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208
XII.2. Cng thc tng qut Axit hu c: R(COO)n R: Gc hirocabon ha tr n, c th l H, c th l khng (zero,0) n: nguyn, 1 (n = 1: Axit hu c n chc n 2: Axit hu c a chc) n2 x0 CxHy + n y + n 2x + 2 y 2x + 2 n (R: Gc hirocacbon ha 1, c th l H) x0 CxHy + 1 y + 1 2x + 2 y 2x + 1 (n 0 ; k = 0, 1, 2, 3, 4,.) n0 m: 0; 2; 4; 6; 8; n0 m: 0; 2; 4; 6; 8; CnH2n + 1COOH CnH2nO2 R-COOH (n 0) (n 1)
CxHy(COOH)n
Axit hu c n chc:
R-COOH CxHy-COOH
Gio khoa ha hu c
209
Bi tp 99 Vit cng thc tng qut c mang nhm chc ca cc cht sau y: a. Axit hu c n chc no mch h. b. Axit hu c n chc. c. Axit hu c n chc, cha mt lin kt i C=C trong phn t, mch h. d. Axit hu c cha hai nhm chc axit, no, mch h. e. Axit hu c n chc, cha mt nhn thm trong phn t, ngoi nhn thm cc gc hirocacbon cn li ch gm lin kt n mch h. f. Axit cacboxilic a chc (ba nhm chc axit), khng no (mt lin kt i C=C, mt lin kt ba CC), cha mt vng trong phn t. g. Axit hu c n chc no mch h c cha 18 nguyn t C trong phn t. Bi tp 99 Vit cng thc tng qut ca: a. Cht hu c ng ng axit acrilic. b. Axit hu c ng ng axit fomic. c. Cht hu c ng ng axit benzoic. d. Axit hu c ng ng axit tereptalic. e. Axit hu c ng ng axit oxalic. f. Cht hu c ng ng vi axit xiclohexancacboxilic. g. Axit hu c nh chc, cha mt lin i C=C, mch h. XII.3. Cc c tn (ch yu l tn ca axit hu c n chc no mch h) Ankan Axit ankanoic (Mch chnh l mch C cha nhm COOH v di nht, C ca COOH c nh s 1) Axit cacboxilic (Hu ht axit hu c c tn thng thng, nn thuc lng tn mt s cht thng gp) Th d: H-COOH Axit metanoic (CH2O2) Axit fomic CH3COOH (C2H4O2) Axit etanoic Axit axetic Axit propanoic Axit propionic; Axit metylaxetic Axit butanoic Axit n-butiric; Axit etylaxetic Axit 2- metylpropanoic Axit isobutiric; Axit imetylaxetic
CH3CH2COOH (C2H5COOH; C3H6O2) CH3CH2CH2COOH (C3H7COOH; C4H8O2) CH3-CH-COOH CH3 (C3H7COOH; C4H8O2)
Gio khoa ha hu c
210
CH3CH2CH2CH2COOH (C4H9COOH; C5H10O2) CH3-CH-CH2-COOH CH3 (C4H9COOH; C5H10O2) CH3CH2CH2CH2CH2COOH (C5H11COOH; C6H12O2) CH3CH2CH2CH2CH2CH2COOH (C6H13COOH; C7H14COOH) CH3(CH2)6COOH (C7H13COOH; C8H16O2) CH3(CH2)7COOH (C8H17COOH; C9H18O2) CH3(CH2)8COOH (C9H19COOH; C10H20O2)
Axit pentanoic Axit n-valeric Axit 3-metylbutanoic Axit isovaleric Axit hexanoic Axit caproic Axit heptanoic Axit enantoic
Axit octanoic Axit caprilic Axit nonanoic Axit pelacgonic Axit ecanoic Axit capric
Mt s axit bo (axit bo cao, gp trong cht bo, ch yu dng este vi glixerin) thng gp: C13H27COOH C15H31COOH C17H35COOH C17H33COOH C17H31COOH C17H29COOH Axit miristic; Axit tetraecanoic Axit panmitic; Axit hexaecanoic Axit stearic; Axit octaecanoic Axit oleic; Axit cis-9-octaecenonic Axit linoleic; Axit cis, cis - 9, 12 - octaecaienoic Axit linolenic; Axit cis, cis, cis 9, 12, 15 - octaecatrienoic
Mt s axit hu c n chc khng no: CH2=CH-COOH CH2=C-COOH CH3 CH3-CH=CH-COOH Axit propenoic; Axit acrilic Axit 2- metylpropenoic; Axit metacrilic Axit 2-butenoic; Axit crotonic (dng trans)
Gio khoa ha hu c
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CH2=CH-CH2-COOH CH2=CH-CH2-CH2-COOH CH3-CC-COOH CHC-COOH Mt s axit a chc: HOOC-COOH HOOC-CH2-COOH HOOC-CH2-CH2-COOH HOOC-(CH2)3-COOH HOOC-(CH2)4-COOH HOOC-(CH2)5-COOH HOOC-(CH2)6-COOH
H C HOOC C COOH COOH C HOOC C H H
Axit 3-butenoic; Axit vinylaxetic Axit 4-pentenoic; Axit alylaxetic Axit 2-butinoic; Axit tetrolic Axit propinoic; Axit propiolic
Axit etanioic; Axit oxalic Axit propanoic; Axit malonic Axit butanioic; Axit sucxinic (Acid succinic) Axit pentanioic; Axit glutaric Axit hexanioic; Axit aipic (Acid adipic) Axit heptanoic; Axit pimelic Axit octanioic; Axit suberic
Axit maleic; Axit cis-butenioic
COOH
Axit ptalic; Axit o-ptalic; Axit 1,2-benzenicacboxilic; 1,2-icacboxi benzen Axit isoptalic; Axit 1,3 benzenicacboxilic; m-icacboxibenzen
COOH
COOH
Gio khoa ha hu c
212
COOH
HOOC-CH2-CH2-CH-COOH Axit glutamic; Axit -aminoglutaric; NH2 Axit 2-aminopentanioic CH2-CH-CH-CH-CH-COOH OH OH OH OH OH OH HOOC-CH2-C-CH2-COOH COOH Axit gluconic; Axit 2,3,4,5,6-hexahiroxihexanoic
Bi tp 100 Vit CTCT ca cc cht sau y: Axit acrilic; Axit axetic; Axit benzoic; Axit fomic; Axit aipic; Axit oxalic; Axit glutamic; Axit metacrilic; Axit lactic; Axit tereptalic; Axit isovaleric; Axit propionic; Axit panmitic; Axit gluconic; Axit malonic. Bi tp 100 Hy cho bit CTCT ca cc cht sau y: Axit stearic; Axit n-butiric; Axit picric; Axit butanoic; Axit lactic; Axit xitric; Axit oleic; Axit propenoic; Axit phenic; Axit - aminoaxetic; Axit enantoic; Axit cloaxetic; Axit limonic (axit xitric, acid citric); Axit metacrilic; Axit 1,3,5 benzentricacboxilic. XII.4. Tnh cht ha hc XII.4.1. Phn ng chy CxHy(COOH)n
Axit hu c
(x +
y+n )O2 4
(x+n)CO2 +
y+n )H2O 2
Gio khoa ha hu c
213
CxHy-COOH
Axit hu c n chc
(x +
y +1 )O2 4
(x + 1)CO2
y +1 )H2O 2
3n + 1 ) O2 2
(n + 1)CO2
+ (n +1)H2O
Ch : Axit hu c n chc no mch h c CTPT dng CnH2nO2 (cng dng vi este n chc no mch h) nn axit hu c no m khi t chy to s mol H2O bng s mol CO2 th l axit hu c n chc no mch h. Cc axit hu c a chc hay c vng khi t chy u to s mol H2O < s mol CO2. (Tng t, este no khi chy to s mol H2O bng s mol CO2 th l este n chc no mch h, cc este khc khi chy u to s mol H2O < s mol CO2) XII.4.2. Axit hu c c y cc tnh cht nh mt axit v c yu
Nhm chc axit hu c, COOH, nhm cacboxyl, coi nh tp hp gm hai nhm: nhm OH (nhm hiroxyl) v nhm CO (nhm cacbonyl). Lin kt gia O v H trong nhm hiroxyl t n b phn cc. i in t gp chung gia O vi H b ko v pha O c m in (3,5) ln hn so vi H (2,1). K bn nhm hiroxyl c nhm cacbonyl (CO) rt in t nn cng lm tng thm s phn cc ca lin kt gia O vi H, cng lm cho i in t gp chung gia O vi H cng b ko v pha O. iu ny lm cho H trong nhm cacboxyl rt linh ng (tc H cng mang nhiu in tch dng, d b tch ra di dng ion H+). Do khi ha tan axit hu c vo dung mi nc (H2O), vi s h tr ca dung mi nc rt phn cc, s hirat-ha, th c s phn ly mt phn to ion H+ v ion m gc axit hu c trong dung dch. Tuy nhin s phn ly ion ny khng nhiu, nn axit hu c c y cc tnh cht nh mt axit v c (phn ly to ion H+) v axit hu c l axit yu (khng phn ly hon ton m ch phn ly mt phn to ion, cn a s dng phn t khng phn ly).
2, 5
C O
3, 5
O << H
3, 5 2, 1
C th axit hu c c v chua, dung dch axit hu c dn in c, axit hu c lm i mu qu xanh ha , pH dung dch axit < 7. Nguyn nhn ca cc tnh cht ny l do axit hu c c phn ly ion to H+ trong dung dch. Th d: H-COOH
Axit fomic dd
H-COO
Ion fomiat
H+
Ion hiro
Gio khoa ha hu c
214
CH3-COOH
Axit axetic
dd
CH3-COO
Ion axetat
H+
Ion hiro
RCOOH
OH
Baz
RCOO
Mui ca axit hu c Mui cacboxilat
H2O
Nc
Th d: CH3COOH
Axit axetic
+ NaOH
Xt
CH3COONa + H2O
Natri axetat
Nc
2HCOOH
Axit fomic
+ Ba(OH)2
Bari hiroxit
Ba(HCOO)2
Bari fomiat
+ 2H2O
Nc
CH2=CH-COOH + KOH
Axit acrilic
Kali hiroxit
CH2=CH-COOK + H2O
Kali acrilat
2nR-COOH
Axit hu c
Oxit baz
M2On
Mui axit hu c ca KL M
2M(R-COO)n
nH2O
Th d: 2CH3COOH
Axit axetic
Natri oxit
Na2O
2CH3COONa
Natri axetat
H2O
HOOC-COOH + CaO
Axit oxalic Canxi oxit
Canxi oxalat
CaC2O4
+ H2O
Nc
2C6H5-COOH
Axit benzoic
+ K2O
Kali oxit
2C6H5-COOK
Kali benzoat
H2O
Axit hu c tc dng kim loi (ng trc H trong DT kim loi) to mui v kh hiro
K Ca Na Mg Al Mn Zn Cr Fe Ni Sn Pb H Cu Ag Hg Pt Au nR-COOH
Axit hu c
M(R-COO)n
n H2 2
Th d: 2CH3COOH + Fe
Axit axetic St
Fe(CH3COO)2
St (II) axetat
H2
Hiro
Gio khoa ha hu c
215
3H-COOH + Al
Axit fomic Nhm
Al(H-COO)3
Nhm fomiat
3 H2 2
Hiro
Natri
Hiro
HOOC-CH2-COOH + 2K
Axit malonic
Kali
KOOC-CH2-COOK + H2
Kali malonat
Hiro
CH3CH2COOH
Axit propionic
+ Hg
Thy ngn
Ch : Trong cc loi hp cht hu c, ch c axit hu c mi tc dng c cc kim loi (khc kim loi kim, v ng trc H trong dy th in ha, nh Mg, Al, Zn, Fe,) to kh hiro thot ra (v mui). (Ru, phenol ch tc dng c kim loi kim).
Axit hu c tc dng c mui ca axit yu hn to axit mi, mui mi Axit hu c tuy l mt axit yu, nhng n cn mnh hn cc axit rt yu khc nh axit cacbonic (H2CO3), phenol (C6H5-OH), Nn axit hu c y c kh cacbonic (CO2) ra khi mui cacbonat, y c phenol ra khi mui phenolat,
2R-COOH
Axit hu c
Mui cacbonat
CO32
2R-COO
Mui cacboxilat
+ +
Kh cacbonic
CO2
+ H2O
Nc
R-COOH + C6H5-O
Axit hu c
R-COO
Mui cacboxilat
Mui phenolat
C6H5-OH
Phenol
Th d: 2CH3COOH + CaCO3
Axit axetic Axit etanoic Canxi cacbonat vi
Ca(CH3COO)2
Canxi axetat
+ CO2
Kh cacbonic
H2O
Nc
H-COOH +
Axit fomic
C6H5ONa
H-COONa +
Natri fomiat
Natri phenolat
C6H5OH
Phenol
CH3COOH
Axit axetic
+ NaHCO3
CH3COONa +
CO2
+ H2O
Gio khoa ha hu c
216
Lu - L.1. Cht hu c no tc dng c vi mui cacbonat to kh CO2 thot ra th phn t cht hu c phi c cha nhm chc axit hu c (COOH).
- L.2. Ngi ta thng cn c vo tnh cht axit hu c to bt kh CO2 khi cho tc dng vi mui cacbonat nhn bit axit hu c, cng nh tch ly ring axit hu c ra khi hn hp cc cht hu c: Cht hu c no to bt kh khi nh vo cc vi (CaCO3) (hay cc mui cacbonat khc) th l axit hu c; Cho hn hp cc cht hu c trong c cha axit hu c tc dng vi bt CaCO3 c d, th ch c axit hu c phn ng to mui canxi cacboxilat. un nng ui cc cht hu c bay i, ch cn li mui canxi cacboxilat v CaCO3 cn d. Sau cho dung dch H2SO4 va vo cc mui ny (cho t t cho n ht thot ra bt kh CO2), thu c CaSO4 kt ta v dung dch axit hu c. Sau c th chng ct phn on thu c axit hu c tinh khit. 2R-COOH
Axit cacboxilic
CaCO3
Canxi cacboxilat
Ca(R-COO)2
+ CO2
Kh cacbonic
+ H2O
Canxi cacboxilat
Ca(R-COO)2
+ H2SO4
Axit sunfuric
Axit hu c
2R-COOH + CaSO4
Canxi sunfat
Th d: 2CH3COOH + CaCO3
Axit axetic Canxi cacbonat
Ca(CH3COO)2
Canxi axetat
+ CO2
Kh cacbonic
+ H2O
Ca(CH3COO)2
Canxi axetat
+ H2SO4
Axit axetic
2CH3COOH +
Axit axetic
Canxi sunfat
CaSO4
- L.3. Cng c th cn c tnh cht axit hu c lm i mu qu xanh (qu tm) ha hay axit hu c ha tan c cc kim loi khng phi l kim loi kim, nh Mg, Al, Zn, to kh hiro thot ra nhn bit axit hu c cng c. Bi tp 101 Cho bn cht hu c gm: Ru etylic, Phenol, Benzen v Axit axetic. a. Vit phng trnh phn ng (nu c) ca mi cht trn ln lt vi cc cht: Na; NaOH; Na2CO3. b. T kt qu cc phn ng trn hy sp theo th t tng dn s linh ng ca H trong cc phn t cht hu c trn. Bi tp 101 Cho cc cht hu c sau y: Glixerin, Ru metylic, Axit fomic v Toluen. Cho mi cht trn tc dng ln lt vi: K, Cu(OH)2, Mg. a. Vit cc phn ng xy ra (nu c). b. So snh mnh tnh axit ca bn cht hu c cho trn.
Gio khoa ha hu c
217
Bi tp 102 A l mt cht hu c cha mt loi nhm chc mch thng c cng thc nguyn (cng thc thc nghim) l (C3H5O2)n. Xc nh CTCT ca A v c tn cht ny, bit rng cht ny khng lm mt mu nc brom v tc dng c mui cacbonat lm si bt kh. S: Axit aipic Bi tp 102 A l mt cht hu c cha mt loi nhm chc c cng thc dng (CHO)n. Xc nh cc CTCT c th c ca A, bit rng a mol A tc dng ht vi Mg c d th thu c a mol H2. S: 3CTCT axit hu c nh chc Bi tp 103 Nhn bit cc cht hu c sau y ng trong cc bnh khng nhn: Axit axetic; Acrolein; Axetanehit; Axit fomic; Axit acrilic v n-Propylaxetilen. Bi tp 103 Nhn bit cc cht lng sau y cha trong cc l mt nhn: Etylenglicol; Axit metacrilic; Benzanehit; Ru etylic; Axit propionic v phenol. Vit cc phn ng xy ra. Bi tp 104 t chy hon ton 7,2 gam cht hu c A cn dng va 33,6 lt khng kh (ktc). Sn phm chy gm hi nc v 6,16 lt CO2 (27,30C; 1,2 atm). a. Xc nh CTPT ca A. Bit rng khi lng phn t ca A nh hn khi lng phn t ca benzen. b. Xc nh CTCT ca A, c tn A. Bit rng A tc dng c vi mui cacbonat to kh CO2. c. Vit phng trnh phn ng ca A vi: - H2 (Ni xc tc, t0) - Mg - Vi sng - Cu(OH)2 - Xa - Nc brom - Vit phn ng trng hp A Khng kh gm 20% O2; 80% N2 theo th tch (C = 12 ; H = 1 ; O = 16) S: Axit acrilic Bi tp 104 t chy hon ton 4,3 gam cht hu c X cn dng 19,8 lt khng kh (27,30C; 1,4 atm). Sn phm chy ch gm H2O v 8,8 gam CO2.
Gio khoa ha hu c
218
a. Xc nh CTPT ca X, bit rng khi lng phn t ca X nh hn khi lng phn t ca toluen. b. Xc nh CTCT v c tn X, bit rng X tc dng c vi Mg to kh thot ra v X mch h, phn nhnh. c. Vit cc phn ng: - Trng hp X - X vi nc vi - X vi vi - X vi H2 (c xc tc Ni, un nng) - X vi Ba - X vi vi sng d. T X v axetilen, vit cc phn ng iu ch thy tinh hu c (plexiglas, poli metylmetacrilat). Cc cht v c, xc tc coi nh c sn. Khng kh gm 20% O2, 80% N2 theo th tch. (C = 12 ; H = 1 ; O =16) S: Axit metacrilic
XII.4.3. Phn ng este ha (Phn ng to este)
H2SO4(), t0
CH3-C-O-H + CH3-CH2-OH O
Axit axetic Ru etylic
H2SO4 (), t0
CH3-C-O-CH2-CH3 + H2O O
Etyl axetat Nc
H2SO4(), t0
Metyl metacrilat
CH2=C-COO-CH3 CH3
+ H2O
Nc
H-C-O-H O
Axit fomic
CH3-CH-CH3 OH
Ru isopropylic
H-C-O-CH-CH3 O CH3
Isopropyl fomiat
+ H2O
Nc
+ CH3CH2CH2OH
Ru n-propylic
H2SO4(), t0
CH2=CH-COO-CH2CH2CH3 + H2O
n-Propyl acrilat
H2SO4(), t0
C6H5-COOH + C6H5-CH2-OH
Axit benzoic Ru benzylic
H2SO4 ()
C6H5-COO-CH2-C6H5
Benzyl benzoat
H2O
Gio khoa ha hu c
219
OH
2CH3 OH R u metylic
H2SO4() t
0
2H2O
COOH
CH2OH
t0 H2SO4() t0 H
+
0
CH2OOC
COOCH2
+
2CH3CH2OH Etanol
2H2O
3 CH2=CH COOH
H2SO4 t
0
Axit acrilic
3H2O
XII.4..4. Phn ng th H ca axit hu c bi clo (Cl2) Nguyn t H l nguyn t H lin kt vo C ca axit hu c. Cacbon alpha (C) l C lin kt vo nhm chc axit COOH. Nguyn t H ca axit hu c tng i linh ng (do ng k bn nhm COOH rt in t), nn cc nguyn t H ny d b thay th bi cc nguyn t Cl (ca Cl2) vi s hin din ca nh sng. Nu Cl2 dng d v thi gian phn ng lu th ln lt cc nguyn t H ca axit hu c c thay th ht bi cc nguyn t Cl (ca Cl2).
H R C C OH H O Axit cacboxilic
+
Cl2 Clo
a s
H R C C OH
Cl O Axit a-clocacboxilic a s
H R C C OH Cl O
Cl2 Clo
Axit a -clocacboxilic
Th d: H H-C-C-O-H HO
Axit axetic
+ Cl2
Clo
H H-C-C-O-H Cl O
Axit cloaxetic
HCl
Hiro clorua
Gio khoa ha hu c
220
H H-C-C-O-H + Cl2 Cl O
Axit cloaxetic Clo
Cl H-C-C-O-H Cl O
Axit icloaxetic
+ HCl
Hiroclorua
Cl H-C- C-OH + Cl O
Axit icloaxetic
Cl2
Clo
Cl Cl-C- C-OH Cl O
Axit tricloaxetic
+ HCl
Lu L.1. mnh tnh axit tng dn nh sau: CH3-COOH < Cl-CH2-COOH < Cl2CH-COOH < Cl3C-COOH
Ka: Axit axetic 1,75.105 Axit cloaxetic 1,35.103 Axit icloaxetic 5.102
Nguyn nhn l nguyn t Cl rt in t (Cl c m in 2,8; C c m in 2,5; H c m in 2,1). Do s nguyn t Cl cng nhiu th s rt in t cng mnh, nh hng lan truyn n lin kt gia O v H trong nhm COOH, lm cho H cng linh ng, d b phn ly to ion H+ hn, tc tnh axit mnh hn.
L.2. Trong dy ng ng axit hu c n chc no mch h th thng mnh tnh axit cc cht gim dn theo chiu tng khi lng phn t ca chng. Nguyn nhn l khi khi lng phn t tng, tc gc hirocacbon R (trong R-COOH) tng dn nn n cng y in t mnh hn v nhm COOH, lm gim s phn cc ca lin kt gia O vi H, lm gim s linh ng ca H, tc lm gim tnh axit.
Tnh axit cc cht gim dn nh sau: H-COOH > CH3-COOH > CH3-CH2-COOH
Ka: Axit fomic 1,77.104 Axit axetic 1,75.105 Axit propionic 1,34.105
Nguyn nhn mnh tnh axit khc nhau l do: Nhm cacbonyl rt in t mnh hn nhn thm, nhn thm rt in t mnh hn hai hiroxyl k cn, gc hirocacbon Rmch h y in t mnh hn H. Th d: mnh tnh axit cc cht tng dn nh sau:
Gio khoa ha hu c
221
<
Nc
Bi tp 105 So snh mnh tnh axit cc cht sau y: Axit axetic; Ru etylic; Axit propionic; Phenol; Nc; Axit fomic; Glixerin; Ru metylic; o-Cresol. Bi tp 105 Hy chn hng s Ka thch hp: 1018 ; 1016 ; 1,9.1016 ; 7,94.1016 ; 6,76.1011 ; 1,3.1010 ; 1,34.105 ; 1,75.105 ; 1,35.103 ; 2,69.103 ; 5,75.102 ; 0,59 cho cc cht di y: Phenol; Axit cloaxetic; Nc; Axit floaxetic (Acid fluoroacetic, F-CH2-COOH); Ru metylic; Axit propionic; p-Cresol; Axit trifloaxetic; Etylenglicol; Axit ifloaxetic (Acid difluoroacetic); Ru etylic; Axit axetic. XII.5. ng dng XII.5.1. T axit hu c iu ch c cc este, a s este c mi thm hoa qu, c dng lm hng liu cng nh dung mi
R-COOH
Axit hu c
R-OH
Ru
H2SO4(), t0
R-COO-R + H2O
Este
Nc
H-COOH
Axit fomic
CH3-CH2-OH
Ru etylic
H2SO4(), t0
H-COO-C2H5
H2O
CH3CH2CH2COOH + C5H11OH
Axit n-butiric
Ru isoamylic H2SO4(), t0
CH3CH2CH2COO-C5H11 + H2O
Isoamyl n-butirat (mi da)
H-COOH + CH3OH
Axit fomic
Ru metylic
H-COO-CH3
+ H2O
Nc
V mi ca este, cc sch thng khng thng nht nhau, v thc ra mi ca tri chn l hn hp ca nhiu este khc nhau. n-Amyl fomiat (HCOOC5H11) : mi anh o Isoamyl fomiat (HCOOC5H11) : mi mn Etyl n-butirat (C3H7COOC2H5) : mi m Isoamyl isovalerat (C4H9COOC5H11) : mi to Hexenyl axetat (CH3COOCH2CH=CH-CH2-CH2-CH3): mi thm trong du con c cung
Gio khoa ha hu c
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Dung dch CH3-COOH 2-5% (sn phm ca qu trnh ln men gim t ru etylic, ng, mt) c dng lm gim n. 3CH3COOH + Al
Axit axetic Nhm
Al(CH3COO)3 +
Nhm axetat
3 H2 2
Hiro
6CH3COOH + Al2O3
Axit axetic
Nhm oxit
2Al(CH3COO)3 + 3H2O
Nhm axetat Nc
Nhm axetat l mt mui tan nhiu trong nc, nhng khi em un nng dung dch n b thy phn to nhm axetat monobazic (CH3COO)2AlOH v nhm axetat ibazic CH3COOAl(OH)2 khng tan trong nc. V vy nhm axetat c dng trong cng nghip nhum lm cht cm mu (gi mu lu phai). St axetat, Crom axetat cng c tnh cht tng t (mui St, Crom II hay III u c).
2CH3COOH + CuO
Axit axetic
ng (II) oxit
Cu(CH3COO)2
ng (II) axetat
+ H2O
Nc
2CH3COOH + PbO
Axit axetic
Ch (II) oxit
Pb(CH3COO)2 + H2O
Ch (II) axetat Nc
ng (II) axetat, Ch (II) axetat c dng lm bt sn. Ch (II) axetat ngm nc, Pb(CH3COO)2.3H2O, rt c, c v ngt (ng ch). Dung dch mui ch axetat bazic, CH3COOPb(OH), gi l gim ch, c dng trong y hc cha bng v bong gn.
2CH3COOH + CaCO3
Axit axetic
Canxi cacbonat
Ca(CH3COO)2
Canxi axetat
+ CO2 + H2O
Kh cacbonic
Canxi oxit t0
Ca(CH3COO)2 + H2O
Canxi axetat
CH3-CO-CH3
Axeton
+ +
Canxi cacbonat
CaCO3 HCl
CH3COOH + Cl2
Axit axetic
Clo
Axit cloaxetic
Cl-CH2COOH
Hiroclorua
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ONa Cl
+
Cl
+
Xt
Cl
Mui natri ca axit cloaxetic c tc dng dit c v lm rng l cy. Ngi ta dng mui ny iu ch 2,4-D (axit 2,4-iclophenoxiaxetic) v 2,4,5-T (axit 2,4,5-triclophenoxiaxetic). nng rt thp dung dch hai cht ny c tc dng kch thch s tng trng ca thc vt. Tuy nhin nng cao hn, dung dch hai cht ny li c tc dng dit c v lm rng l cy. Hn hp da cam m M dng trong chin tranh Vit Nam gm 50% 2,4-D v 50% 2,4,5-T dng este ca ru n-butylic. Trong 2,4,5-T c ln tp cht dioxin cc k c, cht ny gy tc hi rt ln cho nhiu ngi cho n hin nay, mc d chin tranh i qua lu.
Anhirit axetic c iu ch t phn ng ca axit axetic vi xeten, CH2=C=O, cht ny c to ra do s loi nc ca axit axetic nhit cao.
CH3-COOH Axit axetic CH2=C=O Xeten
+
H2O N c
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COOH OH
+
H2SO4()
Axit salixilic
XII.5.3. T axit axetic iu ch c nha PVAc, PVA; T axit metacrilic iu ch c thy tinh hu c (plexiglas); Axit aipic iu ch t nilon-66; T axit tereptalic iu ch c t polieste; T axit -aminoenantoic iu ch c t enang; Axit benzoic c tnh st trng, dng bo qun thc phm; Axit xitric (Acid citric, Axit limonic, Axit chanh) c dng trong thc phm, ung;.
CH3COOH + Axit axetic CH CH Axetilen TH t 0 , Xt t
0
, Xt
n CH3COONa
Natri axetat
Dung dch Xu t
CH2 C
CH3 OH R u metylic TH t 0 , Xt
H2SO4 t
0
CH2
CH3
+ H2O
N c
n CH2
COOCH3
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0
n HOOC
COOH + n
HO-CH2-CH2-OH Etylenglicol
Xt
Axit tereptalic
C O
TN t
0
, Xt
NH (CH2)6 C O T enang
Bi tp 106 T isobutan vit cc phng trnh phn ng iu ch: Poliisobutilen; Thy tinh hu c (polimetylmetacrilat; plexiglas). Cc cht v c, xc tc c sn. Khng dng phn ng ehiro ha. Bi tp 106 T isopentan, vit cc phn ng iu ch: Cao su isopren; Poli (2-metylbuten-2); Poliisobutilen; Plexiglas. Cc cht v c, xc tc c sn. Bi tp 107 T p-xilen v metan, vit phng trnh phn ng iu ch t polieste. Bi tp 107 T vi, than , vit phng trnh phn ng iu ch: PVC; 1,1-icloetan; Cao su Buna; Cao su clopropren; PVAc ; PVA. XII.6. iu ch XII.6.1. Oxi ha hu hn anehit, c axit hu c tng ng
R-CHO +
Anehit
1 O2 2
Oxi (KK)
Mn
2+
R-COOH
Axit hu c
R-CHO + Ag2O
Anehit
AgNO3/NH3 ; t0
R-COOH
Axit cacboxilic
2Ag
Bc kim loi
Bc oxit
R-CHO + 2Cu(OH)2
Anehit (Cht kh)
R-COOH
Axit hu c
+ Cu2O
+ 2H2O
Cc phn ng iu ch axit hu c t phn ng trng gng ca anehit, cng nh cho anehit tc dng Cu(OH)2 un nng, ch l cc phn ng l thuyt, khng dng trong thc t iu ch axit hu c. V thnh phm rt tn km, hn na, cc phn ng trn c thc hin trong mi trng baz, axit hu c to ra s hin din dng mui, ch khng phi axit.
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Th d: CH3-CHO +
Etanal Axetanhit
1 O2 2
Oxi
Mn
2+
CH3-COOH
Axit etanoic Axit axetic
CH2=CH-CHO +
Propenal Acrolein
Bc oxit
Ag2O
AgNO3/NH3 ; t0
CH2=CH-COOH + 2Ag
Axit propenoic Axit acrilic Bc
C6H5-CHO + 2Cu(OH)2
Benzanehit ng (II) hiroxit
t
2+
C6H5-COOH + Cu2O
Axit benzoic ng (I) oxit
+ 2H2O
Nc
HOC-CHO + O2
Etanial Glioxal
Mn
HOOC-COOH
Axit etanioic Axit oxalic
AgNO3/NH3; t0
p-HOC-C6H4-CHO + 2Ag2O
Anehit tereptalic
Bc oxit
0
p-HOOC-C6H4-COOH + 4Ag
Axit tereptalic
Bc
HOC-CH2-CHO + 4Cu(OH)2
Propanial Anehit malonic ng (II) hiroxit
R-CH2OH
Ru bc mt
2 [O]
R-COOH
Axit hu c
H2O
Nc
CH3-CH2OH + O2
Ru etylic (Cht kh)
Axit axetic
CH3-COOH + H2O
Nc
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ng (II) oxit (CuO) oxi ha ru bc nht to anehit, anehit c th b oxi ha tip bi CuO to axit hu c tng ng.
R-CH2OH
Ru bc 1 +
+ CuO
ng (II) oxit
t0
R-CHO
Anehit
+ Cu
ng kim loi
Nc
H2O
R-CHO
Anehit
CuO
ng (II) oxit
t0
R-COOH + Cu
Axit hu c ng
R-CH2OH +
Ru bc 1
2CuO
ng (II) oxit
t0
Axit hu c
Th d: CH3-CH2-CH2OH + 2CuO
Ru n-propylic
t0
ng (II) oxit
Nc
C th dng dung dch kali icromat trong mi trng axit sunfuric (K2Cr2O7/H2SO4) oxi ha ru bc 1 to axit hu c tng ng, cn icromat b kh to mui crom (III). icromat c mu da cam, sau phn ng ty theo nng ru (ru etylic) m icromat b mt mu da cam t hay nhiu. Do , c th dng Cr2O72-/H+ pht hin lng ru t hay nhiu trong hi th ca mt ngi. Cnh st giao thng yu cu cc bc ti thi vo ng ng cc ha cht ny t c th bit ti x c ung ru hay khng v ung nhiu hay t m cho php tip tc li xe hay phi b gi li.
-1 +6 +3 +3
KMnO4 (kali pemanganat kali, thuc tm) oxi ha ru bc 1 to axit hu c tng ng (axit to ra trong mi trng baz, nn dng mui kali ca axit hu c, mun c axit th em axt ha mui ny bng axit mnh nh HCl, H2SO4); Cn KMnO4 b kh to mangan ioxit (MnO2).
3R-CH2OH + 4KMnO4
Ru bc 1
3R-COOK R-COOH +
Axit hu c
Kali pemanganat
R-COOK + H+
Axit mnh
K+
Th d: 3CH2=CH-CH2OH + 4KMnO4
Ru alylic
Kali pemanganat
XII.6.3. Tng hp axit axetic t axetilen (phng php hin i iu ch axit axetic)
CHCH +
Axetilen
Nc
H2O
[CH2=CH-OH]
CH3-CH=O
Anehit axetic
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CH3-CHO +
Anehit axetic
1 O2 2
Oxi (KK)
Mn2+
Thay v dng axetilen, ngi ta cn dng etilen em oxi ha bng oxi vi cht xc tc gm PdCl2/CuCl2 100C, p sut 30 atm, cng thu c anehit axetic. Sau em oxi ha tip anehit axetic bng oxi ca khng kh, c mui Mangan (II) axetat lm xc tc, 70C, s thu c axit axetic, nh vit trn. 2CH2=CH2 + O2 Etilen Oxi
PdCl2/CuCl2 ; 100C ; 30 atm
2CH3-CHO
Anehit axetic
XII.6.4. Chng khan g, thu c axit axetic G, gm ch yu l xenluloz (cellulose) v lignin, c chng khan trong ni kn 400 500C. Dn hn hp hi thot ra qua h thng lm lnh lm ngng hi. Thu c mt cht nha en gi l hc n hay gudron lng lp di v mt hn hp lng nh hn, gm nc (H2O), axit axetic (CH3COOH), metanol (CH3OH) v axeton (CH3-COCH3) nm lp trn. Ly hn hp lng ra, cho vi vo chuyn axit axetic thnh mui canxi axetat. Chng ct ht nc, metanol v axeton. Cn li canxi axetat cho tc dng vi axit sunfuric ri em chng ct thu ly axit axetic.
Axit axetic
2CH3COOH
CaO CaCO3
Ca(CH3COO)2
Canxi axetat
+ + +
[ 2CH3COOH +
Axit axetic 2CH3COOH Axit axetic
Ca(CH3COO)2
Canxi axetat
Kh cacbonic
+ Ca(OH)2
Canxi hiroxit (Vi ti)
Ca(CH3COO)2
Canxi axetat
Nc
2H2O ]
Ca(CH3COO)2
Canxi axetat
+ H2SO4
Axit sunfuric
2CH3COOH +
Axit axetic
CaSO4
Bi tp 108 t chy hon ton mt hn hp gm A ba cht hu c n chc, no, mch h c cng CTPT th cn 7,84 lt O2 (ktc). Sn phm chy gm 6,72 lt CO2 (ktc) v 5,4 gam H2O. a. Tm CTPT. Vit CTCT ca ba cht hu c v c tn mi cht. Bit rng t khi hi ca hn hp A bng 2,55. b. Vit phng trnh phn ng ca mi cht vi: Na; NaOH; Na2CO3; Dung dch AgNO3/NH3; C2H5OH; CuO. (C = 12 ; H = 1) S: C3H6O2 Bi tp 108 Hn hp A gm hai cht hu c n chc mch h ng phn. t chy ht m gam hn hp A cn dng 6,72 lt oxi (ktc). Sn phm chy ch gm kh cacbonic v nc. Cho sn phm chy hp th vo bnh ng nc vi d, khi lng bnh tng 16,8 gam v thu c 30 gam kt ta.
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a. Tnh m. Cc phn ng xy ra hon ton. b. Xc nh CTPT, CTCT mi cht trong hn hp A. Bit rng khi nh hn hp A vo cc vi th c hin tng si bt kh. c tn tng cht trong hn hp A. c. Vit phng trnh phn ng ca mi cht vi: CaCO3; H2; dd AgNO3/NH3; dd Br2; Ru alylic; dd NaOH; v phn ng trng hp ca mi cht. d. T hn hp trn, vit phng trnh phn ng iu ch poli metylmetacrilat. (C = 12 ; H = 1 ; O = 16) S: C3H4O2
Bi tp 109 ( 8, B TSH mn Ha) 1. un nng mt axit a chc c cng thc (C4H3O2)n (trong n < 4) vi mt lng d hn hp A gm hai ru u c cng thc chung l CmH2m + 2O (c mt H2SO4 c), c mt hn hp B gm cc cht hu c cng chc. Khi un nng p (gam) A 1700C (c mt H2SO4 c) c V lt hn hp kh hai olefin ng ng k tip nhau. Cho p (gam) A tc dng ht vi Na thu c x (lt) H2; nu t chy ht p (gam) A c y (lt) CO2. a. Vit CTCT ca axit, bit rng axit khng lm mt mu dung dch nc brom. b. Cho bit trong hn hp B c th c nhng cht g? 2. a. Lp biu thc tnh x v y theo p v V. b. Khi p = 2,24 gam, V = 0,784 lt, hy xc nh CTCT ca hai ru, bit rng khi cho hi ru qua bt Cu nung nng to ra sn phm u c kh nng cho phn ng trng gng. c. Tnh % v khi lng cc cht trong A (theo s liu cu 2b) (Cho cc th tch kh o ktc; gi thit hiu sut cc phn ng u 100%) (H = 1 ; C = 12 ; O = 16) 11,2 p 9V V S: C6H4(COOH)2; x = ; y = ; 66,96% C3H7OH; 33,04% C4H9OH 2 7 Bi tp 110 ( 17 B TSH mn Ha) Cho 800 gam t n tc dng ht vi nc ta thu c 100 lt C2H2 27,30C v 2,464 atm. 1. Tnh % khi lng ca canxi cacbua trong t n. 1 2. Ly lng C2H2 trn cho hp nc ( 700C, c mt HgSO4) ta c sn phm 2 A. Chia A thnh hai phn bng nhau: Mt phn kh bng H2 (c mt Ni, t0) thu c cht B; Mt phn oxi ha bng O2 (c mt Mn2+) thu c cht D. Cui cng cho B tc dng vi D khi c mt H2SO4 c, ta thu c sn phm E. Tnh khi lng E, bit hiu sut ca cc phn ng hp nc, kh, oxi ha, este ha u bng 80%. 1 3. Ly lng C2H2 trn un nng vi than hot tnh (6000C) ta thu c hn hp 2 kh gm C2H2 v kh sn phm, trong kh sn phm chim 75% th tch. a. Tnh hiu sut phn ng. b. Lm lnh kh sn phm ti nhit phng th thu c bao nhiu ml cht lng (d = 0,8 gam/ml) (C = 12 ; H = 1 ; O = 16)
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S:1. 80%
2. 112,64g E
3. 90%; 146,25 ml
Bi tp 111 ( 50 B TSH mn Ha) Cho 50 ml dung dch A gm axit hu c R-COOH v mui kim loi kim ca axit tc dng vi 120 ml dung dch Ba(OH)2 0,125M, sau phn ng thu c dung dch B. trung ha Ba(OH)2 d trong B, cn cho thm 3,75 gam dung dch HCl 14,6%, sau c cn dung dch thu c 5,4325 gam mui khan. Mt khc, khi cho 50 ml dung dch A tc dng vi H2SO4 d, un nng thu c 1,05 lt hi axit hu c trn (o 136,50C; 1,12 atm). 1. Tnh nng mol ca cc cht tan trong A. 2. Tm cng thc ca axit v ca mui. 3. Tnh pH ca dung dch 0,1 mol/l ca axit tm thy trn, bit in ly = 1%. (Ba = 137 ; Li = 7 ; Na = 23 ; K = 39) S: RCOOH : 0,3M; RCOONa: 0,4 M; CH3COOH- CH3COOK; pH = 3
CU HI N PHN XII
1. Axit hu c l g? Cho th d minh ha. 2. c tn cc cht sau y: HCOOH; CH2=CH-COOH; n-C5H11COOH; CH3COOH; HOOC-COOH; CH2=C(CH3)COOH; HOOC(CH2)4COOH; C6H5COOH; p-HOOC-C6H4-COOH; C15H31COOH; HOOC-CH2-COOH; C17H35COOH; n-C4H9COOH; i-C3H7COOH; C17H33COOH; CH3CH2COOH; C2H3COOH; o-HOOC-C6H4-COOH; CH3CH2CH2CH2COOH; Cl-CH2-COOH. 3. Vit CTCT cc cht sau y: Axit acrilic; Axit benzoic; Axit oxalic; Axit lactic; Axit stearic; Axit tereptalic; Axit aipic; Axit oleic; Axit metacrilic; Axit panmitic; Axit axetic; Axit picric; Axit fomic; Axit cloaxetic; Axit isovaleric; Axit propionic; Axit butanoic; Axit phenic; Axit isobutiric; Axit caproic; Axit gluconic; Axit citric; Axit malonic; Axit n-butiric; Axit pentanoic; Phenol; Anilin; Nitrobenzen; Benzanehit; Stiren; Vinyl clorua; Isopren; Cloropren. 4. (TSH khi B, 2005) 1. Cho 6 hp cht hu c n chc, mch h c cng cng thc phn t l C4H8O2. Vit cc cng thc cu to thu gn ca cc cht . 2. Hn hp X gm mt ankan v mt ankin c t l phn t khi tng ng l 22 : 13. t chy hon ton 0,2 mol hn hp X, thu c 22 gam CO2 v 9 gam H2O. Xc nh cng thc phn t ca ankan v ankin. (C = 12; H = 1; O = 16) S: C3H8 ; C2H2 5. (TSH H Nng, 2001) Mt hn hp A gm axit hu c X v este Y ca axit hu c n chc. Cho A tc dng va vi dung dch NaOH. Chng ct hn hp sn phm th thu c 9,3 gam mt hp cht hu c B v 39,4 gam hn hp mui khan. Cho cht B tc dng vi Natri d thu c 3,36 lt H2 (ktc). Cho B tc dng vi Cu(OH)2 thu c dung dch
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c mu xanh lam. em ton b hn hp mui khan trn nung vi vi ti xt thu c mt cht kh D duy nht (hirocacbon) c th tch 8,96 lt 27,30C v 1,1 atm. 1. Xc nh CTCT ca B, bit MB < 93 vC. 2. Tnh s mol ca X, Y trong A. 3. Xc nh CTCT ca X, Y. (H = 1; C = 12; O = 16; Na = 23) S: B: Etylenglicol; 0,1 mol X; 0,15 molY; X: Axit malonic; Y: imetyl malonat
6. (TSH H S Phm v H Lut tp HCM, 2001) Hai cht hu c A, B (cha C, H, O) u c 53,33% oxi theo khi lng. Khi lng phn t ca B gp 1,5 ln khi lng phn t ca A. t chy ht 0,04 mol hn hp A, B cn 0,10 mol O2. Mt khc, khi cho s mol bng nhau ca A v B tc dng vi lng d dung dch NaOH th lng mui to ra t B gp 1,1952 ln lng mui to ra t A. Bit cc phn ng xy ra hon ton. Tm CTCT ca A v B. (C = 12; H = 1; O = 16; Na = 23) S: A: CH3COOH; B: HO-CH2-COOCH3 7. (H Cn Th, 2000) Cho s bin ha sau:
(A) (X)
len men
C2H5OH
(B)
Xc nh CTCT thu gn ca (X), (A), (B) v vit cc phng trnh phn ng xy ra (mi mi tn l mt phn ng)
8. (H Cn Th, 1999) Hon thnh s phn ng sau di dng cng thc cu to:
A X
NaOH (1 : 1) t0 NaOH
CH4
C2H5OH
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