NNG KHIU HA HC

Hc sinh c kh nng t duy Ton hc tt nhng khng c kh nng quan st,

nhn thc cc hin tng t nhin
V d: Hn hp A gm mt axit no n chc v hai axit khng no n chc cha mt lin kt
i, k tip nhau trong dy ng ng. Cho A tc dng hon ton vi 150 ml dung dch NaOH 2
M. trung ha ht lng NaOH d cn thm vo 100 ml dung dch HCl 1 M, c dung dch D.
C cn cn thn D c 22,89 gam cht rn khan. Mt khc t chy hon ton A ri cho ton b
sn phm chyhp th ht vo bnh ng lng d dung dch NaOH c, khi lng bnh tng
thm 26,72 gam. Xc nh cng thc cu to c th c ca tng axit v tnh khi lng ca
chng trong A.
Gii bnh thng
Gi cng thc ca axit no l: CnH2n+1COOH, cng thc chung ca 2 axit khng no l:
C mH 2m1COOH vi s mol tng ng l x v y
CnH2n+1COOH + NaOH CnH2n+1COONa + H2O
x
x
x
C mH 2m1COOH + NaOH C mH 2m1COONa+ H2O
y
y
y
CnH2n+1COOH +
x

3n 1
O2 (n+1)CO2 + (n+1)H2O
2

C mH 2m1COOH+

(n+1)x

(n+1)x

3m
O2 ( m+ 1)CO2 + mH2O
2
( m+ 1)y
my

y
Phn ng trung ho NaOH d:
NaOH d + HCl = NaCl + H2O
0,1
0,1
0,1
Theo phng trnh:
NaOH phn ng vi cc axit hu c = 0,3 0,1 = 0,2 mol
lng mui ca cc axit hu c = 22,89 - 0,1.58,5 = 17,04 gam
tng khi lng bnh NaOH l tng khi lng CO2 v H2O
x y 0,2

C h phng trnh: (14n 68)x (14m 66)y 17,04

[(n 1)x (m 1)y]44 [(n 1)x my]18 26,72

(x y) 0,2

14(nx my) 66(x y) 2x 17,04

62(nx my) 44(x y) 18x 26,72

Gii h phng trnh trn, ta c: x = 0,1 ; y = 0,1 ; nx + my = 0,26

n + m = 2,6. Vi m 2 nn n = 0 v m=2,6
Cng thc ca 3 axit l: HCOOH ; C2H3COOH v C3H5COOH
Gii c nhn xt:
1

KL mol TB ca 3 mui bng

17,04
= 85,2
0,2

KL mol TB ca 3axit bng 85,2 22 = 63,2

Vi cng thc tng qut CnH2nO2 v Cm H 2 m-2O2 (vi m > 3) ta thy:
Tng khi lng C + H bng (63,2 0,2) (32 0,2)= 6,24 gam, kt hp vi tng khi lng
CO2 v H2O bng 26,72 gam tnh c s mol CO2 bng 0,46 v s mol H2O bng 0,36.
3n 2
T CnH2nO2 +
O2 n CO2 + n H2O
2
Cm H 2 m 2O2 + 3m 2 O2 m CO2 + ( m - 1) H2O
2
Suy ra s mol Cm H 2 m 2O2 bng 0,46 0,36 = 0,1 v s mol axit no cng = 0,1

0,46
= 4,6 khi m > 3 th n 1 n = 1 ng vi H COOH
0,1
(63,2 0,2) (46 0,1)
KL mol TB ca 2 axit khng no =
=80,4
0,1

v n + m =

ng vi 2 axt khng no k tip l C2H3COOH (72) v C3H5COOH (86)

Hc sinh c kh nng quan st, nhn thc cc hin tng t nhin dn n
nim say m Ha hc nhng kh nng t duy Ton hc cha tt
V d: Hy xc nh khong cch gia 2 nguyn t iot trong 2 ng phn hnh hc ca C2H2I2
vi gi thit 2 ng phn ny c cu to phng.( Cho di lin kt C I l
2,10 v C=C l 1,33 ).
ng phn cis- :
H

H
C

dcis = d C= C + 2 d C I sin 300.

= d C= C + d C I

1200

300

= 1,33 + 2,1 = 3,43

ng phn trans- :
d trans =2 IO
IO =

IC 2 CO 2 2 IC CO cos120 0

I
I

H
C

2,12 +(

1,33 2
1,33
) -22,1
cos1200
2
2

1200

C
H
I

2,5 d trans =5,0

2

PHT HIN NNG LC HC SINH GII

A. NNG LC TIP THU KIN THC
2. Hy vit phng trnh ho hc biu din qu trnh quang hp cy xanh: Tnh khi lng tinh
bt thu c, nu bit lng nc tiu th l 5 tn v hiu sut quang hp l 60%.
3. Khi nitro ha 10 g phenol bng axit nitric 50%, thu c 17g hn hp cc hp cht nitro trong
phn khi lng ca ni t l 17%. Xc nh hiu sut nitro ha bng % so vi l thuyt.
4. Hi nhng cht no v iu kin no phn ng vi nhau tao nn nhng cht sau y ( y
khng ghi h s ca cc sn phm phn ng):
1) propanol 1.
2) propanol 1 + NaCl;
3) propanol 1 + NaOH.
4) glixerin + natri axetat.
5. Vit cc phng trnh phn ng trong dy chuyn ha sau:
2
4
170
A
0
C

H SO d

H2SO42lo ng
B
HO

2
4
170
D
0
C

H SO d

ddBr2

CH3-CHBr CHBr-CH3.

Bi 5: Hy cho bit cu trc lp th v gi tn cc oxit hnh thnh khi epoxiha cis v

trans but-2- en bng axit m- clopebenzoic. Nu nhn xt v cu trc ca cht u v sn phm
epoxi ha.
Vit c ch ca phn ng gia buten 2 vi Ar COOOH
* Vi cis but- 2- en :
H
H
O
C

H
C

CH3

CH3

CH3

cis-but-2,3-en
oxitoxit
cis-2,3-buten

CH3

*Vi trans but-2- en :

H

H
O

H3C

C
C

H3C

CH3

C
C

CH3

trans-2,3-buten
oxit
trans- but-2,3-en oxit

* Nhn xt : Ha lp th ca anken vn c bo ton i vi epoxit. y l phn ng c th

v mt lp th.
3

* C ch phn ng: electron ca lin kt i trong anken tn cng SN2 vo oxi ca nhm
OH trong peaxit. Kt qu l chuyn oxi ca Ar-COOOH n C=C to ra epoxit.
B. NNG LC T DUY TON HC
V d 1: ng (Cu) kt tinh c dng tinh th lp phng tm din.
*Tnh cnh lp phng a() ca mng tinh th v khong cch ngn nht gia hai tm ca hai
nguyn t ng trong mng, bit rng nguyn t ng c bn knh bng 1,28 . *Tnh khi
lng ring ca Cu theo g/cm3. ( Cu= 64).
HDG:
Theo hnh v ta thy: 1 mt ca khi lp phng tm din c AC =
a
r
2 =4 Cu
D
C
4 1, 28
a=
= 3,62 ()
M
2
a
Khong cch ngn nht gia 2 tm ca nguyn t l AM
AM = 2 rCu = 1,28 2 = 2,56 ()
A

*S nguyn t Cu trong mt t bo c s n = 8

1
1
+ 6 = 4
8
2

(nguyn t)
64 4
m
d=
=
= 8,96 g/cm3.
23
6, 02.10 (3, 62 108 )3
V
V d 2. Phn t X c cng thc abc .Tng s ht mang in v khng mang in trong phn t X
l 82. Trong s ht mang in nhiu hn s ht khng mang in l 22, hiu s khi gia b
v c gp 10 ln s khi ca a, tng s khi ca b v c gp 27 ln s khi ca a. Tm cng thc
phn t ng ca X.
HDG:

Gi s ht proton, ntron, s khi ca nguyn t a l: Za ; Na ; Aa

Gi s ht proton, ntron, s khi ca nguyn t b l: Zb ; Nb ; Ab
Gi s ht proton, ntron, s khi ca nguyn t c l: Zc ; Nc ; Ac
T cc d kin ca u bi thit lp c cc phng trnh:
2(Za + Zb + Zc) + (Na + Nb + Nc) = 82
(1)
2(Za + Zb + Zc) - (Na + Nb + Nc) = 22
(2)
Ab - Ac = 10 Aa
Ab + Ac = 27Aa
T (1) v (2) : (Za + Zb + Zc) = 26; (Na + Nb + Nc) = 30 => Aa + Ab + Ac = 56
Gii c: Aa = 2 ; Ab = 37 ; Ac = 17. Kt hp vi (Za + Zb + Zc) = 26
Tm c : Za = 1, Zb = 17 ; Zc = 8 cc nguyn t l: 1H2 ; 17Cl37 ; 8O17
Cng thc X: HClO.

C. NNG LC TI HIN, LIN H V VN DNG KIN THC

V d 1. Hy dng k hiu lng t biu din cc trng hp s lng electron trong mt
obitan nguyn t.
HDG:
1. C ba trng hp:

hoc

Obitan nguyn t
trng
c 1 e
c 2 e
V d 2. Liu php phng x c ng dng rng ri cha ung th. C s ca liu php l
s bin i ht nhn.
59
27

Co

n1

X?

X?

60
28

Ni

(1)
+

...

h = 1,25 MeV. (2)

a) Hy hon thnh phng trnh ca s bin i ht nhn trn v nu r nh lut no c p

dng hon thnh phng trnh.
b) Hy cho bit im khc nhau gia phn ng ht nhn vi phn ng oxi ho-kh (ly th d t
phn ng (2) v phn ng Co + Cl2 CoCl2).
HDG:
a) nh lut bo ton vt cht ni chung, nh lut bo ton s khi v bo ton in tch ni
ring, c p dng:
in tch: 27 + 0 = 27 ; S khi: 59 + 1 = 60 X l 27Co60.
59
60
27Co + 0n1 27Co .
S khi: 60 = 60; in tch: 27 = 28 + x x = 1. Vy c 1e0.
60
60
+ 1e ;
hv = 1,25MeV.
27Co 28Ni
b) im khc nhau:
Phn ng ht nhn: Xy ra ti ht nhn, tc l s bin i ht nhn nguyn t mi. VD b/
trn.
Phn ng ho hc (oxi ho kh): xy ra v electron nn ch bin i dng n cht hp
cht.
VD: Co + Cl2 Co2+ + 2Cl CoCl2.
Cht dng trong phn ng ht nhn: c th l n cht hay hp cht, thng dng hp cht. Cht
dng trong phn ng oxi ho kh, ph thuc vo cu hi m phi ch r n cht hay hp cht.
Nng lng km theo phn ng ht nhn: ln hn hn so vi nng lng km theo phn ng ho
hc thng thng.
V d 3. Hy dng sec-butyl bromua minh ha cho cc phn ng sau:
a) Thu phn theo SN1
b) Tch E1 vi Ag+
c) Phn ng SN2 vi NaI
GII
a) CH3-CH2-CHBr-CH3 CH3-CH2-CH+-CH3

b) CH3-CH2-CHBr-CH
3

Ag
H2O

c) CH3-CH2-CHBr-CH
3

NaI
SN 2

HOH
SN 1

CH3-CH2-CH+-CH3

CH3-CH2-CH I-CH3
5

CH3-CH2-CHOH-CH3
E1
H

CH3-CH=CH-CH3

V d 4. a/ un nng butaien 1,3 vi Stiren thu c sn phm duy nht X: C 12H14 sn phm
ny c th b hiro ho theo s :
X

+ H2, Ni

250C, 2atm

+ H2, Ni
1000C, 100atm

Xc nh cng thc cu to ca X, Y, Z, gii thch s khc nhau v iu kin phn ng hiro

ho. Bit rng s mol H2 tham gia phn ng ca giai on sau gp 3 ln s mol H 2 tham gia phn
ng giai on 1.
b/ Khi trng hp Isopren thy to thnh 4 loi polime, ngoi ra cn c mt vi sn phm ph
trong c cht P (1-metyl-3-isopropyl xiclohecxan) c th to ra t cht Q.
Vit cng thc cu to 4 loi polyme v cc cht X, Y.
HDG:
a/ CH2=CH-CH=CH2 + CH=CH2

CTCT X (C12H14)

C6H5

CTCT Y:

CTCT Z:

S d phn ng (2) cn iu kin t o, p cao hn p (1) v lk trong vng benzen nhiu hn lk

ca vng C6H9.
b/ Cng thc cu to 4 loi polime
CH3

CH2 CH

CH2 C
CH CH2 n

CH2

C
CH3

CH2

H
C

C
CH2

CH3

CH2
C
CH3

Dng cis
CH3

CH2

P:
C

CH2

CH CH3

CH3

CH3

Dng trans
CH3

Q:

D. NNG LC KIM CHNG

V d 1. Cht rn A l kim loi hoc l mt trong cc cht MnO2, KMnO4, K2Cr2O7, CaOCl2,
khi ho tan 15 gam A v dung dch HCl th to ra 8,4 lt n cht kh B bay ra (ktc). Hy chng
minh rng B khng th l Cl2
HDG:
MnO2 + 4H+ + 2Cl- Mn2+ + Cl2 + 2H2O
2MnO4- + 16H+ + 10Cl- 2Mn2+ + 5Cl2 + 8H2O
Cr2O72- + 14H+ + 6Cl- 2Cr3+ + 3Cl2 + 7H2O
OCl22- + 2H+

Cl2+ H2O
Theo phng trnh thu c 8,4 lt Cl2 (0.375 mol) th cn
0,125 s mol A 0,375 23,7g mA 47,6 gam.
iu ny tri gi thit mA = 15. Vy B khng th l Cl2
V d 2 : C cn bng N2O4 (k) 2 NO2 (k) . Cho 18,4 gam N2O4 vo bnh dung tch 5,904
0
lt 27 C . Ti cn bng ha hc, p sut ca kh trong bnh bng 1atm. Nguyn l chuyn dch
cn bng ha hc ni rng khi gim p sut th cn bng ca h s dch chuyn v pha lm tng
p sut. Hy chng minh iu .
HDG:
S mol ban u N2O4 = 0,2
[ ]
Tng s mol lc cn bng = 0,2 + x =

N2O4 (k) 2 NO2 (k)

0,2 x
2x

PV
1 5,904

= 0,24
RT 0,082 300
x = 0,04 mol

s mol NO2 = 0,08 ; N2O4 = 0,16

PNO

PN O

2 4

nNO

nN O

2 4

Gi s p sut gim n 0,5 atm th

P
1

0,5 P 6

P(NO2) = 0,217 atm ; P(N2O4) = 0,283 atm T s

( PNO ) 2 1
1
Kp =

2
PN O
6
2

2 4

2
6P + P 0,5 = 0

PNO

PN O

2 4

0,217
0,767 > 1
0,283
2

Vy, khi gim p sut cn bng s dch chuyn theo chiu to NO 2 (lm tng s mol kh lm
tng p sut)
V d 3: C th ha tan 100 mg bc kim loi trong 100 mL amoniac 0,1M khi tip xc vi
khng kh c khng ?

Cho Kb(NH3) = 1,74. 10 5 ; KL mol (Ag) = 107,88

7

Hng s bn ca phc Ag(NH3)+ = 103,32 ; Ag(NH3) 2 = 107,23 ;

Th oxiha-kh chun E0(Ag+/Ag) = 0,799 V ; E0(O2/OH ) = 0,401 V

(Hm lng oxi trong khng kh l 20,95% theo th tch)
HDG:

Phn ng to phc : Ag+ + NH3 Ag(NH3)+.

Ag+ + 2NH3 Ag(NH3) 2

V tnh ton theo phng trnh phn ng ta thy c kh nng Ag tan ht, do :
s mol Ag =

0,1

= 9,27. 10 4 ;
107,88

s mol NH3 cho = 10 2 > s mol NH3 cc i to phc = 18,54. 10 4 ;

* Cn phi kim tra kh nng ha tan bng nhit ng hc :
+
Ag + e Ag

0
+
E1 = E 1 + 0,059 lg [Ag ]

O2 + 2H2O + 4e 4OH .

PO
0,059
lg
E2 = E +
4
OH
0
2

V khi cn bng E1 = E2 nn tnh c E2. Trong dung dch NH3 0,1 M

5
3
1/2
1/2
[OH ] = (Kb.C)
= (1,74. 10 .0,1)
= 1,32. 10 .

0,059
0,2059
= 0,561 V
lg
4
1,32 10 3
E2 E10
5
+
+
lg [Ag ] =
= 4,034 V [Ag ] = 9,25. 10
M
0,059

E2 = 0,401 +

Nng tng cng ca bc trong dung dch : ( gi s [NH3] 0,1 M )

+
+
+
2
S = [Ag ] + [Ag(NH3) + Ag(NH3) 2 ] = [Ag ] ( 1 + 1[NH3] + 2[NH3] )

= 9,25. 10

( 1 + 10

2,32

+ 10

5,23

) = 15,5 M >> nng tnh ha tan hon ton

bc kim loi . Vy cc iu kin nhit ng thun li cho s ha tan.

V d 4 : Cc - aminoaxit ti im ng in th dng ion lng cc l nhiu nht, mc d c
ba loi ion cho di y u c bt c gi tr pH no.
R - CH - COOH

- H+

- H+

R - CH - COO

+NH
3

+NH
3

(A)

(C)

R - CH - COO
NH2
(B)

a) Xc nh gi tr pH ti nng ion lng cc ln nht ?

b) Hi vt alanin chuyn v cc no pH < 5 ? pH > 8 ?
c) Xc nh hm lng tng i ca ion lng cc C ca alanin im ng in, bit cc gi
+
tr hng s axit pK1 = 2,35 i vi cn bng A C + H ;
+
pK2 = 9,69 i vi cn bng C B + H .
HDG:
Ti im ng in nng ca cc ion tri du bng nhau: [A] = [B] (1)

C . H
Cc hng s axit l : K1 =
A

B . H
K2 =
C

(2)

Theo nh lut bo ton nng : [A] + [B] + [C] = C0

(3)

(4),

( trong C0 l tng nng ca aminoaxit )

+ 2
T (1), (2), (3) ti im ng in : [H ] = K1.K2

(5) hay pH =

pK1 pK 2
2

2,35
9,69 1/2
6,02
+
[H ] = (10
. 10
)
= 10
pH = 6,02
V im ng in ca alanin l 6,02 nn vt di chuyn v pha cc m
pH < 5,0 v v pha cc dng khi pH > 8,0
+
* By gi ta kim chng li [H ] trn bng php tnh ton tm hm lng tng i ca ion
lng cc C ti im ng in:
T (2) :

C
A

K1
K1

K11/2.K21/2 .

1/ 2
H
( K1. K 2 )

C
C
K1 102,35
7,34
7
=
10
hay
2,19.
10
.

= 4680

9,69
A

A
K
10

C
C
1

Nh vy, A B C (2 A C ) 2 A
= 0,99957 1,00
1
C
+
* Sau khi ly o hm ca [C] theo [H ] , trong [C] l hm sau :

C0 .K1. H
[C] =
t phng trnh (2), (3), (4) ta ch tm c mt cc
2
H K 1. H
K1.K 2

+
1/2
tr i vi [H ] = (K1.K2) .

10

E. NNG LC QUAN ST, NHN XT TM CON NG NGN NHT N

KT QU
V d 1. Hn hp gm Mg v Fe2O3 nng 20gam tan ht trong dung dch H2SO4 long, d thot ra
Vlt H2 (ktc) v nhn c dung dch B. Thm dung dch NaOH d vo dung dch B v lc kt ta
tch ra, nung trong khng kh n khi lng khng i c 28gam cht rn. Vit phng trnh phn
ng, tnhV v % khi lng mi cht trong hn hp.
HDG:
Sau khi vit phng trnh phn ng, ta nhn xt: Mg
+O
Mg O
Suy ra:

Fe2O3

Fe2O3

Lng oxi kt hp vi Mg bng 28 - 20 = 8( gam) hay 0,05 mol

V= 1,12 ( dm3) v lng Mg bng (8: 16)x 24 = 12 (gam) chim 60%

V d 2. Hn hp Y gm hai cht hu c A v B cng chc ho hc. Nu un nng 15,7 gam
hn hp Y vi NaOH d th thu c mui ca mt axit hu c n chc v 7,6 gam hn hp
hai Ru no n chc bc nht k tip nhau trong cng dy ng ng. Nu t 15,7 gam hn
hp Y th cn dng va ht 21,84 lt O2 v thu c 17,92 lt CO2 (cc th tch kh o ktc). Xc nh
cng thc cu to ca A v B.
HDG:
Este n chc k tip c dng chung CXHYO2 vi s mol O2= 0,975 ;
CO2= 0,8 nn s mol H2O bng 15,7 + (0,975 x 32)-(0,8 x 44) : 18 = 0,65
Suy ra, tng s mol 2 Este bng 0,65 + (0,8 x 2) - (0,975 x 2):2 = 0,15
Tr s nC bng 0,8 : 0,15 = 5,33
5 < 5,33 < 6
Tr s nH bng ( 0,65 : 0,15) x 2 = 8,66
8 < 8,66 < 10
Vy cng thc phn t 2 Este l C5H8O2 v C6H10O2
7, 6
Kl mol TB ca 2 Ru bng
= 50,66 2 Ru k tip l C2H5OH (46) v C3H7OH (60).
0,15
Suy ra Mui c s C bng 5 - 2 = 3 v s H = 8 - 5 = 3
Cng thc ca mui l C3H3O2Na hay CH2=CH-COONa . Vy cng thc cu to ca A l
CH2=CH-COO-C2H5 v B l CH2=CH-COO-C3H7
V d 3. Cho 9,0 gam hn hp gm bt Mg v bt Al tan ht trong 200 ml dung dch HCl thy
thot ra kh A v thu c dung dch B. Thm t t dung dch NaOH vo B sao cho kt ta t
ti lng ln nht th dng ht 500 ml dung dch NaOH 2M. Lc kt ta em nung n phn ng
han ton thu c 16,2 gam cht rn. Vit phng trnh phn ng. Tnh th tch kh A (ktc),
nng mol ca dung dch HCl v % khi lng mi kim loi ban u.
HDG:

Mg + 2 HCl MgCl2 + H2
Al + 3 HCl AlCl3 + 1,5 H2
HCl + NaOH NaCl + H2O
MgCl2 + 2NaOH Mg(OH)2 + 2 NaCl
AlCl3 + 3NaOH Al(OH)3 + 3 NaCl
11

Mg(OH)2 MgO + H2O

2 Al(OH)3 Al2O3 +3 H2O
Theo phng trnh: s mol HCl = NaOH bng 1,0 mol CM (HCl) = 5 M
S mol H2 bng s mol oxi trong 2 oxit bng

16, 2 9
= 0,45 ( mol)
16

V H2 = 10,08 ( lt)
Cui cng bng cch lp h phng trnh hoc bng php tnh s hc tnh c:
% Mg = 40% v % Al = 60%
V d 4: Hn hp 2 kim loi kim c cho tc dng vi dung dch HCl va ri c cn th
nhn c m1 gam mui khan. Cng lng hn hp c cho tc dng vi dung dch H2SO4 va
ri c cn dung dch th nhn c m2 gam mui khan. Tnh tng s mol 2 kim loi kim
* Nu m2 = 1,1807m, th 2 kim loi kim k tip nhau l nguyn t no?
* Vi m1 + m2 = 90,5. Tnh lng hn hp u v lng kt ta to ra t (m1 + m2)
gam mui tc dng vi dung dch BaCl2 d.
HDG:
2R + 2HCl 2RCl + H2 v 2R + H2SO4 R2SO4 + H2
Con ng ngn nht l coi 2RCl ~ R2Cl2 s nhn thy m2 > m1 do lng gc
SO4 = 96 > lng gc Cl2 = 71. ( tng = 96 71 = 25 )Suy ra:

s mol 2 mui sunfat

m2 m1
25

v s mol 2 kim loi kim

m2 m1
12,5

0,1807m1
25
1,1807m1 25
KL mol TB 2 mui sunfat =
= 163,35
0,1807m1
vi m2 = 1,1807 m1 th s mol 2 mui =

Kl mol TB 2kim loi kim =

163,35 96
= 33,675
2

l Na = 23 v K = 39
Ghp : m2 = 1,1809m1 v m1 + m2 = 90,5 tnh c m1 = 41,5 v m2 = 49
=> S mol mui = 0,3 => lng 2 kim loi kim = 49 - 0,3. 96 = 20,2 (gam)
Ba2+ + SO42- => BaSO4
lng kt ta = 0,3 x 233 = 69,9 (gam)
F. NNG LC SUY LUN, BIN LUN LOGIC
V d 1. Chia hn hp gm 2 ru no mch h P v Q lm 2 phn bng nhau.
- Cho phn th nht tc dng ht vi Na d thu c 0,896 lt kh (ktc).
- t chy ht phn th hai thu c 3,06 gam H2O v 5,28 gam CO2 .
Xc nh Cng thc cu to ca 2 ru, bit rng khi t V th tch hi ca P hoc Q th th
tch CO2 thu c trong cng iu kin nhit v p sut u khng vt qu 3V.
HDG:
12

 S mol H2 = 0,04 ; CO2 = 0,12 ; H2O = 0,17

Do 2 ru u no mch h nn cng thc chung CnH2n+2Ox .(n, x u l tr s TB)
CnH2n+2Ox +

3n 1 x O n CO + (n +1) H O
2
2
2
2

Theo phng trnh tng s mol A + B = 0,17 0,12 = 0,05 mol

CnH2n+2Ox + x Na CnH2n+2- x(ONa)x +
D thy : n =

x
H2
2

0,12
0,04
= 2,4 v x =
2 = 1,6 phi c 1 ru n chc
0,05
0,05

Theo gi thit, s nguyn t cc bon trong mi ru u khng qu 3 nn :

* Trng hp 1 : Ru n chc c s cacbon = 3 (C3H7OH)
Ru a chc cn li c s ccbon < 2,4 v c s nhm OH > 1,6
l CH2OH CH2OH (s nhm OH khng vt qu s cacbon)
* Trng hp 2 : Ru n chc c s cacbon = 2 (C2H5OH)

Ru a chc cn li c s cacbon > 2,4 v s nhm OH 3 C3H8Ox .

Ta c :
2
0,6

2,4

t s mol

0,4

p dng t s ny tnh x :

C2 H 5OH 0,6 3

C3 H 8Ox 0,4 2

x - 1,6
1,6

x 1,6 3
x = 2,5
0,6
2

0,6

* Trng hp 3 : Ru n chc

c s cacbon = 1

(CH3OH)

Ru a chc cn li c s cacbon > 2,4 v s nhm OH 3 C3H8Ox .

Lm tng t trn tnh c x = 1,857. C 2 trng hp 2 v 3 u cho x khng nguyn
(loi). Vy nghim l C3H7OH (0,02 mol) v C2H4(OH)2 (0,03 mol)
V d 2. Cho 2,16 gam hn hp gm Al v Mg tan ht trong dung dch axit HNO 3 long, un
nng nh to ra dung dch A v 448 mL ( o 354,9 K v 988 mmHg) hn hp kh B kh gm 2
kh khng mu, khng i mu trong khng kh. T khi ca B so vi oxi bng 0,716 ln t khi
ca CO2 so vi nit. Lm khan A mt cch cn thn thu c cht rn D, nung D n khi lng
khng i thu c 3,84 gam cht rn E. Vit phng trnh phn ng, tnh lng cht D v %
lng mi kim loi trong hn hp ban u.
HDG:
Cc phng trnh phn ng : Kh B theo gi thit cha N2 v N2O.

5 Mg + 12 H+ + 2 NO 3 5 Mg2+ +
+

4 Mg + 10 H + 2 NO
10 Al + 36 H+ + 6 NO

N2 + 6 H2O

2+

4 Mg + N2O + 5 H2O
10 Al3+ + 3 N2 + 18 H2O

8 Al + 30 H+ + 6 NO 3 8 Al3+ + 3 N2O + 15 H2O

4Al(NO3)3 2Al2O3 + 12 NO2 + 3O2
13

2Mg(NO3)2 2MgO + 4 NO2 + O2

Vi KL mol TB ca 2 kh = 36 v tng s mol 2kh = 0,02 ta c th tnh c s
mol N2 = 0,01 v N2O = 0,01. Sau lp phng trnh theo quy tc bo ton s
mol electron : Al 3e Al3+.
2N5+ + 10 e N2.
x
3x
0,1
0,01
2+
5+
Mg 2e Mg .
2N + 8 e N2O
y
2y
0,08
0,01
dn ti h phng trnh : 3x + 2y = 0,18 v
27x + 24y = 2,16
H phng trnh ny khi gii s cho x = 0. T y ny sinh tnh hung c vn ?
- Theo nh lut bo ton khi lng : 3,84 gam cht E chc chn l Al2O3 v MgO.
T lng 2 kim loi v lng 2 oxit tnh c s mol Al = 0,04
v s mol Mg = 0,045.
Lp li tnh ton nh trn : Al 3e Al3+.
2N5+ + 10 e N2.
0,04 0,12
0,1
0,01
2+
5+
Mg 2e Mg .
2N + 8 e N2O
0,045 0,09
0,08
0,01
ta thy : tng s mol e nhng (0,21) > tng s mol e thu (0,18) chng t cn mt phn N5+ = 0,21
0,18 = 0,03 mol tham gia phn ng khc, khng gii phng kh.

l phn ng :
4 Mg + 10 H+ + NO 3 4 Mg2+ + NH 4 + 3 H2O

8 Al + 30 H+ +3 NO 3 8 Al3+ + 3 NH 4 + 9 H2O
2 NH4NO3 N2 + O2 + 4 H2O
Vy cht D gm : Al(NO3)3 (8,52 gam) ; Mg(NO3)2 (6,66 gam) ; NH4NO3 (2,4 gam) c lng =
17,58 gam. Hn hp ban u c 50% lng mi kim loi.
V d 3. Cht A l mt trong nhng thnh phn c ch s octan thp ca xng. Ankyl ha A bng
isobutan sinh ra hidrocacbon B, c cha hidro nhiu hn A l 1%. Nu reforming, A chuyn
thnh hidrocacbon D. Nitro ha cht D ch cho mt dn xut mono nitro thi. D khng phn ng
vi nc brom, khi un hi lu D vi dung dch KMnO 4 trong axit th thu c axit E. Phn
ng ngng t gia E vi mt lng tng ng ca tetra metylen diamino c dng trong sn
xut mt polime d mua trn th trng. Khi un chy E vi kim sinh ra mt hp cht F, hidro
ha hon ton F cho hidrocacbon X. Cc cht A, X v sn phm hidro ha hon ton D c cng
thnh phn nguyn t. A khng c ng phn hnh hc, khi b ozon phn to ra mt xeton cho
phn ng halofom.
a) Lp lun vit cu to ca A, D, E, F, X. Nu xc tc chuyn A B
b) ng phn no ca E c th to anhidrit vng ? So snh nhit nng chy v tnh axit gia
ng phn v E. Gii thch.
HDG:
- Cc tnh cht ca D nu trn cho thy n l ng ng ca benzen
- Axit E sinh ra khi oxiha D c phn ng ngng t vi diaminohexan to ra nha poliamit nn
axit E l diaxit cacboxylic D l diankyl benzen v phi l dn xut para mi cho mt sn
phm mononitro khi nitro ha E l axit terephtalic.
- Phn ng decacboxyl ha E to ra benzen, cht ny b hidro ha cho xiclohecxan.
( C 6H12
c thnh phn 85,71% C v 14,29% H hay CnH2n )
- Ankyl ha A bng isobutan to ra ankan B c cng thc Cn+4H2n+10.
14

Theo gi thit :

2n 10
= 0,1529 n = 8 cng thc A l C8H16 .
14n 58

- Cht D (diankylbenzen) l para-xilen, cht F l benzen v cht X l xiclohexan

COOH

CH3

(D)

CH3

(E )

(F )

COOH

(X )

- Cht D sinh ra khi thm ha mt trong hai anken c khung cac bon sau : ( nhng nguyn t C
tham gia ng vng k hiu *)

(I)

(II)

- Hidrocacbon A khng c ng phn hnh hc v khi b ozon phn cho mt metyl xeton (phn
ng halofom) nn ni i c hai nhm tng t nhau mt C v t nht c mt nhm metyl. Vy,
ch c b khung (I) mi tha mn iu ny, cht A c th c mt trong hai cu to sau :

* Xc tc chuyn A B l mt axit Liuyt hot ng (nh AlCl3), ng phn ca E c th to

c anhidrit vng l axit ortho-phtalic (axit Y).
* Nhit nng chy (E) >(Y) do (Y) c lin kt hidro ni phn t lm gim lin kt hidro lin
phn t. So snh tnh axit thy c mc khc nhau do u l diaxit
- Ka1(Y) > Ka1(E) do lin kt hidro ni phn t lm tng phn cc lin kt O-H

- Ka2(Y) < Ka2(E) do phn cc lin kt O-H gim bi bn ca anion 1 .

15

XY DNG BI TP BI DNG HC SINH GII

MT S NGUYN TC XY DNG BI TP
T c bn n pht trin t duy.
T c im ring l n khi qut, h thng.
Lp i lp li nhng kin thc kh v tru tng.
a dng, loi hnh nhm tng thm kin thc v gip hc sinh c st.
Cp nht nhng thng tin mi.

MT S BIN PHP XY DNG BI TP

1.
2.
3.
4.
5.
6.
7.

Nhiu cch gii

Thay i mc yu cu (Pht trin Lc bt, chia nh Thay th)
o chiu
Thay i hnh thc
p dng yu cu cho nhiu mc ch
Nhiu yu cu khc nhau cho mt ni dung
Bi tp tng t

16

1. Nhiu cch gii

V d 1: 500C v di p sut 0,344 atm phn ly ca N2O4 (k) thnh NO2(k) bng 63%.
Xc nh Kp; Kc; Kx.
HDG:

CCH TH NHT. Tnh Kp Kc; Kx

N2O4 (k)
[ ]
Phn mol

Kp =

2
PNO
2

PN2O4

1-

1
1

2
1

= 1
1
1

2 NO2(k)

1 + ( l phn ly)

thay = 0,63 tnh c Kp = 0,9

. 0,344

Kc = Kp.(RT)n vi n = 1 v

p dng

tnh c Kc = 0,034

Kx = Kp. P n
Kx = 2,63

CCH TH HAI. Tnh Kx Kp ; Kc

Coi lc u 1 mol N2O4 th c 0,63 mol b phn ly to ra 1,26 mol NO2 . Tng s mol lc cn
bng = 1 + 0,63 = 1,63 . Ta c :
2

1,26
1,63

Kx =
= 2,63 T suy ra Kp v Kc theo biu thc nu.
0,37
1,63

V d 2: Ngi ta d tnh ho tan 10 -3 mol Mg(NO3)2 trong mt lt dung dch NH3 0,5M ;
trnh s to thnh kt ta Mg(OH)2 phi thm vo dung dch ti thiu bao nhiu mol NH4Cl?
Cho KNH3 = 1,8.10-5; Tt Mg(OH)2 = 1,0.10-11
HDG:

CCH TH NHT.
2
2+
iu kin khng to kt ta Mg(OH)2 l [Mg ].[OH ] 10-11.
3

4
0
2+
vi C (Mg ) = 10 th [OH ] 10 .
Cn bng
[ ]

NH3 + H2O NH 4 + OH
0,5 10

x + 10

Kb = 1,8.10-5.

10

17

( x 104 ) 10 4
4
c
= 1,8.10-5 (coi 10 << 0,5 ) x = 0,0899
4
0,5 10
Vy phi thm ti thiu 0,0899 mol NH4Cl khng to c kt ta Mg(OH)2.

CCH TH HAI.
iu kin khng to kt taMg(OH)2 l [Mg

2+

2
].[OH ] 10-11.

4
10
0
2+
+
vi C (Mg ) = 10 th [OH ] 10
[H ] 10
pH 10
Khi thm NH4Cl s c dung dch m baz (NH3 + NH 4 )

NH 4
pHm baz = 14 pKb lg

NH

Thay pH = 10 ; pK = 4,74 ; [NH3] = 0,5 tnh c [NH 4 ] = 0,09

2. Thay i mc yu cu:
2.1. Pht trin:
V d 1 : C bn hp cht thm C6H5-OH (A), C6H6 (B),
tnh cht sau:
Cht phn ng
C6H5-OH
C6H6
Nc Br2
C phn ng
Khng ph.ng
Br2/Fe
Ph.ng 0oC C phn ng
khng cn Fe
HNO3/H2SO4
Ph.ng vi c C phn ng
HNO3 long

C6H5-CH3 (C), C6H5-NO2 (D) vi cc

C6H5-CH3
Khng ph.
C phn ng

C6H5-NO2
Khng ph.
Ch phn ng
khi un nng
Ch phn ng
khi un nng

C ph. khng
cn H2SO4
* Hy sp xp cc cht theo th t tng dn v kh nng d phn ng th vng benzen
Gii thch nh hng ca cc nhm th n kh nng
C6H5-NO2 < C6H6 < C6H5-CH3 < C6H5-OH
* V phn ng th nguyn t Hidro vng benzen thuc loi th Electrophin tc l tng tc
gia h electron ca vng benzen vi tc nhn mang in dng nn mt electron trong
vng benzen cng ln th phn ng cng d dng.Ly C 6H6 lm trung gian ta thy: - Cc nhm
-CH3 ; - OH thuc loi nhm th hot ng ha (nhm y e ; +I,+C) lm tng mt e ca
vng benzen,cn nhm-NO2 thuc loi nhm th phn hot ha (ht e; -I,-C) lm gim mt
e ca vng benzen nn kh nng phn ng th ca A,C > B > D.
-So snh gia A v C th trong phn t A do nguyn t oxi cn i e t do nn c s lin hp p-
vi vng benzen in tch dng c th gii to ti nguyn t oxi mt e trong vng
benzen ca A > so vi ca C kh nng phn ng th A > C .

18

 pht trin bi tp ny c th c nhiu hng:

Hng(I)- Tm k hiu ng vi mi cht.
"C bn hp cht thm C6H5-OH, C6H6, C6H5-CH3, C6H5-NO2 vi cc tnh cht sau:
Cht phn ng
A
B
C
D
Nc Br2
Khng ph.
C phn ng
Khng ph.
Khng ph.
Br2/Fe
C phn ng
Ph.ng 0oC Ch phn ng C phn ng
khng cn Fe
khi un nng
HNO3/H2SO4
C phn ng
Ph.ng vi c Ch phn ng C phn ng
HNO3 long
khng
cn
khi un nng
H2SO4
a/ Xc nh k hiu A,B,C,D cho mi cht.
b/Hy sp xp cc cht theo th t tng dn v kh nng d phn ng th vng benzen Gii
thch nh hng ca cc nhm th n kh nng .
c/ Vit phng trnh phn ng."
Vi hng ny hc sinh phi suy lun ra k hiu ca tng cht da trn cc tnh cht cho, ri
mi gii tng t trn.
Hng(II) -Thay cht thm,ng thi vi tm k hiu cho tng cht:
"C bn cht thm : C6H5-NH2 , C6H5-CH3, C6H5-NO2 , C6H6 vi cc tnh cht sau:
Cht phn ng
A
B
C
D
Nc Br2
Khng ph.
Khng ph.ng
C ph. to Khng ph.
thng
Br2/Fe
C phn ng
C phn ng
Ph.ng 0oC Ch phn ng
khng cn Fe
khi un nng
HNO3/H2SO4
C phn ng C phn ng
Ph.ng chm (c Ch phn ng
khng
cn
th to ra sn
khi un nng
H2SO4
phm meta)
a/ Xc nh k hiu A,B,C,D cho mi cht .
b/ Sp xp cc cht theo th t tng dn v kh nng th nguyn t Br vng Benzen v gii
thch ?
c/ Sp xp cc cht theo th t tng dn v kh nng th nhm NO 2 vng Benzen v gii thch
v sao th t ny khc vi th t phn (b) ?
*A l C6H5-CH3 ; B l C6H6 ; C l C6H5-NH2 ; D l C6H5-NO2 .
* Th t phn ng th nguyn t Br : D < B < A < C
Gii thch tng t bi trn.
* Th t phn ng th nhm NO2 :
C < D < B < A
Gii thch : Do qu trnh proton ha nhm NH2 ca C6H5-NH2 bi HNO3 (v c th c H2SO4)
theo phng trnh: C6H5-NH2 + HNO3 C6H5-NH3+NO3nn cn tr s th nhm NO 2 vo vng Benzen Kh nng th cn km hn so vi C 6H5-NO2 .
Sau , di tc dng ca HNO3 thng thu c sn phm th nhm NO2 v tr meta
+
+
NH2
NH3
NH3NO3

NaOH

HNO3
H2SO4

NO2

19

NO2

Hng(III) - Tnh cht vt l :

III.1. Cho bn cht thm : C6H5-NH2 , C6H5-OH, C6H5-Cl , C6H6 .
Vi cc nhit si :
Cht thm
A
B
C
D
o
o
o
Nhit si
80 C
132,1 C
184,4 C
181,2oC
Hy xc nh k hiu A,B,C,D cho mi cht v gii thch ?
*C6H5-NH2 v C6H5-OH c th to lin kt Hidro lin phn t nn c nhit si cao hn,
chng l C v D.
*Trong phn t, do nguyn t oxi c m in = 3,5 ln hn m in ca Nit = 3,0 nn
Lin kt Hidro trong C6H5-OH bn vng hn nhit si cao hn. Vy : C l C6H5-OH , cn
D l C6H5-NH2 .
* Phn t C6H5-Cl l phn t phn cc c Mol phn t = 112,5 g ln hn Mol phn t ca C 6H6= 78
nn phi c nhit si cao hn B l C6H5-Cl cn A l C6H6 .
III.2. C 5 cht hu c: cis- CHCl=CHCl ; trans- CHCl=CHCl ;
cis- CH3- CH=CHCl ; trans- CH3-CH=CHCl v trans- CH3-CH=CH-COOH
vi cc gi tr momen lng cc sau y:
Cht hu c
A
B
C
D
E
0,00
1,89
2,13
1,97
1,71
(D)
Hy ch r A,B,C,D,E ng vi cht no? Gii thch.
*Phn t trans- CHCl=CHCl l A v 2 nguyn t Cl to ra 2 vect momen lng cc cng
phng, cng ln nhng ngc chiu nn trit tiu .
*Hai phn t trans- CH3-CH=CH-COOH v trans- CH3-CH=CHCl s c momen lng cc
ln hn (2,13 & 1,97) v nhm CH3- th y electron, cn nhm -COOH v nguyn t Cl th ht
electron nn to ra 2 vect momen lng cc cng phng, cng chiu. Tuy nhin, do nhm
-COOH ht electron mnh hn -Cl nn trans- CH3-CH=CH-COOH l C
cn
trans- CH3CH=CHCl l D
* Phn t cis- CHCl=CHCl l B v 2 nguyn t Cl to ra 2 vect momen lng cc cng ln,
nhng khng cng phng v khng c s b tr v momen lng cc nn ln hn (1,89D). Cn
phn t cis- CH3- CH=CHCl c 1 nhm -CH3 y electron,to vi nguyn t Cl ht electron 2
vect momen lng cc khng cng phng, nhng c s b tr mt phn momen lng cc
nn nh hn (1,71D) n l E .

20

2.2. Lc bt hoc chia nh:

V d 1: Bi thi olympic ha hc quc t ln th 28 sau y qu di v c th ct lm i:
Hai hidrocacbon ng phn A v B cha 85,7 % cacbon theo khi lng.
a) Vit cng thc tng qut tha mn iu kin ny.
b) Phn ng ca mi cht vi ozon v x l tip theo vi bt km trong axit to sn phm hu c
duy nht C. S oxi ha hp cht C cho mt sn phm duy nht l axit cacboxylic D. S liu
ph cho thy tt c cc nguyn t hidro trong hp cht D (tr hidro ca nhm cacboxyl) u
thuc nhm metyl. Khi lng ring ca hi D quy v iu kin tiu chun (0 0C, 1 atm) l 9,1
g/l . Vit cng thc cu to ca hp cht D khi trong dung dch nc v khi pha hi.
c) Vit cng thc cu to ca hp cht C. Vit cng thc cu to cc ng phn A v B. Vit cc
phng trnh phn ng ca qu trnh chuyn A hoc B thnh C v D.
d) Khi phn ng vi dung dch kali pemanganat trung tnh trong nc, hp cht A phn ng d
hn hp cht B. Trong phn ng ny, A to thnh mt hp cht
F duy nht cn B to thnh .mt hn hp ng phn G1v G2 theo t l 1:1.
Vit cc phng trnh phn ng ca qu trnh chuyn A thnh F, v B thnh G1v G2.
e) Cc hp cht G1v G2 phn ng d dng vi axeton c mt axit to cc hp cht H 1 v
H2. Vit cng thc cu to ca H1 v H2.
f) Cc hp cht A v B phn ng vi brom. Mt trong cc sn phm ca cc phn ng ny khng
cc (mo men lng cc ca phn t ny coi nh bng khng) v khng c tnh quang hot.
Vit cng thc ha hc lp th ca sn phm ny, v phng trnh to thnh cht y. Hy xc
nh cu hnh tuyt i ca cc nguyn t c tnh i xng gng trong phn t ny( nu c)
v nh du chng theo quy tc c tn R v S bng cch ch nh ng R hoc S ti mi tm
lp th.
g) Anken phn ng vi peaxit (peoxiaxit) dn n s cng hp mt nguyn t oxi vo lin kt
i to mt vng ba cnh c cha oxi. Phn ng "epoxi ha" ny c tnh lp th c th r
rt dn n s lu gi cc v tr tng i ca cc nhm th trn lin kt i m nguyn t oxi
gn vo. S epoxi ha hp cht A bng axit peaxetic to thnh mt hp cht duy nht K. Trong
cng iu kin B to thnh mt hn hp ng phn L 1 v L2 (theo t l 1: 1). Hp cht K c
tnh quang hot khng? Vit cng thc ha hc lp th ca K ch r ha hc lp th ca n.
Mi hp cht L1 v L2 c tnh quang hot khng? Vit cng thc ha hc lp th ca L 1 v L2
ch r ha hc lp th.
Phn th nht c th dng cc phn a, b, c, d, e. Khi li gii:
a) Cng thc tng qut: CnH2n.
b) Theo gi thit cht D phi c nguyn t cacbon bc 4 lin kt trc tip vi nhm COOH v
ba lin kt cn li u vi cc nhm CH3.
Vy cng thc ca D l: (CH3)3C COOH. (Khi lng mol phn t = 102). Khi lng
mol phn t pha hi = 9,1 22,4 = 203,84 gn gp i khi lng mol phn t ca
(CH3)3C COOH cho thy pha hi D tn ti di dng dime.
Cu to ca D:
CH3
CH3
OH O
H3C C COOH + H2O
H3C C COO + H3O+
O HO
CH3
CH
3

trng thi hi

trong dung dch n c

21

c) Sn phm ozon phn l mt andehit tng ng mi b oxiha to ra axit duy nht.

(CH3)3C

C(CH3)3
CH

C(CH3)3

CH

CH

CH
(CH3)3C

Cu t o A

Cu t o B
Cu to C: (CH3)3C CHO. Do C l sn phm duy nht nn A v B l cc anken i xng
dng R CH = CH R
Phng trnh phn ng A
C
D
(CH3)3C

C(CH3)3

O3

(CH3)3C

C(CH3)3

[O]
Zn
2(CH3)3C-COOH
2(CH3)3C-CHO
H3O+

O O

d) Phn ng ca A
(CH3)3C

F
C(CH3)3

KMnO4

C(CH3)3

(CH3)3C
HO
H

Phn ng ca B

OH

G1 + G2.

(CH3)3C

KMnO4

(CH3)3C
HO

C(CH3)3

C(CH3)3
OH

(CH3)3C
+

HO

C(CH3)3
OH

Hn h p trit quang

e) Cu to cc cht H1 v H2 (sn phm phn ng ca G1 v G2 vi axeton)

C(CH3)3
C(CH3)3
(CH3)3C
(CH3)3C
O

O
C

C
CH3

H3C

H3C

CH3

hay
C(CH3)3
(CH3)3C

O
O

C(CH3)3
(CH3)3C

O
O

Phn th hai cn lp li cu a v mt na cu b (n ch...u thuc nhm CH3) hoc c th

thit k theo kiu khc xc nh cu to A, B, D, sau ni tip cu f, g v c li gii nh
sau:
f) Sn phm brom ha khng phn cc to ra t B, v phn ng cng brom theo c ch AE xy
ra theo kiu trans, ngha l mt nguyn t Br tn cng vo
pha ny ca ni i th nguyn t Br cn li s tn cng
Br(-)
vo pha kia(pha i lp). gii thch iu ny ngi ta
C
C
22

Br

cho rng: cacbocation trung gian sinh ra t giai on chm ca phn ng c th tn ti di

dng vng ba cnh nn mt pha ca lin kt C C b n ng, ch cn li mt pha trng
cho anion Br tn cng. Cu to lp th ca sn phm ny c th c biu din mt
trong ba kiu sau:
Br
C(CH3)3
hoc
(CH3)3C

Br
H
(CH3)3C

Br
Phng trnh to thnh sn phm ni trn:
(CH3)3C
Br

C(CH3)3
H

hoc

Br

(CH3)3C

Br

C(CH3)3

C(CH3)3
Br

Br
R
C(CH3)3

Br
C(CH3)3

g) Cu to ca K , L1 , L2 .
(CH3)3C

C(CH3)3

(CH3)3C

C(CH3)3

(CH3)3C
O

K (Khng c tnh quang ho t)

L1 v L2 (C tnh quang ho t)

23

C(CH3)3

2.3. Thay th :
V d 1: Bi s 4 trong K thi olympic ha hc quc t nm 2000 ti an Mch c ni
dung:Mt hp cht A c trong t nhin, ch cha C, H, O v c thnh phn % lng cc nguyn
t: C = 63,2%; H = 5,3%;
O = 31,5%
a) Xc nh cng thc thc nghim ca hp cht A.
b) Ph khi ca cht A nu trong hnh 1, cng thc phn t ca A th no?
c) Lc mt dung dch ca A trong ete vi dung dch NaOH trong nc. Sau khi lc, khng cn
A trong pha ete. Lc mt dung dch khc ca A trong ete vi
dung dch NaHCO3 trong nc. Vn cn A trong pha ete. A thuc loi hp cht no?
d) Hp cht A to c gng bc vi thuc th tollens. Nhm chc no c trong A?
1
e) Ph H-NMR ca cht A ghi ti 300 MHz c nu trong hnh 2a v 2b (dung mi CDCl3
(7,27ppm), cht chun tetrametylsilan). Cc vch ti 3,9; 6,3 v 9,8ppm l vch n, hnh 2b
phng i vng 6,9 7,6ppm. ( di ha hc cho sn). Vch 6,3 ppm bin mt khi thm mt
git D2O. Cng mt vch di v pha c tr s ppm b hn khi pha long vi CDCl3. Hai hin
tng trn cho bit iu g?
f) Vit 4 cng thc cu to c th c ca cht A.
g) Hy cho bit cu to ca mnh b mt ng vi cc mi ti 137 v 123 n v khi lng trong
ph khi.
h) Hai trong s cc ng phn ca A c tr s pKa thp hn cc cht cn li. Vit cng thc cu
to ca hai cht ny.
Ta c th thay cc d kin v ph cho trong bi nh sau:
1. Mt hp cht A c trong t nhin, ch cha C, H, O v c thnh phn nguyn t cu to
gm: 63,2%C; 5,3% H; 31,5% O.
a) Xc nh cng thc nguyn v cng thc phn t A, bit MA=152
b) A tc dng c vi dung dch NaOH trong nc, nhng khng tc dng c vi dung dch
NaHCO3 trong nc. A c th to c gng bc vi dung dch Ag(NH3) 2 . Khi un nng A vi
axit HI, cht hi bc ra c dn vo dung dch AgNO3 trong ancol thy to thnh kt ta AgI.
Hy vit bn cng thc cu to c th c ca hp cht A. Gi tn mi cht theo danh php h
thng.
c) Khi thm vo A mt git D2O hoc khi pha long A vi CDCl3 th nhit si ca A thay i
th no? Gii thch.
d) Hai trong s cc ng phn ca A c tr s pKa thp hn cc cht cn li. Vit cng thc cu
to ca hai cht ny.
Cng thc nguyn v phn t: C8H8O3.
Bn cu to ng phn:
O

O
O

OH

(C)

(B)

CH3 (A)

OH
H3C

OH

CH3

CH3
HO

(D)

* Thm D2O to ra lin kt hidro lin phn t vi A nhit si tng; cn khi pha long A vi
CDCl3 lm gim lin kt hidro lin phn t nhit si gim.
* Hai cu to (A) v (C) c pKa thp hn cc cht cn li
24

V d 2: Mt bi thi v ph c ni dung sau: Mt hp cht hu c c cng thc phn t

C9H8O2 , ph hng ngoi ca n c cc nh hp th 765, 708, 935, 980, 1450, 1500, 1580,

1
1620, 1680 v mt di hp th rng 3000 2500cm . Xc nh cu to ca hp cht trn.
1
1
1
2500 3000 cm : OH ; 1680 cm : C=O ; 1620 cm : C=C ;
1
1
1450, 1500 v 1580 cm : C=C (vng benzen) ; 980 cm : =C H (trans -) ;
1
1
935 cm : O H ; 756 v 798 cm : C H (vng benzen). Vy cht hu c trn c cng
thc cu to C6H5 CH = CH COOH v c cu hnh trans.
Ta c th thay bng cc kin thc sau:
- Lp cng thc phn t theo phng php phn tch lng nguyn t
0
- Phn ng vi H2(xt Ni, t ) theo t l s mol 1: 4, nhng ch phn ng vi dung dch brom theo
t l mol 1 : 1
- Tan c trong dung dch NaHCO3 trong nc
- Phn ng vi butadien 1,4 to ra dn xut c 2 vng
- Vit phng trnh iu ch cht ny t axetylen v cc cht v c
V d 3: Bi s 26 trong Ti liu chun b thi IChO 33 ti n l bi thc hnh c ni dung:
Tng hp 1 phenyl azo 2 napthol ta c th thay bng s :
NH2
OH
HCl

NaNO2
HCl

1-phenyl-azo-2-naphtol

Cu trc ca sn phm l :
A l mui cloruaanilin
B l mui benzen diazoni

OH

3. o chiu:
V d 2: a) Vit phng trnh phn ng hon thnh dy bin ha sau:
CH3
H3C C
CH3

CH2 CH3

+ Cl2
askt

+ KOH

- H2O

(sn phm chnh)

b) C th o chiu li nh sau: Tm cu to cc cht trong s sau:

H3 C
CH3
H2O
+ Cl2
+ KOH
X
B
A
C C
askt
H2O
H2SO4 c, t0
CH3
H3 C
Bit phn t cht X c cha nguyn t cacbon bc 4.

25

CH3

CH3
CH2 CH3 + Cl2

H3C C

askt

H3C C

CH3 Cl

CH3

CH3

CH3
H3C C

CH

H3C C

CH3 + KOH
CH3

CH3
CH

CH3

H+

H3C C
CH3

+
CH

CH3

chuyn v
- H+

CH CH3
+
CH3 OH2

H3C C

CH3 OH
H3C

CH3 + KCl

CH

CH3 OH

CH3 Cl
H3C C

CH3 (A) + HCl

CH

CH3
H3C C

+
CH

CH3

CH3
CH3

H3C
H3C

- H2O

(B)

(D)

CH3

4. Thay i hnh thc:

V d 1: Cho Xiclopropan Propen c H1 = - 32,9 kJ/mol
Nhit t chy than ch = 394,1 kJ/mol (H2)
Nhit t chy Hidrro = 286,3 kJ/mol (H3)
Nhit t chy Xiclopropan = 2094,4 kJ/mol. (H4) . Hy tnh:
Nhit t chy Propen, Nhit to thnh Xiclopropan v nhit to thnh Propen?
C th thay i hnh thc nh sau: (mang tnh cht trc nghim)
i vi qu trnh ng phn ho Xiclopropan thnh Propen c
H = 32,9 kJ/mol
Hy b sung vo bng sau:
Cht
Nhit chy Ho298 (chy) (kJ/mol)
Nhit sinh Ho298 (kJ/mol)
C (than ch)
394,1
H2
286,3
Xiclopropan
2094,4
Propen
C th thit lp chu trnh Born-Haber tnh ton, hoc dng phng php t hp cc cn
bng : * Ta c: Phng trnh cn tnh l
CH2=CH-CH3 + 4,5O2 3CO2 + 3H2O
H5 = ?
phng trnh ny c t hp t cc qu trnh sau:
CH2=CH-CH3
C3H6 xiclo
(-H1)
C3H6 xiclo + 4,5O2
3CO2 + 3H2O
H4
Cng 2 phng trnh ny ta c phng trnh cn tnh H5 = H4- H1
Vy, nhit t chy propen = 2094,4 ( 32,9) = 2061,5 kJ/mol
* Tng t: 3 ( C + O2 CO2
H2 )
1
3 ( H2 + O2
H2O
H3 )
2
3CO2 + 3H2O C3H6 (xiclo) + 4,5 O2
(-H4 )
26

3C + 3H2 C3H6 xiclo

H6 = 3H2 + 3H3 - H4
H6 = 3( 394,1) + 3( 286,3) ( 2094,4) = 53,2 kJ/mol
* Tng t nhit to thnh propen l:
H7 = 3H2 + 3H3 - H5 = 20,3 kJ/mol
V d 2: Hp cht hu c X c cng thc C5H4O2 phn ng vi thuc th Sip v vi
phenylhidrazin. X tham gia cc phn ng theo s chuyn ha sau:
KMnO4
H2
KCN
HCl d
t0
C6H8N2
C4H8Cl2
C5H4O3
C4H4O
C4H8O
X
T hp c

(B)

(A)

xc tc

H 3O +

(F)

(E)

(D)
C6H10O4 (G)

H2N(CH2)6NH2

Tni lon 6,6

Bit A tan c trong dung dch NaHCO3 , D tan c trong H2SO4 c, lnh v khng lm
mt mu dung dch KMnO4 , ng thi ph hng ngoi ca D ch ra khng cha nhm chc
OH. Hy xc nh cu to ca X v cc cht t A n G.
C th thay i hnh thc nh sau:
Cht hu c X c thnh phn khi lng 62,5% C; 4,17% H v 33,33% O. X phn ng vi
thuc th Sip v vi phenylhidrazin. Khi oxiha X bng dung dch KMnO4 to ra axit hu c A,
decacboxyl ha A thu c hp cht B . B b kh bi hidro c xc tc cho sn phm D tan c
trong H2SO4 c, lnh v khng lm mt mu dung dch KMnO4. Ph hng ngoi ch ra D
khng cha nhm chc OH, tc dng ca HCl vi D thu c dn xut dihalogen E. S th
SN2 cht E bi KCN to ra cht F m sau khi thy phn th sn phm sinh ra c th ngng t vi
hexametyleniamin cho T nilon 6,6.
Theo bi cng thc thc nghim ca X l C5H4O2 , sn phm c th ngng t vi
hexametyleniamin to t nilon 6,6 l axit adipic
HOOC (CH2)6 COOH (C6H10O4).
Qu trnh t X n cht ny khng c s gim nhiu s nguyn t cacbon nn cng thc phn t
ca X l C5H4O2 .
- T E n F tng thm 2 nguyn t cacbon v mch ca E, F ging axit adipic cho thy F l
dn xut xianua NC (CH2)4 CN v E l Cl (CH2)4 Cl
- E c iu ch t D khi tc dng vi HCl d (2 Cl thay th 1 O), ng thi D c mt nguyn
t oxi khng thuc chc OH v khng bn vi H2SO4c, lnh D l mt ete vng no. B khng
no to ra bi s decacboxyl A nn B l mt d vng 5 cnh cha oxi v A c nhm COOH nh
vo d vng .
- Cht X c nhm cacbonyl v phn ng vi thuc th Sip v phenylhidrazin ng thi b oxiha
to ra axit A, suy ra X l mt fufuran.
KMnO4

O
(X)

CHO

t0

COOH

(A)

xt

(B)
H 3O +

O
(D)

HOOC-(CH2)4-COOH (G)

27

KCN

HCl d

H2

Cl

Cl
(E)

H2N-(CH2)4-NH2

CN CN
(F)
Tnilon-6,6

5. Nhiu yu cu khc nhau cho mt ni dung kin thc:

V d 2: Phn ng oxiha ct mch gluxit bi HIO4 c nhiu mc ch khc nhau. (cc nhm-CHOHv -CHO H-COOH; -CH2OH H-CHO; >C=O CO2)
a) D Arabinoz l ng phn cu hnh C2 ca D Riboz. xc nh cu to ca n ngi
ta thc hin cc phn ng sau :

3OH
CHHCl
2)1)BrH2 3/OH 2O HOOCCOOH + HOCH2-COOH
DArabinoz
A HIO4 B
Hi D Arabinoz c cu to vng 5 cnh hay 6 cnh ? V cu to
Nu l vng 5 cnh th :
OH

CHO
OH
H
H

OH

OH

OH

OCH3

OH

CH3OH OH
HCl

CH2OH

OH

H
CH2OH

(D-Arabinoz)

OCH3
HIO4

CHO
CHO

COOH

Br2
H2O

H
CH2OH

COOH
COOH
CH

CH2OH

OH

CH2OH

Kt qu tri gi thit, vy D Arabinoz c cu to vng 6 cnh

OH

CHO
OH
H
H

OH

OH
OH

OCH3
H

OH

OH

CH2OH

CH3OH OH
HCl

CH2

(D-Arabinoz)

OH

OH

OCH3

HIO4 CHO

CH2

Cu to vng ca D Arabinoz l :

OH
HO

COOH

CH2

CH2OH

O
HO

HO
OH
b) Nu phng php phn bit D glucoz vi D fructoz
Oxiha bng HIO4 :

28

H3O+

COOH

CH2

hay

OH

Br2

CHO

O
OH

COOH

OH

CHO
H

OH

OH

OH

HO

H
HO

OH

OH

+ 5 HIO4

HCHO + 5 H-COOH

- 5 HIO3
H

OH

H
CH2OH
CH2OH

(D- Glucoz)
CH2OH

HO

CH2OH

HO

HO

OH

OH

OH

OH

CH2OH

+ 4 HIO4
O

2 HCHO + 3 H-COOH + CO2

- 4 HIO3

CH2

(D-Fructoz)

Cho hi sn phm sc qua dung dch nc vi ta nhn c D Fructoz

CO2 + Ca(OH)2 CaCO3 + H2O
* C th dng phng php n gin hn l: cho dung dch Br2 tc dng vi 2 cht, nhn c
D-glucoz lm mt mu brom do b oxiho thnh axit.(D-Fructoz khng b oxiho)
6. Son nhng bi tng t:
V d 1: Cho phn ng CH2 = CH2 + Br2 (dung mi CH3OH). Nu thm NaCl vo hn hp
phn ng th thu c sn phm no ? Nu thm HCl vo hn hp phn ng th thu c sn
phm no ? Vn tc phn ng trong mi trng hp trn c thay i khng ? Gii thch.
Phn ng xy ra theo c ch cng electrofin, c 2 giai on chnh l :
* Giai on 1: (l giai on quyt nh tc phn ng) tiu phn tch in dng tn cng vo
mt trong 2 nguyn t C mang lin kt .
* Giai on 2 : Anion tn cng vo phn tch in dng trong sn phm trung gian to ra sn
phm cng.

* i vi thm NaCl : Br2 Br+ + Br .

CH2 CH2 + Br

(+)

Br CH2 CH2

Br

Br CH2 CH2 Br

Cl

Br CH2 CH2 Cl

OCH3

* i vi thm HCl :

HCl H+ + Cl .
29

Br CH2 CH2 OCH3

Khi Ion H+ s tn cng trc

Br
+

CH2 CH2 + H

(+)

CH3 CH2 Br

Cl

CH3 CH2

CH3 CH2 Cl

OCH3

CH3 CH2 OCH3

V giai on 1 quyt nh tc phn ng nn thm NaCl khng lm thay i tc phn

ng, cn thm HCl (H+) s lm thay i ng k tc phn ng.
Bi tng t l:
Phn ng ca n butylamino vi NaNO2 v HCl xut hin 2 ancol C4H10O;
2 anken C4H8 v 2 dn xut halogen C4H9Cl. Vit cu to cc cht trn v ngh mt c ch
gii thch.
2
CH3CH2CH2CH2NH2
HNO
CH3CH2CH2CH2 N 2 C4H 9 + N2.
2 H 2O
+H2O
(+)

CH3-CH2-CH2-CH2

+ Cl +

-H

CH3-CH2-CH2-CH2OH

(C4H10O)

CH3-CH2-CH2-CH2Cl

(C4H9Cl)

CH3-CH2-CH = CH2

(C4H8)

Chuyn v
+ Cl +

(+)

-H

CH3-CH2-CH-CH3

+ H2O

Cl
CH3-CH2- CH - CH3

(C4H9Cl)

CH3- CH = CH - CH
3

(C4H8)

CH3-CH2- CH - CH3

(C4H10O)

OH

V d 3: Thu phn hon ton 1 mol polipeptit X cho ta:

2 mol CH3-CH(NH2)-COOH (Ala); 1 mol HOOC-CH2-CH2-CH(NH2)-COOH (Glu)
1 mol HOOC-CH2-CH2-CH(NH2)-COOH (Glu)
1 mol H2N-(CH2)4-CH(NH2)-COOH (Lys) v 1 mol His.
Nu cho X tc dng vi 2,4-(NO2)2C6H3F (k hiu ArF) ri mi thu phn th thu c Ala,
Glu, Lys v hp cht (Y)
N

CH2 - CH - COOH

CH2 - CH - COOH

NH2

NH

Ar

(H p cht Y )

(Histidin hay His)

Mt khc nu thu phn X nh enzim cacboxipeptiaza th thu c Lys v mt tetrapeptit.

Ngoi ra khi thu phn khng hon ton X cho ta cc ipeptit Ala-Glu, Ala-Ala v His-Ala. Xc
nh cng thc cu to v tn ca polipeptit X.
T s mol v cng thc cu to ca cc aminoaxit suy ra X l mt pentapeptit.
- T kt ta thu phn sn phm phn ng gia X vi ArF suy ra u N(u cha nhm NH 2 t
do ) ca X l His.
- T sn phm thy phn X nh enzim cacboxipeptiaza suy ra u C (u cha nhm COOH
t do ) ca X l Lys.
30

-Khi thu phn khng hon ton X cho cc ipeptit: His- Ala, Ala- Ala , Ala- Glu.
Trt t sp xp cc aminoaxit trong mch : His-Ala-Ala-Glu-Lys
Cng thc cu to ca X:
H2N
N

CH

CO

NH

CH2

CH

CO

NH

CH

CO

NH

CH3

CH3

CH

CO

(CH2)2
COOH

NH

CH

COOH

(CH2)4
NH2

(Lys)
(His)
(Glu)
(Ala)
(Ala)
(c th vit cu to trong c nhm : CO-NH- gia Glu v Lys c to ra bi nhm -COOH
v tr ca Glu vi nhm -NH2 v tr ca Lys).
Bi tng t l:
Khi thu phn hon ton 1 mol tripeptit X thu c 2 mol axit glutamic
( HOOC(CH2)2CH(NH2)COOH ), 1 mol alanin ( CH 3CH(NH2)COOH ) v 1 mol NH 3. X khng
phn ng vi 2,4-initroflobenzen v X ch c mt nhm cacboxyl t do. Thu phn X nh
enzim cacboxipeptiaza thu c alanin v
mt ipeptit Y. Vit cng thc cu to ca X , Y v gi tn chng.
Tripeptit X c cu to theo trt t Glu-Glu-Ala. V theo d kin u bi aminoaxit ui (ui
C) l Ala, nhm NH2 ca aminoaxit u (u N) to thnh lactam vi nhm -COOH ca
n v Glu th nht, nhm -COOH ca n v th Glu hai dng chc amit CONH 2 (do thu
phnto ra NH3). Vy:
Cu to v tn gi ca X (Glutamolactam--yl glutaminylalanin)
H

H
N

CH

CO

NH

C
C
H2

CH

CO

NH

CH3

(CH2)2

CH2

CH

CO - NH2

Cu to v tn gi ca Y (-Glutamolactam--yl glutamin):
H
N

CH

C
C
H2

CH2

CO

NH

CH

COOH

(CH2)2
CO - NH2

31

COOH