LAPORAN RESMI PRAKTIKUM KIMIA ORGANIK/PROSES KIMIA NOJUDUL PRAKTIKUM : 5 /REKRISTALISAS! DAN PENENTUAN TITIK LELEH NAMA TEMAZISOKHI ZALUKHU NIM 210802007 FAK/JUR FMIPA/S1 KIMIA (GROUP/PARTNER Al2 ASISTEN IRENE ANGGRIANI SITEPU DEPARTEMEN KIMIA. FAKULTAS MATEMATIKA DAN ILMU PENGETAHUAN ALAM UNIVERSITAS SUMATERA UTARA MEDANTemazisathi Zalukhu ‘10802007 No. Naya Date — ade BAB y REKRUTALISAS! DAN PENENTUAN TITIK LELEH Namo: Temazisohi Zalukhu Nim + 20802007 Goup tA Partner: 2 : —_Asisten {vere Aragon site) pln an CanscanerT.PENDAMUILIAN 11 Later Gelakang Kristalisasi_ —_ memegang —perdinan yong sanger penting ola- faye “velit kimia. Hal hi mmengingat —kuvong lebih 70% daivi pr oduk- produk —kimio —dihauilkan colon —bentuk—_paclataw [kvistal. Keu- Intungon ovis mengkasilkan —produk dalam ‘bentuk —paclati emtora fain adalah —brayo transportosi —lebsh_ murah, padoton lebih fahaw —terhadop —Fevtsakan —akibat — Eeyacknya cekomm posts; lan bentiE ~paclatan _lebrh memuclahkan ——dollaw peng epotkka, dow penyimpanamaa . “kristalisasi —dikategorikaw — sebaga’ sclah satu proses pemiSchan yong —episien. - Poda umumnya fan clavi a ose’ Fritalsor odalch untuk — pembahan dan penurniam, Adap. un sosaran — dovi_ proses kristalisosi_ adalah _ menghasilkan_pro- luk kristal yang mempunyar——Eualitas seperti yang _dling- inkow ,kualitas ersfal —antara lath dopat _ditentukan avi t- jo parameber —berikutyaitu: distibusr ukuran _bristal (crystal size visitation, oso), Femumion — Eristal (crystal purity) dan bentuk krie [tol Cerystal habit (shape). facla proses kristalisasi _-Rrisfal_ dapat di- peroleh dari felehan (melt crystallization) atow lavutam Carystal Wization grow sulttion ). Qari Feduo proses int yang palirg Eerie Idijumpai di indwt doth —Erisfolisos; dari lavutan, Kristolisosi lari “Jlaritonterdividovi “dua phenomena yang berbeola : pembentuk lav inti bistal/nubleosi (nucleation! don petumbuhan — bristol eryatal |growth) Baik — nukleas; maupun _pertumbuhan _ kvistal _memerluk- am kordisi - supersoturari dovi Tarutannya, Supersaturasy _didepenaik- om seknga’ —perbedaan —antoro —korsentras’.aktua dalam lavutan daw korsentvasi —dimoma pasa coir seca Tenmedinaynik. bert leeimbangan dengan rosa poolot (keloruFon), Keadaan —superscitu. asi_~ copat diperoleh dengan beberapa cara pil: degan pauka- han sulu:frendinginan untuk sistem —yarg _gradien kurva Feloruto- rviyo —posttre ola pemavatw untuk sistem yong gradien Kurva [kelovulomnyo negatig), “dengan —pemisahow _pelorut [biocmya dengan penquapon) ofau dengan _periavnbahom bakan tertentu “Cdvownn out ogent). Poca cliagyam —Forsentrast terhcclap suku , kelout- an “sucka” avon digambarkaw — sthagaeFurva —kelorutan_(solu- [bility] . Felarutaw“suatu Eohan eda yang hark terhaclap F- [evaikan —sulu (gradien —positie) tébopi ae Juga yar turun te |ehodeyp kercikath “suhu “Cgraclien negeiti) . Ado baba yomg ay- den wo keoutamygrsovgat leon, api ae wg og.TEMaD SOR COMING No, 200802007 _ Dale — 2 rerwasalohaw a - ae Aergapa massa _Fristal yong dihovilkaw —gouh_ lebi grav masa savmpel yang digunakan > ts Tyan Prcobaow a Untuk“ wergetalnis —pengettian dari kristalsast’ | rebistalisos’ _, Fristal = UnluEmergéfohui iri ivi baka pelarut yang boik untuk rekrstalins Untuk mengetoluf yu pertumibuhon histal dopa mempengarhy Kemurniow sin tu sevyowo basil rebvistalisast. = Unt mvergelahut pelanit ypng Tebih balk onluk rebritalsos? dar’ Felanifan Suaty senyowa 59 groom dalam methanol werdhdth daw 300 gr(teoml daw methawel dirgin con Fekwitan cb at 7.2 grim ch 95% dan 0,22 grlvcon Poo 3c = Untuk menggtaulfungs] dar’ peniodaant wonta = urtuk —mengetohuf —olasan _ditakukor wi Felouéan = Untuk“ wengetahi poor —yavg — menpergarht —adsorpst > Untuk mengelahuy —pembualan orang ake secara_ lengkap = Untuk mergetohut 2 cara aktivasi arog _aktip = Untuk mengetohui —pergoplikosian _prinsip like diulye lke = Untuk mengetahui pungsi variasipenambaham —avong alti A apo oan sia 5 _ = Da i jertian dave basi, rekristalisast , bristol = Dont mergelahu Oi alan pelanit yong boi untuk rekristaliiast = Papat mergetohui tu potumibulow — Frifol dpat menyergoruhj — kemurnian sualu — senyowa hosil — rekritaltost - = papal mengetahuy —pelovut yong leh boik untuk rekrislalteas; don Felavutan —suatu serpin 59 grligo ml dalam methanol mendith bun 300 gi{ too ml chlo ethanol digin dav kelonufan chin oir 3.2 gr fcoml poda 95% dan 0,22 grltto ml pad 98 ee = papot ment pugs’ dav’ peniadagw worn |= Popa rene ui olasa— dilakukaw wy? Felavtoun = Dapat mengelabus —eaktor yar wempengaruli adorpsi = Dopat —mergetahuy —pembueifan ~avang —aktie seanrat fergihap al 2 cova aktivosi aang aktie pergapliasian prinip like dis fungsi vos? pevasibakaBwazisokhi Zaluthu -2oge2oo7 —____ No 15 Metodolgi _percaboan — = Wi Kelavutan Beduarkan privsip like dialve like ito dimara senyawa polar akan lant dalaw feb polar dam Senyeuvo rompdar akan lorut dalam pelant non polar. = Wi Penicdoan ware Tidsorkan poda penyercran warn yong mélekot pach permukoan welekut snfetir atou alowi —menggunakan avang aktie —sehugat atborben = Rebiistalibast Proses_ pemurnion ial seav0 —vehrsfolinsi dengan cara _melovatban brat dengan pelarit —yory Seuai diertai — dengaw porcumbalan cwong abtie detgan pentbentukan —Frital dengan menggunatan — wetode perguapanan _|goduk= gad Tabu dalam gelas inte Pet Temavisobhi Zalukhu TINDAUAN — PUITAKA _ Biasanyo — kompromi — terbaik Idan fualitat —vistal—dicapai dengan 1 hingga—suhu kar pada —_pevmukaak ponaselndin gabts. rer kodon jgivav — tanpo—imendopatkaw — bristol ait pode suhw kava, ——_ pels atau “bahtaw dengan menempatkan tabu langsung di penongas @ . lau pendinginay dapat —sangat —_dipeilambat “dengan menyangga tabu dalam Kita berisi ait pee sul Torutaw con membiarkan —keduornya Imendingin seco _spontan Jepenuhnya ke sulu’ kumar. Proseduy becepot dav paling wremucstan —heulya chpot ditetukan dencyun elspeimen. (Ault 4. 1998) Sering kali senyowor yong akan dimumikem —secemikian _vupa ehinggs tidak “oda pela fungal yang dapat ditemukan wre melokukan —rekristalior’ dengan sukser , Geberopa senyowa — memiliki per ilokuKeloruton —sedemikian —tupo_Sehivgga —sebagian bear _pebvut melorutkannya — dergnn— sargat bait pode thu yerdah “chin tinggi lctau fidlok ~~“ membubarkan mereka sina seal’, Daloum fouus seperti? itu, compuran pelovut “have digurakan Sampel petloma — dilavutkan werggurazan yuma —wirumum peowt meric yang muda lar: ut (pdloruF bait. sdlanjutnya, semnentora —lovutan — dijoga_m endekat? —titih didih damm pergnduban tenuis enews, pelavut diva. Yio soumnpel —sedikit—lavut ‘cehnil bunt] ditarnkohtan —tder demi teles; lperowbahan ini menghosilkan _pembertukow Eeteruhan dimana Felean pelovut yong buruk “mengena? lavutan “yang dierdapkar sonyawe, eetapi kekeruhon devgan cepat” menghilang saat sebogion _barar ary. Ean dikecck; parambahan seketes dem) —setele pelant yong bua ai tanyutEow sanpon kekeruhannyo hilang. (Polleros p. a. 2000) Pros rekistalsasy melibattan ““pelarut ~padatin dalam pent yang — sesvai pach sul tinggi don mentungkinan _ krifal untuk terbentuk kembab packer penainginan , séhivgga —_kotoran tefap Bera Ida __dolam —Tarutaw.” tebnik ini, yovig seca Cebus diabul _tekistaliges lactam “fekopi lebih seringcisebut —sebogoiErifalisasi , dibahad dalam loots “tri. Pordlekaton alteratip — wielbattan —peleburcw — pochkow banpa. cdoxys pelorué dow Femudian —wewbarkor — Fristal terbentuk Fembxly sdringga itulan” “pergoter — tertinggaldalcun — fedleha . Mefode ini tidak sering —diguiakan di latorotorivwn. erganiE arena evista serivg terbentus dari _yninyat “rental “yong mengancluyg —pengontar dan sul umbuk ~ [memtsatnkan “podatan “muri yang dinginecin (Gilbert 9.C avd Martin sF. 2016) TANAMLTemaioth 2alubhy No, 20802003. J Date — ee TODOLOGI “PERCOBRAN lar. 1 Alot nol Nama Alok Ukurow | Merk. | [a [éelas kur ~__ |Pyree Cowon powelan = ~ Hot plate = S bung Teak - | yee Pipa kapiler = = rong 5 = 2 3 4 5 | weroco e = 6 z g Penongas ait = . Galan Nama Gahan Karbon _abtie met cinol EFavel Garoun_ mggris Benzena brett eter kaput boys baworna Gullo puts aselon =|s[@[=[=[al=}=peol=/ele Eloroporiv ‘kamper olole [a] of | al Bula lel} 18 Galo _bwiing — jor.3 -prosedu’ —_Percoboan lu 3.1 Wii Felorutom = pimasubkon sampel Fecal —pelotut (bareena, aseton, dietilete, Horror) = pikeocol- = Piamatt perubahan yang togecl itl .3.2 Wi Perindaan Ware. _ _ ~~ bilorutkan —sanpel Eom pearet yang souer [= pitambeltten barb at vibecoeNo 2 Date — ie: =Diownoliperubahan yg teyod? B33 Rebristalisast a _ = Dilarutkan sampel — fodat dala peloraF paves chlo —_gumnlah minimum clan itamkakean bats dich ith pelarat yang” seu? = PidineyngeanTonufan semra—potahanFirgga sil Eamar clan dlonjettem dalam “oly wikuk _panbenkukan —bristal. ota in = Dipschbew bristol yung focPentike- pearing vatkuim ae = Deu triste Ta po di =e sua yang sah - Hikeirgtan Frist seboluw aang dan ditentukan titit lelelyc, 0.3.4 Porentuan THE leleh bristol dipacleh = Piwosuéean scape! bubué feng hingga_Eetinggion 2-3 cn kedaleww _pipa__bapiler yong stlah satu ung doegel = ditenpattecinpipa_bapilar di alet qk teleh - = Piseuaitan lov Pemcwasuin —schfagn —suilw nar pada tingkal hepalar Sedang =pratat renting teh stlogaireilayg sult —antora germukcon Pencalra hingga habs melelehTemanisofni 2dluehu a M4 Flowsheet teonutay ‘ompl ait _—_ is «— diivesuktan kedaloun tobung yeaksy _——————— robing TE] Pahang ar [robuy or] Frsbang [+ difawibaliian dergoor—-difawibohhem de. | dtantahtom |e difaniatan de- beneena an agelon A di eler | roan Floregonn + ditecok ie diocol. + clitccok dike diwali penbahan |e diamabt peridaow |e dianalt peelalin |e dewalt prulolo wang eyed yang bead yong fegoch (pig tegect ail Trasil Hasil Hast Bui Penjadaan Warne sampel = inasub Fei Fedalow tobung reaks? eS 1| frabang Taobung or fe ditabahbawn 0.1 fe atanabitew 0.1 gw le ditowbahkaw os gram gram cian ablig orang aktic avave abtie i dikocok le dikaok fe dikocok le didigntkan fe idiom kon le didtameow [e daring Je dloring ¢ disovivg I diowati pauivotow (© dianati_peulohan © diawati — perubohon peg, op yang; tect yong tejadi [Rast] Rastt | tosil _Temaaisgthi zalubhy ‘20802007 Date -. — €. Rebristallicas = —__| Taampet 2 : += dimasuFFow a” gram sawipel clam oquoolert para <= dimosukban ~ tatu didth a a Cc - ~ + didinginkaw— Gnufow secaraperlalran naa subw kena = MauyuFton perdingian dala air eww pontertokeun triste +—_dipiaitcin “tantal “yong tetantuk cyan. penyoving —vaitum — did bristal +—_dikeringbaw <—_ ditimbang + _ditertukan “tite Teleh Has! b Penenfucn ili teleh evistal yang olperleh Sampelhasil” rebristalizns: +— dirosubtav ke dalam —pipa_Rapiler <= dieloktan pipa_tapiler_dialet tiie leh = dissuaibon Tu jemanasa, <= diamatiperubahow yore tegadi - = dak hastgo HosilTemarisokh See maki ME WASIC DAN PEMBAHASAN $7.4 dala Rerecbaan A. yt Kelovutan — scumpol _—_—|— . lt Pelowut: gz #6. -Sompet tquades | tretanal t_| tonto ttt +4 - _ “Keferangon: +44 = sangat | +4 = bw + = seclikit lovut == tidak larut B. Uj Peniciclan Wear No-|_sompel peautahon wortg sekelah cifamtattan wanna awol [on grown oveuig | 02. gram ovary 0,5 glam alktie atti ouong aR «| rate orange beng benting | bentng ¢- Rekristabbasi NO] pelakuan pengavnatcin 1 |pikasulkan dengan alu dla tompung Haus 2 [vimesuekan agram Fecal beater glasr 4 gram 3 |[pitambahkan dengan aquadet seccobuciyer = 4 padi hingga lant lorut 5. |bitambabkan os gram cary abtie 3 grown © | pitoab arutanhitom F | | bisaving altrat bering || 8 | pivapkan Tedapat bristal brisket garawt 9 | didinginkan Te [_ | to | Dikevingkow keri, uw bittmbang 1.5512 gramTemoaisokbi zalul No, -2toBon007 Date Fr. 2 Reaks dan Pshituigan TET 2.1 Reaksi — fercabaan ©. 2.2 Perhitngan wiketahuy wessa awial = 4 gram massa akhir > 1.5512 gram Ditanys = mas stall yarg dimurnikon gawols + messohistal = masa awal- Moga akhin 4 grom - 1.5512 gram = 2, 4489 gram ‘lo ralat = Nteart ~ fpraktek| toa! Ateari 4 agiom ~ 15500 er 4 gram > 61.2% fe 3 Penbcabasan Pooa __perecknan — wassaristal— yarg diheulkin Tela SRE chiben. ding wos awal pode proses rekritalsasi dikareraban pack pray int_sompel”“mergalam? panumian dimara 2at-eat tambahan paca sa pel seperttpernuliy cw alepas = dan diserap _eleh aang akte zak peworna yong disérap oleh rang aFtie akan meny ebab kaw moiuturnga mess kristat dan bridal” yang —dlpeoleh menjadi lebih muri.mansorni 20lukhy No. -2lagor007_" _ [EA Kesimpulan =a - = Pengerlion —kristalisast , retristatlisas, kristal — istalisonr proses yang mergeluartan eat telarut cbr) satu lovutan don membentuk krista. = = Rebristalisost , etrik pemurnian satu eat pect dari cumpuran Pergotomya —dergnn cara mengkristalkan — kembali eat tewebut sefelah diforutkan “dergan —pelirit yong sevai? kristal, satu” “pocktan —gaitu atom, molekul atau fon yang pengusun nyo takenios searateatuy ohn polanya berulng melebar seca tiga dimensi > Civi- iri Fakon pelwut yong baik uvtuk _ rebistalisasy A. menpunyos days pelorut yong tinggt pec suby_fingg? clan ceyp. Pelarut” “semakin fw srry Egan menue — srhu « 2 dapat “melnuthan pengofor —dletgan much —waloupun dalam jumlh SedibiE 3. hows dopat wenghistalkan 20 ype dimurntfan 4 horus “rampu _meryingkikan pargptor Git at murni peck temperabur velati¢ _tendah . > tajupeitumbuhan krista copat wenpergniuhi —Femuenian suaku segue hast! rebvistalisosi Toy pertumbukan Beit! adblah fakfor tin. yong _meperapiuh? —ukuran Erol, “aika qu Say Bidal yprg bear kan tebenluk. (qu _jertumhihow feistell ug fewer genuh fermbenlukan indi _biista” yar ban djengaiuh oleh“ semakin fingginyo cago Tewat jenuh.—formpm itt Foto akan serrakin cepat terbenfué —sehingge clapatdikefahuj Remurniannya , = Pelarut lebih taik untuk rekitalias chit Febnitan siaty Sn 59 gr/oo mt dailain methanol menciclth chin aogrlioml olalayn wefan aingin caw keavutan alae qagitcoml cada 95°C dai 0.2291 (roam eda 40 ——Pelared yang taah Fark talahsenypico 59 er com dalam melhanal _wmerdidh “yang — Felarutonrya selsar 7,2 grhaoml poelo Sulu 95 eC, Pelorut ini aikatakaw (ebih baie tnvero ap mempunyarFelorukan yping “tinggi dam “sulu didihhpebarubry m tified pelarutinya tidak lebih dow, dite tele vat Tedetyarg aw dikistalkan ,Tana? j i Zl ot = RUNgsi dari Peniocacan — wave ergs’ wtuk — menghilangkon eat _pengotor yang “merenpel = Alon dilakukan wi kelorufan untuk mengetohui pelarut mana yong sever untuk melarutkon sim pel tersebut = Faklor yang meMperpahi akon 1. Walt fontak, mamunginkan proses dgusi can penampelan _molebul cclortat letuguy ~ lei bak 2.Karakerstie colavbak, kemampuan _ochorpt —meniygkat dengam meniglatrya Paat oleh ccbottnt chin menirgkatnya po lanisabi- litasocborbat- 3. sw mélebul odbabat , WidroksiT can quiino mening thatkan en Kewainpuan parison Nitrogen —_mengi katkan — Kemeumpuow Penyist aclu pemukean , serakin bear Gwar pamutcn adsorber, maka aban samakin barack zak yang akan teradlsorps’ 5 -Konseniresi adsoba, semakin tinggi berentrasi adethot dala Tarufan make serakin bavgré imal sultans’ yang teCumput eacle pemukoan — ocbeien & suhy_, semabin tinggi swhu , coya adsorpsi_semarkin _finggi 7.eH, pH lareden —mreiyergmuhy below fan ton (aan clam attivifa gegus eurgss —fodo Brostbar daw Fempetisi ion lapiin pacer poses acborps; Seccpattn Perepdubkan, vila pergycllitan lamer atkoin pos caborpsi_ hetlangsury mor yuges, ~ Pembuoton arcing aktie secaia_lengkap 1 othidresi, prose pamanasay ayn shu 105¢ untuk meng kon kadar air 2. Kavbonas’ , Peranaaw - petawor, dickeukow gode suku 7 ty0¢ entuk ‘kam (coh Os. pemancsam . peitane , dilakukc pace. suhu zp0% util maghesilkm tea deh efanol pemmesan Karbon, teyeicl pemutusan senna organi j—Ratben twggn! pcielcr SuhTarazisorhi Zalybhy No, —2ia8o200% = Date a = da cara akttwasi —avong aktig as ~~ s.aktivas! Einia , wengunatan —bahan-bahan Fimo sdegn?_lakan Pengakticamiya untuk weneoh clou memulur conta —fatkonnya LAKlivosi_ gtk, dep» melakukon pemanesan pada sty terterttr untuk —revoaFickon lay _wemecah ikaton korhomnya = Pengophtasan prirsip tike dole Tike bacosaikan Prrnsip like disolve Tike , dimana serypue polar cbav tnt dalain pelarut pelor “dan seryouwa nenpoloy atan (art clam pebnrt non polar. Hol ini dtagan pado yi Felorfan sampal ~ Fuingsi_varigsi_ penarmbahgn -arong abtie bilokutcn untuk mengetohut — seboropa Besar macs, orang able yong dapat _merpengoruki —_(eakst 2. Savon = Sebaitnya praktian selanyutnya —belajar separtner sebum prablitum = Kbaiknyo puaktikow selanyubnya —merguasar —glewshel = Sébaiknya prattikon” selanyutryo _aFtie scot pabiEuim ~sebaiknyo partne Fam (ebth kompak loge > Sehoitnyo —“ortner “tom? Cebit abtip —_ = Sekoiknya —asisten tetap —meyago ewehaton agar chpat _mengosistensiAult A. 1998. Techniques ard Experiments for oiganie chemistry . Stxth edition Caligornio + Univesity Science Books foge 52 Gilbert g.c and martin s.P. 2016, Experimental organic chemistry Miniscale and _Miscroseale Approach . Sixth edition . usa: Cengage learning Page 92 “ Palteres .k. 2000. Experimental Orgavic chemistry Usk. John wiley & Jens. ine Poge 70 pln an CanscanerSIXTH EDITION Techniques and Experiments for Organic Chemistry ADDISON AULT “When | saw the crystals coming, | danced about the laboratory.” —Charles Loring Jackson [abet bisa aal esd eae edTechniques and Experiments for Organic Chemistry SIXTH EDITION Addison Ault Cornell College ao University Science Books Sausalito, CaliforniaPaine k Binders Maple Book Manufacturing Group ‘This book is printed on acid-free paper. Copyright ©1998 by Addison Ault Reproduction of translation of any part of this work beyond that permitted by Section 107 or 108 of the 1976 United States Copyright Act without the permis- sion of the copyright owner is unlawful. Requests for permission or further Information Would be sddrenad to the Permiaions Deparement, Univendry nce Books. Library of Congress Cataloging in- Publication Data Ault, Addison, “Techniques and experiments for organic chemistry/ by Addison Ault. ~ 6th ed. p em, Includes index. manossorea7e 1. Chemistry, Organie-Laboratory manuals, L Title. QD261L.AK4 1907 B47" 007H-de2 1814 cir in the United States of America 987654321 pln an CanscanerDon't cool too fast When is DON'T RUSH! If an excess of solvent has been used to minimize the problem of crystallization in the filter paper, some solvent can be removed at this point by distillation. This operation will also serve to bring back into solution any crystals that may have separated during filtration. In all cases, the filtrate should be reheated, if necessary, to dis- solve any crystals that may have formed and to give a clear solution. Crystals that form when the hot filtrate hits the cold flask are likely to be less pure than those that separate more slowly from solution. 9.5 Cooling for Crystallization After the filtrate from the hot filtration has been adjusted to the de- sired volume and all solid has been brought back into solution, the filtrate is allowed to cool. ‘The rate of cooling determines the size of the crystals. Slow cool- ing tends to favor fewer and larger crystals; fast cooling tends to favor more and smaller crystals. Very large crystals are to be avoided be- ‘cause they often occlude the solvent and its dissolved impurities, Very ssmall crystals are undesirable because itis difficult to wash them free ‘of the solvent and the soluble impurities, and they take longer to dry. Needles between 2 and 10 mm long are fine, as are prisms 1 to 3 ‘Usually the best compromise of speed, convenience, and quality ‘of crystals is reached by allowing the solution to cool to room tem- perature on a ‘ing surface such asa cork ring. Some- times you can hurry the cooling without getting overly small crystals iby swirling the flask in a beaker of water at room temperature, or ‘even by placing the flask directly in an ice bath, The rate of cooling can be slowed greatly by supporting the flask in a beaker of water at the temperature of the solution and allowing both to cool spontanc- ‘ously to room temperature. The fastest and most satisfactory proce- dure ean be determined only by experimentation. ‘often a good idea to finally cool the mixture from room temperature to 0°C (or to the freezing point of the solvent if it is above °C) in a mixture of ice and water. Cooling below 0°C is not often done, since colder baths are not so easily prepared and other problems related to the condensation of water vapor from the air in the form of water or frost require special techniques and apparatus. If the crystals are collected too soon, some material will be lost that would have separated from solution on further standing. The minimum acceptable time for crystallization varies from a few min- utes for some substances to days for others, and it can be determined only by experiment. To tell whether one-half hour is enough, two pln an CanscanerCENGAGE LEARNING LABORATORY SERIES for pele Uae iag ola tanta ee] Organic Salita A Miniscale and Microscale Approach Paes y a kod] John C. Gilbert Rn EL)Experimental Organic Chemistry A Miniscale and Microscale Approach SIXTH EDITION John C. Gilbert Santa Clara University Stephen F. Martin University of Texas at Austin o™s CENGAGE ** Learning”N6 CENGAGE ** Learning: {perimental Organic Chemitry:A Minieate © 20%6, 2011 Cengage Lenrming ‘end Microscale Approach, SIith tition wort o2-200.208 Joe ©. Gioert and Stephen F. Martin Product Dlectar: Mary Foch Prod Manager: Kista Mastroiano Content Developer: Thomas Martin Managing Sewloper: ler McCay Product Amita: Morpaa Carey ‘Associate Meda Developer Fitabeth Woods ‘Senior Marketing Manager ule Schuster ‘At sed Cove Ditection,Produetion ‘Management, and Composition: Lumina Datamaties, Ine Manutactaring Planner: dy Inouye Corer image: © Images created using VIDA {44.4.0] from Opent'ye Scientific Sftirare, inc. 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Forther permintion: question car be emaied 2 L [prrmisionrequestonengege com Ubeary of Congress Control Number: 2014948051 (sun 97305-00048 Cengage learning 20Charvel Center Street Bodton, MA 0220 vA (Gergage Learning isa teading provider cf customaed bearming shu thons with office locations around the globe, Including Singapore the United Kingdom, ‘Australia, Mexico trai, and japan. Locate your local office at wore cones comipiobal, Cengage Leatring produc ls aneeptesented i Carta by Netson Eeucalion, ‘To learn mone about Cenpae Leathing Solutions, vs warm e@ngage.com, Purchase any of our products at your loca collage stow oat ou preferred ine ‘sore wana cengagebrain.com, ee ES eae reer ae naa sens rar area aera eats reese eT pn eran Casco2 Experimenta Organi Chemistry Gilbert rat Martin ‘owing to the expense of the needed purification process oF to decomposition that may occtr duting storage and shipment. ‘Organic chemists devote considerable effort to isolating pure products, the ulti= imate goal being to obtain a substance that cannot be further purified by any known experimental lechniques. This chaplee focuses on the purification of solids by recrys- tallization and their characterlzation by the physical property of melting points. 3.2 RECRYSTALLIZATION Recrystallization of solids is a valuable technique to master, because itis one of the most common methods used fo purify solids. Other techniques for purifying solids ineludte subtimation (Sec. 2.20), extraction (Chap 5), and elromatography (Chap. ). Nevertheless, even when one of these alternative methods of purificas tion has been used, the solid material thus isolated may still be recrystallized to “The process of recrystallzation Involves dissolving the solké In an appropriate solvent atan elevated temperature and allowing the crystals to re-form on cooling, so thatany impurities remain in solution. This technique, which is technically called solution recrystallization but is more commonly referred to simply as reerystalist- tian, is discussed in this chapter. An alternative approach involves melting the solid in the absence of solvent and then allowing the crystals to re-form 30 that impuri« ties are left in the melt, This method ix not offen used in thie organic laboratury because the crystals often form from a viscous «il that contains the impurities and froin which it is difficult to sepparate the desired puire solid. Its interesting to nike, silicon used in computer chips. - - Alimost all solids are more soluble ina ot than in a eald solvent and solution crystallization lakes advantage of this fact. Thus, I you Fit lasolve a sll ivan Amount of hat solvent insufficient to dissalve it whan cold, ceystaks should form when the hot solution isallowed to cool. The extent to which the solid precipitates depends on the difference in its solubibity inthe particular solvent at temperatures between the extremes used. The upper extreme je determines by the boiling point of the salvent, whereas the lower limit is usualy dictated by experimental conve> rience, For example, an joewater bath is often used to cool the solution to 0 °C, wherens jeesalt and dry ice-acetone baths are commonly used to cool solutions to 20°C and —78 °C, respectively (Sec: 2.10), The sold should be recovered with sreiter efficiency at these temperatures, provided the solvent itself dics aot freeze. the impurities present in the original slid mixture have dissalved and resin ddisolved afler the solution is cooled, isolation of the crystals that have formed shoul éeally provide pure material Alternatively, the impurities may not dimelve 24 all in the hot solution and may be removed by filtration byfore the solution is cooled, Tho erystals that subsoquntly form should be puree than the original solid mixture. Solution recrystallization is seldam quite #0 simple in practice, but these two iealized generalizations do ouitine the basic principles ofthe technique Even ater a solid ha hen secrytaline it may sill ot be pire. Tham iti lenpor- tant ty determine the purity ofthe sample ancl co of the easiest methods to do this is by determing tw neting pint of the wld, This tehique is dexribe in Section 3.3. ‘Solution recrystallization involves the following miype: 1. Selection of ans appropriate solvent, 2. Dissolution of the solid to-be purified in the solvent near of at its boiling point. gry mnie sta tens coh apenas enh th sn im ely ng rete te ae secant sas apenas coeseama ewe noay ps toga cemapararcongre nat nea anes or tenapaeae ent pn eran CascoECLA B UL) bel Dt apes eee 5 Zs BS bee OTE aC CCITT Pe)EXPERIMENTAL — BENE NEMICTRY DANIEL R. PALLEROS University of California, Santa Cruz pln an CanscanerSENIOR ROOUCTION FOMTOR ast Soin SENIORAARKETING MANAGER Chany Ray senon peste ain Gers oe |LLUSTHAMONEDTTORS San ya ad a mioro orm coves rere conn covcert ‘kLustaATIONS ‘Thin eh wae wet in 03 Pom Lh by Late Wut a pent an rnd by Gouri Tecan wns ety Leigh ‘The peas print scatter paper GP Copyright 200 Wey Some Aight ern No pt of ti pubicallon may be reproduced. vod in erewa sysem or transite in any fom ot by any means. ebectonic. mechanical, ghowepying. recon. seating loretherwse, except tn permite under Sections 17 or 108 ofthe 197% United States ‘Copyright Ac, witout elber the prior writen pereision of the Publisher, or tuchoriasion though pustnent of the appropri pe copy fee wo we Coppa ‘Clearance Center, 222 Rosewood Drive, Danvers, MA 01923, (PR) 730-8400, a5 (778) 750-4870, Roques othe Publisher for permission sx be adres 1 the Peeminsions Bepurtiont, John Wily & Sons, Ie 11] River Steet, Hbohen, NF-OTONA, (201) 748-4011, fa (201) 748-6008, B-Mal: PERMMELSQ@ WILEY. COM, "To onder teks oe Fr cso service plese, all (MO. CALL- WILEY (228-8945), Lira af Congress Cataloging in Pblintion Dube ie. et Taper crank chemitey Dl Kl “m ches yeah tees ine, ISANOA7L-20080 3 kote pape) {.Chemiary, Orpni Labeshy arn | Tie QOSLFAS was Saran aent ar ‘red nthe Utd Staten Ame wovsresd pn eran Casco4.4 RECRYSTALLIZATION FROM MIXED SOLVENTS ‘Often the compound to be punted is such that no single solvent can be found to cry out the reerytalzation stccesahuly Some compounds have such a solubility behavior that nos! solvents ether dissalve theen very well at low and high temperatures o¢ do ‘ot dissolve them at all In wich cases mintures of elven should be used. ‘The sample is first dished using the minimum amount of a balling solvent fn which itis ccadily saluble (good solvent). Nex, while the solution is hept neat trailing with continuous string, the solvent in which the sample is sparingly soluble had solvent) ix aclded drop-wive: thi addition revult in the formation of douelines where the drops of the bad solvent hit the sokuton (lhe compound precipitates}, but the cloudiness rapidly dhappears asthe bulk the solution bs weed: the deop- wise adaition of the bad solvent is continued until the cloudless persists. At this port. a hot solution. The soltion is removed from the heat source, hot Bltered if necessary, and allowed 0 cystallie at Sow temperature I is vacwum-itered anu washed on the fiter using a cold aliquot of the mixture of the solvents. This mixture should have the same proportion of good and bad solvents as used inthe recrytaliation. LE ‘ach a mixture carinot be reproduced it is advisable to wash the crystals with a cold aliquot of the bad solvent. When the proportion of solvents needed to carry out a recrysallzation from a mined salvent i alady known, the solvents can, be mined from the beginning and the mistune used an if it were a single solvent. ‘Solvents used as a pai for recrystallization should be miscible (soluble in ach other) and have relatively close Boiling, points. See the savent miscibility chart at the beginning of Unit. ifthe boiling points aze too different, the composition aif Se mbt Wil cange ering boli. Good pe of recryullenton sere are cethanal-water; methanol-water; acetone-petroleum ether, toluene-petroleum ethet; cethanol-toluene, and acetic acd-water, In each of these alr, the frst solvent listed {sir most applications, the good solvent and the second one is the bad one. 4.5 MICROSCALE RECRYSTALLIZATION tification of small amounts of solids (20-200 mg) can be saccessfully achieved by ‘microscale recryallzation. Macro and microscale recrstllzations are based on the ‘ume princplex: they difer only in some operational axpecta. viding wenecessary "ransers iv the ey 10 handing sell amounts of chemicals. There is a special type of slaseware called the Craig tube to carry ut microscale recystallzations (Fg, 4.98), Tithe microscale recystallzation, dissolution of the sample and recovery ofthe ‘crystal after cooling are perform in the Craig tube. The crystals are recovered by centrifugation instead of filtration. The Craig tube comatats of a lower and an upper part Ths lower part is used to dsantie the sample. The upper pat, which resembles a plunges whet the ciclo fr the ud ered y cet. The of the plunge and the mouth ofthe hube ace made of ground glass. “The sample i dasolved in the hot solvent in the lower section of the Craig tube while stirring constantly by rolling a microwpatula between the thumb and the index finger. no insoluble impurities are present. the wystem i alowed to cool down and the crystals are recovered by centriugtion. To recover the solid, the plunger i inserted in the mouth af the tube. A piece of thin copper were ora length of thread i ted ‘around the stem of the plunger as shown in Figure 49h. and the whole assembly is inverted and placed in a centrifuge tube. The system ts spun down sn a {rabeat 3 neue Grcon 36) rng cestegaoon gad ans cag ground glass int and the solidi reiained on the tread of the plunger (Fig, 4.9). The assembly is removed fram the censifuge and the Craig tube is retrieved with the help of the hanger pln an Canscaner