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VII. XICLOANKAN (CICLOALCAN, CICLAN, XICLOPARAFIN, HIROCACBON VNG NO)

VII.1. nh ngha Xicloankan l mt loi hirocacbon m trong phn t ch gm lin kt n v c mt vng khp kn. VII.2. Cng thc tng qut CnH2n VII.3. Cch c tn Ankan Th d:
CH3 Xiclopropan (C3H6) CH3 Metylxiclopropan (C4H8) CH3 Xiclobutan (C4H8)

n3

Xicloankan (Mch chnh l mch vng. Cc nhm gn vo vng coi l cc nhm th gn vo xicloankan)

CH3 1,2-imetylxiclobutan (C6H12) CH3

Xiclopentan (C5H10)

H3C (C9H18)

CH2CH3

1,3-imetyl-2-etylxiclopentan

Xiclohexan (C6H12)

H3C HC H3C

CH2CH3

1-Metyl-3-etyl-5-isopropyl xiclohexan (C12H24)

Xiclooctan (C8H16)

Xicloheptan (C7H14)

VII.4. Tnh cht ha hc

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Tnh cht ha hc ca xicloankan (nht l cc vng 5, vng 6, cng nh cc vng ln hn) c bn ging nh ca ankan. Ngha l xicloankan thng ch cho c phn ng th vi halogen X2 khi c s hin din ca nh sng hay un nng, xicloankan khng b oxi ha bi dung dch KMnO4. Tuy nhin vi cc xicloankan vng nh (vng 3, vng 4, nht l vng 3) cn c tnh cht nh mt hirocacbon khng no, v n cho c phn ng cng to sn phm m vng. Nguyn nhn ca tnh cht ha hc ny l do cc vng nh c sc cng gc ln (sc cng Baeyer, gc CCC trong xiclopropan bng 600, gc CCC trong xiclobutan bng 900, ng l gc CCC ca lin kt n l 109028 ging nh trong ankan) nn khng bn. Chng tham gia phn ng cng hay phn ng ng phn ha to sn phm m vng bn hn. VII.4.1. Phn ng chy CnH2n +

3n O2 2

t0

nCO2

nH2O

VII.4.2.. Phn ng th

Th du : + (C5H10) Xiclopentan + (C6H12) Xiclohexan + (C4H8) Xiclobutan Br2 Brom

0 300 C

Br

HBr

(C5H9Br) 1-Bromxiclopentan
0 450 C

Hirobromua

HNO3 Axit nitric

NO2 (C6H11NO2) Nitroxiclohexan

H2O

Cl2 Clo

ah sag n n

Cl (C4H7Cl) Cloxiclobutan

HCl Hiro clorua

VII.4.3. Phn ng cng

Xiclopropan v xiclobutan cho c phn ng cng hiro (H2) to ankan tng ng vi s hin din ca niken (Ni) hay bch kim (Pt) lm xc tc v un nng, nhng un nng mnh hn so vi khi cng hiro vo anken. Cc xicloankan khc (xiclopentan, xiclohexan,...) khng cho c phn ng ny.

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Xiclopropan cho c phn ng cng vi Br2 (trong dung mi CCl4), vi dung dch HX m c (HCl, HBr, HI), cng nh cho c phn ng cng vi dung dch axit sunfuric m c (H2SO4). Do xiclopropan cng lm mt mu dung dch Br2 nhng chm hn so vi anken, ankin.
+
Xiclopropan

H2
Hiro

Ni (Pt) t
0

(C3H6)

(800C)

CH3CH2CH3 (C3H8)
Propan

+ (C4H8)
Xiclobutan , Xiclopentan

H2
Hiro

Ni (Pt)
0 t (120 C) 0

CH3CH2CH2CH3
(C4H10) n-butan

H2 Ni (Pt), t0 Xiclohexan

+ (C3H6)
Xiclopropan

Br2

CCl 4

Dung d brom ch

Br-CH2-CH2-CH2-Br (C3H6Br2)
1,3-ibrompropan Br2 / CCl4

,
Xiclobutan Xiclopentan

, Xiclohexan

+ Xiclopropan

HX ()
Axit halogenhiric a a m c Axit sunfuric

CH3-CH2-CH2-X
1-Halogenpropan n-Propyl sunfataxit

(X: I, Br, Cl, HSO4)

HX

VII.4.4. Phn ng ng phn ha

Khi cho xiclopropan i qua nhm oxit (Al2O3) 1000C, n s chuyn ha thnh cht ng phn l propen.

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Al2O3 , 1000C

(C3H6)
Xiclopropan

CH3-CH CH2 (C3H6)

Propen, propilen

VII.5. ng dng

T xiclohexan, metylxiclohexan thc hin phn ng ehiro-ha vi cht xc tc, nhit thch hp c th thu c cc hirocacbon thm tng ng l benzen v toluen (phn ng reforming)
Xt, t0 (MoO3/Al2O3)

+ (C6H6)
Benzen Pt, t0, p

3H2
Hiro

(C6H12)
Xiclohexan

CH3 (C7H14)
Metylxiclohexan

CH3 (C7H8)
Toluen

3H2
Hiro

VII.6. iu ch VII.6.1. Cho dn xut ihalogen ca ankan, trong 2 nguyn t halogen cch xa nhau, tc dng vi natri (Na) hay km (Zn) s thu c xicloankan tng ng (ging nh phn ng Wurtz)
CH2 CH2 CH2 CH2 CH2 CH2 CH2 Br Cl CH2
1,3-iclopropan

Cl Zn
Ke m NaI Ancol loa g, 1250C n

CH2 CH2 CH2

Xiclopropan

ZnCl2 Ke clorua m

Br + 2Na
Natri

CH2 CH2 CH2

CH2 + CH2 2NaBr Natri bromua

1,5-ibrompentan

Xiclopentan

Phng pha na thg dug e u che p y n c n ie xiclopropan. Dug kim loa ke n i m cho hie suatohn so vnatri. Vca vog kha, hie suapha g ratha. u t t i i c n c u t n n t p

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VII.6.2. Nhit phn mui canxi ca axit icacboxilic, to xeton vng, ri kh xeton vng ny bng hn hng km trong axit clohiric

CH2 CH2 CH2 CH2

CH2 CH2 CH2 CH2

COO Ca COO CO +

t0

CH2 CH2

CH2 CH2

CO CH2

+ CH2

CaCO3
Canxi cacbonat

Canxi aipat

Xiclopentanon

Xiclo pentanon

(p Clemmensen) Hiro nguye t i sinh n m

4[H]

Zn-Hg/HCl

CH2 CH2 Xiclopentan

CH2 + H2O

CH2 CH2 CH2

COO Ca COO
t
0

CH2 CH2 CH2

Xiclobutanon

CO

CaCO3
Canxi cacbonat

Canxi glutarat

CH2 CH2 CH2 CO + 4[H]

CH2
Zn-Hg/HCl (Clemmensen)

CH2 CH2

CH2

H2O

Xiclobutanon

Xiclobutan

VII.6.3. T aren ng ng benzen, cng nh t phenol iu ch c xicloankan

+
(C6H6) Benzen

4H2
Hiro

Ni t0 (C6H12) Xiclohexan

OH
Phenol

3H2
Hiro

Ni, t0

OH
Xiclohexanol

OH
Xiclohexanol

H2SO4 180 C Xiclohexen

0

H2O
N c

+
Xiclohexen

H2
Hiro

Ni,t0

Xiclohexan

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Ghi ch: Hn hng ca mt kim loi l hp kim ca kim loi v thy ngn. Thy ngn l kim loi duy nht hin din dng lng iu kin thng thng, do n ha tan c nhiu bt kim loi to hp kim tng ng. Hn hng cn gi l amalgam.

Th d: hn hng natri: hp kim natri v thy ngn hn hng thic: hp kim thic vi thy ngn hn hng bc: hp kim bc vi thy ngn
Bi tp 49 C ba bnh, mi bnh cha mt kh ring, gm: propan, xiclopropan v propen. Hy nhn bit cc bnh kh trn bng phng php ha hc. Vit cc phn ng xy ra. Bi tp 49 Phn bit cc kh sau y ng trong cc bnh mt nhn: Axetilen, Etilen, Etan v Xiclopropan. Vit cc phn ng xy ra. Bi tp 50 A l mt xicloankan. T khi hi ca A so vi nit bng 3. A tc dng vi Cl2, khi chiu sng, theo t l mol nA : nCl2 = 1 : 1 ch to mt dn xut monoclo duy nht. Xc nh cng thc cu to ca A. vit phn ng xy ra. c tn cc tc cht, sn phm. (C = 12 ; H = 1 ; N = 14) S: Xiclohexan Bi tp 50 X l mt hirocacbon. Mt th tch hi X vi 2,625 th tch metan c cng khi lng (cc th tch hi, kh trn o cng iu kin nhit , p sut). a. Xc nh CTCT ca X, c tn X. Bit rng X khng lm mt mu tm ca dung dch KMnO4. b. Y l mt ng phn ca X. Vit cc phng trnh phn ng theo s sau y (mi mi tn l mt phn ng): X dd Br2 X1 dd NaOH, t0 X2 CuO, t0 X3 O2, Mn2+ X4

Y dd Br2 Y1

dd NaOH, t0

Y2 CuO, t0

Y3 O2, Mn2+ Y4 H2, Ni,t0 Y5 (Axit lactic)

(C = 12 ; H = 1) S: X: Xiclopropan
Bi tp 51 A, B l hai hirocacbon ng ng lin tip (MA < MB). 1,568 lt hn hp hi X (ktc) gm hai cht A, B c t chy hon ton bng 44,8 lt khng kh (ktc) c d. Th tch hi nc thu c bng th tch kh CO2 (cng iu kin). Cho tt c cc kh thu c sau phn ng chy vo mt ng p trn chu nc. Th tch kh trong ng l 45,981 lt 150C, ct nc trong ng cao hn so vi mc nc ngoi chu l 4,08 cm (xem hnh). p sut kh quyn l 750 mmHg, p sut hi nc bo ha 150C l 12,7 mmHg. Thy ngn c t khi l 13,6.

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a. Xc nh CTPT, CTCT ca A, B. Bit rng B tc dng Cl2 theo t l mol 1 : 1 ch to mt dn xut monoclo v B khng tc dng vi dung dch kali pemanganat. b. Tnh % khi lng mi cht trong hn hp X. Vit CTCT cc ng phn ca A, B v c tn cc ng phn ny. Coi N2, O2, CO2 khng ha tan trong nc. Khng kh gm 20% O2, 80% N2 theo th tch. (C = 12 ; H = 1)
c.

S: 50% xiclopropan, 50% xiclobutan

Bi tp 51 Hn hp A gm hai cht X, Y lin tip trong dy ng ng ca benzen. t chy hon ton 2,9 gam hn hp A bng lng O2 ly gp i so vi lng cn. Cho tt c cc kh sau phn ng chy vo mt ng p trn chu nc, th tch phn kh trong ng l 12,66 lt 250C. Mc nc trong ng thp hn mc nc ngoi chu l 68 mm (xem hnh). p sut kh quyn l 760 mmHg. p sut hi nc bo ha 250C l 23,7 mmHg. Khi lng ring ca thy ngn l 13,6 g/cm3. a. Xc nh CTPT ca X, Y. Vit cc CTCT c th c ca X,Y. c tn cc cht ny. b. Tnh % khi lng ca mi cht trong hn hp A. Coi O2, CO2 khng ha tan trong nc. Ly 3 s l trong s tnh ton. (C = 12; H = 1)

S: 63,448% C7H8; 36,552% C8H10

Bi tp 52 Hn hp A gm hai hirocacbon X, Y ng phn. t chy ht m gam hn hp A. Cho sn phm chy hp th vo dung dch D (gm 1,8 lt dung dch Ca(OH)2 0,05M), thu c 3 gam kt ta v dung dch E. Khi lng dung dch E ln hn khi lng dung dch D l 6,3 gam. Dung dch E tc dng dung dch NaOH thu c kt ta na. a. Tnh m. b. m gam hi A 136,50C, p sut 912 mmHg c th tch 1,4 lt. Xc nh CTPT ca X,Y. c. Cho bit : dd NaOH, t0 X2 (a chc) X dd Br2 X1
Y Cl2, 5000C

Y1

dd NaOH, t0

Y2 (n chc)

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Xc nh CTCT ca X, Y. Vit phn ng theo s trn v c tn X, X1, X2, Y, Y1, Y 2. Cc phn ng xy ra hon ton. (C = 12; H = 1; O =16; Ca = 40) S: m = 2,1g; X: xiclopropan, Y: propen
Bi tp 52 Hn hp X gm hai hirocacbon A, B ng phn nhau. Ly m gam X em t chy cn dng V (lt) khng kh (ktc). Cho sn phm chy hp th vo 500 ml dung dch Ba(OH)2 0,24M, thu c kt ta mu trng v dung dch D. Dung dch D cho tc dng vi dung dch KOH d, thu c 7,88 gam kt ta na. Khi lng dung dch D nh hn khi lng dung dch Ba(OH)2 lc u l 5,84 gam. a. Tnh m, V. b. Xc nh CTPT ca A, B. Bit rng 4 th tch hi X c cng khi lng vi 7 th tch kh oxi (o trong cng iu kin v nhit v p sut). c. Cho bit c cc phn ng theo s sau y: H2, Ni, t0 (1) A1 Cl2 , as, 1: 1 (2) A2 dd NaOH, t0 (3) A3(n chc) A

B A3

dd Br2 (7)

(4)

B1
(8)

KOH / Ru, t0 (5)

B2

H2O, HgSO4, 800C (6)

B3

B3

A3

Mi mi tn l mt phn ng. Xc nh CTCT ca A, B v vit cc phn ng xy ra theo s trn. Cho bit A khng tc dng dung dch Br2 cng nh dung dch KMnO4, B c cu to dng cis. Cc phn ng xy ra hon ton. Khng kh gm 20% O2, 80% N2 theo th tch. (C = 12; H = 1; O = 16; Ba = 137) p s: m = 2,24g; V = 26,88 lt; A: Xiclobutan; B: Buten-2

CU HI N PHN VII
1. Xicloankan l g? Cho th d minh ha. 2. Hy cho bit cng thc chung dy ng ng ca cc cht sau y: Xiclohexan; Xiclohexen; Benzen; Stiren; Etinyl benzen (Phenyl axetilen); n- Hexan; Isopren; Isobutilen; Axetilen; Vinylaxetilen.

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3. c tn ca cc cht sau ay:

H2C H3C CH3 CH3 CH3 CH3 Cl CH CH2

CH3

CH CH2

H3C

CH3

4. Vit CTCT ca cc cht sau y: a. 1-Metyl-2-isopropylxiclobutan b. 1-n-Butyl-3-isobutylxiclohexan c. n-Amylxiclooctan d. Xiclopentylxiclopentan e. 1,3,5-Trimetylxiclohexan f. 1-Vinyl-3-alylxicloheptan g. Toluen h. Cloropren (2-Clobut-1,3-ien) 5. Vit phng trnh phn ng theo s sau: X (C3H6) dd Br2 Y dd NaOH Z
CuO, t0 CuO, t0

T (Anehit a chc) D (Tp chc)

A (C3H6)

dd Br2

dd NaOH

6. C hp cht hu c no trong phn t khng cha lin kt i, lin kt ba m cho c phn ng cng hay khng? Gii thch v cho th d minh ha cho cu tr li. 7. A l mt hirocacbon. t chy ht 1 mol A, thu c 4 mol CO2 v 4 mol H2O. Xc nh CTCT ca A. Bit rng A khng phn nhnh, A khng lm mt mu dung dch KMnO4 v t A c th iu ch cc cht khc theo s sau:

A D

H2, Ni, t0 CuO, t0

B E

Br2, t0 , 1:1 H2, Ni, t0

C (Sn phm chnh)

H2SO4 (), 1800C

dd KOH HBr

D C

F (SP chnh)

Vit cc phn ng xy ra theo s trn.

8. A l mt hn hp gm hai hirocacbon ng ng lin tip. t chy ht 1,68 lt hi A (ktc) ri cho sn phm chy hp th vo bnh ng dung dch nc vi lng d, th

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khi lng bnh dung dch nc vi tng 17,05 gam v trong bnh c 27,5 gam kt ta. Cn nu t chy hon ton m gam A cn dng 36,96 lt O2 (ktc). a. Xc nh CTPT ca hai hirocacbon trong hn hp A. b. Tnh % khi lng mi cht trong hn hp A. c. Tnh m. d. Vit tt c cc ng phn c th c ca cht c khi lng phn t ln trong A. c tn cc cu to ny. (C = 12; H = 1; Ca = 40; O = 16) S: 27,27% C3H6; 72,73% C4H8; m = 15,4g

9. Hn hp A gm 3 cht X, Y, Z thuc dy ng ng xicloankan: X (CxH2x); Y (CyHy); Z (CzH2z). Trong x < y < z ; Z v X cch nhau k cht trong dy ng ng. t chy hon ton a lt hi hn hp A (ktc) th cn dng b gam O2. 1,4b 3a 1,4b k<x< a. Chng minh: 3a 3a b. Xc nh CTCT ca X, Y, Z v c tn cc cht ny. Cho bit Y cho c phn ng cng H2 (c Ni lm xc tc, un nng); k = 2 v X, Y, Z c mch cacbon khng phn nhnh. c. Tnh % khi lng mi cht trong hn hp A nu a = 10,08 lt; b = 100,8 gam; S mol ca Y bng trung bnh cng s mol ca hai cht X, Z v cng d kin nh cu (b). (C = 12; H = 1; O = 16) S: 14,29% C3H6; 28,57% C4H8; 57,14% C6H12 10. t chy hon ton 1,04 gam mt cht hu c D cn va 2,24 lt kh O2 (ktc), ch thu c kh CO2, hi H2O theo t l th tch V CO2 : V H 2O = 2 : 1 cng iu kin
nhit v p sut. Xc nh CTPT, CTCT ca D, bit t khi hi ca D so vi hiro 52, D cha vng benzen v tc dng c vi dung dch brom. Vit phng trnh phn ng xy ra. (C = 12 ; H = 1 ; O = 16) ( TSH khi A, nm 2005) S: Stiren

11. Hn hp X gm hai anken k tip nhau trong dy ng ng. t chy hon ton 5 lt hn hp X cn va 18 lt kh oxi (cc th tch kh o cng iu kin nhit , p sut). 1. Xc nh cng thc phn t ca hai anken. 2. Hirat ha hon ton mt th tch X vi iu kin thch hp thu c hn hp ru Y, trong t l v khi lng cc ru bc mt so vi ru bc hai l 28 : 15. a) Xc nh % khi lng mi ru trong hn hp ru Y. b) Cho hn hp ru Y th hi qua CuO un nng, nhng ru no b oxi ha thnh anehit? Vit phng trnh phn ng. (C = 12 ; H = 1 ; O = 16) ( TSH khi A, nm 2004) S: 1. C2H4 ; C3H6 2.a) 34,88% i-C3H7OH, 53,49% C2H5OH, 11,63% n-C3H7OH

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