KIM NGHIM THUC DA

VO NHM CHC

NI DUNG
1. Kim nghim hydrocarbon v dn cht halogen

2. Kim nghim cc hp cht cha nhm OH

3. Kim nghim cc hp cht cha nhm carbonyl 4. Kim nghim cc hp cht cha nhm chc ether 5. Kim nghim cc hp cht cha nhm chc carboxylic. 6. Kim nghim cc hp cht cha nhm chc ester 7. Kim nghim cc hp cht cha nhm chc amin 8. Kim nghim cc hp cht cha nhm chc amid

I. KIM NGHIM HYDROCARBON V DN CHT HALOGEN

Cc hydrocarbon thng dng lm t dc hoc lm thuc nhun trng nh vaselin, du vaselin, parafin V mt ha hc, chng kh tham gia cc phn ng. xc nh cc hp cht ny, ch yu da vo cc tnh cht vt l nh trng thi, mu sc, ph hp th t ngoi... xc nh thnh phn ha hc, tin hnh oxy ha v xc nh sn phm to thnh. Tc nhn oxy ha thng dng l oxyd ng hoc lu hunh CxHy + CuO CO2+ H2O + Cu2O
CxHy+ y S2
4

y H2S
2

xC

 H2O c xc nh do to thnh cc git nc trn thnh ng nghim. CO2 to thnh c xc nh bng phn ng to ta vi dung dch calci hydroxyd:
CO2
+

Ca(OH) 2

CaCO3 + H2O

H2S c xc nh bng dung dch ch acetat:

H2S

Pb(CH3COO)2

PbS + 2CH3COOH

1.2.HP CHT CHA HALOGEN

Cc hp cht cha halogen c s dng rng ri trong iu tr. l cc hp cht cha flo, clo, brom v iod v c th di dng mui halogenid hoc dng kt hp cng ha tr vi carbon.

1.2.1. Hp cht halogen dng mui kt hp

Cc hp cht ny thng tan trong nc v lc to ra ion halogen. xc nh cc ion ny, thuc th thng dng l dung dch bc nitrat.
X+

AgNO3

AgX

NO3+ 2H2O

Ta khng tan trong cc acid v c, tan trong NH3:

Ag X

+ 2NH4OH

[Ag(NH3)2]Cl

phn bit cc halogen, da vo hnh dng v mu ta to thnh: Ta AgCl trng xm, vn Ta AgBr mu hi vng Ta AgI mu vng.

Tip
Tuy nhin, xc nh chc chn l halogenid no, phi da vo th oxy ha kh ca chng. Cho vo dung dch cha ion halogenid nc clo (dung dch clorua vi, dung dch cloramin...) v cloroform th: Nu trong dung dch cha ion clo: Mu khng i Nu cha ion brrom, lp cloroform c mu vng. Nu cha ion iodid, lp cloroform c mu nu

Cl- + Cl2 Br- + Cl2 I+

Cl- + Cl2 Br2 + ClI2

+

Cl2

Cl-

nh lng halogenid: Phng php ph bin nht l phng php o bc

X+

AgNO3

AgX

NO3-

Xc nh im kt thc bng o in th hoc ch th mu Trong trng hp dng ch th mu, tu pH mi trng m dng ch th mu thch hp. Nu pH t 7 n 10, dng phng php Mohr (ch th Kali cromat:

AgNO3d-

KCrO4

AgCrO4

KNO3

Trong trng hp ny, nu pH > 10 s to ta Ag2O; nu pH < 7 s to Cr2O72- v Ag2Cr2O7 tan trong mi trng acid

 Nu mi trng acid, phi dng phng php Volhard, ch th phn st amoni, cht chun amoni sufocyanid:
AgNO3
+

SCN-

AgSCN

NO3-

Mt git tha SCN- phn ng vi Fe3+ to ta phc mu :

SCN

Fe

3+

Fe(SCN)

2+

Trong phng php ny, nu nh lng ion clorid th phi thm vi ml nitrobenzen vi mc ch bao ly ta AgCl khng cho chng tan ra v tch s tan ca AgCl ln hn AgSCN.
Phng php Fajans: Phng php ny dng ch th hp ph.
Nguyn tc l ngay sau im tng ng, ta AgCl mang in tch dng (d Ag+) trn b mt ta. Mt anion hu c mang mu thm vo s lin kt trn b mt ta, mu thay i.

1.2.2. Hp cht halogen dng lin kt cng ho tr

nh tnh v nh lng cc hp cht ny, nguyn tc l chuyn chng sang dng ion

Tu theo mc lin kt ca halogen vo carbon m c th bin chng sang dng ion bng cc thuc th khc nhau:

nh hng ca halogen ln bn ca lin kt C X: Nu lin kt trn cng 1C v cng chu nh hng ging nhau ca cc nhm th bn cnh th bn ca lin kt gim dn t F > Cl > Br > I (do bn knh tng dn
nh hng ca gc hydrocarbon: bn gim dn t vng thm, mch vng, mch h

 S lng halogen trn C: Nu s lng tng, bn lin kt tng (do km phn cc) nh hng ca nhm th khc: Cc nhm th m in ni chung lm gim bn ca lin kt Sau y l mt s phn ng hay dng: 1. un si vi dung dch KOH trong ethanol
++ t RX KOH K X + ROH Phn ng ny p dng cho tt c cc hp cht hu c cha halogen, tr halogen gng vo nhn thm m v tr ortho hoc para khng c nhm th m in +
0

2. Tc dng vi NaI trong aceton

AX + NaI Na X + RI Phn ng ny dng xc nh clo v brom. Ta NaI khng tan trong aceton

++

3. Tc dng vi natri carbonat khan v un nng

RX + Na2CO3

NaX + CO2

H2O

y l phng php s dng ph bin nht trong cc dc in

Sau khi v c ha, vic nh tnh v nh lng c tin hnh nh cc mui halogenid trn i vi hp cht hu c cha iod, do lin kt khng bn nn vic xc nh d dng hn.

 i vi tt c cc hp cht gn iod, tr gn vo nhn thm, ch cn un nng, gii phng hi iod mu tm i vi hp cht gn iod vo nhn thm, cn thm acid sulfuric v un nng (levothyroxin)

i vi hp cht gn fluoro, lin kt cng ha tr rt bn vi carbon. bin sang dng ion fluorid, phi un ch phm vi kim loi kim.

II. KIM NGHIM CC HP CHT CHA NHM OH

2.1. ALCOL

2.1. ALCOL
Alcol l nhng hp cht, trong phn t cha 1 hay nhiu nhm OH lin kt vi carbon mch h, mch vng hoc mch nhnh ca hydrocarbon thm.

L tnh: Tt c cc alcol (tr enol) u l nhng hp cht trung tnh; c nhit si rt cao (do lin kt hydro). Monoalcol vi C < 11 l nhng cht lng, nh hn nc tan: T C1 n C3 trn ln vi nc mi t l. Polyalcol l cht lng nht hoc cht rn, v ngt

2.1. ALCOL
Ho tnh:

L ho tnh ca lin kt O - H v ho tnh lin kt C - OH

1. Phn ng xy ra trong lin kt O H (alcol bc 1 v 2)

- D xy ra theo th t: Bc nht > bc hai > bc 3. - Th nhm OH trong lin kt C OH theo chiu ngc l Oxy ho alcol bc 1 v 2 thnh aldehyd v ceton:
R CH2OH
+

K2Cr2O7 + 8H+ R CHO

+8H +

(R)2 CHOH + K2Cr2O7

(R)2 CO

+ 2Cr 7H2O 3+ + 2Cr + 7H2O

Sn phm to thnh c xc nh bng pp thch hp (phn sau)

2.1. ALCOL
Phn ng ny khng xy ra vi alcol khng no do s oxy ho s xy ra ti lin kt khng no ny. Phn ng acyl ho (to ester): Thng dng l phn ng to acetat hoc benzoat

-Tc dng vi acid acetic khan hoc natri acetat trong v acid sulfuric c:

R CH2OH + CH3COOH RCH2OOCCH3 H2O RCH2OH + C6H5COCl C6H5COOCH2R + H2O nh tnh, cc acetat ca alcol thp c mi thm; cc benzoat ca alcol khng tan trong nc. nh lng bng cch xc nh ch s acetyl ho

2.1. ALCOL
Cho vo ch phm 1 lng d anhydrid acetic acetyl ho, tch sn phm acetyl ho ri nh lng bng pp tha tr. Phn ng Xantogenic: Tc dng vi carbon sulfid trong mi trng kim, thm mui ng (II) to ta mu nu

KIM NGHIM HC CHA NHM CARBONYL

Hp cht cha nhm carbonyl l nhng hp cht trong phn t cha nhm C= O, nguyn t C ny lin kt vi hydro, alkyl hoc aryl to ra aldehd, ceton, quinon. Phn ng chung cho cc hp cht ny l phn ng ngng t: Vi hydroxylamin to oxim, vi hydrazin to hydrazon, semicarbazid to semicarbazon, vi 2,4-dinitrophenylhydrazin... R1 R1 R2 C N OH + H2O R2 C O + H2N OH

R1 R1 C O

H2N NH2

R1 R2 C N NH2

H2O

R1 R2 C O + H2N NH C NH2

S R1 R2 C N NH C NH2+ H2O

R1 R2 C O

O2N H2N HN

NO2 R R C N NH

O2N NO2

Cc phn ng ny xy ra trong mi trng acid yu v to ta

3.1. ALDEHYD
L tnh: L nhng cht c tnh trung tnh. Formaldehyd v acetaldehyd l nhng cht kh c mi c bit. Cc aldehyd mch h vi s carbon trung bnh l nhng cht lng linh ng n snh nh du, c mi d chu. Cc aldehyd thm l nhng cht lng hoc rn. Ho tnh: Tnh kh v tham gia phn ng cng Tc dng vi bc nitrat trong amoniac (phn ng Tollen) to ta bc kim loi, vi thuc th Fehling to ta , vi thuc th Nessle to ta nu en ca thu ngn kim loi
O R C H
+ 2[Ag(NH3)2]NO3 + H2O

RCOOH+ 2Ag +NH3+ NH4NO3

ALDEHYD
O R C H + K2[HgI4] +3KOH RCOOH
+ Hg + 4KI + 2H2 O

O R C H

COONa NaOOC 2+ O CH HC O Cu HC O O CH COOK KOOC

Cu2O + RCOOH

Cc polyphenol, aminophenol v cc - hydroxyceton (cc ng n, cortison...) v mt s hp cht khc cng cho phn ng tng t. Tuy nhin, phn bit, dng thm phn ng ngng t nu trn. Cc aldehyd thm khng cho phn ng vi thuc th Fehling

ALDEHYD
Phn ng vi natri bisulfit hoc thuc th Schiff: Tc dng vi thuc th Schiff (dung dch Fuchsin lm mt mu bng kh sulfur (SO2): To mu hng n mu . C ch phc tp, bn cht phn ng cng. Tc dng natri bisulfit to ta. Cho ta tc dng vi dung dch kim hoc acid s gii phng tr li aldehyd.
O R C H
+

NaHSO3

R CH

OH SO3Na

V vy, ngoi vic dng nh tnh cc aldehyd, thuc th ny cn c dng phn lp cc aldehyd.

3.2. CC CETON
L tnh: Cc ceton l nhng cht trung tnh. Cc ceton c t carbon l nhng cht lng nng, linh ng, c mi ether; tan trong nc v ether. Cc ceton cha nhiu carbon l nhng cht lng snh nh du hoc cht rn.

Ho tnh: Khng c tnh kh. Song di tc dng ca nhm carbonyl lm cho hydro gn vo cc nguyn t carbon bn cnh tr nn linh ng v c mt s phn ng sau. Tuy nhin, do cc phn ng ny khng c hiu nn trc khi tin hnh cc phn ng ny, cn tin hnh trc cc phn ng: Xc nh nhm carbonyl bng phn ng ngng t Dng phn ng vi natri hydrosulfit tch aldehyd

CC CETON
1. Phn ng Legal: Tc dng vi natri nitrofrussiat (Na2[Fe(CN)5NO] trong mi trng kim to mu khc nhau. Mu khng bn, acid ha bng acid acetic thng chuyn sang mu xanh. C ch cha xc nh.
Cc ceton mch h, mch vng, cc aldehyd, 1,3-diceton (enol), -cetoester, ester ca acid malonic u cho phn ng ny. Cc hp cht khng ln phn ng l benzophenon, benzaldehyd v formaldehyd.

2. Phn ng vi meta-dinitrobenzen: Tc dng vi meta dinitrobenzen trong cn v kim ha to sn phm c mu vng m. Cc hp cht to mu
vi trong phn ng Legal cng to mu trong phn ng ny.

CC CETON
Do nhy ca phn ng cao nn hay c dng nh lng cc hp cht ceton khi hm lng thp (dch sinh hc) 3. Phn ng to iodoform: Cc methylceton v acetaldehyd (nhm CO lin kt vi H hoc C) khi tc dng vi iod trong mi trng kim to iodoform I2 + 2NaOH NaOI + NaI + H2O
CH3 CO R
+ 3NaOI

CI3CO R+ 3NaOH

CI3CO R + NaOH

CHI3 + R COONa

CC CETON
Phn ng ny khng xy ra vi acid acetoacetic, song mt s hp cht trong iu kin phn ng s b thy phn hoc oxy ha thnh nhm chc methylceton hoc acetaldehyd gy phn ng. Mt s v d:

CH3CH2OH + NaOI CH3CH(OH)R + NaOI

RCOCH2COR + NaOH

CH3CHO + NaI + H2O CH3COR + NaI + H2O

RCOONa + CH3CO R

3.3. CC ENOL
Enol l ng phn ca 1,3-diceton hoc l - cetoester v lun tn ti di dng h bin ceto-enol
R C CH2 CO R O R C CH2 COO R O Ha tnh: R C CH CO R OH R C CH COOR OH

Tnh acid ca nhm OH (to mu vi Fe3+ hoc Cu2+) Ha tnh nhm carbonyl (ngng t) Ha tnh ca lin kt i (phn ng cng) Ha tnh nhm methylen hot ng

3.4. CC QUINON
Quinon l nhng hp cht, trong phn t cha nhm C= O lin kt trc tip vo nhn thm Tnh cht: L nhng cht rn. D b kh thnh hydroquinon; mt s cht khng cho phn ng ngng t vi hydrazin. Ngoi ra, cc quinon cho phn ng c trng to quinhydron c mu khi tc dng vi phenol
OH O O HO

3.5. CC NG N
1. L tnh: L nhng cht rn, trung tnh, v ngt 2. Ha tnh: Ha tnh ca polyalcol Ha tnh ca nhm aldehyd (tnh kh) k c ng -hydroxyceton. Phn ng ngng t (to osazon)
R C O + R NH NH 2 HC OH 3 R' R C N NH R + R NH2+ NH3 C N NH R R'

3.6. NH LNG
i a s hp cht cha nhm carbonyl, nh lng da vo phn ng ngng t. Ring aldehyd, cn da vo tnh kh v tham gia phn ng cng 1. Phn ng vi hydroxylamin Thm mt lng d hydroxylamin, nh lng hydroxylamin d bng phng php o acid. Nu dng hydroxylamin hydroclorid: Acid gii phng c nh lng bng phng php o kim. 2. Dng 2,4-dinitrophenylhydrazin: Phn ng xy ra hon ton. nh lng sn phm bng phng php cn ta, cc ph hoc chun oxy ha kh, ph hp th kh kin trong mi trng kim

4. KIM NGHIM DA VO NHM ETHER

1. L tnh: Ether l cht trung tnh, khng phn cc, khng tan trong nc; trong s cc hp cht cha oxy th ether c nhit si thp nht 2. Ha tnh: Hot ng ha hc km. Phn ng xy ra gia lin kt phn cc R - O a. Tc dng vi HI:

R O R' + HI

RI + R'OH

Phn ng ny xy ra vi ether bo, ether va bo va thom Trong trng hp R > R' th s to R'I + ROH

4. KIM NGHIM DA VO NHM ETHER

Nu un nng, to 2 alkyl iodid 0 t R O R'+ 2HI RI + R'I + H2O Ether bo thm, p ch xy ra hon ton khi un si:
0 t Ar O R' + HI

ArOH + R'I

Da vo alcol, alkyliodid v phenol to thnh T b. Tc dng vi nhm clorid:

Phn ng d dng vi aryl-alkylether to phenolat nhm:

3Ar

O R' + AlCl3

Al(ArO)3+ 3R'Cl

4. KIM NGHIM DA VO NHM ETHER

Acid ha hn hp phn ng ri chit phenol vo ether v xc nh phenol trong lp ether.

5. KIM NGHIM DA VO NHM COOH

1. L tnh: Cc monocarboxylic c < 5C l nhng cht lng, mi c bit. Cc acid c nhiu C hn v acid dicarboxylic l nhng cht rn. Cc acid mch h, cc hydroxyacid v mt s aminoacid tan trong nc. C v chua. 2. Ha tnh: Tnh acid gim dn theo th t: Acid mch h > mch vng > mch vng thm. Dicarboxylic > monocarboxylic Mch ngn > mch di. Carboxylic > enol > phenol

5. KIM NGHIM DA VO NHM COOH

.. + R C O H O
Lm giy qu xanh Tan trong dung dch kim (tr - hydroxyacid) Tc dng vi mui to mui mi. Tc dng alcol to ester Tc dng vi amin to amid Tc dng thionyl clorid to clorid acid Mt s phn ng c bit

5. KIM NGHIM DA VO NHM COOH

Thng dng bc nitrat to ta trng nh tnh v nh lng acid nitric gii phng
R COOH + AgNO3 R COOAg +HNO3

- Mt s acid dicarboxylic c th to ta mu trng vi ion calci hoc bari:

COOH COOH
+

Ca

2+

COO COO

Ca

- Cc - aminoacid v pyridincarboxylic to mui phc c mu vi Cu2+(mu t tm n xanh)

5. KIM NGHIM DA VO NHM COOH

O R CH C OH H2N
+
+

Cu2+

R CH C H2N Cu
2

O O

Cu2+

COOH

N O Cu O
2

Hoc tc dng vi Ninhydrin to mu n tm

5. KIM NGHIM DA VO NHM COOH

Tc dng vi ethanol, cc acid bo t C to ester mi thm H2SO4 + R COOH C2H5OH R COOC2H5 + H2O Khi tc dng vi thionyl clorid to clorid acid, kh SO2 v hydroclorid

RCOOH + SOCl

RCOCl + SO2+ HCl

Cc acid c phn t lng thp, phn ng xy ra nhit thng; cc acid c phn t lng cao phi un nng. Pht hin SO2 bng giy tm KIO3 v h tinh bt, clorid acid bng phn ng to hydroxamat. Cc acid khng thm gia phn ng gm acid oxalic, acid oaminobenzoic, meta v para hydroxybenzoic...

5. KIM NGHIM DA VO NHM COOH

O R C Cl
+

NaOH + H2N OH

O R C NH OH + NaCl H O 2

O 3+ R C NH OH + Fe

O Fe (R C NH O) 3 + 3H+

Phn ng to hydroxamat dng tnh vi cc anhydrid acid, ester.

Phn ng decarboxy ha: Nu cnh nhm carboxylic c nhm th m in hoc dy ni i, khi un nng d dng gii phng kh CO2.

Acid malonic : CH2

COOH COOH

CH3 COOH CO2

5. KIM NGHIM DA VO NHM COOH

Acid acetoacetic: CH3 C CH2COOH 100 CH3COCH3 + CO2 O
0 t Acid phenylacetic: C6H5 CH2COOH C6H5 CH3 + CO2

C6H5 CH CHCOOH
COOH 0 t OH

C6H5 CH CH2 + CO2

OH
+

CO2

Pht hin CO2 bng dd Ca(OH)2. Phn ng to fluorescein:

Cc acid 1,2-dicarboxylic thm cng nh mch h v cc dn cht ca chng, khi tc dng vi resorcin to phm mu

5. KIM NGHIM DA VO NHM COOH

O C OH C OH O HH OHHO
200
0

O O HO OH O

COO

OH

nh lng: Phng php o kim: i a s acid hu c l cc acid yu nn mi trng cn - nc, ch th thymolphtalein hoc phenolphtalein. Cc acid rt yu phi chun trong mi trng khan (dung mi dimethylformamid, ethylendiamin, n-butylamin, cht chun methylat natri, tetrabutylamoni OH.

5. KIM NGHIM DA VO NHM COOH

Phng php ester ha: Tng t nh lng alcol, song dng methanol d v xc nh nc gii phng bng pp K.Fischer. Phng php gin tip: Tc dng vi mui bc hoc calci to ta, acid tng ng gii phng nh lng o kim.

6. KIM NGHIM DA VO NHM ESTER

1. L tnh: L nhng cht trung tnh. Nu c t C th cc ester l nhng cht lng, mi thm, tng s C th chng chuyn dn sang dng snh ri thnh cht rn. 2. Ha tnh:

Thy phn: Phn ng xy ra trong mi trng acid cng nh mi trng kim R C OR' + NaOH R COONa + R'OH O nh tnh, xc nh acid hoc alcol to thnh. nh lng, dng kim d v chun li bng acid

6. KIM NGHIM DA VO NHM ESTER

- i vi cc ester kh thy phn nh ester phn t lng cao th phi un si lu hoc dng dung mi l alcol hoc ethylenglycol. - Cc ester ca alcol bc 3, ester thm m v tr O c nhm th th phi thy phn bng cch un si vi HCl 15%.

Phn ng to hydroxamat st: C ch phn ng nh clorid acid. Phn ng vi amoniac to amid: Phn ng ny xy ra vi ester c phn t lng thp

R C OR'+ NH3 O

R C NH2+ R'OH O

Cc amid thng l cht rn v xc nh bng o im chy.

7. KIM NGHIM DA VO NHM AMIN

Amin l dn cht ca amoniac khi thay th 1 hay nhiu nguyn t hydro bng gc hydrocarbon

R1 NH2 ; R1 NH R2 ; R1 N R2 R3 Ty thuc nhm amin gn vo carbon m phn bit amin bc nht, nh, ba v amin thm
Tnh cht chung ca cc amin l tnh base v gim dn theo th t: Bc 3 > bc nh > bc nht > NH3 > thm v phn ng chung l to mui khi tc dng vi acid. Trong kim nghim, thng dng phn ng to mui kt ta nh picrat, acid ptl ln (silicovolframic...)

NH3

7. KIM NGHIM DA VO NHM AMIN

Phn ng vi acid nitr (HNO2): - Amin bc nht (mch thng v thm) khi un nng to N2

R NH2+ HNO2 t R OH+ N2+ H2O

NH2
+

HNO2 t

OH
+

N2+ H2O

- Cc amin bc 2 (thng phi un nng, thm) to nitro samin mu vng, khng tan trong nc, tan trong ether

R1 NH R + HNO2

R1 N R + H2O N O

7. KIM NGHIM DA VO NHM AMIN

Phn ng vi acid nitr (HNO2): - Amin bc nht (mch thng v thm) khi un nng to N2

R NH2+ HNO2 t R OH+ N2+ H2O

NH2
+

HNO2 t

OH
+

N2+ H2O

- Cc amin bc 2 (thng phi un nng, thm) to nitro samin mu vng, khng tan trong nc, tan trong ether

R1 NH R + HNO2

R1 N R + H2O N O

7. KIM NGHIM DA VO NHM AMIN

- Cc amin bc 3 khng cho phn ng, tr amin thm m v tr para cn hydro, to p. nitroso tan trong ether,kim ha, lp nc c mu xanh. R2 R2 + N R1 + HNO2 + 2HCl NH . Cl ON R1 i vi amin thm bc nht, nu lm lnh to mui diazoni:

NH2

HNO2

HCl

N N . Cl

+ 2H2O

7. KIM NGHIM DA VO NHM AMIN

Phn ng vi fluorescein clorid: Ch amin bc 1 v 2
Khi un nng chy amin bc 1 v 2 vi fluorescein clorid v km clorid khan to phm mu rodamin
COOH Cl
Cl

COOH
+

Cl

RNH2 (2R2 N)

Cl O NHR N(R2)
+

RNH (R)2N

Cc amino khc nhau c mu khc nhau. Cc amin mch h c hunh quang di n t ngoi. Cc nitril v cc amid cng cho phn ng ny.

7. KIM NGHIM DA VO NHM AMIN

Phn ng acyl ha: Cc amin bc nht v bc 2 (do cn H) nn cho phn ng acyl ha (tng t alcol) to amid. Thuc th thng dng l acetyl clorid, anhydrrid acetic ( nh tnh do to ta); benzoyl clorid (benzoyl ha) to dn cht; hoc p.toluensulfoclorid to dn cht v phn bit.

(R)2NH + Cl CO R'
R NH2+ Cl SO2 CH3

(R)2N CO R' + HCl

R NH O2S
CH3 + NaCl +2H2O
+

7. KIM NGHIM DA VO NHM AMIN

R R1 NH + Cl O2S CH3
R N O S 2 R1

CH3+ HCl

Vi amin bc nht, sn phm cn H nn c tnh acid, ta tan trong dd kim. Vi amin bc hai, sn phm khng cn tnh acid nn ta khng tan trong kim. Cc phn ng chn lc:
Phn ng to isonitril: Cc amin bc nht khi tc dng vi cloroform trong mi trng kim to isonitril c mi c trng
R NH2+ CHCl3 + KOH
+ + 3KCl + 3H2O R N C

7. KIM NGHIM DA VO NHM AMIN

Phn ng simon: Cc amin bc 2 (tr amin thm), khi tc dng vi acetaldehyd v natri nitrofrusiat trong mi trng carbonat kim loi kim cho sn phm c mu xanh n tm. C ch phn ng cha bit. Phn ng vi carbon sulfid CS2:

Cc amin bc 1 v 2 (tr amin thm), khi tc dng vi CS2, thm ion nikel to mui, amin bc 1 mui tan, bc 2 khng tan trong nc; un si phn hy to mi c bit
R CS2 + R' NH
2+ + N R' 2+ N R' Ni .[R' NH2] [S C ] [ S C S ]2Ni S

7. KIM NGHIM DA VO NHM AMIN

0 NH R R HN t S C S C S Ni S

2R

N S + H2S + NiS

Phn ng to mui bc 4: Cc amin bc ba v i a s amin d vng, khi tc dng vi methyl iodid hoc benzyl clorid s to methyl amoni iodid hoc benzylamoni clorid + R [R3 N CH3] . I R' N R''+ CH3I

N + CH3I

N CH3]+. I

Cc diarylalkylamin v triarylamin khng phn ng

7. KIM NGHIM DA VO NHM AMIN

Mui bc 4 c xc nh bng thuc th l acid naphtoquinon sulfonic to naptoquinon c mu n tm
O

SO3H

+ [CH 3 N R3 ] .X

HO O

CH N R3
+ H2O + SO2

Cc amin bc nht v cc cht c nhm methylen hot ng cng cho phn ng ny. Phn ng cng hp vi mui kim loi nng: i a s amin d vng v amin bc 3, khi tc dng vi mui kim loi nng to ta; thng dng thuc th HgCl2

7. KIM NGHIM DA VO NHM AMIN

NH LNG AMIN:

Phng php trung ha: - o acid trc tip: p dng cho cc amin c tnh base mnh nh amin mch h. Ch th methyl hoc xanh bromocresol, dung mi cn-nc. - o acid mi trng khan: L phng php ph bin nht. Dung mi hay dng l acid acetic khan, ch tm kt tinh hoc o th, cht chun acid percloric
i vi cc mui ca amin c cc phng php sau:

7. KIM NGHIM DA VO NHM AMIN

- Phng php trung ha: * nh lng o kim, dung mi cn - nc, cht chun NaOH, ch th phenolphtalein hoc thymolphtalein. * Thm acid, nh lng o kim, ch th o th. Xc nh th tch gia 2 im un - Phng php o bc: * nh lng bng AgNO3 bng pp Fajan (ct hp ph)

- nh lng to cp ion: * To cp ion vi ch th acid - base, chit cp ion bng dung mi hu c. nh lng da vo hp th nh sng hoc nh lng trc tip bng cht chun ion.

8. KIM NGHIM DA VO NHM AMID

1. L tnh: Amid l nhng cht rn c im chy tng i cao. Cc amid c phn t lng thp tan trong nc; i a s amid khng tan trong ether. 2. Ha tnh: Phn ng thy phn bng acid hoc kim:
R CO NH2 H2SO4 RCOOH +NH4HSO4

R CO NH2 NaOH RCOONa + NH4OH

8. KIM NGHIM DA VO NHM AMID

* Khi thy phn bng acid: xc nh acid to thnh, ct (nu acid d bay hi); hoc chit bng ether ri dng cc phng php nh tnh, nh lng acid tch. xc nh amin, kim ha. Amin bay hi em ct, khng bay hi, chit bng dung mi hu c ri xc nh * Khi thy phn bng kim: Tch amin trc (ct hoc chit ring). Amin bay hi lm xanh qu , nh lng bng chun acid d trong bnh ct. Cc amid c tnh acid:

8. KIM NGHIM DA VO NHM AMID

.. R C N R' O H
Tan trong dung dch kim Tc dng mui kim loi nng, mu to ta hoc mu.

Phn ng vi acid nitr HNO2:

R CO NH2 + HONO R COOH + N2+ H2O

Cc amin bc nht cng cho phn ng, song sn phm l alcol.

R NH2 + HONO

R OH + N2+ H2O

8. KIM NGHIM DA VO NHM AMID

Phn ng phn hy Hofman to amin: Phn ng ca amid mch h m cn NH2 vi s C < 7; amid thm ca acid monocarboxylic, khi tc dng vi nc brom hoc clo trong mi trng kim s b oxy ha phn hy to amin:
2R

CO NH2+ Br2 + 2KOH

2R

NH2 + CO2 + 2KBr

Phn ng Biure: Cc hp cht c 2 nhm CONH2 nh sau, trong mi trng kim, tc dng vi mui ng to mui c mu
CONH2 H2NCONH2 ; H2C CONH 2 CONH2 ; HN CONH 2

CONH2 CONH2

8. KIM NGHIM DA VO NHM AMID

H2C CONH2 CONH2 KOH H C CO NH Cu 2+H C CO N Cu/2 2 2 CO CO NH 3

Phn ng ny gi l phn ng Biure v khi un nng s gii phng biure H2NCONHCONH2

9. KIM NGHIM DA VO NHM IMID

O O C NH C
Ha tnh nhm chc imid tng t amid, song tnh acid mnh hn. Cc php th nh tnh, nh lng thng da vo tnh cht ny. V d:

CONHCO + AgNO3

CONAgCO

10. GII THIU PHN NG OXY HA KH

S oxy ha ca mi nguyn t trong phn t l s dch chuyn i in t lin kt gia cc nguyn t trong phn t. in t lch v nguyn t no th nguyn t c s oxy ha -1 v nguyn t kia l + 1. V d:

H2O2 + 2KI
+1 1 00 1

2HCl
+1

2H2O + I2 + 2KCl 2(H

1 1

H O O H

O H)

Vy, 1 phn t H2O2, tng s oxy ha ca Oxy l - 2, sau phn ng bin thnh - 4, tc l cht nhn 2e (cht oxy ha.

10. GII THIU PHN NG OXY HA KH

Cc v d khc:

CH2OH HO CH O HO OH

I2

CH2OH HO CHO O O

O+ I

HO C C OH O O

KMnO4

CO2 + Mn2+

Cn bng cc phn ng trn

10. GII THIU PHN NG OXY HA KH

Cho phng trnh phn ng: A + I2 = A- + 4I- + 4H+. Bit phn t lng ca A l 176,1. - Cn bng phng trnh phn ng. - Tnh 1 ml dung dch iod 0,1 N tng ng bao nhiu mg cht A? - Tnh s mg cht A cn cn nh lng?

10. GII THIU PHN NG OXY HA KH

Trong chuyn lun " paracetamol" ca dc in Vit Nam 3, phn nh lng c ghi:"...Ha tan khong 0,3 g ch phm trong mt hn hp 10 ml nc v 30 ml dung dch acid sulfuric long. un si hi lu trong 1 gi. Lm lnh v pha long vi nc thnh 100 ml. Ly 20 ml dung dch ny, thm 40 g nc v 15 ml acid hydrocloric long, 0,1 ml feroin. nh lng bng amoni ceri sulphat 0,1 N cho n khi xut hin mu vng. 1 ml amoni ceri sulphat 0,1 N tng ng vi 7,56 mg C8H9NO2. Gii thch cch tin hnh? Vit phng trnh phn ng nh lng.

10. GII THIU PHN NG OXY HA KH

Cng thc cu to ca paracetamol:
NHCONH2 Ptl: 151,2 OH

Phn tch cng thc cu to ny trnh by cc phng php nh lng c th.

10. GII THIU PHN NG OXY HA KH

Cho cng thc cu to::

Phn tch cng thc cu to ny trnh by cc phng php nh lng c th.

HT