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Chương V - HYDROCACBON NO (ANKAN, XICLOANKAN, Chương VI - HIDROCACBON KHONG NO (ANKEN, ANKAĐIEN, ANKIN) Chương VII - HIDRO CACBON THOM (BENZEN và đồng đẵng của BENZEN, một số HIDROCACBON THOM) Chương VIII - DAN XUA.T HALOGEN -ANCOL-PHENOL (Dẫn xuất HALOGEN, ANCOL, PHENOL) Chương IX - ANDEHIT -XETON -AXIT CACBOXYLIC (ANDEHIT- XETON, AXIT CACBONXYLIC)
TRUONG D�I HQC KHOA HQC Tl/ NHIEN - D�I HQC QUOC GIA THANH PHO HO CHI MINH 2016 NGUYEN THANH VAO CHUONG V: HYDROCACBON NO Hidrocacbon no la hidrocacbon ma phan ill chi chua lien kSt don, cac nguyen tu cacbon d�u tr;;tng thai lai h6a sp , cftu true tu di�n BAI 23: ANKAN I D6ng ding, d6ng phan, danh phap -Ankan (hay parafin) la nhung hidrocacbon no, mach ho Dong dang: - Ankan don gian nhftt la metan CH4• ;i ? Ten g9i Cong thuc Metan Etan Propan Butan Pentan C 2H6 C H8 C4H10 CsH12 c� Nhi�t d9 (OC) -162 -89 -42 -0,5 +36 , SOl Ten g9i Cong thuc Nhi�t dQ soi (°C) Hexan Heptan Octan Nonan §ecan C 6H14 +69 +98 +126 +151 +174 C1H16 CsH1s C9H20 C10H22 - Cong thuc t6ng quat: C0H2n+2 (n 2:: 1) *Chung minh: +G9i n la s6 nguyen ill C phan ill ankan + c6 (n-1) lien kSt don C - C phan ill +Mdi C c6 electron h6a tri + n C c6 4n electron h6a tri, ma mc3i lien kSt C - C su d\Jllg hSt electron h6a tri + s6 electron su d\Jllg vao lien kSt C - C la 2.(n - 1) electron +S6 electron h6a tri l;;ti cua cac nguyen ill Cdung d� lien kSt vm H la: 4n - 2.(n - 1) = 2n + bing chinh s6 nguyen ill H Cong thuc chung cua ankan la C0H2 n+2 • D6ng phan: - Cac ankan c6 d6ng phan m;;tc cacbon Vidu: +CH4, C2H6, C3 Hs: chi c6 m9t d6ng phan +C4H10: c6 d6ng phan H2 H2 H3C-C -C -CH3 va +CsH12: c6 d6ng phan H2 H H3C-C-C -CH CH3 - B�c cua m9t nguyen ill c la s6 c lien kSt tn,rc tiSp v6i n6: +Ankan ma phan ill chi chua C b�c I va C b�c II (khong chua C b�c III va C b�c IV) la ankan khong phan nhanh 99 TRUONG D�I HQC KHOA HQC TV NHIEN - D� HQC QUOC GIA TBA.NH PHO HO CHI MINH 2016 NGUYEN THANH VAO I I H2 H2 H2 H3C-C -C -C -CH3 II II II +Ankan ma phan tu c6 chua C b�c III ho�c C b�c IV la ankan phan nhanh I CH3 l1v I I H3C-C-CH3 I JCH3 Danh phap - Ten g9i cua tit ca cac ankan day d6ng dfulg d�u �n cung bfulg an - Ten g9i cua g6c hidrocacbon tucmg tµ ten cua ankan tucmg ung, chi d6i duoi an duoi yl Gdc hidrocacbon c6 dm;rc ta bo bat di H phan tu ankan Vi d-1.1: - CH3 (metyl), -C2H5 ( etyl), -C3 H7 (propyl) G6c ankyl nguoi ta thuong d�t la R- MQt s6 gdc ankyl thuong g�p: I H3C-C isopropyl CH3 3.1 Ten thU'ong: *Cftn nho: S6C Ten m;;i.ch chinh met et Prop but pent hex hept oct non 10 dee -Ankan m;;i.ch thing: them tiSn t6 nVi d-1,1: CH3 -CHr CHr CH3 : n- butan CH3 - CH2 - CHr CHr CH3 : n- pentan -Ankan c6 nhanh -CH3 H o C gAn cu6i m;;i.ch: them tiSn t6 iso- H2 H3C-C-C -cH3 I 1sopentan CH3 -Ankan c6 nhanh -CH3 o C gAn cu6i m;;i.ch: them ti�n t6 neo CH3 H3C-C-CH3 I neo pentan CH3 100 TRUONG 0�1 HQC KHOA HQC TV NHIEN - o� HQC Qu6c GIA THANH PHO HO cHi MINH 2016 NGUYEN THANH VAO 3.2 Ten qu6c t�: - Ch9n m�ch C dai nhftt lam m�ch chinh - Danh s6 thu tg cac nguyen tu C m�ch chinh, bilt dAu tit m�ch gAn nhanh hem Ten ankan = vi tri nhom th� + ten nhom th� + ten m�ch chinh - Cac bu6c g9i ten: +Bu6c 1: Chon m�ch dai nhftt chua nhi€u nhanh nhfit lam m�ch chinh +Bu6c 2: Danh s6 C tren m�ch chinh cho t6ng s6 vi tri nhanh la nho nhfit +Bu6c 3: DQC ten nhanh theo thu tg chit cai, n�u c6 nhi€u nhanh gi6ng ta them ti�p dAu ngfr di (2), tri (3), tetra (4 ), penta (5), Vi d\l: H2 H H H H3C-C-C -C-C-CH3 15 CH3 CH3 CH3 H2 H H H3C-c-c-c -CH3 21 31 C H CH3 s - etyl -2 - metylpentan 2,3,5 - trimetylhexan II Ciu true phan tfr ankan: Str hinh lien k�t phan tfr ankan: - Cac nguyen tu C ankan d�u & tr�ng thai lai h6a sp3• - Mdi nguyen tu C n�m tren dinh cua tu di�n d€u ma dinh la cac nguyen tu H ho{lc C - 06c lien k�t d�u gAn b�ng 109,5° - H6a t:ri cua C hAu nhu da bao hoa 2, Ciu true kh6ng gian cu.a ankan: 2.1 Mo hlnb pbio tii': - Mo hinh r6n - Mo hinh d�c: 101 TRUONG D�I HQC KHOA HQC TV NHIEN - D� HQC QUOC GIA TBA.NH PHO HO CHI MINH 2016 NGUYEN THANH VAO 2.2 Ciu trang: H H H , , Cau tr�ng che khuat cAu tr�g ban 1ech H , H H Ct-b H H H H "' -H H H H H H Ct-b , H Ct-b H Ct-b H , Cau tr�g ban 1ech Cau tr�ng che khuat - Cong thuc cua ankan bi€u di€n khong gian: phai duqc bi€u di€n dung tr�g thai lai h6a, t�i mdi cacbon cac lien k€t don phai t�o duqc hinh tu 17: chat ran - M�ch cacbon cang phan nhanh lam be mijt ti€p xuc giam ddn d€n lgc Van der Walls giam lam cho nhiet d(> soi giam - TAt ca cac ankan d€u hfiu nhu khong tan nu6c vi khong c6 lien k€t hidrogen gifra ankan vai nu6c, nhung tan duqc dung moi huu co: benzen, Vi ankan (long) la nhiing dung moi khong phan C\fC nen hoa tan duqc nhiing chAt khong phan ClJC - Ankan la nhiing chAt khong mau IV Tinh chit boa hoc: Phan frng th� halogen (uu tien th� H ir nguyen tfr C bac cao): -T6ng quat: anh sang C� + Ch CH 3Cl (clometan) + HCl anh sang CH 3Cl + Cli CH 2Cli (diclometan) + HCl 102 TRUONG D�I HQC KHOA HQC TV NHIEN - D� HQC QUOC GIA TBA.NH PHO HO CHI MINH 2016 NGUYEN THANH VAO anh sang CH2Ch + Ch CHCh (triclometan) + HCl CHC13 + Ch anh sang + anh sang CC14 (tetraclomentan) + HCl CiH6 + Cl2 + CiH5 Cl + HCl - Kha nang phan ung cua halogen theo thu tµ: F > Cl > Br > I - Phan (mg th� halogen uu tien th� a cacbon b�c cao hem, nen chi�m ti 1� 16n 1cm, nen yeu cAu vi�t san phdm chinh cAn chu y vdn d� Cl H 3C-C -CH sp chinh + HCl CH - clo - - metylpropan as H H 3C-C-CH2CI spphu• + CH3 - clo - - metylpropan H2 H CIH 2C-C-C -CH I CH as H2 Cl H3C-C-C -CH3 ► I CH3 +HCl HCI H H 3C-C-C -CH3 I CH3 H2 H H3C-C-C -CH2CI I CH3 Nh�n xet: S6 luQllg cac san phAm th� ph\l thu(k vao cAu t�o m�ch C cua ankan Phan frng tach H va crackinh: -Tdng quat: 2CH4 1S00° C, lam lanh nhanh CH=CH + 3H2 103 TRUONG D�I HQC KHOA HQC TV NHIEN - D� HQC QUOC GIA TBA.NH PHO HO CHI MINH 2016 NGUYEN THANH VAO Phan frng chay: 3n + CnH2n+2 + -02 to ➔ nCO2 + (n+1)H2O Vid\l: to C3Hs + 502 ➔ 3CO2 + 4H2O - Phan (mg toa nhi�u nhiet, san ph§m chay hoan toan luon c6 nco2 < nHzO, day la di�u d�c trung cua ankan, va ta luon c6 bi€u thuc: Ilankan = IlH 20 - Ilco • *Chung minh: D6t chayx mol ankan CnH20 + ta dugc: x -+ Gia su: nank an nx (n+1)x (mol) = nH2 - nco2 (1) dung thi ta c6: Ilankan = (n + l)x - nx = nx+ x - nx = x ( dung bfing s6 mol x ban dfiu) V�y(1) luon dung Phan frng phan buy: - Phan huyboi nhiet: 1000 ° c, kh6ng c6 kh6ng khf CnH2n + nC + (n+l)H2 - Phan huyboi clo: t0 , anh sang C\lC tim C0H2n + + (n+l)Cli nC + 2(n+l)HC1 Phan frng crackinh: crackinh CnH2n + ➔ CxH2x + - Di�u kien: + CyH2y• {n = x+y x>l y> n�u crackinh m(>t ankan r6i toan b(> san phdm dem d6t chay thi chinh la d6t chay ankan - Luu y: ban dfiu Phan frng nitro boa va sunfoclo boa: to R - H + HONO2 ➔ R - NO2 + H2O Vid\l: to CH3 - H + HONO2 ➔ CH3 - NO2 + H2O as R - H + SO2 + Ch ➔ R - SO2Cl + HCl Vid\l: 104 TRUONG D�I HQC KHOA HQC TV NHIEN - D� HQC QUOC GIA TBA.NH PHO HO CHI MINH 2016 NGUYEN THANH VAO Phll'ong phap gifr nguyen mach cacbon: 200 ° c ROH+2Hld�c -+ RH+ H2O+ lz Vidv: 200 ° c CH3 CH2CH2CH2OH+2Hld�c -+ + CH3 CH2 CH2 CH3 +H2O+ lz PhU"ong phap tang mach cacbon: ete khan R-X+2Na -+R-R+2NaX Vidv: ete khan C2HsCl+2Na C2Hs-C2Hs+2NaX - Chu y: tdng hgp tu hai lo;;ti d�n xudt halogen co gdc ankyl khac se thu dugc h6n hgp ankan nhung kho tach khoi vi co nhiet d(> soi khac Phmmg phap giam mach cacbon: v6i toi, xut, t0 R-COONa+ NaOH R-H+ Na2 CO3 Vidv: v6i t6i, xut, t0 CH3 COONa+ NaOH CH4+ Na2 CO3 - Trong phan ung ch9n voi toi, xut dS lam kho h6n hgp phan ung va ngan khong cho NaOH lam thung dng nghi�m thuy tinh (SiO2 ) co phan ung: SiO2+2NaOH -+ Na2SiO3 + H2O - Co thS giam m;;tch cacbon bfulg phucmg phap crackinh - D�c bi�t phan ung: 2HCOOK+2NaOH -+ H2+ Na2 CO3 + K2 CO3 V Di�u ch�: PhU"ong phap crackinh: To aken, ankin + H6(Ni, t0): Ni, Vidv: t0 CnH2 n+ H2 � CnH2 n + z Ni, t C2�+ H2 � C2H6 Mot s6 phmmg phap rieng di�u ch� CH4� cao,t CH3 COONa+ NaOH � CH4 t + Na2 CO3 Al4 C3 + 12H2O -+ 4Al(OH) + 3CH4 t 105 TRUONG D�I HQC KHOA HQC TV NHIEN - D� HQC QUOC GIA TBA.NH PHO HO CHI MINH 2016 NGUYEN THANH VAO BAI 24: XICLOANKAN A � I I)},ong dang, cau true , - Xicloankan la nhfmg hidrocacbon no, m�ch vong, c6 cong thuc chung C0H20 (n� 3) - Cac cacbon xicloankan deu tr�g thai lai h6a sp3 , cac nguyen ill cacbon khong n�m cung mijt ph&ng II D6ng phan danh phap: Cach vi�t d6ng phan: - Ve m�ch vong 16n nhfit r6i thu nho dfui, chu y t6 hgp l�i cac nhanh - Them cac nguyen ill H vao dam bao h6a ttj C Vi d\l: Danh phap: Ten xicloankan = s6 chi vi tri nhanh + ten nhanh + ten mach chinh + an Chu y: danh s6 cho t6ng chi s6 nbanh la nho nhfit Vi d\l: I\ ,, CH3 L.-Y' H3C metyl - xicloankan �CH3 1,2 - dimetylxiclpropan III Tinh chit boa hoc: - Xicloankan vong 3, c6 g6c len ket nho hem 109,5 ° nen sue can vong 16n, khong ben, d6 de tham gia phan ung cng m6 vong: H2 /c " H2C CH2 xt ► -1 H2 H3C-C -CH3 - Cac phan ung khac tucmg tµ ankan IV Di�u ch�: /CHa I CH3 H2C I H2 C '- / o xt, t , P C H2 H2 hexan 106 TRUONG D�I HQC KHOA HQC Tl/ NHIEN - D� HQC QUOC GIA TH.ANH PHO HO CHi: MINH 2016 NGUYEN THANH VAO PHUONG PH.AP GIAI BAI T4P ANKAN I T6ng guat: - CTPT: C0H2n+2- Kh6i luqng phan nr M = 14n + - Danh phap: Phai xet m�ch chinh la m�ch nhi�u C nhfrt, r6i danh s6 thu tµ tir vi tri nhi�u nh6m th� nhfrt II Bai tap theo phan 1111g: Phan frng th� Cli/ Brl.: - Phuong trinh tong quat: CnH2n+2 + xCh ➔ CnH2n+l Clx + xHCl Vi dy.: Cho m9t ankan A tham gia phan ung th� v&i clo theo ti 1� 1: thu dugc m9t dful xufrt hidrocacbon cua clo c6 ti kh6i vm H2 la 53,25 Xac dinh cong thuc phan nr cua A: D C6H10B C4H10 C CsH10 A C3Hs Htr6n� din: The til� : x =1 A: CnH2n+2 + Ch + CnH2n+1Cl + HCl D�n xufrt hidrocacbon cua clo la: C0H20+1Cl vm M = 14n + 36,5 = 53,75.2 + n = ➔ A: C5 H 12 Phan frng chay: - Phuong trinh chay t6ng quat: 3n+l CnH2n+2 + 02 + nC02 + (n+1)H20 Ilankan = nH20 -nco2 nco2 nco2 = nH2o nH2o-nco2 - San phdm chay thu dugc g6m CO2 va H2 0, n�u: +Lam l�nh va ngung 1\1 thi th6 tich giam la th6 tich cua H2 +Cho san phdm qua binh d\fllg H2 S04 dijc n6ng thi H2 bi gitr l�i, kh6i luqng binh tang la kh6i luqng H2 +Cho san phdm qua binh d\fllg dung dich NaOH/KOH thi kh6i luqng binh tang la kh6i luqng CO2 va H2 +Cho san phdm qua dung dich Ca(OH)2/Ba(OH)2 thi kh6i luqng binh tang la kh6i luqng CO2 va kh6i luqng H2 0, k�t tua thu dugc la CaC03 /BaC03 : Kh6i luqng dung dich tang la: 6m = (mco2 + mH2 0) - mJ S6 C = Kh6i luqng dung dich giam la: 6m = mJ - (mco2 + mH20 ) Vi dy.: D6t chay hoan toan m nx -+ X da chuc N�u bai toan cho m9t hay mot h6n hqp cac axit cacboxylic thu9c cung m9t day d6ng ding tac dl)Ilg voi NaOH theo ti 1� mol 1: ho�c tac d1,mg vm dung dich Ba(OH)2 theo ti 1� mol 2: thi d6 la cac axit don chuc DNaOH nNaOH _ - mmu61-maxit � X = 22 Daxit _ mmu6i-maxtt 8Ba(OH)2 � 133 _ x- Ba(OH)2 Daxit LU11 y: - N�u la axit no, don chuc, m�ch ho ta c6 th� d�t CTTQ la C0H2n+ COOH ( �O) ho�c CmH2mO2 (m �1)(cho phan ung chay)ho�c la RCOOH cho phan ung trung hoa - Axit fomic c6 phan ung trang b�c c6 nh6m chuc andehit phan tu - Kh6i luqng chfrt rful sau phan ung: mR&n = mmu6i + mNaOH/Ba(OH)2 (n�u bazo du) Cac vi du: Vi du· 1: Trung hoa hoan toan 1,76 gam m9t axit don chuc hfru co X bing dung dich NaOH vua du roi co c�n dung dich sau phan ung thu duqc 2,2 gam mu6i khan Tim X A CH COOH B C2H 5COOH C C3 H 7COOH D C4H 9COOH H11'6'ng din: CTTQ cua X la RCOOH: RCOOH + NaOH ➔ RCOONa + H2O (R+45)g (R + 67)g 2,2 g 1,76 g Cu mol axit phan ung vm NaOH thi sau phan ung san phdm sinh tang 22g V�y cu x mol axit phan ung vm NaOH thi sau phan ung san phdm sinh tang 0,44g -+ x = 0,02 -+ MRcoo H = �·:: = 88 -+ R + 45 = 88 -+ R = 43 (-C3 H 7) V�y X la C3H1COOH Vi du 2: T�ng hoa hoan toan 11,25 gam mot axit hfru co cAn 500 ml NaOH 0,5M X la: A HCOOH B HOOC - COOH C CH 3COOH D Khong th� xac dinh H11'6'ng din: CTTQ cua X la R(COOH)x : nNaOH = 0,5.0,5 = 0,25 (mol) + xH2O xNaOH -+ R(COONa)x R(COOH)x + x mol (R + 45x)g 199 TRUONG D�I HQC KHOA HQC TV NHIEN - D� HQC QUOC GIA TBA.NH PHO HO CHI MINH 2016 NGUYEN THANH VAO 11,25 gam 0,25 mol L�p ti 1� R = va x = V�y X c6 CT la (COOH)2 : axit oxalic Vi du 3: Trung hoa a mol m9t axit hfru ca X cdn 2a mol NaOH D6t chay hoan toan m9t th� tich hai axit X thu duqc hai th� tich CO2 (cung di�u ki�n) CTPT cua X la: D Khong th� xac djnh C CH3 COOH B HOOC - COOH A HCOOH HU'ong din: CTTQ cua X la R(COOH)x R(COOH)x + xNaOH ➔ R(COONa)x + xH2O Trung hoa a mol X cdn 2a mol NaOH X c6 nh6m -COOH D6t th� tich hai X th� tich CO2 X c6 hai nguyen n'r C phan tir V�y X chinh la HOOC-COOH: axit oxalic Vi du 4: D� trung hoa hoan toan 4,12 gam h6n hqp hai axit hfru ca dan chuc m�ch ho la d6ng d�ng k� ti�p thi cdn 500 ml dung dich NaOH 0,1 M Tim CTPT cua hai axit va tinh kh6i luQ'llg mu6i khan thu duqc: A {C2H5 COOH, C3 H7COOH}; 4,23g B {CH3 COOH, C2H COOH}; 5,22g D {C2H5 COOH, C3 H1COOH}; 5,22g C {HCOOH, CH3 COOH}; 4,23g HU'ong din: CT chung cua hai axit: RCOOH nNaOH = 0,05 (mol) RCOOH + NaOH RCOONa + H2O 0,05 mol +- 0,05 0,05 mol 4,12 MRCOO H = - = 82,4 R + 45 = 82,4 R = 37.4 0,05 CTPT cua hai axit la C2H COOH va C3 H7COOH mmudi = (37,4 + 67).0,05 = 5,22(g) n,ng 3: D6t chay Khi d6t chay m9t axit cacboxylic ma thu duqc nco2 = nH zO thi axit d6 la axit no dan chuc Vi du 1: D6t chay hoan toan m gam m9t axit dan chuc, no m�ch ho X thu duqc (m - 0,25) gam CO2 va (m - 3,5) gam nu6c Tim X A HCOOH B HOOC-COOH C CH3 COOH HU'ong din: CTTQ cua X la CnH2nO2 nH2O CnH2n02 + 02 nCO2 + n.44 gam n.18 gam (14n + 32) gam m gam (m - 0,25) (m - 3,5) 44n 18n , , Ta co t1 l"y: = m = 75 m-0,25 m-3,5 14n+32 44n , " e: Ta co t'l = - n = l 5,75 5,75-0,25 V�y CTPT cua X la CH2O2 hay HCOOH Vi du 2: D6t chay hoan toan 0,1 mol h6n hqp X g6m hai axit hfru ca la d6ng d�ng k� ti�p ta thu duqc 6,6 gam va 2,7 gam nu6c a) Tim CTPT cua hai axit b) Khi cho 0,1 h6n hqp X tac d1,mg v6i luQ'llg du AgNO3 /am6niac thi kh6i luQ'llg k�t tua thu duqc? HU'ong din: a) nHzO = Il co2 = 0,lS(m ol) hai axit la axit dan chuc no m�ch ho 200 TRUONG D�I HQC KHOA HQC TV NHIEN - D� HQC QUOC GIA TBA.NH PHO HO CHI MINH 2016 NGUYEN THANH VAO CT chung cua hai axit la : C n: H 2n: -+ n = 1,5 V�y CTPT cua HCOOH va CH3 COOH b) n = 1,5 -+ nHcooH = nctt cooH = 0,05 (mol) Chi c6 HCOOH tham gia phan ung trang guong HCOOH -+ 2AgJ 0,1 mol 0,05 mol-+ mAg = 0,1 x 108 = 10,8 gam Chuy: - Khi d6t chay mQt axit cacboxylic khong no (1 n6i doi C = C) don chuc thi: naxit = nco2 - Il tt o, n r - Khi cho axit cacboxylic m�ch ho tac d'1tlg voi dung dich brom , hidro thi ty 1� :21� la s6 lien , �rt ket 1t phan tu axit - Khi chuy@n hoa axit mu6i, n@u bi@t kh6i luQ11g truoc va sau phan ung thi nen dung nh�n xet v� sµ tang giam kh6i luQ11g d@ tinh s6 mol phan ung BA.I T�P AXIT CACBOXYLIC Bai 1: Hein hqp X g6m axit hfru co don chuc, d6ng ding k@ ti@p Lfiy m gam X dem tac d'1tlg h@t voi 12g Na thi thu duqc 14,27g chfit dln va 0,336 lit H2 (dktc) Cung m gam X tac d1,mg vua du voi 600ml nuoc Br2 0,05M Cong thuc phan tic cua hai axit la: A C3 H2O2 va C4H4O2 B C3 H4O2 va C4H6O2 D C3 H6O2 va C4HsO2 C C4H6O2 va CsHsO2 Bai 2: Tr6t chay hoan toan 0,15 mol m