1

Chng 9. Chun kt ta Lm Ngc Th

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

T kho: C s ha hc phn tch, Chun kt ta, Chun , ng chun hn hp, Cht ch th ha hc.

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 9 Chun kt ta ........................................................................................... 2 9.1 9.2 9.3 9.4 9.5 ng chun kt ta ......................................................................................... 2 ngha ca ch s khi tnh ng chun ........................................................ 4 Nhng yu t nh hng n tnh r rng ca im cui..................................... 4 ng chun hn hp....................................................................................... 7 Nhng cht ch th ha hc ca phng php chun kt ta ......................... 10

Chng 9 Chun kt ta
Nhng phng php chun da trn s to thnh mui bc t tan l nhng phng php phn tch c bit t lu. Cho n by gi, nhng phng php vn thng c s dng xc nh bc v nhng ion nh clorua, bromua, ioua v tioxianat. ng dng nhng phng php chun kt ta trong cht chun khng phi l mui bc m l nhng hp cht khc cn tng i hn ch.

9.1 ng chun kt ta
Trc khi nghin cu chng ny, sinh vin cn n li nhng lun im c s v tan ca kt ta chng 5. ng chun c ch cho vic la chn ch th v c php tnh sai s trong chun . V d sau y s ch r cch xy dng ng chun kt ta xut pht t tch s tan ca kt ta to thnh. V d: Hy dng ng chun 50 ml dung dch KBr 0,005 M bng dung dch AgNO3 0,010 M. Chng ta tnh pBr v pAg mc d thng ch cn tnh mt trong 2 i lng y l (la chn i lng no l do nh hng ca cc ion n tnh cht ca ch th quyt nh). im u: u php chun chng ta c dung dch Br 0,00500 M, Ag+ cha c. Do pBr = log(5,00.103) = 2,30; gi tr pAg khng xc nh c. im sau khi thm 5 ml thuc th: Nng ion bromua trong trng hp ny h thp do kt ta c to thnh v do c s pha long dung dch. Do :
CNaBr = 50,00 0,005 5,00 0,010 = 3,64.103 M 50,00 + 5,00

Thnh phn u t s l lng milimol NaBr ban u, thnh phn th 2 l lng milimol AgNO3 thm vo. Ion bromua tn ti trong dung dch do phn NaBr cha b chun v do tan ca AgBr, do nng chung ca Br ln hn nng NaBr cha b chun mt lng bng tan ca kt ta, ngha l: [Br] = 3,64.103 + [Ag+]

S hng th 2 trong tng s phn nh s ng gp ca AgBr vo nng Br, m mi ion Br c to thnh t mt ion Ag+. Nu nng NaBr khng qu nh th c th b qua s hng th 2, ngha l nu: [Ag+] << 3,64.103 ion.g/l th [Br] 3,64.103 ion.g/l pBr = log(3,64.103) = 2,439 = 2,44 C th tnh i lng pAg mt cch thun tin khi s dng logarit m din t tch s tan ca AgBr: log([Ag+][Br]) = logT = log(5,2.1013); log[Ag+] log[Br] = logT = 12,28 hoc pAg + pBr = pT =12,28 pAg = 12,28 2,44 = 9,84 C th tnh mt cch tng t nng Br v Ag+ cc im khc ca ng chun cho n im tng ng. im tng ng: im ny khng c d c AgNO3 v NaBr, do : [Ag+] = [Br] Thc hin nhng php thay th tng ng trong phng trnh tch s tan chng ta c: [Ag+] = [Br] = 5,2.1013 = 7,21.107 mol/l pAg = pBr = log(7,21.107) = 6,14 im sau khi thm 25,10 ml thuc th: Trong dung dch c d AgNO3, do :
CAgNO3 = 25,10 0,010 50,00 0,005 = 1,33.105 M 75,10

v [Ag+] = 1,33.105 + [Br] 1,33.105 ion.g/l

Thnh phn th 2 bn phi phn nh lng ion Ag i vo dung dch do tan ca AgBr, thng c th b qua i lng : pAg = log(1,33.105) = 4,876 = 4,88 pBr= 12,28 4,88 = 7,40 Nhng im b sung xy dng ng chun sau im tng ng c th thu c bng cch tng t.

9.2 ngha ca ch s khi tnh ng chun

Tnh ng chun gn im tng ng thng khng c chnh xc cao bi v n da trn c s s dng hiu s hai s ln gn nhau v gi tr. V d, khi tnh nng AgNO3 sau khi thm 25,10 ml dung dch AgNO3 0,010 M; t s trong cng thc tnh (0,2510 0,2500) ch cha 2 ch s c ngha. Do , nng AgNO3 trong trng hp tt nht cng ch c th tnh vi chnh xc n 2 ch s c ngha. Hn na lm gim sai s khi lm trn, chng ta kim tra php tnh vi chnh xc n 3 s l v lm trn sau khi tnh pAg. Khi lm trn hm s p, cn nh rng (chng 2) logarit gm c phn c tnh (nhng ch s bn tri du phy ngn cch vi s l thp phn) v phn nh tr; phn c tnh c din t ch bng s s nguyn trong gi tr ly logarit. Do ch c th lm trn phn nh tr n s tng ng ca ch s c ngha. Trong v d c phn tch trn y, cc im ca ng chun tch bit khi bc nhy chun . Chng ta c kh nng tnh bc nhy vi chnh xc cao. Chng ta c th a ra pAg im u bng 2,301, nhng chnh xc t c ngha bi v, trc ht chng ta quan tm n vng gn im tng ng. Do , y cng nh khi xy dng cc ng chun khc, chng ta s lm trn hm s p n 2 s sau du phy. chnh xc khng cao cng hon ton tha mn bi v iu quan trng cn bit l s bin i ca hm s p ch khng phi l gi tr tuyt i ca n. Nhng bin i ln v t ph thuc vo sai s trong php tnh.

9.3 Nhng yu t nh hng n tnh r rng ca im cui

c s r rng v do d dng xc nh c im cui ca php chun, iu cn thit nht cn bit l gn im tng ng ch cn thm mt lng nh cht chun cng lm cho hm s p bin i r rt. Do , cn thit phi xt nhng yu t nh hng n gi tr bc nhy ca hm s p trong qu trnh chun . Nng thuc th: bng 9.1 dn ra nhng kt qu tnh theo phng php c phn tch trong v d dn ra trn y. Tnh ton c tin hnh i vi 3 nng ion bromua v ion bc khc nhau 10 ln. Nhng kt qu tnh ton pAg i vi c 3 trng hp c din t trn hnh 9.1, minh ha r rng nh hng ca nng n ng chun . Khi tng nng

cht cn chun v cht chun, s bin i pAg vng gn im tng ng tr nn r hn. 1. Chun dung dch Br 0,0500 M bng dung dch Ag+ 0,100 M. 2. Chun dung dch Br 0,00500 M bng dung dch Ag+ 0,0100 M. 3. Chun dung dch Br 0,000500 M bng dung dch Ag+ 0,00100 M. Hin tng tng t cng c quan st thy nu thay th pAg trn trc tung bng pBr.

Hnh 9.1 nh hng ca nng thuc th n ng chun 25,0 ml dung dch NaBr

Bng 9.1 S bin i pAg v pBr trong qu trnh chun nhng dung dch c nng

khc nhau Chun 25,0 ml Br 0,0500 M bng AgNO3 0,100 M pAg 0,00 10,00 20,00 23,00 24,90 10,68 10,13 9,72 8,41 pBr 1,30 1,60 2,15 2,56, 3,87 Chun 25,0 ml Br 0,00500 M bng AgNO3 0,010 M pAg 9,68 9,13 8,72 7,41 pBr 2,30 2,60 3,15 3,56 4,87 Chun 25,0 ml Br 0,00500 M bng AgNO3 0,001 M pAg 8,68 8,13 7,72 6,50 pBr 3,30 3,60 4,15 4,56 5,78a

Th tch AgNO3 (ml)

24,95 25,00 25,05 25,10 27,00 30,00

a b

8,10 6,14 4,18 3,88 2,58 2,20

4,18 6,14 8,10 8,40 9,70 10,08

7,10 6,14 5,18 4,88 3,58 3,20

5,18 6,14 7,10 7,40 8,70 9,08

6,33 6,14 5,95 5,78 4,58 4,20

5,95a 6,14 6,33b 6,50b 7,70 8,08

Trong trng hp ny gi thit [Ag+] <<CNaBr khng ng Trong trng hp ny gi thit [Br] << C AgNO3 khng ng

Hiu ng c ngha thc t khi chun ion bromua. Nu nng bromua ln s dng dung dch bc nitrat 0,100 M th im cui c xc nh d dng v sai s chun s cc tiu. Ngc li, i vi cc dung dch c nng 0,001 M, s bin i pAg hoc pBr nh n mc l, kh khn xc nh im cui. Trong trng hp sai s chun phi ln. Nng thuc th nh hng tng t n bc nhy ca php chun theo cc loi phn ng khc. xy ra hon ton ca phn ng: Hnh 9.2 minh ha nh hng ca tan ca sn phm phn ng n ng chun khi dng dung dch AgNO3 0,1 M lm cht chun. R rng l s bin i pAg ln nht c quan st thy khi chun ion ioua. Ion ioua to hp cht vi bc t tan nht so vi tt c cc anion ang nghin cu. iu m bo phn ng xy ra hon ton nht. Bc nhy km t ngt nht c quan st thy phn ng xy ra km hon ton nht ngha l php chun ion bromat. Bc nhy trn ng chun theo phn ng m sn phm l hp cht ca bc c tan trung gian, cng s c gi tr trung gian. Mt ln na, chng ta nhn xt rng, nh hng l c trng i vi ng chun theo cc loi phn ng khc.

Hnh 9.2 nh hng ca hon ton ca phn ng xy ra n ng chun 25,0 ml dung dch anion 0,050 M bng dung dch AgNO3 0,100 M

9.4 ng chun hn hp
Nhng phng php c xt trong mc trc c th m rng cho hn hp ion to vi cht chun nhng kt ta c tan khc nhau. Chng ta xt php chun 50,0 ml dung dch cha 0,080 M ioua v 0,100 M clorua bng dung dch bc nitrat 0,200 M. V bc ioua t tan hn nhiu so vi bc clorua nn khi thm cht chun vo, u php chun ch ring bc ioua to thnh. ng chun s tng t ng chun ioua c m t trn hnh 9.2. Cn c bit ch n vic thit lp gii hn m , kt ta bc ioua xy ra khi s to thnh bc clorua khng ng k. Khi xut hin nhng phn u tin ca kt ta bc clorua th tch s tan ca c 2 kt ta t c. Chia h thc ny cho h thc kia, ta c:
[I ] [Cl ]

8,3.1017 1,82.10
10

= 4,56.107

[I] = 4,56.107.[Cl]

v thu c h thc [I] = 4,56.107.[Cl] R rng l trc khi kt ta bc clorua xut hin, nng ca ion ioua phi h thp n gi tr ch bng mt phn rt nh nng ion clorua. Ni mt cch khc, bc clorua khng c to thnh gn nh n chnh im tng ng ca ion ioua hoc cho ti khi thm khong 20 ml cht chun. Trong trng hp ny nng ion clorua c k ti c s pha long bng khong:
CCl [Cl ] = 50,0 0,100 = 0,0714 mol/l 70,0

v [I] = 4,56.107.0,0714 = 3,26.108 mol/l Phn trm ioua khng kt ta im c th tnh nh sau: Lng milimol ban u ca I = 50,0.0,080 = 4,00 % I khng kt ta =
3,26.108 70,0 100 = 5,7.105 4,0

Nh vy l cho n khi nng ioua cha b chun bng khong 6.105% lng ban u, bc clorua vn cha to thnh nn ng chun phi tng t ng chun mt mnh ioua. Xut pht t , na u ca ng chun c dn ra bng ng m nt trn hnh 9.3. Ngay khi kt ta AgCl bt u xut hin, s gim nhanh chng pAg t ngt dng li. Thun tin nht l tnh pAg t tch s tan ca bc clorua: [Cl] 0,0714
Ag + = 1,82.10 0,0714
10

= 2,55.109 mol/l

pAg = log(2,55.109) = 8,59 Tip tc thm bc nitrat s lm gim nng ion clorua v ng cong chuyn thnh ng cong c trng cho php chun mt mnh clorua. V d, sau khi thm 25,00 ml cht chun:
CCl [Cl ] = 50,0 0,10 + 50,0 0,080 25,0 0,200 75,0

Hai s hng u tin t s l s milimol ca clorua v ioua tng ng, cn s hng th 3 l s milimol cht chun thm vo. Nh vy: [Cl] = 0,0533
[Ag + ] = 1,82.1010 = 3,41.109 mol / l 0,0533

pAg = 8,47 C th tnh phn cn li ca ng cong nh trng hp chun mt mnh clorua.

Hnh 9.3 Nhng ng chun 50 ml dung dch cha 0,100 M Cl v 0,0800 M Br hoc I

Hnh 9.3 ch r rng, ng chun hn hp l lin hp hai ng chun ring bit. Trn ng cong ta thy hai bc nhy chun . C th hy vng rng, s bin i pAg gn im tng ng th nht s cng nh nu tan ca hai kt ta cng gn nhau. Hin tng c quan st thy khi chun hn hp cc ion clorua v bromua. iu c thy r rng trn hnh v. Trong trng hp ny gi tr pAg u php chun s thp hn bi v tan ca bc bromua cao hn tan ca bc ioua. Sau im tng ng, hai ng cong trng nhau. Nhng ng cong thc nghim tng t c din t trn hnh 9.3 c th thu c bng cch o th ca in cc bc nhng vo dung dch. Bng phng php c th xc nh nhng cu t ring bit trong hn hp.

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9.5 Nhng cht ch th ha hc ca phng php chun kt ta

Tc dng ca cht ch th ha hc thng da trn s xc nh bng mt s bin i mu hoc c ca dung dch. Cht ch th phn ng la chn hoc l vi cht chun hoc l vi cht cn chun hoc l vi sn phm ca phn ng chun . V d, khi chun cht A bng thuc th B vi cht ch th (In) c kh nng phn ng vi B, cc phn ng c th xy ra nh sau: A+B In + B AB InB

Tt nhin l tnh cht ca InB cn thit phi khc bit ng k vi tnh cht ca In. Ngoi ra mt phi nhn bit c mt lng InB nh n mc l sau khi to thnh InB, s tiu tn B khng nhn thy c v cui cng hng s cn bng ca phn ng vi s tham gia ca ch th cn phi c mt gi tr nh th no gn im tng ng, khi [B] (hoc pB) bin i s xy ra s bin i t ngt [InB]/[In]. iu kin cui cng d thc hin nht khi pB bin i ln. Chng ta xt s chun 3 dung dch (bng 9.1 v hnh 9.1) vi cht ch th bin i hon ton mu trong vng pAg = 7 5 lm v d. R rng l chim vng pAg nu, trong mi trng hp i hi mt th tch cht chun khc nhau. Nh, t nhng d kin ca h chun ct th 2 bng 9.1, r rng l ch cn t hn 0,10 ml dung dch AgNO3 0,100 M, ngha l s bin i mu bt u sau khi thm 24,95 ml cht chun v kt thc trc khi thm vo 25,05 ml. Khi c th hy vng s bin i mu t ngt v sai s chun cc tiu. Ngc li, khi chun bng dung dch AgNO3 0,001 M s bin i mu bt u khi thm vo khong 24,5 ml v khi kt thc thm vo 25,8 ml. Trong trng hp ny khng c kh nng xc nh im tng ng. Khi chun bng dung dch 0,010 M, mu bin i im cui i hi mt lng nh hn 0,2 ml mt cht, trong trng hp ny c th dng cht ch th nhng sai s xc nh im tng ng s kh ln. By gi chng ta xt, cng chnh cht ch th i vi cc trng hp ca nhng php chun c m t bng cc ng cong trn hnh 9.2, s thun tin v c hiu qu n nhng no. Khi chun cc ion bromua v ioua, ch th s v c bn di dng AgIn, do sau khi thm nhng phn bc nitrat u tin, s bin i mu khng quan st thy. V bc bromua v ioua c tan thp nn n trc im tng ng khng xy ra s to thnh mt lng ng k AgIn. Theo hnh 9.2, pAg cn thc t ln hn 7 n tn trc im tng ng khi chun bromua v thm ch sau im tng ng khi chun ioua. Trong c 2 trng hp, s d ion bc l cn thit mu bin i hon ton tng ng vi t hn 0,01 ml cht chun. Do sai s chun khng ng k. Cht ch th vi khong pAg = 5 7 khng thch hp chun clorua bi v s to thnh mt lng ng k AgIn bt u khong 1 ml trc im tng ng v tip tc cho ti khi thm vo d khong 1 ml. Trong trng hp ny khng c kh nng xc nh chnh xc im cui ca php chun . Ngc li, vi khong ch th pAg t 4 n 6 hon ton thch

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hp. Khng c ch th ha hc thch hp chun ioat v bromat bi v bc nhy chun qu nh (hnh 9.2). Nhng v d v s dng cc cht ch th chun kt ta bng ion bc c dn ra trong cc mc sau. S to thnh kt ta th 2 - phng php Mohr: S to thnh kt ta th 2 c mu khc vi mu ca hp cht kt ta l c s xc nh im cui theo phng php Mohr. Phng php Mohr c ng dng rng ri khi chun clorua v bromua bng dung dch bc nitrat chun. Ion cromat c dng lm ch th, im cui php chun xut hin kt ta bc cromat Ag2CrO4 mu gch. tan ca bc cromat cao hn nhiu tan ca bc halogenua. Do , khi chun theo phng php Mohr, bc cromat cha c to thnh khi thc t tt c halogenua cha kt ta ht. iu chnh nng cromat c th ngn nga s to thnh bc cromat cho ti khi nng ion bc cha t ti nng tnh ton l thuyt i vi vng im tng ng khi chun halogen. V d: Sai s 0,1% tng ng vi 0,025 ml i vi th tch 25 ml cht chun. Nng ion bc c tnh ton nh chng 5 bng 4,78.106 mol/l sau khi thm 24,975 ml dung dch Ag+ 0,100 M v bng 3,81.105 mol/l sau khi thm 25,025 ml cng dung dch vo dung dch Cl 0,05 M. C th thay i nng ion cromat cn thit to thnh Ag2CrO4 trong khong no chun qu hoc chun cha ti khng ln hn 0,025 ml. Khi thm 24,975 ml cht chun, kt ta Ag2CrO4 c th xy ra nu: [ CrO2 ][Ag+]2 T 4 Nu:
12 CrO2 = T > 1,1.10 = 0,048 mol / l 4 [Ag]2 (4,78.106 )2

v khi thm 25,025 ml cht chun, nu:

12 CrO2 1,1.10 = 7,6.104 mol / l 4 5 2 (3,81.10 )

Nhng tnh ton ch r rng, chun chnh xc theo phng php Mohr, c th gi nng cht ch th trong mt khong kh rng, gia 0,0008 v 0,05 M. Nhng trong thc t nng ln hn 0,005 M mu vng m ca ion cromat s cn tr mu ca bc cromat. Ngi ta thng s dng nng cromat nh hn 0,005 M mt cht. Khng th tnh ton lng ti thiu cromat cn phi c to thnh m mt c th nhn bit m ch xc nh c bng thc nghim. Trc khi pht hin mu ca bc cromat, dung dch b chun qu trung bnh 0,05 ml dung dch 0,1 M. Ch sai s trong sai s kt qu ca php chun , nn trong thi gian phn tch ngi ta thng lm th nghim trng. t mc ch ngi ta xc nh s tiu tn ion bc cho mt th tch nh vy huyn ph canxi

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cacbonat khng cha ion clo vi chnh cht ch th . Dung dch v kt ta thu c sau php chun trng c dng lm chun rt thun tin chun lp li. Php chun ha dung dch bc nitrat bng cch chun natri clorua tinh khit theo phng php Mohr l mt bin php khc lm gim i ng k sai s ch th. Xc nh "nng ng lng chun " nh vy s khng nhng gip tnh ton s tiu tn qu dung dch chun m cn cn nhc c nhng kh nng khc xc nh s i mu ca nh phn tch. Cn ch n axit ca mi trng bi v khi tng nng ion hiro, cn bng:
2CrO2 + 2H 4
+

2 Cr2O7

+ H2O

s chuyn dch v bn phi. tan ca icromat bc cao hn kh nhiu tan ca cromat bc, do i vi phn ng ch th trong mi trng axit i hi nng ion bc ln ng k nu phn ng ni chung c th xy ra. Trong mi trng kim c th lng xung oxit bc: 2Ag+ + 2OH 2AgOH(rn) Ag2O(rn, en) + H2O

Nh vy, php xc nh clorua theo phng php Mohr cn phi c tin hnh trong mi trng trung tnh hoc gn trung tnh (pH = 7 10). C th gi nng ion hiro trong khong mt cch thun tin bng cch thm vo natri bicacbonat, canxi cacbonat hoc natri tetraborat. S to thnh phc mu - phng php Volhard: chun bc theo phng php Volhard c th s dng dung dch tioxianat chun: Ag+ + SCN AgSCN(rn)

Ion st (III) lm cho dung dch c mu khi thm nhng git dung dch tioxianat d u tin c dng lm ch th: Fe3+ + SCN Fe(SCN)2+

Php chun cn c thc hin trong mi trng axit ngn nga s kt ta st (III) di dng hiroxit. C th d dng tnh c nng ch th m sai s chun tin ti khng nh s c ch r trong v d sau y. V d: Bng thc nghim ngi quan st c th pht hin mu Fe(SCN)2+ nng trung bnh l 6,4.106 M. Cn to ra nng Fe3+ bng bao nhiu khi chun 50 ml dung dch Ag+ 0,050 M bng dung dch KSCN 0,100 M, sai s chun tin ti khng? sai s chun bng khng, mu ca Fe(SCN)2+ cn phi xut hin nng Ag+, cn trong dung dch bng nng tng cng ca tioxianat: [Ag+] = [SCN] + [Fe(SCN)2+] = [SCN] + 6,4.106 hoc:

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T [SCN ]

1,1.1012 [SCN ]

= [SCN ] + 6,4.106

Bin i: [SCN]2 + 6,4.106 [SCN] 1,1.1012 = 0 [SCN] = 1,7.107 ion.g/l Hng s bn ca Fe(SCN)2+:
K = 1,4.102 = [Fe(SCN)2+ ] [Fe3+ ][SCN ]

By gi chng ta thay th nng [SCN] bo m to thnh mt lng Fe(SCN)2+ nhn bit bng mt im tng ng vo phng trnh hng s bn:
1,4.102 = 6,4.106 [Fe3+ ] 1,7.107

[Fe3+] = 0,27 mol/l Khi chun theo phng php Volhard, nng khng bt buc phi cht ch. Tht vy, nhng tnh ton tng t nh va c tin hnh ch r rng nng st (III) trong khong 0,002 1,6 mol/l mt cch l thuyt, sai s s khng vt qu 0,1%. Trong thc t ngi ta cng pht hin rng, nng vt qu 0,2 mol/l, mu ring ca cht ch th gy tr ngi cho s pht hin phc tioxianat. Do ngi ta to ra nng st (III) thp hn (thng l khong 0,01 mol/l). ng dng phng php Volhard xc nh ion clorua: Thng ngi ta ng dng phng php Volhard xc nh gin tip clorua. Thm vo mu clorua d mt lng xc nh dung dch bc nitrat chun v lng d ion bc c xc nh bng php chun ngc bng dung dch tioxianat chun. u th c bit ca phng php Volhard trc cc phng php xc nh clorua khc l kh nng chun trong mi trng axit mnh bi v nhng ion nh cacbonat, oxalat v asenat (to mui bc t tan trong mi trng trung tnh) khng cn tr. Khc vi cc halogenua bc khc, bc clorua tan nhiu hn bc tioxianat. Do phn ng: AgCl(rn) + SCN AgSCN(rn) + Cl (8.1)

gy tr ngi cho s pht hin im cui php chun theo Volhard. V vy ta quan st thy s tiu tn qu mc ion tioxianat v xut hin sai s phn tch m. Gi tr sai s ph thuc vo nng cht ch th.

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trnh sai s lin quan vi phn ng gia tioxianat v bc clorua ngi ta s dng ch yu hai bin php. Bin php th nht l to ra nng cht ch th cc i c php (khong 0,2 M st (III)). Bin php th hai ph bin hn l tch kt ta bc clorua trc khi chun ngc bng dung dch tioxianat. Php chun mt phn nc lc sau khi lc bc clorua cho kt qu tt nht trong iu kin kt ta ng t tt. S tiu tn thi gian cho php lc tt nhin l nhc im ca phng php ny. Dng nh phng php c ng dng rng ri nht l phng php Caldwell v Moyer. Theo phng php ny, ngi ta ph ln kt ta bc clorua mt lp nitrobenzen ngn nga n tip xc vi dung dch. C lp kt ta bng cch lc hn hp vi mt vi mililit nitrobenzen trc khi chun ngc. Cht ch th hp ph: Cht ch th hp ph l nhng cht hu c b kt ta hp ph hoc c gii hp t b mt kt ta c to thnh trong qu trnh chun . Trong trng hp l tng, s hp ph hoc gii hp c quan st thy gn im tong ng v km theo khng ch s bin i mu ca dung dch m cn c s to thnh hp cht mu trn b mt kt ta. Phng php da trn s s dng cht ch th hp ph i khi c ngi ta gi l phng php Fajans k nim nh bc hc cng hin nhiu cho s pht trin phng php ny. Cht mu hu c fluoretxein c dng khi chun ion clorua bng nitrat bc l mt cht ch th hp ph in hnh. Trong dung dch nc, fluretxein phn li mt phn thnh ion hiro v ion fluoretxeinat tch in m, lm cho dung dch c mu vng lc. Ion fluoretxeinat to mui bc c mu m t tan. Nhng khi s dng cht mu lm ch th, nng ca n khng bao gi t tch s tan ca fluoretxeinat bc. u php chun clorua bng cc ion bc theo phng php Fajans, cc anion cht mu hu nh khng b kt ta hp ph. Thc t chng y b mt kt ta tch in m do hp ph cc ion clorua. Sau im tng ng, nhng ht kt ta mang in tch dng do s hp ph mnh cc ion bc d; trong nhng iu kin ion fluoretxeinat i vo lp ion i. V vy, trn b mt kt ta xut hin mu c trng cho fluoretxeinat bc. Cn nhn mnh rng, s bin i mu xy ra do qu trnh hp ph (ch khng phi do qu trnh kt ta), bi v tch s tan ca fluoretxeinat bc khng t c trong thi gian chun . S hp ph l thun nghch: cht mu b gii hp khi chun ngc bng ion clorua. ng dng thnh cng cht ch th hp ph th cht kt ta v ch th cn c nhng tnh cht sau: 1. Nhng ht kt ta phi c c kch thc ca ht keo bi v b mt ca kt ta pht trin mnh, hp ph c lng ln cht ch th. 2. Kt ta phi hp ph bn cc ion ring bit. Chng ta thy (chng 7) tnh cht l c trng i vi kt ta keo. 3. Cht mu dng lm cht ch th cn phi c gi chc trong lp ion i bao quanh nhng ion b hp ph u tin. Ni chung s hp ph loi c quyt nh bi tan thp ca mui to thnh gia cht mu vi cc ion ca mng li tinh th. ng thi nhng hp cht phi c tan ln khng xy ra s kt ta chng.

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4. pH ca dung dch cn phi c gi mc xc nh. Ion dng lm dng hot ng ca phn ln cc cht ch th hp ph l axit hoc baz lin hp vi phn t cht mu nn c kh nng lin kt vi ion hiro hoc ion hiroxil to thnh phn t ban u khng hot ng. Do , ngi ta to ra gi tr pH no m dng ion ca cht ch th chim u th. Php chun vi cht ch th hp ph nhanh, chnh xc, ng tin cy nhng ng dng ca n tng i b hn ch bi s t phn ng kt ta c kt ta v nh hnh c to thnh nhanh chng. Khi c mt cht in li nng cao, im cui ca php chun vi cht ch th hp ph tr nn km r rng do s ng t kt ta lm gim b mt trn xy ra qu trnh hp ph. Phn ln cc cht ch th hp ph l axit yu, do lnh vc ng dng ca chng b gii hn trong cc dung dch trung tnh hoc axit yu v cht ch th ch yu tn ti dng anion. Ngi ta bit mt s ch th hp ph cation chun trong cc dung dch axit mnh. Vi nhng cht ch th , s hp ph cht mu v s nhum mu kt ta c quan st thy khi c d anion kt ta, ngha l khi cc ht mang in tch m.
Bng 9.2 Nhng phng php kt ta o bc in hnh

Cu t cn xc nh AsO43, Br, I, CNO, SCN CO32, CrO42, CN, Cl, C2O42, PO43, S2

Phng php xc nh im cui Phng php Volhard

Ghi ch Khng cn tch mui bc Trc khi chun ngc lng Ag+ d, cn tch mui bc Chun tip theo lng Ag+ d trong phn ng: BH4 + 8Ag+ + 8OH 8Ag(rn) + H2BO3 + 5H2O

Phng php Volhard

BH4

Phng php Volhard bin dng

Epoxit

Phng php Volhard

Chun lng Cl d sau khi ch ha bng hiro clorua Kt ta K+ bng lng d B(C6H5)4 bit, thm d Ag+ to kt ta AgB(C6H5)4 v chun ngc Ag+ d

K+

Phng php Volhard bin dng Phng php Mohr Ch th hp ph Phng php phn tch

Br, Cl Br, Cl, I, SeO32 V(OH)4+, cc axit

Chun trc tip bng dung dch

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bo, cc mecaptan Zn
2+

in ha Phng php Volhard bin dng Phng php Volhard bin dng

Ag

Kt ta di dng ZnHg(SCN)4. Lc v ha tan trong axit, thm d Ag+; chun ngc Ag+ d Kt ta di dng PbClF. Lc ha tan trong axit thm d Ag+; chun ngc Ag+ d

Cui cng, cn ch mt s cht ch th hp ph phn ng vi kt ta cha bc c tnh cht nhy sng gy tr ngi khi lm vic vi chng. Nhng phng php khc xc nh im cui: Trong gio trnh cc phng php phn tch cng c c m t nhng phng php in ha pht hin im cui trong mt s phng php chun kt ta. ng dng ca phng php chun kt ta: Trong phn ln trng hp, php chun kt ta da trn s s dng dung dch bc nitrat chun, i khi phng php ny gi l phng php o bc. bng 9.2 dn ra nhng v d in hnh v ng dng phng php o bc. Chng ta nhn thy rng, nhiu phng php xc nh trong nhng php xc nh nu da trn php kt ta cu t cn xc nh bng mt lng d chnh xc dung dch bc nitrat v chun tip theo bng dung dch kali tioxianat chun theo Volhard. C hai thuc th c th dng c di dng cht chun u nhng kali tioxianat ht m mt cht gy kh khn cho php cn m cao. Nhng dung dch bc nitrat v kali tioxianat bn trong thi gian lu khng gii hn. Bng 9.3 lit k nhng phng php chun khc dng cc thuc th khc thay th cho mui bc.
Bng 9.3 Nhng phng php chun kt ta khc

Cht chun K4[Fe(CN)6] Pb(NO3)2

Ion cn xc nh Zn2+ SO42 MoO42

Sn phm phn ng K2Zn3[Fe(CN)6]2 PbSO4 PbMoO4 Pb3(PO4)2 PbC2O4 ThF4 Hg2X2

Cht ch th iphenylamin Eritrozin B Eosin E ibromfluoretxein Fluoretxein Alizarin Bromophenol chm

Pb(CH3COO)2

PO43 C2O42

Th(NO3)4 Hg2(NO3)2

F Cl, Br

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NaCl

Hg22+

Hg2X2

Bromophenol chm