| il ~ (06 thé nhin biét thai diém két thie phn mg bing céch theo doi qué trinh gidi phéng sin phim cia phan img: trong phan img didu ché ethyl bromid, do san phim ethyl bromid lign tye durge eft ra khoi hén hyp phan img sang binh himg duéi dang giot dau ling xuéng bén dudi lop nude cdt, do 46 ¢6 thé nhan biét thoi diém két thie phan img khi cée gigt dau kh6ng con duge eft sang nita, ~ Hoe 06 thé dling chét chi thj mau 48 nbn biét thoi diém két thic phan img tong hop hitu co. Vi dy: + Déi véi phin img diazo hod, 48 kiém tra xem phin tmg diazo héa da hoan toan hay chua ngudi ta sir dung gidy chi thj tim hé tinh bot dé phat hign phat hién acid nitro du, 2HNO2 + 2KI + 2HCl + hb + 2KCl + 2H2O + 2NO Tod duge gidi phéng sé téc dung véi tinh bét lam cho gidy KI tm hé tinh pot chuyén tir mau tring sang mau xanh, 4 + D6i voi phan img thuy phan tinh b6t c6 thé kiém tra phan img da hoan | ton hay chua ngudi ta lay vai giot hin hgp phin img dé ngudi, them 1-2 giot dung dich Lugol. Khi nao hén hgp phan tmg khéng cho mau xanh tim véi thuoe thir Lugol (hay néi céch khée la khong lim mét mau nu cia dung djch Lugol) thingimg dun. - Nhin biét thai diém két thie phan tmg boi sy mat mau ca nguyén ligu dau, néu nguyén ligu dau cia phén img c6 mau con sin phim tgo thanh khéng mau hoe c6 mau khée véi nguyén ligu ban dau. Vi dy phan img oxy hod toluen bing thudc tim KMnOs, Khi hén hop phin img c6 tia nu va dich phin img trong suét khéng mau thi cé thé két thie phan tmg (vl KMnOs (Mn*) tan trong nuée tg0 thanh dung dich cé mau tim sau phan img bj khir tao thanh MnO, (Mn“) két tia min mau néu). 4.11. Mét 86 thiét bj due sir dyng co ban trong ting hgp hiru cot 4.11.1. May khudy tir gia nhigt M6t 86 phan img téng hop hitu co cé thé dién ra & nhiét d6 th4p hode nhiét 49 phong, tuy nhién c6 nhtng phin ing téng hep btu co hn hop phin — obi Sie img lai cn duge khudy tron va cung . cp nhiét. May khudy tir gia nhiét 1a mét thiét bj durgc ding phé bién trong Thanh khufy tir tong hop hitu co véi myc dich trén, Dia tir Cugn day din 05 dong dign chay qua Bang dieu khién 454.11.2. May edit quay & dip lye gidm Sinh hin <———4] Van xa chan Nat digu chinh khéng 9 *+—2 t6c 46 quay Binh hing Binh chita hon dung méi cit hgp ct i Noi cdch thuy Nat diéu chinh nhigt d6 Hinb 16. BO cat quay 6 ap Ie gidm thuémg duge sit dung trong tng hgp hitu co. Trong téng hop hitu co may edt quay & ép le giam durge sit dung dé cét Jogi hoan todn ho§e mOt phan dung m6i ra khéi hn hgp phn tmg. Phuong phép nay gidm dang ké thi gian so véi vigc cO can dung méi hoje cAt dung méi ra khdi hén hgp phan img 6 ap sudt khi quyén, dic biét phuong php nay rét ¢6 ¥- nghia khi hgp chat httu co dé bj phén huy bai nhiét dé cao. Ngoai céc thiét bj co ban trén, trong téng hyp httu co cén sir dung mat s6 - Bé diéu nhiét - May lic siéu am. - Thiét bj phan tng sir dung ky thuat vi song... 46BALI HYDROCARBON VA DAN CHAT HALOGEN Mye tiéu hoe tp 1. Trinh bay diege cée phan tng dinh tinh: cdc logi hydrocarbon, dén chdt halogen, aicol, Thee hién duge cdc thi nghiém dink tinh cde logi hop chat néu trén. . Gidi thich duge cae két qué thi nghiém. Viét duge cde phucong trinh phan ting xdy ra. 1.CO SO LY THUYET 1.1. Hydrocarbon Hydrocarbon 1a cdc hgp chét hitu eo chi chia hai loai nguyén t6 la carbon va hydro. Cac hydrocarbon thuong khéng tan trong nude, nhumg dé tan trong céc dung méi khéng phan cye, ; Hydrocarbon no, hydrocarbon eyclanic 1a nhimg hgp chét rét bén ving, ching khéng tham gia phan img cOng hgp, khéng bi oxy hod béi céc chat oxy hoa manh nhu KMnO, 6 diéu kién thudng. Phan img hod hoc dac trumg la phan ‘ing thé theo co ché géc tyr do (Sk). Hydrocarbon khéng no (cé lién két di, lién két ba trong phan tit) c6 khé nang phan img cao dé tham gia phan img cOng hop theo co ché Ai dign tir (Ar), dé bj oxy hod. ; Hydocarbon thom bén ving véi cdc chét oxy hod, tham gia cdc phan img thé ai dién th (Se), Hydrocarbon da nhan thom ngung ty thudng tao phite phan ti & dang két tinh khi téc dung véi acid picric: 1H 1H NO, NO, Phite 1.2. Din chat halogen C6 thé diéu ché cdc haloform (CHX) bang eich cho alcol ethylic tc dung v6i halogen trong méi trudng kiém. Phan tng diéu ché iodoform (CHIs) tinh thé mau vang nhat, mii hdc dc trung; xay ra qua céc giai doan sau: 1h + NaOH ~> NaOl +20 C:HsOH + NaOI — CH3CHO + Nal + #20 Dis Sy ass CUR CH3CHO + 3NaOl > ClsCHO + 3Na0H ~CHscho 47CLCHO + NaOH -> CHby + HCOONa Din chat halogen dé dang tham gia phan img thé 4i nhn. Khi dun néng a chat halogen vei dung dich kiém trong nude, sé xay ra phan (mg thuy phan: R-X + OH” > R-OH + X™ 7 Phat hign ion halogenid tao thanh cia phan img thuy phfin bing phan img y, co dic hiéu tao két tla bac halogenid voi dung dich AgNOs trong méi tring acid: X+AgNO; —-H’, agxd +NO3" Trong bai thyc tap nay sinh vién sé khéo sat mot s6 tinh chat vat IY va ting chat hod hoc co ban cia mot sé hydrocarbon dai dién cho hydrocarbon no (hexan, cyclohexan), hydrocarbon khéng no (tinh diu chanh: chita limonen, a. pinen va B-pinen), hydrocar- bon thom (toluen, naphthalen). Con d6i véi diy chat halogen, tinh chdt d@ tham gia phan tmg thé i nhén duge chtmg minh thong qua phan (mg thy phén cloroform trong méi tring kiém va diéu ché iodoform tralcolethylic, 2. HOA CHAT - DUNG CY 2.1, Hod cht - n-Hexan - Thuée thir Tollens (AgNO3/NH,OH) - Cyclohexan - Dung dich I, 5% - Toluen - Dung dich KMnOs 1% - Naphthalen - Dung dich NaOH 10% - Tinh dau chanh ~ Dung dich H2SOy 10% - Acid picrie bao hda - Dung dich HNO3 10% - Cloroform - Dung dich brom trong nude 2.2. Dung cy - Ong nghiém nhé - Nhigt ké - Céc thuy tinh 100m1 ~ Kep g6 - Ong dong 10m! - Gidy quy tim -Déncdn - Luéi amiaing 3. NOI DUNG THC HANH ‘So TT| Cée thi nghigm va cae buée tin hanh 3.1. | Hydrocarbon 3.1.1. D6 tan ciia hydrocarbon trong mét s6 dung méi (made, aleol ethylic) | Lay 2 ng nghigm, cho vao m@i dng 3 gigt toluen (hode cyclohexan), ri lan lugt thém vao timg éng: éng 1: 1 ml nude (20 giot), dng 2: 1 ml alcol) lethylic (20 gigt). Lic kj, quan sét va két lun vé d6 tan ca hydrocarbon} 48c trong céc dung mdi trén, ha la ng fag Fog 3.1.2. [Phan ting voi dung dich brom trong mde Ly 4 dng nghigm, cho vao mdi dng 1 ml (20 gigt) céc hydrocarbon khéc| Inhau: hexan, cyclohexan, toluen; tinh dau chanh. Sau d6 cho thém vao Ibi éng 2-3 giot duiig dich brom trong nue, Hic ky. Dé yén. Quan sét Imau trong céc dng nghigm, nhan xét, gidi thfch bing phuong trinh phan] | img va két luan, i Phan ting voi dung dich KMnO« long (1%) ‘Lay 4 dng nghiém, cho vao mdi éng 1 ml 20, gigt) cAe hydrocarbon khac| lahau: hexan, cyclohexdih, toluen’’ tinh dau chanh, Sau d6 cho thém vio mdi éng 2-3 giot dung dich KMnOy 1%, lac ky. Quan sdt mau cita hai lép| ichét long trong éng nghiém va nhdn xétou4 AHH, 1 dy hy y Sau dé thém 3-4 gipt dung dich HaSOx 10% vao éng nghiém vn edn maul | cia thude tim, Léc’ kf. Quan sat mau ciia hai lop chat long trong Ong nghiém. Nhén xét, gidi thich biing cdc phuong trinh phén img va két ludn. '3.1.4. Phan tng tao picrat naphthalen [Lay 1 dng nghiém, cho vao dé 1 ml (20 gigt) dung dich naphthalen bao hoa trong ethanol va 1 ml (20 gigt) dung dich acid pictic bio hoa trong ethanol. Lic k, quan sat, nhfn xét, giai thich bing phuong trinh phan! img va két Iwan, Dan chat cia hydrocarbon 1a ché iodoform tit aleol ethylic Lay 1 ng nghiém, cho vao 46 2 ml nude edt, 5 giot aleol ethylic. Bur] cdch thuy nhe (60°C), sau d6 thém 10 giot dung dich 125%, lic déu. Thém| [tir tir timg gigt NaOH 10% dén khi mdt mau nau. Lac ky. Quan sat, nhén| \xét hién tugng, gidi thich bing céc phuong trinh phan (mg va két lun. Thuy phéin dan chat halogen trong moi trudng kiém Lay 1 dng nghiém, cho vao 46 1 ml (20 gigt) NaOH 10% va 3 gigt| cloroform. Bun néng hén hgp céch tpi ye dy vita lac, dén khi hdn| hop déng nhét. Dé ngudi. Acid hod hon hop ae ting bang HNOs 10%, ‘Kiém tra bing gidy qui tim. Thém 3-4 giot dung dich thudc thir Tollens, Lac ky. Quan st, nhan xét hign tuong, giai thich bing cde phuong trinh| iphan img vakétludn. 4 “voile (oa (Oh be) 4. CAU HOL LUQNG GIA 1. Trinh bay cfc phin img phin biét hydrocarbon no va khéng no 4a thye hién trong bai thy tap. 2. Trinh bay phan (mg xdc dinh nguyén té halogen trong hop chat hiu ca. 3.2. | 3.2. & 49OO J BAI2 f ALCOL VA PHENOL Myc tigu hge tap 1. Trinh bay diege ede phan ting djnh tinh: alcol, phenol va cde dipheno), 2. Thc hign duge cde phn img dinh tinh ede hep chat néu trén. 3. Gia thich diege két qué: céc thi nghigm. Viér depe ede phucomg trinh py, ling xay ra. 1.COSO LY THUYET 1.1. Alcol Céc alcol chia duéi 4 nguyén tir carbon hoa tan trong nude & bt KY t7 18 nao, ting sé nguyén ti carbon lim gidm kha nang hoa tan trong nude. Tang s6 nhém hydroxyl trong phan ts, lim tng kha néing hod tan trong nude (glycerin tan trong nude & bat ky ty 1é nao). Nguyén tir hydro trong nhém hydroxyl cia monoalcol cé tinh linh déng, chiing cé thé bi thay thé boi céc kim logi hoat Ong nhu natri kim loai, tgo ra natri aleolat. Natri alcolat dé bj thuy phéin tao ra alcol ban dau va kiém: 2ROH + 2Na -> 2RONa+ Eat RONa + HO + ROH + NaOH Nguyén tt hydro trong nhém hydroxyl cia Polyalcol cé tinh linh dng hon monoaleol, Ching 06 thé tgo ra alcolat khi téc dung voi hydroxyd cia kim logi kiém nang, nhw Cu(OH)2 tao phite mau xanh dam, CH2-OH i i 2 f° Oo a CHa MN 2CH-OH + Cu(OH}2 ——e» oy ‘O-CH + -2H,0 CH,-OH CH;-OH ~~ HO-CHa Ton phic (tgo mau xanh cia dung dich) 1,2. Phenol Phenol 1a dan chat cla hydrocarbon thom, trong dé mét hay nhiéu nguyén tir hydro cia nhén thom duge thay thé béi mét hay nhiéu nhém hydroxyl (-OH). Cfp dign tir p ciia nguyén tt oxy trong nhém hydroxyl lién hop voi he ign tir n cia nhén thom (lién hgp p, 2), nén phenol cé tinh acid manh hon alcol. Déng thoi do higu tng lién hop +M ciia nhém -OH lam ting mat 46 dién tir cho nhan thom, dac biét la cdc vj tri ortho va para, cdc tac nhn ai dién tir d2 dang tan céng vao céc vj tri nay. 50| Nhém -OH lim hoat hoa nhan thom déi véi cdc tac nhan oxy hod, do d6 phenol dé bj oxy hod hon ede hydrocarbon tuong img. Trong bai thye tp nay, ching ta sé lam mot s6 thi nghigm minh hoa tinh chat hod hge co ban eta cée phenol sau: “Ten phenol | Céng thite edu tao | Ni it do ndng chay °C) | Nhiét do sdi ro Phenol on 2 182 Resor | (Resorcinol) . 10 a] Fiydroquinon wl ma a oe 1.2.1, Phenol thé hign tinh acid yéu Dung dich phenol trong made cé tinh acid yéu, khi tac dung voi dung dich kiém hay dung dich cdc mudi kiém carbonat, tgo ra phenolat bén vimg. CécHsOH + OH -» CsHsO” + H2O Khi tac dung v6i acid, phenol duge tao ra tir dung dich phenolat: CoHsO" + HY + CoHSOH 1.2.2. Phenol dé dang tham gia phan img thé i dign tir (Sz) Céc tée nhén thé ai dign tir dé dang tin ng vao cdc vi tri ortho va para so voi nhém hydroxyl (-OH). Oren 1.2.2.1. Phan img véi brom . Bromo hod phenol bing dung dich muée brom xay ra nhanh, tao hgp chat két tinh mau tring: 2,4,6-tribromophenol, HH OH Br. Br + 8B | + shor H,0 r Khi tée dung véi lugng thita brom, tao ma 2,4,4,6- tetrabromocyclohexadienon 6 mau ving: Br Br Br “Br 2,4,4,6-tetrabromocyclohexa-2,5-dienon 1.2.2.2, Phan img nitroso hod phenol (Phan mg Liebermann) 51Phenol ¢6 vj tri para tyr do, Ichi phan img véi acid nitro (HNO2) moi 5 tgo ra p-nitrosophenol c6 mau xanh djm, din xudt nay khi c6 ‘mat acid sy dic dé dang ngung ty. véi phenol(dt dé cho indophenol c6 mau 46 hdng va tan trong dung dich kiém lai cho anion indophenolat o6 mau xanh luc. wo) tN, Hono —_— od si dam ot) oF te =e H Indophenol (46 hdng) Anion indophenolat (xanh lye) 1.2.2.3. Phin img ngung ty phenol yéi aldehyd formic trong moi trudng acid sulfuric dc (Phan img Marquis) Cae phenol phan dng véi thuée thir Marquis (formol/H2SOs 4c), tao sin pham ngung ty c6 mau dd. Phan tmg ngung ty c6 thé xay ra @ vj tri ortho hoe para so nhém ~OH, phuong trinh phan img sau diy minh hoa phan tmg ngung ty xay ra 6 vj tr para: ‘OH Crom wa nC )-o8 4,4"-methylendiphenol iso; {>on H,S0, oH 4-(4-hydroxybenzyliden)cyclohexa-2,5-dienon 1.2.3. Phiin img cia cde phenol véi dung djch FeCl, Cae phenol va céc hop chét chira nhém hydroxyl phenol, cho phan ‘ng voi dung dich FeCl; trong nuée tao nhting mau khde nhau, dic trmg d6i voi méi logi phenol. Mau d6 duge cho 1a do két qua cia sy tao ra ion phitc phenolat v6i sit (II). FeCl + 6ArOH — 6H + 3CI' + [Fe(OAr)s]* - Vi dung dich phenol, dung djch resorein cho mau tim sim. - Voi dung dich hydroquinon bao hoa, lic dau chuyén mau xanh 14, sau chuyén thanh nau. Dé yén, tao thanh tinh thé hinh kim mau xanh t6i. 52OH | tS eo | FeCh iO HH Hem p-benzoquinon Quinhydron 1.2.4. Phain img oxy hod cite phenol . . Cée phenol d8 bj oxy hod hon hydrocarbon thom, Sy oxy hoa dé dang cia phenol so vi hydrocarbon thom tuong img 1a do anh hung ctia nhom hydroxyl, im tng 49 linh dOng cita céc nguyén tir hydro lien két véi nguyén tt carbon cia nhan thom. 2. HOA CHAT - DUNG CY j 2.1. Hod chat || Glycerin (€¥e wa dung dich 20%) = Formol (dung dich 37 - 40% |] Ethanol tuyét di formaldehyd) | -Alcol isoamylic = Dung djch NaNO2 0,1% | -Dung dich CuSOs 10% = Dung dich FeChs 1% -Phenol (tinh thé va dung dich bao - Thudc thir Tollens (AgNOx/NH:OH) hoa trong nuéc) ~ Dung dich Bro/H20 - Dung dich bao hoa trong nuéc cia - Dung dich NaOH 10% resorein va hydroquinon ~ Acid sulfuric (dic va dung dich 10%) 4 2.2. Dung cu i Ong nghiém, céc thuy tinh, mat kinh déng hé, dén con. Oa sq RO | 3.NQIDUNG THY'C HANH | S6TT Cac thi nghiém vA céc bude tién hanh [31 /Aleot in 3.1.1. }D6 tan cua aleal Ter Babe, 2 Oe fy Lay 3 dng nghiém, cho vio méi éng 5 gigt mot trong céc chat sau day: lalcol ethylic, alcol isoamylic, glycerin, Thém vio méi éng 2 ml nude cat, Lac ky. Quan sét, nhan xét hign tugng, gidi thich va két ludin, 3.2.2. )|Phdn ting cia polyalcol vdi dong hydroxyd \Léy 2 dng nghiém, cho vao méi éng 10 gigt dung dich CuSO, 10% va 10] lgiot dung dich NaOH 10%, Lac ky. Thém 4 gigt dung dich glycerin 20%| lvao éng 1 va 4 giot alcol ethylic vao dng nghiém 2. Lic ky. Quan sét, Inhgn xét hién tugng, gidi thich bing céc phuong trinh phan img va két| un > Le dell tye a La SME TE Brathoy a os ed 53|Phenol JS |Sw 1@0 thanh va phé huy phenolat Thém 1 ml nude ct vio dng nghiém 6 chita vai tinh thé phenol (hogs igiot phenol nguyén chét, hn y khong 8 réy ra tay vi phenol s& pg bong). Lic déu, Sau 46 thém vai gigt dung dich NaOH 10%. Lic mnhan xét. Tiép d6 thém vai gigt dung dich H2SOs 10%. Lic du. Qua Meee xét hign tugng, gidi thich bing cdc phuong trinh phan img yj | t 5 ~ [Lay 3 dng nghigm, cho vao mdi éng 5 giot dung dich bao hod trong nu Phan tg ctia cdc phenol voi dung djch FeCh iota mét trong 3 chit (phenol, resorcin, hydroquinon), thém tiép Iml (20) |giot) nude ct vao cde éng chita phenol va resorcin; dung dich bao hoal ‘rong nude ciia hydroquinon khéng pha loang. Lic déu. Sau 46 thém vad /m0i Ong nghiém 2 gigt dung dich FeCls 1%. Lac déu. Quan sat, ghi nhfo| | Peet (mau hod tinh thé) 46i véi timg logi phenol trén, giai thjch bling cdc iphuong trinh phan img va két ludn, 2” ake. p ae ered =~ 3.23. ) KZ [Phan ting oxy hod ede phenol vf : [Lay 3 éng nghiém, cho vao méi éng 1 ml (20 gigt) dung dich bao hoa| [ong nude cia mét trong 3 chét (phenol, resorein, hydroquinon). Sau 46, [them vio méi éng 3 git dung dich thude th Tollens. Dun céch thuy séij fahe 5 phat. Quan sét, nhan xét hién tuong, gidi thich bing céc phizong itrinh phan img va két luan. \Phan tg nitroso hod phenol (Phan tmg Liebermann) Cho 5 giot H2SOs dic vag Sng nghiém, thém 2 gigt phenol bio hoa trong lnuée. Lam lan’ bing ‘nude dé 5 phuit, them vao dé 1 gigt dung dich] INaNO2 0,1%, hén hop chuyén mau & bé mit tiép xtic cia hai lép chAt| long, lac déu hén hop. Rét cdn than hin hgp phan img cé mau trén vad Imét dng nghiém to 6 chita 5 ml muse edt, (ol! Natl Ul... de aya Lay 1 ml hén hgp da pha loding dé kiém hod bing dung dich NaOH 10% ., sau 46 acid hod hén hyp néi trén bing dung dich H2SOs 10%. Lac ky, |Quan sét, nhfin xét hign tung, gidi thich bing céc phuong trinh phn img| Iva két luan. [Phan img ngung tu phenol voi aldehyd formic trong mai tring acid lsulfiarie dic (Phan tong Marquis) Trén‘mat kinh déng hé cho 3 giot dung dich formol, thém 3 gigt HeSO,| \dac, tron déu bing dila thuy tinh. Sau dé, thém vai tinh thé phenol, ding| ldiia thuy tinh tron déu. Quan sat, giai thich va két lun. 4 34[trong muréc, Sau 46 thém timg gigt nudc brom. Lac déu. Thém nude brom| Icho dén khi xudt hin tia tring. Gidi thfch bing céc phuong trinh phan] limg va két lugn. 4, CAU HOI LUQNG GIA 1, Trinh bay phan img ding da phan biét monoalcol va polyalcol. 2. Phan tmg nao chimg t8 phenol cé tinh acid, nhung la mgt acid yéu? 3. Trinh bay cée phan tmg thé 4i dign tir dc trung cita phenol? 4, Trinh bay phan img dé x4c dinh nhém -OH phenol? Ye . bi 3.2.6. |Phén tmg ciia brom véi phenol trong dung dich mde [Lay 1 dng nghigm, cho vao dé 1 ml (20 giot) dung dich phenol bao hoal } | I 4 j i i | 9 Vaan aig Ye ch Tm ar. bie 2 555B BAI3 ALDEHYD VA CETON Mye tidu hye tip 1. Trinh bay duge eée phan img dinh tinh aldehyd, ceton. 2. Thye hién dirge cdc thi nghiém dinh tinh aldehyd, ceton. 3. Gidi thich duge két qué cde thi nghiém. Viét duge cde phirong trinh phéy ing xdy ra, 1. COSO LY THUYET Aldehyd va ceton la nhimg hgp chét hia co 6 chita nhém carbony, (©C=0) trong phan tit, i R Ar, R, An An Nox my N N\ c=0 Yc=0 Sc=o No= = =0 7 i? i? ee © Se=0 Fe: Aldehyd Ceton Céc tinh chét hod hoc co bin cia aldehyd va ceton 1.1, Phan img cng hop vo nhom carbonyl (>C=0) Phan img c6ng hgp vio nhém carbonyl (>C=0) xy ra theo co ché cng hop 4i nhdn (An). \ Vm Domo + BA, NEO ew Ny A +t NX pu 4 cham Ng thank Na ‘Tac nhiin phan (mg cé thé 1a LiAIHh, NaBHh, nuéc, alcol, NaHSOs, HCN, thuéc thir Schiff, hop chat co magnesi (RMgX). Ceton khéng cho phan img cong nude va da sé khong tic dung v6i thudc thir Schiff. - Phan ing cia aceton véi natri bisulfit Khi lac ky dung dich natri bisulfit bao hoa véi aceton sé thu duge hgp chét bisulfitic két tinh. Hyp chdt nay khéng bén va bj pha huy trong méi tru’ng acid. g b+8- yeh ONa === >c-oNa ==> >¢-0H LY be Sou Sona 56~ Phan ting ctia aldehyd véi acid Fucsinosulfuro (Thudc thie Schiff) NH, H,S05 CO ‘Acid fucsino sulfuro ; SOsH khong mau ~ HCI Qe LO SNH, Ci HN’ yH Fucsin base mau 43 07 Son oon R Nie | 2 4 ero HSO3 NH, Ht o Qty he AK! ROS WN, R Oo HN’ Y % | ‘Mau tim héng ~ Phan teng thay thé nguyén tit oxy cita nhém carbonyl (Phan img ngung ty) Co ché phan img (theo co ché xtic tac acid): \_ Ht \ + HO fro + HhN-G fre ° (G: OH, NH-CéHs, NHCONE...) Thue chét, day la phan img c6ng hop 4i nhan vao nhém carbonyl va loai nude tao sin pham ngung ty. Téc nhan phin img 1a hydroxylamin, | __ phenylhydrazin, semicarbazid, thiosemicarbazid... + Phan ieng tao aldoxim va cetoxim. Hydroxylamin 1a hop chat khong bén, dé bj phan huy va dé nd, thudng ding 6 dang mudi hydroclorid. Muén giai phéng hydroxylamin vé dang ty do, phai cho hydroxylamin hydroclorid téc dung v6i base yéu. 2 [NH2OH.HCI] + NajCO3 -» 2NH2OH + 2NaCl + E20 + COz a + uycon — BS on + H,0 HC HC Acetoxim + Ngung tu véi phenylhydrazin tgo thanh céc phenylhydrazon 37€\-cno + vaew—) —> Crome) “HO Aldehyd benzoic 1.2. Phan img oxy hoa Aldehyd dé bj oxy hod hon ceton, Véi cdc téc nhan oxy hod nh¢ nhur thud | thir Tollens, ddng (II) hydroxyd, aldehyd chuyén thnh acid tuong (mg. Phan tmg véi thudc thir Tollens (Phan img trang gong): HCHO + 2[Ag(NHs))]OH -» HCOONH, + 2Ag) + H20 + 3NH3 Phan ‘mg v6i ding (I) hydroxyd: HCHO + Cu(OH), +» HCOOH + 2cu0H) + 120 2Cu0H + CwOl+ HO Benzaldehyd rit d& bj oxy hod, dé hon nhidu so voi aldehyd mach ha, Aldehyd benzoic bj oxy hoa béi oxy cia khong khi tao ra acid benzoic két tinh mau tring: CHO COOH ox Oz khong khit 1.3. Phin ing tao haloform Cée methylceton (CHsCOR) va acetaldehyd la cde hgp chét chira nhém CHsCO- cho phan img halogen hod trong méi tnrmg kiém tao sin phdm haloform CHX; (cloroform, bromoform, iodoform), Phan tng tao iodoform cia aceton: CHs-CO-CHs + 3h + 3NaOH -> IC-CO-CH;+ 3Nal +3H20 13C-CO-CH3 + NaOH > CHI} + CHsCOONa | 2. HOA CHAT VA DUNG CU | 2.1. Hod chit - Formol ~- Benzaldehyd ~ Aceton - Alcol ethylic - Dung dich CHsCOONa 10% - Acid acetic dic \ - Thudc thir Schiff (fucsin base/natri bisulfit) - Phenylhydrazin = Thuéc thir Tollens (AgNO3/NH,OH) - Natri carbonat ~ Dung dich lp 5% trong dung dich KI - Dung dich HCI 2N - Dung dich NaHSO; bao hoa trong nuéc —~- Dung dich NaOH 10% - Hydroxylamin hydroclorid - Dung dich CuSO 5% 58rr 2.2. Dung cy Ong nghigm, cdc thuy tinh, mat kinh ddng hd, dén edn. 3. NQLDUNG THYC HANH [SIT Cac tht nghi¢m va cde bucéc tién hank 3.1. [Phin img cng hyp vao nhém carbonyl [Cho vao 3 dng nghiém: éng 1 - Iml ml dung dich formol, éng 2 - ImI ac ludn. 3.1.1.|Phdn img vdi thuoc thie Schiff (Acid fucsinosulfura) lA éng 3 ~1 gigt aldehyd benzoic va T ml alcol ethylic. Sau d6, thém vao mudi dng 2 giot thudc thir Schiff. Lac du. Quan sdt ngay rdi nhan xét va két 5.1.2.|Phan img ctta aceton voi NaHSOs luan, Cho vao éng nghiém 10 giot aceton, ml (20 gigt) dung dich NaHSOs bao hoa trong nudc. Lac kf sé thdy xudt hién tua tring va éng nghiém néng| én, Thém 5 gigt dung dich HCl 2N. Lac déu sé thay khéng cdn taa, Quan| Isat, nhan xét hign tugng, giai thich bang cc phuong trinh phan tmg va két| Phin tng cia aceton vai hydroxylamin [Cho vao éng nghiém 0,25g hydroxylamin clohydrat vai Iml (20 gjot)nusc Jodt. Thém tir tir 0,25 g NaxCOs dén khi hét bot CO>. Lic KY. Gan ld ‘Wich! Itrong, 1am lanh trong cbc nutée dé 10 phiit, thém vao 46 3 gigt aceton, lac ky. Lam lanh, sé xudt hign tia mau tring xép. Quan sat, nhdn xét hién| ‘trong, gidi thich bing cae phuong trinh phan tng va két ludn. 6 Lah, Phan ting tao phenylhydrazon ugn, jCho vao dng nghiém 2 ml nude cat, 5 gigt CH;COOH diac, 5 giot| ICHsCOONa 10%, 3 giot phenylhydrazin. Lac déu. Thém 3 giot| lbenzaldehyd. Léc kj. Dun séi céch thuy dng nghi¢m 5 phdt. Quan sat, inh@n xét hign tugng, gidi thich bing c4c phuong trinh phan (mg va két 3.2. [Phin img oxy hod aldehyd 3.2.1.|Phan ting vai thudc this Tollens ([4g(NH3)2]OH) bing cdc phuong tri mg va két lun. ICho vao éng nghigm 1 ml formol. Thém vao 3 gigt thuéc thir Tollens. Dun cach thuy éng nghiém s6i 5 phit. Quan sét, nhén xét hién tugng, gidi thich 3.2.2.|Phan img voi Cu(Ol 59 Cho vao éng nghiém 1 ml formol va 1 ml dung dich NaOH 10%. Thém| Aap chl|_> a doe NB day tk Leo, Wad he Sais Lie 0 3 gipt dung dich CuSO, 5%. Dun céch thuy éng nghiém soi 5 phat. Quan sét, nhgn xét hign tuong, gidi thich bing ede phuong trink phan img) agaIva két udn. 3.2.3.|Phdn tmg te oxy hod cita benzaldel [Trén mat kinh ddng hd, nho 2 ne benzaldehyd, Dé yén mt Ite ngoai khong khi, Quan sét, nhén xét hign tung, gidi thich bing céc phuong tring] phan img va két lugn. 3.3. [Phan img tao iodoform z (Cho vao Ong nghigm 2 ml nude edt va 5 giot aceton. Thém 10 giot dung] dich Ip 5%. Lae d&u. Thém ty tir timg gigt dung dich NaOH 10% én kh mat mau, Léc ky. Quan sét, nhan xét hién tugng, giai thich bang phuong trinh phan img va két ludn. 4. CAU HOI LUQNG GIA 1. Trinh bay cée phan img dinh tinh dé nhan biét hop chat ¢O nhém carbonyl? 2. Phan img ciia aldehyd v6i tude thir Schiff xéy ra o nhiét d6 thutmg hay nhigt 46 cao? Vi sao? 5. Hay gldi thich tai sao khi lam phan img tao acetoxim phai cho NayCOs vao dung dich hydroxylamin hydroclorid aén khi hét bot CO2? - Hop chét chita nhém carbonyl e6 céu tao phan tir nhu thé nao thi sé cho phan tg tao haloform?vy Bai 4 ACID CARBOXYLIC Muc tiéu hoc tap 1. Trinh bay duge cdc phan ting dinh tinh ctia acid carboxylic. 2. Thue hign dege cde phan img dinh tinh cia acid carboxylic, gidi thich duge cdc hign trong va viét duege phucong irinh cde phan tng dinh tinh cita acid carboxylic, 3. So sdnh duce khé ning phan img ctia acid carboxylic mach hd va acid carboxylic thom; acid monocarboxylic va acid dicarboxylic. 1,CO SO LY THUYET 1.1. Acid carboxylic Acid carboxylic (RCOOH) Ia din chét cia hydrocarbon hi thay thé mét hay nhiéu nguyén ti cia hydrocarbon bing mét hay nhiéu nhém carboxyl (- COOH). Tuy theo sé nhém carboxyl; cdu tao cla mach hydrocarbon ma ngubi ta phan logi acid carboxylic thinh: acid monocarboxylic, acid polycarboxylic, acid catboxylic thom, acid carboxylic mach hé...Cée acid carboxylic mach thing 6 s6 carbon cao, acid thom tén tai & trang thai rin, cdc acid mach thing dau day 1a cée chat léng linh dng. BY tan trong nude cia cée acid gidm Khi s6 carbon trong phan tt ting, nguge lai, d6 s6i cla cde acid tng Ién khi s6 carbon trong phén tir ting. Cc mudi kiém cita acid carboxylic tan t6t trong nude. CAc acid carboxylic c6 cfc tinh chét de trumg nhur tinh acid, phan img tao mu6i vdi kim logi, oxyd _ kim loai va hydroxyd kim loai; phan tmg decarboxyl; phan img do ct ditt lién két C-O trong nhém carboxyl (COOH) nhur phan tmg tao este, amid, halogenid acid; phan img dic trag cia gde hydrocarbon cia acid... Trong bai thye tap nay ching ta sé khao sat mt sé tinh cht dién hinh cia acid carboxylic. 1.2. M@t s6 tinh cht dic trung cia acid carboxylic 1.2.1. Tinh acid Acid carboxylic c6 tinh acid yéu, yéu hon cdc acid v6 co, voi pKa ~ 5. Tinh acid ca céc acid carboxylic phy thudc vao cdu tao cia géc R va sy cé mat cia cdc nhém thé cé trong phan tir. Céc nhém thé uit dign tir lam ting lye acid cia céc acid carboxylic, nguge Igi, céic nhom thé day dign tir lm gidm lye acid ca céc acid carboxylic. Dung dich trong nude cia cdc acid cé kha ning 1am chuyén mau cdc chi thj mau nhu gidy quy, methyl da cam,... Cac acid c6 thé tao mu6i v6i kim loai: 2CH;COOH + Mg > (CHsCOO:Mg + Hat Mu6i sit acetat dé thuy phén theo céc phuong trinh phan tmg sau day 61