14:38 lecture 4 Kinetics of Hydrometallurgical Processes Fan alah MBE a DE E+ 1G clots gb “Tesmobynanies Oe Aad! Aigee DGs- aE Ne ae $851 3 economic Wyss F glows S Kindes J) Thermodynamics vs. Kinetics ) + Is the reaction possible?) ct How fast is it? 7 200) 400 Thermodynamics reveal that C can be combusted at room T + However no comb. Until heating Eq spf p20 a4 Fine coal burhs faster’ “= than lump pieces + The more O, the faster it burns + It says that NaCl is highly soluble in water + However, no dissolution or very slow at no mixing also vavorte Kinetics has great and economic importance Scanned with CamScanner* Or [3 LEN poy Combutien —» Salid—gos 10, 1m lhaggens 00 cudoce fore \. poe wus “SES AUS Shas G3 ‘gs KEM YS aD p pDo Y excess Or aor) Ase lt su D & marxing ¢ io + Mack RE [Ad JIB 3 33 TE No MW Scanned with CamScanner. ‘Shiudvee Ao Cinnabar/red/hexagonal/S.G.=8.1 [soluble}in) fa Importance of stud ing Kinetics + Process design (fast, slow, residence time, etc.) 7 ae . t. + Provide knowledge about reaction mechanism ~— a Determine the rate controlling step diffusion or chemical reaction) Ree — Reactions take place in steps — The slowest step determine the reaction kinetics — This step is called rate controlling step (rate determining step) Sake aon fe for ny nb 6° + Determine the activation energy — We will focus on Heterogeneous system Solid-Liquid Reactions , 2S Kindies Je} 'o gh coliRe 529 72, 08 @ ig 4) Effect of crystalline form + Solubility can vary greatly with different crystalline forms of the same solid 5 Example aes) [a a5 dradute cinnabar/black /tetrahedron/S.G.=7.7/ sm eet — Boehimite/S.G.=3.160libIelin NAOH at 125°C < oo ‘eo — Diaspore/S.G=3.44/ [ein NaOHiat J se 25 many cone 227 ow + Even different lattice planes may have hee tet different solubility ee ee — Fe,0, in HCI Te etc ate oe Scanned with CamScanneryg! oles Jo JO iS ale a 9) a GOS dose BP 73% Ne ‘ C Ser WE eas alt yFosin ah. E62 © et bes tah PP aly -3 o® Jood 0B be Vas Boranelss "23 ? [ens Shudwe, Yoruwda 1 wiocial Foren]s 6d VAT shod fe ES pal) Shdwe HOE V1 SANS yy 52) SalubilS J) bob GSI ipekis SRE bos i X, e ifr GW Feces I WV wey (> Formule N-S bole cs oh WS os OG oT olane 2 Ber KEL OS Slane Scanned with CamScannerBoundary layer (Effect of mixing) + Origin of boundary layer concept (Nernst Layer) ua) = Veco a0) Rate of dissolution of solid C in liquid can be expressed as: + The a of dissolution of solid in water increased with the increase of ag because of the 5 co Physical process + The rate of dissolution not greatly influenced by T increase lecrease <20kJ/mole . (Chenoa process, process three cases Yt, © SF renin SC, a. Fast reaction ta ee Rate =Aaci, lel) = kAIC], = constant b. Slow reaction (cl.= IC) ; the rate wil depend on the reagent cone. [R] Rate = ko AIR] OF O22 Le) Gsabsb 05 vr us\e b. intermediate process i Genthe Pos (CLR) stl 12252 815 ANeagett J i ob sis 23 de Scanned with CamScannerLi L Desc, . . : san toe AE, ARM wa ny beaker Birserer Vaud > Solid Oissah tee = = E BHD arte costed 3 wars oe ESTE ay SG ge Cop! ol ' 4 a 2 NV 'WS 5 oe d 553 J Vl SS Soh 1 dod o bolle n& Dhysieod Coke ck: ; Process Me Gs Yaucden 43 2) SL (meen) § de U Mving J LL hens : ee SSL tole Nya) Vocar SULT 20 fv. bl Teng 2 We @ LS ai ae Ahapie i acess exp open ie a Ptr Process 3 late, Scanned with CamScannerBoundary layer (Effect of mixing) g ° [Diffusion-controlfed.feactions can be characterized from Chemically controlled/reactions by Boleke p30 UD @2Q xo 3) wad Effect of fluid {Effect of fluid velocity] {Effect of fluid velocity] * nin a) ~— Effect of temperature ,» ote ne 4 mene, § ev Boundary layer (Effect of mixing) + §-23Mixing will reduce the layer layer > higher rate (Rate~rpm*);a< 1 eA ‘can be obtained experimentally by plotting Log(Rate) vs. log(rpm) sys J) &o)3) “ joe de win Gaon eels > | abies spade 3 Offision plocess ings ue 65a espedat — re entetsn 955) Scanned with CamScannerEffect of temperature « For[diffusion controlled} process (Ea<20 kJ/mol) ene _AT_1 segs | Ragusa melee Gane [Eun Rate~T wakion) Fen + For{chemically controlled|process (Ea>40kJ/mol) ‘olid-liquid reactions Fa, Acvexi k= tous Ae 'Rr os eg Lemp Onges + For solid-solid reactions (Ea>8001 j/mol) D=Doe Fo/ ep 2agon. depend on eng, + For Hydrometallurgical reactions = Atlow T normally chemically controlled — Athigh T diffusion controlled 0 ea hemp eae Pa ne and ene 100, 130°C 1S mee te yale and Eee 1997. Reaction Rate Amount of Substance disappeared (formed) time of observation + Rate = aA + bB>cC + aD where a, b, ¢, and dare the coefficients for the balanced ‘equation, the rate is expressed as: Oe digateatteedt A ea s- 1468) =4 Rate = 3 : ‘Concentration (mol) @ Factors to consider: 1. Reactants concentration 2. Temperature 3. Mixing 4. Particle size (area and shape) B Time (8) Scanned with CamScannerSolid interface . Area of interface: fine particles reacts faster than large particles large surface area + GROTH of interface Sa nba serra BS? Rd Nn SLL INTE = Area offdise oF plav@)s constant —rate eis Saas 7 2 Area offiperdor pellet changes with time ~rate changes continuously cot T&S B61, Usd ASO oer Rake 5dpfo p38) 208 2 BI lop 023 Geometry of interface Example: Sphere For chemical reaction control (assume 1* order) aw Wemass, time, A-area of 4 + Rate= — 4% = KAC intortace Asuae =" C-cone. of acid (Cons) =" we + Area will decrease with time a cP A=4m? i w=tartp> r= Gas To. A= ang wis AY an( 2) wie = ew? 3 Rs Secon) A a tan(2) wie = ew” 3 ut Se assuming C is high (constant) AB a4 he. casbvaled al = el ie ae Tle aR SeqeSharcaseatemtte so a scant interms & Peadked sclid Scanned with CamScannerinverms & Fracken Ceaded Geometry of interface Example: Sphere In terms of fraction reacted for sphere Wo Bae @ ; rf La is Bren HF ann . w =4nrp aw 3 Rate= SF =kAc] aman? ¢ = dW = 4nr?pdr ~Anpr? = anh To r ¢ -f arate f de * Po ke nora ee . rs a-ni =X a “ Oe ——— Home work: repeat that for cube it For onggadede SUE Wecbonde ab:L Ba coZba Formation of solid products ‘A( uid) + B(Golid) —fuid products ieee 1. Roasting of sulphide ores “+f andsotid products |2ZnS(¢) + 30,8) +2Zn0(8) + 280,(8) ey, cept ot ci sce patie 2. Metals from their oxides me Oo en Fe,0,(s) + 4H,(g) >3Fe(s) + 44,0(g) Te fy Ting Pac sits SE So mmtine tinaty 9 ‘ispeaing Fakig a or ss 2 2 pata xe ‘ |, ND Stag nie Scanned with CamScanner0 e Yords to UA, Wedsly oy Or! 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Scanned with CamScanner' Formation of solid products + Such reactions are called topo chemical reactions cr) — Porous product Gg — Non porous product gz Sens a MD dl bl Sads ia of porosity 9.3, wehbe sow 2 1 Mp pp. Me Mr-molecular weight of product and reactant subeae 9 ds Bos FALE) Pr Pxdensity of product and reactant £ log @- stoichiometry factor of reador- ig + Examples 2Al + 3/50, Al,03 2 [——) nonporous CaC03>Ca0+CO0, ; = 6332-95 =) porous 00/2.72 art LEO Exceptions this ru is when gofous eeceriel ® , ecurs due to "ference REST ot hema expansion (ovdaton of Rare earth metals), 2 of reaction product (oxidation of Ma fo 20) se 3 BE, syyan g seb2l Bo wcll SHE ML Lager 7) © & cadks fe Nor eo ne pila Aa Sena 612 20126) SW da,tt) Sb! — ed ZL ovatels 31 d250 ou Model a + For noncatlytic reactions two models are available: sion model 2.(Shrinkingléoreymodel (SCM): ow 3 141 ssive convel oh (PCM): reactant reacts with reaction occurs at the outer solid oe oS + material througout surface ~ p= Beret eet i i ~ ae = ‘Radial pasition * eae Figure 25.3 According to the sbrinking-core model, reaction pro- igre262 Accoiig othe progesine-convenon model a ae seactionpro| ceedsala narrow font which moves ato the soi parce Reactant es sy trophont the sb pur ‘cou cometed ws he oa! pases oy. Scanned with CamScanner@ Snning core onobeh D Crogeesive coos eset waste 2) 3 cone I 55 6) SiS ho LE solid Ngee Lee! a sald Deore Noe v¥n sho bb Wh a . sis bad ew sot seh Seg cone. 1 Glo Hobs GUEs! le © aaB Ls FP 17 GUL Sffusion Windrous JI O? a2 2 pS 5 < NOH : a EA D5 LRA! US BI ate, 202 Rage 3st § 629 SI de des bib conc, 3 ete Jie | ales aebovot [sx6I R20 a> (sy sphere nu Ge saipor eebshch 3 bod dugits 3 OMSL oe yo Satins 11 25 voll BN gb om Blt suena SOLS nessizge ysey te 6% Core N StIbs Ash layer 1 bsG Bo! 2) exposed 6 1 tw, BX NOG 2 L gpiatag Js) Ua vb Gicces st KIS ? Scanned with CamScannerShrinking core model spherical particle + steps|fox the modeting fet eo sk* . oe — Diffusion of reactant A through > * boundary layer to the solid ee the des? SY surface fo desiga j vow Resided Diffusion of A through ash layer <8 — Reaction of A with solid surface — Diffusion of product back through ash layer — Diffusion of product through boundary layer in the main body of the fluid a Hatch nag 46 te Alay ee Tyas so se Radia poston © Shrinking core model spherical particle Diffusion through ash layer Surtace of srinking “Omescted core urtace of parle o- Bk nal Ws GoD Redcar. SL Fy ase BS, dos tab pA Zo 1Gstve nunbert moe of eager siting n (Oe Rees ero seco to Ftsow AC grep p E=—4nr DE Integrating from C, to C and from r, t0 fo J m-4% ‘Dror For diffusion-controlled process, C;=0 > c-G= But the rate of change of N is ~ to is the number of moles of reagent diffusing through shell thickness rfp i.e J 11(@)s Moles of unreacted solids and Mis molecular weight. Ua xP | Tit a? aN eo anpe Lo g tO \ Liak: 73 eens Key SFordrinatlle Pog Scanned with CamScannerShrinking core model spherical particle pone A tt a mh Mat Rearranging and ging and Integrating from, to rand from 0 tot MDC) “We 4-473 eo he = t= aye o72_ it aan | ap] ~ 2 BB -a ah Equation hiold up to 90%) conversion. The deviation ® because the correction for ee ilelle Toe 058 Wot | Yolume change was not taken jh 2 = io account Bros > 3 cl berg Se He ‘HEfusion Hetoush ash lager The plot of 1-3X—(1—X)* Vs, twill yield a straight ine Shrinking core model 6) spherical particle Ifwe take [Yolume correction changelinto account, the model equation Di z ‘MDC 2y_ ax a 3 bec c S come No ote pac — [ES = 1 + @— DAP = A=" Where My and pqrmolecular weight and density of [Se ee | reactant, fo tar ne ie oa 1Vy vp, Vq, molecular volume of product "ssi © = By, andreactant Equatiorfiotds up to 100% ae conversion. shoichiome tic AS Vowar JQ>5 Coert. Scanned with CamScanner” — «penn Erinn S (titans ummary Table oo 281 Comenion-Time Expres Table 264 Convenion Tine Espen for Vass Shapes af Pais, Siskng Core Made at z ees fax, Lox fax, wait 7 : g L = half thickness | = _2L_ = Pal? = a i com Taney TT ORC i r w) t i = fea Qa Le eae xpi Xo an 3 ESO aS oe Woo R ' rah cote ge RO ST yer 2 eee eet "once a & _ fax Sod Laraa-xyeezd—xy sy Fat“ %)? : Se a sf uw BE on ie, & fei-a-a om ch aa 5 aa Not eee ‘ paRa 5 on @) Ach OSB 2 BC ‘ eee = Lar panice. | L=1-G-ay? @D ete FE (= constant) a [Not applicable ipo ee rom aot are in BG Example + In the preparation of copper sulphate, 1_kg of copper in the form of 2-mm diameter spheres was dissolved in sulphuric acid with air agitation. If in the first 10 minutes, | [0% of charge was dissolved, how long it would take to solubilize the charge completely 100% cemesion Scanned with CamScannerSolution Asan? eae wore Hee Ga el As sa yhwrr is Ww dw. a shi we K So da shal 3) es 1 a W3-w3 tt 1 0. 1*10 T 0 = ore eS * = 7 =294min we wee 0-0.93 Scanned with CamScannerSolution If in 10 min ¥0.Lkg‘s dissolved >? Thi in is required to dissolve the remaining 0.9 kg This is wrong Because the rate of reaction is not constant and it decreases with the decrease ofsurface area we need to link the rate with the change of surface aitea Assu lo \Wo—weight of initial sphere fy Weight of sphere at tim Scanned with CamScanner