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Chng trnh Ha hc

Bin son: V Hng Thi

III. ANKEN (ALCEN, OLEFIN, DNG NG ETILEN, )

III.1. nh ngha Anken l mt loi hirocacbon m trong phn t c cha mt lin kt i C=C mch h. III.2. Cng thc tng qut

III.3. Cch gi tn
Ankan Anken

CnH2n (n 2)
( C thm s ch v tr ca lin kt i, t pha sau hoc pha trc, c nh s nh. Mch chnh l mch cha ni i v di nht)

Ankan Th d: CH2=CH2

Ankilen

(Nh trn)

(C2H4) (C3H6)
1

Eten ; Etilen Propen ; Propilen 1- Buten ; Buten - 1 ; n- Butilen 2 - Buten ; Buten - 2 ; 2 - Butilen 2 - Metylpropan ; Isobutilen

CH3-CH=CH2
4 3 2

CH3-CH2-CH=CH2
1 2 3 4

(C4H8) (C4H8) (C4H8)

CH3-CH=CH-CH3
1 2 3

CH3-C=CH2 CH3
5 4 3 2 1

CH3-CH2-CH2-CH=CH2
1 2 3 4 5

(C5H10) (C6H12)

1 - Penten ; Penten - 1 ; n- Amylen 4-Metyl-2-penten; 4-Metylpenten-2

CH3-CH=CH-CH-CH3 CH3
6 5 4 2

CH3
3

CH3-CH-CH2-C- CH2-CH2-CH3 (C11H22)

1

3,5-imetyl-3-n-propyl hexen-1

CH3

CH=CH2

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5 6

4 7

CH3
2

CH3-CH-CH = C-CH-CH3 CH2-CH3 Cl Ghi ch

2,5-imetyl-3-clohepten-3

G.1. Lin kt (sigma, xch ma) l mt loi lin kt cng ha tr, c to ra do s xen ph dc theo trc i xng ca cc obitan (orbital, vn o) nguyn t to lin kt. Vi hai obitan nguyn t khi xen ph dc theo trc i xng to lin kt th hai trc i xng ca hai obitan ny trng lp ln nhau (chng ln nhau). Th d: H + H H H

HH

(H2)

Hai obitan s hnh cu ca hai nguyn t H trc khi xen ph to lin kt

Xen ph dc trc i xng

Lin kt s-s

Cl

Cl

Cl Cl
Xen ph dc trc i xng

ClCl
Lin kt p-p

(Cl2)

Hai obitan p hnh s 8 cn i ca ca hai nguyn t Clo

H
Obitan s hnh cu ca H

Cl
Obitan p hnh s 8 ca Cl

H Cl
Xen ph dc trc i xng

HCl
Lin kt s-p

(HCl)

G.2. Lin kt (pi) l mt loi lin kt cng ha tr, c to ra do s xen ph bn ca cc obitan nguyn t to lin kt. Vi hai obitan nguyn t p khi xen ph bn to lin kt th hai trc i xng ca hai obitan nguyn t ny song song vi nhau v cng thng gc vi trc ni hai nhn nguyn t (trc lin nhn).

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Hai obitan p, c hai trc Xen ph bn, hai trc i xng i xng song song song song v cng thng gc vi trc ni hai nhn

Lin kt p-p

G.3. Mt lin kt n cng ha tr gm mt lin kt . G.4. Mt lin kt i cng ha tr gm mt lin kt v mt lin kt . G.5. Mt lin kt ba cng ha tr gm mt lin kt v hai lin kt . Th d: CC CH CO C=C

CC
2

C=O

NN
2

G.6. Lin kt km bn hn lin kt v in t trong lin kt cng linh ng hn so vi in t trong lin kt . in t c th di chuyn trn nhiu nguyn t trong phn t , cn in t ch di chuyn trong vng khng gian bao quanh hai nguyn t to lin kt. G.7. C s quay t do quanh mt lin kt n, nhng khng c s quay t do quanh mt lin kt i cng nh mt lin kt ba cng ha tr. V khi quay nh vy th lin kt c trong lin kt i, lin kt ba s b ph v.
Th d:

CC

CO

G.8. di lin kt n di hn di lin kt i, di lin kt i di hn di lin kt ba.

A )
0

Th d:

d C-C (1,54 A0 )

>

d C=C (1,34 A0 )

>

d CC (1,20

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G.9. iu kin mt cht c ng phn cis, trans (ng phn Z, E; ng phn hnh hc; ng phn khng gian; ng phn lp th) l: + Phn t cht phi c cha t nht mt lin kt i C=C + V mi cacbon ni i phi lin kt vi hai nguyn t hay hai nhm nguyn t khc nhau. Hai nguyn t hay hai nhm nguyn t tng ng lin kt vo hai nguyn t cacbon ni i nu nm cng mt bn mt phng ni i (mt phng ) th c ng phn cis (Z), nu hai nguyn t hay hai nhm nguyn t tng ng ny nm hai bn mt phng ni i th c ng phn trans (E). Hin nay, ngi ta dng cis-trans ch hai nhm th ging nhau cng mt bn hay hai bn mt phng ni i, cn dng Z-E ch hai nhm th c cng mc u tin cng mt bn hay hai bn mt phng ni i. A C=C B Cis B B Trans A A C=C A B

AB A B A A ( A tng ng A, A c th l A) B B ( B tng ng B, B c th l B) Nguyn nhn ca ng phn cis-trans l do khng c s quay t do quanh lin kt i C=C, nn hai cu to cis, trans hon ton khc nhau. Th d: CH2=CH2 (Etilen) khng c ng phn cis, trans CH3-CH=CH2 (Propilen) khng c ng phn cis, trans CH2=CH-CH2-CH3 (1- Buten; Buten-1) khng c ng phn cis, trans CH3-C=CH2 (Isobutilen) khng c ng phn cis, trans CH3 Buten-2 c ng phn cis, trans: H C=C
1 2 3 4

H Cis-2-buten CH3 CH3

CH3 H C=C

CH3-CH=CH-CH3 2-Buten (Buten-2)

Trans-2-buten

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CH3-CH2-C=CH-CH-CH3

(2,4-imetylhexen-3) c ng phn cis-trans CH3-CH2 CH3 CH3-CH2 C=C H C=C CH(CH3)2 CH(CH3)2 Cis Trans

CH3

CH3

CH3 H Bi tp 19 Vit CTCT cc ng phn cis- trans, nu c, ca cc cht sau y: a. Stiren (C6H5-CH=CH2) b. 1,2-icloeten (Cl-CH=CH-Cl) c. HOOC-CH=CH-COOH d. Axit metacrilic [ CH2=C(CH3)COOH ] e. Hexen-2 f. 2,4-imetylhexen-3 Bi tp 19 Vit CTCT cc ng phn cis-trans (nu c) ca cc cht sau y: a. Axit xinamic (C6H5-CH=CH-COOH) b. Axit acrilic ( CH2=CH-COOH ) c. Crotonanehit ( CH3-CH=CH-CHO ) d. Nitrinacrilic ( CH2=CH-CN) e. Benzanaxetophenon (C6H5-CH=CH-CO-C6H5) f. 3,4-imetylhexen-2

III.4. Tnh cht ha hc III.4.1. Phn ng chy

CnH2n
Anken (Olefin)

3n/2 O2

t0

nCO2 n mol

nH2O n mol

Lu Khi t chy anken thu c s mol nc bng s mol CO2 , hay th tch hi nc bng th tch kh CO2 (trong cng iu kin v nhit v p sut).

III.4.2. Phn ng cng Hiro (Phn ng hio- ha)

Phn ng cng l phn ng trong phn t mt cht nhn thm vo phn t ca n mt hay mt s phn t khc to thnh mt phn t sn phm. iu kin mt cht cho c phn ng cng l phn t cht ny phi c cha lin kt hoc vng nh ]
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CnH2n
Anken Olefin

H2
Hiro

Ni (Pt), t0

CnH2n +2
Ankan Parafin

Th d:
-2 -2 0 -3 +1 -3 +1

Etilen (Cht oxi ha)

-1 -2

CH2=CH2 (C2H4)

H2
(Cht kh)
0

Ni t0

CH3-CH3 (C2H6)
Etan

-2 +1 -3 +1

Propen, Propilen
(Cht oxi ha)

CH3-CH=CH2 + H2 (C3H6)

Ni t0

Hiro

CH3-CH2-CH3 (C3H8)
Propan

(Cht kh)

Lu L.1. Trong phn ng anken cng H2, th H2 ng vai tr cht kh, cn anken ng vai tr cht oxi ha. Do ngi ta cn ni dng H2 kh anken nhm to ankan hay anken b kh bi H2 to ankan. L.2. anken cng hiro th cn dng cht xc tc v nhit thch hp. Nu thiu mt trong hai iu kin ny th c th phn ng khng xy ra. L.3. Phn ng cng H2 vo anken thng xy ra khng hon ton. Ngha l sau phn ng, ngoi sn phm ankan, c th cn c hai tc cht l anken v H2. Ch khi no gi thit cho phn ng xy ra hon ton hay hiu sut 100% v c H2 d hay va th tt c lng anken c lc u mi phn ht to ankan. Bi tp 20 Hn hp kh A gm 0,5 mol etilen v 22,4 lt H2 (ktc) c cho vo mt bnh kn c cha mt t bt Ni lm xc tc. un nng bnh mt thi gian, thu c hn hp kh B. a. Hn hp B c th gm cc cht no? Tnh khi lng hn hp B. b. Bit rng trong hn hp B trn c cha 2,8g mt cht X m khi t chy to s mol nc bng s mol CO2. Tnh % th tch mi kh trong hn hp B v tnh hiu sut phn ng gia etilen vi hiro. (C = 12 ; H = 1) 80% S: a. 16g b. 36,36% C2H6 9,09% C2H4 54,55% H2 ; Bi tp 20 Hn hp kh X gm 0,3 mol propilen v 3,52 lt H2 (27,30C, 1,4 atm) c cho vo mt bnh kn c cha mt t bt Ni lm xc tc. un nng bnh mt thi gian, thu c hn hp kh Y. a. Hn hp Y c th gm cc cht no? Tnh khi lng hn hp Y. b. Cho bit trong hn hp Y trn c cha 6,6 gam cht Z, m khi t chy Z th thu c s mol CO2 nh hn s mol H2O.

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Tnh % th tch mi kh trong hn hp Y v tnh hiu sut phn ng propilen cng H 2. (C = 12 ; H = 1) S: a. 13g b. 42,86% C3H8 42,86% C3H6 14,28%H2 ; 75% III.4.3. Phn ng cng halogen X2 (Ch yu l cng brom, Br2) CnH2n
Anken

Halogen

X2

Dn xut ihalogen ca ankan

CnH2nX2

Th d: CH2=CH2
Eten, Etilen

Br2
Nc brom

(C2H4)

1,2-ibrometan, Etylenbromua

CH2-CH2 Br Br (C2H4Br2)

Propen, Propilen

CH3-CH=CH2 (C3H6)

Br2
Nc brom

1,2-ibrompropan, Propylenbromua

CH3-CHBr-CH2Br (C3H6Br2)

Lu L.1. Anken cng brom d dng. Ch cn dung dch brom, khng cn brom nguyn cht, v phn ng xy ra c ngay c trong bng ti. Do phn ng cng brom vo anken xy ra hon ton, c brom d th ht anken hoc ngc li. L.2. Cc anken lm mt mu nc brom d dng, iu ny cng ng vi cc hp cht khng no ni chung (c lin kt i C=C, lin kt ba CC trong phn t), v c phn ng cng brom vo lin kt i, lin kt ba gia C vi C. Ngi ta thng vn dng tnh cht ha hc ny nhn bit anken, cng nh cc hp cht khng no ni chung.

Bi tp 21 Mt hirocacbon X khi cho tc dng vi clo to nn mt dn xut clo Y Nu ha hi Y 4 th tch kh CO2 c khi lng tng ng trong th thu c mt th tch bng 9 cng iu kin. a. Xc nh cng thc ca X. b. Nu X tc dng vi clo theo ch to cht Y duy nht, xc nh CTCT ca X. c. Phn bit cc cht: metan, X, CO2, N2 v H2, ng trong cc l khng nhn. (C = 12 ; H = 1 ; O = 16 ; Cl = 35,5) S: a. C2H6 hay C2H4 b. CH2=CH2 Bi tp 21 A l mt hirocacbon. A tc dng Br2 to sn phm l mt dn xut brom B. Nu cho B ha hi th thy mt th tch etan bng 7,2 th tch hi B tng ng khi lng (trong cng iu kin v nhit v p sut). a. Xc nh CTPT c th c ca A. Vit cc phn ng xy ra.
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b. Nu A tc dng brom ch to mt sn phm duy nht l B. Xc nh CTCT ca A. c tn A. Bit rng A l ng phn hnh hc ca A (A dng cis).Vit phn ng xy ra. (C = 12 ; H = 1 ; Br = 80) b. A: CH3-CH=CH-CH3 (trans) S: a. C4H8, C4H10
Bi tp 22 Hn hp kh A gm etilen v hiro. Cho 6 gam hn hp A vo mt bnh kn c cha mt t bt Ni lm xc tc. un nng bnh mt thi gian, thu c hn hp kh B. Dn hn hp B qua bnh ng nc brom c d, c 4,48 lt hn hp kh C (ktc) thot ra v khi lng bnh brom tng thm m gam. T khi hi ca C so vi hiro bng 11,5. a. Tnh m. b. Tnh % khi lng mi kh trong hn hp B v tnh hiu sut phn ng cng hiro ca etilen. (C = 12 ; H = 1) S: a. m = 1,4g b. 75% C2H6 ; 23,33% C2H4 ; 1,67% H2 HS = 75% Bi tp 22 Hn hp kh X gm propilen v H2. Cho 6,5 gam hn hp X vo mt bnh kn, c cha mt t bt niken lm xc tc. un nng bnh mt thi gian, thu c hn hp kh Y. Dn hn hp Y qua bnh ng dung dch brom d, khi lng bnh brom tng thm m gam v c 1,76 lt hn hp kh Z (27,30C; 1,4 atm). dZ/metan = 2,225. a. Tnh m. b. Tnh hiu sut phn ng cng gia propilen vi hiro. (C = 12 ; H = 1) S: a. m = 2,94 gam b. HS = 80%

III.4.4. Phn ng cng nc (Phn ng hirat ha)

Anken (Olefin)

CnH2n

H2O

Nc

H3PO4 t0, p [ H2SO4 (l), t0 ]

Ru n chc no mch h

CnH2n + 1OH

Th d: CH2=CH2 (C2H4)
Etilen

H2 O

H3PO4 280 - 300 C , 70 - 80 atm

0

Etanol , Ru etylic

CH3-CH2-OH (C2H5OH)

CH3-CH-CH3 OH
Propen , Propilen

CH3-CH=CH2 + H2O

H3PO4 , t0, p

(Sn phm chnh)

Nc

CH3-CH2-CH2-OH
(Sn phm ph)

Ghi ch: Qui tc Markovnikov

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Khi cng mt tc nhn bt i xng vo mt anken bt i xng th sn phm chnh c to ra l do phn ion dng ca tc nhn lin kt vo cacbon ni i mang nhiu H hn, phn ion m ca tc nhn lin kt vo cacbon ni i t H hn. Sn phm ph th ngc li. Th d: OH CH3-CH2-C-CH3 CH3
H3PO4 , t0, p

CH3-CH=C-CH3 + H2O CH3 Nc

2-Metyl-2-buten

(Sn phm chnh) Ru tert-pentylic

3-metyl-2-butanol ( Sn phm ph )

CH3-CH-CH-CH3 OH CH3 OH CH3-C-CH3 CH3

CH3-C=CH2 + H2O CH3 Nc

Isobutilen

H3PO4 , t0, p

(Sn phm chnh) Ru tert butylic

(Sn phm ph) Ru isobutylic

CH3-CH-CH2-OH CH3

III.4.5. Phn ng cng HX (HF, HCl, HBr, HI)

Anken

CnH2n

HX
Hirohalogenua

to, xt

Dn xut monohalogen ca ankan

CnH2n + 1X

Th d: CH2=CH2
Etilen

HCl
Hiroclorua

to, xt

CH3-CH2-Cl
Clo etan Etyl clorua

CH3 - CH - CH3 2-Clo Propan Cl Isopropyl Clorua CH3-CH=CH2 + HCl

Propen, propilen t0, xt (Sn phm chnh) Hiro clorua

(Sn phm ph) 1-Clopropan, n-propyl clorua

CH3- CH2- CH2- Cl

Br CH3- C- CH3 CH3

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t0, xt

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CH3-C=CH2 + HBr CH3 Hirobromua

Isobutilen

(Sn phm chnh)

CH3- CH- CH2- Br CH3

(Sn phm ph)

III.4.6. Phn ng trng hp

Phn ng trng hp l phn ng trong cc phn t ca cng mt cht kt hp li to thnh cht c khi lng phn t ln hn. Cht c khi lng phn t ln c lp i lp li bi cc n v mt xch ging nhau.

nA

TH ( t , Xt )

(A) n

n: h s trng hp

Anken thuc loi hirocacbon khng no, phn t c cha lin kt i C=C (1, 1) nn gia cc phn t ca cng mt anken c th cng vi nhau c, tc anken cho c phn ng trng hp.

nC x H 2 x
Th d: n CH2=CH2
Etilen

TH

(C x H 2 x ) n
Anken Polime ca anken

TH ( t , Xt )

(-CH2-CH2-)n
Polietilen Nha P.E

n CH3-CH=CH2
Propilen

TH ( - CH - CH2 t , Xt ) CH3

Polipropilen, nha PP

Bi tp 23 Vit cc phn ng trng hp c th c ca C5H10. c tn tc cht, sn phm thu c. S: 5 phn ng Bi tp 23 Vit cc phn ng trng hp c th c ca C4H8. c tn cc tc cht v sn phm. S: 3 phn ng

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III.4.7. Phn ng b oxi ha bi dung dch KMnO4 (Kali pemanganat, thuc tm)
-1 -1 +7 0 0 +4

3 R-CH=CH-R + 2 KMnO4 + 4 H2O

Anken (cht kh ) Kali pemanganat (cht oxi ha)

3 R-CH - CH-R + 2 MnO2 + 2 KOH OH OH

Ru a chc Mangan ioxit (kt ta mu en)

3 CnH2n
Anken

+ 2 KMnO4 + 4 H2O
Kali pemanganat

3 CnH2n(OH)2 +
Ru a chc

Mangan ioxit

2 MnO2

+ 2 KOH

Th d:
-2 -2 +7 -1 -1 +4

3 CH2=CH2 + 2 KMnO4 + 4 H2O

Etilen (Cht kh)
-1 -2

Kali pemanganat (Cht oxi ha)

+7

3 CH2 - CH2 + 2 MnO2 + 2 KOH OH OH

Etilenglicol
0 -1

Mangan ioxit
+4

3 CH3-CH=CH2 + 2 KMnO4 + 4 H2O

Propilen
-1 -1 +7

3 CH3- CH - CH2 + 2 MnO2 + 2 KOH OH OH

Propylenglicol
0 0 +4

3CH3-CH=CH-CH3 +2KMnO4 + 4H2O

Buten-2 (Cht kh) (Cht oxi ha)

3CH3-CH-CH-CH3 +2MnO2 +2KOH OH OH

1,3-Butaniol

Cc anken lm mt mu tm ca dung dch KMnO4 l do c phn ng oxi ha-kh trn, nn dung dch KMnO4 cng thng c dng nhn bit cc anken (cng nh cc hp cht khng no khc).

III.5. ng dng
III.5.1. T anken iu ch c polime tng ng (Thc hin phn ng trng hp)

Th d: n CH2 = CH2
Polietilen (Nha PE)
Trng hp

Etilen

(- CH2 - CH2 -)n

(t0, xt)

III.5.2. T anken iu ch c ru n chc no mch h, ru nh chc no mch h

Anken

CnH2n + H2O
Nc

H3PO4 t0, p

Ru n chc no mch h (Ankanol)

CnH2n + 1OH

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Anken

CnH2n +

Nc brom

Br2

Dn xut ibrom ca ankan

CnH2nBr2
t0

Dn xut ibrom ca ankan

CnH2nBr2

2NaOH
Dung dch xt

Ru nh chc no mch h

CnH2n(OH)2

Th d: CH2=CH2 + H2O
Etilen
H3PO4 , 280- 3000C , 70- 80 atm

Nc

CH3-CH2-OH
Ru etylic

CH3-CH=CH2 +
Propen, Propilen Nc brom

Br2

CH3 - CH-CH2 Br Br
1,2-Dibrompropan, Propylen bromua t0

CH3-CH-CH2 Br Br

2NaOH
Dung dch xt

CH3-CH-CH2 OH OH
1,2-Propaniol , Propylenbromua

(Hoc cho anken CnH2n tc dng trc tip vi dung dch KMnO4 ta cng thu c ru nh chc no mch h CnH2n(OH)2 nh bit III.4.7)

III.5.3. T anken iu ch c ankan tng ng

CnH2n + H2 Anken , Olefin Hiroo Th d: CH2=CH2 + H2
Etilen Ni , t0 Hiro Ni , t0

CnH2n + n
Ankan , Parafin

CH3-CH3
Etan Ni , t0

CH3-CH=CH-CH3
2-Buten

+ H2

CH3-CH2-CH2-CH3
n-Butan

III.5.4. T etilen iu ch c ru etylic, anehit axetic, axit axetic, este etylaxetat, ietyl ete
CH2=CH2
Etilen

+ H2O

H3PO4 , 280-3000C , 70-80atm

Nc

CH3-CH2-OH
Ru etylic

CH3-CH2-OH +
Ru etylic

CuO

t0

ng (II) oxit

Anehit axetic

CH3-CHO

+ Cu + H2O
ng

Nc

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CH3-CHO

Mn2+

CH3-COOH
Axit axetic

CH3

C OH

CH3

CH2

OH

H2SO4 t
0

CH3 C O CH2 O Etylaxetat

CH3

H2O Nuoc

O Axit axetic
2

Ruou etylic

CH3 CH2 Etanol

OH

H2SO4
0 140

CH3

CH2 O CH2 Dietyl ete

CH3

H2O Nuoc

III.5.5. Kh etilen cn c dng gi tri cy cho mau chn. V etilen c tc dng kch thch s hot ng cc men lm tri cy mau chn.

III.6. iu ch anken III.6.1. ehirat- ha (tch nc, loi nc) ru n chc no mch h, thu c anken (olefin)
CnH2n + 1OH
H2SO4 () , 1800

Ru n chc no mch h (n 2)

CnH2n
Anken, Olefin

H2O
Nc

Th d: CH3-CH2-OH
Etanol
H2SO4 () , 1800

CH2=CH2 + H2O
Eten, Etilen Nc

CH3-CH2-CH2-OH
Ru n- propylic

H2SO4 () , 1800

Propen, propilen
+

CH3-CH=CH2 + H2O

CH3 CH OH

CH3

H2SO4 (d)
0 180

CH3 CH

CH2

H2O
Nuoc

Ruou isopropylic, 2- Propanol

Propen, propylen

CH3 CH3 CH2 CH OH CH3 CH3

CH CH CH3 Buten (san pham chinh)

2

H2O Nuoc

2 - Butanol

Ruou sec butylic

-

CH2 CH Buten (san pham phu)

1

CH2

H2O

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Lu
L1. Ru no m sau khi ehirat ha thu c anken hay olefin th l ru n chc no mch h v phn t c cha s nguyn t C 2. Ru ny c cng thc tng qut l CnH2n + 1OH vi n 2. L.2. Qui tc Zaitsev: Khi mt ru n chc no mch loi nc thu c hai anken khc nhau, th anken to ra nhiu hn (sn phm chnh) l ng vi mt H C c bc cao hn. Cn anken to ra t hn (sn phm ph) l ng vi s mt H C c bc thp hn. (Hay sn phm chnh ng vi anken c mang nhiu nhm th hn, hay ng vi anken c cha nhiu H hn).
Th d: CH3-CH2-CH=C- CH3 + H2O CH3
(8 H; 3 nhm th) (Sn phm chnh)

II

III

CH3-CH2-CH-CH-CH3 H2SO4 () OH CH3 180oC

CH3-CH=CH-CH-CH3 + H2O CH3

(4 H; 2 nhm th) (Sn phm ph)

CH3-CH2-CH=CH-CH3 + H2O
II I H2SO4 () 180oC

CH3-CH2-CH2-CH-CH3 OH

(5 H; 2 nhm th) (Sn phm chnh)

CH3-CH2-CH2-CH=CH2 + H2O
(2 H; 1 nhm th) (Sn phm ph)

CH3-CH=CH-CH2-CH2-CH3 + H2O
II II

(5 H; Sn phm chnh) H2SO4 () 180oC

CH3-CH2-CH-CH2-CH2-CH3 OH

CH3-CH2-CH=CH-CH2-CH3 + H2O
(4 H; Sn phm ph)

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III

III
H2SO4 ()

CH3-CH -CH2-CH-CH2-CH3 CH3 OH CH3

CH3-C=CH-CH-CH2-CH3 + H2O CH3 CH3

(7 H; Sn phm chnh)

180oC CH3-CH-CH=C-CH2-CH3 + H2O CH3 CH3

(6 H; Sn phm ph)

III.6.2. T Ankan iu ch Anken (thc hin phn ng cracking)

C n H 2n+2
Ankan Parafin

cracking C n ' H 2 n '+2 + C n n ' H 2 ( n n ') (t o , p, xt )

Ankan Parafin (n<n) Anken Olefin

Th d:
Propan

CH3-CH2-CH3

cracking Metan

CH4 + CH2=CH2
tilen

CH3-CH2-CH2-CH3
n- Butan

CH4 +
Cracking Metan

CH2=CH-CH3
Propen

CH3-CH3 + CH2=CH2 Etilen Etan CH4 CH3-CH2-CH2-CH2-CH3

n- Pentan Cracking Metan

+ CH2=CH-CH2-CH3
Buten-1

CH3-CH3 + CH2=CH-CH3 Etan Propen CH2=CH2 + CH3-CH2-CH3 Propan Etilen CH2=CH2 + CH4 + CH2=CH2 Metan Etilen Etilen

III.6.3. Ankin

Anken
C n H 2n2 + H 2
Ankin

Hiro

Pd ( Paladi ) C n H 2n to

Anken

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R-C C-R
Th d:
CH CH Axetilen
+

H2

Pd to

R-CH=CH-R

H2 Hidro

Pd to

CH2

CH2 CH3 CH CH2 Propen

Etilen

Pd CH3 C CH + H2 o t Propin Hidro

phn ng cng H2 vo ankin to ra ch yu l anken th dng H2 khng d v dng xc tc Palai (Pd) (khng dng Ni, Pt lm xc tc).

III. 6.4. Dn xut monohalogen ca ankan tc dng KOH trong ru, un nng, to anken
R-CH2-CH2-X

KOH ,t / Ruou Ruou ,t

0

R-CH=CH2

HX

R-CH2-CH2-X + H2O
Th d:

KOH

R-CH=CH2

KX

,t CH3-CH2-Cl + KOH Ruou CH2=CH2

Clometan, Etyl clorua
0

+ KCl
Kali clorua

+ H2O
Nc

Etilen

,t CH3-CH2-CH2-Br + KOH Ruou CH3-CH=CH2 + KBr + H2O

III.6.5. ,- ihalogenankan tc dng vi bt kim loi km hay ng, thu c anken

R-CH-CH-R + X X Th d: CH2-CH2 Br Br + Zn
+

Zn

R-CH=CH-R

+ ZnX2

CH2=CH2

ZnBr2

CH3
1,2

CH Cl

CH2 Cl CH Br

Zn
Kem

CH3

CH
Propen

CH2

ZnCl2
Kem clrua

- Diclopropan

CH3

CH Br

CH3

Zn

CH3

CH

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3,4 - Dibrombutan

CH 2 - Buten

CH3

ZnBr2 Kem bromua

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Lu Ngi ta thng p dng phng php iu ch ny tch ly ring anken ra khi hn hp cc cht hu c. Cho hn hp cc cht hu c c cha anken tc dng vi nc brom th anken b gi li v c phn ng cng brom v to sn phm ha tan trong nc brom. Sau cho bt kim loi km vo, s ti to c anken.

CnH2n + Br2
Sn phm cng brom

CnH2nBr2 CnH2n
Anken

CnH2nBr2

+ Zn
Km

Km bromua

ZnBr2

Th d: Tch ly ring etilen ra khi hn hp gm hai kh metan v etilen. Cho hn hp hai kh trn qua nc brom c d. Tt c etilen b gi li v c phn ng cng brom. Metan khng tc dng vi brom dung dch, khng ha tan trong nc ca dung dch, thot ra khi bnh ng nc brom, thu c metan. Sau cho bt km lng d vo phn dung dch cn li, s ti to c etilen. Etilen to ra, khng ha tan trong nc, thot ra, thu c ring. CH4 + Br(dd) + + Br2 Zn Zn X CH2-CH2 Br Br CH2=CH2 ZnBr2 + ZnBr2

CH2=CH2 CH2-CH2 Br Br

Br2(cn d) +

Bi tp 24 9,7g hn hp A gm hai ru sau khi ehirat ha hon ton, thu c 4,564 lt hn hp kh gm hai olefin ng ng lin tip (171,990C; 1,2 atm). a. Xc nh CTPT ca hai ru trn. b. Tnh %khi lng ca mi ru trong hn hp A. (C = 12 ; H = 1 ; O =16) S: 61,86% C3H7OH; 38,14% C4H9OH Bi tp 24 8,98g hn hp X gm hai ru. Cho lng hn hp X dng hi trn qua H2SO4(), un nng c s tch nc hon ton, thu c 3,7184 lt hn hp hi hai anken ng ng lin tip ( 180,180C; 836mmHg). a. Xc nh CTPT hai ru trn. b. Tnh khi lng mi ru c trong hn hp X trn. (C = 12 ; H = 1 ; O = 16) 5,28g C5H11OH S: 3,7g C4H9OH

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Bi tp 25 Thc hin phn ng cracking propan thu c hn hp kh A gm: etilen, metan v propan cha b cracking. Hy tm cch ly ring etilen tinh khit ra khi hn hp A. Vit cc phn ng xy ra. Bi tp 25 Ly 2,24 lt (ktc) isobutan em thc hin phn ng cracking. Thu c hn hp A gm ba kh. a. Tnh khi lng hn hp A. b. Trong hn hp A trn c 3,36g mt kh X m khi t chy to s mol H2O bng s mol CO2. Cn hai kh kia, mi kh khi t chy u to s mol H2O ln hn s mol CO2. Tnh hiu sut phn ng cracking v % th tch mi kh trong hn hp A. c. Nu phng php ha hc tch ly ring kh X ra khi hn hp A. (C = 12 ; H = 1) S: 5,8g hn hp A ; HS 80% ; 44,44% CH4 44,44% C3H6 11,12% C4H10 Bi tp 26 t chy hon ton 2,8g cht hu c A mch h cn dng 6,72 lit oxi (ktc). Sn phm chy ch gm kh cacbonic v hi nc vi s mol bng nhau. a. Xc nh cng thc chung dy ng ng ca A. b. Nu cho 2,8g cht A trn vo dung dch brom d th thu c 9,2g sn phm cng. Tm CTPT, cc CTCT c th c ca A. c tn cc cht ny. c. Cho bit A c mch cacbon thng, khng c ng phn cis, trans. Xc nh cng thc ng ca A. Vit phn ng A vi HCl v vit phn ng trng hp A. Tnh h s trng hp ca A nu polime thu c c khi lng phn t 210 000 vC (C= 12 ; H = 1 ; O = 16 ; Br = 80) S: C5H10 ; 6 CTCT ; n = 3000 Bi tp 26 t chy hon ton 3,36g cht hu c X mch h bng 8,064 lt O 2 (ktc) va . Sn phm chy ch gm CO2 v H2O c s mol bng nhau. a. Xc nh dy ng ng ca X. b. Nu cho 3,36g cht X trn tc dng vi nc brom d th thu c 12,96g sn phm cng. Xc nh CTPT v cc CTCT ph hp ca X. Gi tn cc cht tm c. c. ng phn X1 ca X c ng phn cis, trans. Vit phng trnh phn ng hirat ha X1 v phng trnh phn ng trng hp X1. Tnh khi lng phn t ca polime thu c nu h s trng hp l 4000. (C = 12 ; H = 1 ; Br = 80) S: X: C4H8 ; 224 000 vC Bi tp 27 14g hn hp hai anken A, B tc dng va vi 200ml dung dch KMnO4 1M. a. Xc nh CTPT ca A, B v tnh % s mol ca mi cht trong hn hp hai anken trn nu B l ng ng k tip sau ca A.

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b. Xc nh li cc CTPT c th c ca A, B nu A, B c t l s phn t gam tng ng l 1 : 2. (C = 12 ; H = 1) S: a. 66,67% C3H6 ; 33,33% C4H8 b. C6H12 , C2H4 ; C4H8 , C3H6 ; C2H4 , C4H8
Bi tp 27 Hn hp A gm hai olefin X, Y hn km nhau 28 vC trong phn t. Thy 5,18 gam lng hn hp A trn lm mt mu va 120ml dung dch KMnO4 0,5M. a. Xc nh cc CTPT c th c ca X, Y. b. Cho bit ch c olefin c khi lng phn t ln (Y) mi c mt ng phn hnh hc duy nht (dng trans i vi n). Xc nh CTCT ng ca X, Y. Tnh % khi lng mi cht c trong hn hp A. (C = 12 ; H = 1) b. 32,43% C3H6 67,57% C5H10 S: a. C4H8 , C6H12 ; C3H6 , C5H10 Bi tp 28 Hn hp A gm hai hirocabon ng ng lin tip. t chy hon ton a gam hn hp A ri cho sn phm chy hp th ht vo dung dch X c ha tan Ba(OH)2 d, thu c 55,16g kt ta v dung dch Y. Khi lng dung dch Y nh hn khi lng dung dch X l 36,9g. a. Xc nh dy ng ng ca hai hirocacbon trn. b. Tnh tng s mol hai hirocacbon trong a gam hn hp A. c. Xc nh CTPT hai hirocacbon trong hn hp A. d. Xc nh CTCT ca hai hirocacbon trn. Bit rng mch cacbon ca chng c dng neo. Tnh khi lng mi cht c trong a gam hn hp A. (C = 12 ; H = 1 ; Ba = 137 ; O = 16) S: b. 0,05 mol d. 1,44g C5H12 , 2,58g C6H14 Bi tp 28 t chy hon ton x gam hn hp X gm hai hirocacbon mch h ng ng lin tip. Cho sn phm chy hp th ht vo nc vi trong d, thu c 50g kt ta v dung dch thu c c khi lng gim 19g so vi khi lng nc vi lc u. a. Xc nh dy ng ng ca hirocacbon trong hn hp X. b. Nu cho x gam hn hp X ha hi ht th thu c 3,024 lt hi ( 136,50C; 76cmHg). Xc nh CTPT v tnh % khi lng mi cht trong hn hp X. (C = 12 ; H = 1 ; O = 16 ; Ca = 40) 60% C6H12 S: 40% C5H10

CU HI N PHN III
1. Olefin l g? Hy cho bit cng thc chung dy ng ng ca n. 2. Vit CTCT ca cht 8-amino-2,7,7-trimetyl-4-etyl-3-n-propyl-5-isopropyl-2octen; c tn cht CH3-CH-CH2-CCH3-CHC2H5-CH2CH2-Cl CH=CH2 CH3

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3. Lin kt l g? Lin kt l g? V hnh th d minh ha s xen ph obitan

nguyn t to ra hai loi lin kt ny.

4. So snh di lin kt gia C vi C trong cc phn t etan, etilen v axetilen. 5. So snh di lin kt gia C vi O trong cc phn t ru etylic (CH3CH2OH)

vi anehit axetic (CH3CHO); di lin kt gia N vi N trong cc phn t N2, H2N-NH2, CH3-N=N-OH.
6. So snh di lin kt gia C vi N trong cc phn t: Metylamin (CH3NH2),

Ankyl isoxianat ( R-N=C=O ) v Nitrin acrilic (CH2=CH-CN).

7. Nu iu kin mt cht c ng phn cis, trans. Cho mt th d minh ha. 8. Vit CTCT cc ng phn cis, trans (nu c) ca: 1-Brom-2-clopropen; 1,2-

iphenyleten; Isobutilen; Heptaien-2,4 ( CH3-CH=CH-CH=CH-CH2-CH3 ).

9. Nguyn nhn no m c ng phn cis, trans? Ti sao buten-2 c ng phn cis, trans cn buten-1, cng nh n-butan khng c ng phn cis, trans? 10. Vit CTCT cc ng phn olefin ca penten m khi hp nc cho ta sn phm

chnh l ru bc ba. Vit phng trnh phn ng khi cho etilen tc dng vi: Br2, dung dch KMnO4 v HCN. Vit phn ng ng trng hp gia propilen vi butaien-1,3. (B tuyn sinh i hc mn ha)
11. Cht do PVC c iu ch t kh thin nhin theo s sau (hs : hiu sut)

CH4

hs 15%

C2H2
3

hs 95%

CH2=CH-Cl

hs 90%

PVC

Hi cn bao nhiu m kh thin nhin (ktc) iu ch c 1 tn PVC (bit CH4 chim 95% th tch kh thin nhin). (B tuyn sinh i hc mn ha)
12. Khi mt mt phn t H2O, axit HOOC-CHOH-CH2-COOH c th to thnh hai

axit l ng phn cis, trans ca nhau. Vit CTCT hai axit ny. (B tuyn sinh i hc mn ha)
13. Khi cracking butan to ra hn hp gm parafin v olefin trong c hai cht A v B. T khi hi ca B so vi A l 1,5. Tm cng thc ca A, B. (B tuyn sinh i hc mn ha)

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14. Hn hp kh A gm H2 v mt olefin CnH2n c t l s mol l 1 : 1. Cho hn hp A qua ng ng Ni nung nng, thu c hn hp kh B c t khi hi so vi H2 l 23,2. Hiu sut phn ng l b%. a. Tm biu thc lin h gia n vi b. b. Nu hiu sut phn ng b = 75% - Tm CTPT ca olefin. - t chy hon ton hn hp B v cho ton b sn phm qua bnh ng 128 gam dung dch H2SO4 98% th nng ca H2SO4 b pha long thnh 62,72%. Tnh % th tch ca mi cht trong hn hp B. Tnh khi lng mi cht trong hn hp B. (C = 12; H = 1; S = 32; O = 16) 1 46,4b (90,8 ) b. C4H8 60% C4H10 ; 20% C4H8 ; 20% H2 S: a. n = 14 100 34,8g C4H10 ; 11,2g C4H8 ; 0,4g H2 15. A l mt hirocacbon. em t chy mt lng A cn dng 84 lt khng kh (ktc). Cho sn phm chy hp th ht vo 30 lt dung dch Ca(OH)2 0,01M, thu c kt ta T v dung dch D. Khi lng dung dch D ln hn so vi khi lng dung dch nc vi em dng l 21 gam. Nu em un nng dung dch D thy c xut hin kt ta. a. Xc nh CTPT ca A. Bit rng t khi hi ca A ln hn 2 v nh hn 2,8. b. Xc nh CTCT ca A, nu A c cu to dng trans. c. Vit CTCT v c tn tt c cc ng phn ca A. d. Tnh khi lng kt ta T. e. em hiro - ha A, thu c B. So snh nhit si gia B vi cc ng phn ca n. Khng kh gm 20% O2, 80% N2 theo th tch. Cc phn ng xy ra hon ton. (C = 12; H = 1; Ca = 40; O = 16) c. 10 P d. 10 gam T S: a. C5H10 16. Cho hirocacbon A tc dng vi brom trong iu kin thch hp, thu c mt dn xut cha brom c t khi hi i vi hiro l 75,5. Xc nh CTPT, vit cc CTCT c th c ca A. Xc nh CTCT ng ca hirocacbon A nu A tc dng vi brom ch thu c mt sn phm hu c. ( thi khi A, 2004, c sa cha) (C = 12 ; H = 1 ; Br = 80) S: C5H12 17. Ti sao t gp anken trong t nhin, trong khi ankan gp rt nhiu trong t nhin? 18. Ti sao ngi ta gi anken l olefin? (Olefin ngha l g?) 19. Ti sao ngi ta c th cn c vo lng etilen sn xut ca mt nc hng nm nh gi nn cng nghip ha hc ca nc ?

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