Bi s 1.

1. Th no l s lai ho sp3, sp2, sp? 2. Lin kt xichma(), lin kt pi() l g? Trn c s s lai ho cc obitan nguyn t hy m t s hnh thnh cc lin kt trong phn t CH4, C2H4, C2H2. Bi gii. 1. a. Lai ho sp3: - Xt cho nguyn t cacbon. 2 2 2 Cu hnh electron: 6C 1s 2s 2p . Lp electron ngoi cng:

Trng thi c bn

Trng thi kch thch

Mt obitan 2s t hp vi ba obitan 3p to ra bn obitan mi(4 obitan lai ho sp3) hon ton ng nht v c dng khc vi cc obitan ban u. Bn obitan lai ho sp3 c cc trc to vi nhau mt gc 109028' v hng v bn nh ca mt hnh t din u. S lai ho ny c gi l lai ho sp 3 hay lai ho t din.
z 2pz

2s x 2px

y 2py sp3

b. Lai ho sp2: Mt obitan 2s t hp vi hai obitan 2p cho ba obitan lai ho sp2 hon ton ng nht. Ba obitan lai ho sp2 ny c trc to vi nhau mt gc 1200 v hng v ba nh ca mt tam gic u. S lai ho ny gi l lai ha sp2 hay lai ho tam gic.
2p
1200

2p 2s
2 sp

Mi nguyn t C cn mt obitan 2p c trc thng gc vi mt phng cha 3 obitan lai ho sp2.

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10

90 2

8'

c. Lai ho sp: Mt obitan 2s t hp vi mt obitan 2p cho hai obitan lai ho sp hon ton ng nht. Hai obitan lai ho sp ny c trc nm trn mt ng thng nhng hng v hai pha khc nhau. S lai ho ny gi l lai ho sp hay lai ho ng thng.

2p 2s

sp

Mi nguyn t C cn hai obitan 2p c trc thng gc vi nhau v thng gc vi trc ca hai obitan lai ho sp. 2.a. Lin kt xichma(): - Lin kt c hnh thnh do s xen ph ca cc obitan dc theo trc ni hai ht nhn nguyn t(xen ph trc).
p p

s-s

v.v...

b. Lin kt pi(): - Lin kt c hnh thnh do s xen ph bn ca hai obitan p c trc song song vi nhau. Vng xen ph nm hai pha ca ng thng ni hai ht nhn.

CH4
- Nguyn t C trng thi lai ho sp3. - Bn obitan lai ho sp 3 ca C xen ph vi 4 obitan s ca nguyn t H to thnh 4 lin kt .

H
C

H H

H H

Phn t c dng t din u.

C2H4
- Hai nguyn t C u trng thi lai ho sp2. - Mi nguyn t C s dng mt obitan sp2 xen ph vi nhau v hai obitan sp 2 cn li xen ph vi obitan 1s ca hai nguyn t H to nn cc lin kt . Cc nguyn t C v H nm trong cng mt mt phng.
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H
C C

Hai nguyn t C cn hai obitan 2p khng tham gia lai ho c trc song song vi nhau v thng gc vi mt phng cha cc nguyn t C v H. Hai obitan ny xen ph bn vi nhau to thnh lin kt .

H
C

H H

H H

H
C2H2

- Hai nguyn t C trng thi lai ho sp. - Mi nguyn t C s dng mt obitan lai ho sp xen ph vi nhau v obitan sp cn li xen ph vi obitan 1s ca nguyn t H hnh thnh nn cc lin kt . Cc nguyn t C v H nm trn mt ng thng.

Mi nguyn t C cn li hai obitan 2p khng tham gia lai ho, chng xen ph bn tng i mt to ra hai lin kt .
C

------------------------------------------------------------------------------------------------------Ghi ch - Obitan lai ho c kh nng xen ph cao hn so vi obitan cha lai ho. - Lin kt tng i bn do vng xen ph gia hai obitan tng i ln. Lin kt t bn do vng xen ph gia hai obitan khng ln. - Lin kt n: gm 1 lin kt . Lin kt i: gm 1 lin kt v 1 lin kt . Lin kt ba: gm 1 lin kt v 2 lin kt . - Tng t nguyn t C, khi tham gia lin kt nguyn t N cng c th cc trng thi lai ho sp3(R1 R2 R3N), sp2(RCH = NOH), sp(HC N), v.v... - Do s xen ph trc ca cc obitan khi to lin kt n(lin kt ) nn c s quay t do xung quanh trc ni hai ht nhn nguyn t to lin kt m vn bo ton lin kt. Lin kt i, lin kt ba vi s xen ph bn ca cc obitan to lin kt nn lm trit tiu s quay t do xung quanh trc ni hai ht nhn nguyn t to lin kt.
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Bi s 2.
1. Cho bit kiu lai ho v loi lin kt(, ) ca cc nguyn t trong cc hp cht sau: ClCH2 - CHO; CH2 = CH - CN; CH2 = C = O 2. Cho bit kiu lai ho ca cc nguyn t C, N, S, Br trong cc hp cht sau: CH3 - CH3; CH2 = CH2; CH CH; C6 H6; CH2 = C = CH2; NH2OH; H2S; BF4-; HO - C N. Bi gii. 1.

Cl p

CH2 sp3

CH sp2

O sp2

CH2 sp2 CH2 sp2

2.

CH sp2

C sp O sp2

N sp

C sp

CH3 - CH3 : CH2 = CH2 : CH CH C6H6 : :

C sp 3 C sp 3

C sp 2 C sp 2
C sp C sp
C sp 2 C sp C sp 2

C sp 2

CH2 = C = CH2 : NH2OH: H2S : Sp BF4- :

N sp 3

Bsp 3

HO - C N : Csp - Nsp.

Bi s 3.
1. So snh di lin kt:

a.

* b' a' b* CH3 a CH2 CH3 CH3 CH CH2

CH3

c*

c'

CH l CH CH2

Gia (a , b , c ); (a', b', c').

b. CH

CH

CH2

CH

CH

CH2

CH

Gia (m, n, l).

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2. So snh gc lin kt, di lin kt C - C, C - H, phn cc ca lin kt CH gia cc cht sau: C2H2; C2H4; C2H6 Bi gii. 1. a. Do s lai ho cc obitan ca nguyn t cacbon m ta c bn knh ca cacbon lai ho:

C sp3 > C sp 2 > C sp .

C th:

rC

sp 3

= 0,771A 0 ; rCsp 2 = 0,665 A 0 ; rC

0 0

= 0,602 A0
sp

a* > b* > c* v a' > b' > c' ( bi lin kt cng tng th di lin kt cng gim). C th: C sp 3 C sp 3 = 1,54 A ; C sp 2 C sp 2 = 1,30 A ; C sp C sp = 1,20 A
0

b. Tng t phn a ta c: n > l > m. c. - Gc lin kt: V cc nguyn t cacbon trng thi lai ho khc nhau th gc lin kt khc nhau.

109 28'

120

180

C sp 3

C sp 2

C sp

Gc lin kt trong C2H6(C lai ho sp 3)< C2H4(C lai ho sp2) < C2H2(C lai ho sp). - di lin kt C - C: bi lin kt cng tng th di lin kt cng gim. C2H2 < C2H4 < C2H6. - di lin kt C - H: Do s lai ho ca nguyn t cacbon nn: di lin kt C - H: C2H2 < C2H4 < C2H6. - phn cc ca lin kt CH: Do cc trng thi lai ho khc nhau th nguyn t cacbon c m in khc nhau.

sp 3

< C

sp 2

< Csp

C th:

sp 3

= 2,5 ; Csp 2 = 2,8 ; Csp = 3,3

phn cc ca lin kt CH: C2H6 < C2H4 < C2H2. c. Xiclohexan - 1(S),3(S) - iol.

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Bi s 4.
Khi cho 2 - brombutan v 2 - metyl - 3 - trimetylamonipentan tc dng vi dung dch KOH/C2H5 OH thu c nhng sn phm no? Bi gii. 1.

CH3 CH CH CH3 + CH3 CH2 CH2 CH2 Sn phm chnh Br Sn phm ph ------------------------------------------------------------------------------------------------------Ghi ch Qui tc Zaixep. Trong phn ng tch nucleofin, nhm X(Br, H2O+, ...) tch ra cng vi nguyn t cacbon bn cnh c bc tng i cao hn to ra olefin c tng i nhiu nhm th hn hai nguyn t cacbon mang ni i. - HBr Br H CH 3CH 2 I H C C C C H H H OH H I' OH Br CH 3CH CH H CH2 H OH H H 3C H HO H C C C C Br H CH 3 II H II'

CH3 CH2 CH CH3

KOH/C2H5OH

CH 3CH2 H CH 3 H 3C Trng thi chuyn tip II n nh hn I bi c nhiu nhm ankyl hn. Sn phm II' bn hn (nhit hiro ho 119,54kJ/mol) sn phm I'(nhit hiro ho 126,94kJ/mol). Lp th phn ng tch. Qui tc Ingol: S tch lng phn t ch xy ra d dng khi m 4 trung tm phn ng nm trong mt mt phng v cc nhm th c tch ra dng trans(v tr anti) i vi nhau. KOH/C2H5OH CH3 CH2 * CH CH3 CH3 CH CH CH3 - HBr Dng cis hay trans Br Xt mt i quang v nhn dc theo trc C2 - C3: H Br CH3 CH3 H CH3 C Br H C CH3 H CH3 CH3 H H H H Cu dng bn OH trans - 2 - buten

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Br CH3 CH3 H H H CH3

CH3 Br CH3 H H OH H H CH3 C C H

cis - 2 - buten Cu dng km bn ------------------------------------------------------------------------------------------------------CH3 2. CH 3 CH CH CH 3 CH3 CH 1 2 3 4 OH Sn phm Hopman(chnh) CH 3 CH CH CH2 CH 3 CH3 - N(CH3)3, HOH H 3C N CH 3 CH 3 C CH 2 CH 3 CH
Sn phm Zaixep(ph) CH 3 Qui tc Zaixep khng p dng c vi X c th tch ln, ht electron. Gii thch. - Mun xt s to thnh sn phm Zaixep ta nhn dc theo trc C2 - C3: C2 C3 OH H H CH 2CH 3 CH 3 CH3

H H CH3
Sn phm Zaixep(ph)

C CH2CH3

H3C H3C

CH3 Cu trc ny rt khng bn.

- Nhn dc theo trc C3 - C4:

C4 C3 OH H H CH CH 3 H 3C H 3C N H CH 3 CH 3

H CH3 H
Sn phm Hopman(chnh)

C CH(CH3)2

CH 3 Cu trc ny bn hn.

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Bi s 5.
t chy hon ton mt hirocacbon A ri hp th ht sn phm chy vo mt bnh ng dung dch Ca(OH)2. Sau th nghim thy khi lng bnh tng 26,24 gam. Lc thu c 20 gam kt ta. un si nc lc mt thi gian lu li thu c 10 gam kt ta na. Khi cho mt lng A bng ng lng t chy trn vi clo 3000C thu c hn hp C gm 4 sn phm dn xut cha clo ca A l ng phn ca nhau vi hiu sut 100%. Hn hp C c t khi hi so vi H2 nh hn 93. Xc nh cng thc ca A v tnh thnh phn % theo khi lng mi cht trong hn hp C. Bi gii. Ghi ch Trong phn ng th halogen ca ankan, thc nghim cho thy, nu coi kh nng phn ng ca CI - H l 1 th kh nng phn ng ca CII - H v CIII - H nh sau: CI - H CII - H CIII - H 1 3,9 5,1 Clo ho 27 C 0 1 4,3 7,0 Clo ho 100 C 1 3,3 4,4 Clo ho 300 0C 0 1 82 1600 Brom ho 127 C ------------------------------------------------------------------------------------------------------0

A + O2 t CO2 + H2O Khi dn sn phm chy vo dung dch Ca(OH)2 th hi nc ngng t cn CO2 c phn ng: CO2 + Ca(OH)2 CaCO3 + H2O (1) c th c: 2CO2 + Ca(OH)2 Ca(HCO3)2 (2)
0

mbnh tng =

mCO2 + m H 2 O

un nng nc lc li thu c kt ta chng t c (2), v: 0 Ca(HCO3)2 t CaCO3 + CO2 + H2O

1),( ( 3 ) (2 ), nCO2 = nCaCO 3 (1) + 2nCaCO 3 (3 ) =

(3)

n H 2O =

26,24 0,4.44 = 0,48mol 18

20 10 + 2x = 0,4mol 100 100

nCO2 < n H 2O A l ankan CnH2n + 2.

CnH2n + 2 +
0 3n + 1 O2 t nCO2 + (n + 1)H2O 2

n 0,4 = n = 5. A : C5H12. n + 1 0,48

Ta c: C5H12 + nCl2 C5H12 - nCln + nHCl

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dC / H2 =

M C 72 + 34,5n = < 9,3 n = 1, 2, 3. 2 2

C5H12 n 1 3 2 > 11 3 > 10

CH3 - CH2 - CH2 - CH2 - CH3

CH3

CH CH3 CH3

CH2

CH3
S dn xut clo

>6

>6

CH3

C CH3

CH3

A l:

CH3

CH CH3

CH2

CH3 (n = 1) CH2 Cl CH3 Cl2, 3000C 1:1 CH3 CH CH3 CH3

I II

CH CH3 CCl CH3

CH2

CH3

CH2

CH3

CH3

CH CH3

CH2

CH3

CH Cl CH2

CH3

CH CH3

CH2Cl

Kh nng phn ng vi clo ca H - C : H - C : H - C III = 1 : 3,3 : 4,4

% CH2 Cl
Tng t:

CH CH3 CCl CH3

CH2

CH3 =

6.1 6.1 + 2.3,3 + 1.4,4

. 100% = 30%

%CH3

CH2

CH3 = 22%

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% CH3 %CH3

CH

CH

CH3 = 33% CH2Cl = 15%

CH3 Cl CH CH2 CH3

l % mi cht v s mol cng l % v khi lng ca mi cht do chng c khi lng phn t bng nhau.

Bi s 6.
Khi cho isobutilen vo dung dch H2SO4 60%, un nng ti 800C thu c hn hp gi tt l i - isobutilen gm hai cht ng phn ca nhau A v B. Hiro ho hn hp ny c hp cht C quen gi l isooctan. C l cht c dng nh gi nhin liu lng. C cng c th c iu ch bng phn ng trc tip ca isobutilen vi isobutan khi c mt axit v c lm xc tc. Hy gi tn C theo IUPAC v vit cc phng trnh phn ng gii thch s to thnh A, B, C.

Bi gii. H2SO4 H+ + HSO4-

CH3

+ C CH2 + H

CH3

C CH3 CH3

CH3

(1)

CH3

CH3

C CH3
CH3

CH3 + CH3

CH2

CH3

C CH3 CH3

CH2

C CH3

CH3 (2)

CH3
CH3 CH2 C CH3 CH3 Zaixep -H CH3

CH

CH3

CH3

C CH3

CH3 CH3 CH3 (A) (> 80%) C CH3 CH2 C CH2

H sinh ra li quay v (1). Qu trnh xy ra lin tc.

CH3 (B) (< 20%)

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CH3 CH3 C CH3 CH (A) C CH3 CH3 H2/Ni CH3

CH3 C CH3 CH2 CH CH3 CH3

Isooctan(C) 2,2,4 - trimetylpentan (Qui c c ch s octan l 100)

Isobutilen vi isobutan khi c mt axit v c lm xc tc cng to ra C: C ch ca qu trnh tng t trn nhng ch khc qu trnh: CH3 CH3

CH3

C CH3 CH3

CH2

C CH3

CH3 + CH3

CH CH3

CH3

CH3

C CH3

CH2 (C)

CH CH3 CH3 CH3 C CH3

+ CH3 CH3 sinh ra li lp li (2). C nh vy.

H3C

Bi s 7.
Hon thnh phn ng theo dy bin ho sau:

dd Na2CO3 A Propilen Cl2 CCl4

A'

Cl2 B CCl4

NaOH c Hn hp hai cht cha 2 nguyn t Cl

Zn, t0

B'

(CH3)3COK Hn hp cht (CH3)3COK Hn hp cha 1 nguyn hai hirocacbon C t Cl

B' Bi gii.

AgNO3/NH3

CH2 = CH - CH2Cl + HCl (A) CH2 = CH - CH2Cl + Na2CO3 + H2O CH2 = CH-CH2OH + NaHCO3 + NaCl (A') CH2 = CH - CH3 + Cl2

400 500 C
0

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CH2

CH

CH2 + Cl2 Cl

CCl4

CH2 Cl

CH Cl

CH2 Cl (B)

CH2 CH2 CH Cl Cl CH2 + NaOHc Cl Cl CH2

CH

CH + NaCl + H2O Cl CH2 + NaCl + H2O

CH2 C Cl Cl

CH2 + Zn

CH2

Cl Cl C CH2 + (B')

ZnCl2

CH2 Cl

CH

CH + Zn Cl

CH2

C CH2 + (B')

ZnCl2

CH3

CH

CH2 + Cl2
CH2

CH3
CH CH C CH2

CH Cl

CH2 Cl
CH2 CH

CH3

CH Cl

CH2 Cl

(CH3)3COK - (CH3)3COH - KCl

CH3 CH3 CH3

Cl (CH3)3COK CH2 C CH - (CH3)3COH CH3 C Cl - KCl CH2 C CH2

CH2 CH3

C C

CH2 AgNO /NH 3 3 CH

Cl C CAg + CH2

Bi s 8.
Su hirocacbon A, B, C, D, E, F u c cng thc phn t C4H8. Cho tng cht vo brom trong CCl4 khi khng chiu sng th thy A, B, C, D tc dng rt nhanh., E tc dng chm hn, cn F th hu nh khng phn ng. Cc sn phm thu c t B v C l nhng ng phn quang hc khng i quang(ng phn lp th i - a) ca nhau. Khi cho tc dng vi H2(Pd, t0) th A, B, C u cho cng mt sn phm G. B c nhit si cao hn C. 1. Xc nh cng thc ca 6 hirocacbon trn. Gii thch? 2. So snh nhit si ca E v F. 3. Nu c C, D, E, F. Hy nu phng php ho hc nhh bit chng.

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1. Cc ng phn c th c ca C4H8:

Bi gii.

CH3 CH3

CH2

CH

CH2 CH3

CH3 CH3 CH2

C CH3 CH

CH2

CH H2C H2C

CH

CH CH3

CH2 CH2 H2C H2C H2C

CH CH2 CH2 CH2

CH3

- V F hu nh khng phn ng vi Br2/CCl4, nn F l:

- E tc dng chm vi Br2/CCl4, nn E l:

H2C

CH

CH3

- V A, B, C c hiro ho u cho cng mt sn phm G chng t A, B, C c khung C nh nhau, nn cn li D:

CH3

C CH3

CH2

- V B, C tc dng vi Br2/CCl4 cho nhng ng phn quang hc khng i quang ca nhau(c t nht 2 *C), nn B v C l ng phn cis - trans ca nhau. Do B c nhit si cao hn C nn B l ng phn cis(phn cc hn).

B: CH3 C H C

CH3 H

C:

CH3 C H C

H CH3

A: CH3 - CH2 - CH = CH2 C ch(cng hp trans):

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H C H3 C Br C C

H CH 3

H Br2 H3C Br C H3C Br C C

Br C (1) Br H CH 3 Br

H CH 3

(2)

(1) H H3C

H C Br H CH 3

(2)

Br H

CH 3 Br

H Br

H CH 3

CH 3

CH 3 Br

Br CH 3 Br H

H CH 3

Br

H CH 3

Br CH 3

CH 3 H Br CH 3 I (Threo)
CH3 Br2 H H Br Br

CH 3 H Br CH 3 II Br H

H3C C H (C) C

H CH3

CH3 III Erythro(meso)

(I, III); (II, III) l nhng cp ng phn quang hc khng i quang. 2. ME = MF v d dng thy (E) > 0; (F) = 0 nn E c nhit si cao hn F.

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3. Nhn bit C, D, E, F. - Dng dung dch Br2 nhn ra F v khng phn ng. - Cn li D, E, F cho tc dng vi dung dch KMnO4 long, ngui. E khng phn ng nn nhn ra. - C, D em hp nc(H+) ri cho hai ru tng ng tc dng vi (HClc + ZnCl2). Cht no vn c ngay l ru bc 3 sn phm ca D. Cht no vn c kh chm l sn phm ca C(ru bc 2). Cc phng trnh phn ng:

CH3 CH CH (C) CH3

CH3

Br + Br2 CH3 CH Br Br CH CH3

CH2

C CH3 CH2

Br2

BrCH2

C CH3

CH3

H2C

CH

CH3 +

Br2

CH2 Br

CH2

CH Br

CH3

3CH3

CH

CH

CH3 + 2KMnO4 + 4H2O

3CH3

CH OH

CH OH

CH3

+ 2 MnO2 + 2KOH CH3

3CH2 C CH3 CH2 CH3 + 2KMnO4 + 4H2O 3CH2 OH C OH CH3 + 2 MnO2 + 2KOH

H2C
CH3 CH3 CH C

CH
CH CH2

CH3 + KMnO4
CH3 + HOH + HOH H+ H+

khng phn ng
CH3 CH3 CH3 C CH3 OH CH2 CH OH CH3

CH3

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CH3 CH3 C CH3 CH3 CH2 CH OH CH3 CH OH CH2 OH OH + HCl

CH3 ZnCl2 CH3 ZnCl2 C CH3 CH3 CH2 CH Cl H+ CH3 CH CH2 CH3 CH CH2 OH CH3 + H2O(chm) Cl + H2O(nhanh)

CH3 + HCl

OH2 OH

- H2O

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