 100-nm f a . Soc <10A 10 A~ 1000 A> 1000 A 2: oe >108 pm 3° G08 <1000 pm 1000 pm— m mien cata _Sepavln 108 pm nul, thus it ean be seen by of particles is large The sir Jy not pass through ked q filter paper. I is naked eye and d yeous system ae es expressed in ther units also as given below Three types solutions NS. CHARACTERISTICS OP TRUE SOLUTIONS, COLLOIDAL SOLUTIONS AND SUSPENSIO! So] Property | True Solutions Colloidal Solutions Suspensions ature smogencous Heterogeneous | Heterogeneous 2 |pauesie | Lsrmmremoe | Bewen tO 10% | Morethan 10m or © | diameters) | 1 nm(ie,<10.A) or Tnimto 1000 nin 1000 nm > 100008 a | Filuabity Pass trough orinary Pass through ordinary Do not pass through filter filter paperas well filter paper but not paper and animal ssminelmenboee, | through animal rere membrane. 4 | Setting Do not settle Do not settle, Settle on standing. 5 Visibility Particles are Scattering of light by Particles are visible to invisible, the particles is naked eye or under a observed under ultra- microscope. microscope. 6 | Diffusion Diffuse quickly. Diffuse slowly. Do not diffuse. 7. | Appearance | Clearand Transluscent. Opaque, transparent spersed phase and Dispersion Medium 4.3.1 Dispersed phas + (Discontinuous phase) : It is the component present in small proportion and is just like a solute in a solution. For example in the colloidal solution of silver in water (silver acts as a dispersed phase) 4.3.2 Dispersion medium : (continuous phase) : It is gener ly the component present in excess and is just like a solvent ina solution. For example, in the colloidal solution. of silver in water. Water acts as a dis, 4 Classification of Colloids 4.4.1 Classification based on the physical s dispersed phase and dispersion medium De the physical state of dispersed phase and dispersi whether these are solids, liquids or gases, eigh Colloidal systems are possible. spersion medium,i. SURFACE CHEMISTRY EASE CHEM MS DIF FEIN ETYPESOF COLLOIDAL SYSTEM Se] pipersed an [Colloidal System No] paense | ner fine insecticide sprays Joa rst, Fi resol at liquids | Kops, eh a : ov ‘Smoke, volcante dust, haze Foam or troth Soap father ‘ Acroxol ab sali smoke, volcan Lemonade Hoth, fea, shipped e 7 | Gm Lagat ' ulsified otk, mneeiviies 4 7 Liquia Laut Haale Milk, emulsified wt hos Siti im) Sob Most pats, starch im water, protems, gold sol, ansen vulphide sol, ik “ Soh Sold fon Pumice stone, styrene suber, foan rubber PY tigi Solid Gls Cheese, butter, boot pulish, jelly, curd iui sali ie x | soa Solid Solid sols Ruby pass, some fem stones and alloy (eolouned jt 4.4.2 Clasillcation based on Natur Aion between Lyophobie colloids (water hating) : “The eotluidal valunens 'd phase and dispersta + Lynphitic cattoidy (w Avophilic colloids.” ¥ loving) ¢ “The colloidal im which the particles of the dispersed phase havea preat affinity forthe disy DISTINCTION BE iu which there ix nu affinity between particles of the dispersed phase and the dispersion mediun are called lyaphobic colloids.” Lyophobic colloids (water hating) in which there is wa affiniry ‘The caloidal solutions heaven particles of the dispersed phase and the dispersion medium are eatled lyophabie colloids clectrolyte Hydration Examples Addition of smaller quantity of clectrolyte has litle effect Extensive hydration Gum, fakes place ch, proteins, rubber ete ike As,S, ete, TWEEN LYOPHILICAND LYOPHOBICSOLS perty 1 yophitic (suspensiody Lyophobie Sols (Emulsoidy Suiface tension Lower than that of the medium hat oF the medium Viscosity Much higher than that of the ame as that of the medium edi Reversibility Reversible Inreversible Stability More stable Less stable Visibility Particles can't he detected even Particles can be deteeted under under ultramicroscope ultamicroscape. Migration Particles may migrate in either Particles migrate either towards direction or do not migeate in an thode or anode in an electrie clectrie field because do not carry field because they carry charg any charge. 7-| Action af Coagutation takes place No hydration Metals like Ag and Au, hydrox Fe(OH), metal sulphides44.3 Classitic; ‘ ‘tion based on types of particles of Phase Depending a articles af the PON the type oF the 9 ‘Nsperved phase, the colloids ave elsif e totlees Multimotecutar cotlaids : Whi on dissolution, atone on sinaller mol les of substances thavi i atiameter hess thaw Voom) ayy D agas Ne together to form particles of colloidal Mimensions, the particles thus. formed je ealled multimotecutar colloids Wn these sols the dispersed phase consists ofa Meso atoms or molecules with malgculsr S26 Tess than Lain Kor example, sols af gold atoms Sulphur (SQ rmwiccules. In these colloids, the partie held together by Vander Haat’ forces. Uhey hi lvephilic character Macromotect colloids : These are the substances having bug sive molecules (called macromolecules) which on issolution form size in the colloidal range, Such substances, are called macromoteentar colloids DIFF These macromolecules forming the dispersed phase are enctally pulymers having very high molecular n lecules are starch, cellulose, Naturally occurting macromolecul . gelatin ete, Artificial macromolecules “ee s suchas nylon, polythene, plasties, ie poly ete. Ther solutions are quite stable and The palystyrem have pe sith tue solution in many 6 The ecules are flexible usually uphobie charac ¢ the substances which normal electrolytes at low concentration but behave, as colloidal particles at higher lion of aggregated particles. The aggregates particles thus formed are called micelles. both lyophilic Their molecules conta nd lyophobic groups. The colloidal behaviour of such substances is due to the formation of aggregaies oF clusters in solutions, Suet ‘egated particles are called micelle: ERENCE BETWEEN DIFFERENT TYPES OF COLLOIDS Mulino jar colloids: Maer eeular coll s Associated colloids 1 They are formed by the -agurcgation ofa luge number of atoms or molecules whieh generally have diameters less sols of gold, sulphur, ete They are molecules of large size,e.g, polymers likerubber, aylon, stareh, protein They are formed by of aggergation of a large ete. no. of ions in concen- trated soluti sol, 2 Theirmolecularmasses are hot very high masses, They have high molecular ‘Their molecular masses are generally high, 3 Their atoms or molecules are held together by weak van der Waals forces. Micelles are the clusters or aj regated patticles formed by «sociation ofolloid in sohution. The commen examples of micelles are soapsanddtergems. The formation of micelles t above lakes place ‘panic temperare called Krafitemperature( Tal shove a particular concentration called critical micellization concentration (CMC), They are capable of forming ions, Micelles ny contain as many as 100 moleculesor more, Due to long chain, the van der Waals forces holding them are comparatively stronger, tration, greater are the van der Waals for For example sodium stearate (C,,11,, COON) isa typical example of such type of molecules. When sodium stearate and C,,H,,COO™ions. ©,7Ha,COONa = C,,H.COO" + Nat Sodan stearate is dissolved in water, it gives Na* Stearate ion The stearateions associate to form ionic size. micelles of colloidal has long hydrocarbon part of C Srophobie and COO py: Hy, radi i Which is art which is lyophilie.451 ion of Soaps : When oildroplet comes in ising contact with soap solution, the stearate ions arrange themselves around it in such a way that hydrophobic parts, ofthe stearate ions are in the oil or grease) and the hyddrophile As hydrophilic partis pobar, these pot with the water molecules present sound the ole result the oil droplet is puilled away from the surf celle which i 1 away with the excess of water Hi a eee os ° (a) Grease or oil on surface of cloth (b) St (6) Tonic micelle formed suri the stearate ions of soap molecules help in making a stable emulsion of oil with water which is washed away with the excess of water, It may be noted that a sheath of negative charge is formed around the oil globule Similarly, in case of detergents, ¢.g,, sodium lauryl sulphate, viz, CH\CH,),, OSO; Na*. the polar group is OSO; alongwith the long hydrocarbon chain, It is an example of an anionic detergent as anions associate together to forman ionic micelle, similar to that of soap. A well known example of a cationic detergent forming an associated colloid is thatof cetyl uimethy) ammonium bromide, CH,(CH,), ,(CH,),N’Br, “6 General Methods of preparation of Colloids Lyophilie and lyophobic colloidal solutions (or sols) are generally prepared by different types of methods. Some of the common methods are as follows 4.6.1 Preparation of Lyophilic colloids : The lyophilic colloids have strong affinity between particles of dispersed phase and dispersion medium.These colloidal ° jearate ions arranged around the oil droplet unded by sheath of negative charge. solutions are readily formed by simply mixing the dispersed phase and dispersion medium under ordinary conditions For example, the substance like . clatin, gum, starch albumin etc. pass readily into water to give colloidal solution They are reversible in nature because these can be precipitated and directly converted into colloidal state 4.6.2 Preparation of Lyophobic colloids 4.6.2.1 By oxidation : A colloidal solution of sulphur ean be obtained by bubbling oxygen (or any other oxidising like HNO,,Br, etc.) through a solution of hydro sulphide in water 2H,S + (or any other oxidising agent) —+> 211 +28 4.6.2.2 By reduction : A number of metals such as stlver gold and platinum, have been obtained in colloidal state by tweati \ the aqueous solution of their salts. with a suitable reducing agent such as formaldehyde, phenyl hydrazine, hs Peroxide, stannous 2AuCl; +3.5nCly —> 35nC] hydrogen eee chloride + 2Au iold 0 —> 24u +3H1COOH + 6HE ele 2duCl, + 3HCHO +311,“SURFACE CHEMISTRY eesesesFNHN-.._—_—_ — The gold sol, thus prepared, has a purple colour and is called purple of cassis 4.6.2.3 By hydrolysis : Many salt solutions are rapidly hydrolysed by botlin nple, ferric hydroxide and aluminium hydroxide sols are dike solutions of their salts, For solutions of the corresponding > Fe(OH), + 3HCI obtained by boiling FeCl, + 31,0 ehlondes Similarly silicic avid sol is obtained by the hydrolysis of sodium silicate 4.6.24 By double decomposition : Asol oF arsenic sulphide by obtained by passing hydrogen sulphide through a cold oxide in arsenious water 5,43, solution — of AsO, + 311,S—> As, 4.6.2.5 Mechanical dispersion : In this method. the substance is first ground to coarse particles. Its then mixed with the dispersion medium to get # suspension. The ision is then grinded in colloidal mill. It consists of suspé two metallic dises newly touching euch other and rotatin tions at a very high speed about 7000 in opposite dir revolulion per minute. The space between the dises of the inill is so adjusted that coarse suspension is subjected to eat shearing force giving rise to particles of colloidal size. Colloidal solutions of black ink, paints, varnishes, dyes ete sre obtained by this method 1 SEMERGE meng tremendous heat generates by this method and give colloidal solution, The colloidal solution prepared is stabilised by adding a small amount of KOH to it erat cteioces Brede's arc method 4.6.2.7 By Peptization : The process of convertinga freshly prepared precipitate into colloidal form by the addition of suitable electrolyte is ealled peptization. The electrolyte is used for this purpose is called peptizing agent or stabilizing ‘agent. Cause of peptisation is the adsorption of the ions of the electrolyte by the particles of the precipitate. Important peptizing agents are sugar, gum, gelatin and electrolytes. Freshly prepared ferric hydroxide can be converted into colloidal state by shaking it with water containing Fe or OH ions, viz. FeCl, or NH , OH respectively. Fe(OH), + FeCl, —>[Fe(OH), Fe?” +3Cr- From Colloidal parties Preeiptate — elecratyte otFe(onl, “Fecr, of FolOH), Preparation of calla! so by peptisation | ro Callas Mill 4.6.2.6 By electrical dispersion or Bredig’s are metho Ths method is used to prepare sols of platinum, silver, copper old The metal whose sol is to be prepared is made as two immersed in dispersion medium such water ete. The dispersion medium is kept cooled by ice. An electric are / ne are js struck between the electrodes. The 4.7 Purification of colloidal solution ‘The colloidal solutions prepared by the above methods usually contain impurities especially clectrolytes which can destabilize the sols. These impurities must be eliminated to make the colloidal solutions stable. The following methods ‘are commonly used for the purification of colloidal solutions. 4.7.1 Dialysis The process of separating the particles of Joid from those of crystalloid, by means of diffusion col through a suitable membrane is called dialysis. U's prine is based upon the fact that colloidal particles can r a parchment orcellophane membrane whil through of the electrolyte can pass through it. iple not pass le the ionsSURFACE ChmMinTiy fee Dialysis The colloidal solution is taken in a bag (parchment paper). The bag is suspended in fresh water, The impurities slowly diffused out of the bag le gel frequently to avoiel solution The distilled water is chs ation of the erystalloids otherwise they may start in be used for back into the bag. Dialysis removing //c} from the ferric hydroxide sol Hlectrodialysis The oilinary process of dialysis s slow To increase the pace of purifieation, the dinlysis is is called carried out by applying electric field, This pro electrodialysis. Kidneys in the human body act as dialysers to purify blood which is colloidal in nature. The important application of dialysis process in the artificial kidney machine used for t ion of blood of the patients whose e purifies kidneys have failed to work, The artificial kidney machine works on the principle of dialysis. = CRYSTALLAOIDS © = COLLOIDS ADDITION OF IMPURE SOL DISTILLED WATER SOLUTION or CAYSTALLODS 2 CELLOPHANE on PARCHYENT BAG ——- Eleetso-dialysee 7.3 Ultra ~ filtration : Sol particles directly pass through ‘dinaty filter paper because their pores are larger (more an 14 or 1000mj2) than the size of sol particles (less an 200m 1). If the pores of the ordinary filter paper are ade smaller by soaking the filter paper in a solution of +atin or colloidion and subsequently hardened by soaking in fomvsldehyute, the heated filer paper may re aud alloy the trae solation parties te rekon as era = filter snl the Fitters 1s known as alera = filtration, Dy using ata ATA Ultra € ted frony setting, The sot partictes are ntrifugatio at under the action af pravity by prev Aanetic impacts of the molecules af the mednumy The setting, ny haph speed centrifugal fore can be enhanced by w vin 15,0000 or more revolutions pet mite. Suet machines are known as ultra-centrifuges 4.8 Properties of colloidal solution of colloidal solutions are The main characteristic proper 4.8.1 Physical properties lal sols are heterogeneous in Heteragencous nature : Colloid nature, They consists of two phases and the Dispersion Medium the Dispersed Phase The colloidal solutions are quite stable. Then ate of motion and do nat se Stable nat particles are in the bottom of the container. Filterability : Colloidal particles are readily passed thro the ordinary filter papers. However they special filters known as ultralilers (parchment paper). 4.8.2 Colli Due to formation of assox of colligative properties like relative decrease in vapour pressure, elevation in boiling point, depression in freezing point, osmotic pressure are smaller than expected ‘an be retained by © properties : (ed molecules, observed values Fora given colloidal sol the number of particles will be very small as compared to the true solution, 4.8.3 Mechanical properties : Brownian movement : The colloidal particles are moving at random in a si motion, ~ sag his type of motion is called Brownian movement.y SURFACE CHEMISTRY The re on of brownian motion fs thatthe molecules of the Uispersion medium are constantly colloiding with the ppaticles of the dispersed plhase Dittusion : The so parnclesclitfoseFrosthighr concentration stom region, However die 10 they diffane a a fesser speed Seatimentatio particles sete down under gravity ata very stow rate. This phenomenon is used for determining the molecular mass of 484 Opti When | I pss th gh a sol, its path becomes visible because of seating, of light by patticles.Itisealled Tyndalt 1. This phenomenon was studied for the first time by Tyardalt. The illuminated path of the beam is called Tyndall cone, In a ieuesolution, there areno particles of suffctenily larg diamerer to seater light and hence no Tindall effect ‘s observed. The Tindall effect has also been observed by an instrument culled W microscope. wiengscore Tyndall effect 4.8.5 Flectrical properti Colloidal panicles 'yan electric charge and the dispersion ‘neclium has an opposite and equi charge, the system as a whole being eleetrieally neutral. The presence of equal and similar charges on colloidal particles is largely responsible ability 10 the system because the mutual forces «frepulsion between sitsilarly charged particles prevent them fiom coalesei ind coagulating when they come closer 10 fone another: The origin ofthe charge due 10 the preter fn the sol particles in mast eases is ‘ential adsorption of either positive or negative ions on their surface, The sol particles acquire I charge in any ane oF more ofthe followin 4.9.1 Duc to the dissociation of the surface molecules: Some colloid particles develop cleetrical charge due to the “e molecules. The charge ton the colloidal particles is balanced by the opposit ccharyed ions inthe sol, For example, an aqueous solution of soap (sodium palmitate) which dissociates into ions a8.C\p Hy COONa = Cys Hy COO” + Na The cations (Na") pass into the solution while the an (C\ Hy. COO~ hav yendeney to form aggregates due {uaetive frees present in the hydrocarbon chains 4.9.2 Duc to frictional electri the frie ation : It is believed that nal electrification due to the rub ing of the dispersed phase particles with that of dispersion medium, results in some charge on the colloidal particles. Th dispersion medium must also get some charge, because the friction. Since it does not earry any charge, the theory does not seem to be correct 4.9.3 Due to selective adsorp of ions : The particles constituting the dispersed phase adsorb only thase ions preferentially which are common with their own lattice ions, For example, when a small quantity of silver nitrate (AgNO) solution is added to a large quantity of potassium iodide (KI) solution, the colloidal particles of silver iodide adsorb 1” from the solution to become negatively charged, (at this stage Kt is in excess, and I~ being common to Agl) CoB adie? fA eas “Tees But, when a small quantity of potassium iodide (KZ) sole tion is added toa large quantity of silver nitrate solutior (AgNO, ; the colloidal silver iodide particles adsorb Ag* from the solution to become pas vely charged, (at thi stage AgNO, is in excess und Ag” is common to Agl). Agl + Ag™ ‘Sanity (hemeaion — _(AglAg® ‘SeemOe cum LA eit mmesrn(Aat Si) similarly, the ferric hydroxide colloidal particles develop rositive charge due to th sorption of Fy!" ions from he solution Fe(OH), + Fe" ——>Fe(OH),.1 off" lonson i} Ferric hydroxide colloidal particles develop negative charge Fe(OH), +OH” —> Fe(OH), OH (Cotlovdal fin excess) Negatively charned eric parce) Tyrone callodal particle) Fe(OH),+Cl’ — Fe(OH), - Cl” (Colecial” (in excess) Negatively charge fest pari) Tyrone clon! partie) 10 Electrophoresis ‘The phenomenon of movement of colloidal particles under an applied electric field is called electrophoresis. 1f the particles accumulate near the negative electrode, the charge on the particles is positive, On the other hand, if the sol particles accumulate near the positive electrode, the charge on the particles is negative. (5 erectciosoredts (8) anercecopho Process of electrophoresis 4.10.1 Electrical double layer theory :The electrical Properties of colloids can also be explained by electrical double layer theory. According to this theory a double Layer of tons appear atthe surface of solid. The ion preferentially adsorbed is held in fixed part and imparts charge to colloidal Particles. The second part consists ofa diffused mobile layer of tons. This se cha \ hat on the Fined part The existence of upper Fixed and diffuse parts of double ayer feads to ap of a difference of potential, known as seta potential op electrokinetic potential, Now when electer fields employed the particles move (cleetraphorests) ag LK rat aie aot ook igh aat {NOS agh ork agl agtine: rixéo NOME! FxXED MOBILE: FRER DFFUSED LAYER LAYER DIFFUSED LAYS Formation of electrical double layer 4.102 it the movement of the dispersed. particl jectro-osmosis moving by sentipermeable is prevented fr membrane. Electro-osmosis is a phenomenon in which dispersion medium is allowed to move under the mnfluence of an cl Arical field, whereas colloidal particles are nol allowed to move. The existence of electro -osmosiy hits suggested that when liquid is forced through a porous material of a capillary tube, a potential difference is setup between the two sides called as streaming potential. 11 Stability of sols Sols are thermodynamically unstable and the dispersed phase (colloidal particles) tend to separate out on long standing duc to Vander Waal’s attractive forces. Nowever sols tend to exhibit some stability due to 4.11.1 Stronger ‘pulsive forces between the similarly charged particles : All colloidal particles in any sol possess similar charge. Therefore, due to the electrostatic repulsion these are not able to come closer and form aggregates. Thus Sttonger repulsive forces between the similarly charged Particles in a sol promote its stabilitya \CE CHEMISTRY 2 Particle-solvent interactions :Due to strong particle- ent (dispersion medium) interactions, the colloidal ticles get strongly solvated. Due to solvation, the zctive distance between the colloidal particles increases, d therefore, the Vander Waal’s force of attraction creases. As a result, the particles are not able to form gregates. Lyophilic sols are mainly stabilized by solvation fects due to strong interactions between the sol particles and the dispersion medium. “The phenomenon of the precipitation of a colloidal solution by the addition of the excess of an electrolyte is called coagulation or flocculation.” 4.12.1 By electrophoresis : In electrophoresis the colloidal particles move towards oppositely charged electrode. When these come in contaet with the electrode for long these are dise ged and precipitated 4.12.2 By mixing two oppositely charged sols : When oppositely charged sols are mixed in almost equal proportions, their charges are neutralised. Both sols may be partially or completely precipitated as the mixing of ferric hydroxide (+e sol) and arsenious sulphide (ve sol) brings them in precipitated form. This type of coagulation is called ‘mutual congulation or meteral coagulation. 4.12.3 By boiling : When a sol is boiled, the adsorbed layer is disturbed due to increased collisions with the molecules of dispersion medium. This reduces the charge on the particles and ultimately they settle downto forma precipitate 4.12.4 By persistent dialysis : On prolonged dialysis, the traces ofthe electrolyte present inthe sol are removed almost completely and the colloids become unstable. 4.12.5 By addition of electrolytes : The particles of the dispersed phase é¢., colloids bear some charge. When an electrolyte olyte ws added to sol, the colloidal particles take up ‘ons carrying opposite charge from the electrolyte. As a result, their charge gets neutralised and this causes the uncharged, particles to come closer and to get coagulated or precipitated, For example, if BaCl solution is added 10 + ions are attracted by the negatively As,S, sol the F id their charge yets neutralised. This charged sol particle ils to coagulation. 4.12.6 Hardy schulze rule + city of different electrolytes is different The coagulation capa It depends upon the valency of the active ion are called Aocculating ion, which is the ion carrying charge opposite to the charge on the colloidal particles. Greater the valency greater will be its of the active ion or floceulating ion coagulating power” Coagulating power of an electrolyte is directly proportional to the valency of the aetive ions (ions causing, coagulation). For example to coagulate negative sol of As,S, , the coagulation power of different cations has been found to decrease in the order as, Al°* > Mg™ > Na* Similarly, to coagulate a positive sof such as Fe(OH), the coagulating power of different anions has been found to decrease in the order : [Fe(CN),|*" > POF > SOF > Clr 4.12.7 Coagulation or flocculation value: “The minimum concentration of an electrolyte which is required to cause the coagulation or flocculation of a sol is known as flocculation value.” or “The number of millimoles of an electrolyte required 10 bring about the coagulation of one litre of a colloidal solution is called its flocculation value.” Thus ,a more efficient flocculating agent shall have lower flocculating value.SURFACE CT eS SEY 1 FLOCCULATION VALUES OF SOME E ECTROLYTES Note: Congulating value or flocculating value o 4.12.8 Coagulation of lyophilie sols : There arc two factors \which are responsible forthe stability of Iyophilic sols. These factors are the charge and solvation of the colloidal particles, When these two faetors are removed, a lyophilic sol can be coagulated, This is done by adding electrolyteand by adding suitable solvent. When solvent such as alcohol and acetone are added to hydrophilic sols the dehydration of dispersed phase occurs. Under this condition a small quantity of electrolyte can bring about coagulation. [3 Protection of colloids and Gold number Lyophilic sols are more stable than lyophobic sols. Lyophobic sols can be easily coagulated by the addition of small quantity ofan electrolyte. When a lyophilic sol is added to any lyophobie sol, it becomes less sensitive towards electrolytes. Thus, lyophilic colloids can prevent the coagulation of any lyophobic sol. “The phenomenon of preventing the coagulation of a lyophobic sol due to the addition of some lyophilic colloid is called sol protection or protection of colloids.” The protecting power of different protective (Iyophilic) colloids is different, The efficiency of any protective colloid is expressed in terms of gold number. Sot Electrolyte | Flocculation|Sol Electrolyte] Floceutati value(mM) value (mM) NaCl 510 95 KCI W5 93 ASS, Cac, 065 Fe(OI), 020 (-vely charged) Mec on (ively charged 022 ost AIcl, 0093 AL(SO,), 0.096 AMINO), 0.095 i coagulating power 4.13.1 Gold number: Zsigmondy introduced a term ca gold number to describe the protective power of diffe colloids. This is defined as, “weight of the dried protec which when added 10 10 ml agent in milligram: standard gold so! (0.0053 to 0.0058%) is just sufficies prevent a colour change from red to blue on the addi is equal of I ml of 10 % sodium chloride solution, gold number of that protective colloid. LYOPHILIC PARTICLES (PROTECTING PARTICLES) LYOPHOBIC PARTICLES (PARTICLES BEING PROTECTED) Protection of colloids Thus, smaller is the gold number, higher is the prow action of the protective agent. 1 Protective power « — Gold numberjURFACE CHEMISTRY —— GOLD NUMBERS OF SOME HYDROPHILLC SUBSTANCES St. Hydrophilic Gott Hydrophilic Got ‘No, substance: number substance number \ Gelatin 0005-001 04-10 2 Sodium casemate OL 2 3 Haemoglobin 03.007 8 4 Gumanbie o1sa2s The protective colloids play very significant role i stabilisation ofthe non-aqueous dispersions, steh as paints, printing ans Osnvald inwoduced congo 4.13.2 Congo rubin numb sbin number to account for protective nature af colloids. I is defined as “ihe amount of protective colloid in milligrams which prevems colour change in 100 ml of 0.01 % congo rubin dye to which 0.16 g equivalent of KCL is added. [4.14 Application of colloids 4.14.1 Purification of water by alum (coagulation) : Alum which yield _4/'* ions, is added to water to coagulate the negatively charged clay particles. 4.14.2 In rubber and tanning industry (coagulation and mutual coagulation) : Several industrial processes such as, rubber plating, chrome tanning, dyeing, lubrication ete are ‘of colloidal nature. In rubber plating, the negatively charged pasticles of rubber (latex) are made to deposit on the wites or handle of various, tools by means of el ctrophoresis. The article on which rubber is to be deposited is made anode. In tanning the positively charged colloidal particles of hides and teathy id by impregnating them in re coat negatively charged tanning materials (present in the barks. of trees). Armong the tanning agent chromium salts are most commonly used far the coagulation of the hide material and the process is called chrome tanning, 4.14.3 Artificial rains : It is possible to cause artificial rain by throwing the electrified sand or silver iodide from an aeroplane and thus coagulating the mist hanging in air. 4144 § sive sol consisting of €0 ke precipitatio “Ths, these particles are removed by passin chamber provided with highly positively charged metallic knob. 4.14.5 For consists of negatively charged clay particles of colloidal the elay particles of deltas (Coagulation) : River water dimension, When the river falls into the se are coagulated by the positive Na*,K*,Mg?* ions etc. present in sea water and new lands called deltas are formed, Blood consists of negatively 4.14.6 Clotting of bloo charged colloidal particles (albuminoid substance). The colloidal nature of blood explains why bleeding stops by applying a ferric chloride solution to the wound. Actually ferric chloride solution causes coagulation of blood to form 4 clot which stops further bleeding. 4.14.7 Colloidal medicine : Argyrol and protargyrol are colloidal solution of silver and are used as eye lotions. Colloidal sulphur is used as disinfectant, Colloidal gold, caleium and iron are used as tonics 4.14.8 Photographie plates : These are thin glass plate: coated with gelatin containing a fine suspension of silve bromide. The particles of silver bromide are colloidal in nature Berns mulsions are the colloidal solutions in which both th dispersed phase and the dispersion medium are liquids” A good example of an emulsion is milk in which fat globul are dispersed in water. The size of the emulsified globules generally of the order of 10-Sm. Emulsion resemble lyophot sols in some propertiesa rr OT TT 5.1 Types of Emulsion Depending upon the nature of the dispersed phase, the emulsions are classified as: phase, the emulsions are classified as; 5.1.1 Oil-in-water emulsions (OV) : Theemulsion in which oils present asthe clispersed phase and wateras he dispersion ‘medium (continuous phase) iscalled a oil-in-water emulsion, Milk isan example ofthe oil-in-water type of emvlsion, Ln rilk liquid fat globules are dispersed in water Other examples are, vanishing cream ete Water droplets 5.1.2 Water emulsion (W/O) : The emulsion in which water forms the dispersed phase, and the oil acts as the dispersion medium is called 2 water-in-oil emulsion. These emulsion are also termed of emulsions, Butter and cold cream are typical examples of this types of emulsions. Other examples are cod liver oil ete, 2 Preparation of Emulsions Emulsions are generally prepared by vigorously agitating a mixture of the relevant oil and water by using either a high speed mixer or by using ultrasonic vibrators. The emulsions obtained by simple mechanical stirring are unstable. The ‘wo components (oil and water) tend to separate out. To »btain a stable emulsion, a suitable stabilizing substance is enerally added. The stabilizing substance is called ier or emulsifying agent, The emulsifier is added along wat the oil and water ithe Bees Foy py substances which cam act & eImuiies aye se dete gens long chain sulphonic cit, yephitic cottons gelatin, albumin, easein ete ulsifier Natu Different emulsifiers may act difte ly an the ease at particular emulsion Forexample, © Sodium oleate is used to prepare ail-in-w emulsions. ‘* Magnesium and calcium oleates in-oil (W/O) emulsions. When calcium oleate is addled to an cwulsion stabilized by sodium oleate, the stability of the system decreases. At a certain r 10 of Nat Cait» the oil-in-water emulsion becomes unstable. If the (2) wns concentration is increased further very quickly, then the reversal ofthe emulsion type occurs, that isthe oilsin-water cemulsion gets converted into a water-in-oil type. 5.4 Identiti mn of emulsions Several methods are available to find out whether an emulsion is of the oil-in-water type or of the wat in-oil type emulsion. An emulsion can be identified as follows. $4.1 Dilution test: Add water tothe emulsion. the emulsion can be diluted with water this means that water acts as the dispersion medium and it is an example of oil-in-water emulsion. In ease it is not diluted, then oil ac as dispersion ‘medium and itis an cxample of water-in-oil emulsion. 5.4.2 Dye test : An oil soluble suitable dye is shaken with {heemulsion, 1fcolour is noticed on looking ata drop of the emulsion, its oil-in-water type emulsion. In case the entire background is coloured. itis an example of water-in-oil type 5.4.3 Condueti fest : Add small amount ofan eleciralyte (6-8 KCI to the emulsion, If this makes the emulsion clectrcally conducting, then wateris the dispersion medium. fwater is not the dispersed phase.5.1 Emulsions show Mont alll the Acteristic properties of Solution such as Brownian movement, Tyndall Sleet, electrophoresis ete $2 These are o ‘gulated by the addition of electrolytes Fontaining polyvalent metal ions indicating the negative eharge on the globules 5.8.3 The size ofthe dispersed partiel nulsions in larger thaw those im the sols. It ranges tran 1000 A to 10,000 A. Monweverthe size is smaller tha uwtcles in suspensioins, 4 Emulsions can be converted into two separate liquids. by heating, centrifuging, f ng ele. This process is also known as demuls 5.6 Applications of emulsions 5.6.1 Concentiation of ores in m allurgy 5.6.2 In medicine (Fimulsion water-in-oil type) 5.6.3 Cleansing action of soaps. 5.6.4 Milk, which is an important constituent of our diet an emulsion of fat in water. 5.6.5 Digestion of fats in intestine is through emulsification,