Thermodynamics ya. * <=... io of heat absorbed in a reversible change tbsarbed is éalled entropy change. 2" definition of entropysyThe unit of entropy is cal /°K a : a + Entropy change during phase change : Heat is absorbed or evolved, when.there is a phase change. | There “aré three phases: (1) solid_@) liquid G) gas, ‘The heat can change the sybstance from solid phase to liquid phase is known as fusion he san change in liquid at definate melting point. So entropy change is-as-given below = . Solid ===> liduig MSpitoe ™ aq — { ir ‘ ; An, Tes Yo C ASjsion™ where, A Hision = Heat of fusion Ty = Melting pointThe bet which can change the naan 1 at of vporiston can change 0 2 ‘hangs Is piven below 4 BSrponr) = a a oe 2 where, 4H, = Heat of vaporistion + Entropy change during reversible process = The change of « system from one ste to another may occur either ing reveruble or ina ireverile way. Suppose a gas is enclosed in ylinder with piston and kept in a const, Suppose the gas undergoes an isothermal and reversible expansion from volume ¥ 10 F ducing which it bsonbs 4, quantity of heat from the reser, Faopy change a8 = & tin in entropy by the gas as, = topy by en Loss in entropy by the source aS, ~~ 4 T Net entropy change as, = — & ry change as, - £ - Lag If we compress the gas isothermally and Feversibly from ¥ 16 ¥, volume i 0 Y, ‘eat given out by the gus is ~4, and eat gained bythe resercir i's Etopy change aS, = — & + & For the complete cyclic process entropy change, AS a5, +45, <0 ‘The shove observation lads to two vary importa condoms Fin. even ‘hoogh pats of an slated system may experience «change in etry. The envoy cians fF heer cate sytem hen» reveal thal ching er Secondly, the ttl entropy change for reves isothermal cyle 210 tnd ence atthe end ofthe cycle te sem has the sume eno at thas inal, Entropy The process our by ill own, without the help of ouside free i one Airetion, ae known as spontaneous process, I cannot cceur by self in the oposite Airetion. Therefore all spontaneous processes are thermodynamical hrevernible snge during irreversible process : All natural process occurring ate ieversibe in nature Bx. © (1) Heat transfer from hot end 19 cold end (2) Expansion of gas from high pressure to ow prose Soppose # system is kept at higher temperature, say T)* K. It approaches 1 lower temperature level TK. ‘The entopy change in frst positioncaemtey (Semester tl) (Chor 202) Toacore we 8 3 tha, ene College Pipa Tee wae of Sn spontances proces im eae. ines re emo ney nica he dion of me te Entropy of for an ideal g eh as ea serena a ot empenewed Pre Tom Clee ie, ving of pss a pemeeses Poses #267 Sere ae accra ceen Sr ig nem ny ok is nine IE es Ia the dordr, The ‘entopy of iting of gar has poste vate Sgppee one et gue essing », moked volume tt mined wih tc ps ansing my motes wth volume Yi The resting solution baving total Somme is Ft Yy At conan temperate and pes the change in eaopy, eee s-5-eee "initia volume eben i wie Mie shone pee * ‘The tot esropy change will be, AS 45, + aS, 5 hen 2 mini het ep hee wtfowtpte gates] but ¥; and Fy have postive values ae * fis Fo ng Ha Thermodynamics SD emg ELSON SES SESS, CoStar cnten care em. So Cer Tor otha icing Of : Sopp mole fiction of fi gat i X, sed mole fncson of ether gm it Xen we tat on i (at constant temperature gm.mol volume) ™ my Rod Sug =~ Bm In Xy + my In Xq) when my + If tral moles of gas my + my = 1 then, een at He Bn eget nom Tt BSpq= = RBH +H) 0 This equation is appli when tah moles of « ga 1 one f 4 Sion tre eerey fenton = ‘When sate of the syiem cheba, work i it and coery eeechemistry (Semesterill (Chem 20 Mermodynauncs ver Cllese ar eo, oO roch » seal sae SSE pees 0 acs ee ei in more_imporent thatthe SSE, aries sponte ea ones energy 0 wei ae Sar gnany change (8 £). eTOBY chan Porcher a constant volume, ial - ane A an, Wich ee iret sytem, a5 re fcate of OE ond a a cary of aod iis way ea han va of 35 fon we oduct The ue ene fants represented by A ad 6 () Maxum ork con (4) (2) Fe ee fictions (2) Mesieam werk fonction Notes is deft portant wo decide the spontanity ofa reaction jechely So two thermodynamic stat a=E-TS ‘As E,T-S me sate function inthe mathematical equation of A.A is also ae fain Ail sage = 4) = = 1,8) Mia me: 4, ~ 2, %S, aaa Ay =~ HS) - = 7,5). =~ E) - 5, 748) ‘a fr conta empertre, T, = Ty = 44> ab- ras ‘Accor w ft law of th a AE 2) A= maf Therefore, the decease inthe change of halt fee energy fonction a constant somperatute is egal Ao the maximum work done. 4 is called maximum ce cc This is av referred to ar Halmbltz fre energy or Valnboltz Tincton ® (ibs foe energy fu “ee ibs free encry function is denote by Gs mathemati exresion i G-H-TS Therefore i is used during the change at consant pressure. HLT, S being the state fonctions in the mathematical expressions of ‘At inital stage: G, = My ~ TS, Ae last stage! Gy = Hy ~ TrS 46=6,-6, = hy ~ TaS)- Hh = TS. But at constant temperate, Ty = TT BG HH) — GS = 18) = AH- TO, - 5) = aW-Tas According to definition of enthalpy H-e+hv pie aps rars var ecealeee. n= AE+ Pay Setanta anes opton (0, aG- E+ Par Tas 0 —aaa oe a ba Aecordng © o'r r= a,-4 mast~? Qs sa-On-w erat copaina w= woik done by the stem pay = work that con be done by the system AG = se (pontaneous retin) = 0 equlibiom rection) + ve (aomspontancous reaction) + Gibbe-Helmoltz equation: —_~ L\ rset defition of te ey. “4 G-4-15 be HES PY Ges vos Lets tke ifereaation, ag = dE + Pay + vaP - Tas ~ Sar According to 1 and 2° law of thermodynamics, y= de + Pav y= Tas = dy + Va dq ~ Sat = ve ~ sar ut a constant pressure dP = 0 (ep = ~sar lal sons nell am ee Prermodynamlce This equation is known as Gibbs Halmoke equ ange with temperature and phere + The variation office energy change with variation of temperature and presse may now be considered G=H-TS ban Esry G-E+ evo e 3 a= ae + pav + var ~ ras ~ sar According 10 and 2° aw, > ly ~ aE + de, dy = Tas dy = de + PAV 4G = dy + VP ~ dy ~ Sat = vap ~ sar “ system undergoes, ‘well a5 change “This equation gives change of free energy whe reversibly, a change of pressure as well as change of pressure of temperature 1 pressure remains constant, dP = 0. We ean wit equation (1) 9 Below, (On = ~Sat @) « «Bho (On the other hand, if temperature remains constant dT” =(semester (Chem 209 cltage Coerat td appeal ne OE ” aaa fiona @ ATaK Tepe sb weve tne i E ie inal state and Gi the fal sey, “ae ee cee ie soit MPC Noy ot este change in pres nn is given BY er oy ne Bee comm ces 80 © 275K 18 gm HO = 1 mle! — > 1440: Swope. -f we as MO 527 a kt cian, Y= AT 2) Prove that le mets spontaneously at 25°C temperatere. er (leat of fasion = 1460 eal-mete-!) Here, 8S. 85am * 8 Somntng _ Alla alee 2 T t 7 ao | (ew a SS, a = s27— (BY) - 52743 f 2 « oh ag Si ~ 043 cal K? ‘From # moles of gas, Here A Siu > 0 -. lee melts spontaneously. G~ ner in (8) When 2 motes of water converted into vapour, caleulate its entropy change. im (Heat of vapourisation = 9720 cal mole") Ge eer in as a h as Ste fe ~ ee ? a Examples Cae oy anger alata pocon ID = 2298 9241 alle! OK 4 a+ te 7 r (9) One mote of water filed in Thermose Mask at 100°C. Calculate its entropy Gm Fo sits mee dg = change at room temperature, 45-0 (Cp = 36 caldeg moleidatey act a rea 210 tn a x5x-1) = =1798:53 camo! = 1 «36 (100 ~ 25) = nl ne ae 8 Speman ~ 220 = 9.89 eu. 20500) 56 catideg ea ee a is == 658+ 9.89 AG (203°K) (between 25 t0 354C) ~ =2A0ON (20500) a9950 calidep, Pole (AG) (mts a Op gue 9S ma Mr ted garg + 44024881] are 00 x «58 a ie ae erie eee 4 Snaing ~~ (my tn X, + mz Im X) Questions Sancti (3c intact aie aetna ne cat ie char ay hres oa a ee gen pe tener ?) ACI bar pressure, 1 mole H, and one mole N; gas are mixed at constans = era a ee Ea rp coos ras 4 Derive the free energy change equation with temperature and. premute Sau 2 [my nk, +m, In XG) +830 316 oe Sg * S21!rae Collage Chemisty (Semesters) (Chem-202) Unit 1B) Chemical Kinetics 1. Theories of reaction rates = ‘Ooce the ae constant of ection bas Bee determined at to temperature Srivtar et any ther cmpertre To aterpet the constants of the eqution and ‘Tincortcal ame work. To tis effet two principal approaches were made 12) Me transition state theory Collision theory of bimolecular gaseous reactions = ‘According tothe Collision theory it is necesary forthe seating molecules to collide mo that bimolecular reaction may occur Secondly by Collision the reacting (botcales should be activated to energy of activation, ony then reaction wil take place. a 162 is the number of molecules colliding por mi per second in s system containing 1 mole of reactants pet lie. Suppose “9's fraction of the molecules that are activated. Then specific rte 4 ~ 29 for reaction, A + 4 > products For gascous reaction Z and ¢ can be calculated fom kinetic theory of gases For the reaction between two identical molecules (4 * A) the rate of the reaction, @ £2200 ae ‘nergy of activation where Z is number of Collisions per ml per second, “E and "A is gas constant, T's temperature (°. Again, rate of reaction = [4]? = Kx? where Cis specific rate constant and ‘n’ is concentration of A’ molecules per mi i raumber of From kinetic theory of HE the no. of Colson perm per second (aeryé (FE)” where, 0 = diameter of molecules M = molecular weight of reactant kez com iy) Where 2° = Collision number Le. number of collisions per second per mt of the gas. When there is only one molecule per mi According Colson ear) oe Colson proucs on rota melee Mower he ay recon a ech 10 Clans may ge at preci molecule. Hence the etn aye cece nach cas Kapzeen hes, P= coton it has vas 11 105 P= when 1 alison profuces one produc: molecule while P= 10% wet 10° Colson ny give one produ malenia College Chemistry (Semester) (Chem-202) Teacanis A and B of molecular weight My a Fraction beeen two diferent ser 424] iM, 14, ctnn ante 2°= | <= mean Callison diameter 3. Activated complex theory of bimolecular reactions = (Absolute Theory oF Transistion State Theory) = Derive rate constant equation by thermodynamially by using absolte thor, of reastion ‘Scientist Eryng has shown explanation of trasition st complex theory). According to this theory, in chemical reaction. mole actnts are not resulting ino prodacts diel but there is «situation in which Tpotecales of reactants are produced activated complex. This complex decomposes st specific rate and gives product. 1 ist Products Reactants (Activated complex) ‘Assume that, bimolecular reaction is as follow \ A+B whee co Ee Product ‘ Concentration a . ‘where, = ete constant |= Equilibrium constant between reactants and ativated complex For above chemical reaction, rate of reaction is directly proportional 10 the concentration of activated complex a as i Fane ar where, m= state constant = respectively, Therefore, equ sensant for above tason ab ene a Now, mie of reason for any second order chemical reaction it Proportional to the multiplication of concentration of reactants. taki cn,coGH, +300, ‘Athenits derived a elation between specific ate constant (Kan tempeatre of the reaction (7K) To 7s0e here, = specific rte constant, R= gas constant, T= absolute temperate, 4 frequency factor, = enerpy of activation (minimum energy required for reaction 0 take place), This is one form of Arheneous equaton “Taking logarithm, ie Tonk oy € = lose 4 ~ “This is usual form of Antenius equation. A graph (Figure 1) of Long K agninst Ee gives saight lie with slope tan @ “Knowing X we can calculate T _ Pe T3058 ‘ the energy of activation £, and fom the intercept # on Y-aris we get the value of be 4 The Anenius law may be represented by dink | Ea Ea oe logy k= ae where, k= specific rate constant and Ea = energy of activation. Se laeetee Ceol trent Salk | where ky and ky are specific rate constants &t T;* Tapas oat wt A nar me = ane TAS ee te a ari® a eae eee Baim. ait Finn weve BE ‘ This nian sow ela ws Wyne doe ood 44, ~ totaman mt To arin. earth peel eine But according cliion theory beng eer ne De where, P= collision factor / $= number of callision ‘rs the transition sate of Activated complex Sy accepted be peace GO ay of inci AO 4./ Rffect of temperature on reaction rates : With nese in empeatae he rte fection and hence the ate eons increases sever fl. I he cond order Secamposion of gaseous CH,CHO. te ‘ne of reaction inreases 480 fold by 4 rive of 160%. Similarly the rate & decomposition of acetone dierberyic wid increas 2000 times by a 60°C ch in temperature Chena Kineton ‘COXCH,COON}, ——> GH CORN, + 260, ofthe reaction (7K) beacon Comte, T= sbeokte tempering, = cee aie BS cover Chait (cinimam eoey required for eaton to take place). This i one form of Arthencous aking logan, Noa #~ We A = Ee ‘This is usual form of Arthenive equation. A graph (Fgare 1) of Lot K againt = Ber“ the energy of activation Ey and from the iatreept 1 on Y-axis we get the value of logy 4 ‘The Arthenius law may be sepresened by dink 4 sive sigh Hine with slope tan @ = wg R we can calculate a Ea ee ee 7 where, = specific ate constant and Fa = energy of activation. Integrating, jemt-la passer neh) 0” Tome where ky and fy are specific rate constants &t T,°K and T,°K respectively.eit a I a nme corey of ction 648 DE Storming Be Bj : Aine is equal to te =< IF cesroncen, Tooter’! san ts opel Go eo To erhenion of Arvbenins Ea geeelien aye Ceomsiter the following reversible rea nh he a —— oh as of the forward rscion =f (4) (81 teh 8 pan of the Backward reaction ~ fy (C] (D] [Equations (7) and (8) ae known as Athens equations 2 (A) 1) = (C1 DI Imtgratng equations 1) and 8), we ge ia) = int, =~ B's consam ) ey _ ae te ~ (ata) 7 ne - Be u ® Ee + consant (4) 0 From thermodynamics, Van't Hoff eqsation is Equations (9) and (10) can be putas deka 7 hed oUt wh oC = i = ae BT ilaer pi, ting he vate of i fom equation 2) in equation (), we Bet [rea est) oy In equation (13), Ss constant. I is generally known as fequeny factor dint - fof the reaction. £ is known as energy of activation. >: e “ quation (12) is Known as integrated form Of Arthenius equation Thus equston (12) expresses the temperature dependence of I in tems of ‘hed, 16 A and E Both A and E are characteristics of the reaction. aa Van Hof propoed that equation (4) can be split up into two equi 2 follows dink, aT 8awe Cater Chemiey (Bemerteri80 (Chom eg me os A eh of nt tv fie nega me = ee fee spe {_“Befivation of Arebenios Equation eae ofthe becknd maton = (C1 12] am, 4 ia im) = 4 (e110) a. = (121 eam ca ponte 2 Fr Sentai, Vt Het eto is doe at aa 2 Frnt rune of es eqtion 2 in equation 2), we pet a a 4) toy ae, ae ae wer 1 ttc" Pn et pe 0 sb stp ito tw equation 8) 4 wr 7” quations (7) and (#) are known st Arhenet eqmtons rung equations (7) and (8). we pet Bs comment Uo) bh mye-Be = B+ commune Ua) Equations (9) and (10) can be putas fad ef wt by wd In more gener YReae In equation (14) & constant is generally known a8 frequency factor of the reaction. E is known as energy of activation “Equation (12) is known as integrated form of Amhenius equation. ‘Thos equation (12) expresses the temperature dependence of tin terms of 4 and F Both A and E are characteristics of the reaction. ur\ohne fy7 6 10? teamed! ee! 2+ The setation energy for the decomposition of 0, into NO, and 0, {20 eal the tegueney factor (A) Is 43 = 10! sec, calla the rate conta at 27°C. = 200 im: Rate cone = 4! eros” sane ee oo = a9 90 be kane > ht t a0, = A200 wet Actnatin cers tr the doompon og tag 4 = 136635 — 17982 1 pag S813 k= 43m x08 The rate content of reston ners 26 ties on increasing the ‘emperatare by 10°C. Cale the actaton eer, im tempest (23031987 x 298 308 = 16st at x oe? [AL27* Crate constant oa reaction 5% 10 Ht mot sect and a °C, rate constant 1.5 10° Bt mot se. Find out the activation ener sand Arvencous frequency tater usar lr oa]Ta 1.97 x 300 B 10080 «al 4 dons bs * Me A T5ehT 5 ony = bons © Spar oto _) = ony 150 + (Sap L907 35) == 2m = 64197 ~ 9608 ony 4 = (3864 4227 10" et Specie rate constant of decomposition of gaseous HI at S86 K | me 517» 107 and at 78K ie 3984 % 10%. Calealae activation emery and frequency factor A at 856 K hae by = 3517x107 T, = 556K Ro 39xw? T= HK Now, Sl tl ag tw i, Zone [7 | 230 «197586 4701 3.954 10" EF 0 5317 x10 = 460531 cl Rate cout t= 44-337) A= 3517 107 1 Frequency factor A= 10196 x 10! geet ee Chemial Kinether = 16 see Clelate he vv 0 Ain Are Rate constant k= 4-10 nso % 08% 10+ ee = 40% 109 « 135 x 100 4a 544 100 weet [AL © temperature, the rate of meting of metal in 05 M HCY is 1.7 mpmiday aod at 0" C1 e372 mpmiay Fd out the activation of eeray of the reaction. = 372 maldey Be » Sella , Toe ay & 1 Boe wg, £,+ 2 EO, tote 1987x303 x13 gg 372 2308 x LISD ogy, TF Ame T.-K 33K = 210017 at [Activation energy fr reaction is 24700 cal AL27 C, the rate coustant {s4 x 10 see, Caleulate the value of A in Arrhencous equation be ae oeltT Eno: Am - set hy logo = loay0A - Saar agg ag logy = lee * Toh RF= (4am + 17982 ss = nso Te aT an 399 10? oe --2s09 + 234 encion at 27°C 20d 37 Cay ate “he rate comtats for te ." Bleep cart ts = 8 ae! or repent, Bg tt x 11: The rate constant for »wnimelcnlar rection a 36 K and 886K are eit TEL ioe nad 35 5 102 Me wat! sc rapectney Find ot the coer, cthalpy of the reaction nd Arve, Tevation eurgy forthe forward and reverse tensions, n= 3904 eee cee wk oa lE F ams ‘The activation cy f he fad etn ‘Te cine cy fo te fad acon, po Baas 0k 6 Ly SHO an 7% Mew 5310 2.0 41.987 « 300 310 = LIB KAI x 3100 H10 pp, 7 % > 45578 cal mot! peat ‘Activation energy | _ {Activation ener Pie elaine A, (es Seen Fauy~ Fans” BE ese of stacey of reaction) Buin Fay = -3908 ‘ aoe ( a= AH- Anat) Egy = 45478 + 3906 Ray les oe ein, 9 n= +1935 - ao Po aa bx 12: Far the recemiation of Paine inthe panots phase, the specie rate a a. veratent me 57.6K is 22% 10 mi! and activation meray Ey ata. ‘cal mot, Caleulate frequency factor 4. Mth boty — ema Ni chin 2 me RA BED ot log K = LRA = Soeee Clee Chen (Senet) 43600 Goey ee WS % 1.987 x 457.6 S.sane = log - 2600 log - 2082 og = 2082 ~ 46576 (Converting 5.3424 in nuericy = totes A> Aaiilog of 161624 A= 1453 x 10% see Ex. 13 + The activation energy for the decomposition of HE is 44300 cal hy, the following. reaction, if heat of formation for oné mole of 4, (SH = 1350 cal, then calulate the energy of activation for the revery Hyg * Flag) SM ihe * pho Mo Calculate the frequency factor ACK = 3:5 107 lt mot! see“! at $86, ‘Ams: The reversible reaction is —- Hy == Mw * Fhe Therefore, the disci of HI can be represented as, 2h) SP Hy + Tyg) For this reaction, A.M = 2 1350 = 2700 ot For this reaction, E, = EAH = 44300 ~ 2700 = 41600 cal A = de AE or log tag d= ab dle 2.303 RT i igh FRe 2 ret beg eek 4 ar where, K = 35 x 107 B, = 41600 cal Reise ee a, eg = log 5 » i0°) + 100 = 738 sect Ex. 16: Decomponion of formic ad on gold surface fallen ft ew of Aes, For th a 0" C.K = 88s we! nad a 18S 292% Wo tet Caled! te aca srg ned nes hea"? as AO on ork aoe lh 5 leo oe EPS) 2 ee 02x st SB ee coe T.-M v2 = a3 K T= Ws 97 = 40K sani? og Toad x LAT 16 er he et rer econ, t 7 there constant 7.0 10-7 and 57 Gite 99 x 10 Calealate the activa hm =i - rir [E] weer, 7, = 7.4273 = 280K Ty=S1+ 2 = 330K att P= Antlog —27411 = Aatilog 52589 ae OFF wim x 10% Kyn7x 107 Knox 10+ Now 20x 105 = 62499 x 10% « 1314 x 108 x Ro 1987 = 176 x 10? ——————————pr Cage Chemisty (Semester dt) (Chen gen teh x (02 x 2304 197 2 aor «10° Tn, wa ctepalis Seamer Me aks “ey, a Ht be Jp ae ct cncneton = 1 mel core Catenin of T= 35% 104 cm (aa) am zea (242) eis tr, = nf aos per 60x10? Ba? 600 x 10 z= enqomns 97s 65x Px (AEDES SY TH me nn ci 18 8 a anatase ered me Coin “activation enthalpy and activation entropy. S Am: Hee 8 * 290 eal ma R= 1987 120+ 190 = 4 K, = 910% 1 ae! saree Lewe asin Kpeun os Was wie ce gf sng Rone nt ain em 1s stration enc. 4, =a, = a = 28900 — (1.987 x 403) 25100 cal] Texto 7380 185, = -1027396 cl mot® 1, activation entropy =~ 10.796 cal mat Questions EEE os Ty Bova te colon principle for bimolecular ganas reaction {@) Explain activation complex thon {G)_Evplain the effect of temperature on revcsion rte (6) Derive Arhenious equation CO re cosa fra mio sre mes SC fen 18 Ee ot the activation ene. e, = S806 K eat wot (Toe ots cons fre dcogston of NOs 38 6 2 A Ta and 24x 10" ae respensvey abate the cain me and frquency far Ae, = 256047 eat mat, A= 228 10" weEy" -ssaooid ysey v st uondiospe ayn ss200sd Mops # St Uondiosqy -uouswouayd nq v s! wondiosge afm wousuousyd 228F2n6 © Ht sonore tis -yuaquospe aq Jo aaupins ay) Wo K[uo a9e|d Soyer aes eal i a oe ynoysnonp painqustp st 2ouRIsq! L 30 pljos yp Jo 4INq aur inoysnosNy ae Fnosy) UTES ay} SUIEUIAA ayequOSge jo asoyd oq pur pinby, ay Jo Inq ay NOY es uonenuasti0s uordiosqe Jo asvo ayn wy ‘wondsOspE Se UMOUY St uouswouayd yons uatp “pinbyy 10 pryos ayy Jo HING SOHN 94. UT PasnypIP A[ars]dUTOd SF >IN]os jy " wuaquospe aiqeuns Xq_poqiospe nnjos ut quaseid sajnozjow 21nJos awog i 9g WED YHA “O19 [OM “IDEN AH! ae swuaquospe jo aoeyins ay wo paquospe sia yory (19 *N “fog *{4N go 9H) sase# snouwa axe a1ayy, “Ta sayBqUOspE SE MOY AIF UqIospE jo soeyins 24} UO Paqiospe aI0 YOIyNs s[PLDIEUE Pros 40 sand2[OU! snoaseA 24] 919 pd Wd “BY 9 (eurunpy) §O%[y ‘98 worIs ‘jeooseyD “32 yuaquospE ndiospe yotyM Jo aoujins oy wo [eLDeM YL ‘amyeU UL ofW2WIOXD sfempe st ssaoo1d uoNdIospy swarsks ay yo. st aoeid sayer + suiay jo woniuyad 0 wou laospe seu pans @ ye sajoed se pouyap st uondsospy 7“sore soups ‘Bung Jo aygnde st 8 aur 51 Stoo sows ung 1eoqW94D © waguospe 1 smioy sojnaoyour se8 e4p esse wr pane 50H sqouqe> 3 OOL % OF °F He om amped 69 8 0 ss PP a ooh ay 9 estes ‘6 pomaur ptaads 4q pauedanl 20 INDcenit (Sementer ID (Chen 29g, Sa heer EN am eit A eee = ‘enc of cheisarton OS aes in the UPPEF YEE OF the sig oe ges ot ae Ta ms (b) Bay alcohol (eyadin of hse oe ‘iol neo i ot ron a ow emperat chan ie task eg. OFyeen ssh a chemical ssorion aoe emo Se eae a a syn inter ope ene IY of ct a at a ar a tee ites a Se ree eect ieee a i oi tal = This graph can be easily. “expsned using Lang s+ In BET equation valve if ¢ se This isotherm explains the s+ Examples of Type Ill ‘Type LV Adsorption Isotherm The intermedia tn DET egation ra has to be very iene | ‘comparison to |. mealies Examples of Type a me servos on too (@) atbored at “95 98 on (Fe) say ind Ne Ng) abated a= 1n Adsorption Taher Type Ill Adrien Lterm Glas shows Lape dein fran Linge mnie <<< 1 Type Ml Adsorption Isotherm obtained. formation of matiayr. se There is no Nath porn in :— the curve which indicates tht | Type IIL Adsorption Isotherm monolayer formation is missing, ‘Adsorption Isotherm are Bromine (Br,) at 79C 0” silica gel or Todine () * 79°C on silica ge oA lower pressure rion of graph is quite similar © T3PE TL This explains formation of monolayer followed bY smultlayer.— dpe sis ofa pony of gars The Equation is spplicable to he als & ZK Where C is the concentration of the solute 2 Equations (1) and (2) predict the effet of adsorption of B28es (or solute) at constant ty Preset i tation mae ‘rere gman eet of en ad Yon = = log e+ Log Pc tog & = tog k + Log c 0) ‘This equation io he form y = mx + © and gives stright ine graph log P(e) log C Figure:3 Ig = is ploued aginst log P oF log C. a stright line shouldbe obtained as shown in the Hgure3. ‘The slope of the line gives the value of + and the intercept on Y-axis gives the valve of tog K and 4 = 2 = slope ‘Thus by using equations (2) and (4, the value of K and m canbe calculated om the raphe. Acetic acid or onllic acid solution is adsorbed om activated hucoal for which the Freundlich equation can be writen a8 © F Zach “C° isthe concentration of he sition of equim, © ithe amount ‘cid adsorbed on one gram of activated charcoal, 1 lop K + |; oe C Hence tog =ion Fn et ta orcs oe bing tHe relationship betuecn geet Lan z ct et os eS Soe7008 te mane surface per se ot es cont ta see Ten 6, eal nance ace wee ht Mls» a wis an of melee condensing othe hich condense on the surface is condensation isnot aking pss say on (0) Where @ square Sc wile acface at ing ace fy he g2s molecules, 1 the faction ofthe aes sleady covered sxx efter vo ig Rao demi tgs ma emit =) We ; (eisconsnnt. But ra of ropes one prs = (= = Woe {CLangaics Adsorption toterm = fee petal ont oferta soared Coro ses of ene a tt Frenti ites af evens § Si ea deceengeoteticrey Bes an EERE TSN : Tat an anton inter do he low Se es chem i aed 0 he llwing sssumpins sere mi arent samme 6 be simoecl i ert anean é o- ey Teen From kinetic theory of gases it follows that number of molecule striking the surface is proportional to the pressure of the sas ne? no KP “ Where Kis the propotonliy constant Now ES Tat ean To 4) (oecaue n ~ KP) ‘anak? a pean, toyy mo an KP Whore Ky i» com> (Semester) (Chem 202, ‘ sa a joa to toe ollowin form aman er. EE i paring w esa eee ra ep! es er BP. "Teer spas mppoed it one mobo ink ei se se OTS ce atic en ad ) ze co) ‘wre K, ~ pepoonliy constant, x= amovint of adsorbate, mt = amount of set ‘Thin intact te amount of ss adsibed per unit mass ofthe adsorbent sper be faction ofthe rie covered. Saag he vale of # in equ (9) me ge, By mulling wan p This equa ——— fl m ot fy At How pressure Hf pressure is low, we may consider that most par of the surface is availabe for adsorption ic. (1 - @) may fe taken nearly equal Instead of (1 — 0) a m= 70 we can wit an=70 on ot ¢ aoecnemity (Semester) (Chem 299 in Cte ia See epee ae ol a At tigh preare fips en arte, BO 8 rn ‘Questions —— ~ sudsorption and chemisorption sarmion (i) physica 4 ak {for adsorption. - expla ee ae, per ee Te Tecan ee Sear neers ow ky ie: is independent pressure Discuss « A low temperate there is physical adsorption ut thier bem ind ; , ee eaaaael ol ee ne netetn at high pressure = = 7 (5) Im physical adsorption the beat of adsorption is low, but chemical aaa F fesrption is associated with large beat of sorption - explain Teste inne jos £4 tr hat vl uae aes a a aa Oe nt mgm ont Hi ‘corrected for low temperature or high temperature aha same! Cine an plein rt (1) Gas makes filled by activated charcoal and used to absorb poisonous &2 Differentiate between physical and ehenical sisorption errata rereet © Nhe rae « agrees oo te 4 [2 te be cant in reg ad i Gn wd ‘activated charcoal, , de aeUnit 111(B), 1. Characteristic of catalysis (i) Thee are many types of Aiterent for ifferent catalyst (i) Wa cay fowy The ete of « catalysed reaction catalyst (0) The increase in ate of trate coosant K = Ae Where Kis speciic Ei ery of activa (oA camlpst (iy Some rections are slow due to high energy of activation 2.0) @ “The fiat reaction is catalysed by MoO, while the second reaction is cats by Nickel efned a catalyst asa substance which changes the rate ofa chemical reactos and romans utchanged atthe end of the reaction, (vi) Each caialys is specific for a spevifi reaction. (ix) Reaction with diferent catalyst may yield diferent products ez, Hcoon MSH, 1,9 + C0 coo cottege Chamietry (Semerter Il) (Chem 2p, oir Catalysis is) Methanol rom CO and Hy fe ofthe reaction Without being ung je which Increases the ra STrcrll reaction te called cata vray and heir mecasism of ©STOS a dy \6)Plymescion of seas — pg A 7) Bosch proces fe eg a) Mantis of ac wi tom etna | stetensseme | | Feraermrapier toll heel the end ts cl in se reason, tis regenerated proporal tothe concentration of te HeS0, (10) Deacon's races for Cl, hy -areation ay be de to decrease in energy of statin, Homogencous catalysis In such reactions by cats i in th same phase a he reactants an eating ‘omem is homogencous throughout ) Desomposition of acetaldchyde vate constant, is gas constant, 4 is collision number a vo When & decreases K, a well 8 tate ofthe reac, does not fet the equity constant of «reaction ugly 5 ee Gligy + Oy +h ose ae * Hah reacts a8 cast cH,cHO, 2kc10, —> 2KCI + 30, Ny + 3H; —» 2NH, In some reactions the rte of reaction decreases. Hence Oswald eau on SE H+ co,w ‘nuae Catloge Chemisty (Semester) (Chem 269, aC nacon when bv canbe vt we he ae oF TEHION Berea ecume the cae of ects high When te cata is ed, TY Of aE ee ETE creation creases, The ctl reaction pS in ep, (i) CH,CHO + 1, —> CHLI + HT + CO Gow) tae weed a8 beeps tear exenplag eg @ cay + —- CH + 1, (sd (2) Mafactire of Ni, by Haters pe ‘Other examples of Homogencous catalysis are ‘Combination of SO, seam and atmospheric xy PESERCE Of igs, oxide (etal) 280yp + 2420 * On — o by * May Mem |, 0) Hydrogenation of verb inte prance o ay + cals Ui fom of mane pn ‘converted into form of ghee (ely lke eh 191, 21,50, te this reaction, catalyst and reactant are inthe gaseous state, i) Hydrolysis of cane sugar in aqueous solution inthe presence of «mien i 38 cays. Cia riay * Haq EY CHO sag) * CA Pny Giucore Frcs 4. Enayme catalysed reactions: Eyes are prota molecules haces age nemo cami eins is plans and armas. ‘Enzymes ace specie for sei eo, an 0 tere ae a many ees 1 number of reactions Tolling are some of che xampls of Earyne cata (a) Oxidation of hana o nate ai by mendes sets ‘GyH,0n + 0, SSE ci,co0H + H,0 Here, catalyst aswell ar reactants ate inthe liquid phase. ‘Prepeition of hydrochlorie acid fom Hand Cl, in presence of water vapour as cay. Tag * Clap DLs 20, (B) Heterogeneous Catalysis some cbemicl reactions the catalyst remains in a different phase han of tne etn. The sytem is homogeneous 5 far as reactants are concerned bit it becomes heterogeneous by the inroduction of solid catalyst ‘eg. Ethylene reacts with hydrogen in presence of Nickel (old) Pelee Citen In heterogeneous catalytic reactions due 1 adsorption of reactions on cata ‘he initial enery dereaes, thus the distance between molecules of reat becomes lst. So the inter molecular forces becomes more effective. Activa energy becomes less and hence the rate of reaction increases. (2) aversion of cane sopar by iverase Eayme er 04 + Cathe Callan * 120 Giacore Frectoe (2) Conversion of starch wo mshan in rence of Gas (ato) C;,40,), + 40 2 Heat conve i it et woe we Glee onves src © ONE” we College Chemiy (Semester) (Chem 209) Fotiowing are the general characteristics of Emayee catatyte Gy Eeapmes donot dintard the final sta of equilibrium of Fevers racy, (2) Genely, te rac of te reaction is approximately ropetion othe concenteaing of Enzyme 8) Atop temperature, their catalytic fiieny is Found maximum. At 109%. (heir efficiency i completely destoyed G4) Enzymes canbe poisoned and activated like ordinary ety. HCN, 1,5 ag (C5, ae the tual poisons (5) Uteavioiet mys tend 10 destroy Enzymes (6). Eneywor are coupslated by dition of small quantitis of electoytes, eshing fn the los of thoi catalytic activi: (7) The activin of enzymes distrbed by small addition of frcign subst (8) Enzymes work ficiently berween proper pit range Derivation of the Michaelis Menten Equation for Enzyme Kinctiy “The Mictclr Mente equation, mich gives the velocity ¥ ofthe reaction a tems ofthe ssc concentration (S wy. Ro ‘The we ofthis equation implies seve assumption, which roquze tof ‘iplaaion. The reaction schome below is ofr refered 10 a8 the Michaelis Mena ton. - “ & ort ky s 2a), . = aie vf) Whee, E+ Base > Sebarate 8 Emme subse. compen P= Prades eked ‘To deive equation | from he ¥ which ee —— follows frm sat vm ty (85) —_—— ae sep, 90 that theo iat nay EES wont es Ge by eo mp. er Now we obtin mow wef co le ee cee smote wef expeions ets s couple re sepa nae aA sa ES ew ‘We now assume tha the rex isin ne whe hea 15] sey cont, wih a me om paneer or eth forward Tee es ae epedai epion 3 lw a ser that _ A TELUS. ~ hy (69+ 4 1) 19 Some rearrangement gives ws equtioe 5: ALES Cue 9) ‘We simplify equation Sy combining the thre rat const no one, wich is clled K,., the Michaels Menten rte constant, ti: ‘This allows us t0 rewrite equation S this way: 12S) - as An commie iman snes ‘Set thatthe total amount of e278 rs‘\ a Nirav College Chemistry (Semester-II!) (Chem.2o, ach reaction. We express that fact in equation 8, 1e concentration: and is always regenerated after ¢ ‘ [£5 is the total (or equivalently initial) enzyms [2,) = (41 + (ES) When equation 8 is solved for [£]. ry we can eliminate [E] from equation 7 substitution: (4) - 6) 15) — (pg) a Now rearrange and solve equation 9 for [ES] to obtain an expression wig, depends only on [S} (1S 2 nd [S] + Kw a When equation 10 is substituted into equation 3, we are almost finished: [45] (5) rr 2 fg] Ry We now come to the last important assumption necessary to arrive at equation 1. Observe that the maximum rate for reaction 2 occurs when the greatest possible proportion of the enzyme is combined with substrate all the time, which occurs whe: [S] >> [E]. If we assume that this is the case, then we can write Vax = y (Eo) 2 just as we did to obtain equation 3. Substituting equation 12 into equation 11 products the desired result -equation 1, the Michaelis-Menten equation vse Sol. Ky +15) a Question: 1. Mims oo 1. What is catalyst ? Give characteristics of the catalyst. “2, Discuss the mechanism of catalysis. (Menton equation) 3. Explain : He Homogeneous and heterogeneous catalysis giving suitable examples. 4 Write notes on : (1) Enzymatic catalysis tees