1

Chng 12. Chun Axit Baz trong mi trng khng nc Lm Ngc Th

C s ha hc phn tch. NXB i hc quc gia H Ni 2005.

T kho: Chun axit-baz, Phn ng axit-baz, Dung mi aproton, Dung mi hn hp, im cui.

Ti liu trong Th vin in t H Khoa hc T nhin c th c s dng cho mc ch hc tp v nghin cu c nhn. Nghim cm mi hnh thc sao chp, in n phc v cc mc ch khc nu khng c s chp thun ca nh xut bn v tc gi.

Mc lc
Chng 12 Chun Axit Baz trong mi trng khng nc............................... 2 12.1 Dung mi chun khng nc...................................................................... 2

12.1.1 Phn ng axit - baz trong dung mi lng tnh............................................... 3 12.1.2 Phn ng axit - baz trong dung mi aproton v dung mi hn hp ............... 9 12.1.3 Pht hin im cui khi chun trong dung mi hn hp ............................. 9 12.2 ng dng phng php chun trong dung mi khng nc ........................... 10 12.2.1 Chun trong axit axetic bng ...................................................................... 10 12.2.2 Chun trong dung mi baz ........................................................................ 12 12.2.3 Chun trong dung mi aproton hoc trung tnh ......................................... 13

Chng 12 Chun Axit Baz trong mi trng khng nc

chng 10 chng ta bit khng th chun c nhng axit hoc baz c hng s phn li nh hn 1.108 bi v phn ng xy ra khng hon ton v rt kh xc nh im cui. Nhng c th chun nhiu hp cht trong s nhng hp cht k trn trong dung mi khng nc, bi v cc dung mi ny c kh nng lm tng tnh axit hoc tnh baz ca cc hp cht . Nhng dung mi khng nc c s dng thnh cng chun nhiu cht kh tan trong nc. ng tic l nhng d kin nh lng cn thit xy dng ng chun trong dung mi khng nc thng khng c hoc khng , do ch c th nh gi chun mt cch nh tnh.

12.1 Dung mi chun khng nc

C th chia dung mi theo tnh cht ca chng thnh 3 loi: Dung mi lng tnh: dung mi lng tnh l nhng dung mi c c tnh axit v tnh baz, t ion ha hoc proton phn. Mc d nc l dung mi lng tnh in hnh nht, nhiu hp cht khc cng th hin tnh cht tng t thng qua cc phn ng. 2H2O 2C2H5OH 2HOAx 2NH3 hoc l di dng tng qut:

H3O+ + OH
+ + C2H5O C2H5 OH2

H2OAx+ + OAx

+ + NH2 NH4

2SH

+ +S SH2

y SH l phn t dung mi lng tnh, SH2+ l proton solvat ha; S l baz. Trong bng 12.1 dn ra nhng gi tr hng s proton phn ca mt s dung mi ph bin nht.
Bng 12.1 Hng s proton phn ca mt s dung mi thng dng nht 25 C
o

Dung mi Nc Metanol Etanol Axit focmic Axit sunfuric Axit axetic Amoniac (50oC) Etileniamin

KS 1,01.1014 2.1017 8.1020 6.107 1,4.104 3,6.1015 1.1033 5.1016

Hng s in mi 78,5 32,6 24,3 58,5 >84 6,2 22 14,2

Khc vi nc v ru, mt s dung mi lng tnh nh axit axetic, sunfuric, focmic th hin tnh cht axit r rng hn tnh baz nhiu v ngc li, nhng dung mi nh amoniac hoc ietyliamin li c tnh baz mnh hn tnh axit. Dung mi aproton hoc dung mi tr: Nhng dung mi ny khng th hin tnh axit hoc tnh baz v khng proton phn mc ng k. Benzen, tetraclorua cacbon, pentan thuc loi dung mi ny. Cui cng cn c mt dy dung mi nh xeton, ete, este v nhng dn xut ca pyriin. Nhng dung mi ny c tnh baz v khng biu l tnh axit, chng khng c xu hng proton phn.

12.1.1 Phn ng axit - baz trong dung mi lng tnh

Thay th dung mi thng c nh hng su sc n hon ton ca phn ng axit baz. Trong mc ny, chng ta s xem xt nh hng ca dung mi lng tnh n hon ton ca phn ng axit - baz. hon ton ca phn ng axit - baz: c th hnh dung phn ng xy ra khi chun baz yu B bng dung dch chun axit mnh trong nc dng:

B + H3O BH + H2O

(12.1)

v hon ton ca phn ng xy ra c th c c trng bng gi tr ca hng s cn bng:

K cb BH+ = Kb = H O+ K H2O [B] 3

(12.2)

R rng l, hng s cn bng ca phn ng trn bng t s hng s phn li baz B v tch s ion ca nc. Mt cch tng t, hon ton ca phn ng gia axit yu HA v baz mnh c th c biu din bng hng s cn bng:
K cb A Ka = = OH K H2O [HA ]

(12.3)

C th dn ra nhng t s tng t cho nhng phn ng trong dung mi khng nc. V d, nu chun baz yu B bng axit mnh trong axit focmic khng nc, chng ta c th vit:
+ + B + HCOOH2 BH + HCOOH

(12.4)

+ y HCOOH2 l proton solvat ha, tng t nh H3O+ trong dung dch nc. Hng s cn bng ca phn ng :

K cb =

+ HCOOH2 [B]

BH+

K 'b KS

(12.5)

y K 'b l hng s phn li baz B trong axit focmic, ngha l: B + HCOOH BH + HCOO ;
+

K 'b

BH+ HCOO = [B ]

(12.6)

Cn KS l hng s proton phn ca axit focmic:

+ 2HCOOH HCOOH2 + HCOO; + KS = [ HCOOH2 ][HCOO]

(12.7)

V nng ca dung mi HCOOH thc t khng bin i nn i lng , ging nh trong trng hp tch s ion nc, c bao hm trong KS. Chun axit yu HA bng natri etilat trong etanol, c th d dng hnh dung dng:

HA + C2H5O A + C2H5OH

(12.8)

y dung dch natri etilat C2H5ONa trong etanol c dng lm dung dch chun baz mnh. Ging nh trong cc v d trn y, hon ton ca phn ng c th c c trng bng hng s cn bng:
K cb A K' = = a C H O+ K S [HA ] 2 5

(12.9)

y K 'a l hng s phn li ca axit HA trong etanol: HA + C2H5OH

+ C2H5 OH2

+A ;

K 'a

+ A C2H5 OH2 = [HA ]

(12.10)

v KS l hng s proton phn ca etanol:

+ 2C2H5OH C2H5 OH2 + C2H5O ; + KS = [ C2H5 OH2 ][C2H5O]

(12.11)

Nhng v d ch r rng, hon ton ca phn ng ph thuc c vo hng s phn li ca cht b chun, c vo hng s proton phn ca dung mi. S c mt ca c hai hng s phn li trong phng trnh chc chn s lm d hiu hn nu xem mi phn ng axit - baz nh cuc chy ua ginh proton. V d nh, chiu su ca s xy ra phn ng (12.4) ph thuc vo vic, nhng phn t dung mi HCOOH chy ua vi nhng phn t baz B ginh ly nhng ion hiro H+ thnh cng n mc no m chng ta bit rng s ion li b hn ch do s hp thc ca phn ng. Hng s phn li KS v K 'b quyt nh hiu qu ca mi hp phn trong cuc cnh tranh . Mt cch tng t, c th hnh dung phn ng (12.8) nh cuc chy ua ginh ion H+ gia cc anion A v C2H5O m ginh thng li thuc v ion no trong chng l do cc i lng K 'a v KS quyt nh. T nhng bn lun trn y, r rng l nhng php chun axit - baz trong cc dung mi c hng s proton phn thp chim u th. Ngoi ra, nhng phn ng axit - baz s xy ra hon ton hn trong cc dung mi c gi tr K 'a v K 'b ln. Hai iu kin gii trn y khng phi l hon ton c lp vi nhau v cng khng th c on quyt nh s la chn dung mi lng tnh cho php chun khng nc. nh hng ca cng axit hoc cng baz ca dung mi ln tnh cht ca cht tan: Hng lot nhng dung mi lng tnh nh axit focmic, axetic, sunfuric d dng cho proton hn l lin kt proton v do c xem nh nhng dung mi axit. Trong nhng dung mi nh th, tnh baz ca cht tan c tng ln ng thi tnh axit gim xung. V d nh, khng nn chun anilin C6H5NH2 trong dung dch nc bi v hng s baz ca n khong 1010 nhng trong axit axetic bng, alinin l baz mnh hn nhiu bi v kh nng tng tc vi dung mi ca n c tng cng. V d: hng s cn bng Kb ca phn ng:

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+ C6H5NH2 + HOAx C6 H5 NH3 + OAx

cao hn kh nhiu so vi Kb ca phn ng tng t trong nc. C6H5NH2 + H2O

+ + OH C6 H5 NH3

Trong khi , nhng dung mi axit li c kh nng lm tng cng baz, cn i vi axit chng biu l tc dng ngc li, ngha l lm gim cng ca chng. Axit clohiric l axit mnh trong nc nhng ch phn li mt phn trong axit axetic bng. Nhng axit l yu trong nc, trong dung mi axit cn tr thnh yu hn. Nhng dung mi nh etileniamin, amoniac lng c i lc mnh vi proton v do l nhng dung mi baz. Trong mi trng ca chng, nhng tnh cht axit ca cht tan c tng cng. V d, phenol c hng s phn li trong nc khong 1010 tr thnh axit mnh trong etileniamin v c th chun c bng dung dch kim chun. Cng baz trong cc dung mi loi th ngc li, b gim xung. Nc v ru no mch thng nh metanol v etanol c dng lm v d cho nhng dung mi lng tnh trung tnh. Nhng dung mi ny c kh nng cho v nhn proton km nht so vi nhng dung mi cng loi xt trn. Nhng iu quan trng cn nh l, iu khng c ngha l tnh axit v tnh baz ca chng chnh xc bng nhau. nh hng ca hng s in mi ln tnh cht ca cht tan: Hng s in mi c trng cho kh nng tch cc ht mang in tch tri du. Trong dung mi c hng s in mi cao, v d trong nc ( DH2O = 78,5 ), ch i hi cng ti thiu tch cc ion mang in tch dng v m, cn i vi cc dung mi c hng s in mi thp, v d axit axetic (DHOAx = 6,2), mun thc hin qu trnh tch cn tiu ph nng lng ln. Metanol v etanol c hng s in mi tng ng l 33 v 24, theo tnh cht ca mnh chng chim v tr trung gian. Gi tr hng s in mi ca mt s dung mi c dn ra bng 12.1. Hng s in mi ca dung mi c th hin nh hng ln n cng axit hoc baz ha tan, bi v do kt qu ca qu trnh phn li, nhng ion tch in tri du c to thnh. V d nh, nu axit yu khng tch in HA ha tan trong dung mi lng tnh SH, qu trnh phn li i hi sinh ra nhng ht tch in. HA + SH SH2+ + A Mt qu trnh tng t cng c quan st thy khi ha tan baz khng tch in B: B + SH BH+ + S Do , c th hy vng rng, trong cc dung mi nh vy, ging nh trong nc, nhng phn ng tng t s chuyn dch v bn phi mc ln hn so vi trong cc dung mi nh metanol v etanol, bi v xy ra phn ng phn li ch i hi mt cng nh. Hiu ng c th rt d nhn thy; v d nh, hng s phn li ca axit axetic trong nc khong 105,

cn trong etanol nh hn, khong 1010. Cng ca nhng axit tng t khc cng gim xung nh vy. Nu phn ng phn li khng bao hm giai on sinh ra in tch th cng axit hoc baz t ph thuc vo hng s in mi ca dung mi. V d, s bin i hng s in mi ca dung mi SH s khng nh hng n cn bng: BH+ + SH A + SH SH2+ + B HA + S

La chn dung mi lng tnh chun axit - baz: hon ton ca phn ng axit baz t l thun vi gi tr hng s phn li ca axit hoc baz ha tan v t l ngc vi hng s proton phn ca dung mi. Ngoi ra, hng s phn li ph thuc vo tnh axit hoc tnh baz v hng s in mi ca dung mi. Nh vy l, la chn thnh cng dung mi cho mt php chun cn ch 3 yu t c lp. 1. Hng s proton phn ca dung mi. Sao cho i lng ny cng nh cng tt. 2. Tnh cht axit - baz ca dung mi. chun baz yu, dung mi c tnh cht cho proton (ngha l dung mi axit) l thch hp. chun axit yu cn chn dung mi c tnh cht nhn proton tt. 3. Hng s in mi ca dung mi. Tt nht l s dng dung mi c hng s in mi cao. Ngoi ra, dung mi la chn phi ha tan tt cht cn phn tch. chun baz rt yu, nn chn axit axetic bng lm dung mi, bi v axit ny c kh nng cho proton v lm tng cng baz ha tan. Hng s proton phn ca axit cng cn thch hp (3,6.1015), thp hn ca nc mt cht. Nhng c lp vi nhng u th trn, axit axetic li c hng s in mi thp. Hai u im quan trng hn mt nhc im nn axit axetic l dung mi tt nht chun baz yu; nhng khi chun axit yu, axit axetic li thua nc bi v c tnh cht nhn proton yu hn. Xem xt kh nng s dng axit focmic lm dung mi axit. Tng t nh dung mi axit axetic, nhng axit focmic c kh nng cho proton mnh hn nc. Ngoi ra, khc vi axit axetic, axit focmic c hng s in mi gn vi nc. Phn xt theo hai tnh cht th axit focmic dng nh s l dung mi l tng cho chun baz yu. Nhng ng tic l, hng s proton phn ca axit focmic li ln hn nhiu so vi nc hoc axit axetic. Do , mc d c hai phm cht rt tt, axit focmic ch c u th cc tiu so vi nc. Metanol v etanol c s dng rng ri lm dung mi chun axit - baz. C hai thuc loi dung mi trung tnh bi v theo tnh cht cho nhn proton, chng rt gn vi nc. u th ca chng so vi nc l tnh cht, chng u c hng s proton phn thp hn. Nhng hng s in mi thp ca c hai dung mi ny lm mt i u th ni trn ca chng. V d, hng s phn li ca phn ln nhng axit khng mang in tch, nh axit

benzoic, trong etanol gim xung hu nh 10 ln so vi trong nc, nhng hng s proton phn li hu nh bng s ln nh vy (8.106) thp hn so vi nc. Do t s K 'a /KS i vi etanol ch cao ln khng ng k so vi nc nn u th trong xc nh im cui khi s dng dung mi rt khim tn. Ngc li, php chun axit tch in, nh ion amoni, trong etanol li mang li ch ln. Trong trng hp ny, trong qu trnh phn li khng xy ra giai on phn chia in tch.
+ + C2H5OH NH4 + NH3 + C2H5 OH2

+ Khc vi s phn li ca axit benzoic, s phn li ca NH4 trong etanol gim xung khng + ng k. Phn ng ca NH4 vi baz mnh trong etanol xy ra hon ton hn so vi trong + nc bi v hng s proton phn ca etanol thp hn so vi nc. Do , php chun NH4 trong etanol c ngha. + V d sau y s minh ha iu : Tnh phn trm NH4 khng b chun im + tng ng khi chun dung dch NH4 0,20 M.

1. Bng dung dch NaOH 0,20 M trong nc. 2. Bng dung dch C2H5ONa trong etanol tuyt i. Hng s proton phn ca nc bng 1.1014, ca etanol tuyt i l 8.1020; hng s phn + li ca NH4 bng 6.1010 trong nc v 1.1010 trong etanol tuyt i. Khi chun trong nc xy ra phn ng:
+ + OH NH4

NH3 + H2O

c c trng bng hng s cn bng:

K cb =

[NH3 ]
+ NH4 OH

Ka 6.10 10 = = 6.104 K H2O 1.1014

Mt cch tng t, khi chun trong etanol:

+ + C2H5O NH4

NH3 + C2H5OH
K 'a 1.1010 = = 1,2.109 K S 8.1020

K cb =

[NH3 ]
+ NH4 C H O 2 5

Trong c hai trng hp, im tng ng, nng chung ca NH3 s l 0,10 M. Khi chun trong nc:

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+ [ NH4 ] = [OH] + ; [NH3] =0,10 [ NH4 ]

Khi chun trong etanol:

+ + [ NH4 ] = [C2H5O] ; [NH3] = 0,10 [ NH4 ] + Nu gi thit rng, im tng ng, trong c hai trng hp [ NH4 ] << [NH3] ta c:

1.

0,10 OH
2

+ 6.104 ; OH = NH4 = 1.103 mol / l

2.

0,10 OH
2

+ 1,2.109 ; OH = NH4 = 9.106 mol / l

+ NH4

Nh vy l, khi chun trong dung dch nc, im tng ng cn li khong 1% + cha phn ng, cn trong etanol tuyt i, ch cn khong 0,01% NH4 cha phn ng. s dng. nn c s proton baz yu

chun nhng axit rt yu, mt s dung mi lng tnh c Etileniamin, H2NCH2CH2NH2, c nhng tnh cht c bn, biu l r nt nht coi l dung mi lng tnh tt nht lm tng cng axit ca cht tan. Hng phn ca etileniamin khong 5.1016. imetylfocmamit HCON(CH3)2 l mt hn etileniamin, c hng s in mi bng 27 cng c s dng thnh cng.

12.1.2 Phn ng axit - baz trong dung mi aproton v dung mi hn hp

Nhng dung mi khng lng tnh c u th l khng chy ua ginh proton vi cc cht tham gia chun ; ni cch khc l, hng s proton phn ca nhng dung mi ny tin dn ti khng. Do , khi chun trong nhng dung mi ny c th t ti hon ton ca phn ng ln. Nhng cht v c c tan gii hn trong cc dung mi aproton, do ngi ta nghin cu s dng nhiu hn hp gia dung mi aproton vi cc dung mi phn cc hn. C th dn ra hn hp benzen-metanol v etilenglicol-hirocacbon lm v d. Nhng ng tic l nhng kin thc c bn v tnh cht v v tng tc ca axit v baz trong cc h nh vy cn thiu v ngho nn. Do , vn s dng cc dung mi hn hp trong cc trng hp c th c gii quyt ch bng thc nghim.

12.1.3 Pht hin im cui khi chun trong dung mi hn hp

Phng php ph bin nht pht hin im cui khi chun trong dung mi khng nc l o th ca in cc thy tinh nh hm s ca nng proton solvat ha. in cc thy tinh s c bn chi tit trong gio trnh phng php phn tch cng c. Nhiu ch th

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c ng dng khi chun trong cc dung mi nc cng thch hp trong dung mi khng nc. Tt nhin l khng th s dng tnh cht ca ch th trong mi trng nc d on tnh cht ca n trong dung mi khng nc. S hn ch trong thng bo v tnh cht ca ch th trong dung mi khng nc dn ti vic la chn ch th, trong a s trng hp, c thc hin mt cch thc nghim.

12.2 ng dng phng php chun trong dung mi khng nc

Chun axit - baz trong dung mi khng nc c ng dng gii quyt nhiu vn . Trong cc mc tip theo ca chng ny s bn lun ti nhng kh nng .

12.2.1 Chun trong axit axetic bng

Nhiu baz qu yu, khng th chun trong nc nhng c th chun d dng trong axit axetic bng. Trong dung mi ny, dung dch axit pecloric chun l axit mnh hn axit clohiric v axit sunfuric c dng lm cht chun. Trong axit axetic bng, natri axetat l baz mnh gn nh bng natri hiroxit trong nc. Do , khi cn thit c th dng dung dch natri axetat chun chun ngc. H s dn n ca cc dung dch trong axit axetic bng: Ging nh phn ln cc dung mi hu c, axit axetic c h s dn n cao hn ng k so vi nc (0,11% trn 1oC so vi 0,025% trn 1oC ca nc). Do , cn c bit ch loi b sai s do s tng nhit khi o th tch. Trong thc t, ngi ta thng phi ghi nh nhit dung dch axit pecloric trong thi gian chun ha, ghi chp nhit trong thi gian chun bng thuc th nu trn v thc hin php o th tch nhit chun ha tng ng vi phng trnh: Vhc =V[1 + 0,0011(Tch T)] (12.12)

y Tch l nhit ca thuc th trong thi gian chun ha, T l nhit trong thi gian hon thnh php phn tch, V l th tch thuc th, Vhc l th tch thuc th c hiu chun. nh hng ca nc: Trong axit axetic, nc x s nh l baz yu v tham gia cuc cnh tranh dnh proton vi dung mi. Do , s c mt ca nc lm cho s bin i pH gn im tng ng km t ngt, gy kh khn cho vic xc nh im cui trong chun axit - baz. Lng nc cho php ph thuc vo dng chun . Khi chun axit rt yu i hi phi thc t hon ton khng c nc. Ngc li, khi chun baz tng i mnh trong dung mi ang bn, hm lng nc c mt thm ch ln ti 3% (theo th tch) cng khng gy cn tr. Trong thc t, c th iu ch axit axetic bng cch s dng anhirit axetic. Nc c trong dung mi phn ng vi anhirit axetic to thnh axit axetic. Lng d anhirit axetic phi c tch ra bi v n c th cn tr php chun .

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Pht hin im cui khi chun trong axit axetic: Tm tinh th v metyl tm l hai ch th axit - baz thch hp cho php chun trong axit axetic. C hai ch th ny c s chuyn mu phc tp. V d nh mu ca metyl tm, theo mc axit ha, mu ca dung dch bin i t tm qua lc n vng. S mt mu tm ch r rng, t ti im tng ng. Mu ca metyl tm bin i khng tht r rng nh mong mun, nhng khi chun baz mnh, sai s c h thp. Khi chun nhng baz rt yu, xc nh im cui bng mt khng chnh xc, cn xc nh bng phng php in th vi in cc thy tinh (xem phng php phn tch cng c). Tiu chun ha dung dch axit pecloric: tiu chun ha dung dch axit pecloric trong axit axetic, kalibiphtalat thng c dng lm cht chun gc. Cn ch l, kalihirobiphtalat trong axit axetic l mt baz mnh, do c th s dng n tiu chun ha dung dch axit. Phn ng xy ra to thnh axit t phn li. ng dng php chun trong axit axetic: S dng axit axetic khng nc lm dung mi cho php chun nhiu hp cht v c v hu c khng th chun c trong dung mi nc. V d, bng cch chun trong axit axetic bng c th xc nh nhng mui natri nh clorua, bromua, ioua, nitrat, peclorat v sunfat. Dung dch axit pecloric chun trong axit axetic bng hoc trong ioxan khng nc c dng lm cht chun. Trong dung mi ny cng c th xc nh cc mui amoni v cc mui kim loi kim ca phn ln cc axit cacboxilic, v d nh amoni benzoat, natri salixilat, natri axetat, kali tactrat, natri xitrat. ng 1 trn hnh 12.1 l ng cong in hnh tng ng vi php chun dung dch natri axetat trong axit axetic khng nc bng dung dch axit pecloric cng trong dung mi . so snh, ng chun l thuyt (ng 2) dung dch natri axetat bng dung dch axit pecloric cng nng vi ng 1 nhng trong nc cng c dn ra trn hnh 12.1.

Hnh 12.1 Hai ng chun dung dch natri axetat 0,075 M bng dung dch HClO4 0,100 M

1. ng chun thc nghim (cht b chun v cht chun u trong axit axetic khng nc).

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2. ng chun l thuyt ca dung dch natri axetat bng dung dch HClO4 u trong nc. Axit axetic khng nc l dung mi c bit thch hp cho chun cc cht hu c c nhm chc amino hoc amid. Khc vi nc, dung mi ny thch hp cho chun trc tip phn ln cc amino axit bng cc dung dch axit chun. Nh nhn xt trong chng 11, cc amino axit tn ti ch yu dng ion lng cc l axit hoc baz khng mnh c th chun . Nhng trong axit axetic bng, s phn li ca nhm cacboxilic thc t hon ton b cn tr nn c th chun nhm amino bng axit pecloric. Trong nhiu v d dn ra trn y, dung dch natri axetat trong axit axetic c s dng lm dung dch chun trong chun ngc.

12.2.2 Chun trong dung mi baz

xc nh cc baz qu yu i vi php chun trong nc, ngi ta s dng mt s dung mi baz. Etileniamin, pyriin, imetylfocmamit, axeton, metylisobutylxeton, axetonitryl v hn hp etilenglycol v ru isopropilic (1 : 1) c dng lm cc dung mi loi . Mt s baz mnh ha tan trong cc dung mi c dng lm dung dch chun. Dung dch natri metilat trong hn hp benzen-metanol c chn lm dung dch chun chun axit yu. C th xc nh mt s phenol v c nhng axit cacboxilic yu nht bng dung dch natri aminoetilat trong etileniamin. C th dng cc dung dch baz mnh nh hiroxit tetrabutylamoni (C4H9)4NOH trong hn hp benzen-metanol, isopropanol, hoc etanol lm dung dch baz chun thch hp cho chun khng nc. Trong cc dung mi baz c th d dng xc nh phn ln cc axit cacboxilic cng nh nhiu phenol. Khi chun mt s mui ca cc baz yu, v d nh, mui amoni, mui ca cc amin bo v thm trong etileniamin hoc imetylfocmamit, bc nhy c quan st thy rt r rng. Trong cc dung mi c tnh baz mnh hn, c th chun c mt s ru v imid.

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Hnh 12.2 Chun hn hp axit trong metylisobutylxeton

Trn hnh 12.2 dn ra ng chun thc nghim hn hp axit trong metylisobutylxeton bng dung dch chun hiroxit ca tetrabutylamoni trong ru isopropilic 0,2 M. Trn trc tung l th ca in cc thy tinh bin i tuyn tnh theo s bin i ca pH. R rn l, trong dung mi ny, axit pecloric mnh hn axit hirocloric rt nhiu, do im cui ca mi php chun c xc nh ring bit. Ta cng nhn thy rng, phenol l mt axit qu yu i vi php chun trong nc nhng trn ng chun trong mi trng khng nc, bc nhy c th hin r rt.

12.2.3 Chun trong dung mi aproton hoc trung tnh

Nhng dung mi aproton rt t c s dng chun bi v thuc th v cht b chun t tan trong cc dung mi ny. Nhng chng thng c s dng trong hn hp vi cc dung mi trung tnh khc. V d, hn hp (1 : 1) ca etylenglycol hoc propilenglycol vi hirocacbon hocc dn xut halogen ca hirocacbon l nhng dung mi tuyt vi i vi mui kim loi kim ca cc axit hu c. chun cc mui , ngi ta s dng dung dch axit pecloric cng trong cc dung mi trn lm dung dch chun . Cng c th chun cc axit yu trong metanol v etanol.