TTHC

MC LC CHNG I: I.1. I.2. I.3. I.4. I.5. II.1. II.2. II.3. II.4. II.5. II.6. II.7. II.8. II.9.
PHN LOI THUC TH HU C ...................................................... 8 S BT HP L CA CCH PHN LOI TRONG HO HU C .................. 8 PHN LOI THEO PHN NG PHN TCH M THUC TH THAM GIA ... 9 PHN LOI THEO YOE.........................................................................................10 PHN LOI THEO FEIGL......................................................................................10 PHN LOI THEO WELCHER..............................................................................10 L THUYT V LIN KT PHI TR ................................................. 13 LIN KT HAI IN T ........................................................................................13 NGUYN T HU HIU .......................................................................................15 CU TO IN T CA NGUYN T ..............................................................16 PHNG PHP LIN KT HA TR (VB).........................................................19 L THUYT V TRNG TINH TH .................................................................19 THUYT QU O PHN T (MO)..................................................................... 30 HNH DNG HNH HC CA CC HP CHT PHI TR............................... 37 CNG TRNG PHI T ...........................................................................41 CU TRC PHN T V TAN......................................................................41
CHNG II:
II.10. PHC CHELATE (VNG CNG) ......................................................................... 42 II.11. S N NG KHNG GIAN V CHN LC................................................42 II.12. BN CA HP CHT PHI TR ....................................................................43 II.13. NG HC CA PHN NG TRONG THUC TH HU C. .....................44 CHNG III: NHM CHC PHN TCH V NHM HOT TNH PHN TCH .. 45 III.1. NHM CHC PHN TCH ....................................................................................45 III.2. NHM CHC PHN TCH CA Th .....................................................................48 III.3. NHM HOT TNH PHN TCH.......................................................................... 50 CHNG IV: NHNG LUN IM L THUYT V C CH PHN NG GIA THUC TH HU C V ION V C ..........................................................................53 IV.1. HIU NG TRNG LNG..................................................................................53 IV.2. HIU NG MU .....................................................................................................54 IV.3. HIU NG KHNG GIAN .....................................................................................60 IV.4. THUYT SONG SONG CA KYZHEOB...........................................................61 IV.5. S PHN LY CA MUI NI PHC ..................................................................62 IV.6. LIN KT HYDRO ..................................................................................................64 IV.7. TCH CHIT I VI THUC TH HU C ..................................................67 IV.8. TCH CHIT CC CHELATE............................................................................... 71
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CHNG V: V.1. V.2. V.3.
TNH TON CC HNG S CA THUC TH V PHC ............ 72
NGHIN CU C CH TO PHC N PHI T ........................................... 72 XC NH HNG S HYDROXO CA ION KIM LOI................................... 77 XC NH THNH PHN PHC.........................................................................82 THUC TH PHI TR O O............................................................... 86
CHNG VI:
VI.1. PHENYLFLUORONE ..............................................................................................86 VI.2. PYROCATECHOL TM...........................................................................................90 VI.3. CHROMAZUROL S .................................................................................................96 VI.4. NBENZOYLNPHENYL HYDROXYLAMINE V NHNG CHT LIN QUAN................................................................................................................................. 103 VI.5. ACID CHLORANILIC V NHNG DN XUT KIM LOI CA N ........... 110 VI.6. NHNG HP CHT POLY (MACROCYCILIC)................................................ 115 VI.7. CUPFERRON..........................................................................................................122 VI.8. THUC TH HN HP O,ODONATING ........................................................127 VI.9. -DIKETONE .........................................................................................................130 VI.10. PYROGALLOR V BROMOPYROGALLOL .......................................139 CHNG VII: THUC TH O-N .................................................................................144 VII.1. THUC TH ALIZARIN COMPLEXONE..........................................................144 VII.2. THUC TH MUREXID ......................................................................................148 VII.3. HYDROXYLQUINOLINE.....................................................................................150 VII.4. ZINCON ..................................................................................................................157 VII.5. XYLENOL DA CAM V METHYLTHYMOL XANH ....................................... 159 VII.6. ASENAZO I V MONOAZO DERIVATIVES OF PHENYL ARSONIC ACID 162 VII.7. EDTA V CC COMPLEXONE KHC.............................................................. 165 VII.8. HP CHT DIHYDROXYARYLAZO.................................................................172 CHNG VIII: THUC TH NN ................................................................................181 VIII.1. BIPYRIDINE V CC HP CHT FERROIN KHC...................................... 181 VIII.2. TRIPYRIDYLTRIAZINE(TPTZ) V PYRIDYLDIPHENYLTRIAZINE........... 189 VIII.3. DIOXIME............................................................................................................185 VIII.4. PORPHYRIN ..........................................................................................................191 VIII.5. DIAMINOBENZIDINE V NHNG THUC TH TNG T .....................201 CHNG IX: THUC TH VI CU TRC S.........................................................206 IX.1. DITHIZONE AND NHNG THUC TH TNG T ....................................206 IX.2. THIOXIN ................................................................................................................212 IX.3. NATRIDIETHYLDTHIOCARBAMATE V CC THUC TH TNG T 220
IX.4. TOLUENE3,4DITHIOL V THUC TH TNG T. ...............................228 IX.5. BITMUT II KHONG CHT II .........................................................................231 IX.6. THIOTHENOYLTRIFLUOROACETONE ...........................................................236 IX.7. THIOMICHLERS KETONE...............................................................................239 CHNG X: X.1. X.2. X.3. THUC TH KHNG VNG .............................................................241 TRI-N-BULTYL PHOSPHATE ............................................................................. 241 TRInOCTYLPHOSPHINE OXIDE.................................................................... 243 DI (2ETHYLHEXYL)PHOSPHORIC ACID.......................................................247 THUC TH KHNG TO LIN KT PHI TR............................251
CHNG XI:
XI.1. THUC TH OXY HA NEUTRAL RED.......................................................... 251 XI.2. BRILLLIANT GREEN ...........................................................................................251 XI.3. THUC NHUM CATION RHODAMINE B......................................................252 XI.4. CC MUI AMONI BC 4 ..................................................................................254 XI.5. TETRAPHENYLASEN CHLORIDE (TPAC) V CC MUI ONIUM KHC 258 XI.6. 1,3DIPHENYLGUANIDINE................................................................................260 XI.7. DIANTIPYRYLMETHANE...................................................................................261 XI.8. NATRI TETRAPHENYLBORATE .......................................................................263 XI.9. CC CHUI ALKYLAMINE MCH DI .............................................................267 CHNG XII: THUC TH HU C CHO ANION ................................................. 272 XII.1. CURCUMIN............................................................................................................272 XII.2. MONOPYRAZOLONE V BISPYRAZOLONE .................................................275 XII.3. 2AMINOPERIMIDINE ........................................................................................278
LI NI U Thuc th h c c nhiu ng dng trong ho hc phn tch, n c s dng trong phng php trng lng, chun , trc quang v trong cc php phn tch cng c khc. Trong phn tch trng lng, vic tm ra thuc th 8-Hydroxyquinoline v dimethylglioxim l mt v d in hnh. Trong phn tch th tch, thuc th hu c quan trng nht l EDTA v nhng cht tng t. Trong phn tch quang hc, nhiu thuc th hu c to sn phm c mu vi ion kim loi, c dng phn tch dng vt cc ion kim loi. Ngy nay, nghin cu thuc th hu c hu nh c mt khp cc phng php phn tch. N h tr cho vic tch, chit, ch th v cc chc nng khc lm tng nhy ca php o. Do mi cht ch th c tnh cht ring, c trng ring v mu v kh nng to phcnn nu c nhng hiu bit c bn v thuc th hu c s gip cho ngi lm cng tc phn tch chn la ng ch th cho php th cng nh tm cc iu kin ti u cho phn ng. Bit c tnh cht ca thuc th, nh phn tch cng c th nh hng tng hp cc thuc th mi u vit hn. Ti liu Thuc th hu c gm 2 phn: phn 1 bao gm ni dung l thuyt ca Thuc th hu c v phn 2 l phn tra cu cc Thuc th hu c v ng dng ca chng. i vi sinh vin chuyn ngnh phn tch cn thit nghin cu phn 1, khi lm chuyn v lm kha lun tt nghip phi nghin cu phn 2. Ni dung phn 1 gm cc phn sau y: M u, Phn loi thuc th hu c, Nhm hot tnh phn tch v nhm chc phn tch, Nhng lun im c bn ca v c ch phn ng gia ion v c v thuc th hu c, Lin kt ha hc trong thuc th hu c, D on ph ca thuc th, Tnh ton mt s hng s ca thuc th hu c v phc ca chng, Phn loi v gii thiu tnh cht phn tch ca thuc th hu c, Cc thuc th quan trng Chng ti trn trng cm n nhng kin ng gp ca cc bn c gn xa ln xut bn sau c hon chnh hn. Cc tc gi
PHN I: L THUYT THUC TH HU C CHNG M U 1. NH NGHA Mt hp cht ho hc c s dng pht hin, xc nh hay tch trong qu trnh phn tch ho hc mt cht hay hn hp ca nhiu cht c gi l thuc th phn tch. Do thuc th phn tch bao gm c nhng cht ch th, cht iu chnh pH, dung dch ra kt ta Vy mt hp cht cha carbon (CO2, CO, CaCO3) bt k hoc trc tip hoc gin tip c s dng trong ho phn tch c gi l cht phn ng phn tch hu c hoc gn hn l thuc th hu c. Nghin cu phn nh gia thuc th hu c vi ion v c v ng dng n vo phn tch thc cht l nghin cu qu trnh to phc. S pht trin l thuyt ho hc trong nhng nm gn y v c bit l s ng dng thuyt trng phi t vo vic nghin cu cc kim loi chuyn tip v phc ca chng gip cc nh khoa hc ni chung v phn tch ni ring hiu su sc nhng yu t nh hng n bn ca phc cht, bn cht ph hp th ca chng v nhng tnh cht qy gi khc. Chng ta s nghin cu thuc th hu c trong khung cnh ca nhng l thuyt hin i ny. 2. U IM CA THUC TH HU C SO VI THUC TH V C Thuc th hu c c mt s u im ni bt so vi thuc th v c; v vy n c s dng rt rng ri trong thc t ca ho phn tch. 1. Trc ht cn ch n tan rt nh ca hp cht to bi thuc th hu c v ion v c. V vy, ngi ta c th ra kt ta cn thn tch ht cc cht bn m khng s mt i mt lng ng k ion cn xc nh. Ngoi ra, hin tng kt ta theo khi dng thuc th hu c cng ch rt t. 2. Thuc th hu c thng c trong lng phn t ln do thnh phn phn trm ca ion c xc nh trong hp cht to thnh vi thuc th hu c bao gi cng thp hn trong bt k hp cht no to thnh bi thuc th v c. V d: Ion cn Xc nh Hp cht to thnh gia Ion cn xc nh vi thuc th Oxyt nhm Al3+ Oxyquinolinat nhm Iodua Tali Tl+ Thionalidat tali Thnh phn % ca ion cn xc nh trong hp cht to thnh vi thuc th 53,0 5,8 61,7 48,6
Thnh phn phn trm ca ion c xc nh thp trong sn phm cui cng lm gim sai s tnh ton, ngha l lm tng chnh xc ca phng php phn tch. Mt khc th
tch kt ta to thnh bi thuc th v c (khi kt ta 1 lng ion cn xc nh nh nhau) do nhy ca phn ng tng ln. 1. 3- Sn phm mu ca thuc th hu c vi ion v c, c cng mu ln v trong nhiu trng hp c cng pht hynh quang ln, do ngi ta c th pht hin c nhng lng v cng nh ion v c v nh lng chng bng phng php o mu hoc o hunh quang mt cch thun li. Thm vo , nhng sn phm mu phn ln l nhng hp cht ni phc nn kh bn v d chit bng dung mi hu c li l nhng thun li khc rt ng k. 4- Cui cng cn ch ra rng, do s khc bit ca rt nhiu loi thuc th hu c nn ngi ta c th chn trong mi trng hp ring bit, thuc th thch hp nht v tm nhng iu kin thun li nht cho phn ng tin hnh v do phn ng phn tch t nhy v la chn cao. 3. MT S C TNH C BN CA THUC TH HU C Khi nghin cu cc thuc th hu c ngi ta thng quan tm n cc tnh cht sau y: tinh khit: Tr mt s t thuc th, hu ht cc hp cht hu c trn th trng l khng tinh khit. Tu theo mi trng hp, c th yu cu c lm sch. V d: Chloranil nh l mt thuc th dch chuyn in tch vi amino acid nn phi lm sch trc kh s dng. y l yu cu u tin trong nghin cu cc thuc th hu c. tan: tan ca thuc th trong dung mi no s quyt nh phng php phn tch ca thuc th y. Bit c tan chng ta s ch ng trong nghin cu. V d: EDTA khng tan tt trong nc (mi trng trung tnh). thay i tan ca n th cn trung ha bng mt baz. 8-Hydroxyquinoline tan yu trong nc, n thng khng tan trong acid acetic dng bng v pha long bng nc, nu phi t hay phc ca n khng tan trong nc. p sut hi: Mt phc c th c p sut hi cao hn cc phc khc. Nhng dn xut ca metoxy hay etoxy c p sut hi cao hn nhng hp cht b m ca chng. Da trn s khc nhau v p sut hi ca cc phi t hay phc ca chng, mt s cht c tch bng phng php sc kh ph. bn: Mt s phc chelate rt bn trong dung mi tr khi phc hnh thnh. Tuy nhin, mt s phc bn vi nhit c tch bng phng php chng ct m khng b phn hu. Mt vi phc nhy vi nh sng v khng kh th phi c bo qun cn thn. phn cc: phn cc ca mt phn t cho bit tan ca n trong dung mi. Mt phn t phn cc s c thun li trong dung mi chit. Bn cnh , s tch da trn s phn cc hay khng phn cc ca phn t cht c chit c s dng mt cch rng ri. 4. HNG NGHIN CU CA THUC TH HU C Hin nay, nghin cu thuc th hu c i vo cc lnh vc chnh sau y: 1. Tng hp nhng thuc th hu c mi. 2. Tm cc phng php phn tch mi theo hng n gin, nhy v chn lc. 3. Nghin cu tc ng ca cc nhm chc. 4. Nghin cu cu trc ca thuc th. 5. Nghin cu ng hc phn ng.
6. Phc nha cy hu c. 7. Cc nhm chit. 8. My tnh v chuyn ha furier. 9. Nghin cu phc dch chuyn in tch. 10. Thuc th cho s pht hunh quang v pht quang ha hc. 11. Cht hat ng b mt. 12. Nghin cu trng thi oxy ho.
CHNG I: PHN LOI THUC TH HU C

Thuc th hu c bao gm rt nhiu loi nn cn thit phi h thng ho chng.
I.1.
S BT HP L CA CCH PHN LOI TRONG HO HU C
Ngi ta c th phn loi thuc th hu c theo nguyn tc rt n gin, l nguyn tc phn loi trong ho hu c (theo cc nhm chc). S phn loi ny ch thun li khi nghin cu nhng hp cht n gin cn khi nghin cu nhng hp cht phc tp n t ra khng p ng c yu cu v cn cha nhiu mu thun. Theo s phn loi th nhng acid phenol carboxylic trong cng mt nhm cn nhng dihydroxybenzene thuc v mt nhm khc. So snh m v ohydroxybenzoic acid vi m v odihydroxybenzene ngi ta thy rng mhydroxybenzoic acid v mdihydroxybenzene (Resocsin) c rt t tnh cht phn tch ging vi ohydroxybenzoic acid (salicylic acid) v odihydroxybenzene (Pyrocatechin). Trong khi c tnh phn tch ca salixilic acid v Pyrocatesin li rt gn nhau. S ng nht tnh cht phn tch trong trng hp ny khng phi l do trong phn t c nhng nhm chc nh nhau m do Pyrocatesin v salicylic acid cng c kh nng to ni phc ln (nh nhm to phc v nhm to mui v tr ortho i vi nhau). V d: cht mu
O2N N N OH
Phn ng vi hydroxide magie trong mi trng kim cn cht mu

N N OH
O2N
. Mc d cng loi vi hp cht trn nhng khng cho phn ng y. Theo tnh cht phn tch th 8oxyquinoline (I) v Anthranilic acid (II) tng i gn nhau hn so vi 8oxyquinoline (I) v 7oxyquinoline (III) hoc l so vi antharanilic acid (II) v Paraaminobenzoic acid (IV)
H2N
NH2
OH COOH
NH2
NH2
OH
COOH
(I)
(II)
(III)
(IV)
Nhng dn chng nu trn chng t rng cch phn loi thng dng cho cc hp cht hu c, th cn c vo cc nhm chc trong phn t thuc th phn loi l khng hp l.
I.2. PHN LOI THEO PHN NG PHN TCH M THUC TH THAM GIA
Theo s phn loi ny, thuc th hu c c chia thnh 9 nhm. 1) Nhng cht to phc mu 2) Nhng cht to mui 3) Nhng cht c kh nng to nhng hp cht cng hp t tan hoc c mu c trng. 4) Nhng cht ch th 5) Nhng cht mu to phc hp th (sn) 6) Nhng thuc th gy nn s tng hp hu c trong phn ng, ng dng vo phn tch. 7) Nhng thuc th c kh nng to phc vng vi ion kim loi (vng theo thnh hoc l do lin kt ho tr, lin kt phi t hoc l hn hp c hai loi ny). 8) Nhng cht oxy ho 9) Nhng cht kh. H thng phn loi ny cng mang nhiu mu thun ni ti: 1- Mt cht c th c trong nhng nhm phn loi khc nhau. V d: Alizarin c th c nhm 5 v nhm 7. Dipyridin cng c th c nhm 1 v nhm 7. 2- Tc dng ca nhng thuc th trong cng mt nhm vi nhng ion v v li c nhng c tnh khc nhau v nguyn tc. V d: Theo s phn loi trn th acid oxalic, ethyeandiamine dumethylglyoxim phi thuc v nhm 7 v chng u to vng vi nhng ion kim loi.
O C O Ca C O O Cu H2N
CH2
H2N
CH2
SO4 3
Nhng bn cht v c tnh ca oxalat can-xi, triethylandiamino ng sunfat, dimethylglyoximat Ni li khc nhau rt c bn (mui, mui phc, mui ni phc). 3- S tch ring nhm cht oxy ho v cht kh l khng hp l v mt cht tu thuc iu kin ca phn ng, c th ng vai tr cht kh hay cht oxy ho. V d: Methyl da cam.
H3C H3C N N N SO3Na
Trong phn ng vi Chlor ng vai tr cht kh cn trong phn ng vi Sn++ li ng vai tr cht oxy ho.
I.3.
PHN LOI THEO YOE
Yoe chia thuc th hu c thnh 11 nhm ln (theo mc ch s dng) v mi nhm ln li c chia thnh nhiu nhm nh (theo cch phn loi trong nhm hu c). Vi d: Nhm ln th nht l dung mi v cht lng ra bao gm nhiu nhm nh: hydrocarbon, ru, ester, ether, aldehydeketone Cch phn loi ny thun tin cho vic chn thuc th nhng v c bn n vn mang nhng khuyt im ca cc cch phn loi k trn. V d: Pyrogallol, pnitrobenzeneazoresocsin, 8oxyquinoline trong cng mt nhm nhng c ch tc dng ca mi hp cht vi ion v c li rt khc nhau.
I.4.
PHN LOI THEO FEIGL
Feigl chia thuc th thnh 8 nhm 1) Nhng thuc th to mui 2) Nhng thuc th to mui phc 3) Nhng thuc th to mui ni phc 4) Nhng thuc th to mui hp cht hp th 5) Nhng thuc th dng trong nhng phn ng tng hp hoc phn hu hu c. 6) Nhng thuc th l h oxy ho kh hu c 7) Nhng thuc th tham gia phn ng vi ion v c dng chuyn vi ni phn. 8) Nhng thuc th tham gia vo nhng phn ng xc tc. Mc d cha tht hon ho nhng cch phn loi ny c u im c bn l da trn c ch phn ng v bn cht sau cng phn loi. Nhng thuc th c xp trong cng mt nhm khng phi v cng thc ging nhau m v tnh phn ng m n tham gia ging nhau.
I.5.
PHN LOI THEO WELCHER
Welcher cho rng nhng thuc th hu c c gi tr nht trong phn tch l nhng thuc th to phc vng cng vi ion phn loi. Cn c vo s ion hydro b ion kim loi thay th trong mt phn t thuc th trung ha to thnh mt vng cng, Welcher chia thuc th hu c thnh 3 loi: Loi 1: Loi 2 ion hydro b thay th. Tham gia vo phn ng phi tr loi ny l ion kim loi v anion thuc th 2 in tch v do c mi bc phi tr in tch ca phc s bng in tch ca ion kim loi tr i 2 n v. Nu s phi tr ca nguyn t kim loi i vi thuc th bng in tch ca ion kim loi th phc to thnh l phc trung ha v thng khng tan trong nc. V d: benzoinxim c hai ion H+ c th b thay th, to vi Cu2+ hp cht phi tr c thnh phn 1:1.
O C C H
C C H N Cu O N C
2HN Cu O
OH2
OH2
CH
Nu s phi tr ca nguyn t kim loi i vi thuc th vt qu in tch ca ion kim loi th phc anion thng tan trong nc c hnh thnh. C th ly cc phc tan Oxalate (Fe(C2O4)3), Citrate (CaC3H4OH(COO)3), tactrate (Fe(C4H4Oc)+) lm v d. Ngi ta thng s dng cc phc ny ngn cn kt ta hydroxide trong mi trng kim. Loi 2: Loi 1 ion hydro b thay th. Phn ng phi tr xy ra gia ion kim loi v anion thuc th 1 in tch v do c mi mc phi tr in tch tng cng ca phc kim loi bng in tch ca ion kim loi tr i mt n v. Nu s phi tr ca nguyn t kim loi i vi thuc th hai ln ln hn in tch kim loi th hp cht trung ho khng tan trong nc c to thnh v trong a s trng hp, c th chit sn phm phn ng bng nhng dung mi hu c. Cn nhn mnh rng, s phi tr thng dng li mc to phc trung ho ngay c trong trng hp nhng v tr cn cha s dng ht. iu c gii thch nh sau: s phi tr tip theo i hi thuc th phi phn ly, v phi ho tan sn phm khng tan. Phn ln thuc th hu c biu l tnh acid rt yu do s phn ly l khng thun v mt nng lng. V d: 8oxyquinoline (HX) tc dng vi Mg2+ to sn phm dihydrat. Mg(H2O6)2+ + HX MgX2 . 2H2O + 2H+ + 4H2O. S phi tr ca Mg2+ bng 6 nhng in tch trng thnh trung ho sau khi hai phn t thuc th tc dng vi mt ion magie. Cn Al3+ to 8oxyquinolat khng ngm nc v s phi tr ca n ng 2 ln ln hn in tch. Phn ln nhng thuc th hu c c ng dng rng ri trong phn tch iu thuc loi ny: nitroso, naphtol, dimethylglyoxim, dithizone, v.v Loi 3: Loi nhng ion hydro khng b thay th. y phn ng phi tr xy ra l do s thay th nhng phn t nc bng nhng phn t thuc th trung ho. Do sn phm phn ng l cation c in tch ng bng in tch ca cation kim loi ban u. Mc d sn phm phn ng thng tan trong nc nhng i khi c th chit bng nhng dung mi hu c nh cation hu c khi lng ln v nhng anion thch hp. V d: C th chit phc ca Cu v Fe vi nhng dn xut ca 1, 10-phenanthroline bng ru cao phn t. Nhng thuc th to s chelate ln hn vi 1 n phn t thuc th (v d ethylenediaminetetracetic acid v nhng thuc th ni chung) khng to chelate khng thuc vo ba loi hp cht k trn.
CHNG II: L THUYT V LIN KT PHI TR

L thuyt phi tr ca Werner vi quan im ho tr ph cho chng ta mt cch gii thch thng nht v s tn ti ca phc cht, nh [Co(NH3)6]Cl3. Trn c s ca thuyt ny, thuyt l nn tn ca ha hc cc hp cht phi tr ngy nay, ta c th gii thch tnh cht, ha lp th ca nhng cht loi tng t. V l thuyt ca Werner c nu ln 20 nm trc khi xut hin khi nim v cu to in t ca nguyn t nn thuyt khng th m t di hnh thc hin i, bn cht ca lin kt ph, hay l lin kt phi tr nh chng ta thng gi. m t bn cht ca lin kt trong phc cht, ngy nay ngi ta s dng rng ri 3 thuyt: Phng php lin kt ho tr (VB) Thuyt trng tinh th tnh in Thuyt qu o phn t (MO) Trc ht cn nn nh li nhng ng gp ca Lewis v Sidwick cho l thuyt lin kt ho hc.
II.1.
LIN KT HAI IN T
Nm 1916, gio s ho hc ca trng i hc Tng hp Canifornia, Lewis pht biu ti Berkle: Lin kt gia hai nguyn t A v B c thc hin bng i in t dng chung ca hai nguyn t. Thng mi nguyn t gp mt in t vo i in t dng chung. Trn c s ca nhng khi nim , Lewis m t cc phn t CH4 v NH3 nh sau: H H : C :H H H : N :H H
: :
Ngy nay ngi ta gi phng php m t l phng php biu phn t Lewis. Biu Lewis cho chng ta thy r rng, nhng phn t NH4+ v NH3 ging nhau im l trong nhng hp cht ny c 2 in t (i in t phn b) lin kt vi mi nguyn t hydro cn i vi cc nguyn t C, N c 8 in t. S khc nhau c bn nht, quan trng nht gia 2 hp cht ny l nguyn t Nit cn mt i in t khng phn chia cho nguyn t hydro. Chnh v vy m phn t ammoniac c kh nng phn ng, n cho i in t t do ca mnh dng chung vi bt k mt nguyn t no khc. Lin kt ny c hnh thnh cng l do mt i in t ngha l cng l lin kt cng ho tr nhng v c hai in t u do nguyn t nit cung cp nn ngi ta gi loi lin kt ny l lin kt cng hp ho tr phi tr. Phn ng ca NH3 vi cc acid to thnh cc mui amoni (1) dn n lin kt cng ha tr phi tr.
H H
+ +
N H H
H H N H H
: :
(2.1)
Song, 4 lin kt trong NH4+ u tng ng. iu chng t rng s khc nhau gia lin kt cng ha tr thng v lin kt cng ha tr phi tr khng ng k. Phn t
ammoniac cng c th cho i din t t do ca mnh dng chung vi nhng ion hoc phn t khc. Nu ion kim loi thay th ion hydro th hnh thnh cc phc anion kim loi (Phng trnh (2.2),(2.4), v nhng phn ng ny ch yu xy ra trong dung dch nc nn ni mt cch chnh xc hn l nhng ion kim loi u tin tn ti trong dung dch nc di dng phc nc (phc aqua) v nhng phn t nc phi tr b thay th bi nhng phn t ammoniac (phng trnh (2.5)(2.8)).
Ag+ + H N H H H H N Ag H
+ +
NH3
H H H N Ag N H H H
++
(2.2)
Cu
++
4 NH3
NH3 H3N Cu NH3 NH3

++
(2.3)
Ni+++ 6 NH3
H3N NH3 H3N Ni NH3 H3N NH3
(2.4) (2.5) (2.6) (2.7) (2.8)
[H : OH 2 ]+ + : NH 3 [H : NH 3 ]+ + H 2 O
[Ag (: OH 2 )2 ]+ + 2 : NH 3 [Ag (: NH 3 )2 ]+ + 2 H 2 O
[Cu (OH 2 )2 ]2 + 4 : NH 3 [Cu (: NH 3 )4 ]+2 + 4 H 2 O

[Ni (: OH ) ]
2 6 +2
+ 6 : NH 3 [Ni ( NH 3 )6 ] + 6 H 2 O
+2
Nhng phn ng tng t, theo Lewis l nhng phn ng acid baz. Theo Lewis acid l nhng cht, nhng phn t c kh nng lin kt i in t (cht nhn), cn baz l nhng cht c kh nng cho in t (cht cho). Kt qu l, phn ng acid baz dn n s to thnh nhng lin kt phi tr theo s : A acid (cht cho) + :B baz (cht nhn) A:B hp cht phi tr (2.9)
Thuyt ca Lewis tng qut hn thuyt ca Arrenius. Theo thuyt ca Lewis th nhng hp cht nh BF3, AlCl3, SO3 v SiF4 cng l nhng acid v u c kh nng nhn in t. Nhng hp cht loi F3BNH3 v C5H5NSO3 thng gi l nhng sn phm cng hp, chng cng l nhng hp cht phi tr.
F F B F
+
H N H H
F H F B N H F H
(2.10)
AlCl3
SO3
+
Cl-
AlCl4
(2.11) (2.12) (2.13)
C 5H 5N
+
C5H5N SO3
SiF4
2 F-
SiF6
2-
Nhng phi t cho i in t ca mnh dng chung vi nhng kim loi v nh vy theo Lewis chng chnh l nhng baz. Ta c th nu ln nhng phn t H2O:, NH3:, (C2H5)3P:, :CO v :NH2CH2CH2NH2 v nhng ion :Cl:, :CN, :OH, :NO2
OOCCH2 OOCCH2 NCH2CH2N CH2COO CH2COO
4-
(2.14) R rng rng EDTA l nhng phi t 2 v 6 rng. Nguyn t c s i in t khng phn chia ln hn mt c th dng l cu nguyn t
(C2H5)3P Pt Cl Cl Cl Pt P(C2H5)3 Cl
(2.15)
II.2.
NGUYN T HU HIU
Nhng kh tr (He, Ne, Ar, Kr, Xe, v Ru) l nhng cht in hnh khng c kh nng phn ng, ch mi gn y ngi ta mi iu ch c mt s nguyn t . t lu ngi ta nhn xt rng, nhng hp cht trong mi nguyn t bng cch thay th i in t chung vi cc nguyn t khc c bao quanh mnh mt s in t bng s in t trong nguyn t kh tr l nhng hp cht rt bn vng, gio s trng tng hp Oxford l Sidwick mang khi nim vo lnh vc phc ca kim loi. ng ta khng nh rng, ion kim loi trung tm s c vy quanh mnh mt s phi t sao cho s in t chung trong nguyn t kim loi t ti nh trong nguyn t kh tr. S in t chung trong nguyn t cht to phc kim loi c gi l s nguyn t hu hiu. V d s nguyn t hu hiu ca Co(III) trong [Co(NH3)6]3+ d dng tnh c nh sau: Co c s nguyn t bng 27, c 27 in t Co (III) c 27 3 = 24 in t (NH3) c 2*6 = 12 in t c dng chung t Vy s nguyn t hu hiu ca Co(III) trong phc (Co(NH3)6)3+ bng 24 + 12 = 36 in
S nguyn t hu hiu ca nhiu phc khc c xc nh bng cch , trong nhiu trng hp bng s nguyn t kh tr. Nhng quy lut cng c nhiu ngoi l. V d nh i vi phc [Ag(NH3)6]+ v [Ni(en)3]3+ th s nguyn t hu hiu bng 50 v 38. Nu s nguyn t hu hiu ca kim loi trung tm lun lun chnh xc bng s nguyn t ca kh tr th c th bit c s phi tr ca ion kim loi trong tt c mi phc. Loi hp cht thng tun theo quy lut s nguyn t hu hiu l nhng hp cht carbonyl ca kim loi v nhng dn xut ca n. Nh quy lut ny c th xc nh chnh
xc s nhm CO trong phn t nhng carbonyl n gin nht cng nh c th d on nhng hp cht ny c th tn ti di dng nhng monomer hay khng. V d nh s nguyn t hiu i vi cc kim loi trong nhng hp cht Ni(CO)4,Fe(CO)5, Fe(CO)4Cl2, Mn(CO)5Br, CoNO(CO)3, v Fe(NO)2(CO)2 u bng 36. tnh s nguyn t hu hiu trong cc h ny c th cng nhn mt cch thun li l CO, Cl-, Br- cho hai nguyn t to thnh lin kt cn NO th cho 3 in t. Cng thc: (CO)5Mn-Mn(CO)5 l cng thc n gin nht trong s nhng cng thc c th c ca carbonyl mangan nu cng nhn mi nguyn t cn c s nguyn t hu hiu bng 36. S in t ca mi nguyn t Mn = 25 S in t ca 5 nhm (:CO) = 10 S in t ca lin kt Mn-Mn = 1 Tng cng l 36 Nguyn t Mn khi to lin kt vi nguyn t Mn khc c th nhn mt in t. Khi mi nguyn t kim loi gp mt in t to lin kt v nh vy mi nguyn t c chung vi nguyn t khc 2 in t.
II.3.
CU TO IN T CA NGUYN T
Trc khi bn lun v nhng vn l thuyt lin kt, cn thit phi nu ln mt cch ngn gn cu to in t ca nguyn t. Nhng in t trong nguyn t ln lt chim cc mc nng lng. Trn mc nng lng u tin c th c nhiu nht 2 in t, trn mc th hai l 8, trn mc th 3 l 18 v trn mc th t l 32. Nhng mc nng lng chnh t 1 n 7 chia ra lm nhng mc nng lng ph: s, p, d, f. Nhng in t ln lt chim cc mc nng lng ph cha in t c nng lng thp. Trong tt c cc bn lun sau ny chng ta gi thit rng in t s trn mc nng lng thp nht. Trong s mc nng lng (hnh 2.1) r rng rng trong mi mc nng lng chnh, mc nng lng ph s c nng lng thp hn mc nng lng ph p, mc nng lng ph p thp hn mc nng lng ph d v cui cng mc nng lng ph d thp hn mc nng lng ph f. S cng ch ra rng mc nng lng ph 3d c nng lng cao hn mc nng lng ph 4s v mc nng lng ph 4f c nng lng cao hn mc nng lng ph 6s. Nh vy mc nng lng ph ca mt mc nng lng chnh c th c gi tr nng lng cao hn mc nng lng ph thp ca mc nng lng chnh tip theo. Mc d rng gi tr ca mc nng lng ph ca mt mc nng lng chnh lun lun phn b theo trt t sau: s<p<d>f, nng lng tng i ca chng trong cc mc nng lng chnh khc nhau cn chiu nh hng ca s bao quanh ca nguyn t ang xt v ph thuc rt nhiu vo s nguyn t ca n. V d nh trong nguyn t Kali mc nng lng ph 3d cao hn 4s. Trong nguyn t Scandi nng lng ca cc mc ph 3d v 4s bng nhau v trong nguyn t km mc nng lng ph 4s li cao hn 3d. hnh dung mt cch gn ng cc cu hnh in t ca nguyn t ta c th s dng s dn ra hnh 2.1.
6d 5f 7s 6p 5d 4f 6s 5p 4d 5s 4p 3d 4s 3p 3s 2p 2s 1s Hnh 2.1: S mc nng lng ca nguyn t
Trn hnh 2.1, qu o c m t bng cc vng trn nh. S qu o ca mi mc nng lng ph tng ng nh sau: s=1, p=3, d=5, f=7. Trn mi qu o c th c ti a l 2 in t v nh vy s in t cc i ca s l 2, ca p l 6, ca d l 10 v ca f l 14. in t sp xp vo mi mc nng lng ph theo nguyn tc Hund. Theo qui tc ny, in t phi sp xp vo cc qu o ca cng mt mc nng lng ph nh th no c s in t khng ghp i ti a. iu c ngha l in t ln lt c sp xp vo cc qu o trng, bi v chng y nhau v c xu th nm trn nhng qu o khc nhau sao cho cng cch xa cng tt c th din t cu trc in t ca N, Ti v Mn nh trn hnh 2.2. 1s N Ti Mn Hnh 2.2: Cu to in t ca cc nguyn t N, Ti, Mn Nhng in t ca phc ph p ca nguyn t Nit v nhng in t ca mc ph d ca cc nguyn t Ti v Mn khng ghp i khng cn thit phi vit tt c cc mc nng lng ph nh trn hnh v. Thng ngi ta ch nu ln nhng in t lp ngoi v kh tr (nhng in t ha tr) bi v chnh chng tham gia vo s to thnh nhng lin kt ha hc. Cui cng cn nhn xt rng: Sau ny tin li ta sp xp mc ph 3d trc 4s, 4d v 4f trc 5s Sau khi nghin cu cu to in t ca nguyn t chng ta cn xt cu to in t ca ion. Ni chung khi to thnh nhng ion dng, in t ha tr b tch ra khi qu o nguyn t ng vi nng lng cao nht. Trong trng hp ca nhng kim loi chuyn tip, nhng in t s ngoi c nng lng cao nht v do nguyn t mt nhng in t ny trc tin. V vy c th hnh dung cu to in t ca Ti3+ v Mn2+ nh hnh 2.3.
Nng lng
2s
2p
3s
3p
3d
4s
1s Ti3+ Mn2+
2s
2p
3s
3p
3d
4s
Hnh 2.3: Cu to in t ca nhng ion Ti3+ v Mn2+ Tip theo cn phi bit dng qu o in t. Ngi ta hiu hnh dng qu o l m hnh hnh hc vng khng gian c xc xut tm thy in t ln nht trn qu o . Chng ta gii hn nhng qu o s, p,d bi v chng thng tham gia vo s to thnh lin kt. Ch cc nguyn t chuyn tip (cc nguyn t t him v actinide) cc qu o f mi tham gia vo s to thnh lin kt in t. Qu o s c hnh dng i xng cu (hnh 2.4), qu o p c hnh dng hnh qu t hng theo mt trong ba trc ta . Qu o px hng dc theo trc x, qu o py hng dc theo trc y, qu o pz hng dc theo trc z (hnh 2.5). Bn trong s 5 qu o d c dng hnh hoa th v mt c hnh qu t v c vnh bao quanh trung tm. Ba qu o hoa th dxy, dxz, dyz hng theo nhng mt phng xy, xz, yz, chng c phn b gia hai trc xc nh mt phng. Qu o th t d x -y hng theo mt phng xy dc theo cc trc x v y.
2 2
Hnh 2.4: Hnh dng khng gian ca qu o s z z y z y y
Hnh 2.5: Hnh dng khng gian ca qu o p.
II.4.
PHNG PHP LIN KT HA TR (VB)
Phng php lin kt ha tr c gio s Pauling (Hc vin K thut California) pht trin v nu ln mt cch d hiu trong quyn sch ca mnh Bn cht ca lin kt ha hc. Ngoi Marie Cuirie, Pauling l ngi duy nht 2 ln c gii thng Nobel (mt ln v ha hc nm 1954, mt ln v ha bnh nm 1962). Quan im ca Pauling nh hng rt ln n tt c mi lnh vc ca ha hc. L thuyt cng ha tr ca ng c kh nng thng nht nhng quan im ca cc nh ha hc v do c ph bin rng ri. Nh thuyt ny, c th gii thch tt cu to v t tnh ca phc kim loi. L thuyt ny c th gii thch c nhng tnh cht khc ca cc hp cht phi tr v d nh quang ph hp th nhng dng nh bng nhng l thuyt khc c th lm nhng vic ny d dng hn. Do , trong nhng nm gn y nhng nh bc hc nghin cu vn ha hc ca cc hp cht phi tr thch th l thuyt trng tinh th, trng phi t v l thuyt qu o phn t hn, Chng ta s ch yu nghin cu cc l thuyt ny. Trc ht cn nghin cu xem phng php lin kt cng ha tr m t s to thnh cc phc cht [CoF6]3- v [Co(NH3)6]3+ nh th no v so snh vi nhng quan im ca l thuyt trng tinh th v l thuyt qu o phn t m chng ta s xt ti sau y. u tin cn nu ln rng [CoF6]3- cha 4 in t khng ghp i trong khi th [Co(NH3)6]3+ tt c cc in t ghp i. Mi phi t (theo Lewis l baz) cho mt i in t to lin kt cng ha tr phi tr. Theo phng php lin kt cng ha tr, cu to in t ca cc phc trn c minh ha hnh 2.6. Lin kt trong trng hp ny l lin kt cng ha tr. Nhng t hp tng ng nhng qu o nguyn t ca kim loi pha ha vo nhau v to thnh dng qu o mi gi l qu o lai ha. Nhng qu o ny to thnh nhng lin kt cng ha tr bn hn gia kim loi v phi t. 3d dxydxzdyz dx2-y2dz2 4s F4p F- F- FNH3NH3NH3 F- F4d
[Co(NH ) ]
3 6
NH3NH3
NH3
Hnh 2.6: S to phc [CoF6 ]3 v [Co(NH3)6]3- theo quan im ca phng php li kt h t Trong 6 phi t phi tr, nhng qu o lai ha hnh thnh do s pha ha nhng qu o nguyn t s, px, py, pz, dx2-y2 v dz2. Su qu o lai ha hnh thnh sp3d2 hng ti nhng nh ca bt din. Ta nhn thy rng i vi phc [CoF6]3- nhng qu o d cng cng c mc nng lng chnh nh qu o s v p. Phc loi ns np3 nd2 gi l phc qu o ngoi bi v nhng qu o d ngoi tham gia vo s to phc. Mt khc, nhng qu o d c chc mc nng lng chnh thp hn qu o s v p tham gia vo s to phc [Co(NH3)6]3+. Nhng phc nh (n-1)d2 ns np3 c gi l phc qu o trong bi v nhng qu o d trong tham gia vo s to thnh chng.
II.5.
L THUYT V TRNG TINH TH
Phng php lin kt ha tr v thuyt trng tinh th tnh in khc nhau v bn cht. Phng php lin kt ha tr xut pht t gi thuyt lin kt phi tr l cng ha tr cn l thuyt tnh in th hon ton bc b c tnh cng ha tr ca lin kt v gi thuyt rng
lin kt gia ion kim loi v phi t l hon ton ion. C th tnh ton nng lng ca lin kt phi tr khi ta s dng nhng phng trnh c in ca th nng, c k ti lc ht v lc y gia nhng ht nhn tch in. Nng lng lin kt = q1q2/r (2.16) Trong phng trnh (2.16), q1 v q2 l nhng in tch ca nhng ion tng tc, r l khong cch gia nhng trung tm ca nhng ion. Ngi ta s dng phng trnh tng t m t c nhng tng tc ca phn t phn cc khng tch in vi ion. Php gn ng cho nhng kt qu ph hp kh tt vi nhng gi tr nng lng lin kt tm c bng thc nghim i vi nhng phc ca nhng kim loi khng chuyn tip. i vi phc ca kim loi chuyn tip nhng gi tr tnh ton trc thng qu nh. S khng tng ng s c b chnh li mt cch ng k nu ch ti qu o ca nhng in t d v gi thuyt v nh hng ca phi t ln nng lng tng i ca nhng qu o d. Nm 1930, ln u tin nhng nh vt l (Beta v Vanflek) hon thin l thuyt tnh in v s dng gii thch mu v t tnh ca cc mui tinh th. L thuyt ny c gi l l thuyt trng tinh th. Mc d l thuyt ny nu ln trong cng thi gian hoc l sm hn mt cht so vi phng php lin kt ha tr nhng 20 nm sau mi c cc nh ha hc bit ti v s dng. Nguyn nhn c th l do thuyt trng tinh th c vit cho cc nh vt l cn phng php lin kt ha tr th li cho mt quan nim kh r rng v lin kt gia cc nguyn t. Nm 1951, mt s nh ha hc l thuyt s dng thuyt trng tinh th mt cch c lp vi nhau gii thch ph ca phc nhng kim loi chuyn tip. V phng php t ra c hiu qu nn ngay lp tc hng lot cng trnh nghin cu c tip tc. Ngi ta lm sng t rng thuyt trng tinh th rt thun li cho vic gii thch bn nh lng nhiu tnh cht bit ca cc hp cht phi tr. hiu thuyt trng tinh th cn hnh dung mt cch r rng s nh hng khng gian ca qu o d (hnh 2.7). Tng tc ca nhng qu o d ca nhng kim loi chuyn tip vi cc phi t bao quanh, n sn sinh ra hiu ng trng tinh th. minh ha thuyt trng tinh th, ta hy xt phc bt din [TiF6]2-. Trong ion Ti4+ t do nm cch bit trong khng gian, hnh dng in t l nh sau: 1s22s22p63s23p6, khng c in t d. Nm qu o 3d trng trong ion c c trng bng cng mt mc nng lng. iu cho php gi thuyt rng in t c th nm trn mt trong s nhng qu o d vi xc xut nh nhau. Nhng qu o tng ng vi cng mt gi tr nng lng gi l qu o suy bin.
ec Nng lng 0,6 0 0 0,4 0 t2
d
Ion kim loi t do (Ti4+)
Phc gi thuyt vi cc qu o d suy bin
Phc bt din [(TiF6)2-]
Hnh 2.7: S mc nng lng ca nhng qu o d ca ion kim loi t do ca phc gi thuyt trong khng c s tch mc bi trng tinh th v ca phc bt din. Trong phc [TiF6]2- ion Ti4+ c bao quanh bi 6 ion F-. Do s c mt ca nhng ion F, tc dng y ca nhng in tch m ca chng gy tr ngi cho s np in t vo qu o d ca ion Ti4+. Ni mt cch khc, nhng ion F- (hoc l nhng phi t khc) khi tin ti gn qu o d lm tng nng lng tng ng ca chng (hnh 2.7). Nu nh 6 ion Fbao quanh ion Ti4+ trong [TiF6]2- phn b trn cng mt khong cch ti 5 qu o d ca Ti4+ th tt c cc qu o d c trng ng vi cng mt gi tr nng lng (chng b suy bin) nng lng tng ng ln hn so vi nng lng vn c ca ion Ti4+ t do. Phc bt din vi tt c cc qu o d suy bin l phc gi thuyt. Phc [TiF6]2- c cu to bt din. tin li cho s nghin cu phc chng ta xem nh 6 ion F- s phn b trn cc trc x, y, z trong h ta Descartes. Trong s phn b nh vy: F z F x F
F F
F y
Cc ion s nm gn cc qu o d x -y v d x nht, l nhng qu o eg (hnh 2.6). S tht l cc qu o eg hng thng ti cc phi t F- trong khi th nhng qu o dxy, dxz, dyz k hiu l cc qu o t2g li hng vo gia cc phi t (k hiu eg v t2g c s dng trong l thuyt nhm ca ton hc, t ch s suy bin bc 3, e ch s suy bin bc 2). Do in t kh chim ch trn qu o eg hn l trn qu o t2g v v vy nhng qu o eg phi c trng bng gi tr nng lng cao hn so vi t2g. S phn chia nh th, nm qu o suy bin ca ion kim loi t do thnh nhng nhm qu o c trng bng nhng nng lng khc nhau l c im ch yu ca thuyt trng tinh th. Hin tng c gi l s tch mc do trng tinh th. Nh trnh by trn, s tch mc nng lng xy ra l do nhng qu o d nh hng khng ng nht trong khng gian nn nhng nguyn t, ion hay phn t bn cch c th lm bin i nng lng ca nhng qu o hng ti chng.
2 2 2
Nhiu sinh vin cho rng rt kh quan nim mt cch r rng v thuyt trng tinh th v quan im tch mc ca thuyt ny. Trn y chng ti trnh by nhng lun im c bn nht da trn c s nhng m hnh khng gian ca nhng qu o d. l con ng ng n i ti thuyt trng tinh th. Ta c th dn ra mt hnh nh vt l nh hnh 2.8. Chng ta hy ch ti hnh 2.8 v gi thuyt rng ion kim loi v lp v in t ca n c hnh dung di dng qu cu n hi bng bt bin. By gi chng ta hy xem qu cu bin i nh th no nu b lp v hnh cu cng (tng ng vi cc phi t) tc dng ln n t bn ngoi. Th tch qu cu b thu nh li v h s c nng lng cao hn, iu ny c khng nh bi s kin l qu cu n hi t ln ln chim th tch ban u sau
khi tch khi lp v rng buc n. S bin i nng lng tng ng vi s tng nng lng pht sinh do s y nhau gia nhng in t trong ion kim loi v in t ca phi t trong phc gi thuyt.
Qu cu bng bt bin (ion kim loi t do)
Qu cu bng bt bin di p lc ca lp v hnh cu (phc gi thuyt)
Qu cu bng bt bin di p lc tc ng vo nhng hng xc nh (phc cht).
Hnh 2.8 : Hiu ng ca trng tinh th c hnh dung mt cch c th nh l p lc ca lp v hnh cu ln qu cu bng bt bin tt c mi hng v nh l p lc ln qu cu khi tp trung vo nhng ch xc nh. Nu by gi lp v cng tp trung lc tc dng ca n vo 6 im ring bit (v d nh ca bt din chng hn) th qu cu s b lm vo trong nhng im y v li ra ngoi nhng im gia cc im y. Do kt qu ca sc p , nn h bt bin c nng lng cao hn 6 im c p lc cao v c nng lng thp hn nhng im gia chng. iu tng ng vi s tch mc ca trng tinh th v nhng im li ra tng ng vi qu o t2g, nhng im lm vo trong tng ng vi qu o eg. Trc y ta nhn xt rng nng lng tng ng ca nhng qu o d ca ion kim loi tng ln khi phi t tin gn ti ion. iu t n cho php hnh dung rng, phc phi km bn hn ion kim loi v phi t t do. Nhng chnh s kin to phc ch r rng phc l dng c nng lng thp hn sao vi ion kim loi v phi t ring l. S tng nng lng ca nhng qu o d ca ion kim loi hon ton c b tr bng nng lng to lin kt gia ion kim loi v phi t. Trong trng phi t bt din nhng qu o t2g v eg ca ion, tng ng vi nhng nng lng khc nhau. Hiu s nng lng c k hiu l o. C th ni rng, do c im hnh hc ca h bt din, nng lng tng ng ca nhng qu o t2g nh hn 0.4o. so vi nng lng ca nhng qu o d suy bin bc 5 ca phc gi thuyt, tc l phc thu c nu nh khng xy ra s tch mc nng lng trng tinh th (hnh 2.7). Cng do nguyn nhn , nng lng tng ng ca nhng qu o eg ln hn nng lng ca qu o gi thuyt suy bin bc 5: 0,6o. Trong phc bt din (v d [Ti(H2O)6+] c mt in t nm trn qu o d c mc nng lng thp nht. Bng thuyt tnh in n gin th khng th xc nh c rng trong phc cht nhng qu o d li tng ng vi nhng gi tr nng lng khc nhau. Do thuyt ny gi thuyt rng in t d cn phi c mc nng lng ca qu o d suy bin gi thuyt. S tht th qu o d ri vo t2g c nng lng nh hn nng lng qu o suy bin gi thuyt 0,4o v do phc s bn hn so vi phc da trn c s m hnh tnh in n gin. C th ni mt cch n gin rng, in t d v do ton b phc c nng lng nh l do n nm trn qu o d(t2g) l qu a c th tch xa phi t nht. i vi phc, gi tr 0,4o gi l nng lng n nh ha bi trng tinh th. Trong bng 1 di y, chng ti s dn ra nng lng n nh ha bi trng tinh th i vi nhng ion kim loi trong phc bt din. Bng 2.1: Nng lng n nh ha bi trng tinh th i vi nhng ion kim loi trong phc bt din S in t d t2g eg Nng lng t2g eg Nng lng n
trong ion kim loi 1 2 3 4 5 6 7 8 9 10
n nh ha 0,4 0,8 1,2 0,6 0,0 0,4 0,8 1,2 0,6 0,0
nh ha 0
1,6 2,0 2,4 1.8
Ta nhn thy rng nng lng n nh ha bi trng tinh th c th tnh mt cch d dng bng cch thm vo gi tr 0,4o cho mi in t chim qu o t2g v gi tr -0,6o cho mi in t chim in t eg. Nh vy, nng lng n nh ha bi trng tinh th i vi h c 5 in t d: Hoc l bng: 3*(0,4o) + 2*(-0,6o) = 0,0o Hoc l bng: 5*(0,4o) + 0*(-0,6o) = 2,0o Ngha l ph thuc vo s phn b 5 in t trn qu o t2g v eg Thuyt tnh in n gin coi ion kim loi nh ht nhn nguyn t c bao quanh bi m my in t hnh cu. Thuyt trng tinh th ngh m hnh tt hn v thuyt ny gi thuyt rng nhng in t d to thnh m my in t khng phi c dng hnh cu do xu hng trnh nhng v tr m phi t chim gi (nhng in t ny to thnh nhng m my in t khng c hnh dng hnh cu bng cch t sp xp mt cch la chn vo nhng qu o c gi tr nng lng thp, hng vo gia nhng phi t). Do , thuyt trng tinh th gii thch mt cch hon ton c th hiu c nguyn nhn v sao nhng tnh ton tnh in n gin cho ta nhng gi tr thp hn v bn ca phc v nhng hp cht ca nhng kim loi chuyn tip. Thuyt tnh in n gin b qua s phn b in t khng theo hnh dng hnh cu v hu qu pht sinh do hin tng nng lng n nh ha bi trng tinh th. Mt trong nhng im gy nn s phn i vic ng dng thuyt tnh in n gin cho lin kt trong phc kim loi l s bt lc ca thuyt ny trong khi gii thch s to thnh nhng phc phng vung. C th chng minh rng nu 4 in tch m c gi xung quanh ion trung tm dng ch bng lc tnh in, th nhng in tch m phi nm nh ca t din. Ch c s phn b nh th, nhng nhm mang in m mi nm khong cch cc i i
vi nhau v chu lc tnh in nh nht. iu ch ph hp vi thc t trong iu kin, nu ion trung tm c i xng cu. Nhng s i xng khng in hnh i vi nhng ion ca kim loi chuyn tip bi v in t nm trn qu o c nng lng thp hng vo gia nhng phi t v do khng c i xng cu. Trong phn cui ca chng ny, chng ta s nu r, thuyt trng tinh th cho php gii thch s tn ti nhng phc phng vung cng nh d on tnh khng bn ca mt s phc bt din.
dx2y2 Nng lng dx2-y2dz2

dxydxzdyz
dx2y2
s p
dz2
e
dxy
dx -y dz
dz
dxydxzdyz
T din
Bt din
T gic lng chp
dxz dyz
Hnh 2.9: S tch mc nng lng bi trng tinh th nhng qu o d ca ion trung tm trong nhng phc i xng khc nhau. Ch s ca l k hiu cho nhng i xng khc nhau. Nh vy,chng ta nghin cu xong trng hp tch mc nng lng ca trng tinh th i vi phc bt din, v s xt nhng phc c cu to hnh hc loi khc. thun tin ta bt u xt s tch mc bi trng tinh th vi cu hnh bt din v theo di xem s tch mc s bin i nh th no khi hnh hc hnh dng bin i (hnh 2.9). Khi chuyn t cu hnh bt din sang cu hnh phng vung, hai phi t no vn nm v tr i din trong bt din b tch ra. Nu nhng phi t trn trc z s nhng v tr nh th no khong cch kim loiphi t ln hn mt cht so vi khong cch ca 4 phi t trong mt phng xy th s thu c cu to t gic (hnh 2.10). iu kin cho php nhng phi t trong mt phng xy tin gn ti ion trung tm. Nhng qu o d tng ng trong mt phng xy s chu lc y ca cc phi t ln hn so vi lc y trong cu to bt din v do nng lng ca nhng qu o d x -y v dxy tng ln (hnh 2.10). Trong khi nhng qu o d trong mt phng xy v yz s chu lc y nh hn ca cc phi t tch xa ra theo trc z thm mt khong cch no . Hin tng
2 2
dn ti s gim tng i nng lng ca qu o d x v s gim khng nhiu nng lng ca qu o dxz v dyz so vi dng bt din.
2
Hnh 2.10: Phc t din, nguyn t trung tm chnh gia Chng ta cng quan st thy hnh nh tng t v s tch mc i vi cu to chp vung, trong mt phi t nm trn trc z cn 4 phi t cn li v ion trung tm phn b trong mt phng xy. S tch hon ton hai phi t trn trc z dn ti s to thnh dng thng vung km theo s tng nng lng ca qu o d x -y v dxy v s gim nng lng ca cc qu o d x , dxz, dyz.
2 2 2
Hnh dung mt cch r rng s tch mc nng lng bi trng tinh th nhng qu o d i vi cu to t din s gp kh khn hn. Trc ht, cn tng tng hnh t din v trong khi lp phng (hnh 2.10) sao cho 4 nh ca t din phn b vo 4 nh ca khi lp phng. Nu by gi ta v cc trc x, y, z sao cho chng i qua trung tm ca khi lp phng v qua cc trung tm ca 6 mt gii hn th c th hnh dung v tr ca 4 phi t tng i theo cc qu o d ca ion trung tm. Nhng qu o d nm dc theo h trc Decartes ( d x -y v d x ) cch xa cc phi t hn l nhng qu o phn b gia cc trc (dxy, dxz, dyz). Do nhng qu o eg ( d x -y v d x ) tng ng vi gi tr nng lng thp, nhng qu o t2g (dxy, dxz, dyz) c c trng bng gi tr nng lng cao hn. Ngi ta pht hin ra rng trong trng hp ny c hiu s nhng gi tr nng lng ca nhng qu o eg v t2g, ngha l b tch mc bi trng tinh th k hiu l t, ch bng mt na o. Do , hiu ng trng tinh th to iu kin thun li cho s to phc bt din hn l cho s to phc t din
2 2 2 2 2 2
T tnh ca phc nhng kim loi chuyn tip cng c gii thch m mn bng thuyt trng tinh th. Nhng kim loi chuyn tip c cc mc nng lng ph d mi ch c in t lp y mt phn, trn nhng qu o theo nh lut Hund s c nhng in t khng ghp i. V d: ion kim loi c 3 in t d (gi l h d3) c th c 3 in t khng ghp i i v 3 i in t , cn ion kim loi c 8 in t d c th c 2 in t khng ghp .
Cht c nhng in t khng ghp i b t ht gi l cht thun t (sc ht tng i yu hn so vi nhng vt liu Ferro t nh st), gi tr lc ht ca t i vi mt cht xc nh s in t khng ghp i ca n.
C th o thun t mt cch tng i n gin bng cn. t mu vo trong ng treo trn cn, ri cn trng lng mu khi c v khi khng c lc tc dng ca t trng. Nu mt cht l thun t th trng lng ca n s tng ln khi t di tc dng ht ca t trng. S tng trng lng l s o s in t khng ghp i trong hp cht. Ngi ta pht hin rng mt s phc ca kim chuyn tip khng tun theo quy lut Hund. V d mt s phc ca Co(III) c cu hnh in t d6 nh [Co(NH3)6]3+ khng b t trng ht (nhng phc ny c tnh nghch t). Nhng phc, trong mt s in t khng ghp i ca ion kim loi trong trng thi kh c ghp i c gi l nhng phc spin thp. Phc ca Co(III). [CoF6]3- thun t v c 4 in t khng ghp i. l v d ca phc spin cao. Trong phc ny, s phn b in t trong nhng ion kim loi to phc tng t nh khi n trng thi kh. S phn b in t ca hai phc c th hnh dung nh sau: v Cc phc ny c nhiu tn, v d: [Co(NH3)6]3+ [CoF6]3: Phc spin thp ni orbital ghp i : Phc spin cao ngoi orbital.
By gi cn phi hiu v sao in t trong nhng h li phn b trn orbital d theo nhng cch khc nhau. Trc ht cn phi cng nhn, s phn b in t c quyt nh bi hai yu t. Th nht, in t c xu hng sp xp nh th no c th c s in t khng b ghp i cc i, ph hp vi quy tc Hund. cho in t ghp i cn tiu tn nng lng ln thng lc y ca hai in t trn cng qu o. Th hai, trong trng tinh th nhng in t d c xu hng chim nhng qu o c nng lng thp ngha l trnh c cng nhiu cng tt tc dng y ca phi t. Nh vy, nu bn t c () ln thng s mt i ca bn do s ghp i in t th in t s ghp i v ta s thu c phc loi spin thp. Khi s tch mc bi trng tinh th () khng ln th in t gi trng thi khng ghp i ca mnh v phc spin cao s xut hin. Hnh 2.11 ch cho ta thy rng gi tr o ca [CoF5]3- nh hn gi tr o ca [Co(NH3)6]3+. Phc c gi tr ln s ch yu l phc spin thp.
0
Co ( NH 3 )6
3+
[CoF6 ]
Phc spin cao
Phc spin thp
Hnh 2.11: Gi tr tng i v tch mc bi trng tinh th (o) i vi nhng qu o d ca phc bt din spin cao v spin thp ca Co(III) Mt s v d khc v s tch mc bi trng tinh th v s phn b in t trong phc c dn ra trn hnh 2.12. Nh trnh by trn y, gi tr tch mc bi trng tinh th quyt nh vic cc in t d trong ion kim loi ghp i hay l tun theo quy lut Hund. i lng ny nh hng nhiu n tnh cht ca kim loi chuyn tip. Mc tch mc
bi trng tinh th ph thuc vo nhiu yu t. Bn cht ca phi t gy nn trng tinh th l yu t c bit quan trng. Ph hp vi nhng khi nim tnh in, nhng phi t c in tch m ln v nhng phi t c th tin gn ti ion kim loi (nng lng ion nh) gy nn s tch mc ln nht. Nhng ion c in tch khng ln khi tin gn n qu o d lm cho nhng qu o ny khng thun li cho in t v mt nng lng. iu ny c khng nh bng thc nghim qua s kin: nhng ion F- c kch thc nh nn gy nn hiu ng trng tinh th ln hn so vi nhng ion c kch thc ln hn nh: Cl-, Br-, I-. V s tch mc bi trng tinh th l kt qu ca tng tc mnh ca phi t vi cc qu o hng ti gia chng nn tch mc ln ch c th t c khi nhng phi t hi t nhng in tch m ca mnh ln qu o. Ta c th hnh dung d dng rng phi t c mt i in t t do (v d nh NH3) c kh nng hi t ln hn so vi nhng phi t c 2 hoc c mt s i in t t do ln hn (III) v (IV)
: Cl :
[Fe(H O ) ]
2 6
3+
Fe(CN )6
]3
[Cu (NH ) (H O ) ]
3 4 2 2
2+
[Ni(CN )4 ]2
Hnh 2.12: S tch mc bi trng tinh th v s phn b in t theo mc nng lng i vi mt s phc. Hai phc u tin c cu to bt din, nhng phc khc (t tri qua phi) c cu to t gic, phng vung v t din (hnh 2.10)
:
[CoCl4 ]2
C th s dng tnh cht nu trn gii thch hin tng, nhng phn t NH3 trung ha in gy nn s tch mc ca trng tinh th ln hn trng hp ca nhng phn t nc hoc l ca nhng ion halogen mang in tch m. Ni chung, ta s thy kh r kh khn khi s dng m hnh tnh in n gin gii thch kh nng gy s tch mc ca trng tinh th ca nhng phi t khc nhau. Ngi ta thy rng, kh nng gim theo trt t dn ra di y: Trng phi t mnh Trng phi t trung bnh Trng phi t yu CO, CN->Phen>NO2>en>NH3>NCS->H2O>F->RCO2>OH->Cl->Br->I gii thch dy cn phi t b m hnh hon ton ch c tnh cht ion tnh in i vi lin kt trong phc v cng nhn rng y tng tc cng ha tr cng tn ti. l l do xut hin thuyt trng phi t. Bin dng ca thuyt trng tinh th l thuyt trng phi t. Theo thuyt ny th trong phc cht cn tn ti lin kt cng ha tr, t nht th thuyt ny cng c th gii thch mt cch nh tnh gi tr tch mc bi trng tinh th gy nn bi nhng phi t khc nhau. Nhng ht nh CO, CN-, Phen v NO2- l nhng phi t to nn trng tinh th mnh nht, chng ta c kh nng to lin kt vi nguyn t kim loi trung tm. Lin kt c th lm tng mnh s tch mc bi trng tinh th. Trng thi oxy ha ca ion kim loi v loi cc in t d ca n cng nh hng n mc tch. Trng thi oxy ha cao ca ion kim loi gy nn s tch mc ln hn. Phc [Co(NH3)6]3+ nghch t v l phc spin thp cn phc [Co[NH3)6]2+ li thun t v l phc spin cao. S tch mc bi trng tinh th trong phc Co(III) gn hai ln ln hn so vi phc ca Co(II). iu c gii thch bng s ghp i cc in t. Gi tr o ln i vi Co(III) c th gii thch nh sau: V ion kim loi c th tch nh hn v in tch cao hn nn phi t tin gn hn v do tng tc mnh hn vi cc in t d cu n. S tch mc bi trng tinh th trong cc phc [Rh(NH3)6]3+, [Ir(NH3)6]3+, ln hn so vi phc [Co(NH3)6]3+. Ni chung s tch mc nhng phc c cha cc in t 5d th ln hn cn s tch mc nhng phc c cha cc in t 3d th nh hn. C th gii thch s kin nh sau: Nhng qu o 5d tri di trong khng gian xa hn v nh vy tng tc vi cc phi t mnh hn. Thnh tu ln nht ca trng tinh th l gii thch thnh cng mu ca nhng hp cht ca kim loi chuyn tip. Hiu s nng lng khng ln trong nhng phc kim loi chuyn tip l hu qu ca chuyn in t t mc nng lng thp ln mc nng lng cao (gia nhng qu o d khng tng ng: t2g v eg) c thc hin nh s hp th nh sng trng thy. l nguyn nhn gy mu ca phc, v d dung dch nc ca Ti(III) mu tm, mu c gii thch bng ph hp th ca phc [Ti(H2O)6]3+ (hnh 2.13). S hp th nh sng ca phc trong vng ph trng thy c gii thch bng s chuyn in t qu o t2g ln eg (hnh 2.14).
% nh sang b hp th bi mu
100
Xanh
Vng
50
0 0 0.2 0.6 0.4 di nh sng () 0.8 1 (x 104)
Hnh 2.13: Ph hp th ca phc [Ti(H2O)6]3+. Dung dch [Ti(H2O)6]3+ c mu tm , v n hp th cc tia vng cho qua cc tia xanh v . eg nh sng 5000 t2g t2g eg
[Ti(H O ) ]
2 6
3+
[Ti(H O ) ]
2 6
3+
Hnh 2.14: S chuyn in t d-d gy nn mu tm ca phc [Ti(H2O)6]3+ Ph hp th ca nhng phc c s in t d ln hn mt phc tp hn v s cch chuyn in t nhiu hn. Phng trnh Plank (2.17) lin h nng lng chuyn in t vi di sng ca nh sng b hp th.
E =
h: Hng s plank (6,62 erg/giy). C: tc nh sng (3,00 cm/giy).
hc
(2.17)
Nng lng c o bng erg trn phn t cn o bng cm. T phng trnh 2.17 c th xc dnh c hiu s nng lng in t i vi nhng qu o d m in t thc hin b chuyn. Thay nhng gi tr h, C v s dng nhng h s chuyn tng ng (s Avogadro 6,021023 phn t/mol) v hng s Ioule 4,18107 erg/kcal) th c th thu c cng thc (2.18)
E =
2, 8 4 * 1 0 5
(2.18)
E: o bng kilocalo/mol v o bng . Ngi ta pht hin cc i trong ph hp th ca [Ti(H2O)6]3+ nm = 5000. Cc i tng ng vi gi tr hiu nng lng gia nhng qu o t2g v eg khong 57 kilocalo/mol l i lng bc nht vi nng lng lin kt. Mc d rng, i lng nh khng ng k so vi nhit hydrate ha ca Ti3+ (phng trnh 2.19) l 1027 Kcal/mol, i lng ny rt quan trng v cn thit hiu ha hc ca cc kim loi chuyn tip. Ti3+(trng thi kh)+H2O[Ti(H2O)6]3+(trong dung dch nc)+1027Kcal/mol (2.19) C s ion ca thuyt trng tinh th cho ta m hnh n gin gii thch nhiu tnh cht ca kim loi chuyn tip, cu to, bn, ph hp th ca phc. Nhng cn nhn xt rng m hnh ion n gin ca thuyt trng tinh th khng cho mt khi nim r rng v lin kt trong nhng hp cht ca kim loi chuyn tip. Mt khc, trong khi nghin cu phc cht, ngi ta thu c nhiu bng chng thc nghim khng nh vai tr ca c hai loi lin kt: lin kt ion v lin kt cng ha tr. Thuyt phn nh trung thnh c hai c tnh y trong lin kt ca phc l thuyt qu o phn t.
II.6.
THUYT QU O PHN T (MO)
Thuyt qu o phn t cng ngy cng ph bin i vi cc nh ha hc. Thuyt ny ch ti c c tnh cng ha tr c c tnh ion ca lin kt ha hc mc d khng nu ln nhng im ny. Phng php MO xem xt s phn b in t trong phn t ging nh l thuyt hin i gii thch s phn b in t trong nguyn t. Trc tin l v tr ca cc ht nhn trong nguyn t v ca cc qu o quay quang chng c xem nh l xc nh, nhng qu o phn t ny (MO) phn b trong nhng vng c xc sut tm thy in t ln nht trong khng gian. Thay th cho s phn b ca mt nguyn t nhng qu o phn t ny tri ra trn ton phn t hoc l trn mt phn ca n. Di y ch dn ra nhng tnh ton dng qu o phn t cho trng hp nhng phn t n gin nht. V s tnh ton da trn c s nhng nguyn tc chung gp nhiu kh khn nn ngi ta thng s dng phng php tnh gn ng t hp tuyn tnh nhng qu o nguyn t (LIKAO). Tt nhin l, MO ca phn t cn phi lm cho ngi ta nh li nhng qu o nguyn t m t phn t c xy dng ln. Xut pht t nhng dng bit ca qu o nguyn t c th s b hnh dung cc dng MO c trng. T hp tuyn tnh cng v tr hai qu o s cho hai qu o phn t c m t trong hnh 2.15. Mt qu o phn t xut hin do s cng nhng phn xen ph ca qu o nguyn t. Cn mt qu o khc xut hin do s tr cc vng xen ph ca AO. Qu o phn t thu c do s cng vng xen ph ca hai qu o s chim vng khng gian gia hai ht nhn, qu o ny c gi l qu o phn t lin kt. Nng lng tng ng vi qu o phn t ny thp hn nng lng ca mi qu o nguyn t s to thnh n. Qu o phn t thu c bng cch tr nhng vng xen ph ca qu o nguyn t khng chim vng khng gian cha nhng ht nhn, c nng lng cao hn nng lng ca nhng qu o nguyn t khi u c gi l qu o phn t phn lin kt. Hiu nng lng ca nhng qu o phn t phn lin kt v lin kt c th tnh c nu ch rng in t ca qu o lin kt nm di tc dng ca c hai ht nhn cn in t ca qu o phn t phn lin kt th ch chu tc dng ca 1 ht nhn.
Tr xen ph Qu o A phn lin kt Cng xen ph Qu o lin kt P P Tr xen ph Qu o Cng xen ph A

A
phn lin B
Qu o lin kt Tr xen ph
Qu o A phn lin kt Cng xen ph Qu o lin kt Hnh 2.15: S to thnh qu o phn t theo phng php KAO T hp nhng qu o nguyn t s cho qu o phn t (sigma). T hp nhng qu o nguyn t p nh ch r trn hnh 2.15, c th cho hoc l qu o phn t hoc l qu o phn t . Trong trng hp qu o phn t mt phng qua hai nhn c xc xut in t tm thy bng khng. in t trong qu o phn t ch nm trn hoc di trc lin kt. minh ha vic s dng MO, c th xem biu nng lng MO vi mt s phn t n gin. Biu nng lng phn t H2 c nu ln hnh 2.16. Trong nhng nguyn t Hydro ring bit, mi qu o nguyn t ch c mt in t. Trong phn t H2 c hai in t cng nm trn qu o phn t lin kt c nng lng thp. Phn t H2 bn hn nhng nguyn t hydro t do bi v c hai in t trong phn t u nm trn qu o c nng lng thp. Hiu nng lng gia nhng qu o nguyn t v qu o phn t lin kt ph thuc vo vn l nhng qu o nguyn t trong phn t xen ph ln nhau nhiu hay t. Xen ph nhiu gy khc nhau ln v nng lng v do lin kt nhau cht, xen ph t th s khc nhau v nng lng nh v trong trng hp ny phn t s c gi tr nng lng ch nh hn mt cht so vi nhng nguyn t ring bit.
AO
MO
AO
Nng lng
s* 1s s H H-H H 1s 1s
Hnh 2.16: Biu mc nng lng qu o phn t ca phn t H2 AO MO AO
Nng lng
s* 1s s H H : He+ He 1s 1s
Hnh 2.17: Biu mc nng lng qu o phn t ca ion diheli. Ion He2+ (ion diheli) l h ba in t, biu mc nng lng ca nhng qu o phn t ca n c nu ln hnh 2.17. V trn mt qu o ch c th dung np 2 in t nn in t th ba phi i vo qu o phn t phn lin kt *, qu o ny tng ng vi nng lng cao hn nng lng qu o nguyn t ca nhng nguyn t Heli ring bit. Nh vy, s np in t vo qu o phn t * c c trng bng s mt i nng lng v do h to thnh km bn hn. iu ph hp vi nhng quan st thc nghim. Nng lng lin kt ca He2+ ch bng 5 Kcal/mol trong khi nng lng lin kt ca phn t He2 l 103 Kcal/mol. Phn t He2 c 4 in t khng bn hn so vi 2 nguyn t Heli t do. Biu mc nng lng MO trong trng hp tng qut i vi phn t AB c din t trong hnh 2.18. i vi phn t ny c th c mt s v hn MO c nng lng cao cng nh nguyn t A v B c th c mt s v hn qu o nguyn t c nng lng cao, nhng iu ng ch l nhng qu o c nng lng thp, trn c in t. Nu nh c hai
loi nguyn t khc nhau th nng lng qu o nguyn t cng khc nhau (v d: nng lng tng ng vi nhng qu o 1s ca nhng nguyn t A v B l khc nhau). Qu o nguyn t nhng nguyn t m in hn c nng lng thp hn. S khc nhau v nng lng ca nhng qu o nguyn t ca hai nguyn t (hnh 2.18 nhng i lng b v d) l thc o mc ion ca lin kt. Trong phn t H2, nhng qu o 1s ca hai nguyn t hydro tng ng vi cng mt gi tr nng lng v do lin kt khng c c tnh ion. AO c 2S Nng lng a 1 MO 2 c 2S AO
a b 1S A
2 a 1 1S B
AB
Hnh 2.18: Biu mc nng lng qu o phn t ca phn t AB. S khc nhau ln v nng lng ca hai qu o nguyn t t hp thnh qu o phn t c c trng bng tnh ion cao ca lin kt. Trong phn t AB, nng lng qu o phn t 1 gn vi nng lng ca qu o 1s ca nguyn t B. iu c ngha l qu o phn t 1 ging qu o 1s ca B nhiu hn so vi qu o 1s ca A. Nu mi nguyn t A v B u a ra mt in t to thnh qu o phn t th s dn ti s chuyn in tch t nguyn t A n nguyn t B bi v gi tr nng lng ca 1 gn vi gi tr nng lng ca qu o nguyn t B hn l ca A. Nhng i lng a v c cn c rt ng ch trong mt mi quan h khc, chng ph thuc vo mc xen ph nhng qu o nguyn t ca A v B v l mc cng ha tr ca lin kt. Trn hnh 2.18: a < c v nh vy c ngha l mc xen ph nhng qu o ca cc nguyn t A v B trong khng gian khng ln trong trng hp 1s, cn trong trng hp ca nhng qu o 2s th ln hn v chng tri di ra xa ht nhn hn. Gi tr nng lng thot ra khi to thnh lin kt AB ph thuc vo s in t v nng lng in t ca cc nguyn t A v B tham gia vo s to thnh phn t. Bng 2.2 minh ha nhng iu trnh by trn. Bng 2.2: Nng lng thot ra khi to thnh phn t AB in t ca A tham gia vo lin kt 1s1 0 1s1 in t ca A tham gia vo lin kt 0 1s1 1s1
Nng lng thot ra khi to thnh phn t AB a+b A 2a+b
1s2 1s2 1s22s1 1s2 1s2 1s22s1 1s22s2
0 1s2 1s2 1s22s1 1s22s2 1s22s2 1s22s2
2a+b 0 c+d C 2c C 0
Biu mc nng lng qu o phn t i vi phc kim loi tng i phc tp hn so vi nhng phn t hai nguyn t n gin. Nhng cui cng da trn biu nng lng qu o phn t cng c th pht hin kh tt nhng c im bit ca phc, v d: [Co(NH3)6]3+ v [CoF6]3- (hnh 2.19). Pha bn tri m t nhng qu o nguyn t 3d, 4s v 4p ca Co2+. Nhng qu o nguyn t c nng lng cao hn hoc thp hn chng ta khng cn ch ti. Khi cng hp 6 phi t th ch cn bn phi ca biu l khc mt cht so vi nhng biu trnh by trn. y ch nu ln mt mc nng lng tham gia vo s to thnh lin kt (i khi ngi ta s dng biu nng lng phc tp hn). V 6 phi t ng nht nn mc nng lng tng ng vi nng lng qu o ca mi phi t. Nng lng qu o ca phi t ni chung thp hn nng lng ca kim loi v v vy lin kt c c tnh ion n mt mc no . Do nhng qu o phn t lin kt ging qu o phi t hn l ging qu o kim loi v s chuyn in t ca kim loi vo nhng qu o phn t y dn n s chuyn in tch t ion kim loi n phi t. Hai qu o d (qu o eg: d x -y v d x ), qu o 4s v 3 qu o p hng dc theo cc trc x, y v z trn phn b phi t. Do s xen ph qu o kim loi v phi t dn n s to thnh 6 qu o phn t lin kt v 6 qu o phn t phn lin kt: s(1), p(3), d(2), d*(2), s*(1), p*(3). Nhng qu o t2g (dxy, dxz, dyz) khng hng ti qu o ca phi t v do khng tham gia vo s to thnh lin kt . Nng lng ca chng khng bin i v chng c gi l nhng qu o khng lin kt.
2 2 2
3 p*
s*
4p Nng lng 4s 3d
u *
dXYdyzdxz d1 p s
2
Phi t
Co(III)
Co ( Fe )
6FAO
AO
MO
3 p*
s*
4p Nng lng 4s 3d
u *
2d1 p s Co(III)
Co ( NH 3 )
3
Phi t
6NH
Hnh 2.19: Biu mc nng lng qu o phn t ca phc spin cao [CoF6]3- v phc spin thp [Co(NH3)6]3+. Nhng in t ca Co(OH) v phn t nm trn qu o phn t ca phc th chng lp y 6 qu o lin kt phn t, tng ng vi 6 lin kt kim loi phi t. Nhng in t cn li phn b trong s nhng qu o phn t khng lin kt (qu o t2g) v qu o phn t
d* (phn lin kt). Qu o phn t d* l kt qu tng tc nhng qu o dx2-y2 v dz2 ca kim loi vi nhng qu o ca phi t nhng v nhng qu o phn t d* gn v gi tr nng lng vi nhng qu o d x -y v d z ca kim loi, chng khc nhau khng ng k. Do , s phn b nhng in t d trn cc qu o phn t t2g v trong s phn b in t ca m hnh trng tinh th nu ln trc y cng vi s in t phn b gia nhng qu o t2g v eg.
2 2 2
Nu s khc nhau v nng lng gia nhng qu o t2g khng lin kt v nhng qu o phn t d* t, th qui lut Hund c thc hin. Phc [CoF6]3- hon ton ging trng hp ny, nhng in t d phn b theo cc qu o t2g, d*2. Hai in t nm trn qu o d* lm gim s in t trn qu o lin kt d v do lm yu lin kt CoF. Nu ln nh [Co(NH3)63+] tt c cc in t c xu th chim qu o t2g. Nguyn nhn ca s phn b nng lng gia nhng qu o t2g v d* hoc l eg theo hai thuyt l khc nhau. Theo thuyt trng tinh th th s tch mc nng lng l hu qu ca tc dng y tnh in ca phi t i vi nhng in t d. L thuyt qu o phn t th ch yu li qui s tch mc cho s to thnh lin kt cng ha tr. Nhng qu o eg ca kim loi v qu o ca phi t xen ph ln nhau cng nhiu th nng lng ca nhng qu o d* cng cao. L thuyt qu o phn t c th gii thch nh hng ca lin kt n bn ca phc kim loi v n gi tr tch mc ca trng tinh th gy nn bi nhng loi tinh th khc nhau. V s gii thch nh lng tng i phc tp nn y ch a ra s gii thch nh tnh. Trn y nu ln rng, lc tng tc cng ha tr ph thuc vo mc xen ph nhng qu o nguyn t ca 2 nguyn t lin kt. Trong cc v d trc ta mi ch nghin cu s xen ph . Trong [Fe(CN)6]4- v trong phn ln nhng phc khc c ng thi c lin kt v lin kt (hnh 2.20). Trong lin kt phi t s dng nh l mt baz Lewis v a i in t ca mnh vo qu o trng eg ( hnh 2.20, d x -y ) dng chung. Trong lin kt ion CN- x s nh l mt acid Lewis v nhn in t t nhng qu o t2g hon thnh ca kim loi (trn hnh 2.21, t qu o dxy). S c mt ca lin kt cng nh ca lin kt lm tng lin kt kim loiphi t v lm cho ion [Fe(CN)6]4- bn mt cch c bit. Trong nhng ion cha oxy nh MnO4- lin kt v cng rt quan trng. Trong trng hp ny phi t (oxy) a in t to lin kt .
2 2
C th gii thch hiu ng trng tinh th ln to bi nhng phi t nh CN, CO v cc phi t khc to lin kt cng bng con ng nh vy. Nhng qu o t2g ca kim loi trong phc bt din hng thng theo nhng lin kt (hnh 2.20). Nh nhn xt trc y, nhng qu o t2g hng ti gia nhng phi t v do khng c th to lin kt . Trong lin kt vi cc phi t loi CN nhng in t t2g mt phn chuyn ti cc phi t. Qu trnh (tng tc lin kt) h thp nng lng nhng qu o t2g. Trn hnh 2.7 r rng rng qu trnh h thp nng lng nhng qu o t2g phi lm tng 0. Tt c nhng iu trnh by trn y ch l phng php n gin ca thuyt qu o phn t. Phng php ny ch minh ha c mt s lun im c bn v s ch li ca thuyt ny. L thuyt qu o phn t rt c hiu qu tnh ton, s ng gp ion v cng ha tr vo lin kt kim loiphi t. Cui cng ta hnh dung mt cch r rng rng c 3 thuyt trong nhng trng hp tt nht cng ch c mt gn ng m thi. C 3 thuyt trn u c th gii thch mt cch nh tnh nhiu c tnh ca phc kim loi. Hin nay c 3 thuyt u c s dng, hoc l thuyt ny hoc l thuyt khc c th thun li i vi mt trng hp no . Thuyt qu o phn t l linh hot nht v c th l gn ng vi s tht nht. ng tic l thuyt ny
l phc tp nht v khng thun li cho mt khi nim r rng, c th v mt ha hc i vi nhng nguyn t lin kt.
Lin kt Fe-CN
Lin kt Fe-CN Hnh 2.20: Lin kt v lin kt trong phc [Fe(CN)6]4-.
Lin kt c to thnh nh s dng qu o d y in t ca ion Fe2+ v qu o phn lin kt ang cn trng ca CN- (xem * trn hnh 2.15).
II.7.
HNH DNG HNH HC CA CC HP CHT PHI TR
Ngi ta xc nhn rng phc kim loi c cu trc rt l khc nhau. Phc ca Ag thng l thng hng, phc ca Be thng l t din. St to cc hp cht carbonyl c cu trc tam gic lng chp, phc ca Co(III) th lun lun l bt din cn ta phi tr quanh mnh 8 nguyn t F (hnh 2.21). Mc d rng phc kim loi c cu trc v s phi tr rt khc nhau nhng ngi ta vn thng hay gp s phi tr l 4 hoc 6, chng thng tng ng vi dng t din v phng vung (i vi s phi tr l 4) v bt din (i vi s phi tr l 6). Khi nghin cu phc kim loi ta s thy r rng v sao dng bt din l thng gp nht. Thuyt lc y ca i in t ha tr cho ta hnh nh gn ng v rt c li d on cu hnh nhng hp cht ca nguyn t trung tm c s phi tr bit. H qu rt ra t thuyt ny l kt lun: Nhng phc c s phi tr l 4 v 6 ch yu c hnh dng t din v bt din. Nhng phc ca kim loi chuyn tip i khi khng tun theo quy lut y v chng c nhng in t d. Thuyt trng tinh th cho ta s gii thch n gin nht v nh hng c th c ca nhng in t d n cu trc ca phc.
OH Be OH Thng hng OH OH T din O2N Co F O2N Bt din NO2 F i lng tr vung F NO2
CO CO CO Fe CO Tam gic lng chp F F
F Fe F F
Hnh 2.21: Nhng hp cht minh ha mt s cu hnh ca phc kim loi. L thuyt ny khng nh rng nhng qu o d c dng hnh hc v hng trong khng gian c bit ng thi nhng in t d nm trn nhng qu o xa ht nhn nht. Nhng in t d trong nhng phc cht c s phi tr l 6 v 4 gy nn s mo m hnh dng bt din v t din. S mo m cu hnh l do phi t trnh nhng v tr m nhng in t d chim xung quanh ion kim loi. V d trong phc [Ti(H2O)6]3+, xung quanh ion Ti3+ c 6 phn t nc do hy vng rng phi t s phn b theo hnh bt din. Nhng cn phi nghin cu nh hng ca nhng in t d ca kim loi n cu trc ca phc. Nu nh trn mc ph d ngoi c khng, nm (khng ghp i) hoc l 10 in t d th nhng in t ny khng gy nn s mo m cu hnh. Mc ph d hon thnh 10 in t, th c s i xng in t hnh cu. Nhng ht tch in (v d phi t) nm trn mt cu c ion kim loi trung tm s chu tc dng ca lc tnh in ng nht, khng ph thuc vo v tr ca ht trn mt cu. Nu trn 5 qu o d c mt in t th ion kim loi cng c i xng cu. Nh vy, trong nhng trng hp ny, nhng in d s khng nh hng g n v tr ca phi t. Phc [Ti(H2O)6]3+ c mt i in t, in t ny s y nhng phi t gn n. Theo thuyt trng th in t ny nm trn qu o t2g c nng lng thp v tri di ra gia nhng phn t H2O. Bi v in t nm trn qu o dxy nn s c s thay i ca cu hnh bt din d on. V qu o dxy nm gn 4 phi t trong mt phng xy nn nhng phi t ny s tch xa ion kim loi hn 4 phi t kia. Hiu ng cng xy ra tng t nu in t nm trn cc qu o dxz hay dyz . V nhng qu o t2g hng ti gia nhng phi t nn nh hng ca in t nm trn mt trong cc qu o s kh nh. S tht khng c nhng bng chng thc nghim v s thay i t gic cu hnh ca phc [Ti(H2O)6]3+ hoc l h d khc. Trong nhng phc bt
din cha 2 hay 3 in t , chng chim cc qu o t2g tri di gia nhng phi t. Mt d c th hy vng s thay i t nhiu cu hnh ca h d2 bt din nhng mt ln na iu khng c xc nhn bng d kin thc nghim. Trong phc d3 bt din nh [Cr(H2O)6]3+ trn mi qu o t2g c mt in t. i vi cc orbital d, mi mt phi t trong s 6 phi t phn b theo hnh bt din, s nm gn 2 in t d v do chu lc y. Trong trng hp ny khng nn ch i mt s thay i cu hnh no c v iu cng khng c pht hin bng thc nghim. Phc [Cr(H2O)6]3+ l h d4 spin cao, ba in t u tin ri vo nhng qu o t2g v khng gy nn s thay i cu hnh bt din. in t th 4 ri vo mt trong nhng qu o eg hng ti phi t. Nu in t nm trn qu o d x -y th n b 4 phi t trn mt phng xy y. S tht, ngi ta thy rng nhng phc kim loi d4 c s phi tr l 6 c cu to thay i trong tt c mi trng hp c nghin cu. V d trong phc MnF3 , mi nguyn t Mn(III) c bao quanh bi 6 ion F, phn b nh th no cho 4 phi t trong s gn vi ion Mn3+ hn 2 phi t khc ( hnh 2.22).
2 2
By gi cn nghin cu s thay i cu hnh bt din do s c mt ca 0, 1, 2, 3, 4, 5 (khng ghp i) v 10 in t gy nn. Nhng h spin cao d6, d7 , d8 v d9 tng t nh h d1, d2, d3 v d4 tng ng (nm in t u tin cho m my in t i xng cu, nhng in t cn li gy nn s mo m). nhng phc d9 c s phi tr l 6 th s thay i t gic cu hnh c th nhn thy ging nh nhng phc d4. Nhng phc ca Cu (II) thng c ly lm v d. Trong phc [Cu(NH3)4]2+, xy ra s thay i t gic mnh n l thu c phc phng vung.
Hnh 2.22: V d hiu ng phc An Telep Nhng cn nhn xt rng nhng phn t dung mi trong dung dch phc loi chim cc v tr di v trn mt phng. Chng nm xa ion kim loi hn nhng nhm nm trn mt phng. S thay i cu trc i xng l h qu ca s lp y tng phn nhng mc nng lng in t (trong nhng trng hp ny l mc ph d) c gi l hiu ng An Telep. Cng cn thit phi xt s thay i cu hnh bt din c quan st thy nhng dng spin thp. Nhng h d6 spin thp tng t nh nhng h d3, 6 in t lp y nhng qu o t2 .V mi mt trong s 6 phi t u nm gn trc tip 2 trong s nhng qu o nn s thay i khng xy ra v ngi ta quan st thy cu hnh bt din u n. Nhng phc d8 spin thp tng t nh nhng h d4. Hai in t cui cng ri vo mt qu o eg v tc dng mnh vi nhng phi t hng v pha qu o ny. S thay i d nhn thy l trng hp khi hai phi t b tch xa ion trung tm tng i nhiu so vi 4 phi t khc. S tht l, hu nh tt c nhng phc d8 spin thp, khng c s ngoi l no u phng
lun. S thay i nhng phc bt din gy nn bi nhng in t d c nu ln trong bng 2.3. Nh vy, chng ta thy s thay i cu trc bt din do nhng in t d gy nn, nhng phc kim loi c th c cu trc t din nhng n t ph bin hn phc bt din v nhng dng bt din thay i. Nu ion kim loi b vy quanh bi 4 phi t th c th hy vng cu hnh t din. Nhng in t d c th gy nn s thay i t din. Bng 2.3: S thay i cu hnh bt din do nhng in t d gy nn. H Spin cao d1, d6 d, d
2 7
Cu trc d on
Ghi ch
Thay i t gic Thay i t gic Khng thay i Khng thay i
Khng quan st thy Khng quan st thy Khng nh bng thc nghim Khng nh bng thc nghim
d3, d8 d4, d9 d5,d10 Spin thp d6 d

3
Thay i t gic mnh Khng nh bng thc nghim
Khng thay i Thay i t gic mnh
Khng nh bng thc nghim Phc di dng vung phng
Cn nhn xt 2 ngoi l, nh thy t 2 v d trn y, nhng phc d8 spin thp, phi t 4 l phc phng vung cng nh nhng phc phi t 4 d9 v d1 spin cao. Nhng phc kim loi cha 0, 5 v 10 in t khng ghp i khng gy nn s thay i ng k nh nhn thy trc y. Trong phc bt din, nhng in t trn nhng qu o hng ti nhng phi t khng gy nn s thay i ng k. Nh vy, nhng phc t din d1, d2, d6, d7 c l l b thay i. Trong nhng h t din d3, d4, d8, d9 hiu ng An Telep th hin kh r rng. Nhng nhng v d ca cc hp cht loi c rt t. Nhng phc t din spin thp khng cn phi bn lun g ti, v nhng v d v nhng phc cht loi ny khng c l s tch mc bi trng tinh th (t) trong phc t din qu nh khng lm cho nhng in t ghp i. Mt d rng d on ha tp th ion phc ca ion trung tm vi s phi t bit l kh chnh xc, nhng d on s phi tr ca ion trung tm l tng i kh khn. S ht tnh in ca nhng din tch m ca phi t (hay l ca nhng phn t phn cc) i vi ion kim loi tch in dng l nguyn nhn gy s phi tr cao. L thuyt lin kt ha tr tin on rng: s ln lin kt gia nhng nguyn t dn ti bn ln ca hp cht to thnh. Xu hng to phc c s phi tr cao mu thun vi nhng yu t tp th v vi s y nhau tnh in gia nhng phi t (hoc l qui tc Pauli). Cn nhn xt rng nhng kim loi chuyn tip thng c s phi tr l 6. S phi tr 4 c quan st thy ch yu nhng phc cht ca nhng anion tng i ln nh Cl, Br, I v O2 hoc l ca nhng phn t trung ha c th tch ln. Nhng kim loi chuyn tip dy th 2, th 3 cng c s phi tr cao, v d l 8.
II.8.
CNG TRNG PHI T
Nng lng y electron trong phc kim loi chuyn tip t obitan t2g n obitan eg thng trong vng kh kin. S hp th sng bc x c th lm cho nhng electron dch chuyn. Ph hp th l kt qu ca nhng nng lng y ny. Cng ca phi t c suy ra t s o ph ca s tch obitan v chng c sp xp nh sau: I- < Br- < SCN- < Ce- <NO3- < F- <NO2- ~ OH- < HCOO- < C2O42- < H2O < -NCS<CH2(NH2)COOH < EDTA4- <Pyridin ~ NH3 < Ethylenediamine ~ diethylenetriamine < triethylenetetramine < dipyridyl< CN-.
II.9.
CU TRC PHN T V TAN
Mt trong nhng yu t nn c ch khi chn thuc th ha hu c trong phng php trc quang, chun v kt ta l tan. tan ca mt phn t trong nc l c mi lin h vi s phn cc ca cc phn t. Mt phn t cha cc nhm OH; SO3H; COOHrt phn cc, tan nhiu trong nc. Mt phn t cha nhm bo hoc a nhn th tan t trong nc, nhng tan tt trong dung mi khng phn cc. Trong phng php trng lng, s kt ta c mi quan h vi tan trong nc. Nhng cht kt ta l nhng cht t tan trong nc. Trong dung mi chit, nhng cht chit nn tan t trong nc nhng tan nhiu trong dung mi hu c. tan ca thuc th hu c rt quan trng trong thuc th phn tch. c trng ca phn ng ca thuc th hu c trong phn tch ph thuc ln vo s c mt ca cc nhm chc v cu trc chnh ca phn t. iu ch nhng hp cht vi s chnh sa cu trc ci thin c trng ca thuc th, bng cch lm tng tan ca chng trong nc hay trong dung mi hu c hoc lm gim tan ca sn phm phn ng. Khi mt cht tan trong nc c lc vi mt dung mi hu c khng trn ln, c s cnh trnh gia hai dung mi. Mt cht phn cc th tan trong dung mi phn cc, cht khng phn cc th tan trong dung mi khng phn cc. Mt th d v s chnh sa cu trc phn t c th tm ra s ng dng ca salinaldehyde nh l thuc th ca hydrazin. V tr ca nhm OH so vi cc nhm nh l =CO, NO2; N=N, nhng nhm ny to lin kt cho nhn vi nguyn t hydro trong nhm OH, nh hng n tan. Nhng hp cht cha nhm OH v tr octo th tan yu trong nc so vi cc ng phn meta hoc para. v tr octo c th do nguyn nhn hnh thnh phc chelate thng qua lin kt hydro. tan ca mt cht trong nc lun lun gim khi thay nguyn t oxi bng nguyn t lu hunh trong phn t, do kh nng to lin kt vi nc ca nguyn t lu hunh yu hn nguyn t oxi. Nguyn t N trong nhm amine l mt trung tm hot ng to c lin kt vi nc. Thng qua s proton ha, nhng hp cht th amoni c hnh thnh t nhng amine. Chng phn cc rt mnh v tan tt trong nc. S proton ha cng c th lm gim kh nng tan trong nc ca cht hu c. Mt vi cht mang nhm COOH trong mi trng acid mnh th tan yu hn trong mi trng acid yu. Trong mi trng trung tnh hoc acid, phenol tp trung ch yu pha hu c sau khi c lc vi nc. Tuy nhin, trong dung dch baz mnh th phenol chuyn v dng ion phenolat mang in tch m v kt qu l n c chit t pha hu c vo pha nc.
Kh nng tan trong nc ca hp cht hu c ph thuc phn ln vo kh nng phi tr vi phn t nc. S hydrate ha nhng hp cht c khi lng phn t ln nhn chung khng thay i tan ca chng so vi nhng hp cht c khi lng phn t b. Khi thay th nhm methyl trong dimethylglyoxim bng hai nhm furyl th lm tng nhy vi Ni ln ba ln. S thay i cu trc c th gp phn lm tng nhy.
II.10. PHC CHELATE (VNG CNG)

Phi t c hai hoc nhiu nhm nhng electron, c th c nhiu hn mt cp electron dng chung vi ion kim loi bng 2 hay nhiu hn lin kt phi tr xung quanh ion kim loi. Nhng phi t nhn chung nh l nhng phi t a lin kt, thng thng gi l phi t hai rng, ba rng, .... Nhng phi t a lin kt to phc vi ion kim loi, c dng phc tp v c gi l phc chelate. Mt nguyn nhn chung l trong phc chelate phi t c cha nhm acid (OH) hoc nguyn t nhng electron. Mt trong nhng nguyn t nhng electron c bn l nguyn t N. Trong s hnh thnh phc chelate, nhm acid mt mt proton v tr thnh anion nhng electron V d: S to thnh phc chelate vi 8Hydroxyquinoline vi Cu2+.
Cu 2+ + 2 N OH N Cu O N O + 2H +
nh hng ca phc chelate: Mt tnh cht ni bc ca phc chelate l bn ca chng khng n nh. Chng ging vi nhng hp cht thm hu c. Khng phi hp cht hu c no cng to c phc chelate vi kim loi. Mt phi t trong phc chelate phi c 2 nhm nhng electron hoc hai nhm acid hoc mt nhm acid vi mt nhm nhng electron. Hu ht cc nhm c tnh acid hu c u cha cc nhm: OH; SH; NH. Phi t cha cc nguyn t O, N, S thng to lin kt phi tr vi ion kim loi. Nhng phi t ny phi nh c trong phn t ti nhng v tr m c th to vi kim loi nhng vng 5 hoc 6 cnh.
II.11. S N NG KHNG GIAN V CHN LC

V s cn tr v khng gian trong cu trc phn t, mt vi thuc th h c c chn lc cao. S tc ng qua li gia cc phn ging nhau hoc khc nhau c th nh hng n tc phn ng. N c th lm nh hng n nhng tnh cht vt l nh: kh nng hp th nh sng, tan, s kt tinh, ... Hu ht bn ca phc ph thuc vo hnh dng ca chng khi nhng obitan trng ca ion kim loi c sp xp theo cc hng m ti cc obitan ca phi t s lp y m khng c s bin dng quan trng. Nhng cu trc ging nhau c th ch khc nhau s n ng khng gian. Nu nhng phi t khng lin kt c kch thc ln, th s bao bc xung quanh nguyn t kim loi ca chng s gy cn tr.
II.12. BN CA HP CHT PHI TR

bn ca cc cht trong dung dch c cho bi cn bng sau: M + nL MLn p dng nh lut bo ton khi lng, hng s cn bng c tnh nh sau:
0 n= AML n n AM AL
AM: hot ca M, 0 n l hng s cn bng ca phn ng. V d : nh hng ca pH ln s cn bng ca acid EDTA. M: ion kim loi, Y l EDTA4M + Y MY H+ HY,H2Y,H3Y.... S nh hng ca hydro ln s cn bng c tnh thng qua Y
Y 4- Y 4- Y = = 234Y' [ H 6 Y ][ H5 Y ][ H 4 Y ] H3Y H 2Y HY Y [ ]
[Y4-] nng ion Y4- t do, [Y] l tng nng ca Y trong dung dch. nh hng ca phi t cnh tranh lm cn bng ca EDTA vi kim loi dch chuyn sang tri. M + Y MY L ML nh hng ca phi t ln s cn bng c tnh thng qua M
M =
[M] [ M']
[M] Nng ion kim loi Mn+ t do trong dung dch , [M] tng nng ion kim loi M trong dung dch. v M c tnh theo cng thc sau:
1 2 3 n =1+K1 [ L] +K 2 [ L] +K 3 [ L ] +......+K n [ L ] M
k1, k2....kn l hng s bn cc phc ML, ML2....MLn. Hng s bn iu kin KM'Y' c tnh nh sau:
K M'Y' =
[ MY ] [ M ][ Y ]
m [ Y ] = Y [ Y'] v [ M ] = M [ M']
suy ra:
K MY =
[ MY ] [ M'][ Y'] Y M [ MY ] [ M'][ Y']
K MY Y M =K M'Y' =
vy hng s bn kin
K M'Y' =
[ MY ] [ M'][ Y']
II.13. NG HC CA PHN NG TRONG THUC TH HU C.

Nhng hn hp phn tch cha mt bn cht giao thoa vi nhau, thng n b tch hoc b che vi nhng thuc th c thun li hn. Hu ht, nhng phn ng trong ho phn tch xy ra nhanh nhng mt vi phn ng chm c s dng ph bin trong ha phn tch. EDTA phn ng nhanh vi hu ht cc kim loi nhit phng. N cng phn ng chm vi Cr(III) nhit phng nhng dng tinh khit phc Cr(III) vi EDTA phn ng nhanh khi c un nng n cng c th c xc tc khi thm mt t bicarbonate. Crom c th c pht hin chn lc da trn kh nng phn ng ca n vi EDTA. Khi phc ca Co(II) vi EDTA hoc Co(II) vi 1(2pyridylazo)2naphthol (PAN) khong pH = 5 th chng b oxi ho bi H2O2. Cc phc ca Co rt bn trong acid mnh. Chloramin c dng phc dch chuyn in tch vi amino acid pH=9, c un nng nhit 60oC trong khong t 3060 pht phc c hnh thnh v chng bn trong mi trng acid trung bnh.
CHNG III:
NHM CHC PHN TCH V NHM HOT TNH PHN TCH
III.1. NHM CHC PHN TCH

Khi nghin cu thuc th hu c ngi ta nhn thy rng: Nhm nguyn t c cu to c trng trong phn t thuc th quyt nh tnh c trng ca n. Ngi ta gi nhm c trng ny l nhm chc phn tch. Sau y chng ta s nghin cu mt s nhm chc phn tch. III.1.1. Nhm chc phn tch ca AgI
Nhiu hp cht hu c cha nhm amine bc 2 (> NH) phn ng vi mui bc. Mt trong nhng hp cht y l rhodamine.
HN S C S C O
CH2
Rhodamine to vi bc rhodaminat bc mu vng (AgOSC3H2ONS2) trong dung dch acid. Feigl cho rng rhodamine c 4 dng tantomer
HN S C S C O S HN C S C
OH
N C S
C
CH2
OH
N C S
CH2
CH
SH
CH2
(I)
HN S C S
(II)
C O R''
(III)
HN C S C O
(IV)
V nhng dn xut ca rhodamine c cu to tng qut
CHR'
CHR'
R= CH3, C2H5. R= C6H5NH=N, C6H5N=N C kh nng phn ng vi AgI cng nh rhodamine nn khng c c s cho rng rhodamine phn ng vi AgI dng tantomer II v IV (nhm OH v SH v ni i trong vng). Hp cht c cu to
NH S CS
L hp cht khng th no chuyn v ni phn to nn lin kt i gia nit v nguyn t carbon khng cha lu hunh trong vng lu hunh cng phn ng vi AgI nh rhodamine. Do , quan im cho rng rhodamine phn ng vi AgI dng tantomer III cng khng ng vng. V vy ch cn c th cng nhn rhodamine phn ng vi AgI dng tantomer I. Nghin cu nhiu dn xut ca rhodamine Feigl nhn dimethylaminolanzyliden rhodamine l thuc th nhy nht ca AgI. xt rng: p
HN S C S
O
CH3
C H
N CH3
Bozoncenckun cho rng mui bc to thnh trong phn ng c cu to V hoc VI.

Ag
N C S
O
CH3
C H
N CH3
Ag
N C S
O
CH3
C H
N CH3
VI
Nhng d kin ca Feigl v ca mt s tc gi khc hon ton ph nhn nhng cng thc cu to trn (V;VI). Bi v ngi ta khng th chp nhn s tn ti loi hp cht ni phc vng 4 nh trn c. Hn na, khng phi tt c nhng mui ca rhodamine (c bit l mui AgI) v ca nhng dn xut ca n u tan trong dung mi khng nc. Vy mui ca AgI vi pdimethylbenziliden rhodamine phi c cng thc:
Ag
N C S
O
CH3
C H
N CH3
Tng kt nhng d kin thc nghim ngi ta cng nhn nhm chc phn tch ca AgI l: S=CNHC= III.1.2. Nhm chc phn tch ca Cu(II)
R CH OH CH OH C NOH C NOH
Nhng axyloinoxim c cng thc tng qut
Cha nhm nguyn t l nhng thuc th c trng ca CuII (phn ng xy ra trong mi trng ammoniac). Nhng hp cht ny ng vai tr nh mt acid kp v to vi Cu(II) mui mu lc khng tan trong nc v c cng thc:
R CH "R O Cu N O C
R"
Khi nghin cu tc dng ca axyloinoxim vi Cu(II) ngi ta chia chng ra lm 2 loi: Mt loi bao gm nhng hp cht to mui vi Cu khng tan trong ammoniac (trong nhng hp cht ny ng bo ho phi t) Mt loi bao gm nhng hp cht to mui vi Cu tan trong ammoniac (trong nhng hp cht ny ng cha bo ho phi t) Mui ng to thnh thuc loi ny hay loi khc l do bn cht nhng gc c trong phn t quyt nh: Nu trong phn t thuc t c gc thm th mui ng tng ng khng tan trong ammoniac. Nu trong phn t c gc bo th mui ng trong nhiu trng hp tan trong ammoniac. Trng lng ca gc khng nh hng n tan ca mui ng trong ammoniac. Feigl ngh cng thc cu to mui ni phc khng tan trong ammoniac ca ng vi xyloxinin nh sau.
R
CH
C N Cu
R"
C th dng tan ca mui thu c trong dung mi khng nc (v d trong chloroform) lm c s ng h ngh ca Feigl. Mui ca ng vi 1,2xyclohexanolonoxim khng tan trong nc nhng tan trong ammoniac. iu c gii thch l cyclohexim bo ho phi t v do khng c kh nng phi tr vi ng. Do , nu phn t cha nhng gc cha bo ho phi tr th mui ng to thnh (do phi tr ni phn) khng tan trong ammoniac. Nu nh nhng gc ny bo ho phi tr th mui ng tan trong ammoniac.
HC O
C N Cu O
C th rt ra kt lun l khi s dng nhng axyloinoxim lm thuc th cho Cu(II) th mui to thnh s khng tan nu vng l vng 5.
C O
C N Cu O
Chnh v vy nn nhng oxim ca methylacetonylcarbinol v chloracetophenol cha nhm nguyn t.

HO C C C N OH
Khng th to vng 5 c nn nhng hp cht ny khng th to mui ng khng tan. Epharan khng nh rng nhm
C C H OH
NOH
Trong nhn thm cng l nhm chc phn tch ca CuII (v d salicylaldoxim to mui ni phc)
C C H O
OH N Cu
Do ngi ta cng nhn 2 cu to nhm chc phn tch ca Cu(II)

C OH C NOH 2HC C NOH
Nm ngoi nhm thm
Nm trong nhm thm
III.2. NHM CHC PHN TCH CA Th

KuzHeop ch ra rng nhng hp cht cha gc AsO3H2 v nhm hydroxyl v tr ortho i vi nhm azo phn ng vi Th. Nhng hp cht sau y tham gia vo phn ng
AsO3H2 N N HO SO3H OH AsO3H2 N N HO OH
SO3H
SO3H
(II)
AsO3H2 N N HO AsO3H2 N N OH OH
HO3S
SO3H
HO3S
SO3H
(III) ng thi KuzHeop cng pht hin cc hp cht nh
(IV)
COOH
OH
OH AsO3H2
HO
N SO3H
C H
(V) Cng cho phn ng tng t vi Th.
(VI)
Nhng hp cht cha gc AsO3H2 v tr para i vi nhm azo v d nh

HO SO3H H2O3As
SO3H AsO3H2 H2O3As N N OH OH
HO3S
SO3H
Mc d to kt ta vi mui Th(IV) nhng khng gy nn s i mu. Tt c nhng iu trnh by trn cho php chng ta cng nhn nhm nguyn t.
B N A HO
A: =N, CH B: AsO3H2, COOH L nhm chc phn tch i vi ThIV. III.2.1. Quan im hin nay v nhm chc phn tch
Ngy nay, khi nghin cu tc dng ca thuc th hu c vi ion v c ngi ta ch n 2 iu c bn nht l cu to ca thuc th hu c v kin trc in t ca ion v c. Cng nhn cu to ca thuc th hu c v kin trc in t ca ion v c quyt nh c ch phn ng gia chng th chng ta khng th cng nhn c mt nhm nguyn t no (trong thuc th hu c) li ch phn ng vi mt ion m li khng c phn ng vi nhng ion khc c kin trc in t tng t. Trn c s , ngy nay ngi ta cng nhn c nhng nhm nguyn t c trng cho phn ng vi mt s nguyn t c tnh cht ho hc gn nhau ngha l nhm chc phn tch i vi mt s nguyn t tnh cht ho hc ging nhau. Quan im trn chng nhng rt ng n v mt l thuyt m cn c ngha thc t ln bi v nu cng nhn c nhng nhm nguyn t c trng ch phn ng vi mt ion th nhng nh phn tch hay ho hc ni chung s chy theo phng hng tng hp ra nhng
thuc th ch phn ng vi mt ion no m thi m iu v nguyn tc l khng th thc hin c (Trng hp iodide phn ng vi h tinh bt ch l mt ngoi l c mt khng hai). Chng ta ch c v s ch c nhng thuc th tc dng vi mt s ion m nhim v ca nhng nh phn tch l phi to nn nhng iu kin cn thit (lm thay i ho tr, to phc, iu chnh pH, tch .) cho phn ng tr thnh c trng cho mt ion no cn xc nh.
III.3. NHM HOT TNH PHN TCH

Trn y, chng ta ni v nhm chc phn tch nhm nguyn t c trng gy nn kh nng phn ng ca thuc th vi ion v c nhng khng phi tt c cc cht hu c cha cng mt nhm chc phn tch u c gi tr nh nhau v mt phn tch. nhy v c trng ca nhng phn ng pht hin mt ion bng nhng thuc th hu c cha cng mt nhm chc phn tch, c th rt khc nhau. Do , ngi ta cng nhn rng trong phn t thuc th, ngoi nhm chc phn tch quyt nh c ch ca phn ng, cn c nhng nhm nguyn t khc khng nh hng n bn cht c ch phn ng. Chng lm bin i tnh c trng ca sn phm cui cng trong mt chng mc nht nh. V d lm bin i tan, c trng, cng mu v bn thu phn Nhng nhm nh vy KulBe gi l nhm hot tnh phn tch. V nhm hot tnh phn tch khng nh hng n c ch phn ng (khng gy nn c ch) nn tc dng c trng ca n phi th hin ng nht trong tt c cc phn ng da trn cng mt hiu ng phn tch (sinh ra kt ta, to mu hoc l s lin hp c hai hiu ng y). Do , s nhm chc phn tch th nhiu nhng s nhm hot tnh phn tch li rt c hn. Sau y l 1 s v d minh ho Bng 3.1: Nhm hat tnh phn tch Thuc th 5(p dimethylamino benzyliden) rhodamine pdimethylamino benzene azophenyl arsenic acid pdimethylamino benzene azo anthraquinone pdimethylamino benzene azo beznyliden camphorxin
H3C N H3C C H C
Cng thc
O C NH C S S
Ion phn ng Ag+
H3C N H3C
H3C N H3C
AsO3H
Zr(III)
[SnCl6]2-
H3C N H3C N
C H
C H3C HON
CH2
C CH3 H2 C C CH2
Hg22+
Tetramethyl pphenylendiamine p,p Tetramethyldiamine diphenylmetan Iodidemethylat (p dimethyl aminostyril

H3C
H3C N H3C
H2 C
CH3 N CH3
CH3 N CH3
Ag+, Cu2+, Hg2+, Hg22+ Pb2+,Mn2+
N H3C
H3C N H3C
C H
H C N CH3
Zn2+, SCN-
T cc dn chng nu trn chng ta d dng nhn thy rng trong tt c cc thuc th u c cha nhm (CH3)2N. S c mt ca nhm ny khng phi l ngu nhin. Mt khc, nhng thuc th nu trn l thuc th c trng nht la chn t mt s thuc th cha cng mt nhm chc phn tch. Do vy chng ta c th suy lun mt cch hon ton hp l rng: Nhm pdimethyl aminobenzene l nhm lm cho thuc th tr thnh c trng hn, nhm l nhm hot tnh phn tch. Trong nhng phn ng to kt ta, khi a nhng nhm Cl-, Br-, CNS, I- vo nhn quinoline, nhn pyridin vo phn t thuc th, hoc bin nhn benzene thnh nhn naphthalen, cng lm cho nhy ca phn ng tng ln. Nhng nhm cng l nhng nhm hot tnh phn tch (V d: nhy tng (khi chuyn hp cht bn tri thnh hp cht bn phi)).
NO ONH4 N NO ONH4
Cufferon
AsO3H O
Neocuferon
AsO3H
Phenyl arsonic acid
Antraquinone-1- arsenic acid
CH3
CH3
2 Methyl pyridine
2 methyl quinoline
CHNG IV: NHNG LUN IM L THUYT V C CH PHN NG GIA THUC TH HU C V ION V C

IV.1. HIU NG TRNG LNG
Khi tng trng lng phn t thuc th nhy ca phn ng to kt ta tng ln r rt, nhng iu ch c thc hin khi: S lm tng trng lng phn t c thc hin phn ca phn t nhm, nh hng n c ch ca phn ng. Nhng nhm lm tng trng lng khng th hin tc dng slovat ho. Hiu ng gi l hiu ng trng lng. Sau y chng ta xt mt s v d minh ho. Bng 4.1: Cc v d v hiu ng trng lng Thuc th 2methyl pirydin (-pycoline) 2methyl quinoline (Quinadine) 2methyl5,6 benzoquinoline
N
Cng thc
TLPT 93
nhy /ml 330 13
CH3
143
N
CH3
193
CH3
2methyl benthiazol
N
173
CH3
S
13
Iodidemethylat 2 methylbenzthiazol
I
N
CH3
166 (khng k iodide)
2,5
C2H5
Khi a nhng nhm solvat ho, nh nhm sulfo vo phn t thuc th th nhy ca phn ng to kt ta gim xung. Ta ly mt v d minh ha Cng thc
SO3H N N
TLPT 378
nhy (/ml) 1
SO3H N N
458
SO3H
SO3H N N HO SO3H
100
538
SO3H
500
(Ni nh vy khng c ngha l khi ta c nhng nhm solvat ho vo phn t thuc th l lun lun gy kt qu m m ngc li, trong nhng phn ng o mu. Chng ta cn to nhng sn phm mu tan th cc nhm solvat ho li gip ta rt c lc). Nh vy, khi chn nhm lm tng trng lng a vo phn t thuc th cn rt thn trng. Nhng gc thm, gc bo v nhng nguyn t Halogen l nhng nhm bo m nht: Nhm th a vo cng cch xa phn xc nh c ch phn ng ca phn t thuc th cng bo m khng gy hiu qu phn tch m. Khi a vo phn t thuc th nhng nhm solvat ho thng lm gim nhy ca phn ng. Nhng nhm ny l: nhm hydroxyl, nhm amino, nhm sulfo
IV.2. HIU NG MU
Mu ca phn t thng lin h vi nhng lin kt i trong phn t v vy trc ht chng ta hy xt c im ca loi lin kt ny. IV.2.1. Lin kt mch lin hp
Lin kt gia 2 nguyn t c to thnh bi nhng orbital S c tnh cht i xng cn, ch hng theo ng ni lin kt 2 ht nhn ca 2 nguyn t c gi l lin kt . Lin kt cng c th c to thnh bi nhng electron p v s. V d nh nhng lin kt HO v HN. Nhng lin kt ny cng l nhng lin kt bi v mt in tch ca nhng m my in t to lin kt l ln nht trn ng ni lin ht nhn 2 nguyn t tng ng. Mt cch tng t, lin kt c th c to thnh bi cc electron sp, min sao mt in t tp trung ln nht trn trc lin kt thng. c im ca lin kt l rt bn nn t b kch thch. Do , nhng hp cht to bi lin kt thng khng hp th nh sng trong min trong thy hoc l trong min quang ph gn t ngoi. Ngoi ra, khi kch thch gc hoc nhng mng khc nhau. Nh vy, nhng hp cht ch to bi nhng lin kt khng phi l nhng hp cht ng ch i vi phng php o mu m nhng hp cht quan trng nht phi l nhng hp cht c ni i. Ngay c khi ch xut hin mt phn lin kt i cng dn ti kt qu l lm chuyn cc i hp th v pha sng di. Ta c th ly ion nitrat lm v d. Khi to thnh ion NO3- c s ghp i cc electron 2px, 2py, 2pz ca nguyn t nit vi mt trong 2 electron p khng ghp i ca mi nguyn t oxy.
Nh vy l trong hp cht to thnh (NO3-) mi nguyn t oxy cn li mt electron p cha ghp i. V O l nguyn t m hn N nn c th cho rng mt trong s 3 electron (ca 3 nguyn t) trng thi t do gy nn in tch m ca ion NO3- cn 2 in t cn li th ghp i vi nhng in t 2s2 ca N to thnh lin kt th 2. Nhng do h qu ca hin tng lai to li nn tt c nhng lin kt gia N v O l nh nhau v phn b trong cng mt mt phng ng thi mi lin kt NO u l trung gian gia lin kt n v lin kt i. S to thnh mt phn lin kt i dn ti kt qu l ion nitrat c cc i hp th min t ngoi 305mm. Trong khi nghin cu v cc phn ng mu, s hp th nh sng ca cc hp cht hu c c cc ni i c ngha c bit quan trng. Lin kt th hai hoc th ba to nn bi cc electron p c gi l lin kt . Lin kt ny c nhng c im ring. V d: trong phn t ethylene CH2=CH2 do lai to sp2 nn cc lin kt nm trong cng mt mt phng l ng nht v gc gia cc lin kt gn vi 1200. Nh vy, mi nguyn t carbon cn li 1 in t p. Nhng in t p ny to lin kt nm trong mt phng thng gc vi mt phng ca lin kt .
c im ca lin kt l km bn v do d b kch thch. Ethylene c cc i hp th 180mm. Nhng cht mu hp th mnh nh sng trong min trng thy thng c trong phn t mt s lin kt i, c bit l nhng lin kt i xen k vi nhng lin kt n to thnh mch lin hp, di tc dng ca nh sng th khng ch nhng electron ring bit b kch thch m c h mch ni i lin hp b kch thch. Do nh hng mnh n mu. C nhiu thuyt gii thch nh hng ca mch lin hp ln mu nh thuyt ph bin nht l thuyt mu kh in t. Theo thuyt ny th khi in t nm trong nhng nng lng c di bng di ca mch lin hp. i vi nhng cht mu n gin c cu to i xng v c mch lin hp thng th c th s dng cng thc sau y tnh di nh sng ca cc i hp th th nht.
= hc 8mCl2 N N = =K 2 E h N+1 N+1
(4.1)
h l hng s plank, C l tc nh sng, E l nng lng lng t hp th, m l khi lng in t, l l di ca mt mt xch ca mch, N l s in t tham gia vo mch lin hp cng chnh l s mt xch ca mch lin hp. Sau khi thay cc hng s vo ta thu c gi tr ca hng s K=63,7. Nh vy i vi nhng cht mu mch thng, i xng, di sng ca cc i hp th trong min trong thy ch ph thuc vo s mt xch N ca mch lin hp. Di y, dn ra nhng d kin tnh ton v thc nghim i vi nhng gi tr N khc nhau trong cht mu xyamine i xng c cng thc cu to nh sau
C2H5
H C
C H
C H
N+
C2H5
Cl-
S mt xch ca mch bt u t C2H5N (bn tri) n =NC2H5 (bn phi) bng N=102n S n 0 1 2 3 S N 10 12 14 16 tnh ton (nm) 580 706 834 959 thc nghim (nm) 590 710 820 930 Nhng d kin tnh ton v thc nghim kh ph hp vi nhau. i vi nhng cht mu khng i xng, s tnh ton tng i phc tp v thng ch c tnh cht nh tnh, tc l s ph thuc tuyn tnh gia di sng ca cc i hp th vo s mt xch ca mch lin hp. Cn nhn mnh rng, phng trnh nu ln s ph thuc ca vo N l hon ton theo kinh nghim ch cha c chng minh bng l thuyt. IV.2.2. Nhm mang mu, nhm tng mu
c im ca nhng cht mu hu c c dng lm thuc th trong phn tch do mu xc nh cc kim loi c cha h ni i lin hp. i vi h ni i lin hp th di tc dng ca nh sng, khng phi ch l nhng in t ring bit m l c h lin hp b kch thch, do nh hng mnh n mu. Vy h lin hp l nhm mang mu ph bin v quan trng; nhng mt cht khi ch cha h lin hp th thng hp th nh sng yu. Cc i hp th s chuyn v pha sng di v cng hp th s c tng cng nu trong phn t ca cht hp th nh sng xut hin nhng in tch ion. Nhng khng phi tt c nhng nhm ion ho (nhm to mui) u c nh hng n ph hp th nh sng. Nhm sulfo SO3H, Cl, F, Br v mt s nhm khc c in tch in t c nh hu nh khng nh hng. Ngc li, nhng nhm cha nhng i in t khng phn chia tc l nhng nhm cho in t nh NH2, (NR2), OH, SH v nhng dn xut ca n li th hin nh hng rt mnh. Nhng nhm c in t hoc l nhng nhm nhn in t v d nh NO2 > C =O NOCN > SO2, N=N v mt s nhm khc cng nh hng tng t. C hai loi nhm ny c gi l nhm tng mu. Khi trong phn t mt cht c cha 2 loi nhm tng mu c c tnh ngc nhau th nh hng n mu li c bit mnh. Ta c th minh ha iu ny qua v d sau y:
NO2
NO2
NO2
OH Bezene 255nm Phenol 275nm
OH Nitrobezene p-Nitrophenol 268nm 315nm
OAnion p-nitrophenol 400nm
Ngi ta quan st thy trt t tng mu ca nhng nhm tng mu nh sau: CH3O < OH < NH2 < (CH3)2N < (C2H5)2N < C6H5NH Nhng ion v c cng c tc dng mang mu v ng gp phn ca mnh vo mu sc ca hp cht to thnh gia ion v c vi thuc th hu c. Bng 4.2 : Nhm mang mu quan trng nht ca cc nguyn t Nhm mang mu MeO MeS MeN MeHal IV.2.3. Nguyn t Cu, Au, Ti, V(IV)(V), Nb, Cr(III)(IV), Mo, W, U, Pu, Mn(II)(VII), Re, Fe, Co, Ni, Ru, Rh, Ir. Cu, Au, In, Sn, Sb, Bi, Mo, U, Fe, Co, Ni, Os. Cu, Re, Fe, Co, Ni, Ru, Pd. Cu, Au, Ti, Sb, Bi, Fe, Co, Ni, Ru, Pd, Os, Ir, Pt. Mt s qui lut to phc mu
Trong nhng cng trnh ca mnh KyzHeob i n kt lun nh sau: Mu ca nhng phn ng gia thuc th hu c v ion v c l do 2 nguyn nhn: Tc dng ca nhm mang mu trong phn t thuc th Tc dng mang mu ca ion v c Nu trong phn t thuc th c cha nhng nhm mang mu th bn thn thuc th c mu v phn ng mu ch l s bin i (i khi l s tng cng ) mu thuc th. Nu ion v c c tc dng mang mu (ion c mu) th phn ng mu c th xy ra gia ion kim loi v thuc th khng mu. Do khng th xut hin phn ng mu gia thuc th khng mu v ion kim loi khng c tc dng mang mu. Phn ng ca cc nguyn t c mu ring vi cc cht mu hu c nhy hn nhng li km la chn hn so vi phn ng mu gia cc ion ny vi thuc th khng mu. V d: xc nh CuII di dng Amonicacat la chn hn xc nh Cu bng dithizone. Ag+, Zn(II), Cd(II) v cc nguyn t khng c mu ring khng cn tr phn ng mu gia Cu(II) v ammoniac nhng nhy ca phn ng ny li thp. H s hp th phn t ca amonicat ng khong bng 120. Xc nh Cu bng thuc th mu nh dithizone, pyridinazoresocsin th nhy hn (h s hp th phn t ca nhng hp cht y khong 2.104 v ln hn) nhng la chn ca nhng phn ng ny li thp. Ag(I), Zn(II), Cd(II) v nhng cation khc cho phn ng mu vi dithizone u cn tr phn ng ny.
Bng con ng thc nghim ngi ta rt ra c kt lun sau y: max ca phc ph thuc vo mc ion ca lin kt kim loiphi t, m ion ca lin kt tt nhin phi ph thuc vo bn knh ion kim loi. Do vy, nu so snh nhng ion c cu to lp v in t ging nhau th ta d dng nhn thy, bn knh ion kim loi cng ln th s chuyn dch max ca phc cng tin gn vi max dng anion t do ca thuc th (dng m lin kt c ion ln nht). Ta c th ly trng hp to phc ca phenylfluoron vi cc cation kim loi ho tr 4 minh ha. Phc c cu to nh sau:
HO O Men+ HO
O
Ion H Ge(IV) Ti (IV) Zr (IV) Anion t do Bn knh ion kim loi ( A0) 0,50 0,65 0,83 max (nm) 468 508 525 540 560 iu ny c th gii thch bng lc ht tnh in i vi nhng electron t do cui mch lin hp. Nhng ion c bn knh nh Ge(IV) ht mnh nn max chuyn mnh v pha sng ngn cn Zr(IV) c bn knh ln nn ht yu. V do max gn vi max ca dng anion t do ca thuc th. Khi cation kim loi to phc mu vi thuc th mu acid th cc i hp th mu ca phc chuyn v pha sng di so vi ph hp th dng phn t (dng acid) ca thuc th nhng thng s chuyn dch ny khng ln bng khi to thnh anion t do (mui natri) ngha l: max dng acid ca thuc th < max phc < max dng anion t do ca thuc th C s chuyn dch cc i hp th nh vy l v ion kim loi lin kt vi u m ca mch lin hp ko in t v pha mnh v nh vy l mch lin hp di ra. V d:
O OH OH O OOH
H2A ( Alyzarin vng) max=400nm
HA ( Alyzarin ) max=520nm
O OO-
A2 (Alyzarin tm) max=620nm

Me Me O O O O O OH
Alyzarin kim loi mu (max=450520nm) Nu s to phc xy ra, trong mt mc tng i, l do nhm mch nhnh ca thuc th v do trng thi in t ca mch lin hp t b ng chm n nn mu ca phc v ca thuc th t khc nhau. V d nhng cht mu azo, dn xut ca salixilic acid, khng thay i mu vng ca mnh khi to phc vi Al3+ v nhng kim loi tng t.
O 2N
OH COOH
Me3+
O2 N
N C
O
O
Me+ O
2H+
Mu ca nhng cht nh triarymetan cng khng bin i khi to hp cht vi nhng phc acid ca kim loi. Cu to mch lin hp ca cation tm tinh th hu nh khng b bin i d ion ngc du l anion Cl- hay anion TaF6- (hoc l nhng cation tng t khc).
H3C N H3C C ClN
+
CH3 CH3
CH3 CH3
Ch c nhng tnh cht khc l bin i: Chloride ca tm tinh th t tan trong benzene, toluene cn hexafloretanat ca tm tinh th li b cht d dng bng benzene. Ph hp th nh sng ca phn chit v ca dung dch nc ca chlorua tm tinh th hu nh ng nht. Trn y chng ta xt hiu ng trng lng v hiu ng mu ring bit nhng trong nhng phn ng to sn phm mu kh tan th mt nhm th c th th hin c hai hiu ng y.
V d: So snh tc dng ca dimethylglyoxim v diphenylglyoxim vi Ni chng ta thy nhng nhm phenyl, mt mt th hin tc dng mnh mu, ng thi mt khc li th hin tc dng lm gim tan. Kt qu l chng ta thu c diphenylglyoximat Ni c mu m hn v c tan nh hn so vi dimethylglyoximat Ni
IV.3. HIU NG KHNG GIAN

Nhng phc bn vng l nhng phc c to thnh do s xen ph nhng qu o lp y ca phi t vi nhng qu o trng ca cation hng ti chng hoc l ngc li. Tuy vy, nhng cu hnh lp th theo d ton i khi khng c thc hin. Nu phc c to thnh do s tham gia ca nhiu phi t mt rng v c th tch ln th nhng kh khn vt l s hon ton gy tr ngi cho s phn b chng xung quanh ion trung tm. Vn s tr thnh phc tp hn nu phi t l a nng. S dng nhng m hnh nguyn t, ta c th bit c tng i nhiu v ho lp th ca nhng phc cht vi cc phi t hu c. Bit bn knh ion, di lin kt trung bnh, gi tr gc lin kt thng thng, ta c th hnh dung cu trc gn ng ca phc, c bit l trong nhng trng hp phi t phng. Nhng bin i khng nhiu v cu trc ca phi t c th gy nn nhng kh khn khng gian cho s phi tr. C th chn 1,10phenanthroline dng xc nh ion Fe(II) v 2,9dimethyl1,10 phenanthroline l thuc th ca Cu(I) lm v d. Phc 1:3 ca Fe(II) vi 1,10 phenanthroline l phc spin thp v c hng s bn ln. Ngoi ra phc cn c mu rt m. Nhng nhm methyl trong 2,9dimethyl1,10phenanthroline gy tr ngi khng gian cho s to phc Fe(II) 1:3, cn phc 1:2 th li l phc spin cao v khng mu. Nhng nhng nhm methyl khng gy tr ngi cho s to phc Cu(I) c t l 1:2. Hiu ng tng nh vy cng c quan st thy trong trng hp ca 6,6dimethyl hoc l 6,6diamino2,2dipyridin. Kch thc ca ion kim loi cng ng vai tr quan trng: ion Cu(I) c bn knh ln do phi t nm cch xa nhau v nhng kh khn khng gian c gim i, ion Al3+ c bn knh nh nn khng th to phc vi 2methyl8 oxyquinoline v nhng dn xut th tng t ca noridin. Nhng thuc th ny li phn ng vi nhng ion c bn knh ln nh Cr3+, Fe3+, Ga3+, Cu2+ v Zn2+. Thm nhm phenyl vo v tr 2 ca oxyquinoline s gy tr ngi cho s to phc 1:3 ca Al3+ v Cr3+. Khc vi 8oxyquinoline, 2methyl8oxyquinoline khng to kt ta vi Al3+. S dng thuc th ny c th d dng chit Ga, In v xc nh chng khi c mt Al3+. Ngi ta cng quan st thy hiu ng khng gian loi khc. l trng hp nhng dn xut th 3,3 ca dipyridin. Da vo nhng v tr y nhng nhm c th tch ln s lm bin dng cu hnh phng ca phi t v dn n kt qu l lm gim s n nh ho do cng hng v lm xut hin sc cng trong lin kt kim loi phi t. Hiu ng tng t cng c quan st thy khi a nhng nhm isopropyl hay fluorbutyl vo v tr 3 ca acetylaceton. Nhng phi t nh th khng to nhng phc mu bnh thng vi Fe(III) hoc l Cu(II). R rng l c th gii thch s kin bng tng tc lp th gia nhm isopropyl v tr 3 v nhm methyl v tr 2 hoc 4 lm cho tnh phng ca vng b ph hu, gy tr ngi
cho s cng hng v ngn cn to phc. N y nhm isopropyl ra xa mch acetylaceton bng cch t nhm methylene vo gia th s to phc bnh thng li tr li. i vi phi t loi nh pocfirin(1) v flaloxyamine(2) kch thc ca nhn trung tm c nh hng ln n bn ca phc. Nhng ion ln nh Hg2+, Pb2+ khng th i vo nhn pocfirin, cn i vi nhng ion khng ln th c th d on rng bn ca phc s gim xung khi bn knh ion gim xung. Do cng ca nhn pocfirin nn mc xen ph nhng qu o ca ion kim loi c bn knh gim dn v phi t cng s gim dn. Tng tc gia Ag+ vi polymethylenediamine l mt v d in hnh khc v nh hng ca nhng yu t hnh hc n qu trnh to phc. Thng nhng vng 5 (vng khng c ni i) c hng s bn ln hn so vi nhng phc tng ng c kch thc khc. Nhng tt c nhng phc ca Ag+ vi trimethylenedianin, tetramethylenediamine, pentamethylenediamine c cu to vng tng ng l 6, 7, 8 li bn hn phc vng 5 vi ethylenediamine. iu ny c gii thch nh sau: Khi kch thc vng tng ln, ho lp th ca lin kt Ag+ c th trong mt mc ng k tin dn ti dng thng hng l dng thch hp vi s phi t 2. Do nh hng ca nhng yu t ho lp th nn kh nng to phc ca nhng dng ng phn khc nhau ca cng mt thuc th cng khc nhau.
IV.4. THUYT SONG SONG CA KYZHEOB

KyzHeob a ra mt hnh tng rt hay d on tnh cht ca thuc th hu c. Hnh tng l s tng t gia nhng thuc th hu c v thuc th v c n gin nht. C th coi s thu phn nh l s biu l ca khuynh hng to lin kt MeOR di tc dng ca thuc th HOR. Nh vy, hon ton c th xem cc th thuc th y nh H OR, ch khc l mt nguyn t hydrogen trong phn t c thay th bng gc hu c R v do c th cng nhn mt cch hp l s tng t ca hai qu trnh. nh hng ca pH ln c hai qu trnh rt tng t. Nhng nguyn t no m mui ca chng b thu phn gi tr pH nh (Sb, Bi,) c kh nng tng tc vi thuc th hu c cha nhm hydroxylenol nng acid cao. Nhng nguyn t m mui ca n b thy phn (Th, Al) i hi phn ng trong dung dch acid thp hn. Nguyn t c mui b thu phn yu hn cn phn ng trong mi trng trung bnh hay kim yu, cn cc nguyn t nh Ca, Sn ch c kh nng tng tc vi thuc th loi ang bn, trong dung dch kim mnh. Trn c s lun im nu trn chng ta c th so snh tc dng ca nhng thuc th loi RSH vi tc dng ca HSH. KyzHeob khng nh rng nhng thuc th loi ny ch tc dng vi nhng nguyn t no c kh nng to sunphua trong dung dch nc. Nh vy Al3+, Mg2+, Ca2+ khng phn ng vi nhng thuc th hu c cha nhm SH. nh hng ca pH ln nhng phn ng vi nhng thuc th y hon ton tng t nh hng ca pH khi kt ta nhng sulfur. Nhng arsenic acid RAsO4H2 gn vi acid arsenic v phosphoric v tnh cht phn tch. Do , nhng ion b kt ta bng nhng acid y trong mi trng acid mnh vi nhng arsenic acid.
S to phc vi nhng amine n gin nht (v ngay c vi nhng amine phc tp hn) hon ton tng t vi qu trnh to amonicat. Ngi ta nhn thy rng kh nng tc dng vi amine ca mt ion tng ln vi s tng bn ca amonicat tng ng, s dng quan im ny chng ta c th gii thch mt cch hp l nhng quan im quan st thy khi kt ta mt s ion bng oxim (oxyquinoline). V d: phn ng kt ta nhng ion to amonicat bn (Cu(II), Ca(II), Zn(II), Ni(II), Cd(II), ) bng oxim xy ra pH thp hn so vi phn ng kt ta chng vi dng hydroxide. iu c th gii thch bng s to lin kt phi tr gia nguyn t N ca nhn quinoline vi ion phn ng. Chng ta dn ra nhng d kin minh ha trong bng di y. Bng 4.3: Cc dng kt ta tng ng cc pH khc nhau pH bt u kt ta Ion Dng hydroxide Dng quinolinate Cu(II) 5,3 2,7 Co(II) 6,8 4,2 Zn(II) Ni(II) Cd(II) 5,2 6,7 6,7 4,3 4,6 5,4
Tm li, chng ta nu ln s tng t gia phn ng thu phn vi phn ng to phc ca nhng thuc th hu c cha nhm OH, s tng t gia phn ng to sunfua vi phn ng to phc ca nhng thuc th hu c ca nhm SH, s tng t gia nhng thuc th loi RaSO3H2 vi H3AsO4, s tng t gia nhng phn ng to ammoniac vi phn ng ca nhng thuc th hu c cha nhm amine. chnh l ni dung ca thuyt song song.
IV.5. S PHN LY CA MUI NI PHC

Trong dung dch nc, mui ca hu ht cc kim loi lun lun in ly kh mnh. Nhng mui ny l mui ca acid v c cng nh acid hu c trong c c mui ca nhng acid th nh m, poxyazoenzeic acid. Ta xt mu ca 3, 4dioxyazobenzene4sulfonic acid (I) trong cc mi trng khc nhau. Trong mi trng acid v trung ho dung dch acid ny c mu vng. Khi kim ho do s chuyn hp cht ny thnh phenolat (II) d phn ly nn mu chuyn thnh hng sm.
OH NaO3S O-
N N
OH
O3 S
N N
O-
33Na
(I) dung dch mu vng
(II) dung dch mu hng sm
4Oxy3metoxyazobenzene4sulfo acid (III) trong mi trng acid v trung ho c mu vng v trong mi trng kim c mu da cam (IV).
OCH3 NaO3S OCH3
-
22Na
NN
OH
O3S
N N
OH
(III) dung dch mu vng
(IV) dung dch mu da cam
i chiu mu da cam khng thm ca monophenolat (IV) vi mu hng thm ca diphenolat (II) chng ta thy rng mu lin quan ti nh hng cong ca hai nhm phenol phn ly bn cnh nhau trong hp cht (II). V khng c kh nng tr thnh nhng phenolat 3,4dimetoxyazobenzene4sulfo acid (V) c mu vng ng nht trong dung dch acid trung ho cng nh kim.
OCH3 NaO3S
NN
OCH3
(V) Theo s nh gi bng mt v theo ng cong hp th th mu dung dch ca nhng hp cht (I), (II) v (V) rt gn nhau. T chng ta thy rng s thay th hydro trong nhm OH bng nhm methyl trong nhng hp cht chng ta ang bn khng th hin nh hng ln mu trong min kh kin. iu cng ng trong nhng trng hp thay th hydro bng gc aryl. Chng ta cng nhn thy mu dung dch ca nhng hp cht c cu to sau y rt gn nhau:
COOH NaO3S OCOC2H5 NaO3S
N N
OH
N N
OH
Tm li, mu ca nhng phenol t do v mu ca nhng ester ca chng rt gn nhau. Ch trong nhng este trong nguyn t hydro ca nhm OH c thay th bng gc aryl hoc alkyl nng, ngi ta mi quan st thy s khc bit v mu sc gia phenol t do v ester ca n, nhng s khc bit thng khng ln. Nhng iu trnh by trn y cho php chng ta kt lun rng s ging nhau v mu ca dung dch phenol v este ca chng lin quan vi s ging nhau v trng thi khng phn ly ca lin kt OH v OR trong nhng hp cht ny. Trong dung dch acid yu 3,4dioxyazobenzene4sulfo acid (I) to ni phc vi Ga. Dung dch phc c mu vng ging nhau nh mu ca monophenolit (IV). Nu nh c hai lin kt ca nguyn t Ga vi oxy ca nhm OH trong Ga thay th hydro, l hon ton ng ho tr th tng t vi nhng hp cht alkyl th, mu ca phc ny phi gn vi mu ca hp cht dimetoxy (V) khng phn ly hoc hp cht khi u (I) bi v ion Ga khng c mu ring. Nhng trong thc t li khng nh vy nn c th cho rng trong phc , mt lin kt GaO mt mc no ion ho ni phn. Chng ta c th m t iu nh sau:
O
-
Ga2+
O
O3S
N N
(VI) Nu chng ta cng nhn quan im trn th s gn nhau v mu sc ca hp cht (IV) v (VI) l hon ton c th hiu c v c th gii thch d dng sc thi nht ca phc Ga(VI). Mu ca phc Ga(VI) rt gn vi mu ca monophenolat (IV) l do trng thi phn ly ni phn ca monophenolat trong mi trng kim. Nhng mu ca phc Ga cng khng th t ti sc thi hng thm ca diphenolat (II) v thc hin iu c hai lin kt ca
Ga vi nhng nguyn t oxy phi ng thi thc hin. R rng, iu kin rt kh ng thi thc hin vi chnh iu kin tn ti phc trong dung dch long. Nhng iu trnh by trn, cho php chng ta suy lun mt cch hp l l c tn ti trng thi phn ly ni phn. Da trn khi nim phn ly ni phn chng ta c th: a) Gii thch mu v nh hng ca pH ln mu ca nhng hp cht v phc cht loi nu trn v nhng loi tng t. b) Tm nhng phn ng mu gia nhng nguyn t khng mang mu v thuc th khng mu (v d hn hp c acid ho ca pyrocatesin vi diaosunfanilic acid dn dn tr thnh khi c mt Zn, Nb, W) c) Thc hin mt s tng hp hu c kh xy ra. V d iu ch cht mu azo t pyrocatesin bng phng php thng (trong mi trng kim) b tr ngi v ng thi xy ra hin tng oxy ha pyrocatesin di tc dng ca hp cht diazo. Khi c mt mui nhm hoc mt s nguyn t khc pyrocatesin phn ng tt v hin tng oxy ho do hp cht diazo gy nn khng xut hin. Phn ng tng hp tin hnh ngay c trong mi trng acid.
IV.6. LIN KT HYDRO

Do nh hng ca s phn ho cc lin kt nn mt loi lin kt mi c hnh thnh, l lin kt hydro. T nm 1912 ngi ta a ra ngh v loi lin kt ny v dng tr li cho cu hi: v sao trong kh ammoniac, methylamine, dimethylamine v trimethylamine l nhng baz yu m hydroxide ca tetramethylamine li l mt baz mnh nh KOH? Ammoniac hoc l nhng dn xut th bt k ca n u c th to vi nc mt loi lin kt c bit lin kt hydro v phc to thnh c th phn ly mt phn thnh cation hay anion hydroxyl theo phng trnh: R3N + H2O R3N ... H O ...H R3NH+ + OHMt khc, v ion R4N+ khng c nguyn t H lin kt vi N nn n khng th lin kt vi ion hydroxyl bng cch ging nh lp hp cht k trn, do hydroxide ca tetramethyl amoni phn ly hon ton trong dung dch nc ging nh KOH. Ngi ta cng thu c nhiu d kin thc nghim chng t rng trong nhng trng hp khc nguyn t H c th lin kt vi hai nguyn t khc, thng l O, N, F, Mt bng chng hin nhin v s tn ti ca lin kt hydro l nhit si cao bt thng ca nhng hydrua ca cc nguyn t y. Lc tng tc gia cc phn t ca mt cht cng ln th nhit si cng cao. nhng iu kin khc nh nhau th ni chung, phn t lng cng ln, lc tng tc gia cc phn t s cng ln. Do nn ta thy H2O, H2Se, H2Te nhit si cn tng mt cch n iu. Nhng iu ch quan st thy cc hydrua ca cc nguyn t nhm IVB (CH4; SiH , GeH4; SnH4). Cn cc hydrua ca cc nguyn t nhm VB (NH3, PH3, AsH3 , SbH3), VIB (H2O, H2S, H2Se, H2Te) v VIIB (HF, HCl, HBr, HI) th thnh phn u tin ca dy c gii thch bng s to thnh lin kt hydro. Do s to thnh lin kt hydro nn nhng phn t nc ln hn H2O n gin.
H H O H O H H H O H
H O H O H O H H
Lc tng tc gia chng cng ln hn dn n kt qu l nhit si tng ln nhiu. Hin tng lin hp nh vy trng thi lng gy nn nhng tnh cht bt thng khc ca cht lng, v nh nc c thm in mi rt cao v t trng cc i 4oC. Bng cch o t trng v s phn b ngi ta chng minh rng nhiu acid carboxylic cng lin hp thnh dng lng phn trng thi hp trong dung dch cng nh trong cc dung mi khng nc, v d i vi acid formic ta c dng diner nh sau:
O H C O H O H O C H
Nhng iu trnh by trn y chng t rng lin kt hydro l mt loi lin kt c tht, n lun lin kt hai nguyn t m in X v Y qua nguyn t hydro. Lc ny cc nguyn t X, Y, H tng i ngn hn so vi khong cch khi m cc nguyn t ny hon ton khng lin kt vi nhau nhng ln hn khong cch ca hai lin kt trc tip gia H vi X v Y. Trong nhiu trng hp nguyn t hydro phn b gn nguyn t X hn Y, c trng hp khi m 2 nguyn t X v Y l nh nhau. Nhng trong mt s hp cht v d NaHF2 (cha ion HF2-) nguyn t H phn b i xng. H to lin kt hydro hon ton khng c ngha l H c ha tr hai, hai trong s 4 in t lin kt cn phi nm trn qu o 2s m thc hin c iu ny, nng lng kch thch phi ln hn nhiu so vi nng lng ph ca lin kt. Ngy nay, ngi ta chp nhn bn lin kt hydro l do lc tnh in ca cc lng cc XH v HY gy nn. V X v Y l nhng nguyn t m in mnh v do vy nhng lng cc XH v YH thng rt ng k. Hn na, nguyn t H khng c lp v in t trong v th tch ca n li nh nn nhng lng cc c th tin st gn nguyn t H. Lin kt hydro cng c ngha trong nghin cu thuc th hu c. Nhiu thuc th hu c tn ti di dng lin kt hydro ni phn t.
O N O H O
onitrophenol Do to thnh lin kt hydro ni phn t nn onitrophenol c nhit nng chy thp (45 C) cn cc ng phn para, meta khng thun li cho lin kt hydro do nhit nng chy cao hn. (ng phn meta nng chy 97oC, ng phn para nng chy 114oC).
o
S to thnh lin kt hydro nh hng r rt n hng s phn ly acid ca cc thuc th hu c. Cc thuc th cha nhm OH v tr para i vi nhm azo c hng s phn ly acid ln.
NaO3S
N N
OH
NaO3S
N N
OH
pK= 8,2
pK= 6,7
Trong khi thuc th tng t, mang nhm OH v tr ortho so vi nhm azo nhng li c hng s phn ly acid thp hn nhiu.
HO
NaO3S
HO
NaO3S
N N
N N
pK= 11,2
pK=11,2
iu ny ch c th gii thch bng s to thnh lin kt hydro ni phn t ca thuc th ny vi nhm azo, nh v d sau y
H
NaO3S
N N
i vi nhng thuc th c cha 2 nhm OH v tr o v o i vi nhm azo, gi tr pK<6 v pK=11. iu chng t ch c 1 nhm tham gia vo cu ni hydro.
OH
NaO3S
H O
SO3H
OH
N N
SO3H
nh hng ca nhm th n bn ca lin kt hydro ni phn t c th thy r trong trng hp Gallion. i vi Gallion c th thy 2 vng thm gi c to thnh bi lin kt hydro theo s sau.
Cl
O
H N N
OH
NH2
2ON
H3OS
SO3H
Nhng nhng d liu thc nghim (pK1=4,2; pK2=12,4) cho ta c s kt lun rng ch c mt lin kt hydro hnh thnh
Cl
OH
NH2
2ON
H3OS
SO3H
bn ca lin kt ny tng ln di tc dng ca cc nhm th NH2 hoc SO3H. Lin kt hydro cng c hnh thnh trong cc hp cht ni phc lm cho s vng tng ln v do vy bn tng ln (Hiu ng chelate). V vy, trong khi nghin cu phc gia kim loi vi thuc th hu c cn ch n loi lin kt ny.
(OH)+ Se Cl
Aso3H
H3OS
SO3H
Be Cl
Aso3H
H3OS
SO3H
IV.7. TCH CHIT I VI THUC TH HU C

IV.7.1. S phn b ca thuc th
HA HA 0
Thuc th HA phn b gia nc v tng hu c : KHA (4.2) Hng s phn s :

K HA =
[ HA 0 ] [ HA ]
(4.3)
i lng KHA khng ph thuc vo pH m ph thuc vo lc ion v nhit . Cn h s phn b :

D HA =
[ HA ] [ HA ]
0
(4.4)
Th ph thuc vo K Thuc th chit thng l acid hu c dng HmR, cc anion ca n to phc chit c vi ion kim loi M. S phn b ca thuc th chit gia nc v tng hu c ph thuc vo pH ca dung dch, v rng khng phi tt c cc dng thuc th chit tn ti trong tng nc iu chuyn c vo tng hu c m ch c mt s dng trong s chng, s phn b ca chng ph thuc v K, pH ca dng dch nc. Nu thuc th chit HmR to ra cc dng chit c Hm+1R, Hm-1R,R, th h s phn b ca n c m t bng phng trnh:
DR = [H m+1R]0 +[H m R]0 +....+[R]0 [CR ]0 = [H m+1R]+[H m R]+.....+[R] [CR ]
(4.5)
IV.7.2.
S phn b ca kim loi
S phn b cc kim loi cng nh s phn b ca thuc th gia hai cht lng khng trn ln xy ra ph hp vi nh lut phn b Nernst, theo nh lut ny th t s cc hot (hay lc ion c nh) l cc nng cn bng ca mt dng xc nh ca cht phn b gia dung dch nc v dung dch hu c khng trn ln, nhit hng nh l mt i lng hng nh. Gi thit rng cation M chit c t dung dch nc bi mt dung mi hu c dng cc phc MR, MR2, MRi vi anion ca thuc th chit HmR, thuc th ny cng chuyn vo tng hu c cc dng HR, H2R, , HiR. Trong dung dch nc xy ra s to phc tng nc cc hp cht MR,MR2, , MRn. Ngoi ra cc cation chit c M tham gia vo cc phn ng to phc cnh tranh vi ion OH v thuc th che L to ra cc h cn bng M(OH)j v MLp. Lc biu thc ca h s phn b c th vit di dng:
DM = ([MR]+[MR 2 ]+...+[MR n ])0 [M]+ [MR i ]+ [M(OH)i + [MLi ]
i=1 i=1 i=1 n j D
[CM ]0 [CM ]
(4.6)
tan trong tng hu c v thc vy chit c th tng ln bng cch to ra cc phc hn hp, lc c cc phn t baz hu c khng tch in tham gia vo bu phi tr bn trong (nh pyridine chng hn ). Khi to ra cc cht hn hp, lm cho gi tr h s phn b ca phc hn hp chit c MRnLq c m t bng phng trnh sau:
[C ] DM = M 0 = [CM ] qn K DM R n Lq [R]n [L]q
[R] [L] +
i j ij j=0 i=0 1
(4.7)
[OH]i
OH i
IV.7.3.
S chit ca cc hp cht ni phc (Cc phc chelate khng tch in)
S chit cation Mn+ bng thuc th chit HR dng hp cht ni phc MRn ho tan trong dung mi hu c c m t bng phng trnh :
+ M n+ +nHRO MR n O+nH Kex
(4.8)
Hng s cn bng:
K ex = [MR n ]0 [H + ]n n [M n+ ][HR]0
(4.9)
Nu v phi ca phng trnh (4.9) biu din qua hng s bn ca phc chit c MRn, hng s phn ly acid ca thuc th K a v hng s phn b K D v K D th ta nhn
HR
MR n
HR
c mt phng trnh mi lin h cc i lng ny vi Kex nh sau:

K ex = MR n K DMR /(K DHR /K a HR ) n
n
(4.10)
Theo nguyn tc, t (4.10) ta thy gi tr hng s chit ph thuc t l thun vi hng s bn MR v hng s phn b ca phc K D v t l nghch vi hng s proton ho KHR v
n MR n
hng s phn b K D
HR
ca thuc th chit. Nu bit K D
MR n
v K D
HR
i vi mt dung mi
hu c cn so snh th theo gi tr Kex i vi mt dung mi c th tnh ton l thuyt gi tr Kex cho dung mi khc. H s phn b DM khi ch chit mt phc duy nht MRn c xc nh bng h thc:
K ex = MR n K DMR /(K DHR /K a HR ) n D M =[MR n ]0 /(M n+ ]+[MR n ])=K DMR /(1+[M n+ ]/[MR n ]) (4.11)
n n
a hng s chit Kex vo (4.11) ta nhn c cc i lng DM v Kex:

n 1/D M =1/K DMR +[H + ]n /(Kex[HR]0 )
n
(4.12)
Trong trng hp, khi DM<< K D v phi ca n s hng 1/K D

MR n
MR n
, c th n gin phng trnh (4.12) bng cch loi t
, lc ta nhn c:
n D M =K ex [HR]0 /[H + ]n
(4.13) (4.14) (4.14)
Hay dng logarit:

logD M =logK ex + npH + nlog[HR]0 + nlogf H+ pH1/2 = (1/n)logK ex log[HR]0 logf H+
IV.7.4. Chit cc phc cha bo ha phi tr v cc phc tch in ( dng cc phc hn hp) a. Cc phc cha bo ho phi tr : Cc cn bng xut hin khi chit cc chelate cha cc phn t trung ha ca thuc th chit, v c bn cng ging nh khi chit cc hp cht ni phc bo ho phi tr, nhng trong cc cn bng tnh ton cn tnh n thnh phn ca phc chit c, v d nu to phc MRn(HR)q theo phng trnh:
M n+ +(n+q)HR 0 {MR n (HR)q }0 +nH
Kex
(4.15) (4.15)
{MR n } ( HR q )0 {H + } K ex = =K ex M ({C'M}{HR}0(n+q) )
y:
M n+ M = C [ M]
logD M =logK ex +npH+ ( n+p ) log [ HR ]0 +nlogf H+
(4.16) (4.16)
1 q pH1/2 = logK ex 1+ {HR}0 logf H+ P n n
b.Chit phc cation (chit phc tch din) Phng trnh chit phc cation c m t bng phng trnh .
M z+ z + ( n+p ) HR 0 +mA= MR n ( HR ) q A m
( z-m-n )
0
+nH +
(4.17)
V
logD M =logK ex ( n + p ) log [ HR ]0 + mlog [ CA ] + npH + alogf H+
(4.18)
V
1 m q pH1/2 = logK ex 1 + log [ HR ]0 log [ CA ] logf H+ n n n
(4.19)
IV.7.5.
Cn bng trao i khi chit cc phc chelate
Cc phn ng trao i chit c dng tng chn lc trong thc hnh phn tch. lm cc thuc th chit thng ngi ta dng cc dung dch cc phc chelate trong cc dung mi hu c, v d dityldithio cacbaminat ch trong chloroform. Khi trn cc tng th ion cn xc nh (cn tch ) M1n+ trong tng nc s y ion MIIm+ trong phn t phc chelate MIIRm v chuyn vo tng hu c dng MIRn , ta c:
m+ mM n+ I +nM II R m ( 0 ) mMR n ( 0 ) +nM II
(4.20)
Ktr
K 'tr = [mRn]o m[CMII ] K e'xm I = [M II R m ]o n [CMI ]m K'exII
(4.21)
V rng K ex =
MR n K DMR
K HR KD HR
n
, phng trnh (4.21) c th vit dng sau nu ch l
M n+ : M = [ CM ]
K 'tr
( = (
M I Rn K DM I R n M I
M II R m
K DMII R m MII
(4.22)
y Ktr l hng s chit trao i . Nh vy, chit trao di hon ton ph thuc vo cc hng s chit iu kin ca cc phc ring bit, vo cc hng s bn v hng s phn b ca chng. iu kin chit tt:
K 'exI K 'exII
(4.23)
K DMII Rm MII
Hay
M R K DM R M M
I n I n
II R m
(4.24)
Nu nh cc ion trao i c din tch nh nhau thnh phn ca cc hp cht chit nh nhau, cc phng trnh n gin hn, v
K 'tr = K'exII K'exI
(4.25)
V iu kin chit tt l:
K 'exI K 'exII
(4.26)
K DMII R m MII
M R K DM R M M
I n I n
II R m
(4.27)
IV.8. TCH CHIT CC CHELATE

Kh nng v hiu qu ca s tch chit ca nguyn t da trn s khc nhau v cc h s phn b v cc hng s iu kin ca s chit ca cc phc chelate cn phn chia. nh gi nh lng hiu qu tch ngi ta dng hai c trng: H s tch S v h s lm giu S. H s tch cc ion MI v MII chit c dng cc hp cht MIRn v MIIRm c xc nh bng t s cc h s phn b ca chng:
SMI MII = D MII
I
D MI
(4.28)
I
Nu nh h s ln hn trong cc h s phn b, v d D M m b hn ng k K DM , th phng trnh (4.28) c th biu din qua cc hng s iu kin ca s chit:
M S I M II
' n'-n'' K exMI [HR]0 = ' + n'-n'' K exMII [H ]
(4.29)
Khi c thnh phn nh nhau ca cc phc chit c (n=n=n) th h s tch c xc nh bng t s cc hng s iu kin ca s chit cc nguyn t cn tch:
M S I M II K exMI = ' K exMII
'
(4.30)
CHNG V: TNH TON CC HNG S CA THUC TH V PHC

V.1. NGHIN CU C CH TO PHC N PHI T
Nghin cu a ra mt phc vo ng dng trong thc hnh phn tch th vic nghin cu c ch to phc l mt bc quan trng. Ch trn c s nghin cu c ch to phc ta mi c th xc nh dng tn ti cui cng ca ion trung tm v phi t cng nh vit c phn ng to phc thc xy ra trong h nghin cu. T c ch to phc ta tnh c hng s cn bng ca phn ng to phc thc v hng s bn iu kin ca phc . Ngoi ra, khi nghin cu c ch to phc cn cho ta mt s d kin cn thit c th hiu su hn v cu trc ca phc, dng tn ti ca ion trung tm v phi t, s proton tch ra khi to phc, ... V.1.1. Nguyn tc Nguyn tc chung l tm phng trnh th hin mi lin h cc dng tn ti ca ion trung tm, ca phi t, s phi tr, s proton, pH. Trn c s thit lp cc th nghim tnh ra c s proton b thay th. Kt qu chng ta bit c dng ion tham gia v hng s khng bn. V.1.2. Cc bc chnh xy dng nghin cu t tn v gi nng ca kim loi, thuc th, phc: n gin chng ta khng ghi in tch ca cc phi t trong h. Gi M l ion kim loi v nng ion kim loi l CM Hm+1R l thuc th v CR l nng thuc th [M(OH)i(Hm-n)q] l phc v CK l nng ca phc Cc cn bng ca ion trung tm trong dung dch: M + H2O MOH + H M(OH) + H2O M(OH)2 + H M(OH)2 + H2O M(OH)3 + H M(OH)i-1 + H2O M(OH)i + H .. Hng s cn bng ca cc phn ng c biu din nh sau:
K1 = [M(OH)].[H] [M]
K1 K2 K3 Ki
Ta suy ra: Tng t
[M(OH)]=
K1 .[M] =K1 .[M].h -1 [H]
K2 =
[M(OH)2 ][H] [M(OH)]
[M(OH)2 ]=
K 2 [M(OH)] =K1 .K 2 .[M]h -2 [H]
Mt cch tng qut: V

Ki =
[ M(OH i ] .[ H ] [ M(OH)i ]
[ M(OH)i ] =K1 .K 2 ...K i .[ M] .h -i

Theo nh lut bo ton nng ban u:
CM = [ M ] + M ( OH ) + M ( OH 2 ) +...+ M ( OH )i
(5.1)
Thay cc gi tr nng ca ion kim loi [M(OH), [M(OH)2], [M(OH)i] vo phng trnh (5.1) ta c:
CM = [ M ] +K1 [ M ] h -1 +K1K 2 [ M ] h -2 +...K1K 2 ...K i [ M ] h -i +CK
CM -CK = [ M ] 1+K1h -1 +K1K 2 h -2 +...+K1K 2 ...K i h -i
Ta c th tng qut nh sau:
[ M] = 1+K .h -1 +K .K
1 1
(CM CK ) -2 -i 2 .h +....+K1 .K 2 ...K i .h
(5.2) (5.3)
[ M(OH)i ] = 1+K .h -1 +K .K
1 1
(CM CK ) K .K ...K i . 1 2i -2 -i h 2 .h +....+K1 .K 2 ...K i .h
Cn bng ca thuc th trong dung dch:

H m+1R H m R+H Hm R H m-1R+H H m-1R H m-2 R+H
K0' K1' K2'
..
H m-( n-1) R H m-n R+H
Kn'
Hng s phn ly ca thuc th trong dung dch l:

K '0 =
[ H m R ] .[ H ] [ H m+1R ]
T c th rt ra c nng ca thuc th theo biu thc:
[ Hm+1R ] =
Tng t
' K1 =
[Hm R] h
K '0
[ H m-1R ] .[ H ] [Hm R]
V c th rt ra:
[ H m-1R ] =K1' [ H m R ] h -1
Tng qut:
K 'n =
[ H m-n R ] .[ H ]
H m- n-1 R ( )
V:
[ H m-n ] =K1' .K '2 ...K 'n .[ H m R ] h -n

CR = [ H m+1R ] + [ H m R ] + [ H m-1R ] + [ H m-2 R ] +...+ [ H m-n R ] +qCK
Theo nh lut bo ton nng ban u i vi thuc th, ta c: (5.4) Thay cc gi tr [Hm+1R] , [HmR] , [Hm-1R] , ... , [Hm-nR] vo phng trnh (5.4)
CR =
' ' ' [H m R].h K1 .[H m R] K1 .K '2 .[H m R] K1 .K '2 ...K 'n .[H m R] +[H R]+ + +...+ +qCK m K '0 h h2 hn
(5.4)
Chuyn qCK qua v tri ta c phng trnh:

h K ' K ' .K ' K ' .K ' .[H R] CR qCK =[H m R] ' +1+ 1 + 1 2 2 +...+ 1 2 n m h h h K0
(5.5)
T y ta tnh c nng cn bng ca thuc th trng thi cn bng: Dng tng qut ca thuc th lc ban u l:
[ H m-n R ] =
Cn bng to phc:
' CR qCK K1 .K '2 ...K 'n . ' ' ' K1 .K '2 K1 .K '2 ...K 'n hn h K1 1+ ' + + +...+ K0 h h2 hn
(5.6)
Phn ng to phc xy ra nh sau:

M ( OH )i +qH m R M ( OH )i ( H m-n R )q +qnH
Kp
(5.7)
p dng nh lut tc dng khi lng ta c phng trnh (5.8)

qn M(OH)i (H m n R)q .[ H ] CK . [ H ] KP = = q q [ M(OH)i ] .[ H m R ] [ M(OH)i ] .[ H m R ] qn
(5.8)
Hng s bn iu kin ca phc () tng ng vi cn bng to phc:

M ( OH )i + qH m n R M ( OH )i ( H m n R )q M(OH)i (H m n R)q CK = = q q [ M(OH)i ] .[ H m n R ] [ M(OH)i ] .[ H m n R ]
(5.9) (5.10)
T tnh c hng s khng bn theo (5.11)

K Kb
[ M(OH)i ] .[ H m n R ] =
CK
(5.11)
Thay phng trnh (5.6) vo (5.11) ta c (5.12)

K Kb =
[ M(OH)i ] .(CR qCK )q

K ' .K ' ...K ' h K ' K ' .K ' CK (1 + ' + 1 + 1 2 2 + ... + 1 2n n )q K0 h h h
' (K1 .K '2 ...K 'n )q h qn
(5.12)
t:
[M(OH)i ].(CR qCK )q B= ' K ' .K '2 .K 3 h K ' K ' .K ' CK (1 + ' + 1 + 1 2 2 + ... + 1 n )q K0 h h h
' Q = (K1 .K '2 ...K 'n )q
(5.13)
Ta c : K cb =
B.Q h q.n K Kb + qn lg H Q K Kb Q
Ly logarit 2 v, ta c
lg B = lg
lg B = qn.pH lg
lg B = f ( pH )
(5.14)
Phng trnh biu din s ph thuc lgB vo pH l tuyn tnh khi h s gc tg=qn l mt s nguyn dng. V q.n l s nguyn dng (q l h s t lng trong phc, n l proton tch ra t mt phn t thuc th do to phc) v ng biu din lg B = qn.pH lg
B= CK (1 + K Kb , ta cn tnh B theo cng thc: Q

' ' ' K1 .K '2 K1 .K '2 ...K 'n q h K1 + + + + ... ) K '0 h h2 hn
Mun tnh B ta cn xc nh CK
CK = C M Ai A gh
Trong : CM l nng ban u ca ion trung tm Agh l gi tr cc i ca mt quang Agh xc nh nh sau:
Cn lu rng ta ch ly gi tr pHi v Ai trn on ph thuc tuyn tnh MN (Cch im un 0 v 2 pha khong 0,5 n v pH) ng biu din lgB=f(pH) c dng nh sau:
Gi tr tg c th c gi tr tg<0, tg>0 nhng v tg=q.n (q.n: s nguyn dng) nn ch nhn ng thng no c gi tr tg l s nguyn dng Nu c cc ng thng lgB=f(pH) cng tha mn iu kin nguyn v dng th c th c kh nng ng thi tn ti trong h hai hay nhiu phc Nu trong h ch to mt phc n nhn th ta ch ly gi tr i no nh hn trong cc gi tr i c tg nguyn v dng V.1.3. Xy dng k hoch thc nghim Pha dung dch ion kim loi v thuc th c nng ph hp vi thc nghim (CM, CR) Xc nh thnh phn phc (q) Cho pH ca phc thay i ti mt nng nht nh t tnh nng CK suy ra B Chn i cc gi tr (i t 0 n i) Lp bng 5.1: Bng 5.1 pHi Ai CK(i) CR-qCK pH1 A1 pH2 A2 pH3 A3 lgB M(OH)i M M(OH) M(OH)2 i=i i=2 i=0 i=1 Kp KP
KKb K Kb
V th v chn ng c h s gc tg nguyn dng (xc nh c i) Bin lun tm nq v KKb T gi tr tg=nq. Nu bit c tg (tg l h s gc ca ng: lgB=f(pH) v q l h s t lng trong phc, ta suy ra n v t tnh c KKb, Kp Xc nh c gi tr i v n th ta bit c dng tn ti cui cng ca ion trung tm v anion thuc th Hm-nR v vit c c ch phn ng to phc. Nu trong h to mt phc khng tan, c tch s tan Tt
lg B =
K Kb T = qn.pH lg t Q CK .Q Tt Q
lg B.CK = qn.pH lg lg A = pn.pH lg Tt Q
A=

(1 +
' ' ' K1 .K '2 K1 .K '2 ...K 'n q h K1 + + + ... ) K '0 h h2 hn
vi
' Q = (K1 .K '2 ...K 'n )q
V.2.
XC NH HNG S HYDROXO CA ION KIM LOI
Bi ton xc nh hng s hydroxo ca kim loi vi thc th hu c c Najarenko V.A. nghin cu. Cho n nay hu ht cc nguyn t kim loi c th xc nh bng phng php ny. V.2.1. Nguyn tc V nguyn tc, ngi ta xy dng phng trnh hm s ion H+ b ion kim loi thay th trong mt phn t thuc th. Chng ta bit r ion kim loi tn ti di dng no tc dng vi phi t mu. Do c th d dng vit ng phn ng ca ion kim loi Mn+ vi nhng ion hydroxidev vi nhng phi t mu HmR. V.2.2. Cc bc xy dng bi ton t nng v gi tn cc cu t tham gia. Mn+ l ion kim loi c ghi l M, c nng CM, M(OH)i phc hydroxo bc i, HmR l thuc th c nng CR, dng nghin cu l Hm-nR, CK l nng ca phc, ion H+ c ghi l H, ion OH- c ghi l OH, q l t l ca phc. Cn bng ca ion kim loi
M + OH MOH MOH + OH M ( OH )2
2 =
3 =
1 =
[MOH] [MOH] = 1[M].[OH] [M].[OH]
[M(OH)2 [M(OH)2 ] = 12 [M].[OH]2 2 [MOH].[OH]
M ( OH )2 + OH M ( OH )3
[M(OH)3 ] [M(OH)3 = 123 [M].[OH]3 3 [M(OH)2 .[OH]
.
M ( OH )i 1 + OH M ( OH )i
i = [M(OH)i [M(OH)i ] = 12 ..i [M][OH]i [M(OH)i 1 ][OH]
[M] =
[M(OH)i ] 1...i [OH]i
(5.14)
t 1...i = 123 ...i

Theo nh lut bo ton nng ta c:

CM = [M] + [MOH] + [M(OH)2 ] + [M(OH)3 ] + ... + CK
(5.15)
C M CK
Thay nng trn vo biu thc (5.15) v rt gn ta c [M] nh sau:

[M] = C M CK = 1 + 1[OH] + 12 [OH] + 123 [OH]3 + ... + 1...i [OH]i
2
1 + 1,i [OH]
1
(5.16)
Hm R H m 1R + H , H m 1R H m 2 R + H , K 2 = H m 2 R H m 3 R + H , K 3 =
K1 =
[H m 1R][H] [H R] [H m 1R] = K1 m [H m R] [H]
[H m 2 R][H] [H R] [H R] [H m 2 R] = K1 m 1 [H m 2 R] = K1K 2 m 2 [H m 1R] [H] [H] [H m 3 R][H] [H R] [H R] [H m 3 R] = K1 m 2 [H m 3 R] = K1K 2 K 3 m 3 [H m 2 R] [H] [H]
..
H m ( n 1) R H m n R + H Kn = [H 1) R] [H m n R][H] [H m n R] = K n m (n [H m (n 1) R] [H](n 1) [H m n R] = K1K 2 K 3 ...K n
CR = [ H m R ] + [ H m 1R ] + [ H m 2 R ] + [ H m 3 R ] + ... + [ H m n R ] + qCK
[H m R] [H]n
(5.17)
[H m R] =
CR qCK K KK KK K K K K ...K 1 + 1 + 1 22 + 1 2 3 3 + ... + 1 2 3m m [H] [H] [H] [H]
[H m 1R] =
CR qCK K 1 K KK KK K K K K ...K 1 + 1 + 1 22 + 1 2 3 3 + ... + 1 2 3m m [H] [H] [H] [H] [H]
[H m 2 R] =
CR qCK KK 1 2 K1 K1K 2 K1K 2 K 3 K1K 2 K 3 ...K m [H]m + + + ... + 1+ [H] [H]2 [H]3 [H]m
[H m n R] = CR qCK K K K ...K 1 2 3n n K1 K1K 2 K1K 2 K 3 K1K 2 K 3 ...K m [H] + + + ... + 1+ 2 3 m [H] [H] [H] [H]
Cn bng ca thc th Trong dung dch thuc th HmR c cc cn bng nh sau: Theo nh lut bo ton nng i vi thc th hu c ta c Thay cc biu thc {[HmR], [Hm1R], [Hm2R], [Hm3R], , [HmnR]} vo cng thc (5.17) v rt gn ta c: Tng qut:
* Lp biu thc tnh S Phc phn ly trong dung dch

M ( OH )i ( H m n R )q M ( OH )i + qH m n R
K Kb M ( OH )i [ H m n R ] = M ( OH ) ( H m n R ) i q
q
(5.18)
CK = M ( OH )i ( H m n R )q
T (5.14) v (5.16) ta c:
[M(OH)i ] = 1...i C M CK 1 + 1,i [OH]i
1 i
[M(OH)i ] =
1...i [OH]i (CM CK ) 1 + 1,i [OH]

1 i i
(5.19)
Thay (5.19) vo (5.6) ta c:
( C CK ) 1...o [OH ] [ H m n R ] K Kb = M (1 + 1,i [OH]i ) CK

i i
i ( C = CK ) 1...i [OH ] [ H m n R ] i 1 + 1,i [ OH ] = M K Kb CK 1
(5.20)
Thay [Hm-nR] t cng thc (5.5) vo phng trnh (5.20) ta c:

(1 + 1,i [OH]i =
1 i
(CM qCK ) ( K Kb CK 1
CR qCK K K ...K x 1 2 n n K KK K K K ...K [H] + 1 + 1 22 + ... + 1 2 3m m [H] [H] [H]
(5.21)
Ta t:
S= (CM CK )[OH]i ( CK CR qCK K K ...K x 1 2 n n )q K K K K K K ...K [H] 1 + 1 + 1 22 + 1 2 3m m [H] [H] [H]
(5.22)
Thay biu thc (5.22) vo biu thc (5.21) ta c:

i S i 1 + 1,i [ OH ] = 1...i 1 K Kb
(5.22)
Ly vi phn 2 v phng trnh (5.22) theo [OH]
[OH ]
1 1,i
[OH]
1...i dS K Kb d [ OH ]
(5.23)
Ly phng trnh (5.23) chia cho phng trnh (5.22) ta c:

dS 1 = Sd [ OH ] [ OH ] 1 + [ OH ]i 1,i
1,i
[OH]
(
i
d ln S 1 = d [ OH ] [ OH ] 1 + [ OH ]i 1,i
1,i
[OH]
(5.24)
Ta bit hm ni phc trung bnh ca Bejum c biu din

n=
[OH]
(1 +
1,i
1,i
[OH ] )
i
T phng trnh (5.24) ta c

d ln S n = d [ OH ] [ OH ]
(5.24)
i lng
n chnh l lch (tg) ca tip tuyn ti mi im ca ng cong ph [OH ]
thc lnS vo [OH] nh sau:

tg 1 [OH]
tg
lnS
Ti cc im tip xc lc ny l gi tr hng s c tm bng th theo nhng phng trnh nh sau: tnh tg =

d ln S d [ OH ]
tg TB = tg1 + tg 2 + tg 3 + tg 4 + ... + tg n n d ln S v gii hn ca d [ OH ]
Trong n l s im trn th. Ta t hm s ph G1 = tg TB = hm G1 khi [OH] tin ti 0:

[OH ] 0
lim G1 = lim
1 + 212 [ OH ] n = lim = 1 [OH ] 0 [ OH ] [ OH ] 0 1 + OH + OH 2 [ ] [ ] 1 1 2

Vy: tgTB = 1, t 1 ta tnh c 2. xc nh 2, ta t hm s ph G 2 =

lim G 2 = lim G1 1 ri ly gii hn ca G2 khi [OH] tin 0: [OH]
[OH ] 0
1 + 212 [ OH ] G1 1 = lim 1 [OH ] 0 [ OH ] [OH ] 0 1 + [ OH ] + OH 2 [ OH ] [ OH ] 1 1 2
= lim
2 2 1 + 212 [ OH ] 1 1 [OH ] 122 OH
[OH ] 0
(1 + [OH] + [OH] ) [OH]

2 1 1 2 1 1 2
= lim
2 Vy : tg 2 = 212 1
[OH ] 0
(1 + [OH] +
(
2 2 212 1 1 2 [ OH ]
OH
2
2 = 212 1
Tng t:
[OH ] 0
lim G3 = lim
2 G 2 22 1
[ OH ] 0
[OH ]
) = 3
3 312 + 1
3 Vy : tg 3 = 33 12 + 1 , v c 1 v 2 ta tnh c 3 3 G3 33 312 + 1
[OH] 0
lim G 4 = lim
[OH ] 0
[OH ]
) = 4
2 2 4 413 + 41 2 22 1
2 2 4 Vy : tg 4 = 44 413 + 41 2 22 1 , ta tnh c 4
. . V.2.3. Phng php th nghim 1. Pha dung dch ion kim loi v phc c nng nghin cu, tm thnh phn ca phc. 2. Thay i pH c nng nht nh. 3. V th v tnh lnS v [OH], ti cc im tip xc lc ny ta tnh t tg = 4. Lp bng 5.2 s ph thuc lnS v [OH] Bng 5.2: S ph thuc lnS v [OH] P(OH)i Ai CK(i) CK1 CK2 CR qCK M i=0 MOH i=1 M(OH)2 i=2 lnS M(OH)3 i=3 M(OH)4 i=4 M(OH)i i=i Kb n [OH ]
P(OH)1 A1 P(OH)2 A2 Ch :
Nghin cu phn ng ny thng nng long v phc phi tun theo nh lut LamberBeer kh rng. i lng v [OH]. Bi ton hydroxo c th tnh c i vi phc tan v kh nng tan trong nc, trong trng hp ny i lng S s biu th qua tch s tan T.
n chnh l lch tip tuyn ti mt im ca ng cong ph thc lnS [OH ]
V.3.
XC NH THNH PHN PHC
V.3.1. Phng php t l phn t (Phng php bin i lin tc mt hp phn). iu ch mt dy dung dch c pH khng i (dung dch m) nng ca ion kim loi khng i, cn nng ca thuc th hu c bin i lin tc hay ngc li. o mt quang ca nhng dung dch ny v lp th ph thuc ca A vo t l nng A
R (hnh 5.1). Me
1 4
2 4
3 4
4 4
5 4
6 4
R M2
Hnh 5.1: Xc nh thnh phn phc theo phng php t l phn t Phc cng bn v cc i hp th ca phc v ca thuc th cng khc bit nhau th ng biu din s ph thuc ca A vo t l biu din xc nh t l gia cc hp phn trong V.3.2. Phng php ng phn t gam Chun b mt dy gm 9 dung dch c pH nh nhau v khng i v c V d chun b 9 dung dch c [Me].10-5M 9 8
R cng gy r nt. im gy trn ng Me
C = const
2 1
C = 10.10
7
M nh sau:
[R].10-5M
9
R Me
o mt quang ca 9 dung dch ny v lp th ph thuc ca A vo t s suy ra s phi tr q (hnh 5.2) A
9 1
8 2
7 3
6 4
5 5
6 4
7 3
8 2
9 1
M2 R
Hnh 5.2: Xc nh thnh phn phc theo phng php ng phn t gam V.3.3. Phng php im ng quang iu ch 10 dung dch ging nh trong dy ng phn t gam. V d iu ch 10 dung dch c
C = 10 *10
9 1
. 8 2 7 3 6 4 5 5 4 6 3 7 2 8 1 9 0 10
[Me].10-5M [R].10-5M
Cho ghi quang ph hp th ca 10 dung dch ny trn my o mu t ghi. Chng ta s thu c quang ph hp th ca 10 dung dch ph thuc vo di sng.
9 1
8 2
[M2] [R]
3 7 10 5 4 6 8 9 Hnh 5.3: Xc nh thnh phn ca phc theo phng php im ng quang

[Me] 3.3 1 = = [R] 6.6 2
Ta c im A l im ng quang (im m 4 dung dch c mt quang bng nhau). T A ta h ng thng gc xung trc honh, ng ny ct cc ng cong hp th nhng im tng ng vi mt quang ca cc dung dch ny bc sng dc c trn trc honh. T cc d kin ny, ta lp th ph thuc cu D vo t s (hnh 5.3). V.3.4. Phng php logarit gii hn
Gi thit ta c phn ng to phc: Me + qR MR q
R suy ra q Me
MeR q 1gK = 1g MeR 1g Me q1g R Kd = [ ] b q q [ Me ][ R ]

q1g MeR q 1gK b [ Me] R = 1g
Khi nng ion kim loi d nhiu v coi nh khng i trong qu trnh to phc th thnh phn lg K b [ Me] l khng i v ta c:
1g MeR q = f (1g [ R ])
M [ MeR 4 ] li t l thun vi A nn cui cng: 1gA=f(lgR). Lp th din t s ph thuc ny ta c ng thng c h s gc tg=q V.3.5. Phng php chuyn dch cn bng V d: ta c phn ng to phc:
Me + qR MR q
V [MeRq] t l vi [Me] t l vi AmaxA nn:

MR q A = 1g Ck = 1g = q1g [ R ] + 1gK b 1g CMe Ck A max A [ Me]
Vy:
1g
A = f (1g [ R ]) A max A
T hm tuyn tnh ny ta tm c h s gc tg=q nh phng php th (hnh 5.4) Trong phng php ny ngi ta ly nng phi t ln rt nhiu so vi nng ion kim loi. V d
[M e ] = [R ]
[R] trong phng trnh: 1g Vy:
A Amax A
1 1 1 1 1 1 1 ; ; ; ; ; ; .... 5 7, 5 10 12, 5 15 17, 5 20
Ck A = 1g = q1g [ R ] + 1gK b A max A CMe C k
1g
A = f (1g [ R ]) A max A
1g
Hnh 5.4 Trong phng trnh 1g
tg=q
Cx A = 1g = q1g [ R ] + 1gK b coi nh bng nng ban A max A CMe Cx
u ca thuc th (v khng th tnh chnh xc nng cn bng ca n c) cho nn phng trnh trn mang tnh gn ng.
PHN II: GII THIU CC THUC TH V NG DNG TRONG PHN TCH
CHNG VI:
VI.1. PHENYLFLUORONE
CTPT: C19H12O5 KLPT = 320,30
THUC TH PHI TR O O
HO HO 7.1.1. Tn gi khc 2,3,7Trihydroxy9phenyl6fluorone 2,6,7trihydroxy9phenylisoxanthene3one. 7.1.2. Ngun gc v phng php tng hp
OH O
y l thuc th c gi tr v mt kinh t. N c tng hp bi phn ng 1,2,4 benzenetriol vi benzotrichloride. 7.1.3. ng dng trong phn tch N c dng nh thuc th o quang v nhy, c tnh chn lc vi Ge v Sn; ngoi ra thuc th cn dng xc nh Co, Fe, In, Mo(VI), Nb, Ti v Zr bng phng php o quang. 7.1.4. Tnh cht ca thuc th Phenylfluorone l mt tinh th bt mu cam, c nhit nng chy ln hn 300oC. Xut hin hunh quang mu hi lc trong dung dch cn pH=8. Trong dung dch kim, thuc th phn ly yu. t tan trong nc (3.10-7M trong 20% ethanol, 25oC), t tan trong ethanol lnh, nhng d tan trong cn b acid ho (HCl v acid H2SO4). N c th kt tinh li t cn b acid ho vi s c mt ca ammoniac.Nhng mu thng mi thng c tinh khit khng tho mn. Phenyfluorone c xem nh mt cht in ly lng tnh, v s phn ly trong 25% ethanol c th c xc nh nh di: H 4L + Vng pKa1=2.3 pKa2=5.8 pKa3=11.3 pKa3=12.3 HL2H2L L3-
SO3H vng cam
cam hng
Ph hp th trong dung dch nc c minh ho trong hnh 7.1

Hnh 7.1: Ph hp th trong dung dch nc 7.1.5. Phn ng to phc cht v tnh cht ca phc cht Phenylfluorone phn ng vi mt s ion kim loi to thnh chelate c mu khng ho tan. Trong dung dch acid 0,1M, Ge (IV) to phc c mu vi t l 1:2 xy ra theo phng trnh:
Ge ( OH )4 +2H 3L Ge ( OH )2 ( H 3L )2 +2H 2
Hng s cn bng trong dung dch ethanol 20% ti 25oC v = 5 c xc nh gn bng 8( 4).1012. Cu trc phc ca Ge(IV) c biu din nh di
Bng 7.1: PHN NG CA PHENYLFLUORONE VI 100g CC KIM LOI Ion kim loi HCl HCl + H2O2 HCl + oxalate HCl+H2O2 + oxalate Fe (III) S S Ge (III) S S S S Hf (IV) S S Mo (VI) S L Nb (V) S Sb (III) S S S S Sn (IV) S S L Ta (V) S L Ti (IV) S L V (V) S W (VI) S Zr (IV) S L y: S: mu m L: mu nht : t hoc khng mu
Kt qu kho st trn phn ng to mu ca phenylfluorone trong acid HCl cho thy ch c 12 kim loi c tm thy c kh nng phn ng vi thuc th. Trong s c mt ca hydrogen peroxide v phi t, s to phc c tnh chn lc cao cho Ge(IV), Sb(III), Sn(IV). Trong php xc nh bng phng php o quang, nhy v chn lc gia tng ng k bng cch chit mi trng acid mnh. c tnh quang ph ca phenylfluorone chelate c tm tt trong bng 7.2, quang ph hp th ca Ge chelate c hng dn trong hnh 7.2. Bng 7.2: C IM QUANG PH CA PHC PHENYLFLUORONE Kim loi Al Al Co(II) Cr(VI) Fe(III) Ga Ge(IV) Ge(IV) Ge(IV) In Mn(II) Mo(VI) Mo(VI) Mo(VI) Nb Nb Ni Sb(III) Sn(IV) Sn(IV) Ta Ti Ti Ti(IV) Ti(IV) V(IV) iu kin pH 3,0 4,0 pH 9,5 11,0, Triton X100 pH 4,5 5,0; NO2-, Zephiramine pH 1,5; 40 EtOH NaOH 0,001N pH 8,0 9,0; CPB(X) HCl 1,2N, gelatin, gm Arabic hoc polyvinyl alcohol HCl 0,5N, chit vi benzyl Alcohol HC l,1 1,5N; CTMAC pH 5,5; gelatin CPC(X) pH 2,0; gm arabic pH 1,5; CPC HCl 0,25 0,3M; EtOH, sau khi cho CHCl3, vi BPA(X) H3PO4 0,3% H2SO4 0,24 0,48N; Triton X100 1000 trong 90 giy pH 8,5 10,0; CTMAB, pyridine H2SO4, gelatin, thiourea pH 1,2 2,0 (HCl), tartarate, gum Arabic, hoc polyvinylalcohol H2SO4 1,8N, CTMAB pH 4,5 pH 7,0 1,0 (HCl), PB(X), chit bng CHCl3 + AmOH (2:1) CPA(X), Cl-, chit bng CHCl3 Furylvinylacroleyphenyl hydroxylamine(X), chit bng CHCl3 pH 1,4 2,2; Triton X350 (X) Op emulsifier (Y) pH 4,0 5,0, 30% EtOH, 0,02% gelatin
T l ML2 ML2X ML2 ML ML2 ML2X2 ML2 ML2 ML2 ML2 ML2X2 ML2X ML2 ML2 ML2 MLX2Cl MLX2Cl ML2X2 ML2XY ML2
max .104 (nm) 540 554 645 500 580 570 510 505 505 540 550 540 518 520 525 620 540 510 505 530 540 550 540 540 530 6,0 13,5 4,8 2,1 8,6 11,4 8,7 14,5 17,1 4,88 9,8 9,6 7,4 3,7 10,0 10,4 3,42 5,93 18 6,39 9,0 17,1 16,3 1,7
Gii hn cho php (ppm) 0 0,2 ~2 0,01 1,7 ~1 0,05 0,5 0,02 0,16 0,2 1,4 0,33 1,67 0,4 6 0 0,6 0 0,4 0 0,33 ~2 0 0,3 0 0,5 0,05 0,1 0,05 10 0 0,2 0,2 2
Zn Zr(IV) Zr(IV)
pH 7,7 8,2, CPB, pyridine HCl 0,1N, stabilized with cyclohexanol pH 4,6, F- , CPC
ML ML2
585 540 560
8,0 13 4,6
01 ~1 07
K hiu cho cationic: CTMAC: Cetyltrimethylammonium chloride CTMAB: Cetyltrimethylammonium bromide CPC: CPB: Cetylpyridinium chloride Cetylpyridinium bromide
Hnh 7.2 7.1.6. Tinh ch thuc th Thuc th c th c tinh ch bng cch cho 1 gam mu vi 50ml ethanol trong thit b Sohxlet, tin hnh chit 10 gi loi b cc cht khng tan. tinh khit c th c kim tra bng cch o s hp th bc x ca dung dch nc c nng 5.10-4% (1N HCl), ( = 462nm, = 4,06.104) S c mt ca cc cht khc c th c kim tra bng php in di trn giy vi dung dch 0,1% c trn ln bi HCl 6N (3ml) ethanol (97ml) dng vi dung dch c cha 0,05% acid oxalic v 30% acid acetic. 7.1.7. ng dng trong phn tch Thuc th trong phng php o quang Phenylfluorone hu nh c s dng rng ri nh mt thuc th dng o quang cho Ge. Mt vi ion kim loi Co, Fe, In, Mo(VI), Nb, Ni, Sn(IV), Ta, v Zn cng c th c xc nh bng thuc th ny. Vic xc nh Ge c th tng nhy bng cch chit phc Ge cng vi lng d thuc th vo trong mt dung mi hu c khng trn ln nh benzyl alcohol hoc chit Germanium chloride trong dung dch HCl vi carbon tetrachloride hoc MIBK, sau , lp tc to thnh phc phenylfluorone trong pha hu c vi s thm vo ca dung dch alcohol ca thuc th. Trong s tng phn vi phng php chit, nhy ca phng php o quang trong pha nc ch bng mt na ca phng php chit, nhng nhy v tc phn ng c th c thay i bng s kt hp cht hot ng b mt cation chng hn cetyltrimethylammonium chloride.
Trong vic xc nh thic Sn, tri li thic khng th tn ti hnh thnh mu thic chelate bi s thm vo dung dch methanol ca phenylfluorone n MIBK c chit ra t SnCl4. Tuy nhin, tin phenylfluorone chelate c to thnh trong dung dch acid pha long, c th c chit ra vi MIBK. Sau khi chit ra mu ca chelate c khuynh hng nht dn trong dung dch. T l ca s mt mu tng dn vi s gia tng nng acid trong dung dch c chit ra. iu kin dng xc nh o quang ca kim loi ca phenylfluorone trong bng 7.2 Xc nh Ge sau khi chit ra vi carbon tetrachloride Ly 20ml dung dch mu HCl 9N c cha 0,5 n 10 g Ge cho vo mt ng dn v thm vo 10ml carbon tetrachloride. Sau lc khong 2 pht tch lp hu c ra. Ly chnh xc 5ml cho vo bnh 10ml v thm vo 1ml thuc th (0,05 g phenylfluorone cng vi 0,43ml HCl trong 100ml ethanol) v pha long n vi ethanol. Sau 5 pht o ti bc sng 508nm.
VI.2. PYROCATECHOL TM
CTPT: C19H14O7S KLPT: 386,38
OH OH
HO C SO3H H4L 7.2.1. Tn gi khc
3,3,4Trihydroxyfuchsone2sulfonic acid, Catechol sulfonephtalein, Catechol tm, PV. 7.2.2. Ngun gc v phng php tng hp C gi tr v mt kinh t. Tng hp t s ngng t ca osulfonephthalein anhydrit vi pyrocatechol 7.2.3. ng dng trong phn tch Nh mt ch th kim loi trong phng php chun phc cht chelate ca nhng kim loi nng. Nh phn ng trc quang cho nhng kim loi khc nhau bao gm: Al, Bi, Ge, Sn, Y, v Zr. nhy c th c ci tin bng vic thc hin phn ng trong s c mt cht hot ng b mt cation. 7.2.4. Tnh cht ca thuc th L loi bt nu thm c nh kim loi mu xanh dng. N rt ht m, v th nn bo qun tht kn. Sn phm thng mi thnh thong c mi v acid acetic m khng hon ton loi b c t s kt tinh dung mi. N tan t do trong nc v cn pha trong nc, t
tan trong cn nguyn cht lnh hoc acid acetic bng v khng tan trong dung mi khng phn cc chng hn: benzene, xylene, Dung dch nc ca Pyrocatechol tm c mu vng v mu ca dung dch thay i theo pH cng nh kt qu tch proton ca thuc th. S tch proton c vit nh c ch ra di y pKa1 pKa2 < 1 pKa3 = 7 82 pKa4 = 9 76 pKa5 =11 7
H5L
H 4L
H3L-
H2L2-
HL3-
L4-
Tm Vng tm Ph hp thu ca thuc th nhng gi tr pH khc nhau c minh ho hnh 7.4 Dung dch nc ca thuc th rt bn trong mi trng acid dn dn b phai mu pH>7,5.
OH OH
HO C SO3
-
O +H+
OH
OH
O C SO3-
H3L+ H+
OH OH
H2L2+H+
OOH
HO C SO3
-
OH+
O C SO3-
HL3H4L + H+
OH OH
+H+
-
O-
O-
HO C SO3H
OH+
O C SO3-
H5L
L4Hnh 7.3
7.2.5. Phn ng to phc cht v tnh cht ca phc cht

Pyrocatechol tm to nn cc lin kt mu vi cc kim loi khc nhau, hu ht trong dung dch acid yu v baz yu c tm tt bng 7.3. Bng 7.3: PHN NG MU CA PYROCATECHOL TM VI CC KIM LOI Ion kim loi pH Mu Ion kim loi Al 2,5 4,0 Hi ta Nd(III) Be 8.0 Ni Bi <1,5 Hi xanh ta Pb 2BO3 6,0 Pr Cd(II) 8,0 Hng Sb(III) Ce(III) 6,5 Sn(II) Co(II) 7,5 Sn(IV) Cu(II) 5,0 Th Fe(II) 7,5 Ti(IV) Fe(III) <2,0 UO22+ Ga 2,5 Mu ta WO42In 7,0 WO42La 9,5 Y Mg 8,5 Zn Mn(II) <3,0 Hi ta Zr Nng ca ion kim loi 5.10-3M. Mu ca phc kim loi l mu xanh ngoi tr s khc bit ca ch th. Phc mu xanh c to thnh trn ch th pH. Cc phn ng mu c bn (chnh) l [ML2-]; [M2L] v [MHL-] M c biu th cho kim loi ha tr 2, c ch ra sau:
M
pH Mu 6,5 7,5 5,5 6,5 <1,5 Hi ta 3,5 0,5 <0,3 <1,5 Mu ta 5,0 <3,0 >3,0 Hi ta 6,3 7,0 <1,0 Hi ta
O ML2- (xanh tm)
O-
O C SO3-
O MHL- (xanh tm)
OH
O C SO3-
O M2L- (xanh)
M+
C SO3-
Hng s bn ca mi loi c tm tt trong Bng 7.4 Bng 7.4: HNG S BN CA PHC CHELATE CA PYROCATECHOL TM Ion kim loi Log KML Log KM2L Log KMHLa Al(III) 19,13 4,95 Bi(III) 27,07 5,25 Cd(II) 8,13 5,86 Co(II) ,01 6,53 Cu(II) 16,47 11,08 Ga(III) 22,18 4,65 In(III) 18,10 4,81 Mg(II) 4,42 3,67 Mn(II) 7,13 5,37 Ni(II) 9,35 6,85 Pb(II) 13,25 10,19 Th(IV) 23,36 4,42 Zn(II) 10,41 7,21 Zr(IV) 27,40 4,18 Ph chnh thay i theo s hnh thnh ca phc chelate c ch ra hnh 7.5. Mc d bc sng hp thu cc i nhng cng hp thu khc nhau ph thuc vo ion kim loi. Ph hp thu tng t c quan st trn nhiu kim loi khc Trong s c mt ca cht hot ng b mt cation, tuy nhin, s chuyn dch m mu v s tng cng ca di hp th c quan st th hin r rng. 7.2.6. S tinh khit v tinh ch ca thuc th Mu thng mi thng khc nhau v cht lng. Nhng mu m khng tinh khit c th tinh ch bng s kt tinh t acid acetic bng. Dng tinh khit trong m acetate (pH 5,2 n 5,4) c mu vng chanh (max = 445nm, = 1,4.104)
Hnh 7.5 Bng 7.5: CHUN PHC CHT S DNG CH TH PYROCATECHOL TM Ion kim loi Bi Cd Co(III) Cu(II) Cu(II) Fe(III) Ga In Mg Mn(II) Ni Pb Th Zn pH 23 10 9,3 56 67 56 3,8 5 10 9,3 9,3 5 2,5 3,5 10 m HNO3 NH3NH4Cl NH3NH4Cl HNO3NH3 Pyridine Pyridine Acetate Pyridine NH3NH4Cl NH3NH4Cl NH3NH4Cl Hexamine HNO3 NH3NH4Cl Mu thay i ti im kt thc Xanh Vng Hi xanh dng hi ta Hi xanh dng hi ta Xanh Vng Xanh Vng Xanh Vng Xanh Vng Hi xanh dng hi ta Hi xanh dng hi ta Hi xanh dng hi ta Xanh Vng Xanh Vng Hi xanh dng hi ta Lu
Fe(III); Hg(II); Th; Zr c chun cng Vt ca kim loi nng khng c ln Chun chm Dung dch chun nng Thm NH2OH
C ln Bi
7.2.7. ng dng trong phn tch S dng nh l ch th kim loi trong chun to phc
Ion kim loi, c th c chun bng EDTA s dng Pyrocatechol tm nh l ch th. Dung dch A 1% c s dng v c th tn tr cho nhiu thng, dung dch c dung mi l nc th n nh v s thay i mu khng b cn tr bi vt kim loi nng, n c ngh s dng thch hp ca ch th ETOO hoc Murexit. S thay i mu vi Bi v Th th rt r rng v th nhng kim loi ny c th c s dng chun ngc trong chun cc kim loi khc.
Hnh 7.6 Bng 7.6: NG DNG CA PYROCATECHOL TM NH THUC TH TRC QUANG Ion kim loi Al(III) Al(III) Al(III) B Be Bi(III) Cd(II) Co(II) Cr(III) Cu(II) Fe(III) Fe(II) Ga Th Th Ti(IV) Ti(IV) V(V) W(VI) W(VI) Y(III) Y(III) Phc chelate kim loi (x 104) H sb Bc sng (x104) pH 6,0 ML2 580 6,8 0 04 pH 9,7 10,2, CTAC(X) ML2X5 670 0,53 0,27 54 pH 10 CPC(X) MLX5 700 3,8 pH 8,55 8,65 ML 494 0,165 0,2 2,0 pH 8,0, CPC(X) MLX5 680 1,5 pH 3,8, acetate 610 4 24 pH 10 CPC (X) MLX5 710 1,0 0,1 7,5 pH 10, CPC (X) MLX5 720 1,2 pH 5,0 6,0, acetate 605 1,1 pH 7 630 4 24 pH 6,2 7 ML2 610 6,2 0 0,6 pH 5,0 6,0, CTMAB (X) ML2X2 605 13,5 0 0,35 pH 6,05 6,4 ML2 580 ~ 7,3 0,56 3,1 pH 3,8, acetate 480 4 24 pH 8,0, CTMAB ML3 660 6,0 0,6 4,0 pH 3,3 3,5, gelatin ML2 690 0,06 0,71 pH 2,0, CPC MLX5 745 7,5 pH 4,0, Zephiramine ML3 660 7,5 0 0,5 pH 2,0 6,0 ML 540 16 pH 1,0, CPC MLX5 670 6,4 pH 8,7, H3BO3 MLX 607 1,9 0-7,8 pH 8,4 9,0, gelatine 665 2,59 0 1,8 iu kina
Zn(II) Zr(IV) Zr(IV)
pH 9,0, CPC pH 3,5 5,0 pH 6,0, CPC
MLX5 ML2 MLX5
690 650 700
1,3 3,26 1,3
0 2,0
S dng nh l thuc th trong php trc quang Ion kim loi c th c xc nh trc tip bng php trc quang trc tip vi Pyrocatechol tm trong dung dch c dung mi l nc c tm tt bng 7.6. Nh m t trc y nhy chc chn c ci tin bi s kt hp ca cation cht hot ng b mt. Thng thng Pyrocatechol tm khng l thuc th chn lc v b cn tr bi nhiu nguyn t. Bi vy phng php ny c th p dng sau khi c s tch thch hp hoc kt hp s dng cht che thch hp. Phc anion vi Pyrocatechol tm c th c chit vo trong dung mi hu c nh l mt cp i ion vi cation ring l, nh vy t c nhy v chn lc ca php xc nh. Xc nh trc quang Sn(IV) vi s kt hp s dng Pyrocatechol tm v cetytrimethylammonium bromide: Chuyn 10ml dung dch mu (0,01 0,1mg Sn) v 5ml dung dch Pyrocatechol tm 103 M trong mt beaker 100ml. Thm 2ml cetyltrimethylammonium bromide 0,1% v pha long n 50ml. Hiu chnh pH ca dung dch n 2,2 bng dung dch ammoniac long, s dng my pH. Chuyn ton b dung dch vo bnh nh mc 100ml v nh mc ti vch. Sau 10 pht, o hp thu s dng cuvet 1cm loi tr nh hng nn bng mu trng 662nm.
VI.3. CHROMAZUROL S
CTPT: C23H16O9Cl2S KLPT: 539,34
COOH
OH
COOH
O
H3C
Cl
Cl
SO3H
7.3.1. Tn gi khc. 3Sulfo2, 6dichloro3,3dimethyl4hydroxyfuchson5,5dicarboxylic acid. 7.3.2. Ngun gc v phng php tng hp Chromazurol S l tn thng mi ca thuc nhum c sn xut bi tp on Geigy; loi thuc nhum ny l mt loi thuc th c ng dng rng ri. Chng ch yu dng mui trinatri. N c tng hp bng s ngng t ca sulfoodichlorobenzaldehyde cng 2,3cresotic acid, km theo qu trnh oxi ha. 7.3.3. ng dng trong phn tch Chromazurol S c dng lm ch th kim loi trong phng php chun phc cht xc nh Al, Ba, Ca, Fe, Mg, Ni v Th; v cng l mt thuc th trc quang cho nhiu ion
kim loi khc nhau nh l: Al, Be, Ce, Co, Cr, Cu, Fe, Ga, Hf, In, La, Mn, Mo, Ni, Pd, Rh, Se, Th, Ti, V, Y, Zn, Zr v F-. Theo nhng nghin cu gn y, phng php trc quang vi nhy cao ca nhng cation k trn trong s hin din ca cht hot ng b mt cationic. 7.3.4. Tnh cht ca thuc th Dng thng mi C23H13O9Cl2SNa3.2H2O l bt mu nu . C kh nng ht m v d ha tan trong nc. Trong dung dch nc, pH = 3 4 c mu cam, pH = 4 c mu vng. Trong mi trng acid pH<0 (HCl 1,2 2,0N) to thnh ta dng t do H4L v li b ha tan trong dung dch acid hn (HCl 8 9N). Gi tr hng s phn ly proton c xc nh ( = 0,1 (NaClO4), 25oC) v ph hp thu trong dung dch nc nhng pH khc nhau c minh ha hnh 7.7 H5L+ pKa1 pKa2 = -1 2 pKa3 = 2 25 pKa4 = 4 88 pKa5 =11 75 4H2L2HL3H4L H3LL cam vng tm COOH 7.3.5. C ch phn ng to phc v tnh cht ca phc Chromazurol S phn ng c vi nhiu ion kim loi khc nhau nh l: Al, Be, Ce, Co, Cr, Cu, Fe, Ga, Hf, In, La, Mn, Mo, Ni, Pd, Rh, Sc, Th, Ti, V, Y, Zn, v Zr to thnh nhng phc chelate tan mang mu. S tng phn gia mu cam hay vng ca thuc th vi mu xanh tm l gii hn mu ca phc chelate. Nhng gi tr pH thp nht m quan st c mu ca phn ng th c tm tt trong bng 7.8. T l gia kim loi v phi t khc nhau ph thuc vo kim loi v cng ph thuc vo iu kin dung dch nh l pH v t l gia thuc th v kim loi.V d, cu trc ngh ca ba loi phc chelate Fe(III) c minh ha hnh 7.8 COOH
Hnh 7.7
Bng 7.8: PHN NG MU CA CHROMAZUROL S VI CC ION KIM LOI KHC NHAU Ion kim loi Be Ce (III) Co (II) Ga In La Mn (II) pH Ion kim loi pH Ion kim loi 2,5a Nd 6,5 U (IV) 5,0 Ni 7,5 UO22+ 8,5 Pb 6,5 VO2+ 1,5 Pr 6,5 Y 2,5 Sr 11,0 Zn 4,5 Th 1,0 Zr 7,5 Ti (IV) 1,0 pH 2,5 2,0 4,0 5,5 7,5 1,0
a: ti pH ny phc chelate c mu nho, nhng pH cao hn phc s chuyn sang mu tm.
Hnh 7.8 A
Hnh 7.8 B
Hnh 7.8 C Trong hu ht cc trng hp ca phng php trc quang s dng Chromazurol S, dung dch quan st c th l hn hp cn bng ca hai hay nhiu loi phc chelate. Do khng chc chn trong vic xc nh c im, tnh cht cc hnh thi phc chelate trong cn bng dung dch, dn n khng chc chn v tinh khit ca thuc th v c rt t cc hng s bn ng tin cy. Tuy nhin nhng gi tr bo co ny cng rt hu ch cho vic nh gi nh tnh phc chelate ca thuc th chromazurol S. Nhng gi tr ny c tm tt trong bng 7.9. Khi quan st s hp th phc chelate ca Chromazurol S, phc chelate Al c minh ha hnh 7.9 l mt v d mc d gi tr bc sng max c th thay i vi tng kim loi, nhng hnh dng ca ng cong th khng khc lm. Khi c mt ca cht hot ng b mt cationnic nh l phc Zephiramine hoc Cethyltrimethylammonium chloride, ph ca thuc nhum t do v phc kim loi thay i mt cch ng ch . Hnh 7.10 m t ph hp thu ca Chromazurol S v phc aluminum ca n trong s hin din ca Zephiramine S cation.
S thay i ph tng t cu phc chelate cng c quan st trong s hin din ca dung mi nc. Hnh 7.11 m t nh hng ca dung mi hu c trong ph hp thu ca phc ng.
Hnh 7.9
Hnh 7.10 Bng 7.9: HNG S BN CA PHC CA CHROMAZUROL S Ion kim loi Al (III) Be (II) Cd (II) Co (II) Cu (II) iu kin Cn bng M + 2CAS ' M(CAS)2 M + HL ' MHL M + 2CAS ' M(CAS)2 M + 2CAS ' M(CAS)2 M + HL ' MHL log K 2,04 4,66 9,1 6,18 4,02 pH 4,2 5,5 11 9,38 Nhit (oC) 30 25 25 20 25 NaClO4 0,1 NaClO4 0,1 NaClO4 0,1 KCl 0,1
Fe (III) Ga (III) Ga (III) Ga (III) Th (IV) VO2+
M + CAS ' M(CAS) M + L ' M(L) M + 2L ' M(L)2 M(L)2 + L ' M(L)3 M + CAS ' M(CAS) M + CAS ' M(CAS)
4,3 13,1 12,9 11,8 4,2 4,8 4,0 4,6
2,7 4,5 4
20 25 25 25 30 25
KCl 0,1 (NaCl + NH4Cl) 0,1 (NaCl + NH4Cl) 0,1 (NaCl + NH4Cl) 0,1 NH4NO3 0,15 -
7.3.6. S tinh ch v tinh khit ca thuc th Hu ht nhng mu thuc th sn c khng tinh khit s dng cho vic nghin cu ho l, mc d chng c th c s dng nh l thuc th trong phng php o quang cho nhng kim loi hoc ch th kim loi cho chun phc cht chelate. Qui trnh c ngh cho qu trnh tinh ch nh sau: Ho tan 40g mu vo 240ml nc v lc b nhng cht khng tan. Thm 50ml HCl v lc kt ta. Ra ta vi HCl 2N v lm kh. Ho tan ta bng 250ml nc v lm kt ta hai ln na nhit 70oC. Sau khi kt ta ln th ba lm kh sn phm. tinh khit ca Chromazurol S c th c xc nh bng quan st hp thu ca dung dch ca nng c bit bc sng thch hp (bng VII.3.3). Php th chnh xc hn c th dng chun in th ca dng acid t do (H4L.2H2O) vi dung dch NaOH. 7.3.7. ng dng trong phn tch Thuc th trc quang Hn 30 ion kim loi c xc nh vi thuc th Chromazurol S. Nhng nm gn y, hp thu phn t ca phc kim loi c tm thy tng cao n 105 khi c mt ca micelle cation; v vy phng php trc quang c nhy cao cho nhiu ion kim loi khc nhau c bo co. Nhng dng Chromazurol S nh l thuc th trc quang li thiu tnh chn lc cho nhiu ion kim loi. Bng 7.10: C IM PH CA CHROMAZUROL S iu kin max(nm) (x104) HCl 1,0N 540 7,80 pH 79 (acetate, borax) 430 2,24 pH >13(NaOH ~ 1N) 600 7,56 Xc nh Be bng phng php trc quang Chuyn ton b dung dch mu c tnh acid nh (180g Be) vo bnh nh mc 25ml. Trn lp nc tch ra, trung ha lng acid d bng NaOH10% bng ch th methyl da cam, thm 1,0ml acid ascorbic 1%, 2,00ml EDTA10%, 5,00ml m acetate. Tip tc thm vo hn hp ny mt lng nh trc NaOH10%, v pha long vi 20ml nc. Thm 2,00ml dung dch Chromazurol S (0,165g trong 100ml nc) v pha long n th tch trn. o hp thu v loi nh hng nn bng mu trng 569nm. nhy l 0,00022g Be cm2 trn thang cn Sandell. Xc nh Be bng phng php trc quang c nhy hn nh s dng cht hot ng b mt Chuyn dung dch nc cha t hn 2g Be vo mt beaker v thm 1,00ml EDTA 1% v 5,00ml dung dch perchlorate sodium 5M. Hiu chnh pH ca dung dch n 4,5 vi
dung dch m acetate v lm bay hn dung dch cn 510ml. Sau khi lm lnh nhit phng tip tc thm 1,00ml dung dch Chromazurol S 0,25% v 2,00ml polyoxyethylenedodecylamine 0,5% (ha tan 0,5g trong nc c cha 0,5ml HCl 5N, sau hiu chnh pH ti 4,5 vi m acetate v pha long ti 100ml). chuyn ton b dung dch vo bnh nh mc 25ml v nh mc ti vch bng nc ct. Sau 15 pht, o hp thu 605nm v loi tr nh hng bng mu trng. nhy l 0,0001g Be cm2 trn thang cn Sandell. Anion nh l perchlorate, nitrate, v chloride khng nh hng. Ch th kim loi trong phng php phc cht Chromazurol S c ngh nh l mt ch th kim loi trong phng php phc cht c tng hp bng 7.12. Mc d mu thay i khng r nt bng Xylenol da cam, nhng n rt hu dng trong chun Al, Cu v Fe ni m Xylenol da cam v methyl thymol blue khng hot ng thch hp. Ch th s dng pha trong nc khong 0,10,4% c th trong nhiu thng Bng 7.12: CHUN PHC CHT CA ION KIM LOI DNG CHT CH TH CHROMAZUROL S Ion kim loi Al(III) Cu(II) Fe(III) Ni(II) Th(IV) Aluminon: Mui ammonium ca acid aurine tricarboxylic. CTPT: C22H23N3O9 KLPT: 473,43
HO O COONH4 COONH4
pH 4 6-6,5 2-3 1-2
m Acetate Acetate Monochloroacetic acid acetic acid Pyridine +NH3 HNO3-NH3
Thay i mu im cui Tm vng Xanh m xanh nc bin Xanh vng cam Xanh tm vng Tm vng
Ch chun 80o
chun 80o chun in th
7.3.8. Thuc th khc c cu trc lin quan
NH4OOC
OH
L cht bt mu nu vng, trong sut v d tan trong nc. Sn phm thng mi, thng c tinh khit khc nhau. tinh khit c th c kim tra bng chy qua sc k lp mng (TLC) vi silica gel. N to mu lp lnh vi ion Al, Be, Cr, Fe v nhng ion t him. V th n c s dng trong php o mu xc nh v pht hin nhng ion ny. Sn mu ny c th tan vi s tr gip ca cht hot ng b mt nonionic nh l Triton X100
(acetate pH 4,8; 1,5ml Triton 20%; 100oC; bc sng 537nm). nh hng ca Fe c th c loi nh s dng kt hp acid ascorbic v acid thioglycolic. Erichrome Cyanime R: 2Sulfo3,3dimethyl4hydroxyfuchson5,5dicarboxylic acid, mui trisodium (CTPT: C23H16O9S, KLPT: 468,43).
HO
COOH COOH O
CH3
C SO3H
CH3
Dng bt mu gch, n d dng tan trong nc v alcohol, cho dung dch mu cam v chuyn sang mu tm khi pH>9. Hng s phn ly acid trong dung dch nc (pKn[n=1 4]) l 1,79, 4,00, 6,91 v 11,14 (=0,1 NaCl, 2022oC). Trong vng acid hoc trung tnh, n hnh thnh phc tan c mu tm vi Al, Be, Ca, Cu, Fe, Mg, Zr, ... v c bit nh l mt thuc th trc quang xc nh Al (pH 6,0, max=535nm). V cng c nhy cao cho Be khi c mt ca micelle cation (Zephiramine) (pH 6,77,2, max=595nm, =105, 18 55ppb).
VI.4. NBENZOYLNPHENYL HYDROXYLAMINE V NHNG CHT LIN QUAN

R ' R (1)
O C R N R'
OH
CH = CH
CH 3
(2)
(3)
7.4.1. Tn gi khc Nhng cht phn ng bao qut trong phn ny c lit k trong bng 7.13, cng vi nhng ng phn ca chng. 7.4.2. Ngun gc v phng php tng hp Tt c nhng cht phn ng sn c trn th trng (1) v (2) c chun b bi phn ng ln lt gia phenylhydroxylamine vi benzoylchloride v cinnamoylchloride. (3) th c chun b bi phn ng gia otolylhydroxylamine vi benzoylchloride. 7.4.3. ng dng trong phn tch Nhng cht phn ng ny c lin quan vi Cupferron v mt cu trc, nhng phn ng ca chng vi ion kim loi l nh nhau, nhng trong nhiu trng hp c th chng mnh hn Cupferron bi v chng n nh hn trong acid v c. (1) v (3) thng dng lm
nhng cht chit trc quang cho nhng kim loi V(V) v Ti(IV). (3) th c trng nht cho kim loi V. Chng cng thng c dng nh l nhng dung mi chit ngn cch nhng ion kim loi khc nh l nhng cht kt ta hoc nhng cht phn tch trng lng nh: Al, Cu (II), Ti (IV) v nhng nguyn t khc. Mt s hp cht c quan h cu trc vi hydroxylamine c thay th c kim tra v tho lun k trong M1, M2, R1. 7.4.4. Tnh cht ca thuc th BPA (1) l nhng si kim loi nh, khng mu, im nng chy l 121oC n 122oC, bn vi nhit , nh sng, khng kh v khng phn hy thm ch trong acid v c mnh ngoi tr acid Nitric (3N). Hu nh khng tan trong nc, ho tan d trong cc dung mi hu c, cng ho tan trong nhng acid v c c nc, acid acetic, v dung dch ammoniac; kh nng tan trong nc: 0,04g/100ml (25oC) v trong ethanol 96% l 10,9g/100ml (22oC). N l n baz c tnh acid, pKa 8,2 ( = 0,1 NaClO4, 25oC); 9,13 (20% dioxane), v 10.20 (40% dioxane, 35oC). CPA (2) l nhng tinh th vng xanh sng, im nng chy l 158oC n 163oC. Tng t nh nhng tnh cht vt l v kh nng ha tan ca (1); kh nng tan trong nc: 0,022g/100ml (18oC), v trong ethanol nguyn cht l: 0,972g/100ml (18oC); pKa= 11,1. BTA (3) l nhng si kim loi nh, khng mu, im nng chy l 104oC, tng t nh tnh cht vt l v kh nng ha tan ca (1). Nhng dung dch nc ca (1) n (3) th khng mu v khng cho hp thu trong vng kh kin. Ph hp thu ca (1) trong vng cc tm v c biu din hnh 7.12. Nhm cht phn ng ny thng dng chit nhng ion kim loi a ho tr d b thy phn t dung dch acid kh m c. Trong mi quan h ny, s phn b ca BPA (1) gia chloroform v acid chlohydric c xem xt k v biu din hnh 7.13. T l phn b ca (1) i vi cc h thng khc c tm tt trong bng 7.14.
Hnh Bng 7.13: NBENZOYLNPHENYLHYDROXYLAMINE V NHNG HP CHT LIN QUAN STT 1 2 Thuc th N-Benzoyl-N-phenylhydroxylamine N-Cinnamoyl-NT ng ngha N-Phenylbenzohydroaxamic aicd, BPA, NBPHA, BPHA N-Phenylcinnamohydroxamic Cng thc phn t C11H13NO2 C15H13NO2 Phn t khi 213,24 239,31
phenylhydroxylamine N-Benzoyl-N-otolylhydroxylamine
acid, CPA N-o-tolyl-benzohydroxamic acid, BTA
C14H13NO2
227,26
7.4.5. Nhng phn ng t nhin v tnh cht ca phc BPA c tng hp u tin bi Bamberger, Ngi ch rng n cho kt ta mu vi nhm nguyn t chuyn tip. Sau , Shome pht hin ra rng cht ny c nhng thun li hn Cupferron trong phn tch trng lng (Ksp i vi GaL3 1,6. 1034; InL3 7,2.1031). Kh nng ha tan ca nhng kim loi c cng trong dung mi hu c cng m ra kh nng ngn cch ca nhng ion kim loi bng phng php chit dung mi. Phn ng vi ion kim loi c th vit l: Mm+ + nHL = MLnm-n + nH+
Hnh 7.13 Bng 7.14: T L PHN PHI CA BPA Pha D CHCl3/H2O 214 CHCl3/HClO4 0,1M 137 5 CHCl3/HClO4 6M 24 1 C6H6/HClO4 1,0M 23, a37b a: Tng nng ca BPA trong benzelne l 1x10-3M b: Tng nng ca BPA trong benzene l 6x10-3M iu kin tt nht phn ng kt ta gia nhng ion kim loi c chn vi (1) v (3) th c tm tt trong Bng 7.15. Cu trc ca dng lin kt cng ca ML2 c th c biu din nh sau:
N O M O C
C
O
O N
Do kh nng ha tan t ca nhng kim loi to phc nn rt t s liu sn c v nhng hng s n nh ca nhng cht phn ng ny. Nhng gi tr bo co c tm tt trong bng 7.16. Bng 7.16: HNG S BN CA BPA Ion kim loi Fe(III) Ga Hf In Th Os(VIII) log KML 5,28 9,2 13,7 9,2 log KML2 2 18,0 13,2 2 18,4 2 7,67 log KML3 3 25,3 12,3 3 26,3 log KML4 12,0 4 17,6 iu kin Nhit 25 3 (NaClO4) 25 2 (NaClO4) 25 0,1(NaClO4) 25 0,1(NaClO4) Nhit phng
Nhng kt ta ca nhng phc kim loi c lit k trong bng 7.14 th tan nhiu hoc t trong nhng dung mi c cc hoc phn cc. Nhng cuc nghin cu qui m tin hnh chit nhng ion kim loi vi (1) nhng t tin hnh vi (2) v (3). Nhng nguyn t m c th chit c vi BPA (1) c tm tt trong bng 7.15. Gi tr pH m ti ion kim loi c th chit nh lng cng c biu din trn hnh 7.14. Qu trnh chit thng c tin hnh trong dung dch acid mnh t c chn lc ca nhng ion kim loi v trnh s thy phn ca nhng ion kim loi a ha tr. S chit trong dung dch aicd hydrochloric th tt hn l trong aicd Sulfuric. Hnh 4 n 9 minh ha nhng c trng chit ca nhng nguyn t t nhm IV n nhm VIII trong h acid (1)chloroformhydrochloric. Nhng hng s chit v t l phn b ca nhng kim loi to phc vi (1) v nhng iu kin tt nht cho qu trnh chit ca mt vi nguyn t quan trng vi (1) c tm tt ln lt trong bng 7.16 v 7.17. Khng c gi tr nh lng sn c cho (2) v (3). Nhng ion kim loi to ta mu vi nhng cht phn ng ny cho nh hp thu n trong vng kh kin khi chng c chit vo trong mt dung mi hu c. Nhng dng lin kt cng ca Vanadium (V) vi (1), ty theo tnh acid ca pha nc, c m t hnh 10. Titannium(IV) tng t nh V.
Nhng c trng quang ph ca php phn tch kim loi quan trng vi (1), (2) v (3) c tm tt bng 7.18. S tinh ch v nhng cht phn ng tinh khit: (1) n (3) c th tinh ch d dng bng cch kt tinh li t dung mi thch hp. (1) T nc nng, benzene, hoc acid acetic. (2) T ethanol. (3) T dung dch ethnol. (1) n (3) t c dng kt tinh tt v tinh khit ca chng c th c kim tra mt cch d dng bng cch quan st im nng chy ca chng. 7.4.6. ng dng ha hc 7.4.6.1 Dng nh l thuc th kt ta v phn tch trng lng Nh m t trong bng 7.14, BPA (1) c dng rng ri trong phn tch trng lng cho mt s lng ln nguyn t. S ngn cch ca chng khi nhng ion kim loi khc c th t c di nhng iu kin c kim sot bi pH v nhng cht che, nh l EDTA hoc acid tartaric. iu kin thun li nht cho s kt ta vi nhng ion kim loi khc vi (1) c tm tt trong bng 7.14. Nhng cht kt ta vi (1) thng c th cn trc tip, nhng trong mt vi trng hp chng phi c t chy oxi ho trc khi cn. ng dng quan trng nht ca (1) l xc nh v ngn cch Nb v Ta ln nhau, vic xc nh trc tip Nb trong dung dch c s hin din ca Ta v mt s ion khc, s ngn cch Nb, Ta v Ti ln nhau, v vic xc nh Zn trong dung dch c s hin din ca Nb, Ta, Ti v V. Tng t nh ng dng xc nh Nb v Ta v ngn cch chng khi nhng ion khc c bo co cho (2) v (3). 7.4.6.2 S dng nh cht phn ng trong qu trnh chit Nh c m t hnh 7.14 v bng 7.19, nhng nghin cu rng ri tin hnh trn qu trnh chit c trng v mt vi s ngn cch mi ca nhng ion kim loi vi BPA (1). S chit ca nhng ion kim loi vi dung dch (1) trong dung mi khng trn ln c l mt chc nng ca thi gian lc, nng ca dung dch (1), dung mi t nhin, loi acid v c, v tnh acid. Nhng dung mi chit l chloroform, benzene, v iso amylalcohol, trong dung mi chloroform c a dng hn. Nng (1) cao hn th cn chit trong acid sulfuric hn l acid hydrochloric. Trong trng hp acid nitric, s chit tr nn t hiu qu hn vi s gia tng nng acid, mc d vy nitrate vn c a dng cho vic chit mt s nguyn t. S chit i vi nhng ion kim loi khc trong dung mi BPA (1) chloroform HCl c minh ha hnh 7.15 n 7.20. Nhng v d c trng v s ngn cch nhng nguyn t khc bng dung mi chit vi (1) c tm tt trong bng 7.19. Nhng nhn t ngn cch cho nhng cp nguyn t khc cng c lit k bng 7.20. 7.4.6.3 Dng nh cht phn ng trc quang Nh cht phn ng trc quang, BPA (1) c nghin cu rng ri hn nhng cht ging nh n. Nhng phc c mu m c chit chn lc t dung dch c tnh acid. 7.4.6.4 Xc nh Vanadium
Vanadium (V) kt hp vi nhng cht ny qua mt dy rng ca tnh acid, dng phc c th c chit vi chloroform. Ti pH 2,5, phc mu g c hnh thnh vi BPA (1) c s hin din ca ethanol, nhng phn ng ny khng c tnh chn lc. Trong acid hydrochloric 5 9N, chit vi chloroform to phc mu ta, v h mu tun theo nh lut Lambert Beer bc sng 530nm. Vi s gia tng nng acid hoc c nh nng ban ngy chiu vo, t trng quang hc ca h s gim. CPA (2) c ngh l cht phn ng chn lc cho V, nhng n khng c trng cho V. Sau , (1) c khng nh l chn lc hn, nhng vn phn ng vi Mo, Ti, v Zr cho phc mu vng n cam nh hng n vic xc nh V dng vt. Cui cng, BTA (3) dng nh c c tnh chn lc cn thit cho V. Trong acid hydrochloric 4 n 8 N, (3) l cht phn ng c trng cho V v c th dng phn tch v nhng cht v c. Phc mu tm c hnh thnh trong dung dch acid hydrochloric, c chit vi carbon tetrachloride hoc chloroform v o bc sng 510nm. Ch c ion Ti l nh hng nhng c th che n bng fluoride. * Cc bc xc nh V trong v cc hp cht v c Phn hy 100g mu dng bt bng cch x l vi acid sulfuric, nitric, v hydrochloric trong chn Platinum, un cn acid sulfuric trn bp. Nung chy phn cn trong chn platinum hoc tt nht l trong chn silica vi potassium pyrosulfate v chit phn nng chy ny vi 10ml nc c cha hai git acid sulfuric 20N. Chuyn dung dch vo mt ci phu chit v thm tng git potassium permanganate 0,02M n khi dung dch c mu hng, sau cho d ti thiu 5 git oxy ha V. Th tch dung dch lc ny nn l 20ml. Thm 2ml dung dch acid sulfamic 0,05M, 2ml dung dch sodium fluoride bo ha, v 20ml dung dch acid hydrochloride m c. Dng pipet thm 10ml BTA 0.02% trong carbon tetrachloride hoc chloroform (khng c ethanol), ng li v lc phu trong khong 30 giy. Sau , c s ngn cch pha, lc lp di qua mt tm xp vi cotton vo mt ci l nh. o hp thu ca dung dch i vi mt mu trng bc sng 510nm.
Hnh 7.21 7.4.6.5 Xc nh Titanium Titanium (IV), nh V(V), hnh thnh dng phc khc vi (1), ty thuc vo tnh acid v pha nc. Trn pH 1, mu ca phc (TiOL2) th t mnh lit hn so vi mu thu c ti nhng acid cao hn v mu c tnh chn lc hn i vi nhng thay i gi tr pH. Khi nng acid hydrochloric tng n 2N, mu ca dng phc TiL4 c hnh thnh (max = 355nm, trong CHCl3). Trong dung dch acid hydrochloric mnh s cho dng phc ML2Cl2 (max = 380nm, trong CHCl3). Mt lng d chloride gi cho dng ion U (IV) khng phn ng vi (1). Nu ion thiocyanate c thm trc khi chit Ti t dung dch acid vo trong
chloroform, mu sc tng mt cch ng k, hu nh chc chn l do dng phc ba ML2SCN. Ging nh nh hng c ghi ch vi (2) v (3). * Th tc xc nh Ti trong hp kim mt t l dung dch mu (khng cha nhiu hn 100g Ti) trong phu chit, thm mt lng va dung dch acid hydrochloric m c acid ha dung dch cui > 9,6N. Thm 10ml dung chloroform 0.1% BPA vo dung dch ny v lc 1 n 2 pht, lc lp di qua mt giy lc kh v o hp thu ti bc sng 380nm i vi mu trng. S hin din ca Fe, Sn, W, V, Zr, v Mo (IV) trn mt vi miligram nu c gim bng Sn (II) th khng c hi. Phc c hp thu ti a ti 371nm, nhng n thng c th o 380nm bi v hp thu ca cht phn ng ti bc sng ny thp hn. * Nhng c tnh khc s dng (1) c dng l mt kim lai ch th trong phng php chun to phc ca In (III), Fe (III), Ti (III) v V (V). Phng php to mu i vi mt s lng ln ion kim loi trn giy hp th vi (1) c nghin cu k tch hoc trn ln nhng ion kim loi. Bng 7.17: IU KIN TI U CHIT ION KIM LOI VI BPA Ion kim loi Bi(III) Ga In Pb Sb(III) Sn(IV) Sn(IV) Tl(I) acid HCl 0,1N pH = 3,1 pH = 5,3 pH = 9,0 HCl 0,1N HCl 0,8N HCl 4N pH = 10,5 Nng ca BPA trong CHCl3 (% khi lng/th tch) 0,6 1,0 1,0 1 0,5 1 1 0,7 thi gian cn nng ion kim bng (pht) loi ti a (mg/ml) 10 12 10 10 10 10 10 8 8 10 10 12 10 10 10 8 % chit 99,4 99,4 99,2 97,4 93,1 94,4 96,1 99,7
Bng 7.19: TCH BNG DUNG MI CHIT VI BPA (1) Kim loi Al Fe, Ti Pa Ta Th Zr, Ti iu kin chit T Urani Al Th, U Pa La Sc Acid (NH4)2CO3 (NaBO3)6 + acid thioglycollic + KCN + H2O2 H2SO4 0,5N HCl 10N + F- 0,025M HCl 1N + F- 0,4M pH = 4,5 (HCl) HCl 2 -5N
Dung mi Benzene CHCl3 CHCl3 CHCl3 IsoAmOH Iso AmOH
Nng ca BPA (1) 0,2% 1% 1% 0,5% 3% 3%
Bng 7.20: HNG S TCH CA CC CP KIM LOI VI (1) Tch Ch yu Th yu Ga In In Pb Nb Pb Sn (IV) Sn Pa Tl Sb(V) Pb iu kin chit Hng s tch Acid Nng CHCl3 (%) pH =3,1 1 104 pH = 5,3 1 104 103 HCl 1N + HF 0,05N 0,2 pH = 9 HCl 0,8N HCl 0,8N hoc HClO4 4N 0,7 1 1 6x102 102 104
VI.5. ACID CHLORANILIC V NHNG DN XUT KIM LOI CA N

CTPT: C4H2O4Cl2 KLPT = 208,99
O Cl OH
HO
Cl O
7.5.1. Tn gi khc 3,6Dichloro2,5dihydroxypbenzoquinone. 7.5.2. Ngun gc v phng php tng hp Dng acid t do v nhng dn xut kim loi ca n nh Ba, Hg (II), La, Sr, Th v Zr Chloranilat c th mua c trn th trng. Acid Chloranilic c iu ch bng cch thy phn cht kim Chloranil. Nhng Chloranilat kim loi c iu ch bng phn ng ca acid Chloranilic vi mui v c tng ng trong nuc nng. 7.5.3. ng dng trong phn tch Acid Chloranilic t do c s dng nh cht phn ng to ta cho nhng ion kim loi nng, a ho tr v cng l cht phn ng ln mu dng trong php o quang cho nhng ion kim loi da trn c s trn phn ng to ta. Nhng Chloranilat kim loi c s dng nh l cht phn ng dng trong o quang cho nhng anion da trn s phn ng ca Chloranilat kim loi to thnh mui kh tan vi anion xc nh v ng thi l s phng thch ion acid chloranilat (HL-) c cng mu cao. 7.5.4. Nhng tnh cht ca acid Chloranilic Tinh th c mu cam (dng bt) nhit nng chy 283oC n 284oC. N c tnh acid baz, pH ca dung dch (nc) bo ho l khong 2, pKa1 = 0,810,01, pKa2 = 2,720,05. N c xu hng thng hoa. N th ho tan rt t trong nc (3,0 g/l nhit phng) cho dung dch mu tm, mu tng t mu ca dung dch KMnO4, d dng ho tan trong dung dch kim hoc trong nc nng, khng ho tan trong hu ht cc dung mi hu c ngoi tr alcohol. N phn
ng vi nhng ion kim loi a ho tr v ion kim loi nng cho kt ta kh tan t nu n tm. Trong dung dch nc c 3 dng (H2L, HL-, L2-), ion acid Chloranilat (HL-) phn b vi mt cao nht trong phm vi pH = 1 2. Hnh 7.22 minh ho cho s hp thu quang ph ca HL- trong min nhn thy c. Peak biu th cng cao nht pH = 1 2, n gim i phn na so vi trc pH = 5 v khng thay i thm na phm vi pH = 5 12. Ging nh peak c theo di trong min UV (max = 332nm). Trong dung dch th khng bn vi nh sng v phai mu dn. Dung dch cn c bo qun ni ti, mt v tt nht pH thp. Khi dung dch nc ca acid chloranilic c trn vi dung dch ion kim loi, c s thay i mu sc do s cu thnh phc vng cng v trong vi trng hp to ta kh tan Chloranilat kim loi, trong dung dch lc mu tm ca dung dch nht i. Phn ng to ta thng dng cho nh lng v mu ca ta gm nhiu loi khc nhau t nu n tm. Nhng Chloranilat kim loi nng v a ho tr th s ha tan b hn nhiu so vi acid Chloranilic. Nhng c trng ny lm nn tng cho s dng trong phn tch kim loi. Nhng phn ng vi nhng ion kim loi khc nhau c tm tt trong bng 7.21.
Hnh 7.22 Mt vi Chloranilat kim loi c kh nng ha tan vo trong nc v i theo sau l hng s cn bng c xc nh trong dung dch nc.
KML M
m+
+ L
2-
MLm-2 M2L2m-2 (25oC, =0,15)3
2Mm+ + L2-
Log KML ca Fe (III) l 5,81; Ni (II) l 4,02 M

4+
+ H2L
ML2+ + 2H+
Log K ca Hf (IV) l 3,73 (25oC, = 3 (HClO4))7 Zr (IV) l 5,76 (25oC, = 2 (HClO4))8 K 2+ ML2 + 2H+ ML + H2L Log K ca Zr (IV) l 3,78 (25oC, = (HClO4))8
7.5.5. Nhng tnh cht ca thuc th Trn th trng c cc loi sn phm Chloranilat ca Ba, Hg (II), La, Sr v Th n nhng dng tinh th khan mu nu t hoc dng bt mu en. Mui Bari c cung cp (mua) dng kt tinh hydrate, n lp lnh nh sng ging nh kim loi. Mt mu c nh thng khng ng nht, tu thuc vo iu kin iu ch. Nhng dn xut kim loi ny th hu ht kh tan trong nc cng nh trong hu ht cc dung mi hu c, ngoi tr mt s dung mi c s phn cc hn, v d: ethylenediamine, methyl cellosolve, acid acetic, pyridin, tetrahydrofuran Bng 7.21: PHN NG CA ACID CHLORANILIC VI ION KIM LOI TRONG DUNG DCH NC Ion kim loi Cm quan Ion kim loi Cm quan
Ag Al Be Ca, Ba, Sr Cd, Zn Co(III) Cr(III) Cr(VI) Cu(II) Fe(II) Fe(III) Hg(I)(II) Hr, Hf
ppt khng c s thay i, phc Ca gy cn tr thm ppt ppt ppt to phc vng phai mu mu m hn mu m hn ppt chi
Mg Mn(II)
phai mu ppt
Mo(IV), W(VI) phai mu Na, K Ni(II) Pb Sn(IV) Th Ti Tl(I) U(IV) Zn t him phai mu t tm ppt ppt tm sng phai mu phai mu t nu ppt ppt
tan ca Bari Chloranilat trong nc l 2,2.10-4M v trong nc ethanol (1:1) l 5,2.10-6M. Mc d tan ca nhng dn xut kim loi th khng bit c chnh xc, nhng tan c th gn ng trong nhng nguyn tc chung ca Bari chloranilat. tan ca Canxi chloranilat trong nuc th tu thuc vo pH, tan nh nht pH = 4,4. tan 8,1.10-9 pH = 3 v tan 1,8.10-9 pH = 7, c th so snh vi tan Canxi oxalat. Khi bc chloranilat kh tan c lc vi dung dch nc cha ion Cl-, kt ta AgCl v gii phng ion Chloranilat acid c mu ta hi , c biu din nh sau: Ag2L + 2Cl- + H+ = 2AgCl + HL(rn) (rn) Ion Cl- t l tng ng vi lng ion chloranilat gii phng ra n c xc nh bng php o quang max = 530nm ( = 200) hoc 332nm. Nguyn tc ny c th ng dng xc nh nhng anion khc. Trn phn ng: ML + X- = MX + L(rn)
-
(rn)
y X l anion cn xc nh v ML Chloranilat kim loi kh tan, ML phi ho tan t hn nhiu so vi MX. Yu cu vic la chn thch hp chloranilat kim loi, h thng dung
mi v pH. Mt vi chloranilat kim loi quan trng dng xc nh nhng anion tng ng c danh sch trong bng 7.22. Bng 7.22: CHLORANILAT KIM LOI V NHNG PHN NG VI ANION Chloranilat kim loi BaL Du hiu tinh th nu tm bt nu en bt xanh xm bt xanh thm bt nu en bt nu bt xm en Anion SO4
2-
iu kin pH 4,0 4,6; trong 50% ethanol, pH 8 m NH4Cl Tartarat pH 4, trong isoPrOH pH 2, trong 50% methylcellosolve pH 7, trong 25% Methylcellosolve
PTP SO42-+ BaL + H+ HL+ BaSO4 H3BO3+BaL+tartarat HL- + phc Baborat 2F- + SrL + H+ HL- + SrF2 2Cl-+Ag2L+H+ HL- + 2AgCl 2Cl- + HgL+H+ HL- + HgCl2 6F- +ThL2 + 2H+ 2HL+ThF62- hoc 2F- + ThL2 + H+ HL+ ThLF2 S2- + CuL + H+ HL- + CuS 6F- + La2L3 + 3H+ 3HL- + 2LaF3 2PO43- + La2L3 + 3H+ 3HL- + 2LaPO4
Gii hn xc nh (ppm) 0,3 100 0,3 10 5 0,05 200
BO33SrL Ag2L HgL F

-
ClCl-
ThL2
F-
0,01 100 0 10, CN-, oxalate, tartarat, citrat gy tr ngi 2 200 3 300
CuL
2-
pH 6,5 7, trong 50% Ethanol hoc trong 50% methylcellosolve pH 7
La2L3
PO43-
7.5.6. Tinh ch thuc th Acid chloranilic c tinh khit cao bng s kt tinh t nc nng. sn phm trn th trng thng c tinh khit cao. Nhng kim loi (tp) c th xc nh c trn tro sunfat. N c th c th nghim bi mt thit b o acid trong dung dch nc vi phn tch trng lng ca chloranilat kim loi (v d kt ta mui canxi pH 4,4, k tip em cn sau khi sy kh 105oC). Chloranilat kim loi dng xc nh anion s i hi nghim ngt trong ho hc lng php v nhng cht lm nhim nh cation trong mui ho tan th khng vt qu gii hn v cng khng d acid chloranilic. C th kim tra c khi ra mu, i theo sau l phn tch nhng cation c trong phn nc lc. Sau cng c th xc nh theo quy trnh. 7.5.7. ng dng trong phn tch
7.5.7.1 S dng nh l thuc th to ta Nhng cation to ta c vi acid chloranilic c th xc nh bng phng php trng lng hoc mt vi phng php khc. Mt vi v d c tm tt trong bng 7.21. 7.5.7.2 S dng nh l thuc th trong php o quang cho nhng cation Ty thuc vo phng php phn tch nh lng, s gim hp thu dung dch ca acid Chloranilic d c nng bit trc bng to ta khng tan chloranilat kim loi. S hp thu c o phn cht lng ni bn trn sau khi li tm hoc phn nc lc sau khi lc. C th la chn, Chloranilat kim loi khng ho tan tch ra c ho tan tr li trong acid mnh hoc dung dch kim EDTA v ion chloranilat (HL-) c phc hi v c th xc nh bng my quang ph. Quy trnh ny i hi s chnh xc cao. Phng php khc thng dng h s hp th ca chelate ho tan c nhum mu cao ca acid chloranilic vi ion kim loi. Chng hn Zr(IV) hoc Mo(VI) Bng 7.23 tm tt mt vi quy trnh o quang ca nhng cation. Dung dch nc ca chloranilic acid hoc chloranilat natri c nng thch hp thng c s dng, chloranilic acid th n nh hn. Dung dch nn gi ni ti mt. Dung dch chun cho o quang c pha ch khi cn. 7.5.7.3. S dng nh l thuc th trong php o quang cho nhng anion Nhng anion c th c xc nh vi s hp thu quang ph, s dng chloranilat kim loi kh ho tan, c s trn nguyn tc miu t phn trn. Trong nhiu trng hp, nng ion acid chloranilat t do th o bc sng 530 nm. Nhiu th d v o quang xc nh nhng anion s dng chloranilat kim loi c tm tt trong bng 7.23. Bng 7.23: XC NH QUANG PH CA NHNG KIM LOI VI ACID CHLORANILIC Ion kim loi Ba, Sr, Zn Ca Ca Mo(IV) Nb W(VI) Zr iu kin pH 5 7, sau khi lc acid chloranilic trong acid yu acid chloranilic (acetic acid, HCl) sau khi lc sau khi li tm ra bng PrOH acid chloranilic sau ho tan kim EDTA 5% chit vi MIBK t HCl 6M, Mo chloranilat + HF 0,4M, sau chit nc H2SO4 0,18 M, c th tch ra, Nb chloranilat c chit vi MIBK t H2SO4 6M + HF 2M. pH 3 4, M2L Ph < 2, ML HClO4 1M + LiClO4 1M; Zr chloranilat i theo l nhng kim loi s tch ra, c chit t HCl 4M vi 7,5% trinoctylamine trong benzene Bc sng xc nh 530nm 550nm 520nm 350nm 340nm 335nm 340nm Phm vi xc nh (ppm) 40 400 0,5 9,6 0,2 0,4 0,02 2
VI.6. NHNG HP CHT POLY (MACROCYCILIC)

7.6.1. Tn gi khc
Nhng hp cht poly (macrocyclic) nh l nhng crown polyether (cng thc cu to ca n c hnh dng nh l vng vng nim) v cryptand (polyazopolyeste a vng ln, cc nguyn t nit ba phi tr ch ra cc nh ca cu trc ba chiu ), m chng c th a dng trong phn tch ho hc v c tm lt v cc dng v tnh cht vt l ca chng trong bng 7.23. Tn gi ca nhng hp cht ny c gi theo qui lut IUPAC th rt l cng knh, thng thng gi l crown v cryptand, thng c s dng cho nhng polyether mt vng v hai vng theo mt cch trt t c nh sn. Trc y, th cho ta bit c tng s nguyn t trong mch vng polyether, crown v s nguyn t oxi trong mch vng chnh. Cn sau ny th cho bit Cryptand v s nguyn t oxi trn mi lin kt cu. 7.6.2. Ngun gc v phng php tng hp Tt c nhng hp cht thuc th c lit k trong bng 7.23 thng c s dng trn thng nghip. Tng hp ca nhng loi thuc th ny c dng trong phng th nghim v mi thuc th c dn chng trong bng c kt qu ring bit trong qu trnh tng hp. 7.6.3. ng dng Nhng cht to phc trong phn chit dung mi, v o trc quang xc nh oxt kim th v nhng ion kim loi kim 7.6.4. Tnh cht ca thuc th Nhng thuc th crown t (1) (6) thng tan t ( mc khng ng k) trong nc v trong dung mi hu c. Ngoi tr CH3Cl, CCl4, Pyridine (C5H5N) v acid formic. V d nh l tan ca (3) trong nhng dung mi hu c khc nhau c tm lc trong bng 7.24. tan ca nhng hp cht crown trong nc gim v tng khi nhit tng, nh thuc th (5) bng 7.25, nguyn nhn l do s ph v ca cc lin kt hidro gia oxi ete v nc kt hp (nc hydrat ho). T l phn b (t l cc nng ca cht tan cho trong cc th tch nh nhau ca hai dung mi khng trn ln c sau hn hp c lc v s cn bng c thit lp) ca (5) gia benzene v nc ln hn 170 25oC, cryptand (7) (9) c coi nh l c s diacid v hng s phn ly proton ca acid lin hp c thng k trong bng 7.29 7.6.5. Phn ng to phc v tnh cht ca phc cht Nhng hp cht poly (macrocyclic) c bit n nh l phi t m h s t lng ca chng bn vng khi to phc cation. c bit quan trng l phi ph hp vi nhng ion kim loi kim ca chng, khng to phc vi nhiu ch s phi t cho nhng ion kim loi chuyn tip. Nhng thuc th (1) (9) l nhng dng phc c tinh th bn v s to phc vi cc cation : Li, Na, K, Rb, Cs, NH4, RNH3, Ag(I), Au(I), Ca, Sr, Ra, Zn, Cd, Hg(I)(II), La(III) , Ti(I), Ce(III), v Pb(II). Trong s cc cation th (5) cng to phc vi Co(II), U(VI) v mt s ion kim loi chuyn tip. Nhng phi t bo ho (5) v (6) l nhng cht to phc tt hn nhng hp cht thm tng ng (2) v (4). Nhng thuc th ny c nhng l ng knh khc nhau trung tm vng macrocycle. Nhng cation khng to phc cng c bn knh ring bit. Hu ht phc bn thng kt hp vi cation m chng c th gn kht vo nhng l h ca phi t. Tuy nhin ph thuc vo
s lin quan cc l h v cation, t s gia phc ca phi t/cation: 1:1; 3:2 v 2:1 cng c bit trc. Cu trc ca nhng phc ny c hin th di dng hnh 7.23
Hnh 7.23
Bng 7.25: TAN CA DICYCHLORHEXYL 18 CROWN 6 (5) TRONG NC Dung mi Nhit tan (mg/ml) 13,4 26 Nc 8,2 53 Nc 3,7 82 Nc 331 26 KOH 1N > 346 26 KCl 1N Bng 7.26: TAN CA KIM LOI KIM KHI KT HP VI HALOGENUA TRONG DUNG MI HU C KHI CHO 50mM DICYCHLORHEXYL 18 CROWN 6 (5) Dung mi Benzene Carbon tetrachloride Chloroform Methylene chloride Tetrahydrofuran Methanol (mM) 0 250 0 250 0 250 0 250 0 250 tan (mM)* NaCl NaBr KCl KBr 0,01 1,8 0,03 2,3 8,7 30 24 0,48 0,6 4,1 0,03 2,7 8,8 34 28 1,1 41 21 37 1,8 44 34 41 5,7 41 17 35 1,8 42 33 42 5,8 0,1 3,6 0,02 1,2 3 0,4 5 0,04 KI 9,2 46 0,8 15 43 44 43 44 45 50
Nng ca mui sau khi khuy dung dch polyether vi mt lng va c 50mM dung dch. Bng 7.27: TAN CA DIBENZO 18 CROWN - 6 (3) TRONG METHANOL KHI CHO 50mM MUI V C 30oC. Mui v c (25mM) tan ca (3) (mM)
Khng mui NaSCN KF RbSCN AgNO3 SrCl2 BaCl2
1,1 23,6 24,7 25,6 22,2 17,9 26,6
bng 7.24 th tan ca polyether macrocyclic trong dung mi hu c khng cao, nhng trong dung dch s hin din ca mui v c, nhng phi t v mui phc s lm tng tan ca chng ng k. Mt vi v d c cho trong bng 7.26 v 7.27 khi cho thm dung mi phi tr nh l methanol th tan ca chng tng rt nhiu ch ra trong b ng 7.26. Mc d tan nhng phc cht ca cation c th hin r rng, anion cng ng vai tr quan trng. Nhng mui ca anion cng nh l F- v SO42- thng th khng tan trong nhng thuc th ny, trong khi nhng mui anion mm nh l I-, SCN- v picrate th tan d dng hn. Thuc th chng hn (3) v (4) c mt di hp th ti 275nm (trong methanol) v nhng vng thm. Kt qu mu vi cation dn n s thay i ng ch trong dy ny c miu t trong hnh 7.24.
Hnh 7.24 Bng 7.28: HNG S BN CA MT S POLYETHER VNG (VNG NIM) Phi t (2) (3) (4) (isomer A) Dung mi W M W/ T M W M Li 0,6 Na <0,3 4,32 4,36 1,5 1,8 4,08 LogKML (250, = 10-4 10-2) K Rb Cs NH4 Ag Ba 2,06 0,8 1,1 1,4 1,6 6,10 4,62 1,35 5,00 3,55 2,18 1,52 1,25 6,01 4,61 Sr Cs 1,30 2,92 0,95
2,3 3,57 3,24 -
(4) (isomer B) (4) Pha trn isomer (5) (6) Trong :
W M M M M W: nc. M: methanol.
1,2 1,6 3,68 4,05 -
1,78 0,87 5,38 5,35 3,49 -
3,49 3,85 3,78 1,9
0,8 -
1,8 3,27 2,64 -
0,9 -
W/T: t l pha trn gia nc v THF 1:1. Hng s bn ng vi nhng phc poly (macrocyclic) cation c tm gn trong bng 7.28 v 7.29 . Hng s bn ca mi cation ln nht khi gia tng kch c vng polyether. Kch thc vng ti u ny cung cp cho s ph hp gia cation v phi t. c miu t trong hnh 7.23. Phc cht cation c to thnh gia crown polyether v nhng ion kim loi, chng c th c chit bng nhng ion thch hp m nhng anion khng trn ln c vo dung mi. Phm vi ca s chit b nh hng bi nhiu yu t nh l hng s bn ca phc, cc loi polyether, anion v dung mi. Qu trnh chit thng c s dng trong php phn tch. Bng 7.29: HNG S BN CA MT S CRYTAND POLYETHER Phi Dung PK1 t mi W 7,28 (7) M/W 6,64 M W 7,50 (8) M/W 6,60 M W 7,85 (9) M/W 6,56 M Trong : PK2b 9,60 9,85 10,53 10,42 10,64 11,00 Li < 20 1,8 2,6 2,50 4,18 > 5,0 5,5 7,58 > 6,0 Na 3,9 7,21 >8,0 5,40 8,84 >8,0 3,2 6,08 6,1 K 5,4 9,75 > 7,0 3,95 7,45 > 7,0 < 2,0 2,26 2,3 LogKML Rb Cs 4,35 < 2,0 8,40 3,54 > 6,0 4,4 2,55 < 2,0 5,80 3,90 > 6,0 ~ 5,0 < 2,0 < 2,0 < 2,0 < 2,0 1,9 < 2,0 Mg < 2,0 < 2,0 < 2,0 < 2,0 2,5 4,0 Ca Sr 4,4 8,0 7,60 11,5 6,95 7,35 9,61 10,65 2,50 <,2,0 4,3 <,2,0 -
W: nc. M: methanol. M/W: t l pha trn gia methanol v nc (95/5).
* Hng s phn ly proton ca acid lin hp. Bng 7.30: HNG S CHIT CA CROWN POLYETHER Phi t (2) (3) Anion Picrate Picrate LogKML (250, = 10-4 10-2) Phn b LogDLb Li Na K Rb Cs Ca B/W -1,24 - 3,31 6,00 5,43 4,28 B/W 2,90 2,9 4,65 3,75 3,07 http://www.ebook.edu.vn
(5) (5) (isomer A) (5) (isomer B) (5)
Picrate Picrate Picrate Picrate Picrate Picrate Picrate Picrate 2,5Dinitrophenol 2,6Dinitrophenol Dipicrylamine
DCM/W DCM/W Hex/W DCM/W Hex/W DCM/W Hex/W DCM/W DCM/W CM/W DCM/W
3,60 0,79 3,56 0,85 -
4,18 -
0,85 6,32 3,58 6,60 6,04 -
10,23
4,20 6,36 3,98 4,26
7,81 7,81
Trong :Hex/W: n hexan / nc. DCM/W: dichlorometan / nc. B/W: benzene / nc. 7.6.6. Tinh ch thuc th Nhng thuc th Crown polyether v cryptand polyether c sn trn thng mi thng c tinh khit cao v hu ht thng c s dng trong ho phn tch. Nhng thuc th cryptand polyether th kh t v c th ti to li bi nhng qui trnh sau: Ho hi dung dch kim loi cryptate trong dung mi khc, lm kh trong chn khng 10 Pa ti nhit phng. Ho tan cht rn (0,1 0,2g) trong 20ml dung dch HCl 6N, lm nng v ho hi li 10-2 Pa. Ho tan cn, bao gm mui kim loi v diprotonated cryptand trong 20ml dung dch HCl 0,1N (nu dung dch gc c cha nhiu anion khc nhau th chuyn nhng mui y thnh dng chlorur). Sau tch ra nhng ion kim loi bng 150ml dung dch HCl 0,1N. Cui cng tch ra cryptand bng 120ml HCl 6N. Lm kh dung dch trong chn khng thu c phi t diprotonated.
-2
7.6.7. ng dng trong phn tch Thay th nhng tnh cht ca hp hp poly (macrocyclic), hn na th k tri qua cho n by gi th chng v cht dn xut ca chng c chp nhn nh l thuc th trong php phn tch. Nguyn nhn chnh ca thuc th ny l khng c du hiu nhn bit trn phc cht kim loi. Tuy nhin, hin gi th chng c dng lm thuc th dung mi chit cho vic tch cc ion kim loi nh l ion trung tnh mang nhng electron chn lc. Trong s nhng thuc th y c s dng mt cch thnh cng trong sn phm thng mi. Tuy nhin nhng hnh dng ca chng nm ngoi cun sch ti liu ny. Trong nhng ng dng phn tch khc bao gm polymer th c cha nhng chc nng polyether trong vic tch cc ion kim v xc nh Hg(II) trong HPLC. Song, nhng ng dng c quan tm l xc nh chit trc quang ca ion kim loi kim bng cch dng crown polyether. Phng php u tin da trn c s hnh thnh phc chn lc ca crown polyether vi ion kim loi kim, tip theo chit dung mi ca nhng cp ion vi ion mu tt nh l Bromo Cresol Green, picrate, v diazoresorxin (C12H7O4N).
Phng php th hai l gii thiu v thuc th chromogenic polyether, m thuc th c chn ln mu khi to phc vi cc ion kim loi kim. 4picrylamino5nitrobenzo18crown6, thuc th ca Takagi C22H25N5O14 (HL) M = 583,47 vC.
Tinh th hnh kim mu cam, nng chy 162 165oC, khng tan trong nc, nhng tan trong cc dung mi hu c v c pKa = 8,79 (10% dioxane, = 0.1 LiCl). Dung dch mu cam ca Chlorofrom khi ho trn trong dung dch ion K+ (vi bc sng cc i hp thu max = 345 420 nm, = 1,49.104 v 144.104, dung dch m mui Li vi EDTA pH = 12,35 ). Chit ion K+ bng CHCl3, dung dch chuyn mu t cam sang vi max = 457 nm, = 2,12.104, 4 40ppm K+. Gi tr logK trong CHCl3/H2O l K+ = -9,13; Rb+ = -9,24; Cs+ = -9,54 (250, pH = 12,35; 0,1M EDTA 4Li ). Bng 7.31: QUANG PH C TRNG CA THUC TH PICRYLAMONOCROWN HL L-b (nm) max (nm) (x104) max (nm) (x104) 55 2.00 445 1.30 390 Thuc th gc (a) 160 0.44 585 0.64 425 4TF 80 2.08 460 1.33 380 6TF Thuc th Trong : (a): 4-Picrylaminobenyl-15-crown-5 (b): ph thuc vo phc cation kim loi kim trong cc l h Crown. C s thay i ca thuc th Takagi. S thay th ca mt trong nhng nhm nito ca mt na picrylamino bng nhm trifluoromethyl s mang kt qu cho s thay th gia thuc th t do v phc kim loi hn l hp cht gc. Quang ph c trng ca nhng thuc th c tm lt trong bng 7.31 khi s dng thuc th 6TF v n c th thc hin trong vic xc nh ion K+ 5 700ppm bng phng php trc quang (pH > 11 vi triethylamine, chit bng CHCl3). Na+, Cs+ v nhng kim loi kim th khng b nhim, nhng Rb+ b nhim nghim trng.
Nitrophenylazo15crown5,2Hydroy5(4nitrophenylazo)phenyloxymethyl15 crown5.C23H29N3O9 ; M = 491,49 vC. Tinh th thm, nhit nng chy 45 55oC, tan trong cc dung mi hu c pKa = 7.97 (10% dioxane, = 0,1 (CH3)4NBr, 25oC). Khi dung dch mu vng 1,2dichloroethane (max = 390nm, = 1,8.104) pha trong dung dch c cha ion kim loi kim Na+ ti pH = 10 [(CH3)4NOH H3BO3], ion kim loi c chit c dng phc ML s cho mu (max = 560nm, = 3,7.104). Gi tr logKex trong H2O /1,2dichloroethane ti 25oC: K+ = -9,84, Rb+ = -9,91; Cs+ = -10,83; Na+ = -10,08. Thuc th c th c s dng cho vic xc nh Na+ trong mu sinh hc, m mu c s tn ti ca Na+ nhiu hn K+.
VI.7. CUPFERRON
CTPT: C6H9N3O2 KLPT: 155,16 7.7.1. Tn ch th v cng thc ha hc Tn ch th: Tn ha hc: nNitrosophenylhydroxylamine, mui amoni. Tn thng thng: Cupferron. Cng thc ha hc: Cng thc phn t: C6H9N3O2 Cng thc cu to:
ONH4 N N O
7.7.2. c im ca ch th Cupferron: To phc vi cc ion kim loi. To ta cc ion kim loi. Chit cc ion kim loi. 7.7.3. Cc tnh cht ca ch th Cupferron: L bt trong sut mu vng nht, im nng chy t 163 n 164oC, thng hoa trn 30oC. Thuc th ny khng bn di nh sng v khng kh. gim ti thiu nhc im ny, thuc th thng c cha trong chai mu nu vi mt t ht amoni carbonat nh l mt cht bo qun. Acid t do (HL) l mt cht rn khng bn mu trng (im nng chy 51oC) v t ng phn hy thnh nitrobenzenediazonium, 4,4dinitrodiphenylamine v cc cht khc. N tan rt t trong nc, nhng d tan trong cc dung mi hu c khc. N l acid n chc, c pka = 4,16 ( = 0,1 NaClO4, 25oC), KD(CHCl3/H2O) pH > 3 vi HCl hoc HClO4 = 142 (nhit phng) KD(ethylacetat/nc) = 285,6 v KD(CCl4/H2O) = 2300 (15oC). 7.7.4. Tnh cht chun ca ch th Cupferron: 7.7.4.1. Phn ng to phc v tnh cht ca phc:
Cupferron l phi t hai rng vi cc v tr phi tr ca oxi vi nhm nitroso v oxi khng mang in tch. Hu ht cc ion kim loi trong bng tun hon c kt ta vi Cupferron trong dung dch nc. Cng nh mt thuc th phn tch, Cupferron khng qu chn lc, nhng tnh chn lc hi cao hn trong dung dch c tnh acid mnh so vi trong dung dch c tnh acid yu. Di iu kin trn, ch Fe(III), Hf, Ga, Nb, Sn, Ta, Ti, V v Zr kt ta. Kh tnh acid gim, cc ion khc u b kt ta. Cc iu kin cho vic to ta vi kim loi ca Cupferrate v tnh ha tan ca chng c tm tt bng 7.32. Nh l cht kt ta ca kim loi, Cupferrate khng qu bn khi sy kh, chng thng bc chy thnh oxit trong php phn tch trng lng. Kim loi Cupferrate khng mang in tch v bo ho phi tr, c th c chit trong dung mi tr, c minh ha di y:
O N N=O Mn+/n
V vy, Cupferron c s dng rng ri nh l mt dung mi chit trong phng php tch cc ion kim loi. Chloroform l dung mi thch hp trong hu ht cc phng php chit. Phng php chit cc ion kim loi vi Cupferron c nghin cu tng tn v pH ca phng php chit nh lng, gi tr ca pH1/2 v nh hng ca hng s chit ln h chloroformnc c tm tt bng 7.33. Khi hu ht cc kim loi Cupferrate khng mu, Cupferron khng c xem nh l thuc th o quang thit thc xc nh hm lng kim loi. Bng 7.32: IU KIN TO KT TA CA CUPFERRATE KIM LOI Ion kim loi iu kin Ag Al Bi Cd Co(II) Cr(III) Cu(II) Fe(II) Fe(III) Hg(I) Hg(II) Mn(II) Ni Pb Sb(III) Sn(IV) Ti Zn Kh nng ha tan (18oC) H2O (mg/L) HCl 1N (mol/L) acid acetic 0,01N (mol/L) 150,0 6.10-4 acid yu 0,9 6.10-4 HNO3 8,4 + 5,46.10-3 40,0 + 1,07.10-2 77,0 + + 5.10-4 acid acetic 1,3.10-3 0,7 2.10-4 0,02 2.10-4 acid mnh 0,02 0,3 + + 7,55.10-3 + + 1,06.10-2 52,0 + 25,0 + 5,5 10-4 H2SO4 2,4 10-4 H2SO4 6,3.10-3 32,0 +
7.7.4.2. Dng Cupferron nh l dung mi chit : Cupferron cc k c ch trong vic tch nhm ca Fe(III), Sn(IV), Ti(IV), U(IV), V(V), Zr(IV) v mt s kim loi khc t cc nguyn t cn li. Trong mt vi trng hp, cc cu
t chnh c tch ra t phng php chit vi Cupferron, cho php tch c hm lng vt trong php phn tch. Trong mt s trng hp khc, mt lng nh cc cht cn phn tch c tch t cc cht nn bng phng php chit kim loi Cupferrate trc khi xc nh. Cc kim loi sau khi chit c thu li bng cch hp th t (HNO3 + H2O2) cn sau khi lm bay hi dung mi hoc bng cch chit ln na vi dung dch acid mnh hn. Tnh chn lc ca phng php chit c th c ci thin bng cch chn acid thch hp trong pha nc v cht che thch hp, nh l EDTA hoc tartarate. y l phng thc thc hnh ph bin thm dung dch Cupferron lng hoc Cupferron rn vo dung dch mu trc khi chit vi dung mi hu c. Bng 7.34 tm tt mt s v d in hnh v phng php tch bng cch chit Cupferron. Cc kh nng khc c trnh by bng 7.33. Bng 7.33: DUNG MI CHIT CA CUPFERRATE KIM LOI Ion kim loia Ag Al Be Bi* Cd Ce(IV) Co(II) Cr(III) Cu(II)* Fe(III)* Ga* Hf* Hg(II) In La(III) Mn(II) Mo(VI)* Nb(V) Ni Pa(V) Pb Pb(II)* Pm(III) Pu(IV) Sb(III)* Sc Sn(II)* Sn(IV)* Ta(V) Th Ti(IV)* Ti(III) U(IV) Chit (CHCl3) pH cho chit nh lng pHb1/2 logKex 35 3,5 3,5 2,51 3,8 1,54 2,07 2 5,08 -0,4 4,5 4,6d 01 3,56 4,5 3,18 3 2,66 2 0,03 9,8e 0 <0 4,92 4,5 0,3 >8 01 0 0,91 5 0,85 2,42 3 0,5 6,22 4 3,4 7 1,5 <0 3,5 <0 9 01 1,53 3 2,06 0 <0 5 7 2 7 <0 01 3,34 0,2 3 6 01 01 3 4,44 0,2 2,5 < 0 4 3 1,5b 8g 0,1
U(VI) V(IV) V(V) W(VI) Y Zn Zr
3b 01 2,5 0,3b 5 9 3
<0 2,9 7,4 <0
4,74
a: Cc nguyn t chit nh lng d dng c nh du bng *. b: Trong dung dch c Cupferron 0,05M . c: Hng s chit nh hng :
K
' ex
[ML n ]org [H + ] n
[M][HL]
n org
Ph thuc vo bn ion v ph thuc vo nng ca phc anion ln [HL]org nu Cupferrate c hnh thnh. Gi tr thu c di iu kin sau: nng HL ban u trong pha nc,nng 0,005M i vi Bi, Ga, Mo, Sc, Th, Tl v Y v 0,05M i vi Be, Co, Cu, Hg, La v Pb; = 0,1 (NaClO4) nhit phng. d: Trong butyl acetat. e: Trong HClO4 1M. f: Trch ly mt phn. g: Trong ethyl ete. Bng 7.34: MT S V D CA H CHIT CUPFERRON Ion kim loi c chit All,Be,Ce(III), (IV), Hf, Nb, Sn(II),(IV),Ta, Ti,U(IV),(VI), V,Zr, t him Ti T _ iu kin pH 5,5 5,7, EDTA, citrate Dung dch kim long, EDTA, tartarate, S2pH 5,5, EDTA, Ce HNO3 0,1N H2SO4 6N Acid v c long 1NHCl Dung mi 4-ethylpentan2-one
Bi, Cd, Co(II), Cu,Mn(II),Mo, Ni,V(V),W,Zn Thp Ag,As(III)(IV), Cd, Co, Hg, Ni, Pb,Se(VI),Te(IV), U(VI), Zn Cht liu lm nhng b phn nhn to trong c th (sau khi hp th t v chit dithizon) U(VI) Ag, Al, As, Cd, Co, Cr, Hg,
CHCl3
Ti Bi, aFe(III), Ga, Mo(VI), Sn(IV), Ti,U(IV), V(V),Zr Mo, W Fe(III),Mo(VI), Sn(IV), Ti(IV), V(V), Zr Bi
MIBK CHCl3 Iso-AmOH CHCl3, hoc ethyl acetat CHCl3
Fe Ga Th Actinoids, Am
Mn, Ni, Pb, Sb, Zn Al, Cr, Mn, U Al, Cr, In, t him Kim loi ha tr III Pu(III)
Ti, V, Zn H2SO4 2N , Fe, Ge, Nb, Ta, Ti, V, Zr pH 0,3 1, Hf, La, U(VI) HCl 0,5 1,5N
CHCl3 CHCl3 Benzene + isoAmOH (1 : 1) CHCl3
a: Bi c th c chit li bng H2SO4 2N, da vo cc nguyn t cn li trong pha hu c. H chit chloroformCupferron ca Al l ng ch . Theo Sandell, Kex ph thuc vo pH v thi gian trc khi chit. Kex c tm ra hn ch qu trnh tng pH v nng ion Cupferron khi qu trnh chit xy ra ngay sau khi thm Cupferron v dung dch Al. Qu trnh chit Fe(III) vi s c mt ca Al c th xy ra dung dch nc hoc trong acid HCl 1Mv sau khi thm Cupferron th qu trnh chit c thc hin ngay lp tc. trnh tnh khng n nh ca dung dch Cupferron, Fe(III), Cu(II), hoc Al Cupferrate c dng chit Mo, Nb, Sb, Sn, Ta, Ti, V v Zr, da vo s trao i ca qu trnh chit. 7.7.4.3. Dng Cupferron nh l cht kt ta: Bn cnh phng php xc nh kim loi bng phn tch trng lng, Cupferron c dng nh cht kt ta tch nhm kim loi. Cc phng php kt ta ion kim loi c tm tt bng 7.32 v mt s v d v phng php tch bng cht kt ta c trnh by bng 7.35. Bng 7.35: MT S V D CA KT TA CUPFERRON Ion kim loi Ga(III) Ga(III) Hf(IV) Ti(IV) U(IV) U(VI) iu kin H2SO4 2N pH 4,55,5, EDTA, hn hp MgO sau khi ng kt ta vi Sn hoc Ti H2SO4 610 v/v % H2SO4, acid tartaric, EDTAa HCl 12 M , HClO4 hoc H2SO4, 05o, sau khi gim NH2OH hoc S2O4 pH7, EDTA, tartarat Ch Tch t Al, Cr, Sc, U(VI), Zn, t him. Ta v hu ht tt c cc ion Be, Ti, U, PO43- (trong Nb-Mo), t Nb n Ta (30:11:30) Tch t Al, Be, Cr, U, Th l ppt ti pH 18 Si, U, V, W, PC43- gy nh hng Bi, Fe, Ga, Hf, Mo, Nb, Pa, Po, Sn, Ta, Ti, V, Zr v actinit ha tr 4 Be v mt lng ln Ti, Zr, F-, CO32-
a: v tr pha ch Cupferron t phenylhydroxylamine v NaNO2. 7.7.5. Cc thuc th khc c cu trc tng t: 7.7.5.1. Neocupferron:
Mui amoni ca nnitroso1naphthylhydroxylamine (C10H7N(NO)NH4, KLPT = 205,21). Bt trong sut mu vng nht, im nng chy t 125o n 126oC. Kh nng tan trong nc (6,0g/100ml 25oC). Tnh cht vt l v phng php to phc tng t nh Cupferron: pKa = 4,1 v KD(CHCl3/H2O) = 1,3.103. N bn hn Cupferron trong dung dch nc v khi lng ca nhm naphthyl c th c xc nh bng phn tch trng lng. 7.7.5.2. nNitrosoncyclohexylhydroxylamine: ng ng cyclohexyl ca Cupferron. Mui amoni c tn l hexahydro Cupferron; im nng chy 140oC v phn ly 250oC. N bn hn Cupferron, trng thi rn tt nh l trng thi dung dch nc (mt dung dch 10-4M trong HCl 6N phn ly 50% sau 4 ngy, trong khi Cupferron phn ly trong mt phm vi no ch trong 65 pht); tan tt trong nc (11,49g/100ml), pKa = 5,58. Phng php to phc tng t nh Cupferron. Cc ng ng alkyl khc, nnitrosoncyclooctyl, nnitrosoncyclododecyl v N nitrosoNisopropylhydroxylamine cng c trnh by.
VI.8. THUC TH HN HP O,ODONATING

7.8.1. Acid chromotropic: 7.8.1.1. Tn ch th v cng thc ha hc: Tn ha hc: 1,8dihydroxy3,6acid naphthalendisufonic, mui disodium. Tn thng thng: Acid chromotropic. Cng thc phn t: C10H6O8S2Na2.2H2O Cng thc cu to:
OH OH
NaO3S
SO3Na
7.8.1.2. c im ca Acid chromotropic: To phc tan c mu vi cc ion kim loi. To mu vi NH3. 7.8.1.3. Cc tnh cht ca Acid chromotropic: Acid chromotropic c phn t lng bng 400,28. L bt trong sut mu vng, khng mi di 300oC, d tan trong nc, nhng khng tan trong dung mi hu c; pKa3(OH) = 5,36 v pKa4(OH) = 15,6 (20oC, = 0,1). 7.8.1.4. Tnh cht chun ca Acid chromotropic: Acid chromotropic hp th trong dung dch CuCl2, t 0,05 n 5ppm (520nm) v formaldehyde (570nm). 7.8.2. Dinitronaphthalenediol: 7.8.2.1. Tn ch th v cng thc ha hc: Tn ha hc: 2,4Dinitro1,8dihydroxynaphthalen, DNNDO.
Tn thng thng: Dinitronaphthalenediol. Cng thc phn t: C10H6N2O6. Cng thc cu to:
OH OH NO2
NO2
7.8.2.2. c im ca Dinitronaphthalenediol: To phc vi cc ion kim loi. Chit cc ion kim loi. 7.8.2.3. Cc tnh cht ca Dinitronaphthalenediol: Dinitronaphthalenediol c phn t lng bng 250,17. L bt trong sut mu cam, im nng chy 180o182oC. Tan t trong nc lnh (dung dch mu cam), tan nhiu hn trong nc nng v tan trong acid acetic v ethanol. 7.8.2.4. Tnh cht chun ca Dinitronaphthalenediol: Trong mi trng acid acetic, dinitronaphthalenediol phn ng vi acid boric to thnh phc anion (ML2-), phc anion ny c th c chit vi thuc nhum cation nh Brilliant Green to thnh toluene nh mt cp ion (t dung dch HCl, pH 2,5 3,5; max = 637nm, = 10,3.104, 0 0,1 ppm B). 7.8.3. Morin: 7.8.3.1. Tn ch th v cng thc ha hc: Tn ha hc: 3,5,7,2,4Pentahydroxyflavone. Tn thng thng: Morin. Cng thc phn t: C15H10O7.2H2O Cng thc cu to:
HO O OH
HO
OH OH O
7.8.3.2. c im ca Morin: To phc c mu vi cc ion kim loi. Chit cc ion kim loi. 7.8.3.3. Cc tnh cht ca Morin:
Morin c phn t lng bng 338,27. L bt trong sut khng mu hoc mu vng nht, im nng chy t 285oC n 300oC; hu ht khng tan trong nc (0,09% 100oC), nhng d tan trong dung dch kim hoc dung mi hu c tr ete v acid acetic. Cht rn chuyn sang mu nu nh s oxi ha; gi tr pKa t proton u n proton th 5 l 1; 4,8; 7; 9 v 13. 7.8.3.4. Cc tnh cht chun ca Morin: Morin l mt trong nhng polyhydroxyflavone c xem nh l mt cht phn tch. Tnh cht quan trng nht l morin l mt loi thuc th hunh quang. Morin cho ra mt hunh quang mu xanh nht ti pH t 4 n 9, nhng n tng ng k nh to phc vi cc ion kim loi nh Al (pH 3; ex = 440nm; em = 525nm); B (HCl long, 365nm, 490nm), Be (NaOH 0,04N, 460nm, 540nm); Ga (pH t 2,5 n 2,9, 400nm, 445nm); Th (HCl 0,01N, 365nm, 404,7nm); Zr; Hf (HCl 2N, 450nm, 502nm); v t him (pH 2,5; 401nm, 501nm). V vy, cc nguyn t ny c th c xc nh bng cch o hunh quang. EDTA v DTPA thng c dng nh l cht che. Morin cng to phc c mu vi cc ion kim loi khc nhau, nh Th (vng), Ga, In, U v Zr (nu trong dung dch kim NH3) v c th c dng nh l mt cht o quang i vi cc nguyn t ny, nhng xc nh hm lng fluor nhy hn nhiu. 7.8.4. Alizarin : 7.8.4.1. Tn ch th v cng thc ha hc: Tn ha hc: 1,2Dihydroxyanthraquinone3acid sulfonic, Alizarin S, Alizarin Carmin, C.I.Mordant Red 3. Tn thng thng: Alizarin . Cng thc phn t: C14H7O7SNa.H2O. Cng thc cu to:
O OH OH
SO3Na O
7.8.4.2. c im ca Alizarin : To phc c mu vi cc ion kim loi. 7.8.4.3. Cc tnh cht ca Alizarin : Alizarin c phn t lng bng 360,27. Mu dnh cho thng mi l mt mui natri, mui hydrat v bt trong sut mu vng nu hoc mu vng cam; d tan trong nc to thnh dung dch mu vng, nhng hu ht khng tan trong dung mi hu c. N tan trong H2SO4 c to thnh dung dch mu cam; pKa2 (OH) = 5,39 v pKa3 (OH) = 10,72 (25oC, = 0,5). Dung dch nc cho bit hp thu ln nht ti bc sng 420nm (pH < 3,5) hoc ti bc sng 515nm (pH > 3,5). 7.8.4.4. Tnh cht chun ca Alizarin : Alizarin to phc tan khng tan c mu vi nhiu ion kim loi v c xem nh l mt cht xc nh Al, F-, v BO33- v nh l mt cht o quang i vi Al (pH t 4,4
n 4,6, = 1,8.10-4 ti bc sng 490nm, t 0 n 0,8 ppm), Be (pH t 5,4 n 5,6; 480nm; = 4,3.103, t 0,2 n 4,7ppm), Zr (pH t 3,9 n 4,6, trioctylamine, chit vi toluene, 538nm), v B (pH t 7,7 n 8,2, EDTA, = 1250 ti bc sng 426nm). Bn cnh cc nguyn t ny, cc ion kim loi di y c xc nh vi Alizarin : In, Mo, Rh, Zn, v t him. Nhiu hydroxyanthaquione bao gm quializarin (1,2,5,8tetrahydroxy anthaquinone, C14H8O6, KLPT = 272,21) c nghin cu nh l thuc th i vi ion kim loi, c bit l Al, Be v B. 7.8.5. Stillbazo: 7.8.5.1. Tn ch th v cng thc ha hc: Tn ha hc: Stilbene 4,4 bis (1azo) 3,4 dihydroxybenzene 2,2 acid disulfonic. Tn thng thng: Mui diamoni. Cng thc phn t: C26H18O10N4S2.2(NH4). Cng thc cu to:
OH HO SO3NH4 CH = CH SO3NH4 OH OH
N=N
N=N
7.8.5.2. c im ca Stillbazo: To phc c mu vi cc ion kim loi. 7.8.5.3. Cc tnh cht ca Stillbazo: Stillbazo c phn t lng bng 646,65. Bt mu nu m, t tan trong nc to ra dung dch mu vng (pH t 3 n 7), dung dch mu cam (pH 9) hoc dung dch mu (pH 11). 7.8.5.4. Tnh cht chun ca Stillbazo: Mc d Stillbazo to phc c mu vi nhiu ion kim loi khc nhau, tm quan trng ca vic ng dng trong phn tch l c xem nh l cht o quang i vi Al khi c mt Fe (pH t 5 n 6, = 1,95 n 3,46.104 ti bc sng t 500 n 520nm, t 0,2 n 1,2ppm). Nng ca Fe (ln n 100 ppm) c th c che bng acid ascorbic. Khi c mt Zephiramine , c th t c nhy cao hn nhiu (pH 10, 570nm, t 0,08 n 0,64 ppm Al). Cc nguyn t khc, nh l B (pH t 8,9 n 9,1, = 1340 ti bc sng 414nm, t 0 n 2ppm), Ga, In, Mo, v Sn, cng c xc nh bng Stilbazo.
VI.9. -DIKETONE
7.9.1. ng phn: diketone c xem nh l nhng thuc th quan trng c nu bng 7.36, cng nh ng phn ca chng, tnh cht vt l, v gi tr pKa ca proton enolic. 7.9.2. Ngun tng hp v phng php tng hp:
Tt c u c gi tr v thng mi. Chng c chun b bng cch ngng t Claisen ca ng v alkyl methyl ketone vi ethyl carbonxylate trong baz. 7.9.3. Cc phng php phn tch: Cc thuc th nh (1) (4), (7), (8), (10), v (11) c dng nh l thuc th chit c kh nng ha tan trong kim loi v trong mt s trng hp, c dng nh l thuc th chromogenic trong cc nguyn t chuyn tip. Nhiu kim loi to phc vi (4)(7), (9), (10) v (11) d bay hi n ni chng c th c phn tch bng phng php sc k kh hoc phng php thng hoa phn on. t him to phc vi (4), (5), (6) v (11) c dng nh thuc th shift (thuc th chuyn v) trong nh ph cng hng t proton. 7.9.4. Tnh cht ca thuc th: Hng s vt l v hng s ion ha ca proton enolic ca thuc th diketone c tm tt trong bng 7.36. H s tan v h s phn ly ca diketone l cc h s quan trng trong qu trnh chit dung mi nh trnh by bng 7.37. Cc thuc th ny khng th hin bt k tn s hp th no trong vng c th thy c, nhng ch ra hp th mnh trong vng UV, cng v hnh dng ca thuc th ph thuc vo bn cht ca dung mi v t s ca keto v dng enol trong hn hp h bin ln.
R C O CH2 C O R R C O H CH C O R
7.9.5. Phn ng to phc v tnh cht ca phc: Sau khi loi proton, dng enol ca diketone c xem nh l mt anion ha tr 1, nh hnh thnh phc kim loi vi cu trc di y:
R C O M 1/n CH C O R
Tt c cc cu trc tng t ca cc phc diketone ph thuc vo cc phc mang in tch ng lp bo ha, chng c m t bng im nng chy tng i thp hn, p sut hi nc tng i cao hn v ha tan tt trong cc dung mi hu c khc nhau. im nng chy, nhit thng hoa, v cc tnh cht vt l khc ca kim loi diketonate c th c tm thy bng nhiu cch khc nhau: i vi phc AA (1); i vi phc BzA (2); i vi phc DPM (4); i vi phc TAA (5); i vi phc HFA (6), i vi phc TTA (7); i vi phc FTA (8); i vi phc PTA (9); i vi phc BFA (10); i vi phc FOD (11). Mi lin h gia nhit p sut ca hi nc vi mt s kim loi diketonate d bay hi c minh ha t hnh 7.27 n hnh 7.31. Bng : H S TAN V H S PHN LY CA DIKETONE Tnh tan (g/100ml)
LogKo
Diketone (1)AA (2)BzA (3)DBM (4)DPM (5)TAA (7)TTA (10)BFA
Nc 17,3 3,9.102 1,3.104 1,7.102 2.10-2 3.10-1
Benzene C th trn 63,3 53,8 -
CHCl3 C th trn 40,5 40,4 -
CCl4 C th trn 30,8 29,2 -
Benzene/ CHCl3/nc CCl4/nc nc 0,57; 1,21 0,50 0,74 3,14 3,44; 3,60 2,82 5,35 0,28 1,62 5,40 0,53 1,73 4,51 0,32 1,30 -
Vng pH tt nht ca s hnh thnh phc ph thuc vo bn cht ca cc ion kim loi v diketone. Trong nguyn tc, phi t c gi tr pKa thp hn to phc vi cc ion kim loi vng pH thp hn. Hng s bn ca kim loi diketonate c quan st trong dioxan v gi tr c trng c tm lc trong bng 7.38 v 7.39. Kim loi diketonate thng khng tan trong nc, nhng tan trong cc dung mi hu c khc nhau. V vy, diketone c chp nhn nh l dung mi cho qu trnh chit. Cc gi tr Kex v pH i vi diketone chn lc c xp thnh ct bng 7.40. Trong trng hp khng c in tch, nhng cc phc ng ngbo ha, nh NiL2.2H2O hoc CoL2.2H2O, s hin din ca dung dch ng lp lm gim s phn ly ca phc vo pha hu c. Tuy nhin, trong mt s trng hp, phn chit v t l chit c th tn dng bng cch s dng kt hp phi t b tr khng mang in nh l pyridine hoc 1,10phenanthroline hoc bng cch chn dung mi tng ng nh MIBK hoc butanol, thay v dng dung mi khng hot ng. V AA (1) l cht lng, hu ht cc ion kim loi c th c chit bng chnh n hoc dung dch ca n trong cc dung mi hu c khc nhau (benzene, carbon tetrachloride, hoc chloroform). Tuy nhin, tnh tan ca mt s kim loi acetylacetonate khng mang in trong pha nc khng th b qua, c bit l khi acetylacetone khng pha long c dng nh cht chit, v tnh tan tng i cao trong nc ca (1) tng so vi tnh tan ca phc trong nc. V vy n c nhiu thun li hn khi dng dung dch ca n trong dung mi hu c. S cn bng chit c th nh hng n BzA (2), DBM (3) v TTA (7) chm hn so vi AA (1). Khuynh hng ny r rng hn so vi TTA v c bit l khi nng anion thp (trong dung dch acid cao hoc trong tng nng thuc th thp). T l cng ph thuc vo tnh cht ca kim loi. Tuy nhin, (7) c s dng rng ri trong qu trnh tch cc nguyn t actinoid v lanthanoid. Gi tr logKex l Am, -7,46; Bk, -6,8; Cf, -9,45; Dy, -7,1; Er, -7,2; Ho, -7,25; Lu, -6,77; Nd, -8,58; Pm, -8,05; Pr, -8,85; Sm, -7,68; Tb, -7,51;Tm, 6,96; v Yb, -6,72. Dung dch ca kim loi diketonate cho bit tn s hp th trong vng UV hoc vng c th thy c, nhng mu ca chng khng r n ni m nhy sng cao hn khng th c c. nhy cng thp tr phi dng cht che thng dng. Ph hp th ca Cu(II) v phc uranyl c minh ha tng ng vi v tr hnh 7.32 v 7.33.
Hnh 7.32: Ph hp th ca Cu(II) 7.9.6. Tinh ch thuc th nguyn cht:
Hnh 7.33: Ph hp th ca phc uranyl
-Diketone bao gm trong phn ny l cc hp cht hon ton xc nh v c th c lm sch bng cch chng ct phn on ti p sut thp. Mu th c lm sch qua phc kim loi ca n nh Cu(II) c th c iu ch d dng bng cch trn dung dch ng acetat vi dung dch ru ca diketone. Sau khi tinh ch bng cch kt tinh li, phc ng c to ra v sau lm sch bng cch chng ct. tinh khit ca diketone c th c kim tra bng cch quan st sc ph kh ca chng hoc bng cch chun trong dung mi kh (trong methanol vi (Bu)4NOH 0,1M, dng ch th Crystal Violet). 7.9.7. ng dng vo phn tch: 7.9.7.1. Dng nh l cht chit: Kh nng tch kim loi bng cch chit dung mi vi diketone c th c nh gi t bng 7.40. Tuy nhin, iu kin chit trong tng trng hp ring bit c th b nh hng nhiu bi nhiu nhn t, nh khuynh hng thy phn ion kim loi, t l chit, nng ca thuc th .v.v Kh nng chit ca mt s ion kim loi vi acetylaceton (1) nh l mt chc nng ca pH c minh ha hnh 7.34 v 7.35. Cc ng cong ng dng vi thenoyl trifluoroaceton (7) c trnh by hnh 7.36.
Hnh 7.34: Kh nng chit ca Be, La, Mo(IV), Sc v Th bng acetylacetone 0,1M trong mi trng pH ca benzene.
Hnh 7.35: Kh nng chit Al, Cu(II), Fe(III) v Sn(II) bng acetylacetone 0,1M trong mi trng pH ca benzene.
Hnh 7.36: Kh nng chit ca Ac, Bi, Pb, Po, Ra, Th v Tl(I)(III) vi MTTA(7) trong mi trng pH ca benzene. 7.9.7.2. Dng nh l cht o quang: Nh trnh by phn trc, nhn chung diketone khng l thuc th qu nhy v chn lc thuc th sinh mu i vi kim loi. Tuy nhin, trong mt s trng hp, chng
c dng nh cht o quang cho qu trnh chit v cc v d c tm tt bng 7.41. Thenoyltrifluoroaceton (7) c s dng rng ri cho mc ch ny. Mt s nguyn t t him cng c xc nh bng cch xc nh hm lng bng php o hunh quang, cc v d c trnh by bng 7.42. 7.9.7.3. Dng nh thuc th bay hi i vi ion kim loi: Mt s kim loi diketonate bay hi nhanh n ni m chng c th c tch bng php ghi sc kh lng hoc bng phng php thng hoa phn on. Cc nguyn t c kim tra nhanh bng phng php sc k kh l Al, Be, Co, Cr, Fe, Hf, In, Mg, Mn, Ni, Pb, Rh, Sc, Th, Ti, U, V, Y, Zr v t him. Mt vi v d c tm tt bng 7.43. Trong thc tin, phc kim loi c ha tan trong dung mi hu c d bay hi (t 0,5% n 5%), nh benzene hoc chloroform, v 0,1 n vi l dung dch c tim vo. Nhit ca b phn tim v my d c bo qun t 20o n 40oC cao hn nhit ct. nhy ca my d phn ln ph thuc vo bn cht ca ion kim loi trung tm hn l ph thuc vo phi t. Vic tch phc kim loi bng phng php thng hoa phn on hoc phng php nu chy vng c nghin cu tng tn. 7.9.7.4. Dng nh NMR thuc th shift: Mt s lathanide diketonate c bit n nh l thuc th shift NMR m n di chuyn cc du hiu proton NMR ca cc hp cht hu c khc nhau c cc nhm chc nng hon ton tri ngc nhau. Vic di chuyn c to ra bi gii hn tip xc nhn to v s nh hng qua li gia phn t hu c v v tr phi tr cha no ca ion thun t lathanide ca chelat. Thuc th shift c trng c tm tt bng 7.44. Phc Eropium c bit di chuyn du hiu proton v pha t trng yu hn v phc Pr v pha t trng cao hn. Cc thuc th ny thng rt d ht m v i khi hydrat ha, chng tr nn rt kh tan trong dung mi hu c. V vy, n thch hp hn trong vic bo qun thuc th trong bnh ht m so vi P2O5. Yu cu ca cc phi t tr thnh 1 thuc th shift l: a) Phc phi c hng s to thnh cao so vi kh nng nhn xt phn t hu c. b) Thuc th shift khng phi a ra du hiu proton trong vng quan st. c) Thuc th shift phi c ha tan va trong dung mi hu c i vi php o NMR Bng 7.41: NG DNG CA DIKETONATE NH L THUC TH O QUANG Ion kim Diketone loin (1) Be Fe(III) Mo(VI) UO22+ V(III) iu kin pH 7 8, EDTA, citrate, chit vi CHCl3 pH 6 8, chit vi butylacetate H2SO46N chit vi AA + CHCl3(1:1) pH 6,5 7,0 chit vi butylacetate pH 2, chit vi AA +
Chelat kim loi Khong xc nh max T s (x103) (ppm) (nm) 0,03 ML2 295 3,6 0,3 ML2 MO2L2 MO2L2 ML3 438 352 365 383 1,63 0,9 0,5 10 70
V(V) (2) Ti(III) Ti(IV) UO22+ fe UO22+ UO22+ (3) UO22+
UO22+ (6) (7) Fe(III) Ce(IV) Cu(II) Cu(II) Fe(III) Fe(III) Fe(III) Ga Ga Ni Ni Pd(II) Pd(II) Pt(II) Rh(III) UO22+
CHCl3(1:1) pH 2 7, H2O2, chit vi AA + CHCl3(1:1) HCl 0,05M, ethnol 50% HCl 0,05M, ethnol 50% chit vi benzene pH 6 7, TOPO, chit vi benzene HNO3, EDTA chit vi CCl4 pH 6,0 Ca- EDTA, chit vi butylacetate chit vi TBP 10% trong isooctane t 15% dung dch ca Al(NO3)3 chit vi tetrapropylammonium hydroxyt trong MBK t trung bnh ca HNO3 + Al(NO3)3 pH 1,5 2,5, chit vi CCl4 H2SO41N chit vi xylene pH 3,5 4, chit vi benzene pH 5,5pyridine, chit vi cyclohexane pH 2 3, chit vi benzene HNO3 2M + NH4NO3 9M, chit vi xylene pH 1, Aliquat 336S, chit vi benzene pH 4,5 6,0, Rhodamine B, chit vi xylene pH 2,4 2,6TPAC, chit vi CHCl3 pH 5,5 8,0, chit vi acetone + benzene pH 5 9, Zephiramine , chit vi 1,2-dichloroethane pH 4,5 8,8, chit vi nBuOH pH 0,8 6,2, chit vi methylpropylketone HCl 6N, chit vi n - BuOH pH 5,2 6,2 chit vi xylene + acetone (1:1) pH 3,5 8,0, chit vi benzene
460 615 382 400 408 410 400 400 415 400 415 455 440 430 340 460 510 500 565 335 hoc 380 420 420 410 430 410 430 430
0,6 3,0 8,5 2,0 12,0 16,1
0,4 8 0,4 8 1 10 0 10 0,5 5
ML3 ML3 ML2 ML2X2 ML3 ML3 ML3Xn ML2X ML2 ML3X ML2 ML2 ML2 ML3 MO2L2
9,3 2,2 27,6 4,9 4,9 4,64 1,07 0,6 1,2 42,0 7,9 39,5 2,0
0,8 10 10 5 80 0,1 1 1 10 05 0 12 2 60 7,2 64 2 20 0,6 6 87,2 60 2 20 0 85
UO22+ V(V) V(V)
chit vi TBP 0,05M trong toluen pH 2 3, chit vi n-BuOH pH 2 3, chit vi butylacetate
MO2L2X
395 420 410
19 3,6 4,5
08 0,8 11 0 10
410* Ghi ch: No, khng chit. a: [HL]org = 0,10M b: Dng chit l UO2L2.HL. c: Carbontetrachloride. d: Methyl propylketone. 7.9.8. Cc thuc th khc c cu trc lin quan: 7.9.8.1. Polyfluorinated diketone: Ngi ta khuyn khch tch kim loi qua phc ca chng vi TTA (5) hoc HFA (6), cc loi diketone khc nhau c iu ch v c nh gi nh l phc kim loi cho phng php sc k kh. Bng 7.43: TCH -DIKETONATE KIM LOI BNG PHNG PHP SC K KH Diketone (1) Phc kim loi c tch (tng ln lt theo thi gian) Be, Al, Cr Sc, Ir, Pd(II), PT(II) Sc, Yb, Ho, Eu t him (tng dn theo bn knh ion) Be, Al, Cr, Fe, Ni Zn, Co(III), Ga, In Be, Al, Sc, Lu, Eu, Tb, Sm Be, Al, Cr, Rh Al, Cr, Rh, Zr Be, Al, Ga hoc Al, Ga, In (5) Ga, Fe, Cu Co(III), Rh(III) Th, U Trans-RhL3, cis-RhL3 Trans-CrL3, cis-CrL3 Be, Al, Cr Co(III), Rh(III) Zn, Co(II), Ni (l phi t hn hp to phc vi di-nbutylsulfoxide) Fe(III), Cu(II) Ct iu kin Nguyn liu ng gi 0,5% SE-30/ht thy tinh 10% Epon -1001/Chromosorb 2% Apiezon-H/hp kh-F 10% Apiezon-N/hp kh-F 0,5% Apiezon-L/Flusin GH 0,5% Apiezon-L/Flusin GH 0,5% Apiezon-L/Flusin GH 0,5% Daifloil 200/chromosorb 0,5% du silic/ht thy tinh hoc thy tinh borosilicate 0,5% DC silicon 710/ht thy tinh 0,5% Daifloil 200/chromosorb 3,8% SE-30/Diatport-S Silicon DC-550/gaschrom CLH 5% DC silicon/chromosorb 1% QF-1/chromosorb 7,5% SE-30/gch chu la 30% SE-30/chromosorb 5% Dexsil 300, SE-30 hoc OV1/ chromosorb W-HP 10% SE-52/chromosorb Nhit (o) 170 115 157 185 200 200 200 12050 135 11520 140 110 170 105 130 90 30100 170 90
(4)
(6)
(7)
Al Al, Cr(III), Fe(III) Be, Al, Fe(III), In, Th In(III), CO(II), Th Ca Zn (l phi t hn hp to phc vi TBP hoc TOPO) Sc, Lu, Er, Dy, Sm t him (tng dn theo bn knh ion) U(IV), Th(VI) Zr (hoc Hf)
(9)
20% Apiezon-L 15% Apiezon-L/Universal 0,5% XE-60/ht thy tinh 0,5% SE-30/ht thy tinh 25% E-301 cao su silicon/Universal 3% OB-101/chromosorb 5% du silicon/chromosorb 10% SE-30/chromosorb hoc 0,1% Apiezon L/ht thy tinh 0,3% DC-QF 1/ht thy tinh OV-3, 101 hoc 17/chromosorb
24050 162 12050 170 230 150240 150260 171 170200
(11)
7.9.8.2. 1Phenyl3methyl4benzoyl5pyrazolone: (PMBP)

H3 C C C O CH N N C O H3C C C O H CH N N C O
Cc nh ha hc ngi Nga nghin cu c l thuc th ny (im nng chy 92oC) nh l mt cht chit. PMBP c nhiu tin li hn TTA (5): tng hp d dng hn 134 v bn hn; kh tan trong nc ( 10-4M pH t 2 n 4) nhng d tan trong chloroform (1,78M); 1,2dichloroethane (1,43M), v heptan (0,03M); 135 pKa (enol OH) = 4,04 ( = 0,01; 20oC); 135 v logD (benzene/nc) = 3,66; logD (chloroform/nc) = 4,0 ( = 0,1); log2 (ZnL2) = 6,56 v logD (benzene/nc) i vi ZnL2 = 3,57. 172 T s chit ca mt s ion kim loi vi PMBP xem nh l chc nng ca pH c minh ha hnh 7.37. iu kin tt nht cho qu trnh chit kim loi vi PMBP c tm tt bng 7.45.
Hnh 7.37: Chit xut ca Cu(II), Ga, In v Tl(II) vi PMBP 0,03M trong mi trng pH xylene 7.9.8.3. 3(Trifluoromethylhydroxymethylene)dcamphor; isopropyltropolone (IPT): CTPT: C10H12O2 KLPT = 164,20
CH3
CH
CH3 HO
Tri vi hp cht gc (tropolone), thuc th ny bn hn, tng hp d hn, v c cc tnh cht chit thch hp hn: pka = 7,04, logD (CHCl3/H2O) = 3,37 (=0,1; 25oC). 2,2 bipyridin hoc triphenylphosphineoxide c dng nh l mt thuc th hn hp trong h chit IPT ca Tb hoc Ga, theo th t.
VI.10. PYROGALLOR V BROMOPYROGALLOL

HO X OH O OH O X
(1 ) X=H
S O 3-
(2 ) X = B r
7.10.1. Danh php: PR: Pyrogllolsulfonephthaline. BPR: 5,5 dibromopyrogallol sulfonepthaline. 7.10.2. Ngun gc v phng php tng hp:
PR c tng hp bng phng php ngng t osulfobenzoic anhydride vi pyrogallol. BPR c to thnh t qu trnh brom ha. 7.10.3. Tnh cht ca thuc th: PR v BPR: l tinh th dng bt mu sm khi kt hp vi kim loi sng t tan trong nc, alcohol v trong dung mi hu c khng phn cc. Trong mi trng acid mnh c mu cam, mu trong mi trng trung tnh, mu tm trong mi trng kim. S phn ly dng acid ca thuc th tng t nh Pyrocatechol Violet, v c vit di dng sau. Hng s phn ly c tng kt dng bng 7.47. H5L+ H4L H3L- H2L2 - HL3 - L4 cam Tm
7.10.4. Phn ng to phc v tnh cht ca phc cht: PR v BPR lin kt vi Phenylfluoronl v phc vi mt s kim loi to thnh dung dch chelate c mu. Dng dung dch ca PR v BPR (mu trong mi trng trung tnh) chuyn sang mu xanh hoc tm khi to phc vi 1 s kim loi nh Al, Cu (II), Ga (logKgal 5,54), Ge, In, Mo (VI), Sb (V), V (V) v W, i vi PR v Bi, Ge, In, Sb (v), Th, Ti, UO22+, V (v), v Zr i vi BPR. Khi Chelate cng tan trong nc, PR v BPR c s dng nh mt ch th kim loi trong phng php chun Chelate v nh thuc th ca phng php trc quang cho cc kim loi. Phc 3 cu t tan t trong nc v kt ta 1 phn, nu nng ca dung dch c trn ln hoc dung dch c s dng lm dung dch chun, phc cng c th c tch trong Nitrobenzene. c im phng php trc quang ca PR tng t nh BPR nhng Chelate anion ca PR v BPR c th c chit trong Alcohol tinh khit hoc dung mi c hng s in mi cao nh 1 cp Ion vi nhng Cation ln c tng hp trong bng 7.52. 7.10.5. tinh khit v tinh ch thuc th: Nhng nguyn liu trong cng nghip thng c tinh khit, nhng c 1 lng c th kt tinh trong nc, thuc th th c th lm sch bng cch ha tan n trong dung dch kim (Na2CO3 hoc NaOH), sau to kt ta bng cch Acid ha. Polyhydrate ca PR hoc BPR, bao gm nhng dng si mu , cn thn sy kh n khi tinh th c mu thm ngm 4 phn t nc. tinh khit ca PR v BPR c th xc nh bng phng php o quang dung dch ca n. PR pH 7,9 8,6 (H2L2-) BPR pH 5,6 7,5 (H2L2-) 7.10.6. ng dng trong phn tch: L ch th kim loi cho qu trnh chun chelate ca Bi, Co (II) , Ni, Pb. Chng cng c dng nh ch th trong phng php trc quang i vi mt s kim loi nng.
max = 542nm; = 4,3. 104 max = 558 nm; = 5,45. 104
BPR c s dng rng ri nh l mt thuc th phn tch hn so vi PR. BPR to thnh phc 3 cu t xm mu vi 1,10phenanthroline v bc c s dng cho vic xc nh trc quang bc v Ag gin tip dng xc nh cc anion, nh cc hp cht halogen, cyanide. S dng nh mt ch th kim loi trong phng php chun Chelate: Nhng Ion kim loi c th c chun bng EDTA, s dng PR hoc BPR nh cht ch th c lit k trong bng 7.48 v 7.49, dng A 0,05% dung dch ethanol (50v/v%) , c th bo qun trong nhiu thng m khng b h hng. S dng nh thuc th trc quang: Nhng Ion kim loi c th xc nh bng phng php trc quang vi PR hoc BPR trong dung dch c tng hp trong bng 7.50 v 7.51. Chelate ca kim loi vi BPR c th c chit vi cation thch hp (hoc kt hp vi acid amine) trong dung mi hu c nh 1 cp ion. Nhng v d c tng hp trong bng 7.52. Mu phn ng ca h AgphenBPR s bin i khi c mt ca phc anion nh: cyanide, thiocyanide, sulfile v cc hp cht halogen. Trn thc t, phng php o quang nh s pht trin cho vic xc nh 1 s anion. 7.10.7. Xc nh Ag bng phng php trc quang, s dng BPR v 1,10phenanthroline: Ly khong 40 ml dung dch mu (110 g Ag) cho vo bnh nh mc 50 ml c cha 1 ml dung dch EDTA 0,1M, 1 ml 1,10Phenanthroline 103M, 1 ml dung dch ammonium acetate 20% v 2 ml dung dch BPR 104M. nh mc dung dch n 50 ml sau em o quang tc th hoc trong vng 30 pht vi cuvet 4cm bc sng 635nm da vo mu trng. Nu c Fe(II) trong dung dch th thm va phenanthroline n khi to phc ht vi Fe(II) v phn ng vi Ag. Khi c mt U(VI), Th, hoc Nb, thm florua hoc hydrogen peroxide trc khi thc hin phn ng to mu. Khi c mt ca cht oxi ha, PR d b oxi ha, lm mt mu v tnh cht ny c s dng cho vic xc nh Ce(IV), Cr(VI), v V(V) bng phng php o quang. Phn ng mu ca phc PRMo (VI) vi protein (max = 600nm, 0 ~ 400 g/10 ml) c s dng xc nh protein trong nc tiu. Bng 7.46: PYROGALLOL V BROMOPHYROGALLOL STT 1 2 Tn thuc th Pyrogallol red Bromopyrogallol Red Danh php Pyorgallol sulfonephthalein, PR 5,5 - Dibromopyrogallol sulfonepththalcin, BPR Bng 7.47: HNG S PHN LY Hp cht pKa2 pKa3 pKa4 pKa5 PR 2,56 6,28 9,75 11,94 BPR 0,16 4,39 9,13 11,27
Cng thc phn KLPT t C19H12O8S 400,36 C19H10O8Br2S 558,15
Bng 7.48: S DNG PYROGALLOL TRONG CHUN CHELATE NH CHT CH TH. Ion kim loi pH m Mu thay i ti im cui chun Bi 2~3 HNO3 cam Co(II) 10 NH3-NH4CL xanh hoc tm Ni 10 NH3-NH4CL xanh hoc tm Pb ~ 5 AcOH-AcONa Tm Bng 7.49: S DNG BROMPYROGALLOL TRONG CHUN CHELATE NH CHT CH TH Ion kim loi pH m Mu thay i ti im cui chun Bi 2 ~3 HNO3 sm cam Cd 10 NH3-NH4CL Xanh Co (II) 9,3 NH3-NH4CL Xanh Mg 10 NH3-NH4CL Xanh Mn (II) 9,3 NH3-NH4CL Xanh Ni 9,3 NH3-NH4CL Xanh Pb ~ 5 AcOH-AcONa Tm t him ~7 AcONa Xanh Bng 7.50: DNG PYROGALLOL NH THUC TH O QUANG Ion kim loi iu kin (pH) Ag 7 Cu (II) 6 Ga 4,5 Ge 5 In 4,7 Mo (VI) 5,0 ~ 5,3 Sb (III) 4,5 Sb (V) 2 ~3 (60) Ti (III) 2,7 W (VI) Ion kim loi VO 2+ W(IV) W (VII) Zr t him T l max (nm) x 104 Nng xc nh 390 1,0 ML 582 0,95 0,25~2,3 ML 530 1,4 0,28~4,8 ML2 500 0,28~2 ML2 580 ML3 587 8,15 0,04~0,3 ML 520 0,25 0,3~3,0 ML 500 0,98 610 7,6 0,6~3,12 ML 576 6 ~1 max (nm) 540 621 610 670 680690 Nng xc nh (ppm) 3~7 0,08~1,4 0,03~2 0,16~1,4 0,3~3
Bng 7.51: DNG BROMOPYROGALLOL NH THUC O QUANG iu kin pH 4,4 HCl 1,0~1,3N Zephiramine 1M HCL, CTMAB (X) 5,0 ~5,4 5,6~7,5, Septonex iu T l ML2 ML MLX2 ML3 x 104
Lu Cht cn tr Cr, Mn, Ti -
0,17 6,5 8,4 4,5 3,3~3,9
Bng 7.52: CHIT CP ION CA CC CHELATE BROMOPYROGALLOR (2) Ion Chelate kim loi
Chit
Vng
kim loi Ge(IV) Nb Ti(IV) Ti(IV) V(V)
kin (pH) 0,5 4,5 5 2,5
t s ML3 ML3 MLX4 MLX2
max(nm) (x104) 550 610 630 610 3,8 2,5 3,75 0,85
Amine (X) Diphenylguanidine
Dung mi Hexyalxohol
xc nh (ppm) 5,4 0,2 2
4(60o) MLX3
di-nIsopentylacetate octylmethylamine 4Amynoantipyrine Gelatine hoc Isoamyalcohol diphenylguanidine Diphenylguanidine Chloroform (1:1)
CHNG VII:
O OH
THUC TH O-N
VII.1. THUC TH ALIZARIN COMPLEXONE

OH CH2N O CH2COOH CH2COOH 2 H2O
C19H15NO8.2H2O (vit gn: H4L) KLPT = 421,36 8.1.1. Danh php: Cc danh php thng dng: 3 [Di(carboxymethyl)aminomethyl]1,2dihydroxyanthraquinone. 1,2Dihydroxyanthraquinone3ylmethylamineN. nDiacetic acid. Alizarin Complexone. ALC. 8.1.2. Cc tnh cht ca ch th: 8.1.2.1. Ch th dng t do: Lun tn ti dng acid t do ngm nc, bt tinh th mu vng nu, nhit nng chy 190oC, hu nh khng tan trong nc, ether, alcohol v cc dung mi hu c khng phn cc, nhng tan d dng trong dung dch kim. Mu ca dung dch ch th thay i theo pH v cc nc phn ly ca ch th c trnh by theo s sau ( = 0,1): H4 L
p K a 1 = 2,40 - COOH
H3 L vng
p K a 2 = 5,54 2 OH
H2 L
2-
p K a 3 = 10,07 N H
+
HL
3-
p K a 4 = 11,98 1 OH
4-
xanh
Quang ph hp thu ca ch th trong dung dch cc gi tr pH khc nhau c minh ho hnh 8.1. 1.4 1.2 1.0 0.8 0.6 0.4 0.2 400 5 Hnh 8.1: Quang ph hp th ca ALC cc pH khc nhau. Hm lng 9.96 ppm trong nc. (1) pH 4.6; (2) pH 7.0; (3) pH 10.0; 600 sng 700 (4) H 11 5
hp th
4 2 1 500 Bc 3
8.1.2.2. Phn ng to phc v cc tnh cht ca phc: Cc ion kim loi to phc mu vi Alizarin Complexone c th c chia thnh 2 nhm. Nhm th nht l cc ion kim loi to phc (MHL) pH = 4,3 4,6, pH ny ch th t do c mu vng. Nhm th hai l cc ion kim loi to phc tm (ML) ti pH = 10, pH ny ch th t do c mu . Nhm 1: Ba, Ca, Cd, Mg, Mn(II), Ni, Sr. Nhm 2: Al, Cd, Ce(III), Co(II), Cu(II), Fe(III), Ca, Hg(II), In, La, Mn(II), Ni, Pb, Th, Ti(III) (IV), Zn, Zr, v t him. Hng s to thnh ca phn ng: M2+ + HL3- ' MHL- lgK = 12,19 (Zn), 12,23 (Ni), 12,25 (Co), 14,75 (Cu). Cn phn ng: HML- + M2+ ' M2L + H+ l lgK = 0,8 (Pb) v 3,5 (Cu) ( = 0,1, 20o ). Cu to ca MHL nh sau:
O H O O O C H2C O CH2 N M OH2 O CH2
OH2
C O
Phc ca cc ion t him pH ~ 4 chuyn thnh mu xanh khi c mt ion F- do c s to phc MLF. Trong cc nguyn t t him th phc ca La(III) v Ce(III) c s i mu nhy nht, v phn ng ny c s dng nh mt phng php quang ph c bit c nhy cao xc nh ion F-. S kt hp ca F- lm suy yu lin kt O H, do n c th phn ly pH = 4 pH ny ch th t do khng phn ly c.
O H O O F
-
OH2
CH2 N
Quang ph hp th ca phc LaHL v LaLF c minh ho hnh 8.2.
1.4 1.2 1.0 0.8 0.6 0.4 0.2
hp th
Hnh 8.2. Quang ph hp th ca phc La-ALC v phc La-ALC-F. (1) LaHL; (2) LaLF; (3) s khc nhau gia LaHL v LaLF; nng 0.002M; F, 20g.
3 400 450 500 550 600 650 700 Bc sng
Phc mu xanh c th c chit vi dung mi hu c nu nh nc ion t him c thay th bng phi t k nc nh alkinamine hay arylamine. Qu trnh chit da trn tnh cht ca dung mi chit v cc amine, v isobuthanol hoc isoamylalcohol cha n diethylaniline 5% N cho kt qu tt nht. Hnh 8.3 minh ho quang ph hp thu ca dng chit.
0.8 hp th 0.6 0.4 0.2 500 550 600 650 Bc sng 700
Hnh 8.3. Quang ph hp th ca phc La-ALC-F trong dung dch iso-amylalcohol cha 5% N,N-diethylaniline; F,0.5ppm.
Cc hng s cn bng ca h thng LaALC v LaALCF c tm tt trong bng 8.1. Bng 8.1: CC HNG S BN CA H THNG LAALC V LAALCF 25oC V = 0,1 (KNO3). Cn bng Hng s cn bng H thng La-ALC lgK202 = 0,28 2M + 2H2L ' M2L2 + 4H+ lgK212 = 5,58 2M + 2H2L ' M2HL2 + 3H+ H thng La-ALC-F 2M + 2H2L + F- ' M2HL2F + 3H+ lgK2121 = 9,70 2M + 2H2L + F- ' M2H2L2F + 2H+ lgK2221 = 14,17 8.1.3. Cch tinh ch v tinh khit ca thuc th: Hu ht cc mu thuc th bn trn th trng c th s dng cho cc vic phn tch thng thng khng cn tinh khit. Nhng i vi nhng php phn tch cn tinh khit th cn phi tinh ch thuc th trc khi dng. Qu trnh thc hin nh sau:
Cn chnh xc 1(g) bt mu cho vo 50ml dung dch NaOH 0,1M, lc dung dch, ri em chit Alizarin 5 ln bng methylenedichloride. Lm lng ch th t do bng cch thm tng git acid HCl v khuy u trong mt bn lnh. Lc phn lng trn mt phu lc thu tinh, ra sch bng nc lnh, v lm kh bng thit b c chn khng. tinh khit ca acid t do c th kim tra bng php o kim hoc chun trc quang vi dung dch chun Al pH = 4. Cc ng dng phn tch: 8.1.4. S dng phc vi Ce hoc La lm thuc th trong php o quang cho Fluoride: Khong pH tt nht cho phn ng to mu l t 4,5 4,7, v bn cht ca cc dung dch m cng nh hng ti nhy ca phn ng. m Succinate c s dng nhiu nht, hn hp dung dch thuc th lc ny s c n nh trong khong 9 thng. Cn m Acetate th c s dng cho phng php chit trc quang. S c mt ca dung mi hu c cng lm tng nhy v Acetone (20% 25%) cho kt qu tt nht. Mu c n nh trong 1 gi. nhy cng c th c tng ln nh dung mi chit. Vic thm natri dodecysulfate cng lm tng nhy phn ng mu ny. Cc cation nh Al, Be, Th, Zr, gy cn tr i vi phn ng mu, chng cnh tranh vi thuc th trong vic phn ng to phc vi F-. Cc cation nh Al, Cd, Co(II), Cr(III), Cu(II), Hg(I)(II), Fe(II)(III), Mn(II), Ni, Pb, V(IV), Zn, cng gy cn tr, chng to phc vi Alizarin complexone bn hn so vi cc ion t him. Cc Anion nh BO3- v PO43cng gy nh hng, chng to phc bn vi cc ion t him. 8.1.4.1. Qu trnh trc quang i vi fluoride trong dung dch nc. Dung dch thuc th: Chuyn mt vi ml dung dch nc cha 47,9 mg Alizarin complexone, 0,1 ml dung dch ammoniac c v 1 ml ammonium acetate vo bnh nh mc 200 ml cha sn dung dch c pha t 8,2 g natri acetate v 6ml acid acetic c trong mt lng nh nc. Thm 100 ml acetone v khuy u. Ri sau thm tip mt dung dch c pha t 40,8 mg La2O3 trong 2,5 ml HCl 2N. Cui cng, nh mc ti vch bng nc ct. Dung dch ny c n nh trong 2 tun. Qu trnh xc nh: Cho mt cht kim yu hoc mu dung dch trung tnh c cha 3 g 30 g F- vo bnh nh mc 25 ml. Thm 8,00 ml dung dch hn hp thuc th ri nh mc ti vch. Sau 30 pht em o ph hp thu bc sng 620 nm. Lm mu trng khng c mu cha F-. 8.1.4.2. Qu trnh chit trc quang i vi Fluoride: Cho 20 30 ml dung dch mu cha 0,5 10 g F- vo trong phu chit 100 ml. Ln lt thm 3ml dung dch Alizarin complexone 0,001M, 3ml dung dch m acetate (pH = 4,4), 8ml acetone, v 3ml dung dch lanthanium chloride 0,01M, ri pha long hn hp ti 50ml. Chit phc mu xanh bng cch lc dung dch nc vi 10ml isoamyl alcohol cha 5% n,ndiethylaniline trong 3 pht trn my lc. Sau khi c s phn chia pha, em o ph hp thu ca pha hu c bc sng 570nm. Lm mu trng l dung dch khng cha mu. nh lut Beer c p dng ng trong khong nng ca F- l 0 10 ppm. 8.1.5. Cc ng dng khc: Alizarin complexone c s dng trong phng php trc quang xc nh cc ion kim loi nh: Al (pH = 4,1 4,3, = 455nm), Cu(II) (pH = 3,5), Mn(II) (trong kim, =
570nm), Co(II), Ni(II) (pH = 4,5, = 500nm), V(IV) (pH = 10,3 10,8, acid ascorbic, CPC). N cng c s dng nh l mt ch th kim loi trong php chun to phc ca Co (II), Cu(II), In, Pb, v Zn nhng trong cc trng hp ny dng xylenol da cam v methyl thymol xanh th tt hn. 8.1.6. Cc thuc th cng h: 8.1.6.1. Sulfonated Alizarin complexon (ALC-5S, AFBS). Thuc th ny tan trong nc nhiu hn so vi thuc th gc. Hot ng ca phc La vi F- c nghin cu mt vi kha cnh, v nhn thy thuc th ny c nhy thp hn so vi thuc th gc. 8.1.6.2. Quinalizarin complexone. Cng thc phn t: C19H15O10 KLHT = 417,33 vC Cng thc cu to:
OH O OH OH CH2N OH O CH2COOH CH2COOH
Phc ca cc nguyn t t him (Ce, Nd, Pr, v Sm) vi thuc th ny hot ng tng t nh phc ca Alizarin complexone. nhy i vi vic xc nh fluoride gp 1,5 ln so vi phc ca Alizarin complexone. N to thnh phc mu vi borate trong mi trng H2SO4 m c, v th c dng xc nh boron trong cc hp cht.
VII.2. THUC TH MUREXID

Cng thc phn t: C8H4O6N5.NH4 KLHT = 284,19 Cng thc cu to:
O O N NH O N H ONH4 H N O
NH
8.2.1. Danh php: 5[(Hexanhydroxy2,4,6trioxo5pyrimidinyl)imino]2,4,6(1H,3H,5H)yrimi dinetrione, mui monoammonium; 5,5nitriloddibarbituric mui amino acid ; amino acid purpurate; amino purpurate. 8.2.2. Ngun gc v phng php tng hp:
C th mua trn th trng. iu ch bng phn ng ca alloxantine vi ammonium acetat trong acid acetic si. 8.2.3. Tnh cht ca thuc th: Murexid l tinh th dng bt c mu ta, c mu xanh sng khi b nh sng chiu vo. N th khng b nng chy cng nh khng b ph v nhit di 300oC. Dung dch vi nc c mu ta nhng mu b phai nhanh. Murexid tan trong nc lnh v ethyleneglycol, tan nhiu trong nc nng v khng tan trong alcohol v ether. Phng trnh phn ly: pKa1=0 H 5L H 4l
-
pKa2=9,2 H3L
-
pKa=10,9 H2L-
S hp th quang ph ca H4L- v H2L- trong dung dch nc c trnh by hnh 8.4 sau:
Hnh 8.4: ph hp th ca murexit v chelat kim loi murexit; , murexit(dung dch trung tnh, H4L ); --------, murexit (dung dch km mnh H2L3-); ,Ca- murexit (CaH2L-) ti pH = 13; ,Cu(II) - murexit (CuH2L-) ti pH = 8.
8.2.4. Phn ng to phc v tnh cht ca phc: 8.2.4.1. Phn ng to phc: Trong dung dch trung tnh hoc dung dch kim ion purpurate hnh thnh phc mu chelate vi cc ion kim loi nh Ca, Cu(II), Co(II), Ni v Zn Mu ca cc chelate ty thuc vo bn cht ca kim loi v pH ca dung dch.
O O N NH H N O
NH
M
N H O
Trong trng hp chelate ca can xi s cn bng c biu din nh sau:
pKa2 =8,2 CaH4L

+
pKa3 =9,5 CaH3L CaH2L-
8.2.4.2. Tnh cht ca phc Cc chelate ca Cu(II), Ni(II), Co(II) c mu vng v chelate ca Zn Ca th c mu vng cam. 8.2.5. tinh khit ca thuc th: Thuc th rn thng thng c cha mt lng nh v phn trm (20%) ca Murexid (amino acid purpurate) v mt lng ln ca uramil, alloxantine, tuy nhin t mu khng tinh khit lm cho n tinh khit th cng rt kh khn. mu c tinh khit cao c th c iu ch t alloxantine tinh khit sao cho ph hp vi tiu chun. xc nh cht th trong thuc th tinh khit bng cch chun vi TiCl3 hoc c th nh gi bng cch o hp th ca dung dch trong nc (0,5mg/100ml bc sng 520nm, = 120.104). TT PH Mi trng Mu thay i Ca 12 NaOH Tm Cu(II) 8 NH3 Vng tm Co(II) 8 NH3 Vng Tm Ni(II) 10 NH3 Vng Xanh tm 8.2.6. ng dng trong phn tch: Murexid c s dng lm ch th kim loi trong chun EDTA. Nhng lm ch th tt nht l dng ngay sau khi pha. Dung dch nc ca Murexid th khng bn, dung dch ethylene glycol 0,1% th c thi gian bo qun di hn dung dch vi nc. Cn thuc th kh c trn ln vi NaOH hoc KOH khan vi t l (t 1:100 1:500) c s dng rng ri hn Murrexid cn c lm thuc th trong phn tch trc quang ca Ca ( pH = 11,3 bc sng 506nm) trong mu thc. 8.2.7. Hng s bn ca phc Murexide vi mt s ion kim loi: PH TT Ion KL 4 5 6 7 8 9 10 11 12 Ca 2,6 2,8 3,4 4,0 4,6 5,0 Cu(II) 6,4 8,2 10,2 12,2 13,6 15,8 17,9 Ni 4,6 5,2 6,2 7,8 9,3 10,3 11,3 Eu 5,34 5,42 Gd 4,90 5,00 La 4,49 4,55 Tb 4,89 4,98 Gi tr t h quy chiu 3 nhit phng, = ~ 0,1. Gi tr t h quy chiu 4 nhit 25oC 0,1; = 0,1
VII.3. HYDROXYLQUINOLINE
Cng thc phn t: C9H7NO
KLPT = 145,16
N OH
8.3.1. Danh php: 8Quinolinol, oxine. 8.3.2. Ngun gc v phng php tng hp: C th tm thy trong cng nghip. Thu c t s sunful ha quinoline, v bng phn ng kim nng chy. 8.3.3. S dng trong phn tch: Nh l mt thuc th tch chit, chit trc quang, v l cht to ta cho nhiu ion kim loi ngoi tr cc cation ho tr mt. chn lc c th c ci thin bng cch chn gi tr pH thch hp v dng nhng tc nhn che. 8.3.4. Nhng tnh cht ca thuc th: L tinh th khng mu hoc kt tinh dng bt trong sut, im nng chy t 74 n 76 C, im bay hi khong 267oC, thng hoa trn 310 (2.10-2 Torr); hu nh khng tan trong nc v erther; d dng tan trong nhng dung mi hu c v nhiu acid nh acetic acid hoc nhng acid v c. S ho tan trong dung mi khan th khng mu, nhng s c mu vng trong mi trng m. 8Hydroxyquinoline th n nh th rn cng ging nh trng thi dung dch, nhng nn bo qun ch ti; pKa (N+H) = 4,85 v pKa (OH) = 9,95 ( = 0,1NaClO4, 250).
o
Nhng d liu hp thu quang ph ca thuc th trong vng UV c tng hp trong bng 8.2. Hn na, nhng thay i r rt ca quang ph c quan st trn mi dng ti nhng vng khc nhau ca proton. Quang ph ca oxine trung tnh trong nhng dung mi hu c th ph thuc rt nhiu v c tnh ring ca dung mi, t cn bng di y th c s bin i bi dung mi phn cc.
N O H O-
N +
Neutral
Zwitter
Oxine c s dng rng ri nh thuc th tch chit cho nhiu kim loi, v h s phn b ca oxine trong nhng h dung mi nchu c khc nhau th c tng hp trong bng 8.3. 8.3.5. Nhng phn ng to phc v nhng tnh cht ca phc: Oxine c xem nh phi t anion ho tr mt to thnh cht khng cnh vi mt khong rng cc ion kim loi. Nhng cation ca ht mang in tch +n v c s phi tr l
2n th c gi l phi tr bo ho chelate khng mang in n khng th ho tan trong nc nhng d dng tan trong nhng dung mi hu c (cu trc (1) ca Fe(III) oxinate l mt v d). Khi s phi tr ca kim loi ln hn 2n, nhng ni khng phi tr ca ion kim loi th thng b nc chim ch c minh ho bng cu trc (2) ca nickeloxinate l mt v d. Mc d loi chelate ny th hon ton khng tan trong nc, n cng khng d dng tan trong nhng dung mi hu c mc d c s hin din ca nc phi tr (dung dch ca ZnL2.2H2O trong CHCl3, 2.10-6).
N O N OH2 O N
Fe
N O O N
Ni
O OH2
V d: khi mt dung dch ca Cd, Zn, Ni, hoc Mg c lc chung vi dung dch chloroform v oxine ti pH thch hp, nhng kim loi c th c chit dng chelate ML2, nhng trong vi pht chng tr thnh dng hydrad ho v tch ra khi pha chloroform. Tuy nhin, nhng chelate c th c chit thnh cng bi nhng pha hu c, bng cch thm cht ph tr khng phi t, nh l pyridine, 1,10phenanthroline, alkylamine, hoc thm d oxine, hoc s dng dung mi phi tr, nh MIBK hoc amylalcohol, nh mt dung mi chit. Oxine thuc nhm phenolic l acid yu, mc phn ng to phc vi ion kim loi th ph thuc nhiu vo khong pH ca mi trng phn ng. Gi tr pH tt nht cho vic to thnh kt ta v cho lng chit vi chloroform c tng hp bng 8.4. Kh nng chit th cng ph thuc vo khong nng ca oxine trong pha hu c. Cc gi tr pH cho bng 8.4 c s dng vi nng ca dung dch oxine t 0,001 n 0,01 M. Nhng hng s chit vi chloroform, v gi tr pH cho 50% chit cng cha trong bng . S chit thng nhanh hn ti nng oxine cao hn v gi tr pH cao hn. Mt vi cht khng mang in, cc phi tr bo ho oxinate kh nng thng hoa di p sut thp, v tnh cht ny c th ng dng tch nhng oxinate kim loi bng vic thng hoa phn on. Nhit thng hoa ca vi oxinate kim loi c cho bng 8.4. Hng s bn ca oxinate kim loi thng c quan st trong dung mi hu c dng nc da vo s t tan trong nc. Nhng gi tr c hon thnh trong bng 8.5. Dung dch chloroform vi nhng oxinate kim loi thng c mu vng v s lin kt c biu din bng cc gi tr r rng, oxine cha lin kt th hp thu rt t. Ngoi tr cc oxinate ca Fe (III) (xanh en) v V (V) ( en) chng c nhng lin kt rt phc tp. S hp thu quang ph ca mt vi oxinate kim loi trong chloroform c cung cp trong hnh 8.5, v nhng c im quang ph ca oxinate kim loi nhng phn quan trng ca phn tch th c tng hp bng 8.6. Mc d kh nng hp thu ca chng th khng c cao, nhng oxine to thnh cc chelate vi rt nhiu ion kim loi, v vy oxine c xem nh mt thuc th hu c thng thng nht cho vic phn tch kim loi. Kh nng chn lc c th c ci thin da vo vic chn pH thch hp v vic che nhng tc nhn trong giai on trch chit.
Hnh 8.5: Ph hp th ca Al, Fe(III) v UO2 oxinates trong chloroform. (1) Oxine; (2) Al 50 g; (3) Fe(III) 100 g; (4) UO22+ (100 g nh U).
Trong chloroform, oxine bn thn n cng c kh nng pht hunh quang yu di nh sng UV, tuy nhin, nhng oxinate ca ion kim loi nghch t th c kh nng pht hunh quang mnh trong iu kin tng t. Da trn nguyn tc ny, s xc nh du hiu hunh quang ca nhng kim loi c a ra. Nhng oxinate kim loi pht hunh quang mnh cho vic xc nh l Al (max = 510nm), Ga (526nm), Nb (580nm), Sc(533nm), Zn (530nm), v Zr (520nm). Nhng dung dch chloroform ca nhng oxinate kim loi biu din kt qu quang phn gim chm kh nng hp thu. Nguyn nhn ny c th l gii do s hnh thnh phosgene trong qu trnh quang phn ca chloroform. 8.3.6. S tinh ch v tinh khit ca thuc th: Oxine l hp cht hon ton xc nh vi im nng chy r rng. Oxine th c th c tinh ch da vo ng oxinate bng s phi t trng vi H2S hoc bng s chng ct hi nc sau khi aicd ho bng H2SO4 im nng chy (73 n 75oC) mt tiu chun rt tt cho vic tinh ch. 8.3.7. ng dng trong phn tch: Dng nh mt cht chit v quang trc: L mt cht chit thch hp ca nhiu oxinate kim loi trong h thng ncchroloform c tng hp bng 8.4. Nhng iu kin cho s chit ca nhng ion kim loi c th cng c tm thy trong bng 8.6 n c tng hp nhng ng dng ca oxine nh l mt tc nhn ca trc quang. S chn la gi tr pH ph hp cho qu trnh chit v vic che nhng tc nhn th rt cn thit cho vic tng chn lc. Chloroform l dung mi c u tin nht cho qu trnh chit. nhy ca vic xc nh trc quang ca nhiu kim loi th khng cao, do phn t gam hp thu trong khong 103 n 104, nhng oxine vn tip tc hu dng l mt thuc th o quang hu dng v n c ng dng rng ri. Dng nh mt ch th kt ta: Nhng thng tin v oxine nh l mt cht phn tch c gii thiu bi Berg nm 1927, trong nhng nm u n c dng ch yu nh l mt tc nhn to ta cho vic tch v phn tch trng lng xc nh nhng ion kim loi. S to ta vi nhiu oxinate kim loi cng c th c xc nh bng phng php o th tch. Oxine phn ng d dng v nh lng vi bromine to thnh 5,7dibromoxine. Nhng oxinate kim loi c ho tan trong HCl m v c x l bng KBr v dung dch KBrO3 d. Sau thm KI, bromate d c xc nh bng cch chun iodine thot ra bng dung dch Na2S2O3 tiu chun.
PFSH (kt ta t dung dch ng th) k thut c gii thiu cho s chun b oxinate kim loi nhng cht nng hn, d dng lc hn, v t nhim bn hn vi phi t d v nhng nguyn t thm vo c chun b bng qu trnh c. Trong phng php PFSH, oxine c to ra bi s thy phn 8acetoxyquinoline (im nng chy t 56,2 n 6,50) kt ta vi (AlL, BiL3, CuL2, GaL3, InL3, MgL2, SbOL.2HL, ThL4.HL, UO2L2.HL hoc (UO2L2)2.HL, v dung dch cha oxine, ion kim loi, v urea (AlL3, BeL2, CrL3, MgL2, NbOL3). Nu ureaza c thm vo trong hn hp th phn ng c th tin hnh ti nhit phng. Phng php sc k c dng kim tra nhanh mt s oxinate kim loi trong mt vi lnh vc nh. Nhng oxinate kim loi c th c tch trong ct hoc trong lp mng. Ion kim loi cng c th tch trn giy lc vi oxine, thm vi ht silica c nh oxine, hoc trn cht cao phn t c nhm chc oxine. 8.3.8. Nhng thuc th khc c cu trc lin quan: 8.3.8.1. 2 Methyloxine (8 hydroxyquinaldine): C10H9NO KLPT = 159,19
N OH
CH3
Lp nh khng mu, im nng chy t 73 n 74oC, nhit nng chy khong 266 n 267oC; pKa (N+H) = 4,58 v pKa (OH) = 11,71 (50% dioxane, 250). Nhng gi tr KD c tng hp trong bng 8.3. C tnh cht vt l hon ton gng nhau v to cnh d dng vi oxine, ngoi l vi Al v Be. Al khng th to ta vi 2methyloxine. iu ny c gii thch bi s b tr trong khng gian ca nhm methyl trn 2 v tr m khng to thnh cu trc ML3 loi chelate vi Al3+ n th c bn knh ion kh nh. Mc d, 2methyloxine l mt cht ging nh oxine nhng khi d nhiu vi Al gy tr ngi cho vic xc nh kim loi. Tuy nhin, theo s vic gn y, Al c tch mt phn vi 2methyloxine trong m acetate. iu ny cng c th c gii thch v s c mt ca ion acetate vi vic hnh thnh mt phn ion vi bischelate (AlL2+) trong s chit chloroform. Be c th to ta vi 2methyloxine to thnh BeL2, trong khi kt ta ny khng hon ton vi oxine. Thuc th ny cng c s dng nh mt thuc th chit trc quang cho mt nhm ion kim loi, gm Mn(II), Pd(II), v V(V). 8Acetoxyquinaldine (im nng chy t 63 n 640) c s dng nh mt tin thn ca 2methyloxine trong phng php PFHS to ta ThL4, CuL2 v InL2. 8.3.8.2. Oxine5sulfonic Acid: C9H7NOS KPPT = 225,22
SO3H
N OH
dng tinh th bt mu vng. D dng ho tan trong nc; pKa (N+H) = 4,10 v pKa (OH) = 8,76 ( 0,250). Chelate c tnh tng t nh oxine, nhng chelate khng ho tan trong nc. Do , thuc th ny c dng nh l thuc th trc quang (Fe(III), Ta(V) v V) hoc nh mt thuc th hunh quang (Al, Cd, Ce(IV), Ga, In, Mg v Zn) cho ion kim loi trong dung dch nc. Khi giai on chit khng cn thit, th qu trnh tng t nh oxine. Hn na, nhy v chn lc c th c loi tr bng vic loi b giai on chit. Kt qu chelate kim loi trong pha nc c th tch ra bi dung mi thm hoc chloroform nh mt cp ion vi mt chui alkylamine hoc Zephiramine cho trc quang. Bng 8.2: C IM QUANG PH CA OXINE
max (nm) (103) Dng Trung tnh (pH 7.6) 239 32,4 HL 305 2,63 Zwitter ion 270 2,84 HL 431 0,064 3,16 251 Cation (pH 1) 1,48 308 H2L+ 1,55 319 30,2 252 Anion (pH 12) 2,88 334 L2,82 352
(Ngun in c cho php bi Ardersen, P.D. v Hercules, D.M., Anal.Chem., 38,1702, 1966. Copyright 1966 Hi ho hc M.) Bng 8.3: S SP XP CC H S CA OXINE V 2 METHYLOXINE(25 0.20, = 0.10) Dung mi hu c OXINE 2-Methyloxine 82,6 45,5 1-Butanol 435 116 Carbon tetrachloride 314 136 MIBK 557 162 Toluene 1003 303 o-Dichlorobenzene 1248 377 Dichloromethane 1670 433 Chloroform Bng 8.5: HNG S BN CHELATE CA CC KIM LOI OXINTE
Ion kim loi log KML log KML2 log KML3 Ag Ba Be Ca Cd Ce Co(II) Cu(II) Fe(II) Fe(III) Ga In La Mg Mn(II) Ni Pb Sc Sm Sr Th UO22+ VO2+ Zn 5,20 2,07 3,36 7,3 9,43 9,15 10,55 13,49 8,71 14,51 12,0 8,66 6,38 8,28 11,44 10,61 6,84 2,89 11,25 10,97 9,96 4,36 5,9 7,68 7,98 9,11 12,73 2 16,83 13,50 2 24,0 7,74 5,43 7,17 9,94 8,09 2 21,3 9,64 2 20,19 8,90 3 24,35 3 22,13 3 38,00 12,49 3 35,5 3 26,80 9 3 19,50 3 3,19 9,42
iu kin ,, mi cht tC NaClO4 0,1 1825 20 0 30 Dioxane 75% 25 Dioxane 50% 25 Dioxane 50% 25 Dioxane 50% 25 Dioxane 50% 25 NaClO4 0,3M 25 NaClO4 0,3M 20 NaClO4 0,1 25 NaClO4 0,1 25 Dioxane 50% 25 Dioxane 50% 25 Dioxane 50% 25 Dioxane 50% 25 Dioxane 50% Ethanol tuyt i 25 NaClO4 0,1 25 NaClO4 0,1 25 NaClO4 0,1 20 Dioxane 50% 25 0,085 25 Dioxane 50%
o
Bng 8.6: NG DNG CA OXINE TRONG QUANG PH Ion kim loi Al Co(II) Cr(III) Ga Ga Hf In Mn(II) iu kin pH 4,5~ 11,3, tartarate, EDTA, H2O2 pH 3,3~9,9, H2O2 pH 6,0~8,0 pH 3,0 ~11,7 pH 2,9 ~3,3, 700 pH 4,5 ~ 11,3 pH>4,0 pH 9,0 ~10,5 T s ML3 ML3 ML3 ML3 ML2X ML4 ML3 ML3
max (nm) (103)
Gii hn xc nh 0,5~5 0,3~3 0,5~8 3,5~10 0,6~12 0,8~18 0,3~7
Ghi ch Khng th tch ti pH <4 Tch vi isoAmOH + CHCl3 Che Al (CN-), U (acetat) Khng tch c ti pH <6
386~390 420 420 393 600 385 395 395
6,97 9,48 7,28 6,47 19,5 22,9 6,67 10,3
Mo(VI) Nb(V) Pd(II)
pH 9,0~10,5 pH 2,8 ~10,5, EDTA, Oxalate pH 3,0~11,2
MO2L2 MO2L2 ML2
368 385 435
7,93 9,75 7,15
0,3~10 2,5~6 0,5~15
Ag, As, Bi, Cd
Nhiu nguyn t ho hc c xc nh bng trc quang vi oxine: Au, Be, Bi, Ca, Cu, Fe, Mg v nguyn t t him, nhng hp th phn t ca nhng oxit khng cao hn 6.103. Mt vn khc c cp n, oxide kim loi c tch bng chloroform.
VII.4. ZINCON
8.4.1. Danh php o{2[(2Hydroxy5sulfophenylazo)benzylidene]hydrazino}benzoic acid, 2 carboxyl2hydroxyl5sulfoformazinbenzene, 5ocarboxylphenyl)1(2hydroxy5 sulfophenyl)3phenylformazan. 8.4.2. Ngun gc v phng php tng hp: Ch th Zincon c mi ni. N c chun b bng cch: cho 2aminolphenol4 sulfomic tc dng vi nhau. 8.4.3. Cch s dng php phn tch: u tin n c gii thiu l mt thuc th (cht phn ng) nguyn th cho Cu(II) v Zn, nhng by gi n cn c s dng l mt cht ch th kim loi v c ng dng rng ri trong ngnh phn tch. 8.4.4. Tnh cht ca cht phn ng (thuc th): Thng c cung cp nh l mui mononatri (NaH3L). N l cht bt mu tm m, n ha tan nh trong nc v ethanol, d ha tan trong kim, to ra mt dung dch m, v n khng ha tan trong cc cht hu c thng thng v nhanh chng phn hy trong dung dch acid. Cu trc ha hc ca Zincon c lin quan n 1 cht l diphenylcarbazone v trong dung dch c s cn bng phn ly proton trong dung dch nc. S khc nhau mu v gi tr pKa trong qu trnh pha ch c th l do mu mu th khng trong sch. Ph hp th ca Zincon pH = 9 (HL3-) c minh hot hnh 8.6.
H2 L H3 L pKa2= 4 - 4.5 H2L2pKa2=7.9(hoac 8.3) HL3pKa3=13(hoac>14) L4-
hng hoc tm
Vng
Vng cam hoc cam
tm
8.4.5. Phn ng v tnh cht ca cc hp cht:

Zincon mu vng (H2L2-) hoc cam (HL3-) pH = 5 9 to thnh dng ML mu xanh l cc chelate tan c vi Co(II), Cu(II), Hg(II), Ni v Zn. H s hp th mol ca cc chelate Cu v Zn l qu cao (CuL, pH = 5,0 9,0, max = 600nm, = 1,9.104; ZnL pH = 8,5 9,5, max = 620nm, = 2,3.104 , chnh v vy m Zincon c xem nh mt thuc th quang cho nhng kim loi ny, ph quang hp th ca Cu(II) v Zn c minh ha hnh 8.6.
Hnh 8.6:Ph hp th ca Zincon v Cu, cc chelat ZnZincon, nng nng thuc nhum 4.0x10-3M, ti pH = 9. 1(1): Nhum; (2): chelat Zn; (3): chelat Cu.
Cu trc ca kim loi cha c lm sng t, tuy nhin c th xem Zincon nh lm mt ch th ph bin nht kt hp kim loi st vi 2 oxi (OH, COOH) v 2 Nit (N=N1NH) khng c s liu no v cng thc ha hc ngoi tr cng thc sau:
2 + HL3 + Zn 2+ ZnL + H
lgK = -1 (hoc -1,8)
8.4.6. Cch lm sch: Zincon t cc ngun cung cp thng mi c th c s dng m khng cn lm tinh khit cho cc mc ch phn tch chung. Tuy nhin, kim tra tinh khit cho cc nghin cu ha l l cn thit, cc cht bn chnh l mui v c c th ly ra bng cch s dng acid dilute acetic, cc cht bn hu c c th cho chy ngc, 8.4.7. ng dng phn tch: 8.4.7.1. S dng nh l thuc th o quang: Zincon l mt thuc th o nh sng tng i nhy cm i vi Cu(II) v c bit l Zn. iu tr ngi chnh ca Zincon l thiu tnh chn lc v tnh n nh thp ca thuc th, v vy, php o trc quang vi Zincon c ng dng vi mu th sau khi tch Zn bng dung mi tch hoc qu trnh trao i anion cc du vt ca NTA (nitrilo triacetic acid) cc mu trong mi trng nc c th c xc nh bng cch o gim ca cht ht. Nc Zn, Zincon 620nm da vo phn ng sau:
NTA + [ Zn Zincon ] [ Zn NTA ] + Zincon
(pH = 8,5 9,5)
Nu NTA thp hn 0,2ppm th c th xc nh bng phng php ny. S xc nh ng thi ca Cu, Fe, Zn trong mt mu th l c th c bi v cc nh hp th ca mi cht khng chng cho ln nhau, phng php ny c p dng cho tin trnh do nh sng chy. 8.4.7.2. Xc nh NTA trong nc thi:
Ha tan 31g boric acid v 37g KCl trong 800ml nc ct iu chnh pH trong dung dch pH = 9,2 vi NaOH 6N v pha long thnh 1000ml. Dung dch km: ha tan 0,440g ZnSO4 + H2O trong 100ml + thm HCl 2N vo bnh nh mc dung tch 1000ml v nh mc ti vch Thuc th ZnZincon: ha tan 0,130g Zincon trong 2ml NaOH 1N, vo bnh nh mc dung tch 1000ml thm 300ml dung dch m v 15ml dung dch km, nh mc ti vch. Thuc th ny nn c chun b mi hng tun khng nn dung dch lu m nn bo qun trong bng ti. - Cch tin hnh: Dng pipet ht 25ml vo cc 50ml vi mi mu chng ct v tiu chun l 5ppm NTA, thm xp x 2,5g nha cation traoi i, dng a thy tinh khuy u vo mi cc. y np bng 1 ci np thu tinh trong v khuy bng my ht chn khng khong 15 pht. mu lc qua giy lc trc khi lc v khng c ra cht kt ta. Dng pipet ht tip 15ml cht lc vo cc th 3 c dung tch 50ml, thm 35ml ZnZincon. Zincon cng c s dng nh l cht ch th kim loi trong ngh. 8.4.8. Cht phn ng khc c cu trc lin quan: Nhiu thuc nhum fozmazan c tng hp v c lng nh l thuc th phn tch, chng c cp nhiu bi bo khc nhau, nhng rt t c ng dng thc t. Mui ny c cng thc chung (1) v (2) c th c xem nh l tin thn ca thuc nhum formazan.
Mui ny thng khng mu nhng d chuyn thnh formazans c mu m cp formazan v th oxi hokh ca cp mui tetrazolium/tormazan thp v chng c th chuyn thnh cc dehydrogenase khc nhau. Do mui ny c p dng rng ri nh l mt thuc th c bit cho vic bo v v xc nh cc cht ln men khc nhau trong cc mu th sinh hc.
VII.5. XYLENOL DA CAM V METHYLTHYMOL XANH

8.5.1. Danh php: Nhng thuc th trong y c lit k bng 8.7, cng vi nhng ng phn ca n. 8.5.2. Ngun gc v phng php ca s tng hp: V mt thng mi, XO c iu ch t s s ha c Mannich 2 acid acetic, v resol vi fomaldehit. Methyl thymol xanh c iu ch t thymol xanh. 8.5.3. ng dng trong phn tch: Nhn bit nhng kim loai nh: Bi, Cd, Hg, Mn(,) Pb, Sc, Th, Zn, Zr v t him.
Nhng tnh cht ca thc th: 8.5.3.1. Xylenol da cam(XO): Nhng mu thng mi cha 2 hoc 3 mui natri, l bt tinh th ngm nc mu sm. Acid t do c th thu c nh dihidrat, n nng chy 286oC( cng l nhit phn hy). Mui kim rt d tan trong nc v tan nhanh trong ru v trong dung mi hu c khc. Nhng mu thng mi thng l hn hp ca XO v na XO vi nhng t l khc nhau (c khong 17% ca na XO). Hng s phn ly acid ca XO gin tip c c th c nhng gi tr khc nhau v ch tng i chnh xc, i khi bi v mu nghin cu khng tinh khit. Nhng gi tr c c i vi mu c lm sch th hin bng 8.8. Dung dch nc ca XO c mu vng pH < 6, mu tm pH > 6. Ph hp thu ca dung dch nc XO trong thang pH ny c minh ha hnh 8.7 8.5.3.2. Methylthymol xanh: Nhng mu mang tnh thng mi c 1 hoc 2 mui natri, n l bt tinh th mu tm sm hay en. N ngm nc v tan ngay trong nc nhng khng tan trong ru ethanol v hu ht nhng dung mi hu c. Dung dch nc c mu xanh (mu hi ch thong qua) v dung dch rt long c mu vng. Ging trng hp ca XO, nhng mu thng mi l mt hn hp methylthymol xanh v na methylthymol xanh (na thymolxanh chim khong 50%) .Hng s phn ly acid ca MTB tinh ch c tm tt trong bng 8.8. Mu ca dung dch chuyn t vng sang xanh khi n mang tnh kim, s thay i ph hp th trong dung dch theo pH c minh ha hnh 8.7, s thay i ny l do 1 hoc 2 proton c trong chnh thuc v ph thuc vo kh nng hp thu cc i ca MTB (XO) theo gi tr pH hay hidro biu din hnh 8.8. Nguyn nhn ca vic thay i ph l do complexon kt hp vi ion kim loi l hon ton tng ng bi 2 proton ca thuc th, khong pH ti u o mt quang th hn ch trong khong t 0 n 6 cho XO v MTB.
Hnh 8.7
Hnh 8.8
8.5.4. Phn ng complexon v nhng tnh cht ca complexon: Mu vng ca dung dch thuc th pH = 0, chuyn sang tm pH = 6 (XO) hay xanh (MTB) khi complexon kt hp vi ion kim loi, c th cn c vo nhng phn ng khc nhau ca chng vi thuc th.
Nhng ion kim loi m thy phn trong khong pH t 0,0 6,0 khi ch th c mu vng (xem hnh 8.9) (phn ng gia ion kimloi vi XO hay MTB thng chm v phi un nng 60 80oC, nhit ny tng ln theo t l ca chng): Ag, Al, Au. Nhng ion kim loi phn ng vi XO hay MTB trong khong pH t 0,0 6,0, nhng ch thy phn khi pH > 6 (y l khong pH tt nht cho vic xc nh mt quang): Cd, Cu, Hg(), Fe().v t him. Ion kim loi m khng phn ng vi XO hay MTB pH t 0,0 6,0, nhng li phn ng pH cao hn. Nhng ion kim loi m thuc th khng c ch cho chng bao gm: Ca, Ba, Sr, Ra. Vi trng hp l MTB, tuy nhin mu ca phn ng l do complexon cho php phn tch ch dng trong gii hn pH t 11,5 12,5 (hnh 8.8) Bng 8.8: HNG S PHN LI ACID CA XO V MTB Thuc th XO(H9L3+) MTB (H9L3+) N a XO(H6L2+) N a MTB(H4L2 + ) MXB (H9L3+) Nhm chc 1 -1,74 -1,76 -0,65 <-2,8 SO3 H 2 -1,09 -1,11 0,53 -1,90
OH
3 0,7 6 0,7 8 <1, 5 2,0 0,0 8
4 1,1 5 1,1 3 2,0
pKa 5 2,5 8 2,6 0 2,6 0 2,8 1 3,4
6 3,2 3 3,2 4 4,3
7 6,40 7,2 7,47 7,6 7,00

OH
8 10, 5 11, 2 10, 9 12, 1 10, 6
9 12, 6 13, 4 12, 5
iu kin =0,2 (NO3-) =0,2 (NO3-) 25o,=1 (KNO3) 25o,=1 (KNO3) 25o,=0, 2
COOH
NH
Bng 8.9: HNG S PHN BN IU KIN CA CC CHELATE Ion kim loi Al Ca Co(II) Cd Cr(III) Fe(III) Hg(II) Mg Mn(II) Mo(IV) Pb Ru(III) Se(III) Th(IV) Zn XO logKML 14,3 3,78 6,78 3,57 3,91 3,23 17,0 9,6 5,95 11,6 MTB pH logKML 2,3 5,5 5,5 3,3 5,9 1,7 HClO40,15N 13,4 5,2 5,9 8,0 3,6 6,4 4,0 2,6 4,0 5,5 pH 10 5,5 5,5 10 10 5,5 5,5
t him
6,3 6,6
4,9
5,5
VII.6. ASENAZO I V MONOAZO DERIVATIVES OF PHENYL ARSONIC ACID

C16H11O11S2Na2As KLPT = 592,29
H2O3As OH OH N N
NaO3S
SO3Na
8.6.1. Danh php: 2(4,5Dihydroxy2,7disulfo3naphthylazo) Neothorin, Neothoion, Uranon. 8.6.2. Ngun gc v phng php tng hp: Trong k thut thng ph bin l mui dinatri. N c tng hp bng s kt ni ca acid 2aminophenularsonic c diazo ho vi acid chromotropic. 8.6.3. ng dng: c s dng nh mt thuc th trc quang cho cc nguyn t: Al, Be, In, Th, Zr, cc nguyn t t him v cc nguyn t actinoid. N cng c s dng nh mt ch th kim loi trong chun chelate ca Ca, Mg, cc nguyn t t him v Th; ng thi n cng l mt ch th trong php chun kt ta. 8.6.4. Tnh cht thuc th: Mui hai natri l mt tinh th dng bt mu sm, d tan trong nc to thnh dung dch c mu cam (max = 500nm pH = 1 8) v kh tan trong hu ht cc dung mi hu c. Hng s acid pKa1 = 0,6; pKa2 = 0,8; pKa3 = 3,5; pKa4 = 8,2; pKa5 = 11,6; pKa6 = 15 (u = 0,1; 20oC). 8.6.5. Phn ng to phc v tnh cht ca phc: Arsenazo(I) phn ng vi nhiu loi ion kim loi to thnh cc cht mu chelate trong dy pH t 1 8. Nhng phn ng xy ra trong dung dch kh acid l nhng thc t quan trng bi tnh chn lc cao hn ca phn ng. Cc phn ng mu xy ra trong dung dch acid chlorhydric (HCl) l: Nb (III), Ti (III), Zr (mu tm), Sn (IV), U, cc nguyn t t him ( cam), Th (xanh tm) v Ta (III) ( tm). Thuc th thng kt hp theo t l 1:1 vi chelate, chng hn nh biu din bn di:
HO AsO3OH
phenylarsonic
acid,
mui
dinatri,
Sc
N H N
Hng s bn ca chelate vi cc ion kim th v La c trnh by nh sau: logKML vi Mg = 5,58; Ca = 5,09; Sr = 4,41; Ba = 4,15 ( = 0,1 KNO3; 25oC) v logKMH2L vi La = 28,8. hp thu quang ph ca cc chelate kim loi trong dung dch nc th ph thuc vo pH. ng cong ca php o quang trn mt dy LaArsenazo I ti cc gi tr pH khc nhau c minh ha trong bng 8.11 l mt v d. Hng s hp th mol ca cc chelate th c s dng tt nng 104, v chng hn nh cc phn ng mu c th c dng cho vic xc nh trc quang hm lng vt cc nguyn t. Cc chelate kim loi th khng mang in tch v c th c chit ra nh mt cp ion vi mt cation ln chng hn nh diphenylguanidinium 8.6.6. S tinh ch v tinh khit ca thuc th: Ansenazo I t cc ngun k thut cung cp thng khng tinh khit mc d chng c th theo nhu cu s dng cho cc mc ch chung nh l mt ch th kim loi. Tuy nhin chng phi c tinh ch s dng cho mc ch ho l. Thuc th ny c th c tinh ch bng cch nh chm dung dch nc ca thuc th vo trong cng mt th tch acid chlorhydric m c kt ta cc tinh th vng cam, em lc ton b kt ta, ra sch bng acetonilite, sy kh 100oC trong 2 gi. Vic tinh ch thuc th c th c xc nh bng cch o hp thu ca dung dch nc ca thuc th bit trc nng . 8.6.7. Cc ng dng phn tch: 8.6.7.1. S dng nh mt thuc th trc quang: Arsenazo(I) c s dng trong cc php o trc quang cc ion kim loi trong dung dch nc v trong php o chit trc quang ca mt cp ion vi ion diphenylguanidinum. Tuy nhin khi cc thuc th loi disenazon(III) cm quang hn, cc thuc th Arsenazon(I) by gi c thay th bng cc thuc th hin ti. Cc v d in hnh vi Arsenazon(I) c tm tt trong bng 8.11. ng dng quan trng thc t ca Arsenazon(I) l c th xc nh c Th trong nhiu loi mu mc d b cc nguyn t Nb, Sn, Ta, Ti cn tr v nh hng ca Zr th rt ng k. 8.6.7.2. S dng nh mt ch th kim loi: Arsenazon(I) c xem nh l mt ch th kim loi trong chun phc cht ca Ca, Mg (pH = 10), Th (pH=1,3 3) v cc nguyn t t him (pH = 5,5 6,5). Mu sc ti im cui ca php chun trc tip chuyn t mu tm sang mu cam hoc cam. N cng c s dng nh mt ch th trong chun kt ta gc SO42- vi dung dch chun BaCl2 (mu chuyn t cam sang tm) nhng dimethylsulfonazo(III) c bit l mt ch th tt nht. 8.6.7.3. Cc dn xut khc ca thuc th acid phenylarsonic: Thorin: 2(2Hydroxy3,6disulfo1naphtylaminlazo) benzennearsonic acid, mui dinatri, Thoron, Thoronol, Naphtharson, Naphthazarin, APANS, APNS.
AsO3H2
HO
SO3Na
SO3Na
Cc nguyn liu t cc k thut cung cp l mui Na1Na5, tinh th dng bt, mui Na1 ( cam), mui Na5 ( a, ri). N d tan trong nc nhng li khng tan trong cc dung mi hu c ph bin. Dung dch nc c mu vng cam trong mi trng acid (max = 510nm, = 1,4.104 ti pH = 1) v mu cam trong mi trng kim(max = 490nm, = 1,4.104 ti pH = 9 10 ) v c mu trong mi trng acid sunfuric m c, pKa3 = 3,7; pKa4 = 8,4 (AsO(OH)2), v pKa5 = 11,8 (OH). N to thnh cc chelate c mu trong dung dch acid 0,1N vi Bi (trong dung dch HClO4 0,02 0,04N max = 535nm, = 9,5.103), Th (pH = 0,5 1,5; ML2 max = 545nm) U(VI) (pH = 3 4; ML2 max = 545nm), Zr v Hf (trong HCl; max = 555nm) v Pu (IV) (trong HCl; 0,05 0,25N; max = 540nm) cc phn ng th c chn lc cm quang kh cao vi cc kim loi ny. Thorin cng c s dng trong vic xc nh bng trc quang ca kim loi khc vng pH cao hn d cc phn ng khng c tnh chn lc cm quang cao; Be (pH = 10, max = 486nm); Rh (III) (pH = 4; gia nhit trong 70 giy; max = 550nm) v cho vic xc nh gin tip fluoride qua chelate Zr. Thorin c th c s dng nh mt ch th kim loi trong php chun chelate ca Bi v Th (pH = 1 3), ti im cui mu dung dch chuyn t sang vng.V n cng c s dng nh mt ch th trong chun U (VI) pH = 2,5 bng acid oxalic. Rezarson: 2,2,4Trihydroxy3arsono5chloroazobenzene. C12H10N2O6AsCl KLPT = 388,60
OH H2O3As N N
HO
Cl
Rezarson to phc mu theo t l 1:1 vi nhiu kim loi, bao gm Cu, Ga, Ge, Ni, Pd v Sn trong nc acid trong bnh vi methanol t 50 70 %. N c ngh nh mt thuc th trong php o trc quang cho Ge v Sn (trong dd HCl, max = 510nm). Bng 8.11: NG DNG CA ARSENAZO I NH L THUC TH TRC QUANG Ion kim iu kin max (nm) (x103) Dy xc nh hng
loi B Be Ca Ce(III) Ga In La Pd(II) Pd(II) Ru(III) Sc Ta Th Ti U(VI) Y H2SO4, 35o, 15 pht pH 11 ~ 12 pH 9,6; GEDTA HCl 0,02N NH2OH.HCl pH 3 ~ 3,5 pH 5,6 ~ 6,2 pH 7 pH 2 pH 12 pH 6 pH 6,1 ~ 6,3 pH 1 ~ 2 pH 1 pH 2,5 ~ 3 pH 3 ~ 7 pH 6 635 580 580 253 550 580 570 565 585 580 570 580 546 580 600 560 6,4 10,0 7,6 58,2 27,5 11,5 14,5 17,0 23 21,2 43,8
nh (ppm) 0~1 0~ 0,15 4~ 0,4 ~ 5,6 2 ~ 10 1~2 1,0 ~ 10,6 0,64 ~ 6,4 1~7 ~ 2,0 0,01 ~ 0,8 0,5 ~ 5 0,1 ~ 2,5 0,2 ~ 1,6 0,2 ~ 5,7 K, Na, NH4 khng nh hng. Tng ca Ca + Mg trong dung dch. La, Fe (cn bng mol) Ce(IV), Cu, Fe, Tl(III),UO22+ nh hng. Cu, Fe(III), Pb, U, Zn, PO43-, tactrac nh hng. Fe(III), U(VI) phi b che. Cr(III), Cu(III), Fe, La, Ru, Y, oxalate, citrate, EDTA, CyDTA nh hng. Nhiu kim loi khc, citrate, oxalate EDTA nh hng. EDTA nh hng. Sau khi tch chit cc kim loi nh hng bng TTA hoc oxine Ti khng nh hng. Ce(IV), F-,SO42-, nh hng. Al, Fe(III), Th, Zn khng nh hng.
VII.7. EDTA V CC COMPLEXONE KHC

8.7.1. Danh php: Nhng thuc nm trong phn ny c lit k trong bng 8.12, cng vi nhng tn gi ca chng. 8.7.2. Ngun gc v phng php ca s tng hp: Tt c u c th mua v c chun b bi s methyl ho cacboxyl tng ng vi polyamine, cng do s ngng t kim ca acid haloacetic hoc bng phn ng trung ho Strecker vi KCN v HCHO (formaldehyde). 8.7.3. ng dng phn tch: EDTA hu nh dnh ring s dng nh mt dung dch chun trong chun phc cht. EDTA v cc complexon khc cng c s dng nh nhng tc nhn che trong nhng trng hp khc ca ho hc phn tch. 8.7.4. Nhng tnh cht ca cc thuc th:
Acid t do ca EDTA l bt tinh th c mu trng v hu nh khng tan trong nc (xp x khong 0,009g/l pH = 1,6) cng nh trong cc dung mi hu c. N tan trong acid v c hoc trong cc dung dch kim. Cc mu cha mt thuc th phn tch EDTA thng l mt dihydrate, mui dinatri ca EDTA (Na2H2L.2H2O), m n c th c tinh ch mt cch d dng bng s kt tinh t nc (11,1g/100g 20oC; 27,0g/100g 98oC) v thnh 99,5% tinh khit sau khi sy 80oC. Sy 100oC hoc cao hn dn n kt qu mt mt phn nc hydrated. Cc thuc th loi complexon, c hnh dng ca acid t do, l bt tinh th trng v rt t tan trong nc, cc dung mi hu c thng thng v tan nhiu hn khi kim ca dung dch tng. Do cc thuc th c tnh lng tnh t nhin, chng cng tan trong acid v c. Hng s phn ly tng nc ca cc thuc th c tng kt trong bng 8.13. Ging nh cc acid amino khc, cc complexon tn ti nh ion lng tnh. 8.7.5. Cc phn ng to phc v cc tnh cht ca phc: Cc thuc th loi complexon t bn v tan chelate vi mt gii hn rng ca cc ion kim loi, loi tr kim v mt s ion kim loi ho tr 1 khc. c tnh khc l kh nng chelating ph thuc vo bn pH. T l phi t vi kim loi l 1:1, ngoi tr TTHA v NTA. Nhng iu ny tr thnh nn tng cho vic s dng complexanes, c bit l EDTA, nh mt dung dch chun trong vic chun phc cht v nh mt tc nhn che trong cc phm vi a dng nh ho hc phn tch. Cu trc ca kim loiEDTA chelate c l c minh ho mt cch ring bit pha di cho 4 s phi tr ca cc ion kim loi, (a) v (b). Cc hng s n nh chelate ca cc thuc th ny c tng kt trong bng 8.13. i vi cht chelate, EDTA c s dng rng ri nht, bi ga c tng i thp ca thuc th, n ang c sn xut rng ri cho ngnh cng nghip tiu dng. Bng 8.12: EDTA V CC COMPLEXON KHC Complexane EDTA Cng thc ho hc
HOOCCH2 HOOCCH2 NCH2CH2N CH2COOH CH2COOH
CH2COOH CH2COOH CH2COOH CH2COOH
CyDTA
H N HOOCH2C HOOCH2C
GEDTA
NCH2CH2OCH2CH2OCH2CH2N
CH2COOH CH2COOH
HOOCH2C
DTPA
HOOCH2C HOOCH2C
NCH2CH2NCH2CH2N
CH2COOH
CH2COOH CH2COOH CH2COOH
TTHA
HOOCH2C HOOCH C 2
NCH2CH2NCH2CH2NCH2CH2N
CH2COOH CH2COOH
HEDTA
HOCH2CH2 HOOCCH2
NCH2CH2N
CH2COOH CH2COOH
NTA
CH2COOH N CH2COOH CH2COOH
Bng 8.13: HNG S PHN LY V HNG S BN CHELATE CA CC COMPLEXON CHN LC EDTA CyDTA GEDTA DTPA (1) (2) (3) (4) 1,99 2,43 2,00 2,08 2,67 3,52 2,65 2,41 6,16 6,12 8,85 4,26 10,26 11,70 9,46 8,60 10,55 logKML 7,32 8,15 6,88 8,70 16,13 18,63 13,90 18,4 7,76 8,64 8,41 8,63 27,9 31,2 23,8 29,7 10,96 12,50 11,00 10,74 16,46 19,23 16,70 19,31 15,98 16,76 15,70 20,50 16,31 18,92 12,50 18,4 23,40 2,54 18,80 21,3 17,8 21,53 18,30 19,69 17,42 22,82 18,38 20,20 17,40 22,74 17,35 18,77 17,10 22,30 14,33 16,27 11,92 16,50 25,1 28,05 20,5 28,6 20,27 22,91 23,0 17,0 18,80 16,94 22,46 29,5 35,40 21,8 24,30 23,12 27,0 18,05 19,89 17,38 22,78 24,95 28,74 29,0 15,50 16,75 15,79 19,48 2,79 4,13 1,17 19,65 20,91 17,81 22,44 8,69 10,32 5,21 9,3 14,04 16,78 12,3 15,50 1,66 2,70 1,38 16,61 17,69 16,28 21,60 18,62 19,4 13,55 20,32
pKa1 pKa2 pKa3 pKa4 pKa5 pKa6 Ag Al Ba Bi Ca Cd Ce(III) Co(II) Cr(III) Cu(II) Dy Er Eu Fe(II) Fe(III) Ga Gd Hf Hg(II) Ho In La Li Lu Mg Mn(II) Na Nd Ni
TTHA (5) 2,42 2,95 4,16 6,16 9,40 10,19 8,67(13,89) 19,7(28,9) 8,22(11,63) 10,06(14,16) 18,65(26,85) 17,1(28,8) 19,2(32,6) 23,29 23,19(26,92) 23,85 17,1 26,8(40,5) 23,83 19,08 26,8(39,1) 23,58 22,22(25,62) 8,10(14,38) 14,65(21,19) 22,82(26,75) 18,1(32,4)
HEDTA NTA (6) (7) 2,51 1,89 5,31 2,49 9,86 9,73 6,71 12,43 5,54 21,8 8,14 13,6 14,11 14,4 17,55 15,30 15,42 15,35 12,2 19,8 16,9 15,22 20,1 15,32 17,16 13,46 15,88 7,0 10,7 14,86 17,0 5,16 9,5 4,83 6,41 9,54 10,83 10,38 >10 12,96 11,74 12,03 11,52 8,84 15,87 13,6 11,54 20,34 14,6 11,90 16,9 10,36 2,51 12,49 5,46 7,44 2,15 11,26 11,54
Pb Pr Sc Sm Sn(II) Sr Tb Th TiO2+ Tl(III) Tm UO22+ VO2+ Y Yb Zn Zr
18,04 16,40 23,1 16,7 18,3 8,63 17,81 23,2 17,3 22,5 18,62 25,6 18,77 18,09 18,88 16,50 29,9
19,68 17,23 25,4 18,63 10,54 19,30 29,25 19,9 38,3 20,46 26,9 19,40 19,41 20,80 18,67 20,74
14,71 16,05 16,88 23,85 8,50 17,27 17,48 16,82 17,78 14,5
18,80 21,07 22,34 9,68 22,71 28,78 48,0 22,72 22,05 22,62 18,75 36,9
17,1(28,1) 23,45 23,81 9,26(12,70) 23,61 31,9 23,58 16,65(28,7) 19,74
15,5 14,61 15,28 6,92 15,32 18,5 15,59 14,65 15,88 14,5
11,39 11,07 12,7 11,53 4,98 11,59 12,4 12,3 18 12,2 9,56 11,48 12,40 10,67 20,8
Cc gi tr ca cc kim loi khc; logKML cho Be(9,27); Cs(0,15); K(0,96); Nb(40,78); Pd(II) (18,5) v Sb(III) (24,8). Cc gi tr ngoc n biu din log ML. Cc gi tr pKa c quan st gi tr trung bnh ca = 0,1 (KCl hoc KNO3) 20oC, tr TTHA 25oC. Cc gi tr logKML c quan st, hu ht cc trng hp, gi tr trung bnh ca = 0,1 (KCl, KNO3 hoc NaClO4) 20 25oC. Cc gi tr cho U(IV). Cc complexane khc EDTA v NTA th t, vic s dng chng ch gii hn trong ho hc phn tch v cc mc ch nghin cu khc. CyDTA to thnh chelate kim loi bn hn so vi EDTA, t CyDTA c tin c nh mt tc nhn che m ion kim loi khng th c che mt cch c hiu qu vi EDTA. GEDTA c bit nhn bit Ca hn l Mg ( logKCaMg = 5,79) v Cd hn l Zn ( logKCdZn = 2,2) trong vic so snh vi c ch to phc ca EDTA. ( logKCaMg = 1,9; logKCd Zn 0). Theo , GEDTA c s dng nh mt dung dch chun chn lc cho Ca v Cd. DTPA v TTHA c du hiu nh nhng phi t octadentate v decadentate, to thnh chelate bn hn EDTA, vi cc ion kim loi c 8 phi t hoc cao hn, v kt qu cc chelate c tnh bn hn i vi s thu phn. Trong cc trng hp ca TTHA, n cng to thnh M2L dng chelate vi Cu(II), Sn(II) (pH t 3 n 4), Al, Cd, Co (II), Ga, Hg(II), Ni, Pb, Ti (vI H2O2), Zn (pH t 5 6), Mg v Zn (pH t 9 10). S tng phn gia Fe(III)EDTA chelate, Fe(III)HEDTA chelate l tnh bn i vi s thu phn trong dung dch kim n da, v th n c xem nh mt tc nhn che cho Fe(III) trong dung dch kim mnh. NTA c xu hng nh mt phi t bn nh, hnh dng cc chelate t bn hn EDTA. S tn ti lng d ca NTA, n hnh thnh ML dng cng nh ML2 chelate.NTA c
s dng nh mt tc nhn che c hiu qu che cao hn so vi EDTA v CyDTA khng c nh mong mun. 8.7.6. S tinh ch v tinh khit ca cc thuc th: Acid t do ca cc complexon c th c tinh ch bng vic ho tan n trong dung dch kim NaOH, theo s kt ta ca acid t do vi phn thm vo ca acid sunfuric pha long n pH = 1 2. Kt ta trng c lc v ra bng nc lnh cho n khi phn nc lc l dung dch cha gc sunfat t do. Disodium EDTA (Na2H2L.2H2O) c th c tinh ch bi s kt tinh t nc nng. Phng php tip theo cng c gii thiu thu c mu tinh khit. Ho tan 10g mu nguyn liu (th) vo trong 100ml nc v thm t t C2H5OH vo dung dch ny cho n khi n chuyn sang c. Sau khi lc dung dch, thm mt lng C2H5OH c th tch bng vi th tch phn nc lc kt ta mui tinh khit. Lc mui bng phu, ra bng acetone, tip n l ether. Sau lm kh mui trong khng kh sut m, sy n 80oC trong 4 gi. Thng thng tinh khit ca cc complexon c xc nh bng vic chun dung dch Zn tiu chun (ch th XO pH = 5) hoc Cu(II) (ch th PAN pH t 4 5) vi dung dch complexon bit trc nng . 8.7.7. Cc ng dng trong phn tch: 8.7.7.1. S dng nh mt dung dch chun in Chelatometry: Php tnh h s t lng trong chelatometry c th c vit dng sau: Mn+ + H2L2- ' MLn4 + 2H+ EDTA l complexon c s dng rng ri nht trong chelatometry, v dung dch tiu chun ca EDTA 0,01M (3,72g Na2H2L.2H2O/l) c gii thiu cho cc kt qu tng qut. Cc phng php c th cho vic xc nh mi nguyn t c tm thy trong cc dng th chelatometry. Tuy nhin, biu 1 c dng trong vic tm ra iu kin thch hp cho s chun v bn cht ca cc ch th kim loi nhn c cc kt qu tt. Cc ion v c v hp cht hu c cng c th c xc nh gin tip bng phc cht. 8.7.7.2. S dng nh mt tc nhn che: Gii hn ca cc ng dng ca complexane nh nhng tc nhn che trong cc phn ng phn tch rt rng m iu khng thch hp tho lun trong tng v d c th. Tuy nhin, bng 8.14 tm tt mt vi v d trong vic s dng EDTA nh mt tc nhn che. Nhng s khc nhau ca cc tnh cht che gia EDTA v CyDTA tri vi phn ng to phc vi cyanua c trnh by trong bng 8.15 nh mu khc. xut chi tit trong vic s dng ca cc complexane nh mt tc nhn che c tm thy trong mt s th khc. Bng 8.14: MT VI V D TRONG VIC S DNG EDTA NH MT TC NHN CHE Phn ng che Fe, Co v Ni vi Natridiethyldithiocarbamate. Fe(III), V(V) vi Tiron Fe, Co, Cu, Ni v Cr vi 2-nitroso1 naphthol Al, Cd, Cr, Cu, Ga, Hg, In, Pb, V, Zr
ng dng Chit trc quang Cu v Bi Php xc nh trc quang Ti Php xc nh trc quang Pd Php xc nh trc quang Ni
(pH = 8,6 10) Php xc nh trc quang Be Bi, Cd v Cr vI Beryllon IV (pH = 7 8) Php xc nh trc quang Fe(II), Ce, Co, La, Mg, Mo, Nd v Pb vi XO Al (pH = 3 3,8) Mo(V) vi 8 hydroxyquinoline Chit U, W(VI) (pH = 2 3)
V t him vi PAR
MT S GII HN CA pH CN LU TRONG QU TRNH CHUN
Gii hn pH v ch th kim loi c xut cho vic chun cc ion kim loi thng thng, gii hn pH m ion kim loi chun c, gii hn pH m ch th ph hp c th dng c, gii hn pH m phc ph c s dng lm cn tr s thu phn ca cc ion kim loi. 8.7.8. Cc ch vit tt ca cc ch th kim loi: BG: BPR: BT: GCR: GTB: HNB: MTB: MX: NN: Bindschedlars Green Bromopyrogallol Red Eriochrome BlackT Glycine cresol Red Glycinethymol Blue Hydroxynaphthol Blue Methylthymol Blue Murexide Calcon carboxylic acid PAN: Pyridylazonaphthol PAR: Pyridylazorescocinol PC: PV: Phthalein Complexon Pyrogallol Red Pyrochatecol Violet
CuPAN: CuEDTA + PAN mixture PR:
TAN: Thiaolylazonaphthol TAR: Thiaolylazoresorcinol TPC: Thylmolphtalein Complexon VBB: Variamine BlueB XO: Xylenol Orange
(Patton and Reeders dye) Bng 8.15: PHN NG CA KCN VI EDTA V CYDTACHELATE KIM LOI Kh nng phn ng ca KCN vi Ion kim loi EDTA chelate CyDTA chelate Hg(II) Phn ng tc thi Phn ng tc thi Cu(II) Phn ng tc thi Phn ng tc thi Pb Khng phn ng Khng phn ng Bi Khng phn ng Khng phn ng Cd Phn ng tc thi Hu nh khng phn ng Ni Phn ng Khng phn ng Co(II) Phn ng Phn ng chm Mn(II) Khng phn ng Khng phn ng Co(III) Khng phn ng Khng phn ng Zn Phn ng nhanh Phn ng kh nhanh Fe(II) Phn ng Phn ng chm Fe(III) Phn ng Khng phn ng
VII.8. HP CHT DIHYDROXYARYLAZO

HP CHT DIHYDROXYARYLAZO
OH HO3S N N
OH
HO3S
OH N N
HO
COOH
O2N
H3L (1)
OH HO N N CH3
H4L (2)
OH NaO3S N N HO SO3Na
HO3S
H3L (3) 8.8.1. ng phn :
H5L (4)
SO3Na
Nhng hp cht azo cng vi ng phn v cng thc phn t c cp trong chng ny lit k bng 8.16. 8.8.2. Ngun v phng php tng hp: Cc hp cht trn u c sn trn th trng. Nhng loi thuc nhum azo ny c tng hp bi cng on chun mc ca phn ng lin hip azo. Chng c gi t cc tn tng ng sau : (1) diazo ha 1amino6nitro2naphthol4sulfonic acid v 1naphthol, (2),(3) v (4) t diazotized 1amino2naphthol4sulfonic acid v 2hydroxynaphthoic acid, p cresol, 2naphthol3, 6disulfonic acid, tch bit. 8.8.3. Cc ng dng phn tch : Cc thuc nhum azo loi ny c dng rng ri nh l cht ch th kim loi trong phng php chelate, c bit cho php chun EDTA ca cc kim loi kim th. Chng thnh thong c dng nh l thuc th trc quang cho canxi v magie trong dung dch nc hoc sau khi chit vo trong dung mi khng c tnh trn ln. 8.8.4. c tnh ca thuc th. Eriochrome Black T (1) lun c cung cp dng mui ca natri dng bt mu tm m c nh kim loi m nht, d tan trong nc v ru, khng tan trong dung mi hu c thng thng. Dung dch nc c mu pH < 6, mu xanh pH = 7 11 v mu cam pH =12. Trong dung dch kim d b oxy ha tr thnh khng mu pKa (H2L-) = 6,3 v pKa (HL2-) = 11,55( = 0,08 ~ 0,008; 18 ~ 200) (2) thng c cung cp dng acid t do c dng bt mu m, tan nh trong nc v ru to ra dung dch mu hng pH < 8. N s chuyn qua mu xanh pH = 10-13 v mu hng nht trong dung dch kim mnh pKa (H2L2-) = 9,26 v (HL3-) = 13,67( = 0,01 KCl; 24oC).
Calgamite (3) cng thng c cung cp dng t do, dng bt mu tm m, d tan trong nc cho dung dch mu ti pH < 7. N s chuyn qua mu xanh pH = 9,1 11,4 v mu cam nh pH > 13. Cc thuc nhum c lit k bng 8.16 hu ht n nh trong dung dch nc, pKa (HL2-) = 7,92 v pKa (HL2-) = 12,50 ( = 0,1; KNO3; 25oC). Hydroxynaphthol Blue (4) c cung cp dng mui III ca natri, dng bt ht m mu tm m, d tan trong nc v ru cho dung dch mu tm pH < 6 n s chuyn qua dung dch mu xanh pH = 7 12 v mu hng pH > 13, pKa (H2L3-) = 6,44 v pKa (HL4-) = 12,9 (= 0,1; KCl, 24oC) Bng 8.16 DIHYDROXYLAZO HP CHT Thuc th Tn ng phn 1(Hydroxy2 naphthylazo)6nitro 2naphthol4sulfonic acid, mui mononatri; Solochrome Black T, Mordant Black 11, C.I. 14645, Erio T, EBT, BT 2Hydroxy1(2hydroxyl4sulfo1 naphthylazo)3naphtoic acid PatTon v Reeders dye Cal , HSN, NANA, HHSNNA, NN 1(1Hydroxy4methyl2 phenylazo)2naphthol4sulfonic acid 1(1Hydroxy4sulfo1 naphthylazo)2naphthol3,6disulfonic acid, mui trinatri, HNB Cng thc phn t v KLPT C20H12O7N3SNa, 461,41
(1)
Eriochrome Black Cancol carboxylic acid Calmagite Hydroxynaph thol Blue
(2) (3) (4)
C21H14N2O7S, 438,41 C17H14N2O5S, 358,37 C20H11N2O11S3Na3 620,46
8.8.5. Phn ng to phc cht v c tnh ca phc cht: Khi s th hin ca nhng ion kim loi hn nhng kim loi kim loi tnh mu xanh ca thuc nhum s chuyn qua nh trong dung dch nc v cc phn ng mu nh vy c tn dng trong php trc quang cho cc ion kim loi hoc trong phng php chelate nh l nhng cht ch th kim loi. Bng 8.17: PHN NG MU CA ERICHROME BLACK T VI ION KIM LOI TI pH 9 Ion kim loi None Al Bi Ca Cd Ce(III) Co(II) Cr(III) Cu(II) Fe(III) Mu Xanh dng Hi Xm Xanh Xm Xanh Hi Xm Xanh Hi Nu ppt Ion kim loi Mu Mg Mn(II) Nd Ni Os(VIII) Hng Pt(IV) Xm Xanh Th U(VI) Xm Xanh V(V) ti W(VI) Xanh dng
Hg(II) La
Xm Xanh dng Hng m
Zn
Phn ng mu ca (1) vi cc ion kim loi khc nhau c xem xt chi tit v tm tt li trong bng 8.17. S thay i cu trc ca thuc th i km theo phn ng mu c ch ra s lc di y. Hng s bn ca thuc nhum vi nhiu ion kim loi c xc nh hu ht bng phng php ph quang k. Nhng gi tr c tm tt trong bng 8.18. Hng s bn c iu kin (logKML) ca (1), (3) v (4) pH 10 l cc bo co nh sau: (1); Ca (3,8); Mg (5,4) ; (3); Ca (3,67); Mg (5,69); (4), Be 3,36); Mg (3,43); Ca (2,82); Sr (2,05); Ba (1,75); La (3,75); Pr (4,03); Nd (4,13); Sm (4,09); Eu (4,10); Ga (3,76); Tb (3,77); Dy (3,71); Ho (3,68); Er (3,60); Yb (3,50); UO22+ (4,10 hoc 3,99). Ph hp th ca mt vi phc chelate kim loi i din minh ha cc hnh 8.9, 8.10, 8.11, 8.12 v 8.13. Cc cht chelate mu c th hin c chit trong dung mi hu c phn cc nh l namyl alcohol cho php trc quang n sau.
3 Molar Absorptivity ( x10 )
4
Hnh 8.9: Ph hp th ca Black T(1) v phc Mg trong nc (1) pH 5 (H2L-) (2) pH 8 (HL2-) (3) pH 13 (L3-) (4) pH 10 (MgL-)
0.6
Absorbance
0.4
3 0.2 0 400
500 Wavelength (nm)
600
700
Hnh 8.10: Ph hp th ca acid Calcon carboxylic (2) vi chelate Ca trong nc (1) pH 3,7 (H2L2-) (2) pH 9,9 (HL3-) Ch th nng 9,1.10-5M (3) pH 13 (CaL2-)
Hnh 8.11: Ph hp th ca Calmagite (3) trong nc (1) pH 2,14 (H2L-) (2) pH 10,29 (HL2-) Nng ch th 9,1.10-5M (3) pH 13,8 (L3-)
Hnh 8.12: Ph hp th ca Hydroxylnaphthol Blue v chelate Ca trong nc (1) pH 3,3 (H2L3-) (2) pH 9,8 (HL4-) (3) pH 13,8 (L5-); pH 13 (CaL3-) Nng ch th 2,4.10-5M
Hnh 8.13: Ph hp th ca chelate Ca v Mg vi Calmagite pH 10 (1) Ca bo ha (2) Mg bo ha Nng ch th 3,5.10-5M V d: ph hp th ca Eriochrome Black T(1) v chelate ca Mg c trong namyl alcohol c ch ra hnh 8.14. Chelate mang in tch m (anion) c th c chit ra vi chui di ion amoni th hin 4 ln nh l Zephiramine hoc Aliquat 336S vo trong dung mi hu c nh : Bng 8.18: HNG S BN PHC CA DIHYDROXYLAZO Log KML Thuc th Ca Ba Mg Mn(II) Zn (1) 5,4 3,0 7,0 9,6 12,9 (2) 5,85 (3) 6,1 8,1 12,52 (4) 6,11 7,11 Log KML2
Mn(II) Zn iu kin Ref. 8,0 7,1 M2 6 24o, =0,1(KCl) 7,71 24o, =0,1(KCl) 4, 9 24o, =0,1(KCl) 6, 10
4 1
500
600 Wavelength (nm)
700
Hnh 8.14: Ph hp th ca Eriochrome Black T v chelate Mg trong namyl alcohol (1) trong namyl alcohol (2) trong namyl alcohol, lc vi dung dch khng cha Mg, pH 11,5 (3) lc vi dung dch cha 0,1ppm Mg, pH 11,5 (4) lc vi dung dch cha 0,2ppm Mg, pH 11,5 8.8.6. S tinh ch v tinh khit ca thuc th: Cc mu thng mi (trn th trng) l tinh khit cho vic s dng nh l mt cht ch th kim loi trong phng php chelate. Tuy nhin chng cng cha mt lng c bn mui hu c v phi c tinh ch khi em s dng trong cc nghin cu v ha l. (1) c tinh ch bi mui ptoluidinium ca n, l thuc nhum trong dung dch methanol m 20% c x l vi ptoluidine kt ta mui toluidinium sau khi lm lnh m cui cng c kt tinh li t nc nng (3) c th c tinh ch bi vic chit t mu kho vi anhydrous ether . (4) c tinh ch bi php sc k trn ct bt cellulose vi propanolethyl acetatenc (5 + 5 + 4) nh l mt cht tch theo cc cng on sau. Mu th c x l vi ethanol nng loi b cc cht khng tinh khit, sau ha tan trong dung dch methanol 20%, ri cho qua php sc k. Phn vng tm pha trn cao c tch na cha thuc nhum tinh khit dng kt ta ca mui natri trihydate do vic thm HCl m c vo cht tch m c. 8.8.7. Cc ng dng trong phn tch: 8.8.7.1. S dng nh l mt thuc th trc quang: Thuc nhum azo ca loi ny c dng rng ri nh l cc thuc th trc quang cho cc ion kim loi khc nhau. Mc d hu ht cc cng on trc quang c thc hin trong
h thng c nc, cc cht chelate mu vn c th c chit vo trong ru cao hn nh ru izoamyl. Tng t chng c th c chit vo cc cht chlor ha nh l chloroform hoc 1,2dichloroethane nh l mt cp ion vi chui di ion amoni thay 4 ln. Cc v d v ng dng phm nhum azo nh l thuc th trc quang c tm tt trong bng 8.19. 8.8.7.2. S dng nh l cht ch th kim loi. Cc thuc nhum azo ny c s dng nh l cht ch th kim loi trong phng php chelate. Hng s phn ly ca proton cui cng trong (2) v (4) l cao qu n ni s thay i mu vi Ca c quan st ti vng pH cao hn ( 12 13) mi Mg kt ta dng Mg(OH)2. V vy chng c xem l cht ch th Ca chn lc trong s hin din ca Mg. iu kin chun vi cc thuc nhum ny nh sau: S chun vi: Eriochome Black T (1) (t mu sang mu xanh ti im kt thc), Ca, Mg, Cd, Zn (pH 10, NH3), Ba, Sr (pH 10, NH3, MgEDTA), Hg(II), In, Pb, t him (pH 8 ti 10),NH3, tartarate, 100oC), Co(II), Ni(pH 10, NH3, MnEDTA), Mn(II) (pH 8 ti 10, ascobic acid, 80oC), Sc( pH 7,5 ti 8; NH3; malic acid; 1000), VO2+ (pH 10, NH3, Mn EDTA, ascorbic acid); chun vi Calcon carboxylic acid (2) (t sang xanh), Ca (pH 12 n 13, KOH); chun vi Calmagite (3) (t sang xanh), Ca, Mg( pH 10, NH3); chun vi hydroxynaphthol Blue (4) (t sang xanh), Ca (pH 10 ti 13, KOH) v Mg (pH 10, NH3). 8.8.8. Cc thuc th c cu trc tng t. 8.8.8.1. Gallion Gallion c s dng nh thuc th trc quang cho Ga (ML, pH = 6, 560nm, = 1,54.104 La, Mn, Pb, Sc, Zn, DCD, t him. S to thnh t 3 phc ca GaGallion Oxine (MLX; pH = 3; 640nm; = 2,3.104 trong buthanol). Th cng hu dng cho vic xc nh ca GaLumogallion cng c khuyn co nh thuc th trc quang cho Al (pH = 5, 576nm) hoc pH = 3,3; 558nm c mt trong h Anta rox CO 890; Ga( pH = 3; 580nm) hoc pH = 3,1 4,3, 553 nm c mt trong h Antarox. CO 890, In( pH = 2,8 6,5; 500nm; Mo(VI) (510nm = 1,13.104 ), Nb (pH = 5,6 7,6; 546nm) Sc (pH = 2; 500nm), Sn(IV) (pH = 1; 510nm) v W (pH = 2,6 3,5; 555nm) hoc nh thuc th hunh quang cho kim loi. S xc nh chit trc quang cho Fe, Sn v Y thng qua 3 phc cht vi Lumogallion diethylether v Nb thng qua LumogallionBPA c bo co bi 3 phn phc cht. Ion chelate Lumogallion vi Cu, Fe, Mo(VI), PD, V(IV) v W(VI) c th cng c chit vi Aliquat 336S trong CHCl3. 8.8.8.2. SPADNS Bt SPADNS c ngh nh thuc th trc quang cho AL (pH = 4 5; 590nm), Ca (pH = 10; 570nm), Pa (pH = 10 11; 570nm), Mg (pH = 8; 570nm), Pd (pH = 2,5 4,5; 550nm), Th (pH = 2,6 3,6; 580nm), Zr (HCl 0,5N; 580nm) v t him ( pH = 5 7,5; 540nm). Anion chelate c th chit nh cp ion vi diantipymethane cho s xc nh trc quang ca Sc ( ML2X2, pH = 5,5 8,5; 580nm) fluoride c th c xc nh khng trc tip trong s bay mu ca chelate Zr (HCl 0,7N, 570nm). 8.8.8.3. BerryllonII Bt mu tm en gi tr pKa cho 5 bc phn ly 2,9; 4,3; 5,71; 7,01; v 10,88( 20oC n c s dng nh l thuc trc quang cho Be (pH = 12 13,2; 600nm), Mg (pH = 11;
640nm, = 1,03.104 ), Th (pH = 2; 620nm), Ti(IV) (pH = 4,1; 580nm, = 6.104) v t him (pH = 7,6; 610nm) v B. Bng 8.19: NG DNG CA PHM NHUM AZO NH THUC TH TRC QUANG Phm nhum azo (1) Ion kim loi Cd Co(II) Co(II) iu kin T l max (nm) (x104) 2,2 5,0 6,62 Dy xc nh (ppm) 0,22~5,6 0,6~18 0,1~ 0,8 Yy t cn tr v ghi ch Trong hp kim Devarda EDTA,DDTC cn tr Mn,Ni,VO3cn tr Ca,Cd,Ce,Fe,Zn cn tr
Mg
Mg
Mg
Zn
t him
pH~6; 1,10 Phenalthroline, ML2X2 522 chit vi CHCl3 TPAC, chit 580 vi CHCl3 pH 5,5~8,2; SCN-; chit 587 vi benzene v Aliquat 336S pH 10,9 ~ 11,3; KCN; 525~30 triethanolamin pH 9,5~11,2, chit v i 545 AmOH hoc BuOH pH 11,2 ~ 12,2, 690* Zephiramine, chit v i dichloroethane pH ~ 6; 1,10 Phenalthroline, ML2X2 522 chit vi CHCl3 pH 6,35 ~ 6,8; diphenyl ML2X2 550~600 guanidine; chit vi iso AmOH Mi trng kim pH 8,2~ 8,8; KCN; EDTA; chit vi Aliquat 336S trong CHCl3 pH 4,2; chit ML2 570
0,1 ~1
2,0
0,5 ~5
0,03~ 0,1
Ca khng cn tr
2,3
0,64~ 3,7
Trong hp kim Devarda
2,6 ~3,5
0,1~ 15
Sau khi s trao i ion phn tch Cd,Cu,Ni,Pb,Zn khng cn tr
(2)
UO22+
1,36
14 ~ 60
(3)
Al Co(II)
ML3
570 580
4,2 0,8
0,1 ~ 0,5
(4)
vi Aliquat 336S trong CHCl3 pH 11,2~12,2, Zephiramine, Mg chit vi dichloroethane pH 11; chit vi Aliquat Mo(VI) 336S trong CHCl3 Kim loi pH6; EDTA kim th UO22+ pH 4 t him pH 6 ~ 10; EDTA
690
6,3
2~7
Ca khng cn tr
575
0,6
ML ML
650 530 65
0,41
1 ~ 600 0,3 ~ 1 ~ 300
Kim loi kim th, Be, UO22+ cn tr
CHNG VIII: THUC TH NN

VIII.1. BIPYRIDINE V CC HP CHT FERROIN KHC
Cc thuc th c cp trong phn ny c lit k bng 9.1 cng vi cc ng phn ca chng. Bng 9.1 STT (1) (2) (3) (4a) Tn 2,2 Bipyridine 2,2,2 Terpyridine 1,10 Phenanthroline 4,7 Diphenyl 1,10 phenanthroline 4,7 Diphenyl 1,10 phenanthroline disulfonic acid, mui dinatri ng phn , Bipyridyl, Dipyridyl,2,2 bipyridyl 2,2,2 Terpyridine o Phenanthroline,4,5 phenanthroline Bathophenanthroline Bathophenanthroline Disulfonic acid, mui dinatri. CTPT C10H8N2 C15H11N3 C12H8N2.H2O C24H16N2 Khi lng phn t 156,19 233,27 198,23 332,41
(4b)
C24H14N2O6S2Na2
536,48
9.1.1. Nguyn liu v phng php tng hp: Tt c cc nguyn liu c bn di dng thng phm. (1) v (2) c iu ch t qu trnh hydro ho pyridine vi FeCl3 hoc c cht xc tc Ziegler 100 200oC. (3) c iu ch bng cch un nng. ophenylenediamine vi glycerol, nitrobenzene, v
H2SO4 c hoc bng phn ng Skraup t 8aminoquinoline. (4a) c iu ch t 8 amino4 aminoquinoline bng phn ng Skraup vi chloropropiophenone. (4b) l 1 sn phm sulfo ho ca (4) vi acid chlorosulfonic sau l s thu phn. 9.1.2. ng dng trong phn tch: C 4 cht trn ch yu c s dng nh mt thuc th trc quang xc nh Fe(II) v cn c dng lm cht che, cht pht hin cc ion kim loi khc. Cc phc chelate st ca chng cng c s dng nh l cht ch th oxi ho kh. 9.1.3. Tnh cht ca thuc th: 2,2bipyridine (1) l mt cht rn tinh th mu trng, nhit nng chy 702oC v nhit si t 272 275oC. N c p sut hi bo ho nhit phng v c trng l phn no c mi d chu. Cht ny d dng b thng hoa hoc chng ct thnh hi, tan c trong nc (khong 5g/L) nhit phng. N tan tt trong ru, ether, benzene, ether du ha, chloroform v acid long. pKa1 = 0,2 v pKa2 = 4,4 ( = 0,1 KNO3, 25oC). 2,2,2Terpyridine (2) l mt cht rn tinh th mu trng, nhit nng chy l 88 89oC. N khng bay hi cng vi hi nc v tan hn ch trong nc, nhng tan d dng trong hu ht cc dung mi hu c v acid long. pKa1 = 1,6 v pKa2 = 3,99 v pKa3 = 3,99 ( = 0,1 K2SO4, 25oC). 1,10phenanthroline (3) l 1 cht bt tinh th mu trng. N ch yu tn ti dng c ngm nc v khi nng chy 98 100oC do qu trnh mt nc. Dng khan nng chy 117oC v d tan trong nc (khong 3,3 g/L nhit phng) v trong benzene (khong 14g/L nhit phng). N tan tt trong cn (khong 540g/L ), acetone, v cc acid long. Bathophenanthroline (4a) l mt cht bt tinh th mu trng hoc c mu vng nht, nhit nng chy 215 216oC v tan nh trong acid long, nhng trong thc t khng tan trong nc trung tnh hoc nc c tnh kim. N tan d trong cc dung mi hu c nh cn, acetone, benzene. Sulfonated Bathophenanthroline (4b) Thng c c dng mui dinatri, c dng tinh th bt mu vng nht hoc hng sng. Mu ca thuc th ty thuc vo lng vt ca st nhim bn vo. N l d cht ht m nhng sau khi sy kh 110oC trong 2 gi ta thy rng khi lng ca n khng thay i khi tng nhit ln 275oC. vng nh sng UV n c mu xanh hunh quang sng v d tan trong nc nhng kh tan trong 1 vi dung mi hu c. Acid t do c dng cht lng snh, thu phn cao, v kh thu c dng rn. Cc thuc th nhm ny u khng mu v khng c kh nng hp th bt k mt tn hiu no vng kh kin. 9.1.4. Cc phn ng to phc v tnh cht ca phc cht: Nhng thuc th nhm ny hnh thnh phc c mu bn vi cc kim loi chuyn tip. Tuy nhin, mt s hnh thnh cc chelate c cng mu khng mnh bng khi chng tn ti trong dung dch nc. Mt s to chelate gn nh khng mu (Cd, Zn, Mn(II) v Ag). Cu(I) v Fe(II) l cc ngoi l khi hnh thnh cc vng cng c mu mnh. Trong cc chelate ny, th (1) v (3) v (4) th hin nh 1 khng mang in tch to thnh ML3 v ML2- loi phc c ion kim loi (Mn+) lin kt vi v tr 4 v 6, theo trnh t nh minh ho hnh 1 Terpyridine (2) th hin nh mt phi t c 3 lin kt, hnh thnh ML2n+, mt loi phc c ion kim loi lin kt v tr th 6.
Mt s gi tr ca hng s bn c lin quan c dng xc nh cc phc kim loi ca pyridine, terpyridine v phenanthroline. Cc gi tr ny c tm tt bng 9.2 n 9.4. Cc gi tr ca Bathophenanthroline (4a) l Cu(II), log3 21,8( 18oC, = 0,1; NaCl, 10% ethanol, v i vi sulfonat Bathophenthroline (4b) l Fe(II), log2 22,3. Cc thuc th nhm ny c ng dng rng ri xc nh Fe, Cu bi v chng hnh thnh cc phc c mu mnh vi nhng kim loi ny. Cc c trng quang ph ca cc phc Co, Cu, Fe, v Ru c lit k bng 9.5, v cc ph hp th ca cc phc Fe(II) vi (1), (3) v (4a) c minh ha hnh 2. Mt s t cc ion kim loi khc cng to cc phc c mu tuy nhin quang ph c trng ca chng rt khc so vi cc phc ca Fe(II) v Cu(I) nn chng khng nh hng n vic xc nh Fe v Cu bng phng php quang ph. Tri vi mu cam m ca phc Fe(II) (Ferroin), mu ca phc Fe(III) (Ferriin) l khng mu hoc mu xanh nht. Cp oxi ho kh Ferroin Ferriin: FeL33+ + e ' FeL32+ khng mu cam c tnh thun nghch rt cao v p ng tt c cc i hi ca mt cht ch th oxi ho kh. Th oxi ho kh ca phng trnh c th c m t bng phng trnh Nerst:
FeL33+ E = E 0 + 0,059 log 2+ FeL3
Gi tr ca Eo thay i tu thuc vo thnh phn ca dung dch v ph thuc vo mc nh hng ca h s hot ca cc thnh phn c trong dung dch v bn ca phc Fe(II) v Fe(III). Bng 9.6 tm tt th ca Ferroin Ferriin cc nng acid khc nhau, cng vi s thay i mu ca chng. Mt s dn xut quan trng ca bipyridine(I) v phenanthroline (3) c dng lm ch th oxi ho kh cng c nu trong bng ny.
Bng 9.2: HNG S BN PHC CA BIPYRIDINE Ion kim loi Log KML Log K ML Ag(I) Ag(II) Cd Co(II) Cr(II) Cu(I) Cu(II) Fe(II) Fe(III) Hg(II) Mg Mn(II) Ni Pb Ti(I) Ti(III) V(II) Zn 3,7 4,25 6,06 ~4 8,0 4,20 4,2 9,64 0,5 2,62 7,13 2,9 9,40 4,91 5,04
2
Log
2 7,22 2 6,8 3,6 5,36 ~ 6,4 2 14,2 5,6 3,70 >5 7,10 2,00 6,88 2 3 6,70 4,67 4,35
iu kin Nhit 25 0,1(KNO3) 25 2,7 20 0,1(NaNO3) 4,60 20 0,1(NaNO3) 3,5 0,1 25 0,1(KNO3) 3,48 20 0,1(NaNO3) 9,55 25 0,1 25 2 17,06 2,8 20 0,1(NaNO3) 27 0,5(LiClO4) ~ 1,1 25 0,1(KCl) 6,53 20 0,1(NaNO3) 20 0,1(NaNO3) 25 1,0(NaNO3) 25 1,0(NaNO3) 3,85 0,1 3,57 25 0,1(KCl)
K ML3
Bng 9.3: HNG S BN CA PHC CA TERPYRIDINE(2) Ion kim loi Log KML Log K ML Cd Co(II) Cu(I) Cu(II) Fe(II) Mn(II) Ni Zn 5,1 8,4 ~9,3 ~13,0 7,1 4,4 10,7 6,0
2
2 18,3 2 20,9 2 21,8
iu kin Nhit 25 25 25 0,1(K2SO4) 25 0,1(K2SO4) 25 25 25 25 iu kin Nhit 25 0.1 20 0,1(NaNO3) 20 0,1(NaNO3) 20 0,1(NaNO3) 25 0,1(K2SO4) 20 0,1(NaNO3) 20 0,1(NaNO3) 20 0,1(NaNO3) 20 0,1(NaNO3) 20 0,1(NaNO3)
Bng 9.4: HNG S BN CA PHC 1,10 PHENANTHROLINE Ion kim loi Log KML Log K ML Ag Ca Cd Co(II) Cu(I) Cu(II) Fe(II) Fe(III) Hg(II) Mg 5,02 0,7 5,78 7,25 9,25 5,86 6,5 1,2
2
Log
K ML3
7,05 5,04 6,70 215,82 6,75 5,25 211,4 219,65
4,10 5,95 5,35 10,03 223,5 3,7
Mn(II) Ni Pb Tl(I) Tl(III) VO(II) Zn
4,13 8,8 4,65 11,57 5,47 6,55
3,48 8,3 24 6,73 4,22 5,80
2,7 7,7 5,20
20 20 20 25 25 25 20
0,1(NaNO3) 0,1(NaNO3) 0,1(NaNO3) 1,0(NaNO3) 1,0(NaNO3) 0,082 0,1(NaNO3)
Trong cc thuc th c lit k bng 9.6, th oxi ho kh ca 5nitro (3) c gi l nitro Ferroin, c in th gn nht so vi th tng ng ca phn ng chun Ceri (+1,19) vi Fe2+, i khi thuc th ny l ch th l tng chun vi dung dch Ceri. Nh trnh by trn, cc cht t (1) n (4a) u th hin nh mt phi t khng mang in, kt qu ca vic hnh thnh phc cation th vn cn gi li in tch dng ion kim loi trung tm. Cc phc cation ny c khuynh hng hnh thnh kt ta khng tan vi cc anion cng knh c ho tr 1 hoc 2, nh l ClO4-, SCN-, hoc CdL42-. tan ph thuc rt nhiu vo s lin kt ca cc phc gia cc anion v cation, v phn ng c th c s dng pht hin hay tch cc anion bng phn ng kt ta. Bng 9.7 tm tt gii hn pha long pht hin cc anion khc nhau bng Fe(bipy)3SO4. Mc d cc kt ta ny khng tan trong nc nhng li tan trong cc dung mi hu c c hng s in mi cao. tan ca Fe(phen)3X2 (X = ClO4-, I-, Br-, Cl-) trong cc dung mi khc nhau c tm tt bng 9.8. V mt s anion c chit vo cc pha hu c nh l 1 cp ion. Mt ln na, h s chit, li ph thc vo s lin kt ca cc phc cation, cc anion c chit v dung mi. Bng 9.9 tm tt t l phn b ca cp Fe(bipy)3 v X2 Fe(phen)3X2. Cc phc cation c to thnh bi biquinoline v cc ho cht c lin quan cng c s dng cho mc ch ny. Cc v d v qu trnh chit cp ion ca cc anion khc nhau vi phc Ferroin c tm tt bng 9.10. 9.1.5. S tinh ch v qu trnh tinh ch ho cht: C 4 cht u c nhng tnh cht c trng ca mt tinh th v d dng c tinh ch bng qu trnh kt tinh li t cc dung mi thch hp, (1) th dung mi l ethanol long, (2) v (4a) th t benzene, cn (3) th vn cn cha 1 nhm hydrat khi kt tinh li t benzene nc hay benzene m. Cht khan th c th c iu ch t benzene hoc ether du ha c loi nc bng qu trnh chng ct. Khi tinh khit thp, (4b) l 1 cht bt mu nu hoc nu vng v rt kh loi i mu nhim bn ny. Dung dch (4b)nc rt nhy vi st v vy phi ht sc cn trng trnh st nhim bn ln nc, ho cht v dng c thu tinh. Mui v c v mt s cht gy nhim mu c th c loi b bng cch ho tan mu th vo mt lng nc nh, sau thm vo ethanol kt ta cc cht gy nhim bn, dng tinh khit ca (4b) c iu ch bng cch cho bc kh dch lc. Chng ta c th kim tra tinh khit ca (1) n (4a) mt cch d dng bng cch quan st im nng chy ca chng hoc chun bng acid perchloric trong mi trng acid acetic vi ch th l naphtholbenzene. Dng phng php ph hp thu xc nh tinh khit ca (4b). Ho cht m tho mn tinh khit th phi p ng nhng yu cu sau: A ( 278,5nm) > 0,70 A ( 535nm) < 0,01 Trong A l hp thu ca dd (4b)10mg/L, cuvet silic 10mm.
9.1.6. Cc ng dng trong phn tch: 9.1.6.1. Thuc th quang ph: Mt s thuc th to mu c nghin cu xc nh hm lng vt St, nhng khng c thuc th no c th snh bng cc thuc th Ferroin. Bipyridine(1), terpyridine(2) v phenanthroline(3) l c ngh cho cc mc ch chung m khng cn c nhy cao hay cc iu kin c bit. Bathophenanthroline(4a) v dn xut xut pht ho (4b) c ngh xc nh hm lng st cao. Vic xc nh c th c thc hin trong mi trng nc i vi (1), (2), (3) v (4b). Tuy nhin, i vi (4a) th cn phi chit phc mu bng dung mi hu c. Khi s dng (1) n (3) , phc st mu cam hnh thnh mt cch nh lng trong khong pH t 2 n 9 (tt nht l t 4 6 ). Trong cc tc cht thng dng lm cht kh chuyn Fe(III) v Fe(II) th hydroxylamineHCl v acid ascorbic l c ng dng rng ri khong pH ny. Th t cho thm cc thuc th cng rt quan trng, v th t thng c dng l: cht kh, cht ln mu v m. hp th tun theo nh lut Beer trong khong nng t 0 8 ppm Fe v 5 50g st trong 10 ml dung dch. bn mu trong khong vi thng. Mc d (1) n (3) c chn lc cao i vi st nhng nu mt vi nguyn t c nhiu trong mu phn tch cng c th gy nh hng. Mc nh hng ca cc nguyn t c th gim bt tu thuc vo pH, lng thuc th ln mu v loi thuc th dng lm cht che v nng ca n. Khi dng citrate v EDTA, khong pH = 5,0 6,5, th t l cc cht c th gy nh hng (t l mol ca ion nh hng/Fe) nh sau Ag(50), Co (<20), Cu (4.18), Mo (<40), Ni(12,5), Cr (<200), Ru (<30), v W (<7). (4a) thng c dng khi cn c chn lc v nhy cao, vi thuc th ny th hm lng ca Fe c th xc nh c l 0,001 0,1 ppm. N cng c chn lc cao i vi Fe bi v ch c Fe(II) mi hnh thnh phc mu pH = 4 trong dung dch nc, v phc ny c th c chit vo isoamyl hay hn hp isoamyl v isopropylether(1:1). Cu(I) cng hnh thnh phc khng mu c th c chit pH 4 nhng khng gy nh hng n vic xc nh Fe, vi iu kin l lng thuc th to mu thm vo to phc vi c Fe v Cu. (4b) hnh thnh phc 3 chelate mu bn trong khong pH = 2 (4b) to phc i vi Fe chn lc yu hn so vi (4a). Mt lng tng i nh Cu, Co, v Cr cng c th gy nh hng do hnh thnh phc mu , nhng (4b) li rt thun tin cho vic xc nh Fe thng thng, v giai on chit c th b qua khi s dng (4b). 9.1.6.2. ng dng lm thuc th hunh quang: (3) thng dng lm thuc th hunh quang xc nh cc cht nh Ag, Cd, Pd, Re, Sc, Zn v t him c hm lng vt Nguyn tc ca phng php l da trn s xut hin ca mu hunh quang trong hn hp to phc c hnh thnh khi c mt phi t th hai, v d nh acid salicylic, acid 2phenyl4quinolinecarboxyluc, Eosine, dibromofluorescein hoc TTA. 9.1.6.3. ng dng lm cht che: Thuc th ca nhm ny thng hnh thnh phc khng mu vi cc ion kim loi khc nhau v c th c s dng nh lm cht che trong phn ng to phc hay php o quang.
(4a) cng c ng dng lm cht che loi b cc vt St, Cu, v mt s ion kim loi no c trong dung dch thuc th dng phn tch hm lng vt kim loi. Sau khi dung dch phn ng vi (4a), phc to thnh v cc cht khng phn ng c loi b d dng bng cch chit vi dung mi khng tan trong dung dch. 9.1.6.4. ng dng lm cht chit: Nh trnh by trn, phc cation st c bn cao v cc anion khc c th c chit vo pha hu c nh 1 cp ion (xem bng 9.10). Trong cc iu kin thch hp, vic chit rt nh lng, v nng ca anion tng ng trong pha nc c th c xc nh bng cch o cng ca Ferroin pha hu c, theo phng trnh sau
Fe ( phen )3
2+ aq 2+ 2 + 2Xaq Fe ( phen )3 + X2 org
9.1.6.5. ng dng lm cht ch th oxi ho kh: Nh trnh by trn, phn ng thun nghch Ferroin ' Ferriin c th c ng dng lm cht ch th trong phn ng oxi ho kh. Mc d, th dch chuyn ca ch th m ti c th quan st s thay i mu quan h cht ch vi th hnh thnh, gi tr c lng ca n phn no bin i tu thc vo cc cu t. Ni chung, v phc mu cam ca Ferroin mnh hn phc mu xanh nht ca Ferriin, khong 9/10 ca Ferroin phi c chuyn thnh Ferriin trc khi nhn ra im thay i mu. theo , th chuyn dch khong 0,05V(0,0591.log[Ferroin/Ferriin], ln hn th to thnh bng 9.7. Ch th c ngun gc t 5nitro1,10phenanthroline l mt ch th l tng thch hp khi chun Ce(IV) ( perchlorate) trong acid perchloric v dd HNO3. 9.1.7. Cc thuc th c cu trc tng t: 9.1.7.1. 4,7dihydroxy1,10phenanthroline (thuc th Snyder)
HO OH HCl N N
Thng dng HCl (H2L.HCl), khi lng mol = 248,67); bt tinh th mu vng (phn hu 475oC). Cht ny tan nh trong nc pH = 1 8 v trong cc dung mi hu c, nhng tan mnh trong cc dung dch kim (pH = 8). Dung dch bn trong nhiu thng thm ch nhit cao, pK1(N+H) = 2,55, pKa2(OH) = 7,28 v pKa3(OH) = 11,5 Thuc th Snyder l 1 thuc th c bit l th do hnh thnh phc mu vi Fe(II) trong dd NaOH 6 n 10 N, bc sng = 520nm; = 1,48.104. Hn na, thuc th ny cn c dng nh mt thuc th trc quang i vi Fe, trong dung dch kim mnh. Tng t, dn xut ca 2,9dimethyl cng c dng lm thuc th i vi ion Cu ( = 400nm; = 1,15.104 trong NaOH 0,5 7 N) 9.1.7.2. Phenyl2pyridylketoxime (2Benzoylpyridine oxime, PPKO)
C HO N N N
C N OH
Trong hai cht ng phn lp th, dng phn ng vi cc ion kim loi khc nhau hnh thnh cc phc c mu v c th chit bng dung dch chloroform. Cht ny hu nh khng tan trong nc v cn nhng li d tan trong ethanol nng, benzene, chloroform, dioxane, ru izo amylic v cc acid v c long. Thuc th ny dng rn v lng u nhy vi nh sng v i khi phi trnh nh sng chiu trc tip; pKa1( H2L*) = 2,84 v pKa2(HL) = 12,19 ( = 0,1NaClO4, 40% acetone, 20oC). Thuc th ny hnh thnh phc c mu vi Fe(II), (III) (), Cu(I) (cam), Cu(II) (xanh), Au( III), Co(II), Pd(II), Pt( II) v UO22+ (vng), v Cr(III) (khng mu) trong dung dch trung tnh hoc kim. Trong dd kim mnh (pH, NaOH 5 10 N), Fe(II) hnh thnh phc mu m (ML2, (max = 545 nm, = 1,52.104, phc ny c th chit vo ru izo amylic. Hn na, PPKO cng c ngh dng xc nh lng vt ca Fe trong mu kim. N cng c dng xc nh Au(III), Cu(II) v Pd(II). Bng 9.7: KT TA CA CC ANION VI [Fe(bipy)3]SO4 Anion Gii hn pha long Anion Gii hn pha long 4Cl 1:10 Fe(CN)6 1:5.000 Br1:50 Fe(CN)631:30.000 I1:1.000 Fe(CN)5(NO)21:20.000 2SCN 1:5.000 PtCl6 1:100.000 VO3 1:40.000 BiCl4 1:10.000 22Cr2O7 1:6.000 SnCl6 1:2.000 2MnO4 1:12.500 HgCl4 1:50.000 2ReO4 1:1.000 CdI4 1:1.000.000 Bng 9.8: tan ca Fe(phen)3X2 trong cc loi dung mi khc nhau (mol/L ti 25oC) I ClSCNClO4 8,8.10-4 * Nc 6,15.10-3 5,08.10-2 2,55.10-1 3,3.10-3 -4 7,9.10 Nitrobenzene 2,95.10-2 6,26.10-3 6,7.10-4 6,2.10-4 6,04.10-3 Nc bo ha nitrobenzene 4,5.10-4 3,29.10-3 5,31.10-2 2,71.10-1 1,59.10-3 Nitrobenzene bo ha nc 3,55.10-2 6,0.10-3 1,27.10-3 2,32.10-4 6,66.10-3 *: Gi tr tnh c bng cch dng in cc mng, ha tan ca Fe(bipy)3(ClO4)2 l 1,9.10-2M Bng 9.9: T l phn b (D) ca cp ion Ferroin (FeL3)2+(X-)2a (25oC) XClO4SCNIBrCl[Fe(bipy)3]2+(X-)2 [Fe(phen)3]2+(X-)2 Nitrobenzene/nc Dichloroethane/nc Nitrobenzene/nc (5.10-4)b (10-4)b (6.10-5)b 4,22 0,077 13,5 (5.10-3)b (10-4)b (2,5.10-4)b 0,39 0,012 1,71 -4 b -3 b (3.10 ) (10-4)b (3.10 ) 0,19 0,004 0,83 -3 b (10-3)b (10 ) 0,06 0,03 (10-2)b 0,003
Dung mi
X Br-
a: n nh trong dung dch m phosphate 1/15M (pH 5,3) b: Gi tr trong ngoc n l nng ban u ca mui Ferroin trong pha nc
VIII.2. TRIPYRIDYLTRIAZINE(TPTZ) V PYRIDYLDIPHENYLTRIAZINE

N N N N N N N (1) L N X N N (2) L, X = H (3) H 2L, X = SO3H X
9.2.1. Nhng t ng ngha Nhng thuc th c bao hm trong on ny c lit k t bng 9.11, cng vi nhng t ng ngha ca chng . 9.2.2. Ngun gc v nhng phng php ca tng hp Tt c dng thng phm sn c thng c cung cp nh l tinh th mui mono hoc dinatri c cha 1 2 phn t nc. (1) c iu ch bng cch t c c ca 2cyanopyridine trong s c mt natri hydroxide. (2) c iu ch bng phn ng tng giai on ca 2cyanopyridine vi hydrazine, sau vi benzyl. (3) l sn phm sulfonate ca (2) vi hi acid sulfuric. 9.2.3. Nhng ng dng trong phn tch. Nhng thuc th o quang cho Fe(II) v Cu(II). Chng cng c dng o quang cht xc nh ca cc kim loi khc, nh l Co, Cr, Ni v Ru. (1) v (3) th thch hp cho vic s dng trong mt h cha nc. 9.2.4. Tnh cht ca thuc th TPTZ (1) l tinh th hnh kim mu vng sng, im nng chy 245248oC, v t tan trong nc ( 0,03g/100ml), nhng tan nhiu trong ethanol. N d dng tan trong acid chlorhydric long v khng tan trong dung mi khng phn cc. Gi tr pKa ca HL+ l 3,10 (25oC, = 0,1 KCl), hoc trong dng khc, gi tr s phn ly nc hai ca H2L2+ l 2,82 v 2,75 (25oC, = 0,23 NaCl). S phn b ca (1) gia dung mi hu c khc v dung dch acid c nghin cu, v gi tr pH1/2 l 1,93 (nitrobezen), 0,38 (phenylcarbiol, 1,20 (chloroform), 2,16 (dichloroethane), 2,50 (trichloroethylen), 1,72 (nbutanol), v 2,28 (npentanol). PDT (2) l tinh th hnh kim mu vng sng, im nng chy 191192oC v tan t trong nc, nhng tan nhiu trong alcohol v cc dung mi khc; pKa (LH+) = 2,95 (25oC). S
phn b t l ca (2) gia chloroform v dung dch acid khc c tng qut trong bng 9.11. PDTS (3) l dng bt c mu vng sng hoc vng xanh, nhit phn hy ln hn 350o, n thng c cung cp nh tinh th mui mono hoc dinatri c cha 1 2 phn t nc, v d dng ho tan trong nc to ra dung dch khng mu hoc sng hng (0,7g/100ml trong NaHL 20oC). Di hp th khng c trng c quan st trong (1),(2) v (3) trn vng kh kin. 9.2.5. Nhng phn ng phc cht v tnh cht ca phc cht TPTZ (1) ,th hin bng mt phi t c 3 nhnh nh terpyridine,v PDT (2)v PDTS(3) th hin bng mt phi t 2 nhnh nh bipridine, hnh thnh HL2- v HL3- loi vng vi ion kim loi c s phi tr bng 6, theo th t. Loi vng vi (1) v (3) c tnh c trng cho kh nng tan trong nc ca chng. Vng st(II) vi (2) ([FeL3]2+) c th c chit vo isoamyalcohol, hoc, nu c mt SCN-, trong chloroform hnh thnh pha acid r rt cha nc, tr thnh nn tng cho vic xc nh vt st trong acid. iu kin hng s cn bng cho phn ng sau
Fe2+ + 3 ( LH + X )
org

([ FeL ] X )
3
2 org
+ 3H + + X
Kex
K=Kex/[H+]3.[X-], c tnh ton bng (9,00,4).1011 (trong H2SO4 1M v NaSCN 0,5M). Hng s bn ca lin kt vng c nh gi trong mt s c gii hn ca nhng kim loi; TPTZ, log2(Co(II)), 9,11; log2(Fe(II)); 11,4; PDTS, log3(Fe(II)), 15,56 ( iu kin ca hng s pH 3,5 n 4,5). Quang ph c trng ca vng kim loi c tm tt trong bng 9.13. Ph hp thu ca FeTPTZ vng (FeL22-) trong dung dch cha nc c minh ho trong hnh
9.2.6. Tinh ch v tinh khit ca cc thuc th: TPTZ (1) v PTD (2) c th c tinh ch bng cch lp li qu trnh kt tinh t dung dch ethanol v ethanolDMF, theo th t, cho n khi nhn c im si chp nhn. PDTS (3) c th c tinh ch bng cch kt tinh t nc hoc bng cch ho tan vi mt t nc, sau thm ethanol vo lng c tinh cht. Th nghim ca (3) c tin hnh ngoi cch quan st bng hp thu ca vng vi Fe (2) bc sng 562nm, s dng vt qu 10 ln ca Fe(II) pH 4,5 (m hydroxylamine acetat) ( = 2,86.104). Mu trng st hin c trong thuc th c xc nh bng cch o dung dch nc 2,5% bc sng t 500 700nm s dng ng o 1cm. Cch khc trong hp thu gia 502 v 700nm c s dng tnh ton c cha st. 9.2.7. ng dng trong phn tch
Nhiu dn xut ca triazine, (1), (2), v (3) c pht hin l thuc th ca st trong hu ht nhng ng dng trong thc t. Trong nhng ng dng ca (2) c kt hp vi chit xut dung mi, (1) v (3) c th c s dng trong h thng dung dch nuc. iu kin tt nht pht trin mu c tm tt trong bng 9.13. S thun li ca TPTZ l c nh hp thu xut hin trong khong bc sng tng i rng v thuc th rt r. Tuy nhin, thuc th khng chn lc i din cho Fe bi v Co, Cu, Cr, Ni v Ru cng hnh thnh phc mu. Anion nh MnO4-, NO2-, v CrO42- cng c nh hng rt ln. PDT v PDTS cng hnh thnh phc mu vi Cu, nhng peak hp thu ca phc Cu(I) c cng yu hn v xut hin bc sng 488nm, phc ny khng cn tr khi xc nh st. Nhng ion cn tr v mc nh hng trong xc nh Fe(II) vi TPTZ v TPTS c tm tt trong bng 9.14 v 9.15 TPTZ v TPTS c s dng xc nh Fe trong huyt thanh v sa vi cch x l s b. Lng nh Cu c th che vi Neocuproine, thiourea, hoc acid thioglycolic. Thuc th vi mi tng quan v cu trc Nhng cht dn xut khc ca asymtriazine c nghin cu thay th cho thuc th ca Fe, Cu, hoc Co. Vi thuc th thnh cng c tm tt trong bng 9.16. Bng 9.11: TPTZ V CC HP CHT TNG T Thuc th (1) (2) Tn Tripyridyltriazine Pyridyldiphenyl triazine Pyridyldiphenyl triazine, sulfonic acid, mui natri Tn gi 2,4,6Tris(2pyridyl)S triazine, TPTZ 3(2Pyridyl)56diphenyl 1,2,4triazine, PDT 3(2Pyridyl)56 diphenyl1,2,4triazine, sulfonic acid, mui natri, 3 (2Pyridyl)56di(4 sulfophenyl)1,2,4triazine, mui dinatri, PDTS, Ferrozine (*) Cng thc phn t C18H12N6 C20H14N4 KLPT 312,33 310,36
(3)
C20H12N4O6Na2.H2O 486,35
(*) Tn thng mi ca cng ty Ho Cht Hach., Lin Doanh.,Ames, Iowa Bng 9.12: SP XP T S CA PDT (2) GIA CHLOROFORM V CC DUNG DCH ACID KHC (CHCl3/acid) Nng acid (M) HClO4 H2SO4 HCl HNO3 0,5 1,0 2,0 5,0 8,0 110 40 13 1,6 0,04 150 150 28 0,20 0,05 190 150 16 4,2 0,66 120 60 13 3,2 1,5 HClO4 + NaSCN (0,5M) 120 70 26 10 1,4
Bng 9.14: CC ION CN TR TRONG XC NH Fe(1,1ppm) VI TPTZ (1) Ion kim loi Nng (ppm) Sai s (%) Anion Nng (ppm) Sai s (%) Ag 102 ppt F502 +0,2 Ba 101 +0,2 Br 556 +0,2 Bi 100 ppt CN 500 Rt ln Cd 100 -0,7 NO2 500 Ln Co(II) 4,8 +3,6 NO3 504 +0,2 3Cr(III) 20,8 +2,4 PO4 528 +0,2 Cu(II) 6,3 +4,8 ClO3 548 +0,2 Hg(II) 100 ppt SCN507 +0,2 K 1067 +0,4 S2O32528 +0,4 2Mn(II) 110 +0,2 MoO4 34 Rt ln Ni 10,6 +2,7 C2H3O2 14400 -0,2 Pb 101 +0,2 Sn(II) 100 -0,2 Khng cn tr Al, Be, Ca, Li, Mg, Sr 99 +0,2 + 223NH , I , SO Th 120 -0,2 4 4 , S2O3 , ClO4 , BO3 , BrO3 UO32115 +0,4 Bng 9.16: QUANG PH C TRNG CA VNG KIM LOI CA MT VI ASYM-TRIAZINE Thuc th 3(4Phenyl2pyridyl)5 6diphenyl1,2,4triazine (PPDT hoc PAT) Ion kim loi Co(II) Cu(I) Fe(II) 2,4bis(5,6Diphenyl 1,2,4triazeno3yl) pyridine Vng kim loi max (nm) (x104) 516 0,22 480 561 0,79 2,87 Ghi ch FeL, pH 37, trong ethanol nc (1:1), cht cn tr 0,27 2,44ppm Fe EDTA, CN Chit vi CHCl3, pH 7 (mu tm) FeL, pH 3 12, (mu tm); nhy cao; vng Co th khng mu
Co(II) Cu(I) Fe(II)
475 510 563 495 560
0,01 1,52 3,2 1,05 3,48
3(4Pheyl2pyridyl)3 phenyl1,2,4triazine
Cu(I) Fe(II)
VIII.3. DIOXIME
9.3.1. Nhng cng thc ng phn: 185
Dioxime c lit k trong bng 9.17, cng vi ng phn v cu trc cu to ca n Bng 9.17: CC DIOXIME STT (1)
H3C HO
CTCT
C N C N CH3 OH
Tn gi 2,3 Butandionedioxime, Dimethylglyoxime, Diethyldioxime, DMG Furildioxime
Cng thc phn t C4H8N2O2; 116,12 C10H8N2O4; 220,18 C6H10N2O2; 142,16
(2)
(3)
1,2 Cyclohexanedione dioxime, Nioxime
9.3.2. Ngun gc v phng php tng hp: C tnh thng mi. c tng hp t phn ng tng ng ca diketone v hydroxylamine (ngoi l i vi (1) l c tng hp t methyl ethyl ketone bng biacetylmonoxime). 9.3.3. Dng trong phn tch: Dimethylglyoxime (1) l mt trong nhng thuc th hu c chn lc u tin c ng dng trong ha hc phn tch. Dioximes t (1) n (3) c s dng rng ri nh mt thuc th kt ta chn lc, thuc th xc nh v thuc th o quang cho cc kim loi Ni, Pd(II), Pt(II), v mt s ion kim loi khc. Trong s 3 ng phn hnh hc khng gian, ch c ng phn anti c kh nng to phc chelate vi ion kim loi.
186
9.3.4. Tnh cht ca thuc th: Dimethylglyoxime 1 l tinh th hnh kim, khng mu, nhit nng chy t 238 240oC (c s phn hy), tan rt t trong nc (0,632 g/L 25oC) v trong CHCl3 (0,052 g/L 25oC) v hu nh c th ho tan trong C2H5 OH 96% (16,3 g/L 25oC) v n d dng tan trong dung dch kim v trong dung dch acid (pH < 1). N b thu phn t t nhit phng v thng hoa nhit t 26 68oC (2.10-2 TORR ) t trng D(CHCl3/H2O) = 0,083 25oC pKa (H3L+) = 8,7; pKa (H2L) = 10,6 ; pKA(HL-) =11,9 ( M = 0,01; KIO4 25oC ) Furildioxime (2), mu thng dng nht l hn hp pha trn t hai ng phn anti v syn theo t l 1:1, tha mn cho hu ht cc ng dng trong phn tch. N l tinh th khng mu hay c mu vng nht, nhit nng chy t 166 168oC (c s phn hy). ng phn anti tinh khit nng chy 192oC v n hu nh khng tan trong nc nhng tan d dng trong acetone, ru v ether v ho tan t trong chloroform (10,6 g/L) benzene v ether du ha D(CHCl3/H2O) = 0,35 (H2L) pKa= 11,6 (50% dioxane 25oC). Cyclohexanedionedioxime (3) l tinh th khng mu nhit nng chy 187 188oC (c s phn hy). (3) tan trong nc nhiu hn (1) (8,2 g/L, 21,5oC ) v c th ti kt tinh trong nc nng pKa (H2L) =12,0 (50 % dioxane 25oC). 9.3.5. Phn ng to phc v tnh cht ca phc: Dioxime (H2L), ng phn anti, to thnh dng phc chelate M(HL)2 vi nhiu ion kim loi chuyn tip ho tr 2. Trong vai tr thuc th phn tch, tnh cht quan trng nht ca (1), (2) v (3) l tnh khng tan trong nc, to phc mu chelate t din (4) vi Ni, Pd(II), Pt(II). Trong ni phn t, lin kt hydro lm n nh phc chelate M(HL)2, v do hp cht phc ny khng d b solvate. Trong trng hp phc chelate ca Ni, vic to vi kim loi yu lin kt kim loi trong trng thi rn cng gp phn lm cho cht khng tan trong nc. Mt khc, phc ca Cu(II) v Co(II) vi dimethylglyoxime tan t trong nc, v v tr phi tr th 5 hoc 6 ca ion kim loi trung tm b lin kt vi phn t nc. Trong trng hp ca phc chelate Pd(II), n khng tan trong dung dch acid hay trung tnh, nhng li tan trong kim yu v nguyn t trung tm c kh nng to lin kt phi tr vi ion hydroxide. V phc chelate Ni khng th to lin kt phi tr vi ion hydroxide, thm ch trong mi trng kim mnh, s khc bit ny trong c ch to phc c th c dung phn tch Ni v Pd. C ch to phc ca thuc th (1), (2) v (3) hu nh ging nhau nhng (2) c li th hn (1) chelate kim loi tan nhiu hn trong dung mi hu c, v mu ca phn ng nhy hn. Mt u im ca (3) so vi (1) l ha tan trong nc ca thuc th 187
cao hn v phn t khi nng hn c th dng chit trng lng mong mun. Hng s bn ca phc trong nc hay dung dch dioxane c tng kt bng 9.18. Bng 9.18: HNG S BN CA PHC CHELATE DIOXIME Thuc th Ion kim loi log KML Cd 5,7 Co(II) 10,8 Co(II) 8,7 Co(III) (1) Cu(II) Fe(II) La(III) Mn(II) Ni Pd(II) Pb Zn Co(II) Cu(II) Fe(II) Mn(II) Ni Zn Co(II) Cu(II) Mn(II) Ni Zn 15 11 10,8 6,6 8,6 11,16 K1K2 7,3 8,1 8,2 10,3 K1K2 6,4 6,9 K1K2 13 13,2 8,2 11,08 K1K2 log KML2 iu kin 5,0 50% dioxane, 25oC 10,2 50% dioxane 9,0 Nc, 25oC 10,0 (log KML3 7,2) 12,5 50% dioxane 9,2 50% dioxane 5,9 50% dioxane 8,6 50% dioxane 10,54 50% dioxane Nc, 25oC 50% dioxane 2 34,1 9,3 50% dioxane 7,2 50% dioxane 10,1 50% dioxane 50% dioxane 221,8 5,4 50% dioxane 7,2 50% dioxane 50% dioxane 2 15,7 12,5 50% dioxane 12,5 50% dioxane 7,2 50% dioxane 11,38 50% dioxane 50% dioxane 2 14,4
(2)
(3)
Tht th v nhn thy, trong hu ht cc trng hp, KML/KML2 1, m ph thuc vo lin kt hydro ni phn t lm n nh phc chelate M(HL)2 trong dung dch. S n nh u th ca M(HL)2 m bo hu nh s to thnh phc M(HL)2 hon ton, p ng c u th ng k cho ng dng lm thuc th phn tch. ha tan v cc cht ha tan phc chelate kim loi trong cc dung mi khc nhau c tng kt trong bng 9.19 V phc chelate vi Ni, Pd(II) v Pt(II) c th chit vo dung mi hu c khng trn ln, chng c th c tch ring tng nguyn t khc nhau bng dung mi chit v c th xc nh bng phng php o quang. Dung mi thng dng nht dng cho vic tch chit l CHCl3, v hng s phn ly ca phc chelate dimethylglyoxime gia h dung mi CHCl3H2O c tnh log KD = -9,93 [Cu(HL)2]; 1,85 [Pd(HL)2] v 2,60 [Ni(HL)2]. Phc chelate ca Ni v Pd(II) c mu vng trong CHCl3 v c th xc nh chng bng phng php quang ph, tuy nhin kh nng hp th phn t ca phc Ni 188
dimethylglyoxime trong CHCl3 khng cao nn t c ngha quan trng trong vic phn tch hm lng vt trong thc t. Mt phng php khc nhy hn xc nh Ni vi (1) da trn s to thnh chelate nu hay trong kim yu, c s hin din ca tc nhn oxy ha nh bromine hay persulfate. Kt qu thu c l phc chelate Ni(IV) [(NiL3)2-] v c th chit nh mt cp ion vi diphenylguanidine. Da theo Zolotov, cu trc ca chelate khng ph thuc vo tc nhn oxy ha trong t nhin, nhng ph thuc vo mi trng. Mt phc trung tnh km bn s c to thnh trong dung dch ammoniac, v mt chelate anion bn s c to thnh trong dung dch NaOH hay KOH. Dioximme c th to nn phc chelate cu trc t din N4 ion kim loi c v tr phi tr trn trc z c th to lin kt c vi nhiu phi t, nh Co(II), (III), Cu(II) v Fe(II), c th to lin kt vi cc anion (OH-, Cl-, Br-, I-v CN-) hoc nhng phn t khng mang in (NH3, piridine, ) to thnh hn hp cc phi t ca phc chelate [M(HL)2]X hoc [M(HL)2X2]. Phc dimetylglyoxime ca Ni, Pd v Pt khng to lin kt cng ghp hoc c lin kt rt yu. V d khi Co(II) cho phn ng vi KI mi trng pH = 4, ri phn ng vi (1) mi trng pH = 6 phc to thnh c mu nu [Co(HL)2I2]2- (max = 435; = 1,06.104). Phn ng ny c tnh chn lc cao cho Co. 9.3.6. ng dng trong phn tch: 9.3.6.1. Dng nh thuc th nh tnh: Dimethylglyoxime (1) to thnh kt ta mu hoc phc mu vi mt s ion kim loi nh vy m chng ta c th s dng cho qu trnh xc nh nhng ion kim loi. iu ny c tng kt bng 9.21 Bng 9.21: XC NH NHNG KIM LOI VI DIMETHYLGLYOXIME (1) Ion kim loi Bi Fe(II) Fe(III) Ni Pd(II) Pt(II) Tc V(IV) iu kin NH3 NH3 0.2 N NaOH NH3 pH=2 (HCl hoc H2SO4 ) Acid, sau khi kh Pt(IV) SnCl2HCl NH3 c mt Fe(II) Chuyn mu Mu vng ppt , ha tan Nu , ppt Vng ppt Xanh Cng thc ca phc M(HL)2 M(HL)2 M(HL)2 M(HL)2 H(HL)2 Gii hn pht hin 14 g/ml 0,4g/0,05ml 0,16g/0,05ml Phc Pd and Pt tan trong NaOH,nhng Pt cao mu ta 0,04 g/100 ml 0.04 g/100 ml 1:5.105 Gii hn pha long 1:7,0.104 1:1,25.105 1:3.105
189
9.3.6.2. Dng nh tc nhn tch chit nhng ion kim loi: Nh c m t trc phc chelate ca dioxime vi Ni, Pd(II), Pt(II) khng tan trong nc v mt vi kim loi khc v chit c th chit ra bng dung mi hu c chng ta c th tch nhng ion kim loi t hn hp nhiu kim loi bng phn ng kt ta hoc hoc chit bng dung mi Ni trong pha hu c c th chit bng dung dch HCl long. Dimethylglyoxime (1) hoc cyclohexanedionedioxim (3) l phn ng kt ta c trng ca Ni trong mi trng NH3 c mt ca tatrat lm cht che khi c mt ca cc ion Co(II), Mn(II) hoc Zn. Tuy nhin phn ng kt ta c thc hin mi trng pH = 5. Thng thng khi thm alcohol vo trong dimethylglyoxime khi un dung dch nng s lm cho Ni v phc chelate to thnh kt ta. Tuy nhin khi iu kin dung dch nng hn 50% lng ta Ni v phc chelate b ho tan trong ru, tan s khng ng k khi tng ru nh hn 30%. Do trong khi s dng ru vi thuc th dimethylglyoxime khi thm th tch ru vo khng vt qu mt na th tch ca dung dch Ni. Trong qu trnh phi km hm nhit si ca ru trong dung dch trnh dung dch bn ra ngoi v khi bn ra ngoi lm hao ht hm lng lm sai s trong phn tch trng lng. Trong phc chelate ca cylohexanedioroxime (3). Thuc th ny tan trong nc, v vy trnh ru thot ra ngoi, y l thuc th c th dng trong phn tch trng lng i vi Bi. Kt ta n mi trng pH = 12, s c mt ca EDTA. Bi c th nh lng bng cch kt ta tch ra khi hn hp dung dch cha hn 30 nguyn t bao gm Ni v Pd. * Pd(II) phc chelate ca (1) hoc (3) cng c th nh lng kt ta trong khong bng dung dch acid (HCl hoc H2SO4) trong iu kin ny nhng ion kim loi khc khng kt ta. 9.3.7. Dng nh thuc th o quang: Nh tho lun trc y chit quang ca Ni v Pd (2) hu nh rt nhy v phng php tc dng vi thuc th (2) n gin. S hp th ca phng php o quang ca Ni trong dung dch kim vi s c mt ca cht oxi ho cng c th chp nhn du hiu xc nh. Trong phng php ny cng hp th ph thuc rt nhiu vo diu kin ca phn ng. Vy mi trng chung (NaOH hoc NH3) c tc nhn oxy ho sau mt thi gian phn ng to ra mu y l iu kin dng nhn bit phn ng. Chi tit ca tng phng php khc nhau c xem k chng khc ng dng ca thuc th vi phng php o quang ca kim loi c miu t bng 9.20. 9.3.8. Dng trong iu kin khc: Nhng thuc th c th dng lm dung dch chun trong chun kt ta ca Ni bng ampe k. Xc nh Co2+ vi thuc th Dymetlyglyoxime chun bng in ct thu ngn v xc tc H2 c bc sng xc nh dng xc nh Co2+ c nhy t (5 20 ppm). Phc chelate Ni (1) v (3) c th tm thy pha tnh trong sc k lng ca mch gm cc hydro carbon khc nhau. 9.3.9. Cc monoxime: 190
Phi t hai nhnh nm trong nhm oxime c a vo 2 v tr ca pyridine, c tc dng nh thuc th st cho Fe(II), v nhng thuc th nh vy c ni n trong phn thuc th Ferroin (phn IX). Mt loi phi t hai nhnh khc c mt nhm oxime, k c salicylaldoxime (5) (H2L, nhit nng chy 50 59oC pK = 9,18; 25oC) v benzoin monoxime (6) (H2L, nhit nng chy 153 155oC pKa = 12, 50% dioxane, 25oC), ngi ta cn gi loi phi t ny l Cupron. C 2 thuc th u to thnh dng phc chelate M(HL)2 trung ha in vi Cu(II), v vi mt s ion kim loi ha tr 2, chng c th c chit vo cc dung mi hu c khng trn ln. V vy chng rt c ch trong vic phn tch cc kim loi.
H C N OH (5) OH H HO C C (6) N OH
Gn y, nhiu dng monoxime dn xut t acetophenone, acenaphthenequione, , c nghin cu lm thuc th phn tch.
VIII.4. PORPHYRIN
Porphyrin l tn gi ca hp cht c vng porphin. Cng thc cu to:
R N N H H N R H2L R N R
L thuc th c nhy cao dng xc nh Cd, Co, Cu (II), Fe(II), Hg (II), Mg, Mn (II), Ni, Pb, Pd (II), Zn v vi kim loi khc. Nhng thuc th dng ny : ,,,Tetraphenylporphin. ,,,Tetraphenylporphin tetrasulfonic acid. ,,,Tetraphenylporphin trisulfonic acid. ,,,Tetra (3Nmethylpyridyl)porphin. ,,,Tetra (4Nmethylpyridyl)porphin. ,,,Tetrakis (5sulfothienyl)porphin. 191
,,,Tetrakis (4Ntrymethylaminophenyl)porphin, tetra (toluenesulfonate). dng thng phm c th dng c. 1. Phng php tng hp v tnh cht ca thuc th: 1.1 ,,,Tetraphenylporphin (TPP): Cng thc phn t: C44H30N4 Cng thc vit tch ra: H2L Cng thc cu to: vi R l
Khi lng phn t: 614,75. Tnh cht: Dng tinh th hnh kim. im nng chy: 300oC. Thng hoa 232oC n 262oC (2.10-2 Torr). Bn trong khng kh, khng tan trong nc v cn. D tan trong benzene, chloroform, DMF v THF. C th tan trong nc (5.105 M) nu c mt ca mt cht hot ng b mt nh natri lauryl sulfate (khong 5%). Hp thu tt bc sng 438 nm (pH < 3,7) hoc bc sng 418 nm (pH < 4,5). b. Phng php tng hp: iu ch bng cch chng ct hi lu hn hp ca pyrole v benzaldehyde ( t l mol bng nhau) trong acid propionic. 1.2 Thuc th ,,,Tetraphenylporphin tetrasulfonic acid (TPPS4) v ,,, Tetraphenylporphin trisulfonic acid (TPPS3): TPPS4: Cng thc phn t: C44H42N8S4O12.12H2O Cng thc vit tch ra: (H2L)(NH4)4 .12H2O Cng thc cu to: vi R l
SO3H
Khi lng phn t: 1221,30. TPPS3: Cng thc phn t: C44H30N4S3O9.4H2O Cng thc vit tch ra: (H2L)H3.4H2O 192
Cng thc cu to: vi
1R
SO3H 3R
Khi lng phn t: 926,98. Tnh cht: Tinh th mu xanh da tri, d tan trong nc. Dung dch tinh khit c mu tm pH = 6 v mu xanh l pH = 4.
Ph hp th ca TPPS3: Quang ph hp thu ca TPPS trong dung dch nc. Trong mi trng acid, ph c trng ca dung dch tinh khit TPPS4 khng xut hin. b. Phng php tng hp: i t TPP: un nng TPP trong mi trng H2SO4 c. TPPS4 v TPPS3 l sn phm ca s th gc SO3H vo H+, ty theo nhit m ta thu c sn phm l TPPS4 hay TPPS3. Pasternack v nhng ngi khc thu c TPPS3 nh l mt acid t do, cn Ishii v nhng ngi khc tch ra c TPPS4 nh l mt mui amoni. C hai u l thuc th phn tch. 1.3 Thuc th ,,,Tetra(3Nmethylpyridyl)porphin [T(3Mpy)P] v ,,, Tetra (4N methylpyridyl)porphin [T(4Mpy): T(3Mpy)P: Cng thc phn t: C72H66N8O12S4 Cng thc vit tch ra: (H2L)(CH3C6H4SO3)4 Cng thc cu to: vi R l 193
N+ H3C
Khi lng phn t: 1363,70. T(4Mpy)P Cng thc phn t: C44H38N8O16Cl4 Cng thc vit tch ra: (H2L)(ClO4)4 Cng thc cu to: vi R l
H3C N+
Khi lng phn t: 1076,64. Tnh cht: L tinh th mu tm, tan chm trong nc. T(3MPy) P tan nhiu hn T(3MPy)P. Dung dch tinh khit ca T(3MPy)P c mu ta nht pH > 2 v xanh l pH < 1. dung dch tinh khit ca T(4MPy)P c mu ta nht pH = 4 ~ 7 v xanh l trong HCl 1M. Trong mi trng kim dung dch tinh khit T(4MPy)P c khuynh hng bm cht vo b mt ca bnh thy tinh. Ph hp thu T(3MPy)P
Quang ph hp th ca T(4MPy)P trong dung dch nc. Thuc th c nng 2,7.10-6 Ph hp thu T(4MPy)P :
194
Quang ph hp th ca T(4MPy)P trong dung dch nc, thuc th c nng 2,3. 10-6 Phng php tng hp: iu ch bng cch chng ct hi lu hn hp ca pyrole v pyridylaldehyde (t l mol bng nhau) trong acid propionic. Tip theo l s th bn bc vi methyl iodide hoc tosylmethylate. 1.4 Thuc th ,,,Tetrakis (5sulfothienyl) porphin [T(5Mpy)P] v ,,, Tetrakis(4Ntrymethylaminophenyl) porphin, tetra(toluenesulfonate) (TTMAPP): T(5Mpy)P: Cng thc phn t: C36H22N4O12S8 Cng thc vit tch ra: (H2L)H4 Cng thc cu to: vi R l
HO3S
Khi lng phn t: 959,12. TTMAPP: Cng thc phn t: C84H90N8O12S4 Cng thc vit tch ra: (H2L)(tosyl)4 Cng thc cu to: vi R l
195
(CH3)3N+
Khi lng phn t: 959,12. Tnh cht: T(5MPy) l tinh th mu xanh l, TTMAPP l tinh th mu tm m. C hai u d tan trong nc. b. Phng php tng hp: iu ch bng phng php chng ct hi lu hn hp ca pyrole v thiophene2 aldehyde hoc pdimethylaminobenzaldehyde (t l mol nh nhau) trong acid propionic. Thc hin qu trnh sulfonate ta c T(5MPy)P, tin hnh th bc bn vi tosylmethylate thu c TTMAPP. PH HP THU V HNG S PHN LY CA CC THUC TH PORPHYRIN Ph hp thu Thuc th max (nm) H2L TTP TPPS4 TPPS3 T(3MPy)P T(4MPy)P T(5ST)P TTMAPP 438 413 417 423 427 411 (x105) 10 4,76 2,80 2,60 3,17 4,93 max (nm) (x105) H4L2+ 418 434 5,00 434 444 456 423 3,80 3,24 3,29 5,14 0,80 5,49 3,65 Hng s phn ly pKa1 pKa2 iu kin
4,86
4,8 4,95 2,3 2,06 6,05 3,81
= 0,1; 25oC 25oC = 0,1NO3; 25oC NO3- 0,1M; 25oC
2. Phn ng to phc v tnh cht ca phc cht: Thuc th porphyrin to phc bn chelate dng 1:1 vi cc ion kim loi khc nhau. Tnh bn ca phc i vi ion kim loi ha tr 2: Pt > Pd > Ni > Co > Cu > Fe > Zn > Mn > Mg > Cd > Sn > Hg > Pb > Ba, khng k n s thay th vo vng porphin. Cu trc Cu (II) chelate ca TPPS4:
196
O3S-
SO3-
N N Cu N N
O3S-
SO3-
Tc to phc hi chm, nht l khi hm lng ion kim loi thp. Tuy nhin tc c th tng ln nu c thm tc nhn xc tc. V d: tc to phc ca Cu(II) vi T(4MPy)P v TPPS3 s nhanh hn nu c mt Lcysteine hoc acid Lascorbic. Tc to phc TPPS4Cu(II) hocZn(II) tng trong imidazole (C3H4N2) hoc bipyridine v T(4MPy)PMg(II) tng trong 8quinolinol. Tc nhn phc c trng cho mi h nhng k thut th khng c gii thch r rng. Ph hp thu ca thuc th d thng xen ph ln chelate kim loi, ta cn loi b nh hng ca thuc th d. H2P H4P2+
S thay i pH (Cu2+, Pd2+)
To phc vi Pb
H2P
PbP
(Zn2+, Co2+, Mn2+, ) S a vo 3 S thay th (Zn2+)

S SO3
197
Tia
S phn ly ca porphyrin hoc phc kim loi
HPLC (Cu2+, Pd2+, Zn2+, Co2+, Mn2+
Phng php u tin tn dng s thay i ph ca thuc th t do nh s acid ha. Porphyrin kim loi bn nh Cu(II)L hoc Pd(II)L th khng d b phn li bi s acid ha v hp thu mnh trong khong m thuc th nhn proton (H4L2+) th khng hp thu. y l nn tng cho vic xc nh nguyn t bng phng php o quang c nhy cao (ppb). Th hai l tn dng s thay i ph ca thuc th t do bi s to chelate vi Pb. Kim loi porphyrin nh CdL, Mn(II)L, hoc ZnL c khuynh hng phn ly do s acid ha. Thuc th d to phc vi Pb(II) l nguyn nhn cho s thay i ph. S tn dng th ba l s m u ca vic th nhm ph hp vo porphyrin gc, nh T(5ST)P ta thu c mt thuc th mi m dy hp thu khng xen ph vo porphyrin kim loi. Th t l s quang phn ca thuc th t do hoc kim loi porphyrin. VD : thuc th d T(3MPy)P hoc T(4MPy)P c th quang phn bi tia sng di nh n hunh quang trong acid ascorbic trong 30 pht. CdTPPS4 b quang phn di n hunh quang, trong khi MTPPS4 cn li th khng phn hy. Dng HPLC th hiu qu trong vic phn tch nhiu nguyn t trong mu th (xc nh Cu(II), Pd(II), Zn) bng thuc th T(4MPy)P). 3. S dng phn tch: Ion kim loi c th xc nh c bng thuc th porphyrin th c gii hn. XC NH KIM LOI BNG PHNG PHP TRC QUANG VI THUC TH PORPHYRIN Thuc th Ion kim loi Zn Kim loi chelate iu kin max Acid acetic bng (nhit phng, 60 70 pht) 551 Phm vi xc nh (x105) (ppb) 0,14 200
Tr ngi
TPP
Cu c nng ln hn.
198
Cu(II)
Cd
Pd(II) TPPS4 Pd(II)
Zn
TPPS3
Cd
Cd
Cu(II) Cu(II) Fe (II) Pb
Ha tan bng Na laurylsulfate, to phc pH 4,7 + 414 NH2OH (100oC, 3 pht), h pH 0,6 1,2 vi H2SO4 Pyridin hoc imidazole, pH 9,0 432 (nhit phng, 10 pht) To phc pH = 3,6 (100oC, 15 410 pht) h pH = 2,5 vi acid chloroacetic To phc pH = 3 (100oC, 15 pht) 419 acid ha bng H2SO4, chit vi Capriquat/benzene. To phc pH = 8,3 11, vi s c em mt ca Cd v 641 bipyridin (nhit phng, 5 pht). pH = 12,5 (NaOH), 2,2bipyridine (5 432 pht) To phc pH = 3, acid L ascorbic (100oC, 8 pht) h 411,6 pH = 2,5 vi acid chloroacetic To phc pH = 4 (100oC, 15 pht) h 434 pH = 2,5 vi acid chloroacetic pH = 4,0 (100oC, 1 em pht) 657 pH = 3,9 4,2 395 (100oC, 15 pht) pH=10,2 (borate), 464 KCN (70oC, 5 pht)
4,7
140
Ag, Hg, Zn > 10g, Pd > 5g
4,3
2,2
360
Cu(II), Zn gy cn tr. c che bng acid tartaric.
2,98
Zn gy cn tr
ex 422
Sau khi chit vi dithizone Sau khi tch Cd, CdI42-
4,45
100
2,15
250
Cu(II) v Hg(II)
4,8 ex 434 1,4 2,75
6 60
Zn Gim hunh quang do H4L2+ Cu(II),Co(II),Mn(II), Pd(II), Sn(II) v Zn Cr(III), In(III), Mn(II), v Sn(II).
20 180 50 500
199
Pd(II)
Cu(II)
T(3MPy)P Cu(II)
Cu(II) T(4MPy)P Zn Mg T(5MPy)P Zn Cu(II) Cd
TTMAPP Pd(II)
Zn
To phc pH = 4,0 + acid L ascorbic (100oC, 7 pht) h pH = 2,5 To phc pH = 6 (100oC, 7 pht) acid ha bng H2SO4 (2 3 N) To phc pH = 3 6 (100oC, 7 10 pht) acid ha bng H2SO4. Phn ng xy ra nhit phng nu c s hin din ca hydroxylamine hoc acid ascorbic. To phc pH > 4,5 (nhit phng), NH2OH.HCl 0,02% hoc acid ascorbic. pH = 9,2 10,8 (100oC, 1 pht) pH = 9,1 10,6 + 8quinolinol (100oC, 60 pht) pH = 5,0 11,0 (100oC, 15 pht) pH = 4,1 5,9 + acid Lascorbic pH = 13 (100oC, 2 pht) To phc pH = 4,5, acid L ascorbic (nhit phng, 2 pht) acid ha bng H2SO4 pH = 5 (acetate) + ferron (nhit phng, 5 pht)
411
2,2
Fe(III) v Pd(II) che bng NH2OH + KI Co(II), In, Pd(II) v V(V)
434
3,5
1 13
419
2,1
Pd(II) gy cn tr c che bng KI, hoc sau khi chit vi Chelex 100
446
2,46
190
Sau khi tch bng dithizone Sau khi chit bng dithizone o quang 2 bc sng : 428nm (ZnL) v 456nm (H4L2+) Sn, I-, ClO4-
437 em 641
2,3 ex 442
0 120 0 100
411 433
5,1 5,9
Co, Zn
432
4,9
Fe(III), Pt(II), V(V)
421
5,1
0 80
Co, Fe. Sau khi chit tch ion ZnCl42-
Nhng ion gy nh hng c che bng nhng tc nhn thch hp hoc s phn tch s b. Dn xut 4carboxyphenyl c kim tra nhanh nh mt thuc th cho Cd v Cu(II) v dn xut nsulfoethylpyridinium l mt dng khc ca thuc th porphyrin ha tan trong nc m khng kt hp trong mi trng acid, cng khng 200
hp thu vo b mt thy tinh trong mi trng kim. Bn cnh nhng ng dng ny, TPPS4 th b phn ly bi KBrO3 vi s c mt ca Ru(III) dng vt, c th xc nh Rb nng rt thp (1010 M). C th xc nh cc kim loi da vo s xut hin hunh quang trong phc ca thuc th porphyrin (Mg v Zn) hoc s tt hunh quang bi nhng kim loi (Co(II), Cu(II), Pb, v Pd(II)).
VIII.5. DIAMINOBENZIDINE V NHNG THUC TH TNG T

H2N H2N (1) NH2 NH2 NH2 NH2 X NH2 NH2 (3) X = H (4) X = Cl (5) X = NO2
(2)
1.Danh php Nhng odiamine thm bao gm trong phn ny c lit k trong bng IX.4.1, chung vi nhng danh php ca chng. Bng IX.4.1: NHNG oDIAMINE THM Thuc th (1) (2) (3) (4) (5) Diamine 3,3 Diaminobenzidine, tetrahydrochloride 2,3 Diaminonaphthalene 1,2Phenylenediamine 5Chloro1,2 Phenylenediamine 5Nitro1,2 Phenylenediamine Danh php 3,3,4,4 Biphenyltetramine, tetrahydrochloride,DAB DAN phenylenediamin Cng thc phn t v khi lng mol C12H14N4.HCl.2H2O; 396,14 C10H10N2; 158,20 C6H8N2; 108,14 C6H7N2Cl; 142,59 C6H7N3O2; 153,14
2.Ngun gc v phng php tng hp Tt c chng u c gi tr thng mi. Chng c to ra bng cch kh nhng hp cht nitro lin kt: (1) t 3,3dinitrobenzidine, (2) t 2,3dinitronaphthalene, (3) t onitroaniline v (4) t 4chloro2nitroaniline vi Sn/HCl. (5) to ra bi s kh 2,4dinitroaniline vi (NH4)2SO4 3. Nhng ng dng phn tch Nhng thuc th ny c chn lc cao cho Se. (1) v (2) c s dng nh l 201
nhng thuc th trc quang trong vng kh kin v vng UV, tng ng. (2) c s dng trong phng php hunh quang. (4) v (5) dng cho trc quang v sc k kh. 4. Nhng tnh cht ca thuc th - 3,3Diaminobenzidine (1): thng c cung cp nh tetrahydrochloride dng bt tinh th, khng mu, to nng chy 328 330oC (c s phn hy). Ho en ngoi nh sng, do cn c gi ni lnh, ti di kh nitrogen. D tan trong nc nhng khng tan trong nhng dung mi hu c khng phn cc. - 2,3Diaminonaphthalene (2): trng thi tinh khit dng bt tinh th, khng mu, nhng nhng mu ( sn phm ) thng mi thng c mu vng hoc xm nu v s oxi ho ca khng kh, to nng chy 190 191oC v hu ht khng tan trong nc lnh, cn nhng s tan kh to > 50oC. c bo qun ni lnh v ti. - oPhenylenediamin (3): dng bt tinh th, khng mu, d ho en trong khng kh, to nng chy 101 103oC v d tan trong nc, cn. Thuc th ny nn c bo qun ni lnh, ti; pKa1(H2L2+) = 0,86; pKa2(HL+) = 4,75. - 5Chlorophenylenediamine (4): dng bt tinh th, khng mu, kh b oxi ho ngoi khng kh hn (1) v (3), to nng chy 72 74oC. D tan trong nc v dng dung dch th thuc th ny cng bn; pKa1(H2L2+) = 0,11; pKa2(HL+) = 4,16. - 5Nitrophenylenediamine (5): dng bt tinh th mu vng sng, kh bn trong khng kh, to nng chy198 200oC. D tan trong nc; pKa(HL+) = 3,07. 5. Phn ng to phc v tnh cht ca phc + Phn ng vi ion kim loi - Nhng odiamin thm ging nh phi t 2 nhnh v tr n,n (chelate c 2 nhm c kh nng lin kt vi ion kim loi) hnh thnh phc mu vi nhiu ion kim loi. VD: thuc th (3) tc dng vi Pt(II) to thnh phc chelate loi ML2 (max= 703nm, = 9,8.104) mi trng trung tnh; thuc th (1) tc dng vi V trong mi trng pH = 2 3 to ra phc chelate loi ML (max = 470nm; = 3310). Tuy nhin, chng l nhng thuc th khng c nhiu ng dng thc t quan trng ging nh nhng thuc th to mu i vi nhiu ion kim loi. + Phn ng vi Se(IV) - u tin tm thy thuc th (1) tc dng vi Se(IV) trong mi trng acid to phc c mu vng gi l piaselenol, n c th c chit vi dung mi hu c pH = 6 7 nh l: benzene, toluene, chloroform, butanol, ethylacetate. Phn ng ny c th c vit:
H 2N H 3N + NH2 NH3+ + H2SeO3 H2N H 3N + N Se N + 2 H 2O
+
H 3O +
- Kt qu l piaselenol sinh ra mu vng v c th c xc nh bng trc quang vng kh bin, iu ny chng minh hnh 1. Sau ny nhiu odiamine thm khc c tm thy hnh thnh piaselenol v nhng thuc th (2), (5) l nhng thuc th chn lc i vi Se(IV). Ngc li vi piaselenol ca (1) th hp th cc i ca piaselenol ca (3) nm vng t ngoi (UV). Trong trng hp ca piaselenol ca (2) 202
th hp thu hunh quang bc sng di hn so vi dng t do ca thuc th (2) iu ny c chng minh hnh 2 v hnh 2 ny c th a ra vic xc nh Se(IV) bng hunh quang vi nhy cao. Nhng c im ph hp thu v ph hunh quang ca piaselenol c tng qut bng IX.4.2 v IX.4.3. - Piaselenol t (3) (5) d bay hi v vy n c th c phn tch bng sc k kh. Hm lng siu vt ca paselenol ca (4) v (5) c th c pht hin bng detector ECD.
hp th
Hnh 1: Ph hp thu ca 3-3diaminobenzidine v piaselenol trong toluene: (1) 25g Se trong 10ml toluene; (2) 5g Se trong 10ml toluene; (3) 3,3Diaminobenzidine (1) trong toluene; nng thuc th, 0,5% trong nc.
Bc sng nm
Hnh 2: ph hunh quang ca 2,3 diaminonaphthalene v piaselenlol ca n. (1) 2,3diaminonaphthalene (ex = 336nm); (2) Piaselenol (ex, = 377nm) Bc sng nm
Bng IX.4.2: C IM PH HP THU CA PISELENOL TRONG TOLUENE D (pH 2) Gii hn xc nh (ppm Se)
Thuc th
Cng iu kin
max (nm) (x104)
nh hng
203
(1)
(2) (3) (4) (5)
phn ng 335 0,78a pH = 2 3; 50oC; 420 1,19b 50pht pH = 1,7 380 1,18 2,2; (378) (4,1)c 120 pht pH = 12,5; 120 335 1,78 154 pht pH < 341 1,84 2580 2,3; 90 (340) (4,90) pht pH < 2; 350 1,55 367 150 pht
5 26
Ce(IV),Cu(II),Fe(III), V(V),SO42-, CrO4- v MnO4Cu(II),Te(IV),NO3-, NO2-, cht oxy ha Bi(III),Re(III),Mo(IV),Sb(III), Sn(IV) Fe(III),Mo(VI), Sn(IV),V(V) nhng Fe(III) v Mo(VI) c th c bo v vi EDTA
~4 ~ 2,5 ~ 2,5
a: Gi tr cho chit mt ln b: Gi tr cho chit ba ln c: Gi tr trong ngoc n cho piaselenol c lp Bng IX.4.3: C IM PH HUNH QUANG CA PIASELENOL Thuc th ex (nm) em (nm) Dung mi Gii hn xc nh (ppm Se) (1) 420 550 600 Toluene 0,02 0,4 (2) 377 520 Cyclohexane 0,001 0,1 (3) 400 448 Cyclohexane 0,01 0,1 6. Nhng ng dng trong phn tch - ng dng thc tin ca nhng thuc th ny ch xc nh Se(IV). V s oxi ho khc th Selen khng phn ng vi nhng thuc th ny, Selen trong mu phi b kh hoc oxi ho v Se(IV). Mt trong nhng cch thun li oxi ho Se2- v So l s dng dung dch m oxi ho kh (Br/Br-) sau khi ph mu t. S kh Se(VI) Se(IV) ta dng Ti(III). - Thuc th (1) c ngh cho phng php trc quang trong vng thy c. iu kin ph hp, thuc th (1) phn ng vi Se(IV) pH = 2 3 50oC. Nhng s cn thit ca phc piaselenol ny phi c thc hin pH = 6 7 bi nh hng ca s proton ho ca nhm amin t do. S chit nhiu ln ca piaselenol vi toluene l cn thit t c s tch 1 cch nh lng (t 60% cho ln tch 1). Ion SO42gy cn nhiu i vi vic xc nh bi vic to kt ta vi thuc th to ra suffate khng tan, nhng c th c che y bng cch thm lng d NH4Cl. Nhng cation ph bin c th c che bng EDTA, Fe(III) c th c che bng F-, PO43- v Cu(II) c th c che bng oxalate. - Thuc th (3) cng c dng nh thuc th to mu vi Se(IV) nhng trong vng UV. Tuy nhin, lng tha thuc th khng c chit vo toluene bi v s chit piaselenol c thc hin pH = 1 2. Hn th na thuc th ny khng b cn nhiu vi SO42- v nhy cao gp 2 ln so vi (1). 204
- Vic xc nh hm lng siu vt ca Se c th t c bng vic s dng phng php hunh quang vi thuc th (2) hoc phng php sc k kh vi thuc th (3) (5). Trong phng php hunh quang, iu quan trng l s dng diaminonaphthalene (2) tinh ch vi nn hunh quang thp quan st = 520nm. Trong sc k kh, dung dch mu (pH1) c x l vi lng d thuc th (4) hoc (5) trong 1h. Phc piaselenol c chit vi 1ml toluene v 5l dd c a vo sc k kh vi iu kin sau. - Ct thu tinh c chiu di 1m, c ng knh 4mm, y cht hp ph chromosorb c kch c li 60 n 80 cha 15% SE 30, nhit ca ct v u d bt in t l 200oC, tc dng ca kh mang 20ml/pht He. - Nhng Cation ph bin,nu khng ln qu gii hn, khng gy nh hng hay nhng phc khng bay hi. C th xc nh lng nh bng 0,15g Se mi ml Toluene. Phng php ny c ng dng xc nh hm lng siu vt ca Se trong acid sulfuric, Telua kim loi, nc bin, nhng mui ng, nguyn liu cy trng v sa . 5.S tinh ch v tinh khit ca thuc th: - Thuc th (1): cht b h hng nh c th c tinh ch bng cch ho tan vo nc, sau cho kt ta vi HCl m c. Nhng kt ta ny c lm kh trn NaOH. Tht khng d dng tinh ch cht ho en. - Thuc th (2) : dung dch thuc th ny c nn hunh quang thp do nn c pha hng ngy. Ho cht ny c kt tinh li trong nc 0,05g ho cht (2) ho tan vo 50ml HCl(0,1N) to 50oC. Sau lm lnh (ngui ) ri dung dch ny c chit 2 ln vi 10ml decalin (C10H18) loi b i nhng g khng tinh khit v a vo li tm ly ra tinh th ho cht. - Thuc th (3), (4), (5): nhng thuc th ny c th c tinh ch li bng s kt tinh li t nhng dung mi kt hp. S tinh khit ca nhng thuc th ny, ngoi tr (1), c th c c on bng vic quan st to nng chy ca chng.
205
CHNG IX:
THUC TH VI CU TRC S
IX.1. DITHIZONE AND NHNG THUC TH TNG T
N N HS C N N H
CTCT: C13H12N4S KLPT: 256,32
1. Danh php Dithizone hay cn gi l 1,5diphenylthiocarbazone, n,ndiphenylC mercaptoformazane, phenylazothioformic acid 2phenylhydrazide. 2. Ngun gc v phng php tng hp c dng trong thng mi. c tng hp bng phn ng gia carbon disulfide v phenyldrazine, km theo un nng cn thn oxy ha hn hp phn ng. 3. ng dng trong phn tch c s dng rng ri trong phng php chit trc quang xc nh cc kim loi nng nh: Cd, Cu, Hg, Pd v Zn v c tnh chn lc v nhy cao. 4. Tnh cht ca thuc th Dng bt tinh th mu tm en c nh kim, im nng chy 165oC n 169oC, thng hoa 40 n 123oC (0,02 Torr). Thc t khng tan trong nc pH nh hn 7 (5 n 7,2.10-5g/l), nhng tan hon ton trong kim (pH >7, > 20 g/l) c mu vng ca ion dithizoneate (HL-) (max = 470 nm, = 2,2.104) v tan trong nhiu dung mi hu c khc. tan trong nhng dung mi chn lc c lit k trong bng X.1.1 Bng X.1.1: PH HP THU TRONG VNG KH KIN TRONG NHNG DUNG MI HU C CA DITHIZONE Dung mi Ethanol Carbon tetrachloride Dioxane nc + dioxane Benzene Chlorobenzene Nitrobenzene 206
tan (g/L,20oC) 0,3 0,512 0,349 1,24 1,43
max (nm) 1st 2nd
(x103) 1st 2nd
R(t s peak) 1,64 1,70 1,72 1,98 1,80 1,90 1,91
Mu Xanh nc bin Xanh Xanh m Xanh
596 440 27,0 16,6 620 450 34,6 20,3 617 602 622 622 627 446 446 453 452 454 31,9 32,4 34,3 34,8 31,9 19,1 16,4 19,0 18,3 16,7
Chloroform
16,9
605 440 41,4 15,9
2,59
Xanh nc bin
Mc d dithizone c cho l mt diacid (phn ly thiol proton v imino proton), khng c du hiu ca L2- trong dung mi nc. Trong s cc gi tr pKa c bo co th gi tr pKa = 4,470,25 l tt nht, n c nh gi t bng tan. H s phn b ca dithizone gia hai pha nc v pha hu c c th c trnh by v n gin ha nh di y nu trong mi trng l baz vi [H2L]aq << [HL-]aq v [H+] << Ka: Ph hp th ca dithizone (H2L) trong carbon tetrachloride, ion dithizonate (HL-) trong nc, v mercury dithizoneate [Hg(HL)2] trong tetrachloride biu din trong hnh 2. Ph ca dithizone trong nhng loi dung mi hu c biu din thnh hai di ph kh r m n c quan h ti hin tng h bin thione (1) v thiol (2), mc d nhim v ca mi pic th hin vi mt loi tng ng nhng cha dt khot.
N N S C N NH H H S C
N N H N N
(1)
(2)
Hnh 2:Ph hp th ca dithizone (H2L) v Mercury(II)dithizonate trong carbon tetrachloride v ca ion dithizonate (HL-) trong nc. (1) Dithizone (H2L) trong CCl4; (2) dithizonate (HL-) trong nc; (3) mercury(II) dithizonate [Hg(HL)2] trong CCl4.
Bc sng nm 5. Phn ng to phc v tnh cht ca phc Dithizone cho phi t S,N, u tin phn ng vi nhng kim loi nh. Nu d thuc th v trong pha nc l mt acid, cation trong pha ny phn ng vi dithizone ha tan 207
trong dung mi hu c to mu phc chnh phn b trong pha hu c.

+ M n + + nH 2 L org M ( HL )n org + nH
Ion kim loi phn ng vi dithizone c minh ha trong hnh 3. Nhng phc ny tan trong cc dung mi hu nh chloroform hoc carbon tetrachloride. Cu trc chnh ca dithizonate cho ion kim loi tetracoordinate ha tr II c th trnh by nh sau (3)
H N N M N S C N
N N
C S N N H
(3) Nu kim loi d hoc pH cao, cc ion kim loi nh: Cu(II), Ag v Hg, cho phc ph m cu trc ca chng c cho (4) v (5) cho nhng cation ha tr II v I, tng ng
N N M N N C S S C N N N M N N N M S C M N N
(4)
Ia H Li Na K Rb Cs Fr Be Mg Ca Sr Ba Ra Sc Y La Ac Ti Zr Hf Th V Nb Ta Pa Cr Mo W U Mn Tc Re Fe Ru Os Co Rh Ir Ni Pd Pt Cu Ag Au Zn Cd HG IIa IIIa IVa Va VIa VIIa VIII B Ib IIb
(5)
IIIb IVb Vb VIb VIIb H C Si Ge Sn Pb N P As Sb Bi O S Se TE Po F Cl Br I At O He Ne Ar Kr Xe Rn
Al Ga In Tl
208
Hnh 3: Kim loi c chit bi dithizone v kt ta di dng sulfide t dung dch nc. Kim loi trong vng m c t en c th tch di dng sulfide t dung dch nc v khng to thnh phc chit dithizone. Kim loi trong khung cn li c th chit bng dithizone t dung dch nc. 6. S tinh ch v tinh khit ca thuc th Dithizone rn bo qun tt trong ti v t lnh trnh khng kh oxy ha , mu thng mi c tinh khit t 30 n 90%, ph thuc vo iu kin tn tr. Thuc th rn th c tinh ch bng cch chit Soxhlet vi ether loi cc sn phm oxy ha, km theo ho tan trong chloroform nng v thm alcohol kt ta. Phng php tinh ch hiu qu hn vi lng mu nh: Lc dung dch c ca mu th trong tetrachloride bng phu thy tinh, sau lc phn lc vi dung dch ammoniac 0,8N chit ion dithizonate. Chit pha nc vi carbon tetrachloride. Cui cng acid ha dung dch vi acid sulfuric kt ta dithizone tinh khit. Lm kh mu trong chn khng. Lng milligram c th c tinh ch bng phng php sc k vi dung dch benzene, trong ct gm c hn hp silicagel c celite 545 hoc sc k giy. tinh khit ca dithzone c th c xc nh bng mt trong nhng phng php sau: a. Phng php trc quang hp th ca dung dch carbon tetrachloride ca nng dithizone c bit o quang 620nm v lp li tng t vi mu trng. tinh khit c tnh bng cch da trn hp th ca phn t gram ca dithizone tinh khit ( = 3,4.104 620nm). b. Phng php th tch Chun dung dch chloroform ca nng dithizone c bit (0,125 mg trong 10 ml) bng dung dch AgNO3 50.10-6 (25,0 ml), loi b pha hu c sau mi ln chit. Chit chun cho n khi phn chit khng cn mu vng, nhng hn hp c mu vng xanh. tinh khit c tnh t gi tr ca dung dch dithizone b ph hy trong chun . c. Phng php t s peak T s cng ca hai m ph nh ln ca dithizone (1 = 602 n 617nm, 2 = 440 n 454nm) c th dng o tinh khit bi v dithizone khng tinh khit hp th di 550nm. Mc d v tr ca hai m ph hu nh khng thay i khi thay i dung mi, nhng t s cng thay i mt cch ng lu . Gi tr trong chloroform v carbon tetrachlororide nh sau: A605/A445(CHCl3) = 2,59 A620/A450(CCl4) = 1,70 7. ng dng trong phn tch Thuc th chit: Phm vi ca ion kim loi c chit vi dithizone trong dung mi hu c c th 209
c tnh t K[H2L]org v pH ca pha nc. S phn li (tch) ca hai hoc nhiu ion kim loi c th t c nh s la chn pH thch hp ca pha nc v nng dithizone trong pha hu c. chn lc cho nhiu ion kim loi c th c ci thin hn bi s kt hp s dng cc tc nhn tr phc (hoc tc nhn che). Mt vi v d in hnh tm tc trong bng X.1.2. Bng X.1.2: CHN LC TRONG CHIT DITHIZONE iu kin Min kim Dung dch kim cha CNDung dch kim mnh cha citrate hoc tartrate Dung dch kim nh cha kp (2-hydroxyethyl) Dithiocarbamate Min acid Dung dch acid nh cha CNPha long dung dch acid cha Br- hoc IPha long dung dch acid cha CN- hoc SCNDung dch acid long (pH=5) cha S2O32Dung dch acid long (pH=4-5) cha S2O32Pha long dung dch cha EDTA Thuc th trc quang: Chit trc quang vi dithizone c th c thc hin bng ba cch: trc quang n mu, trc quang hn hp mu, v trc quang lng sng. Trc quang n mu: Mu dung dch sau khi hiu chnh pH v thm cc cht b tr cn thit, lc lin tc chia carbon tetrachloride hoc chloroform ca dung dch dithizone n khi tt c kim loi bt u tch ra. Giai on cui cng ca qu trnh chit, mu ca dung dch dithizone cn li l mu xanh l cy. Kt hp chit sau khi lc vi vi ammoniac long chit phn dithizone d, dung dch thu c em o trc quang. Nhiu nguyn nhn dn n sai s trong phng php ny. Nu trong mi trng ammoniac qu cao, mt vi kim loi dithizonate c th b phn li, kt qu ph nh sai s. Nu trong mi trng khng mnh, dithizone khng chit hon ton, kt qu c th sai s. Dithizone c th c di chuyn d dng trong dung dch carbon tetrachloride hn trong dung dch chloroform. Bn cnh kh nng thay i phc chnh thnh phc ph do s ty ra ca kim. V th, trong thc t khng th loi b dithizone tha mt cch trit khng hnh thnh vi phc ph. Trc quan hn hp mu: Trong phng php ny, dung dch hu c cha dithizonate kim loi v dithizone d c xc nh. Khi peak thu c ca nhiu dithzonate kim loi hin ra mt cch hn n trong mt vng ni m ng dithizone t do c hp th thp nht, php trc quang thng xc nh ti gi tr max, hp thu dithizone d c n b bng vic o mu trng. Sai s chnh trong phng php ny c th do mt dithizone b oxy ha trong qu trnh phn tch, nhng c th lm gim n gi tr nh nht bng mu trng, nhng t c iu ny th qu trnh phn tch cng nh trong bc chit 210
Ion kim loi c chit Bi, Pb, Sn(II), TL(I) Ag, Cd, Co, Cu, Ni, Yl Zn Ag, Cu, Hg(II), Pb(II) Au, Cu, Pd Cu, Hg CD,Pd, Sn(II), Zn Sn(II), ZN Ag, Hg
phi hon ton ging nhau gia mu phn tch v mu trng. Trc quang lng sng: Trong my quang ph k, hai chm tia sng c bc sng khc nhau c chiu ln lt qua tng cuvet, v s khc nhau gi tr A gia hp thu c o ti bc sng 1 v 2. Khi hai bc sng ring bit 1 v 2 c chn 510nm v 663,5nm tng ng hn hp dithizonate thu ngn v dithizone t do c minh ha trong hnh 4, A t l vi nng ca mercury dithizonate, vy trong phng php ny hp th ca dithizone t do t ng c n b, trnh s dng mu trng.
Bc sng nm Hnh 10.4: Ph hp thu ca dithizone v mercury(II) dithizonate [Hg(HL)2] trong nc. Dung dch Triton X-100 dithizone; 8. Chun b dung dch thuc th Dithizone tan trong kim, nhng khng bn c th khng c s dng cho mc nh thc t. Nhng dung dch c gii thiu nh carbon tetrachloride hay chloroform, nhng tinh khit ca nhng dung mi nh hng ln n bn ca dithzone trong dung dch v hp th trong quang ph ca dithizone. Nng ca dithizone trong dung mi chit khong 0,001% cho php trc quang v 0,01% cho chit dung mi. Dung dch carbon tetrachloride c nh gi l n nh khi che dung dch vi 10% th tch bng acid sulfurous 0,1N v bo qun trong ti v lnh. Trong dung dch chloroform s dng tt trong vic bo qun trong ti hn l s dng cht kh. Gn y, dung dch n nh ca dithizoneate kim loi, v d nh Zn(HL)2, th c gii thiu dng cho khng chit trc quang lng di sng i vi vt nhng ion kim loi nh: Cu(II), Hg(II) hoc Ag. Dithizonate kim loi tan c vi s tr gip ca cht c hot tnh b mt nonionic nh l Triton X100 v dithizone l dng phc ca km, trong situ, acid ha dung dch n pH = 1, m Zn t do th khng nh hng n vic xc nh. Khong 5mg km dithzonate c x l vi phn nh ca dung dch Triton X100 20% trong ci m no, thm dung mi tng t c 100 ml. Dung dch thu c sau khi lc bng mng lc (l 0,45m) thu c dung dch trong sut. Bo qun trong ti v lnh. 211
hp th
mercury(II)dithizonate[Hg(HL)2]
9.Mt s thuc th khc c cu trc tng t Nhng dithizone thay th Dui y l nhng dithizone thay th c tng hp v tnh cht vt l ca chng c nghin cu cho vic s dng nh l mt thuc th phn tch. 2,2 (hay o,o) dichlorodithizone 4,4 (hay p,p) dichlorodithsone 2,2dibromodithizone 4,4dibromodithizone 2,2diioddithizone 4,4diioddithizone 4,4diflorodithizone 2,2dimethyldithizone 4,4dimethyldithizone 4,4disulfodithizone Di(o hay p diphenyl) thiocarbanzone Dinaphthyl (6) v dinapthylthiocarbazone
IX.2. THIOXIN
CTPT: C9H7NS.2H2O KLPT: 197,25
HS N
1. Danh php 8Mercaptoquynoline, 8quinolinethiol 2. Ngun gc v phng php tng hp Thioxin c gi tr kinh t nh l H2 hoc HCL. N c to ra bi s kh ca quinolyl8sunfunylcholoride vi SnCl2 hoc s phn ng ca diazon ha 8amino quinoline vi thioure. Bn thn ca thioxin kh khng bn vi s oxy ha ca khng kh. Diquinolyl88disunfile l sn phm oxy ha ca thioxin, n c dng nh l mt cht tiu biu, n nh v c gi tr thng mi. Thioxin d dng c iu ch bng kh disulfide vi H3PO23. 3. Nhng ng dng trong phn tch Thioxin l mt sunfua tng t ca 8quinolinol (oxine) v c coi nh mt phi t cho S, N hnh thnh phc chelate kim loi vi nhng ion kim loi nh nh l Ag, As, Bi, Cd, Co, Fe, Ga, Hg, In, Ir, Mn, Mo, Ni, Os, Pb, Pd, Pt, Re, Rh, Ru, Sb, Se, Sn, Te, Tl, V, W v Zn. Thioxine c s dng nh l: php o trc quang, hunh quangv l dung mi chit trong phn tch cc vt ca nhng nguyn t ny. 212
4. c tnh ca thuc th Mc d bn thn Thioxin l dng du mu xanh ti, nhng dng dihydrat l tinh th hnh kim c mu ti, nng chy 58 59oC v nhit thng hoa l 99 177oC (2.10-2 Torr). N d dng oxy ha trong khng kh cho ra diquinolyl8,8disulfide. Disulfide c th c to nn bi s oxi ho vi H2O2. Disulfide c dng bt trng, im nng chy 202 204oC v rt n nh. Hidrochloride (HL.HCl) v mui natri (NaL. 2H2O) ca n l dng bt mu vng v nn bo qun di nit trong bng ti, mc d chng n nh hn c thuc th t do. Thioxin tan t trong nc (0,67 g/L 20oC, pH = 5,2) nhng d dng tan trong dung mi hu c nh l l C2H5OH (12,5g/100ml), chloroform, aceton, pyridine, benzene, toluene. N l dung dch nc mu vng cam trong mi trng trung ha nhng bin i mu vng ti trong acid hoc trong kim. Trong pyridine, quinoline, v nhng dung dch khc c mu xanh. Trong benzene v toluene c mu nu. Hidrochloride hoc mui natri ca n d dng ha tan trong nc, acid HCl cha nc v dung mi hu c phn cc, nhng n khng ha tan trong dung mi hu c khng phn cc. Quinolyl8,8disulfide khng ha tan trong nc hoc dung dch kim nhng d dng ha tan trong acid. S phn tch acid ca Thioxin c miu t nh sau:
+ + 1 H 2 L+ h + HL + H L
a2 + HL + H + L H + L
Ka
H+ v H+L- ch r s trung tnh (1) v dng ion lng tnh (2) ca thuc th. Kt
N SH SN+ H
(1)
(2)
C hai dng tn ti nh l hn hp h bin v hng s h bin c th nh sau:

Kt = Ion lng tnh Trung tnh
Nhng gi tr c quan st trn hng s phn li acid v hng s h bin trong nc v dioxan c tng kt trong bng X.2.1, vi s so snh ca 8quinolinol v 8 quinolline selenol Bng X.2.1: HNG S PHN LY ACID CA THIOXINE TRONG NC V TRONG 50% DIOXANE H NC Thuc th 213
Trong nc
Trong 50% dioxane h nc
Kt pKa1 8-Quinolinol 0,04 5,13 Thioxine (8quinolinethiol) 3,8 2,0 8Quinolineselenol 1740 -0,08 Loi H2L+ HL LpH
pKa2 9,74 8,36 8,18
pKa1 3,97 1,74 0,12
pKa2 11,54 9,20 8,50
Bng X.2.2: NHNG C IM PH CA THIOXINE max(nm) (x103) 243 16,57 0-2 316 4,28 14,4 252 17,97 278 5,2 0,82 316 1,6 446 260 19,29 12-14 368 3,25
Quang ph hp th ca thioxin (H2L+, HL, L-) trong nc c minh ho trong hnh1. c im ph ca mi loi c tm tt trong bng X.2.2. H s hp th phn t r rng c bit tng thm khi thioxin b oxi ho trong khng kh. Thioxin c coi nh l mt loi thuc nhum ca qu trnh solvate chromic. Thay i ph ca n vi phn cc ca nhng dung mi bi v thnh phn cn bng ca dng trung tnh v ion lng tnh thay i vi phn cc ca dung mi.V d c ch trong hnh 2 v 3. Thioxin c th chit nh lng t pha nc vo trong chloroform trong dy pH = 2 8,4. T l phn b ca HL pH 6,2 ( = 0,15; 20oC) trong h thng ca dung mi hu c/ nc l: 324(CHCl3), 250(BrC6H5), 160(C6H6), 81(CCl4) v 10,4(iso octan).
hp thu phn t (x104)
Hnh1: Ph hp thu ca thioxine trong nc. (1)pH = 0(H2L+); (2) pH = 5,2 (HL); (3)pH = 13 (L-)
Bc sng nm
214
hp thu phn t (x104)
Bc sng nm Hnh 2: Ph hp thu ca thioxine trong cc dung mi khc nhau. (1) (3) (4) (5) (6) (7) (8) , trong methanol , trong octanol , trong DMF , trong pyridine , trong dichloroethane , trong chloroform , trong acetone nng 3,0M thuc nhum nng 2,5x10-1M thuc nhum nng 1,7x10-2 thuc nhum nng 3,4x10-2M (2) ------ , trong ethanol
(9) . , trong benzene
hp thu phn t (x104)
Hnh 3: Ph hp th ca thioxine trong nc- ethanol. (1) ethanol 100%; (2) 80% ethanol - 20% nc; (3) 50% ethanol 50% nc; (4) 30% ethanol-70% nc; 100% nc.
Bc sng nm Bng X.2.3: CC IU KIN TI U CHO QU TRNH TA V CHIT 215

NHNG ION KIM LOI BNG THIOXINE Ion kim loia As (III) AS (v) Au (III) Bi Cd Cu(II) Hg(I) Hg(II) Ir(III) Mo(VI) Os(III) Pb Pb Pt (II) S kt ta iu kin ti u HCl 3N HCl 1N HCl Acid tartaric Thnh phn (H2L)3MCl3.3 H2O NL5 (H2L)3MCl6. H2O ML3 Mu (nhit thng hoa)b Vng Vng Vng Vng Chit iu kin ti u < H2SO4 3,5N Tan trong hn hp HCl Acid mnh pH 7-11,5 Dung mi CCl4 CHCl3 CHCl3 CHCl3 CHCl3 CHCl3 CHCl3 CHCl3 CHCl3 hay DMF CHCl3 hay Toluene CHCl3 Toluene CHCl3 CHCl3
pH 1-11 (NH3) ML3 Cam - vng pH > 4 HCl 4N-NaOH ML2.H2O Nu (173-232) > HCl 2,5N 3N Acid trung tnh ML.HL. 2H2O - nu Acid mnh HCl 3N pH 2-3 pH > 2,6 ML2 HL3 Vng (77 - 180) Hng pH 7,6 -9 Xanh en (186Mo2L2. H2O Acid mnh 257 ) HL3 ML2 MLCl ML2.H2O ML MOL2 MO2L2 ML2 Xanh tm Vng Vng nht vng Xanh l cy Xm en Vng cam (144190) pH 7,5 pH > 4,5 pH 5-9 pH 9-14 HCl 5NpH 4 pH > 1
pH > 2,3(HCl) HCl 1N Acid yu v kim Tl (I) yu V (IV) Acid W(VI) Zn HCl 5N - pH 5 pH 4,5
a: Ion kim loi khc kt ta vi thioxine bao gm Ag, Co(II)(III), Cu(I), Fe(II)(III), Ga, In, Mn, Ni, Rh, Ru, Sb(V), Se(IV), Sn(IV)(II), Te(IV), V(V). b: Nhit thng hoa 2.10-2 Torr 5. Phn ng to phc v tnh cht ca phc Thioxin phn ng vi ion kim lai nh, dng kt ta khng ha tan hoc l nhng 216
dung dch mu. Thnh phn ca chelate ph thuc vo tnh cht ca acid v acid ca dung dch, s hin din ca anion uc tng kt bng X.2.3 Hng s bn ca chelate thioxine trong 50% dioxane h nc c tng kt trong bng X.2.4. S hnh thnh hng s ca chelate thioxine trong chloroform h nc:
+ n (L ) ( M K ) MLn
n+ aq
MLn ( ML n ) org aq
K'
cng bao gm trong bng. Phn ng ca Thioxin vi ion kim lai trong s hin din ca cc tc nhn bo v khc c u t t m. Hu ht cc tc nhn bo v hiu qu chng li Thioxin l acid HCL c vi (Ag, Bi,Fe, Hg, Mo, Sb, v Sn), thiore vi (Ag, Au, Cu, Hg, Os, Pt v Ra), NaF vi (Fe(III) ,Sn(IV), v kim KCl vi (Ag, Cu ,Co, Fe(II), Ir, Ni, Os, Pd, Pt v Ru). KSCN l mt tc nhn bo v tt nht cho Fe(III) v mt s tc nhn nh l Cd v Zn. Hnh 4 ch ra nguyn t c th chit vi Thioxin vo trong CHCl3. Gi tr pH ph thuc vo phn trm dung dch chit cho mt s ion kim lai i din trong h nc chloroform c minh ha hnh 5. Gi tr ca logDML2(CHCl3/H2O) pH ti u l c bo co nh sau: 4,11 cho FeL2, 6,15 cho HgL2, 2,78 cho PbL2 v 5,92 cho ZnCl2. T l phn b c l c ci thin bi vic kt hp bi tc nhn to phc ph, nh l pyridin hoc 1,10phenanthrolin. D liu v tan ca mt s chelate Thioxin trong nc v chloroform c tng kt trong bng X.2.5.
% chit
Hnh 5: S ph thuc pH vo % chit ca phc thioxine trong nc-chloroform
% chit
Bng X.2.5: TCH S TAN V TAN CA THIOXIANTE KIM LOI Thioxine chelate logKsp (=0,25(NaCl), 20oC) tan trong CHCl3 AgL 2,6x10-4 217
BiL3 CoL2 FeL2 HgL2 MnL2 NiL2 PbL2 VOL2 ZnL2
-46,31 -29,60 -15,94 -26,02 -25,10 -29,44
5,8x10-5 3,1x10-3 1,7x10-2 1,1x10-3 1,2x10-4 7,1x10-2
Hu ht cc chelate Thioxine kim lai ch c mt di hp th n trong dy kh kin, bn thn n rt hu dng trong chit trc quang xc nh vt ca ion kim lai. c tnh quan ph ca ion kim lai Thioxinat l c tng kt trong bng X.2.6. Hnh 6 minh ha mt cch in hnh ng hp th in hnh ca chelate thioxin, chelate Cd v Zn trong CHCl3 a ra hunh quang fluor 535 nm.
hp thu phn t (x104 )
hp thu phn t (x103 )
Bc sng nm Hnh 6: Ph hp thu ca phc Thioxine trong chloroform. (1)GaL2; (2)InL2; (3)TiL. 6. S tinh ch v tinh khit ca thuc th Thioxin (dng baz t do) d dng oxy ha trong khng kh (khng d dng oxy ha vi HCl v mui Na), trong th trng nhng mu oxy ha mt cch khng hon ton dn n s nhim bn vi diquinolyl8,8disunfile (M2S) nhng mu ny khng ha tan trong nc. Mc d cht lng ni trn ca dung dch cha nc thng xuyn c s dng vi nhng mc ch c th, n c th c lm tinh khit bi s chim hu ca dung mi xc nh. Tuy nhin cch tt nht Thioxin t c tinh khit l s tng hp t diquinolyl8,8disulfide. Ha tan 5,5g disulfide trong hn hp 20 ml acid HCl c v 6 ml acid H3PO4 50%, un nng dung dch di bnh hi lu trong nit khong 2 gi, lm lnh v lc dung dch, thm vi git dung dch NaOH trong tin trnh bo ha dng sui nit. Lc kt ta mu vng ca mui natri (phn kt tinh) mt vi gi trong ru cho n kh. 218
Mui natri c tng hp trong phng php ny dng tinh th cha mt n hai phn t nc v n nh nhiu thng di nit. tinh khit ca Thioxin (dng baz t do, HCl hoc mui natri) c th nghim bng chun iot ca nhm SH theo phng php tiu chun hoc thun tin hn l bng phng php TLC vi CCl4isopropyl alcohol (50:3). tinh khit ca diquinol8,8disulfide c th quan st bng im nng chy. 7. Nhng ng dng trong phn tch S dng nh thuc th chit trc quang: Thioxin c s dng nh l thuc th chit trc quang cho nhng ion kim lai nh khc. Tnh chn lc c th c ci thin bng s chn lc iu kin phn ng thch hp (nh acid trong t nhin, tnh acid, tc nhn to phc ph, tc nhn bo v). Mt s mu c tng kt trong bng X.2.6. Tc nhn bo v thch hp l phi c nghin cu trc tin. Mt dung dch cha nc 0,2% Thioxin hidrochloride (0,1g trong 50ml HCl 6N) c c, n c c nh trong bng ti, lnh. Mt dimethanol ca thioxin d dng oxy ha vi disulfide ngay c trong bng ti, lnh v c chun b mi ngy. S dng nh l thuc th hunh quang: Mt s kim lai thioxinates fluorescene trong dung mi hu c v nhng kim lai tng t c th c xc nh bi php xc nh hunh quang. V d c tng kt trong bng X.2.7. Cng hunh quang ph nhiu dung mi s dng. Do vy s la chn tnh cht ca dung mi l quan trng. Nhng ng dng khc: Thioxin c th c s dng nh l thuc th trng lng hoc chun trong phng php ampe. Giy lc c tm vi thioxin c ngh nh l pha tnh cho sc k kt ta ca ion kim loi. Diquinolyl8,8disulfide c th c s dng nh l thuc th sinh mu cho kim lai nu tc nhn kh l hydroxylamine hoc acid ascorbic. 9. Nhng thuc th khc c cu trc tng t Selenoxine (C10H7NSe.H2O (KLPT=226,14)), selenium tng t ca Thioxin, c tng hp, c tnh cht ha l v nhng ng dng phn tch ca n c nghin cu. Althiox (4) l mt phi t trung tnh dn xut t Thioxin v r rng nht cho Rh (400 nm, = 7.103) mt dng lin kt vi nhm definic. Cu trc tng t ca vng cng Rh (5) c th ch ra nh di y. Dn xut sulfonate ha cng c s dng cho nhng mc ch tng t.
219
N S H 2C CH2 CH
C12H11NS KLPT: 201,24 Rh
S H 2C
CH2 CH
(4)
(5)
IX.3. NATRIDIETHYLDTHIOCARBAMATE V CC THUC TH TNG T

C2H5 N C C2H5 SNa S
CTPT: C5H10NS2Na.3H2O KLPT = 225,30
1. Danh php Cupral, mui carbamidat DDTC natri. 2. Ngun gc v phng php tng hp C gi tr thng mi, n c to thnh bi phn ng ca diethylamin v carbon disulfide trong dung dch natrihydroxide. 3. ng dng trong phn tch c s dng nh l mt cht to ta v l dung mi thuc th tch chit cc ion kim loi nh. Cng nh c s dng lm thuc th trc quang cho Bi, Cu, Ni v mt s kim loi khc. 4. c tnh ca thuc th Thuc th ny thng l mt mononatri, mui trihydrate, dng tinh th khng mu. Dng mui khan nng chy 94 n 96oC v tan t do trong nc (35g/100ml , 20oC ) to ra phn ng kim. Mc d thuc th dng rn th bn, nhng trong dung dch acid th b phn hu rt nhanh. Vi nhng gi tr pH tng dn th dung dch tr nn bn hn. Mt dung dch c nng 1% c th c gi trong vi tun v dung dch 0,1% th gi c mt tun. Thi gian mt na dung dch nc tham gia phn ng ha hc l pH < 2 v pH = 5 l 7 giy n 87 pht tng ng. N hu nh khng tan trong dung mi khng phn cc (0,006g/100ml trong CCl4), nhng tan c trong ru. S dng trong vic tch chit th mui diethylammoium thng c dng hn bi v n tan c trong nc, cng nh tan tt trong carbon tetrachloride, chloroform, v mt s dung mi hu c khc. Hn na, trong vic tch chit kim loi trong dung dch acid, mt lng ln dithiocarbamate vn cn li trong dung mi hu c, v th m s phn hu ca thuc th trong acidic c th trnh c. Acid Diethyldithiocarbamic (HL) l mt acid trung bnh yu, pKa = 3,95 (19oC); KD(CCL4/H2O) = 2,4 n 3,4.102 ;KD(CHCl3/H2O ) = 2,30 n 2,35.103. Ph hp thu 220
ca mui natri trong dung dch nc c minh ha trong hnh 1.
hp th
Hnh 1: Ph hp th ca Na-DDTC trong dung dch nc;
Bc sng nm 5. Phn ng to phc v c tnh ca phc DDTC c xem nh l mt anionic phi t 2 nhnh ha tr mt nhn 2 nguyn t sulfur, v to thnh nhng kt ta c mu vi hn 30 nguyn t ti pH > 4. Phn ng xy ra c chn lc hn trong dung dch acid, vi s u tin i vi ion kim loi. Chng hu ht khng c in tch, dng phc bo ha phi tr v c th tch chit ra bng dung mi hu c, nh l chloroform hoc tetrachloride. V d, cu trc ca phc Cu(II) l nh sau :
S N C S Cu S S C N
Mt vi phc c mu nh (Bi, Cu(II), Ni, ...), nhng nguyn t ny c th c xc nh theo phng php quang ph. Phn ng to ta v tch chit cc ion kim loi c tm tt trong bng X.3.1. Tnh chn lc cho vic tch chit ion kim loi c th tt hn bng vic chn khong pH v chn nhng cht che thch hp cho dung dch xc nh. hng s ca phc DDTC bn, c nhng phng php gin tip da trn phn ng song song vi mt ion kim loi khc hoc mt phi t khc thng c s dng thay th trnh xy ra s phn hu phc ca phi t v phc kim loi trong dung dch acid. Gi tr c tng kt trong bng X.3.2. Nh m t trn, mt vi phc kim loi c th c tch trong dung dch chloroform hoc carbon tetrachloride. Gi tr K c k khai trong bng X.3.1. Khi phc kim loi c mu cao, n c th d dng c xc nh theo phng php trc quang sau khi c s tch chit dung mi, bi v bn thn thuc th khng hp thu trong min kh kin. c im quang ph ca phc DDTCkim loi c tng kt trong bng X.3.3. 6. S tinh ch v tinh khit ca thuc th Natri diethyldithiocarbamate c th c tinh ch bi s kt tinh t dng nc t tinh khit cn thit l 99,5%. 221
Mt mu tinh khit s cho dung dch trong khng mu khi ho tan vo trong nc hoc ethanol (0,1%). Xc nh hm lng nitrogen bng phng php kieldahl c th c dng th nghim. 7. ng dng trong phn tch S dng nh l mt thuc th dung mi tch chit: chn lc trong vic tch chit kim loi c th c ci thin bi vic chn la nhng gi tr pH thch hp ca dung dch v vic s dng nhng cht che. Bng X.3.4 tng kt cc iu kin ca s tch chit. Thng th ngi ta cho thm NaDDTC vo dung dch to ta phc DDTC kim loi, theo s tch chit ca phc vi dung mi hu c. Trong nhiu trng hp th tc ca s tch chit xy ra rt nhanh. S c mt ca EDTA s lm gim tc qu trnh tch chit. Do acid ca DDTC khng bn nn khng nn s dng dung dch acid kh mnh tch chit, mc d c chn lc cao cho cc ion kim loi nh chng ta mong i. Chng hn nh trong trng hp, phn ng trao i din ra vi phc DDTC kim loi s c din ra chm hn, hoc vic s dng diethylammonium diethyldithiocarbamate l ph hp hn. S khc nhau trong cc gi tr ca hng s tch chit c iu kin cho nhiu ion kim loi khc nhau c th c tn dng cho s tch chit c chn lc v vic xc nh cc ion kim loi. Khi mt dung dch ng c trn vi mt dung mi hu c ca phc PbDDTC, phn ng di y hu nh s c din ra mt cch nh lng:
Cu 2+ + ( PbL 2 )org ( CuL 2 )org + Pb 2+
V log Kex ca PbL2 v CuL2 theo th t l 7,8 v 13,7 (trong dung dch CCl4). V th, ion kim loi c th c tch ra t dung dch acid kh mnh, ni m dng t do DDTC s phn hu mt cch nhanh chng. Hn na, phc DDTC kim loi khng mu c th xc nh theo phng php trc quang sau phn ng thay th hnh thnh phc c mu r rng. Hnh 2 v 3 biu th kh nng ca s tch chit c chn lc ca cc loi ion kim loi t nhiu dung dch nc c nhiu tnh acid khc nhau. S tch chit kt thc sau khong 2 pht trong hu ht cc trng hp, nhng SeL4 , CoL3 v FeL3 phn ng din ra rt chm. DDTC thng c s dng nh l thuc th o quang cho Cu(II), v k tip l Bi, Ni v mt s nguyn t khc. c im v quang ph ca phc DDTC kim loi c trnh by trong bng X.2.3. Quang ph trong khong nhn thy th khng r rng bi v dng t do ca phc DDTC khng hp thu trong khong nhn thy c (hnh 1). Tuy nhin, hp thu ca thuc th c th gy nhiu n ph UV, mc d s tch chit ca HL tr nn khng ng k pH > 9. V d, Cu(II) (0,002 n 0,03mg) c th c xc nh ti 440nm, sau tch chit nh CuL2 vi n-butyl acetate ti pH = 9 c EDTA. Cc cation nh Co, Cr, Fe, Mn v Ni khng gy nh hng. Bng X.3.1: S KT TA V KH NNG CHIT CA ION KIM LOI VI DDTC
Kt ta pH chit
222
Ion kim loi
T l
tan (iu kin) logKsp-20,66 (=0,3) logKsp-19,6 (KNO3 0,1M, 25oC)
CCl4+ CCl4 CCl4+ CCl4+ CHCl3 CCl4+ EDTA+ (logKex) (logKex) KCN EDTA tartrate citrate 2,6-5 (12,6) 3-6 2-14 2-9 (13,26) 0-9,5 (0,78) 2-6 2-14 (11,9) 2-9 2-9 4-11 4-8 (11,90 4-5,8 4-11 4-11 (16,79) 4-11 (2,33) 4-11 4-11 4-8 (13,70) (1,18) 4-9,8 4-5,5 2-14 2-9 2-9 4-11 6-9 (-4,42) 5-11 4-5,5 4-11 4-8,5 8-9 8-9 4-11 4-6 4-11 4-11 4-11 5-5,5 8-11 (11,18) 3-9,5 (7,94) (11,58) 4-11 8-11 (7,77) 4-11 (>32) 4-11 4-11 2,96 8-11 8-11 8-11 (2,39) 5-7 4-11 4-11 5-11 5-13 5-13 5-13 5,5-11 5-13 10 ~9 5-13 5-9 ~9 5-13 4-8 8-11 8-11 4-5,8 4-11 4-11 4-6 5-13 7-11 ~9 5-13
Ethyl acetate
Ag(I) As(III) Au(III) Bi Cd Co(II) Cu(II) Fe(II) Fe(III) Ga Hg(II) Mn(II) Mo(IV) Nb(V) Ni
ML
ML3 ML2 ML2 ML2 ML3 ML3 ML2 ML2
S 2,1.10-10M logKsp-22,0 (KNO3 0,1M, 25oC) S 1,8.10-7M logKsp-20,06 (=0,3) logKsp-30,21 (NaCl, 25oC) S 3,2.10-10M logKsp-24,5 (=0,3) logKsp-43,79 (KNO3 0,1M) S 1,5.10-4M
9 5-9 3 3 6,5
ML2
Pb Pd(II) Pt(IV) Zn
ML2 ML2
logKsp-19,26 (=0,3) logKsp-23,1 (KNO3 0,1M) S 2,3.10-7M logKsp-21,7 (KNO3 0,1M) S 3,4.10-8M
2-14
Acidic
ML2
logKsp-16,9 (KNO3 0,1M) S 2,5.10-6M
2-9
Bng X.3.2: HNG S BN CA PHC KIM LOI-DDTC Ion kim loi Log KML =logKML.logKML2 223
iu kin
Cu(II) Hg(II) Ni Pb Tl(I) Zn 8. Nhng ng dng khc
14,9 22,2
4,3
28,8 38,1 (3 39,1) 12,9 18,3 5,3 11,4
75% ethanol 20oC =0,1, KNO3 20oC =0,01 =0,01 =0,1, KNO3 =0,01 22oC 22oC 25oC 22oC
N tng c s dng nh l thuc th nhn bit Cu (gii hn xc nh l 0,2g v gii hn pha long 1/5.107), nhng phn ng l khng c tnh chn lc. Thuc th cn c s dng lm cht to ta trong phng php phn tch trng lng. Phc DDTC kim loi cng c th c phn li v xc nh bng sc k kh hoc HPLC. Mt polymer vi nhm chc DDTC hoc ht silicagel lin kt vi phc DDTC c nghin cu nh l mt ion c la chn lin kt. Nhng ion kim loi c hnh thnh trc trn b mt knh ni m DDTC c thng k v kim tra bi tia X trong ph in t vi chn lc v nhy cao. 9. Mt s loi thuc th khc vi cu trc tng t Diethylammonium Diethyldithiocarbamate: CTPT: C9H22N2S2 KLPT: 222,41
C2H5 N C C2 H 5 S(NH2(C2H5)2) S
L nhng tinh th khng mu, nng chy 82 83oC, tan trong nc, chloroform, carbon tetrachloride, v mt s dung mi hu c khc. u im ca thuc th ny trn natriDDTC l n tan c trong dung mi hu c bi v nhng ion kim loi t trong dung dch acid v c c th tch ra vi thuc th ny. Trong qu trnh tch, s lng ca thuc th tng ng vi phc kim loi tn ti trong dung mi hu c vi dng acid phn li. Kh nng tch ion t nhng dung dch acid mnh c tng hp trong bng X.3.5. Kh nng chit t dung dch trung tnh hay baz hu nh tng t nh cch chit ca mui ca Na. Ammonium Pyrrolidinedithiocarbamate: CTPT: C5H12N2S2 KLPT: 164,28
CH2-CH2 CH2-CH2 S N C S.NH4
L APDC, ammonium pyrrolidine-1-carbodithioate; c sn ngoi th trng; l nhng tinh th khng mu, nng chy 142 144oC, d tan trong nc (18,9g/100ml; 200oC) v ru, t tan trong chloroform (0,38g/100ml) v carbon tetrachloride 224
(0,12g/100ml; 200oC). Thuc th dng t do l mt acid yu, pKa = 3,29 ( = 0,01; KCl, 25oC), KD (CHCl3/H2O)=1,1.103). Thuc th ny trong dung dch acid th bn hn DDTC. Chu k bn r pH 1,0, 3,0 v 7,3 theo th t l 63 pht, 175 pht v 170 ngy. V th APDC c dng nh l cht to ta v lm dung mi tch chit cho cc ion kim loi nng trong dung dch acid. Nhn chung, phng php tch chit kim loi bng vic s thuc th APDC tng t nh s dng vi diethylammonium dithiocarbamate trong acid hu c v vi mui natri trong mi trng trung tnh hoc kim yu. Bng X.3.6 l s tng hp phng php tch chit ca cc ion kim loi vi APDC t dung dch acid. Hng s tch chit ca mt s ion kim loi cng c a vo bng trn. tan ca phc APDC kim loi th thng thp hn so vi DDTC kim loi. Nhng dung mi khng c halogen ho, chng hn nh MIBK hoc alkyl acetate, th c s dng nh dung mi tch chit cho s c cn ca mu kim loi nng vi hm lng thp khi chng cho nhng nguyn t c ph hp thu c dng xc nh hm lng kim loi. Ammonium N(dithiocarboxy)sarcosine: CTPT: C4H5NO2S2.2NH4 KLPT: 199,30
-
OOCCH2 N C H 3C
S S2 NH4+
L nhng tinh th bt mu trng, d tan trong nc. trng thi lng n c th c 1 thng. Phn ng vi mt s ion kim loi nng ca hydrogen sulfide v ammonium sulfide to thnh phc kim loi tan. Nhng ion kim loi m n c th c che vi EDTA v ch th kim loi l: ti pH 2 3: Bi, Cd, Co, Cu(II), Fe(III), Hg, In, Mo(VI), Mo(V), Ni, Pb v V(V); ti pH 5 6: Bi, Cd Co(II), Cu(II), Fe(III), Hg, In, Ni, v V(V); ti pH 9 10: Bi, Co(II), Cu(II), Fe(III) v Ni. Thuc th ny c s dng nh mt cht che cc ion kim loi nng trong phn tch ca Zn. Silver Diethyldithiocarbamate: CTPT: (C5H10NS2Ag)2 KLPT: 512,26
C 2H 5 N C C 2H 5 S Ag S S Ag S C N C 2H 5 C 2H 5
L nhng tinh th mu vng nht, hu nh khng tan trong nc, nhng d dng tan trong pyridine hoc chloroform. Thuc th ny b nh hng nhiu bi m v nh sng, v vy n c bo qun trong cc dng c kh c mu ti v ni kh ro. Nhng mu b nhim bn c th c lm sch bng cch kt tinh trong dung mi pyridine. Khi c nhng bt kh xut hin trong dung dch pyridine ca AgDDTC, phn ng din ra nh sau:
225
AsH3 + 6AgL + 3B = AsAg3 .3AgL + 3L + 3HB+ AsAg 3 .3AgL + 3B = 6Ag + AsL3 + 3L + 3HB+
Trong B l pyridine hoc kh nitrogen khc. Kt qu ca phn ng hn hp trn l s hnh thnh nhng ht keo c mu hng nht. Phn ng ny c th s dng cho qu trnh xc nh hm lng nh As trong nhiu loi mu. Mt dung dch chloroform ca AgDDTC cha mt lng nh nitrogen chng hn nh triethylamin (3.10-2M) c dng mt phn ng trung gian thch hp hn, bi v nhng s nh hng ca pyridine c th c ngn nga. Nhng gc nitrogen khc cng c a ra thay th pyridine. Xc nh As theo phng php trc quang: Thuc th: dung dch pyridine 0,5% ca AgDDTC. Dung dch pyridine c th thay th bng dung dch chloroform 0,5% ca AgDDTC, cha 3.10-2M triethylamine, dung dch KI 15% ,dung dch SnCl2 40% , H2SO4 m c. Thit b: hnh 4
Hnh 4: Bnh phn ng xc nh As Qui trnh: Cho mu dung dch lng cha 4 15g As vo trong bnh phn ng v pha long thnh 25ml, thm 5ml dung dch H2SO4 m c, 2ml KI 15%, v 0,5ml dung dch SnCl2 40% .Tip theo tin hnh trn u trong 15 30 pht vi nhng ln lc trn khc nhau. Gn cht c ng thu tinh ngp su vo dung dch acetate ch thng qua vng m bng cao su trn ming bnh lc (trong bnh c cha sn 3ml dung dch AgDDTC). Cho thm 3g bt kim loi Zn vo trong bnh phn ng v xut hin nhanh chng du hiu ca s cng hp. Du hiu s kt thc sau 60 n 90 pht v dung dch trong bnh lc t mu vng nht chuyn sang mu hng. S chuyn i mu ca dung dch trong khong 10-mm v c o bc sng 540 560nm tu thuc vo mu trng. ng hp thu mu ca dung dch c trnh by trong hnh 5.
226
0,3 _
hp th
0,2 _
Hnh 5: Ph hp th ca sn phm phn ng t Ag-DDTC v arsine.10g (+10g Sb).
0,1_
400
500
600
700
Bc sng nm Cc cht gy sai s: S(II) b oxy ha bi acid nitric. Ge, HNO3, v HClO4 b loi b bng s bay hi lin tip vi HCl. S nh hng bi Cu, Fe, Ni, Sb, Se, Sn, Te, PO43-, v mt s nguyn t khc c loi tr bi qu trnh tch AsCl3 t dung dch HCl m c vi pxylene hoc benzene. Nhng ion kim loi chng hn nh Ag, Bi, Cu, Hg, Pb, Pd, Pt v Sb c khuynh hng lng trn b mt Zn, v ngn nga s ho tan ca Zn, nhng cng c th che bng KI. Xanthate:
S R O C SK
Kali ethyxanthate (R = C2H5) v kali benzylxanthate (R = C6H5CH2) c ch nh l thuc th dung mi tch chit cho kim loi tch chit. ng dng ca chng trong ha phn tch v trong s tuyn ni khong th c xem nh l trong the literature Bng X.3.3: C IM PH CA PHC MU KIM LOI -DDTC Trong CCl4 Trong CHCl3 3 Ion kim loi T l Mu max(nm) (x10 ) Bi ML3 Vng 366 8,62 370 23,93 323 15,7 Co(III) Xanh 367 650 0,55 650 Cu(II) Nu 436 13,0 440 12,7 335-350 Fe(III) Nu 2,49 515 515 2,05 600 326 34,2 Ni Vng xanh 393 6,11 395 305 54,8 Pd(II) 345-350 7,13 Pt(IV) 355 5,87 Sb(III) 350 3,37 Te(IV) 428 3,16 227
10,5 0,52 12,1 2,79 5,87
UO22+
nu
380 - 400
390
3,87
Bng X.3.4: S CHIT CA PHC CHELATE KIM LOIDDTC VI CCl4 Cc nguyn Cc t chit nguyn t chit pH khng hon ton =6 Cc nguyn t khc khng c lit k
Cc nguyn t chit pH >11 Ag, Bi, Cd, Co(II), Cu(II), Hg(II), Ni, Pb, Pd(II), Tl(I)(III), Zn. (Ag, Bi, Cu(II), Hg(II), Pd(II) v Tl(III) khng th bo v bng EDTA; Bi, Cd, Pb v Tl(I)(III) khng th bo v bi KCN)
Cc nguyn t chit pH = 9 Fe(III), In(III), Mn(III), Sb(III) v Te(IV) (Sb(III), Te(IV) khng th bo v bng EDTA; Fe, In, Mn(III), Sb(III) v Te(IV) khng th bo v bng KCN)
As(III), Se(IV), Sn(IV) v V(V)
Au, Ba, Ir, Nb(V), Os, Rh, Ru, Pt v U(VI)
Khng th c chit pH = 4 11
IX.4. TOLUENE3,4DITHIOL V THUC TH TNG T.

H3C SH SH
CTCT: C7H8S2 KLPT: 156,26
H2L 1. Danh php 4Methyl1,2dimercaptobenzene, 3,4dimercaptotoluene, dithiol. 2. Ngun gc v phng php tng hp Toluene3,4 dithiol c s dng ph bin trn th trng. N c tng hp bi s kh ca 3,4disulfolnylchoride vi Sn v HCl. 3. S dng trong phn tch Thuc th dng o quang xc nh cc kim loi Ag, Mo, Re, Sn, Te v W, c trng cho Sn. 4. Phn ng to phc v tnh cht ca phc Tinh th khng mu, trong sut, nng chy 31 34oC, nhit si 185 187oC (84 torr ), nD = 1,6378. Thuc th c mi c trng v d dng b oxy ho trong khng kh cho mu vng (du) hoc mu trng ng (C7H6S2)n. Thuc th c bo qun nhit thp v di iu kin kh tr. i vi thuc th ny trn th trng th gii hn nng chy 28 31oC, t ho tan trong cc acid nhng d dng ho tan trong cc dung mi hu c v trong dung dch KOH. Thuc th khng bn trong nc khi lm vic vi thuc th cn c chun b dung dch mi. Dithiol c tnh acid pka1 = 5,34 228
v pka2 = 11 (trong nc 25oC), log KD(CHCl3/H2O) = 4,13 ( = 0,1, 25oC). 5. Phn ng to phc v tnh cht ca phc Dithiol phn ng vi mt s kim loi nh hnh thnh dng phc tan mu hoc dng ta. Mt s c th chit c trong cc dung mi hu c nh chloroform, 1,2 dichlorchroethane, isoamyl acetate hoc DMF. Mu v thnh phn ca phc gi tr pH khc nhau c tm tt trong bng X.4.1 Cc ion kim loi c ha tr cao nh Ge(IV), Mo(VI), Pb(IV), Si(IV), Sn(IV) v W(VI), hnh thnh phc phi tr khng mang in vi ion bidentate dithiolate (L2-) v c th c chit trong nhng dung mi khc nhau. Tuy nhin mt s kim loi c ha tr thp thng hnh thnh phc chelate tan hoc dng phc chelate polymeric c khng tan trong nc ln khng tan trong cc dung mi hu c. Phc polymeric ny c th ho tan c nh cht hot ng b mt (Teepol, Santomerse, Gelatin hoc Triton X100), dng trong o quang xc nh cc kim loi. Km hnh thnh hai dng phc dng ZnL22-(1), tan trong nc to phc chelate mang in, bo ha phi tr. V ZnL(2), l phc chelate khng tan, khng mang in, khng bo ha phi tr, nn khng th chit c. Tuy nhin, phc chelate mang in c th c chit vi cation thch hp nh ion NH4+ trong pha hu c nh mt cp i ion.
0 H 3C S Zn S S S S CH3 H 3C S Zn OH OH
(1)
(2)
V phc chelate khng bo ho phi phi tr khng mang in c th chit c bng s thay th phi tr nc ca phc km vi mt baz khng mang in nh l 1,10(phenanthroline)
0.8 0.6
hp thu Absorbance
0.4 0.2
400
450
500
550
600
Wavelengt h (n m) B c sng nm
Hnh 1: ph hp thu ca phc Sndithiol, Sn 16ppm Ph hp th ca Sn(II)dithiolate mu trong nc c minh ho hnh 1. Mc 229
d dung dch phc km ny tan trong dung mi hu c, dung dch c mu vng nhng n khng c dng cho o quang. Quan st hp th ca Mo(VI)dithiolate trong cc dung mi hu c khc nhau th hp thu phn t cao nht ( = 1,84.104 ti bc sng = 705nm) trong hn hp dung mi acid acetic bngTBPacid phosphoric theo t l 20:5:2 v th tch. 6. S tinh ch v tinh khit ca thuc th Dithiol c th tinh ch bng chng ct chn khng di kh nitrogen. Thuc th d b oxy ha, n c ngh gi kn trong nitrogen, nhit ng bng. Dithiol c chuyn ha thnh dn xut bn hn, nhng dn xut dn ra di y th dn xut cui cng hu nh c s dng rng nht trong thc t.
O H3 C S S C C O CH3 CH3 H3C S S O C C O H 3C S Zn S
(3)
(4)
(5)
Hp cht (3) (5) l bt trng, kh bn v dithiol c th ti ch bi quy trnh n gin (vi (3), (4) dng NaOH 1N vi (5) dng acid v c). tinh khit ca dithiol t do c xc nh bng php chun iot ca nhm SH. tinh khit ca km-dithiol c th kim tra tra bng chun EDTA sau khi x l mu vi HNO3HCLO4. Phn dung mi hi lu li c th xc nh th tch ca nhm SH bng phng php quang ha. Dung dch ca Zn dithiol c th kim tra bi chun EDTA, sau un mu vi HNO3HClO4. 7. Nhng ng dng trong phn tch Thuc th trc quang: Nhng iu kin xc nh vi ion kim loi bng phng php trc quang s dng dithiol kim loi c tm tc trong bng X.4.2. Xc nh thic: un nng dung dch mu cha 3 50g Sn vi 0,5ml dung dch H2SO4 (1+2) trong mt cc thu tinh, un nng cho ti khi dung dch bc hi. Chuyn ton b vo cc (10ml) dng 7ml H2O v nh mt git thioglicolic acid v khuy trn u. Thm 1ml h arabic 0,5% v 0,5ml dd dithiol 0,2% (cho vo dd NaOH 1% cha acid thioglicolic 1%), un v khuy trn cch thy ti 505oC trong mt pht v pha long vi th tch va un xong, em o quang bc sng 530nm v loi tr sai s bng cch lm mu trng so snh. As, Bi, Ge, Mo, Sb, Se v Te lm tr ngi cho phng php. Phng php ny c ngh sau khi tch Sn bng phng php chng ct nh l SnCl4. Xc nh Mo(VI): iu chnh tnh acid ca dung dch mu c cha 100g Mo bng HCl 6 8N v tng th tch l 25ml. Lc u vi dung dch vi 5ml TBP (c bo ho vi HCl) trong 5 pht sau khi tch pha, chuyn ton b phn tch vo cc thu tinh 50ml, thm 25ml acid acetic bng v 2ml H3PO4 sau thm 5 git dung dch dithiol (1g dithiol trong 100ml NaOH 1% v cha 1g thioglicolic acid) v khuy trn u. 230
Tng th tch cn thit vi acid CH3COOH bng v yn trong 3 gi, sau em o quang bc sng 705nm. Bi, Cd, Co, Cu, Fe, Ni, Pb, Sn, Zn v W khong 1000g khng c nh hng. Khi dng Zndithiol th dung dch phi chun b li theo qui trnh chun b nh sau: trn 0,2g Zndithiol vi 2ml ethanol v thm vo 100ml dd NaOH 1%. Sau thm 1ml acid thioglicolic lc v trn u, bo qun trong chai nha. Thuc th c nhy: c tm tt trong bng X.4.1, Dithiol xc nh c nhiu ion kim loi trong nhiu iu kin. Cho cc ion kim loi nh Mo, Sn v W, phn ng to ta khong 5ppm. C th pht hin trong dung dch HCl 1 2N, ch c Pt cho ta mu tm m c th chit ly trong cc dung mi hu c.
IX.5. BITMUT II KHONG CHT II

N C KS S N C S
CTPT: C8H5N2S3K. KLPT: 264,32
HL (KL) 1. Danh php 3Phenyl5mercapto1,3,4thiadiazol2thione, bismuthol 2. Ngun gc v phng php tng hp V phng din thng mi, n c to thnh t phn ng ca phenylthydrazine vi carbon disulfide trong dung dch KOH. 3. Dng php phn tch Dng phn tch trng lng v thuc th kt ta nhng ion kim loi nh. Dng phng php trc quang cho Bi, Se, Te, v mt vi nguyn t khc. 4. Tnh cht ca thuc th Bismuthiol II thng ging nh mui kali, c nhit nng chy 243 248oC (nhit phn hu 250 255oC) v thng khng mu hoc tinh th hnh kim vng nht. Thuc th ca n kh bn, nhng n b oxi ho chm to ra disulfide. N c th ho tan trong nc v trong cn nhng n khng tan trong dung mi hu c. Thiol t do (HL) c th dng tinh th hnh kim khng mu (nhit nng chy t 90 91oC) do s acid ha dung dch nc ca mui kali. Thiol t do th d b oxy ha hn mui kali v khng ha tan trong nc hoc ligroin (im si thp) nhng d ha tan trong dung mi hu c, pKa = 3 (20oC) Dung dch nc (L-) (max = 335nm; = 1,1.104) v trong dung dch chloroform (HL), (max = 330nm) th khng mu. 5. Phn ng to phc v tnh cht ca phc Bismuthiol II th phn ng vi hu ht cc ion kim loi nh trong dung dch nc hnh thnh kt ta c mu vng n mu nu . Kh nng phn ng vi ion kim loi thay i vi pH ca dung dch v cht che ca n, c tm tt trong bn X.5.1. 231
mui
kali,
bismuthone,
Trong nhng phn ng, Bismuthiol II c xem khng th nhn bit c cc anion ho tr 1. N to thnh phc c cho di y.
S N C S N C S Te S N C S N C S S S C N S C N S S C N S C N 0
Phc cht khng mang in c th chit vo trong CHCl3. Ph hp thu ca nhng phc ny rt ging thuc th t do, minh ha hnh 1, thuc th d c loi nh nc pH 7,5 trc khi xc nh kim loi bng phng php trc quang.
hp th
Hnh 1: Ph hp th ca phc Bismuthiol II v Te trong chloroform. (1) phc Te trong Chloroform; (2) Bismuthiol (II) trong chloroform; (3) mu trng. Bc sng nm
6. S tinh ch v s tinh khit ca thuc th Bismutthiol II (mui kaki) th thng b hng bi disulfide trong thi gian di l tr, nhng c th tinh ch bng cch kt tinh li t cn nng. Thuc th c kim tra li bng phng php chun iot ca nhm SH theo phng php tiu chun. 7. S ng dng ca phn tch Thuc th to ta: c ch ra trong bng X.5.1, thuc th Bismuthiol II c th chon lc tt i vi kim loi nh. Sn phm kt ta phi c thnh phn c nh r, khng thay i sau khi sy 100oC. Nhng phn ng kt ta c nhy cao thch hp xc nh ion kim loi dng vt (Bi, kt ta trong HNO3; gii hn pha long, 1:6.106). Thuc th trc quang: ng dng quang trng nht ca Bismuthiol II l xc nh Te(IV) bng phng php chit trc quang. Phc Bismuthol (TeL4) c hnh thnh trong iu kin mi 232
trng acid, sau c chit vo trong chloroform hoc benzene v em o quang. Ph hp thu ca lng d thuc th xen ph mt cch ng k vi phc Te, mt vi phng php di y c ngh cho vic xc nh Te: S hnh thnh phc cht pH = 4,15, s chit ca c hai phc cht v thuc th d pH tng t, sau o s hp th ca TeL4 416nm khi hp thu ca HL l khng ng k. S hnh thnh phc cht pH = 2 3 (Citrate) trong 30 pht, chit TeL4 pH = 6,5, y chit ca HL l khng ng k, sau s o hp th bc sng l 335nm. S hnh thnh phc cht v chit c hai TeL4 v HL HCL 3N hoc pH = 3,5. Quay li qu trnh chit L- vi dung dch m (pH = 7 8), sau o hp th 330nm. nhy ca phng php th nht, th hai v th ba ln lt l 0,026g/cm2 ( = 4,9.103), 0,005 ( = 2,8.104), v 0,0036 ( = 3,5.104), nhng As(III), Fe(II) v Se(IV) cn tr nghim trng. Nhng nguyn t nh l: As(V) (HCL 3 4N, 355nm, = 1,62.104 trong CHCl3), Os(VIII) (Ph 3770 n 780nm, = 4,6.104 trong TBP), Re(VIII) (6 n HCL 7N, 360nm, = 2,2.104) trong isopentyl alcoholacetonenc (1:1:3) Se(pH = 7,5, 330nm, = 3,16.104 ), cng c xc nh vi Bitmut II. 9. Thuc th khc c cu trc tng t Nhng thuc th Bismuthiol khc: Bismuthiol I; 3,5dimercapto1,3,4thiadiazole (1) 3(2Naphthyl)5mercapto1,3,4thiadiazole2thione(2) Thuc th sau cng s dng cho vic xc nh Bi (325nm, = 2,97.104 trong CHCl3), Pd (345nm, = 2,1.104 trong cyclohexane), v Te (326nm, = 3.104 trong CHCl3). 3(2Pyridyl)5mercapto1,3,4thiadiazol2thione (3) c s dng xc nh Bi (pH = 2 3, 340nm, = 2,97.104 trong CHCl3), Pd, Se, Te.
N C HS N N C SH
(1)
N C HS S N C S R
(2): R = (3): R = 2mercaptobenzimidazole (5), v 2
2Mercaptobenzothiazole mercaptobenzoxazole (6). 233
(4),
N C X SH
(4): X = S (5): X = NH (6): X = O
2Mercaptobenzothiazole (Mertax, Thiotax,Captax, MPT), C7H5NS2, KLPT = 167,24; thng th n khng mu hoc dng bt nho vng nht, nhit nng chy 179 182oC. N khng ho tan trong nc nhng n tan trong dung dch kim v ph bin trong dung mi hu c bao gm C2H5OH (2g/100ml; max = 327nm) C6H6 (1g/100ml, 25oC), v acetone(10g/100ml); pKa1 = 7,22 v pKa2 = 11,4 ( = 0,1; 20oC). N tc dng hu ht vi ion kim loi nh n to thnh phc khng tan mu vng n mu vng cam v n c s dng thuc th phn tch trng lng cc kim loi Ag, Au, Bi, Cd (Ksp = 8,9.10-9), Ir, Ni (Ksp = 4,9.10-15), Pb (Ksp = 6,1.10-14) , Pt, Rh v Ru v thuc th dng cho trc quang cho cc nguyn t Au, Bi, Ir, Os, Pd, Pt, Rh v Ru sau khi c chit vi chloroform. Mt vi mercaptobenzothiazole khc c nghin cu s dng nh thuc th chit trc quang. 2Mercaptobenzimidazole (5), C7H6N2S, KLPT = 150,20; ht khng mu lp lnh khi kt tinh li t ethanol 95%, nhit nng chy 303 304oC, pKa = 9,97 ( = 0,1; 20oC), tan t trong nc v tan trong cn. Phc ca thuc th ny hu nh tng t 2 mercaptobenzothiazole, v uc s dng lm thuc th chit trc quang cho Bi (350nm, = 1.104 trong ethanolCHCl3), Hg(II) (pH = 4,5, chit nh HgL2 (Bromocresol Purple)), 410nm, = 3,8.104 trong CHCl3isoPrOH (20;1) v Se (325nm, = 1.104, trong BuOHCHCl3). 1Benzyl2mercaptobenzimidazole c s dng cho xc nh Te(IV) (440nm, = 2,95.104, 1 5ppm). 2Mercaptobenzoxazole (6), C7H5ONS, KLPT = 151,18; tinh th khng mu, nhit nng chy 193 195oC, khng tan trong nc , nhng khng tan trong dung dich kim v dung mi hu c; pKa1 = 6,58 v pKa2 = 11,46, thuc th ny c ngh dng nh mt thuc th chit trc quang cho Os(III), (pH = 5, 630nm, = 4.103) v Ru (III) (pH = 5, 460nm, = 2.103). Bng X.5.1: PHN NG CA BISMUTHIOL II VI ION KIM LOI Ion kim loi Ag Al As(III) As(V) Au(IV) 234
T l ML ML3
HCl 0,2N Vng ppt (X)a n.pb Vng ppt (Y)c Trng ppt(X) vng ppt (X)
pH 4,5, citrate Vng ppt (X) n.p n.p n.p vng ppt (X)
pH 9, citrate Vng ppt (X) n.p n.p n.p vng ppt (X)
pH 9, citrate + EDTA Vng ppt (X) n.p n.p n.p vng ppt (X)
pH 9, citrate + KCN n.p n.p n.p n.p n.p
Bi Cd Co(II) Cu(II) Fe(III) Hg(II) Mn(II) Mo(VI) Ni Os Pb Pd(II) Pt(IV) Re(VII) Ru(III) Sb(III) Se(IV) Se(VI) Sn(II) Te(IV) Te(VI) TI(I) U(VI) V(V) W(VI) Zn
ML3 hoc ML2Cl ML2 n.p ML2
ML2
ML3 ML2 ML2 ML4 ML2 hoc ML4
cam ppt cam n.p (X) ppt (X) trng(X) trng(X) trng(X) n.p n.p n.p vng m vng m vng m (X) (X) (X) vng ppt n.p n.p (X) vng ppt vng ppt vng ppt (X) (X) (X) n.p n.p n.p n.p n.p n.p n.p n.p n.p vng ppt vng ppt vng ppt (X) (X) (X) nu ppt nu ppt nu ppt (X) (X) (X) vng ppt vng ppt vng ppt (X) (X) (X) vng pptd nu ppt (X) vng ppt (X) vng ppt (Y) n.p vng ppt (X) vng ppt (Y) n.p vng ppt (X) n.p vng m ppt (X) n.p trng ppt (X) nu ppt n.p ppt(X) (X) n.p n.p n.p n.p vng ppt (Y) n.p vng ppt (X) n.p n.p n.p n.p n.p n.p n.p n.p n.p n.p vng ppt (X) n.p n.p n.p n.p
n.p n.p n.p n.p n.p vng ppt (X) n.p n.p n.p n.p nu ppt (X) trng ppt (X) n.p n.p n.p n.p n.p n.p n.p n.p n.p n.p n.p n.p
n.p n.p n.p n.p n.p n.p n.p n.p vng ppt (X) n.p vng ppt (X) n.p n.p n.p n.p n.p n.p n.p vng ppt (X) n.p n.p n.p n.p
ML3 ML4
ML4 ML
a (X): kt ta c th chit vo trong chloroform b n.p: khng kt ta xut hin
235
c (Y): chloroform chit c mu vng d: khi kh vi Sn(II) hoc Ti(III)
IX.6. THIOTHENOYLTRIFLUOROACETONE
H S C S C H C O CF3
HL CTPT: C8H5OS2F3 KLPT: 238,24 1. Danh php 1,1,1Trifluoro4mercapta4(2thienyl)but3enone, STTA, monothioTTA. 2. Ngun gc v phng php tng hp Thuc th c dng trong thng mi. iu ch bng cch cho i qua kh H2S trong dung dch acid ethanolic hydrochloric ca 2thenoyltrifluoroacetone (TTA). 3. S dng trong phn tch Dng nh mt thuc th chit v thuc th sinh mu cho nhiu ion kim loi nh 4. Tnh cht ca thuc th Thuc th l tinh th hnh kim c mu , nhit nng chy 61 62oC (hoc 72 74 C); d ha tan trong benzene v carbontetrachloride, tan khng ng k trong dioxane, DMF, v ethanol.Trong ba ng phn c th c, th hu nh tn ti hon ton dng thioenol; pKa(SH) = 3,96, log KD(CCl4/H2O) = 3,49, (CHCl3/H2O) = 4,29, v (C6H6/H2O) = 4,30. S hp th quang ph ca STTA c minh ha trong hnh 1 (max = 370nm; = 1,60.104 trong xylene).
o
Tng t nh cc thuc th thiol khc, n d oxy ha trong khng kh; v th STTA c cha trong ng dng xylanh di nitrogen v ni lnh trong bng ti.
236
0,8_ hp th 0,6 0,4 0,2_ 350
Bc sng nm
400
450
Hnh 1: Ph hp th ca STTA v phc Hg ca n trong xylene.(1) thuc th 5.10-5M, =1,6.104; (2) HgSTTA (47g Hg ), = 3,0.104. 5. Phn ng to phc v tnh cht ca phc STTA phn ng vi kim loi nh to phc chelate c mu , kh bn trong khng kh v d ha tan trong dung mi khng phn cc ging nh C6H6, CCl4 hoc cc ether du m khc, nhng khng tan trong dioxan, DMF, hoc C2H5OH. Tch cht vt l ca mt vi phc STTA c tm tt trong bng X.6.1. Gi tr max ca STTA ph thuc vo kim loi v dung mi. STTA s dng nh l mt thuc th chit v thuc th trc quang cho nhiu ion kim loi nh. hp thu quang ph ca phc STTA v Hg(II)-STTA c biu hin trong hnh 1 Cn bng qu trnh chit ca phc kim loiSTTA c kho st trn nhiu dung mi so snh vi qu trnh chit ca TTA, mt s cn bng c tm tt trong bng X.6.2. Phc Hg(II), log2 = 33,0 v logKex(CHCl3/H2O) = 19,6. Mt s phc ca kim loi vi STTA khng phn hu nhng thng hoa v nhit ca qu trnh thng hoa 1,3 Torr l ca Ni (185oC), Cu (II) (195oC), Pb (150oC), Zn (150oC), Co(II) (140oC), Cd (165oC), v Pd (109oC). Chng c tch ra bng phng php sc k kh. 6. Tinh ch v tinh khit ca thuc th STTA d b oxy ha trong iu kin tn tr thng v vy ta phi lm tinh ch trc khi dng. STTA c th lm tinh ch bng phng php kt tinh t C6H6 hoc ha tan trong ether petroleum, chit vo trong dung dch NaOH 1M, acid ha tng nc vi dung dch HCl 1 n 6M, chit tr li trong ether petroleum, v lm bay hi dung mi n khi thu nhn c tinh th mu . tinh khit c kim tra bng cch chy TLC trn ct Silicagel (0,5mm) vi hn hp ca chloroform v nhexan (3:7) lm dung mi ra gii. Xc nh S l tiu chun khc nh gi tinh khit. 7. ng dng trong phn tch 237
Thuc th trc quang: Mt vi v d in hnh v dng STTA l thuc th trong php trc quang cho mt s kim loi tm tt trong bng X.6.3. Tnh u vit ca STTA l thuc th trc quang c tnh chn lc vi ion kim loi nh. Tuy nhin hp thu phn t khng cao (103), peak hp thu ca phc b xen ph bi peak ca thuc th t do (hnh 1), lng d thuc th c th chit tr li trc khi em o quang hoc theo di v la chn bc sng cho ti u. Thuc th chit: STTA c th tch hn hp ca nhiu kim loi bng cch chit, kt hp pH thch hp trong pha nc. V d Co(II) v Ni c th chit nh lng pH = 5,5 6,0. Sau Ni c chit tr li trong tng nc pH =1,5, Co vn nm trong tng hu c. Hn hp Fe(II), Fe(III) v Cu(II) ch c Cu mi chit c trong dung dch Cyclohexane ca STTA ti pH = 2 (acetate). Sau Fe (II),(III) c chit ti pH = 5 6 , vi s c mt ca pyridine v hydroxylamin nh FeL2. S dng phi t tr th thng c hiu qu cho vic tch nhiu ion kim loi m gi tr pH1/2 kh gn. Vic tch Zn v Cd bng chit STTA l rt kh khn, gi tr pH1/2 (5.10-3 M trong dichloroethanol) ca Zn v Cd ln lt l 4,5 v 4,9. Tuy nhin, khi c 2,2bipyridine ch c Cd c to thnh dng CdL2. S chit tt nht ca Cd pH = 3,6 (vi NaCl 0,1 M) hoc pH = 3,0 (vi NaNO3) ng dng khc: STTA tch ion kim loi bng nhiu cch khc nhau nh chit phn on, thng hoa, TLC, phng php sc k kh, sc k lng trn ct polystyrence. N cn c ngh l thuc th chit cho vic xc nh ion kim loi nng bng phng php ph hp thu nguyn t. 8.Mt s cht c cu trc tng t vi thuc th Dn xut Monothio ca diketone: Monothio l dn xut ca diketone c th c iu ch, nh gi l thuc th chit chn lc v l thuc th chit trc quang cho ion kim loi nh. Monothioacetylacetate, monothiobebzoylacetone, monothiodibenzoylmethane monothiobenzoyltrifluoroacetone, v 3thionaphthoyltrifluoroacetone l nhng v d. Monoseleno l dn xut ca TTA, selenoylacetone, selenoyltrifluoro acetone c th c dng lm nghin cu. Bng X.6.1: TNH CHT CA PHC KIM LOI VI STTA Hp cht HL NiL2 CuL2 ZnL2 CoL2 PbL2 CdL2 238
Mu ca dung dch Nu Olive xanh Vng xanh Nu en Cam Vng
max (nm) 355 358 338 374 362 345 364
(x103) 8,45 7,75 5,60 4,22 7,52 3,70 4,35
max (nm) 373,450 400 395 375 373 383
PdL2 HgL2
Nu
369
6,95
415 370
Dung mi C2H5OH, xylene.
IX.7. THIOMICHLERS KETONE

1. Danh php 4,4Bis(dimethylamino)thiobenzophenone,TMK. 2. Ngun gc v phng php tng hp C trong cng nghip. N c to thnh bi phn ng ca Auramin vi H2S. 3. S dng trong phn tch S dng nh l mt thuc th trc quang c nhy cao vi Hg, Pb v nhiu kim loi qu. 5. Tnh cht ca thuc th dng tinh th bt mu ti, im nng chy 202oC, khng tan trong nc, nhng ho tan trong alcohol to thnh dung dch c mu vng m (max = 457nm; = 2,92.104 trong npropanol 30%). Dung dch ca thuc th cng nh phc ca n nhy cm vi nh sng, nhng dung dch n-propanol c th gi c 40 ngy trong bng ti ti nhit phng. 6. Phn ng to phc v tnh cht ca phc TMK u tin c chp nhn nh mt cht ch th trong chun Hg vi dung dch NaCl chun, nhng gn y n c xem nh mt thuc th trc quang cho Hg v mt s ion kim loi nh, nh l Au v Pb. Nhng ion kim loi phn ng vi TMK ti pH = 3 trong mt mc trung bnh ca nc alcohol to thnh phc mu ta, phc ny c th c tch ra trong iso-amylalcohol. Nhng phn ng vi nhng ion kim loi ny c th c vit nh sau, trong n l 2, 3, 4 ng vi Au, Hg(II) v Pb(II).
N(CH3)2 N+(CH3)2 N+(CH3)2
S- + M
S M/n
N(CH3)2
N(CH3)2
N(CH3)2
Tuy nhin, nhng s thng khng ch ra s kt hp ca phc, bi mt phn thuc th mt i do s oxi ho vi ion kim loi cng c th xy ra (Au(III) Au(I)). 239
S hp thu quang ph ca thuc th v phc Hg c m t trong hnh 1 (max = 457nm; = 2,92.104).
hp th
Bc sng Hnh 1: Ph hp th ca thuc th v phc Hg trong n-propanol h nc (30% th tch npropanol). (1) thuc th, 5.10-3M; (2) Phc Hg(II),5.10-6M, pH = 5,8. Nhng phc vi Hg(II) v Pb(II) th qu bn n ni chng khng b ph hu bi EDTA. Do , EDTA c th c dng nh mt tc nhn che c hiu qu trong vic xc nh Hg v Pb vi thuc th ny. 7. S tinh ch v tinh khit ca thuc th TMK c th c tinh ch bng cch kt tinh tr li t ethanol nng hoc tritrating vi mt lng nh chloroform, sau lc v ra vi ethanol lnh. tinh khit ca thuc th c th c kim tra bng vic quan st sc k lp mng trong hn hp ca alumina v silicagel (1:1) vi benzene l cht mang. Mi cht tinh khit s to thnh mt im. 8. ng dng trong phn tch ng dng chnh ca TMK l trong phng php trc quang xc nh Hg v mt s ion kim loi nh. Vic o quang c th tin hnh ngay trn dung dch nuc alcohol hoc sau khi chit vi alcohol tinh khit. Nhng v d ny c tng hp trong bng X.7.1. nhy i vi Hg l th hin cao nht trong cc thuc th thu ngn, nhy ca Sandell l 0,0013 n 0,0023g/cm2 ( = 15,1 n 8,8.104) vi TMK, trong khi chng l 0,003 n 0,004g/cm2 ( = 6,7 n 5,0.104) vi Dithizone. TMK cng c s dng nh l thuc th nhn ra cc ion kim loi, nh l Pb ( ta; long gii hn 1:107), Hg(II) (xanhxanh l; long gii hn, 1:5.106), Ag ( ta; long gii hn 1:5.106), Cu(I) (camhng; long gii hn 1:106), Au (xanh ta; long gii hn 1:106), v Pt ( ta). Bng X.7.1: NG DNG CA THIOMICHLERS KETONE NH MT TC NHN TRC QUANG Phc Ion kim loi Ag iu kin pH 3,0 T l max(nm) 520 (x104) 8,85 Dung mi chit IsoamOH Ch chn lc thp
240
Au(III)
Hg(II)
pH 3.0, 50% alcohol, pH 3,0 pH 3,2, 2060% alcohol pH 5,8, 30% n propanol pH 3,2 pH 3,0 pH 3,0 pH 2,8
1:2 1:2 1:3
545 545 560
nc 15,0 11,7 nc
khng sai s vi EDTA EDTA c s dng nh l tc nhn bo v 0,0071,5ppm, chn lc cao vi Hg, Ag, Au(III), Pb(II), v Sn(II) nh hng EDTA c s dng nh l tc nhn bo v Ag, Au, Hg, Pt, Rh, Ru, v TI nh hng
Hg(II) Hg(II) Pd(II) Pd(II) Pd(II)
1:1 1:3 1:4 1:4
560 550 520 520 520
15,1 8,8 21,2 16,0 13,0
nc Iso AmOH nc Iso AmOH n BuOH
CHNG X: THUC TH KHNG VNG

X.1. TRI-N-BULTYL PHOSPHATE
CH3(CH2)3O CH3(CH2)3O CH3(CH2)3O P O
CTPT: C12H27O4 P KLPT: 266,32
1.Danh php TBP. 2.Ngun gc v phng php tng hp Trong cng nghip, TBP l cht d tm. TBP c tng hp t cc phn ng gia nbutanol vi POCl3. 3. ng dng trong phn tch TBP c s dng rng ri nh l mt thuc th dung mi chit tch cc ion kim loi a ho tr. 4.Tnh cht ca thuc th Thuc th organophosphorous c th c xem nh l cc dn xut ca acid H3PO4. TBP ln u tin c bit n vo nm 1949 nh l thuc th dung mi chit cc ion kim loi Ce, Th, v U t dung dch acid nitric, mt s loi thuc th organophosphorous cn c dng s dng nh l tc nhn chit. Vic chit cc ion kim loi vi thuc th phosphorous da trn vic to thnh mui solvate nh 241
UO2(NO3)2(TBP)2 thng qua nhm P=O. Cu trc TBP thay i t (1) n (4) l kt qu gia tng s phn cc ca nhm P=O, lm gia tng kh nng chit. TOPO (4) l thuc th rt nh hng n vic chit trong nhm ny. S thu phn trialkylphosphate (1) cho ra monobasic diester (5) v dibasic monoester (6), nhng cht ny c nhiu ng dng quan trng trong ho phn tch.V d: di(2ethylhexyl) phosphoric acid (HDEHP) c dng nhiu lm thuc th chit cc cation. Theo , TBP, HDEHP v TOPO s c x l tch ring. Tnh cht vt l ca TBP: TBP l cht lng, st, khng mu; nhit si: 152oC 154oC; d4: 0,975;nD = 1,4215; tan t trong nc (4,2 g/100 ml, 16oC) v trn ln hu ht vi cc dung mi hu c. Dung mi phn cc khng thch hp pha long TBP khi chit bi v n gy nh hng mnh gia cc phn t trong dung mi v lm gim kh nng chit ca TBP. Nhng dung mi khng phn cc nh CCl4, kerosene, isooctane v benzene thng c dung pha long TBP iu khin kh nng chit v nht ca tng hu c. T s D (CCl4/H2O)=2.10-3,102oC (ti HNO3 1M n 12M v 0,00732 M TBP). 5. Qu trnh chit vi TBP Vic chit cc ion kim loi vi TBP thng thc hin trong mi trng acid mnh vi acid HCl hoc HNO3. V d, Fe(III) c chit ln lt di dng H[FeCl4(TBP)2 v FeCl3(TBP)3 t HCl 6 v 2 M tng ng. Do , s thay i mi trng acid nh hng rt ln n kh nng chit. Vic gia tng mi trng acid cng c th lm gim s thu phn ca cc ion kim loi a ho tr, kt qu l kh nng chit cao hn. Trong vic chit UO2+ t dung dch acid nitric, phn ng c th vit nh sau:
2UO 2+ + 2NO3 + 2TBPorg UO 2 ( NO3 )2 ( TBP )2org
K ex =
UO 2 ( NO3 )2 ( TBP )2 org

2+ UO NO3 [ TBP ]org
Hng s phn ly ca U(VI) c th c vit nh sau:

D=
UO 2 ( NO3 )2 ( TBP )2 org = K ex NO3 [ TBP ]org
UO
2+
Kh nng chit TBP c th c ci thin bng cch dng nng TBP cao hn v nng ion nitrat cao hn, qu trnh chit c thc hin tng lng. Cc mui nitrate nh NaNO3 hoc Al(NO3)3 thng c dng lm tng kh nng chit. Cc mui ny hot ng nh l cc tc nhn gy kt ta. Hng s phn ly ca cc nguyn t trong qu trnh chit TBP khng pha long t dung dch HCl hoc HNO3 trong mi trng acid khc nhau c tng hp trong bng XI.1.1. Khi chit t dung dch HNO3, TBP cng gp vi acid nitric to thnh (TBP 242
HNO3), kt qu l lm gim kh nng chit v nng TBP gim. Vic tip xc lu di ca TBP vi cc dung dch acid lm cho mt phn TBP b thu phn, l nguyn nhn lm thay i tnh cht chit ca TBP. Trong dung dch HNO3 70%, kh nng cng gp ca TBP b chm li nhit phng. TBP cng dng lm tng tr cho s chit phc kim loi vng cng bo ho phi tr khng mang in tch, v d bng phn ng di y:
+ Ln 3+ + 3HL + 2TBPorg Ln ( L )3 ( TBP )2org + 3H
Ln3+ v HL i din cho ion lantanic v diketone tng ng. Gi tr ca Kex i vi mt vi diketone c tng hp trong bng XI.1.2. TBP cng c dng lm pha tnh trong phng php sc k pha o xc nh cc ion kim loi. 6. Tinh ch thuc th Cc cht gy nhim chnh trong sn phm l cc cht hu c pyrophosphates, mono v dibutylphosphates v butanol, c th x l bng cch cho phn ng vi HCl 8N sau phn ng vi dung dch NaOH 0,4% nng hoc Na2CO3 5%, cui cng lp li vi nc nhiu ln. Mu m c lm kh 30oC di chn khng. Bng XI.1.2: S TR CHIT OF CC NGUYN T T HIM VI DIKETONE V TBP TRONG CYCLOHEXANE HFATBP log 2 log Kex 10,84 10,50 10,76 5,05 4,35 4,63 Thuc th chita TAATBP log 2 log Kex -2,22 -2,77 -2,62 FHDTBP log 2 log Kex 10,00 9,96 10,20 10,06 9,95 10,47
Ion kim loi Eu Nd Tm
a: ch yu cho diketone; HFA: Hexafluoroacetylacetone; TAA: Trifluoroacetylacetone; FHD: Decafluoroheptanedione

2 =
ML3 . ( TBP )2 org
+ ML 2 . ( TBP )2 org H
[ ML]org [TBP ]
3
K ex =
3+ M [ HL ] [ TBP ]org 3 2
X.2.
TRInOCTYLPHOSPHINE OXIDE
n C 8H 7 n C 8H 7 n C 8H 7
CTCT
P O
CTPT: C14H51OP 243

KLPT: 386,65 1. Danh php TOPO 2. Ngun gc v phng php tng hp Thuc th ny c gi tr v mt kinh t. N c iu ch t s oxy ha trioctyl phosphine vi acid nitric (HNO3) hoc t phn ng Grignard ca octyl bromide vi POCL3 3. ng dng trong phn tch TOPO c dng ph bin nh l mt phi t khng mang in cho qu trnh chit cc dng phc kim loi khng bo ho phi tr. 4. Tnh cht ca thuc th Thuc th ny dng tinh th khng mu, nhit nng chy 59,5 60oC. N bn trong khng kh v c th c ct gi nhiu thng nhit trong phng m khng b h hng. TOPO d dng ha tan trong cyclohexane (35,6 g/100ml, 25oC) v nhng dung mi hu c khc. N c th c tinh ch da vo qu trnh kt tinh li t cyclohexane. 5. S phn ng vi cc ion kim loi Cc trng thi oxy ha ca nhng ion kim loi ha tr III, IV, V v VI c th c chit t hydrochloric (HCl) hoc acid nitric (HNO3)vi dung dch TOPO trong dung mi tr nh l Hexane (C6H14), Cyclohexane hoc Toluene (C6H8). Phn dung dch chit ra c xem nh l qu trnh solvat ha chloride (Cl-) hoc nitrate (NO3-), v phm vi chit th ph thuc nhiu vo mi trung trung tnh hay acid. H s chit ca nhiu kim loi trong qu trnh chit bng thuc th TOPO t HCl v HNO3 th c tm tt trong bng XI.2.1. Khi nng acid cao hn, th TOPO trong dung mi hu c cng chit acid t TOPO. HA hoc TOPO.2HA, do h s chit ca kim loi gim da vo nng acid. Khi nng cc acid l 2M th kh nng chit ca cc acid s gim dn t HNO3 > HClO4 > HCl. Tuy nhin, vic thm vo nhng mui kim loi (v d, KNO3 trong qu trnh chit t HNO3) nng cao hiu qu chit kim loi bng nhng phn ng muikim loi, nh c v d hnh 1.
244
Hnh1: Chit kim loi vi TOPO t dung dch HNO3 nng NO3- khc nhau.
Thuc th TOPO cng c dng nh mt loi phi t ph khng tch in ci thin qu trnh chit th c gi l phc kim loi khng mang in cha bo ho phi tr. Nh vy hiu qu (synergistic) ca TOPO c th c tm thy thng xuyn trong vic chit cc ion kim loi a ha tr, cc nguyn t t him, cc ion quang ha. C mt vi v d c trnh by trong bng XI.2.2 5. Nhng thuc th khc c quan h v cu trc vi TOPO Trinbutylphosphine oxide , TBPO: Cng thc phn t: (nC4H9)3Po hay C12H27OP Khi lng phn t: 218,33 N l cht rn ngm nc khng mu, nng chy 62 ti 64oC; im si t 127 ti 133oC tng ng vi (1 torr), v ha tan trong nc khong (5,6g/100ml, 25oC, nhng ho tan ny tng hay gim ty thuc vo nhit ) v trong cng dung mi hu c. ho tan ca nc trong TBPO l 37,5g/100 ml 25oC. Cn ho tan ca toluene trong nc l 3,8 khi HCl 0,5N v bng 3,0 khi HCl 1,04N, bng 1,92 khi HCl 2,07N. Ni chung, TBPO cng c nhng tnh cht ging nh TOPO v dng trong vic chit kim loi. Vic chit nhiu ion kim loi t HCl vi dung dch TBPO 1% trong toluene th c nghin cu. Bng XI.2.2: MT VI V D CHIT TR PHC VI TOPO Ion kim loi Actinides Co(II) iu kin HNO3 0,1-0,5M, BMPB 0,05M pH 5-9, BPA hoc -diketone LIX 54(RH), NO3Dung mi chit Benzene hoc cyclohexan Hexane hoc cyclohexane Toluene Ch chit Am, Bk,Cf, Cm[Ac(PMBP)3.(TOPO) ] Chit nh l Co(diketone)2.TOPO;Cu, Fe, Mn, Ni, citrate, EDTA nh hng chit nh l CuR2(TOPO)
Cu(II) 245
Li Lu Mn(II) Mo(VI) Ra(II) Re(VII) Pt(IV) Ti(IV) Zn
4-Perfluoroacyl-5pyrazolone 1-Phenyl-3methyl-4-aroly-5pyrazolone pH 4,75, HFA 0,07M HCl, HNO3, H2SO4 pH 4,6-8,5, TTA hoc PMBP 0,1M ClHCl HCl 710N, TTA HClO4 1M, AA, TTA hoc HFA 0,1M
Cyclohexane Benzene Cyclohexane TBP(X) Hexane hoc cyclohexane Toluene 1,2 dichloroethane CCl4
Tch t Na Chit nh l LuR3(TOPO) v LuR3(TOPO)2 Chit nh l Mn(HFA)2.(TOPO)2 Chit nh l MoO2X2(TOPO)2 Chit nh l Ra(TTA)2.(TOPO)2 chit nh l ReO3Cln(TOPO) Kex = 3,6.103 Chit nh l Ti(TTA)(TBPO) TOPO hnh thnh sn phm cng n nh hn TBP
TBPO th c ng dng Ch yu cho cc tc nhn phc BPA : nbenzoylnphenylhydroxylamine HFA : Hexafluoroacetylacetone PMBP : 1phenyl3methyl4benzoyl5pyrazolone TAA : Trifluoproacetylacetone TTA : Thenoyltrifluoroacetone Tris(2ethylhexy)phosphine C24H51OP: Khi lng phn t : 386,65 TEHPO l mt dung dch nht khng mu, c im si t 205 ti 213oC (2 ti 3 Torr); d = 0,88 v l mt cht d ha tan trong tt c cc dung mi hu c. TEHPO c nhng c tnh tng t nh TOPO v n cng c dng vo vic chit kim loi. 6. Nhng c tnh khc ca thuc th Nhng cu trc chung thng thy ca diphosphine oxides th c nghin cu nh l mt cht chit kim loi.
P O (CH2)n P O
oxide,
TEHPO,
(CH3(CH2)3CH(C2H5)CH2)3PO
n = 26
Nhng phi t c lin kt i th c nh hng nhiu trong qu trnh chit kim loi hn l vic dng phosphine oxide n cht. 246
Trinbutylphosphine sulfide v triphenylarsine oxide c nghin cu nh l mt thuc th phn tch.
X.3.
DI (2ETHYLHEXYL)PHOSPHORIC ACID
CTPT: C16H33O4P KLPT: 322,42

CH2CH3 CH3(CH2)2 C CH2 H O O P OH 2
1. Danh php DEHP, D2EHPA, HDEHP. 2. Ngun gc v phng php tng hp c s dng trong thng mi 3. S dng phn tch Thuc th c dng nh l mt cht trao i cation lng chit tch cation. N c dng nh l pha tnh trong sc k phn b pha o. 4. Thuc tnh ca thuc th N l mt cht lng nht, d = 0,975, im si = 155oC, n tan t trong nc nhng tan nhiu trong dung mi hu c. Thuc th ny c coi nh l mt acid n chc yu pKa = 1,4. N tn ti nh l cht nh hp trong dung mi hu c khng phn cc, logK = 4,7 trong noctane, nhng l mt cht n hp trong ru, log KD(n octane/nc) = 3,3. 5. Chit vi HDEHP Dung dch HDEHP trong dung mi khng phn cc nh l heptan, octan, toluene v CCl4 c dng chit Ce(IV), Hf, Mo(IV), Nb, Sc, Th, Ti, U(IV), Zr v cc nguyn t thuc h Lantan v Actini trong dung dch HCl, HNO3 v HClO4. Tm li HEDHP tn ti nh l mt cht nh hp trong dung mi khng phn cc v c s dng rng ri chit tch cc ion kim loi nng thp theo phn ng:
+ M n + + n ( HL )2org M ( HL 2 )org + nH
Do kh nng chit ph thuc kh cao vo tnh acid ca pha nc. Tuy nhin tnh cht ch tn ti ngay lc . V d nh kim loi kim th c chit di dng M(HL2)2(HL)2 trong dung dch benzene bi thuc th HDEHP, cc kim loi thuc h Lantan c chit di dng ML3(HL)3 bi dung dch acid trong dung dch acid n gin trong dung dch benzene hay heptan v Th c chit di dng ThL2(HL2) bi dung dch HClO4 hay HCl ca acid trung bnh trong dung dch toluene. Khi ion kim loi c chit vi HDEHP trong dung dch ru c cho bi phn ng sau: 247
+ M n + + nHLorg ML n org + nH
HDEHP tn ti nh l cht n hp. Trong mt vi trng hp, HDEHP khng kt hp vi tc nhn solvat TBP chit tch cc ion kim loi di dng MXn(HL)2. S chit ca Sc, Ti v Zr trong dung dch acid mnh nh (Cl-, NO3- hay ClO4- ) v d nh Ga cng c chit di dng HGaCl4(HL)2 trong dung dch HCl xp x 1M cha 50% CaCl2. Hng s phn ly ca ion kim loi trong qu trnh chit vi dung dch HDEHP 50% trong toluene t dung dch HCl vi nhng nng khc nhau c cho trong bng XI.3.1. T s phn b cng ph thuc vo ion kim loi trong t nhin nh (kch thc v tc ng ion), HDEHP v cc ng dng khc ca diakyl phosphat cng c ng dng rng ri lm pha tnh trong sc k phn b pha o trong vic tch cc nguyn t La v Ac. Bng XI.3.1: H S PHN B CHIT ION KIM LOI VI 50% HDEHP TRONG TOLUENE Log D HCl (M) Ion Kim loi 0,01 Ac 2,3 Ag 0 Am 4 Bi Cu 0 Fe 4 La 4 Mo Ni Np Os 1 Pa 4 Log D HCl (M) Ion Kim loi 0,01 0,1 Pb 1,3 -0,7 Pm 4 1,5 Sb 1,2 Sc 4 >4 Sn 0.5 Th 4 >4 Tm 4 >4 U >4 Y >4 Zn 2 0,3 Zr >2 >2
0,1 -0,8 -1,0 1,0 2,2 -1,8 3,2 1,0 1,2 -1,8 >4 0,9 >4
1 -3,7 -2,5 -2,0 -2,7 -3,9 0,2 -2,8 1,4 -3,0 3,3 0,6 >4
1 -2,9 -1,5 0,3 >4 -0,1 >4 1,2 3,1 1,3 -1,7 >2
6. S tinh ch v tinh khit ca thuc th Nhiu mu thng mi thng nhim bn vi ester n, polyphotphat, pyrophosphate, 2ethyhexanol v mt s cht bn mang tnh kim loi v n c lm sch li trc khi dng lm thuc th phn tch. Thuc th HDEHP th c th c lm sch bng vic khuy vi dung dch HCl 16M 60oC. Khi mt cht khng mu c dng chit, n c th c lm sch qua mui ng bng cch sau . Lc dung dch HDEHP 0,5M trong toluene vi mt lng d dung dch NaOH 10% ha tan trong dung dch Na2SO4 bo ha trong 5 pht. Sau khi tch pha, lc phn hu c vi lng d dung dch CuSO4 0,5M trong 5 pht chuyn NaL thnh CuL2. Lm c c phn hu c bng thit b c chn khng kiu quay n khi cn 0,6 ca th tch ban u, sau x l phn cn li vi lng d aceton c kt ta CuL2. Sau ra kt ta vi acetone v sy ta. X l n vi toluene v dung dch H2SO4 4M c dung dch toluene ca HL. Ra lp hu c ny bng dung dch H2SO4 4M trong 248
vi ln loi ng, sau ra sch bng nc. Cui cng lm bay hi toluene v phn nc d tha trong chn khng. tinh khit ca HDEHP c xc nh bng cch chun in th vi dung dch kim chun. 7. Quan h cu trc vi thuc th khc Dialkylphotphate (CnH2n)2PO4: Phn ln cc (CnH2n)2PO4 c ng dng lm thuc th chit nhng ion kim loi v bng nhng my cm bin trong th in cc ion chn lc. Mt s thuc th c din t sau y: Di(nalkylphenyl)phosphate. Aminoalkylphosphate acid. Hydroxydibutylphosphonylpropionic acid. Sulfur trong thuc th ca Organophosphorous: Monothio v dithioalkylphosphate c ng dng nhiu trong thuc th chit chn lc. Mt vi v d sau : R = nbutyl ether. Dialkylphosphorothioic acid R = n-butyl ether. Dialkylphosphoro-dithioic acid R = isooctyl ether. Trialkyl thiophosphate R = noctyl, ether. Trialkylphosphine sulfide (sulfur analogue of TOPO)
RO P RO RO P RO RO RO RO R R R SH OH S S
249
250
CHNG XI:
THUC TH KHNG TO LIN KT PHI TR
XI.1. THUC TH OXY HA NEUTRAL RED

CTPT: C15H16N4.HCl KLPT = 288,78. Tn quc t: 3amino7dimethylamino2methylphenazine hydrochloride. Neutral Red dng bt c mu xanh m nhng khi ho tan trong nc (4%) v trong cn (1,8%) s cho dung dch mu (max = 533nm, trong 50% ethanol). Ngoi ra Neutral Red cn tan c trong xenlosolve (3,75%) v ethyleneglycol (3,0%), nhng khng tan c trong dung mi thm, pKa (NH+) = 6,7. Phn ng oxy ha kh ca Neutral Red c tnh thun nghch v c kh v dng khng mu bi qu trnh oxy ha kh ca khng kh:
N CH3 (CH3)2N N NH2 NH
2H+, 2e
(CH3)2N NH
CH3 NH2
Mu
Khng mu
Trong iu kin khng kh t do pH = 5,3 dung dch Neutral Red khng c mu, sau pht hunh quang mu vng. S hnh thnh ca vt liu hunh quang ny tu thuc vo pH ca dung dch (xy ra chm pH = 2,7 v gn nh khng xy ra pH = 8,2). Chnh hin tng ny gy ra s thay i tht thng mt cch nhanh chng ca in th nn Neutral Red ch l ch th khng bn trong dy pH m vt liu pht quang khng ph hp (Eo = 0,240V, 30oC). i vi nhng dn xut ca azine c th oxy ho kh qu nh nn n ch c dng nh cht ch th trong qu trnh chun vi tc nhn kh mnh nh Cr(II), Ti(III) v V(II).
XI.2. BRILLLIANT GREEN

CTPT: C27H29N2Cl. KLPT = 392,97.
251
H5C2 H5C2
N C
N+
C2H5 C2H5 Cl-
c im: L mt cht bt mu xanh sng. Tnh cht: tan trong nc (9,7g/100ml) cho ra mt dung dch mu xanh (max = 625nm, = 105). Cc loi monocation (R+) m nh hng trong chit sut ion i s tri hn trong lp trung tnh v n s bin i thnh RH2+ trong acid cho ra dung dch mu vng v thnh ROH trong kim. Tuy nhin s bin i ca R+ thnh RH2+ v ROH s b chm khi qu trnh chit hu nh kt thc th ta c th bit c khong pH rng hn (2 8) khi qu trnh chit c thc hin ngay lp tc sau khi thm vo phm mu alcoholic.
XI.3. THUC NHUM CATION RHODAMINE B

CTPT: C28H31N2O3Cl. KLPT = 479,02.
H5C2 H5C2 N O C COOH N+ C2H5 C2H5 Cl-
c im: Rhodamine B l cht bt tinh th mu xanh ti mu tm. Tnh cht: N d tan trong nc (1,2g/100ml), ethanol v cellosolve cho dung dch mu xanh v pht hunh quang mu vng m. N tan t trong chloroform, acetone v HCl 1M (0,11g/100ml). Trong dung dch benzene v ether, Rhodamine B tn ti dng lacton khng mu v pht hunh quang mu xanh nht.
252
H 5C 2 H 5C 2
O C O C O
C 2H 5 C 2H 5
Trong dung mi phn cc nh alcohol, acetone hoc nc, vng lacton m hnh thnh cu trc (R) c mu tm m (max = 553nm; = 1,1.105). c tnh quang ph ca dung dch Choride (RHCl-), max = 556nm; = 1,1.105 cho RH+ ( pH = 1 3, c mu tm pht hunh quang mu vng) v ti max = 494nm; = 1,5.104 cho RH22+ ( pH = -1 0, c mu cam). Rhodamine B to phc vi nhng nguyn t: Au, Ca, Cd, Sb, Si, Mo, V d: Ta xc nh Au bng phng php chit quang ph, dung mi chit l benzene, thuc nhum cation l Rhodamine B iu kin HCl 0,8N, NaCl bo ha, hnh thnh ion i (AuCl4)-R+ , max = 565nm; = 9,7.104. Cc thuc nhum Rhodamine khc: Cng thc cu to chung:
+
X1 X2
O C
C 2H 5 C 2H 5 Cl-
X3 COOC2H5
Rhodamine 6G: X1 = NH(C2H5), X2 = X3 = CH3. L cht bt mu hng hi xanh sng, tan trong nc (5,4g/100ml) cho dung dch mu ti v pht hunh quang mu xanh. Rhodamine 3GO: X1 = NH2, X2 = CH3, X3 = H, dng bt mu hng sng. Rhodamine 4G: X1 = NH(C2H5), X2 = X3 = H. Rhodamine 3C: X1 = N(C2H5)2, X1 = X2 = H, ethylester ca Rhodamine B l cht bt mu tm, tan trong nc cho dung dch mu tm v pht hunh quang mu nu. Thuc nhum ny l dn xut ethylester ca Rhodamine. V trong dung dch nuc n thng tn ti cu trc R+, trong khi Rhodamine B tn ti dng RH+ trong mi trng acid (pH < 3). Trong mi trng acid long tng i, mt proton thm vo ion R+ s to thnh ion RH2+. Gi tr pKa ca RH2+ c xc nh trong dung dch acid sulfuric: pKa(Rhodamine 6G) = -1,1; pKa(3GO) = -0,4; pKa(4G) = -0,21; pKa(3C) = 253
0,02.
XI.4. CC MUI AMONI BC 4

1. Cc lu chung Cc mui amoni bc 4 c mt hay nhiu nhm alkyl mch di ng vai tr quan trng nh l mt thuc th phn tch. Cc ng dng phn tch da trn 2 chc nng ca cc ion amoni bc 4. Mt l dng nh mt thuc th dng cation trong s chit cp ion ca cc kim loi nh cc phc anion. Th hai l dng nh thuc th dng micelle cation trong php xc nh bng o quang hm lng cc kim loi. Nh trong trng hp cc alkylamin mch di, nhiu loi mui amoni bc 4 khc nhau ang cn c s dng nh l cc thuc th dng cation trong vic tch cc kim loi. Cc ion kim loi c chit nh cc phc anion ca cc phi t v c (Cl-, NO3-, SCN-, CN-, ...) hay cc phi t anion v c. Ngc li i vi cc alkylamin mch di, vic chit kim loi c th c thc hin ngay c mi trng trung tnh hoc kim, ti mt chng mc m phc anion trnh c s thu phn, v ion amoni bc 4 khng cn proton tch anion. Cn bng chit vi ion amoni bc 4 c th c vit nh sau:
n ( m n ) R 4 N + Cl + MLm ( R 4 N )m n ( ML n ) n
mn
+ ( m n ) Cl
Trong MLnm-n l phc anion ca ion kim loi (Mm+) vi phi t (L-). Kh nng chit nh hng bi nhiu yu t nh trong trng hp chit alkylamin mch di. Bng XII.4.1 th hin nh hng ca cc dung mi v cc ion amoni bc 4 ln kh nng chit phc st(III)pyrocatechol4sulfonate. Acid pyrocatechol4 sulfonic (H3L) c dng mt cht chelate anion tan mu vi Fe(III) (Fe(HL)33-; max = 480nm) c th c chit vi ion amoni bc 4. Qu trnh chit d dng hn nu tng cc nhm alkyl mch di ca cc ion amoni v tng hng s in mi ca cc dung mi chit. Qu trnh chit s hiu qu hn vi cc ion amoni bc 4 c mch alkyl di hn. Cc dung mi sau c xp theo chiu gim dn trong qu trnh chit phc Sn Pyrocatechol Violet: (C16H33)(CH3)3NBr > (C4H9)4NBr > (C2H5)4NBr Cc ion amoni bc 4 c 1 hay 2 nhm alkyl mch di ho tan tt trong nc v c xem nh l cht hot ng b mt, trong khi cc ion amoni c 3 nhm alkyl mch di hu nh khng tan trong nc nhng tan trong cc dung mi hu c phn cc hay khng phn cc v chng c xem nh l cht lng trao i anion. V vic la chn qu trnh chit cc anion hay cc phc anion, qu trnh chit ni chung s d dng khi gia tng kch thc v gim in tch. Tuy nhin vn xy ra nhiu trng hp ngoi l. V d trong php chit dung dch dichloroethane ca trioctylmethylamoni chloride, khi la chn phc EDTA th FeY(OH)23- > FeY(OH)2- > FeY- v VO2Y3- > VO2HY2-. Irving cng tm ra cc cch la chn chit phc anion cyano nh sau vi tetrahexylamoni erdmanate trong MIBK: M(CN)2 > ClO4- >> M(CN)42- >> Fe(CN)63trong khi vic chn Fe(CN)63- l cao hn ClO4- trong qu trnh chit trioctylmethylamoni chloridechlorobenzene. 254
Bng XII.4.1: NH HNG CA CC DUNG MI V CC ION AMONI BC 4 LN KH NNG CHIT CA PHC Fe-PYROCATECHOL-4-SULFONATE (Hp thu 480nm) Dung mi CCl4 CHCl3 C2H4Cl2 C6H6 C6H4Cl2 C6H5NO2 Hng s in mi 2,23 4,80 10,36 2,28 9,93 34,82 Trimetylbenzyl amoni chloride Tetradecyldimethyl benzylamoni chloride 0,475 0,655 0,242 0,632 0,585 Dialkylmonomethyl benzylamoni 0,623 0,628 0,625 6,250 0,630
* Ghi ch: pH: 9,9 10,1; Fe(III): 1,00.10-4M; Pyrocatechol4sulfonate: 1,50.10-3M; mui amoni bc 4: 0,010M; KCl: 0,10M. Do , nhiu kt qu thc nghim cn c c kt lun trn s la chn qu trnh chit trao i ion vi mui amoni bc 4. Tuy nhin gn nh l kh nng chit ph thuc phn ln vo loi mui amoni bc 4 v loi dung mi c s dng. Nh nhn xt c nu trn, cc mui amoni bc 4 c mt hay hai nhm alkyl mch di c xem nh l cht hot ng b mt, c dng l mt micell dng nng va trn CMC (nng micel ti hn). Cc phn ng to phc trn b mt ca cc micel dng th hon ton khc vi khi chng xy trong dung dch nc n gin, to thnh mt cht chelate vi t l phi t so vi kim loi cao hn l trong h nc. nh hng ny thng cho kt qu l chuyn i hng hng v s gia tng kh nng thu ht phn t gam ca cc phc chelate kim loi c mu. Cc v d s c trnh by trong nhng mc sau. 2. Tm quan trng ca cc mui amoni bc 4 trong phn tch Cc mui amoni bc 4 thng c s dng nh l thuc th phn tch nh: Tetradecyldimethylbenzylammonium chloride (Zephiramine). Cetyltrimethylammonium chloride (CTMAC) v bromine (CTMAB). Hydroxydodecyltrimethylammonium bromide (HDTMB). Dialkylmonomethylbenzylammonium bromide (AMBB) v chloride (AMBC) Dodecyloctylmethylbenzylammonium chloride (DOMBC). Trioctylmethylammonium chloride (Aliquat 336S). + Tetradecyldimethylbenzylammonium chloride (Myristyldimethylbenzylammonium chloride, benzalkonium chloride)
255
CH3 CH3(CH2)15 N+ CH2 CH3 Cl-
C23H42NCl KLPT =368,04
C gi tr thng mi, Zephiramine l mt cp phn tch ca loi vt liu ny. N l mt cht bt thm mu vng nht hay khng mu, c v rt ng v cha mt lng nh nc. N ht m v tan nhiu trong nc, cn v aceton, tan t trong benzene v cng hu nh l khng tan trong ether. Dung dch nc l cht kim yu v si nhiu bt khi lc. CMC 3,7.10-4M hay 1,5.10-3M. D (dung mi hu c/nc): 0,09 (benzene, toluene), 2,4 (1,2dichloroethane), 11(chloroform), 0,10 (carbon tetrachloride), v 0,53 (MIBK). Mui amoni bc 4 c th c phn tch bng phng php chit trc quang cp ion bng cch s dng tetrabromophenolphthalein ethylester trong 1,2dichloroethane (pH 7,5; max = 610nm; = 7,3.104). + CTMAC (Cetyltrimethylammonium chloride) v CTMAB (Bromide) CTMAC (X = Cl).
CH3 CH3(CH2)15 N+ CH3 XCH3
CTPT: C19H42NCl. KLPT = 320,00. CTMAB (X = Br). CTPT: C19H42NBr KLPT = 364,45.
L mt cht bt ht m khng mu c gi tr thng mi, d tan trong nc, cn v aceton. Dung dch nc si bt mnh khi lc. N cng l cht hot ng b mt tng t nh tetradecyldimethylbenzylammonium chloride v thuc th chit cp ion, CMC 1.10-4M. + Trioctylmethylammonium chloride (Tricaprylmethylammonium chloride)
(CH2)7CH3 CH3-N-(CH2)7CH3 (CH2)7CH3
Cl-
C25H54NCl KLPT = 404,16
C gi tr thng mi nh Aliquat 336S hay Capriquat cha nhiu phn nh ng phn C10 v c khi lng mol trung bnh 442. N l mt cht du nht mu nu vng, cha lng nh nc v hu nh khng tan trong nc nhng d tan trong cc dung mi hu c thng thng nh kerosene (100g/100ml, 0 60oC); D(C6H5Cl/H2O) 10 ([Cl-] = 10-3M). Hng s chit trao i anion KexQCl = ([QCl]org.[X-]/[QX]org.[Cl-]) c cho trn h ncchlorobenzene; log KexQCl = 1,34 i vi Br-, 1,81 i vi NO3-, 3,32 i vi I256
, 3,80 i vi PAR-, 4,47 i vi ClO4- v 10,41 i vi Fe(CN)63-. Khi cc ion kim loi c chit nh cc phc anion, kh nng chit ph thuc nhiu vo nng ca acid. Hnh 1 minh ha phn ph thuc acid ca phng php chit kim loi vi Aliquat 336S. Thuc th c gi tr thng mi c th c lm cho tinh khit bng cc bc sau: Ho tan 50g thuc th vo 100ml chloroform. Lc u dung dch vi 200ml dung dch xt 20% trong 10 pht v sau l vi 200ml dung dch natri clorua 20% trong 10 pht. Ra dung dch cn bng vi lng nh nc v lc qua giy lc kh.
Hnh 1 3. Cc ng dng phn tch S dng nh thuc th chit cp ion. Cc phc anion c mu cao c th c chit nh mt cp ion vi ion amoni bc 4 chuyn v dung mi hu c trong phng php trc quang sau . Cc phng php chit cc phc anion hu c v v c khc nhau ang c thc hin v mt s v d thnh cng c tm tt trong bng XII.4.2 S dng nh mt cht cation hot ng b mt.
Hnh 2 Nh phn trnh by trn, qu trnh to phc trn mt phn cch ca micel dng cho kt qu l lm tng nhy phng php trc quang, do s hnh thnh ca cc 257
phc chelate kim loi vi t l phi t i vi kim loi cao hn. Hnh 2 minh ho ph hp thu ca Eriochrome Cyanine R v cc phc chelate Be ca n vi s c mt hay khng c mt cht cation hot ng b mt (Zephiramine). Trong khi ph hp thu ca thuc th t do khng b nh hng nhiu bi s c mt ca cht hot ng b mt, phc chelate Be cho thy mt s chuyn i hng hng ni bt km theo s gia tng cng hp thu. Kt qu l nhy cao hn vi t thuc th mu trng c th thc hin c bng cch s dng cht hot ng b mt cation. Mt th tch ln c th c thc hin trong lnh vc ny, v mt vi v d c tm tt trong bng XII.4.3.
XI.5. TETRAPHENYLASEN CHLORIDE (TPAC) V CC MUI ONIUM KHC

+
As
Cl-
C24H20ClAs KLPT: 418,80
L+Cl-
1. Ngun gc v phng php tng hp C gi tr thng mi; c tng hp bng s phn ng ca phenyl magan bromua vi triphenyl asen oxit. 2. ng dng L mt s kt ta cc anion bng thuc th, c bit l cc anion oxo v cc phc anion. Khi cc cht kt ta ny c chit c vo chloroform, n cng ang c s dng nh mt thuc th chit cho cc anion nh th. 3. Tnh cht thuc th TPAC thu c khi hydrate 2 ln hoc lm khan n khi xut hin tinh th hnh kim khng mu, im nng chy t 256 n 257oC (hay 259,5 n 261oC). Thuc th th rn th n nh. Thuc th d tan trong nc (0,99M, kh nc 25oC), tan tt trong chloroform (0,70M mui khan). N polime ho trong chloroform to dime (2 = [(LCl)2]/[LCl]2 = 163) v tetrame (4 = 4,5.105). Trong mt php o thng, ch 16% thuc th l monomeric trong chloroform 0,06M ca dung dch TPAC. Trong dung dch nc, TPAC tn ti dng monome, hng s phn ly v hng s phn ly ca monome thu c l K = [L+}.{Cl-]/[LCl} = 0,082 ( = 0,1, 25oC) v KD = (CHCl3/H2O) = 3,7 ( = 0,1, 25oC). 4. Phn ng vi cc anion Cc anion oxo v cc phc anion tng i nhiu dng to bi cc mui khng ho tan vi TPAC (v d cho, Ksp(L.ClO4) = 2,6.10-9 v Ksp (L.ReO4) = 3,7.10-9, 20oC), v cc mui ny c th chit nh cp ion vo chloroform hay ging cc dung mi phn cc nh. Tnh tan ca mt vi mui TPAC trong dung mi hu c c tm tt trong 258
bng XII.5.1. Trong mi trng tnh acid va phi, nng cation As khng lm nh hng nhiu bng ion hydro, cho t s chit thng khng ph thuc pH. Tuy nhin, trong trng hp ca cc ion oxo, c th lm cho proton sinh ra lc tnh acid cao, kt qu l t s chit gim i. Cng nh trng hp ca cc phc anion, nng cc phi t anion rt nh hng n t s chit. H s chit ca cc anion chung v anion oxo khc v rng khong pH c tm tt trong bng XII.5.2. S chit cc phc chloro ang c nghin cu chi tit nh mt hm s ca nng HCl. Mt phn kt qu c trnh by trong bng XII.5.3. S chit ca cc phc anion khc nh l phc flo v thiocyanat cng c nghin cu. 5. S tinh ch v tinh khit ca thuc th TPAC c th c tinh ch bng cch thm acid HCl m c n khi bo ho dung dch TPAC kt ta L.C.HCl.2H2O, sau ho tan kt ta vo trong nc, trung ho bng Na2CO3, lm bay hi cho n kh hon ton, chit bng chloroform, sau cng th trong sut, nu t ethanol bng cch thm ether. Dung dch TPAC tinh khit cn phi sch v khng mu. Cc cht khng tinh khit c th cho dung dch c mt cht m c th lc qua giy lc sau x l bng Celit. tinh khit ca TPAC c th c phn tch bng phng php chit chc quang vi cc anion mang mu cao nh chelate VPAR ( = 560nm; = 9,3.104, 0,1 n 5.10-5M TPAC). 6. Cc ng dng trong phn tch S dng nh thuc th chit. TPAC c tha nhn rng ri nh mt thuc th cp ion chit kim loi. iu kin phn ly ca nhiu nguyn t khc nhau c th tm c trong bng XII.5.2 v XII.5.3. Nu anion c mu cao, nh vy cc nguyn t c th xc nh c bng cch o hp th quang hc sau khi chit. Vi v d c tm tt trong bng XII.5.4. S dng hn hp. TPAC ang c dng nh mt thuc th kt ta cc anion trong php phn tch trng lng, nhm phn ly hay xc nh. Php kt ta c hiu qu vi cc anion ln hn mt in t. Thng thng, h s chit cc anion c tnh tan trong nc thp dng cho phng php kt ta nh lng. TPAC cng dng chun cho php chun kt ta cc anion vi im kt thc bng my o ampe hay vi s la chn in cc anion. 7. Tm quan trng ca cc mui Onium khc trong phn tch Tetra phenyl phospho chlorua (TPPC).
259
Cl-
C24H20ClP KLPT: 374,85
L+Cl-
TPPC l bt tinh th khng mu, nhit nng chy 274 278oC v rt d tan trong nc. E1/2= 1,790V (KCl 0,1M). TPPC c tnh cht tng t TPAC trong php kt ta v chit cc anion v ang c dng cho cc mc ch ging nhau. Ksp(L.ClO4) = 4,6.10-9,6, Ksp(L.ReO4) = 2,1.10-9 (20oC), v Ksp(L.(C6H5)4B) = 1,1 n 1,4.10-8. H s chit ca cp ion TPPC trong h chloroformnc th gn ging gi tr ca cp ion TPAC. Cc gi tr E cho mt vi anion nh l Cl- 0,18; Br- 3,4; I- 60; SCN>380; ClO3- > 100; BrO3- 0,5; ClO4- > 200; MnO4- > 300; ReO4- > 600; NO3- 5,0; NO20,1; v CrO4-: 25 (pH = 2,4), 0,05 (pH = 11,5). Cp ion TPPC gin tip tan trong chloroform nhiu hn l cp ion TPAC tng ng. Tetraphenyl stibi sunfat ((C6H5)4Sb.SO4) c bit n chit F- vo chloroform hay tetra carbon chlorua. Triphenyl Selen Chlorua v trietyl telu chlorua. C hai thuc th u l dng bt tinh th khng mu m d dng tan trong nc. C hai cht cng tng t i vi TPAC dng kt ta v chit cc anion. So vi cch dng nh mt thuc th chit v kt ta, cc thuc th cn c s dng nh mt thuc th xc nh Bi m cho kt ta mu cam trong dung dch KI. (gii hn xc nh 0,11g, gii hn pha long 1: 9,5.105.) Vi mui onium khc nh l 2,4,6triphenyl pyri chlorua v 1,2,4,6tetra phenyl pyri acetat c ngh lm thuc th ging nh mc ch trn.
XI.6. 1,3DIPHENYLGUANIDINE
CTPT: C13H13N3. KLPT = 211,27.
NH C NH NH
1. Tn gi khc 260
Molaniline. 2. Ngun gc v phng php ca s tng hp Thng mi sn c. N c tng hp bi phn ng ca Diphenylthiourea vi ammoniac. 3. ng dng trong phn tch Dng c thm mt proton ca thuc th (ion diphenylguanidium) c dng cho vic chit cp ion ca cc ion kim loi nh cc anion phc tp. N cng c gii thiu nh l mt vt cht u tin cho mt acid tiu chun. c tnh ca thuc th: L mt tinh th khng mu, nhit nng chy 148oC (phn hy 170oC) v ch tan t trong nc nhng tan c nhiu trong ru, chloroform, benzene nng, toluene nng. N cng d dng tan trong acid v c long. Dung dch ca n (trong nc) tan mnh trong dung dch kim. Thuc th dng rn c th c bo qun trong mt chai thy tinh c nt y khng b h, nhng thuc th dng dung dch vi nc th khng gi c lu bi v thuc th s b thu phn to thnh urea. Cch thc chit vi Diphenylguanidine: Diphenylguanidine c xem nh l mt nn tng kh vng chc, n tn ti di dng Ion Guanidinium trong acid xem nh l trung tnh. Ph hp vi tnh cht ca n, thuc th ny c th c dng nh mt thuc th cation tch, chit cc ion kim loi dng phc anion mt cch a dng v rng ri. S chit cp ion kim loi khng ch dng tch kim loi m cn c dng o quang sau . cng on cui cng, mu r rt ca ion c chit vi ion diphenylguanidinium, t thuc th khng mu. Mt vi v d in hnh ca vic chit kim loi vi thuc th dipheylguanidine c tm tt trong bng XII.6.1
XI.7. DIANTIPYRYLMETHANE
CTPT: C23H26O3N4.H2O. KLPT = 424,50.
H 3C
N N C C C
O O C C CH2
N N C
CH3
H 3C
CH3
1. Tn gi khc 1,1Diantipyrilmethane; 4,4methylenediantipyrine, DAM, DAPM, MDAP. 2. Ngun gc v phng php tng hp Trong cng nghip n c to bi s ngng t ca antipyrine vi formaladehyde trong HCl. 261
3. ng dng trong phn tch Khi thm proton vo cu trc ca thuc th th c s dng ging nh nhng cation khng ngm nc trong chit cp ion vi nhng anion phc tp v a dng trong qu trnh chit. N th hu nh c s dng ging nh mt dng thuc th to mu cho phn ng gia Ti v mt s kim loi d b oxy ho.. 4. Tnh cht thuc th N c dng n tinh th khng mu, nhit si 155 n 157oC (vi s phn hu) v n khng tan trong nc (0,04%) nhng d ho tan trong dung dch chloroform (17,6%, 20oC), tan t trong dung dch benzene (1,7%) v carbon tetrachlorua (0,28%) cho dung dch khng mu. Thuc th ny bn trng thi rn cng ging nh trng thi dung dch, n l mt baz yu v b proton trong acid trung bnh bi nhm carbonyl vi 1 hoc 2 H+, pKa(HL+) = 9,96 (trong methylethylketone). 5. Cc dng ca thuc th phn tch Thuc th Diantipyrylmethane trong phn tch c 2 dng, mt dng l thuc th cation dng b proton (HL+ hoc H2L2+) v dng th 2 l thuc th mu phi tr vi ion kim loi d b oxy ho. Thuc th dng cation: Khi thuc th b proton thnh cp ion vi nhng ainon phc tp nh Cl-, Br-, I-, SCN-, NO3- v CN- cng kim loi khc. Nhng cp ion ny tan t trong nc, nhng c th chit vo dung dch chloroform hoc didhloroethane. Cc dng ny c dng trong php phn tch trng lng ca kim loi v s phn ly ca kim loi bi dung mi chit. Nhng cp ion trng thi phc tp c dng trong phng php phn tch trng lng l (HL)2CdX4, (HL)2CoX4, (HL)2IrX6, (HL)2ReX6 (H2L)HgX4, (HL)2OsX6, (HL)BiX4 v (HL)TlX4, vi X khng c s hin din ca Cl- ,Br- ,I- hoc SCN-. Nhng ion kim loi m hnh thnh dng mch vng hoc dng phc thiocyanat, c th phn hu bi cp ion chit vi diantipyrylmethane t ion kim loi khng to phc anion. V d Bi, Cd, Cu(II), Ga, In, Sb(III), Sn(IV), Te(IV) v Tl(III) c th chit t HCl 2,5 3N; Bi, Cd, Pd, Sb(III) v Sn(IV) c th chit t dung dch KI 3% acid ho vi H2SO4; Hf, Mo, Nb, Ta, W v Zn c th chit t HF 0,5 4N c cha H2SO4, v Fe(III), Hf(IV), Hg(II), Pd(II), Sc, The, Th, Tl(III) v Zr c th chit t acid trung bnh trichloroacetic c cha H2SO4. Mt vi v d v s tch chit vi diantipyrylmethane c trnh by bng XII.7.1. Thuc th to mu: Mc d c cu trc phi tr chnh xc ca phc cha c bit trc, diantipyrylmethane c dng phc mu vi mt vi ion kim loi d b oxy ho, nh l: Fe(III) (mu cam; max = 450nm, = 5,4.103), Mo(VI) (mu vng nht), Ti (mu vng) v U(VI) (mu vng). Phn ng xy ra vi Ti(IV) th c chn lc cao v nhy ln (HCl 0,5 4N, [TiL3]4+, max = 385 390nm; = 1,5.104, TiO2 = 0,2 3ppm) hn vi H2O2. Phc ny 262
cng c th chit trong chloroform vi s c mt ca thuc th hu c ph hp hoc anion v c ri em o quang. 6. Mi quan h cu trc vi cc thuc th khc Phn ln cc dn xut ca diantipyrylalkane th c xem nh l mt thuc th phn tch. Mt vi v d c trnh by nh sau:
H 3C
N N C C C
O O C H C R C
N N C
CH3
H 3C
CH3
Diantipyrylmethylmethane(1,1diantipyrylethane, R = CH3): thuc th cho Sb(III). Diantipyrylpropylmethane (1,1diantipyrylbutane, R = C3H7): thuc th cho Ir, Rh, v Ru. Diantipyrylbenzomethane (,diantipyryltoluene, R = C6H5): thuc th cho Ti(IV) v V(V). Diantipyryl2hydroxylphenylmethane (R = oC6H4OH): thuc th cho Ti(IV). Hexyldiantipyrylmethane (R = nC6H13): Hu ht tan trong dung mi hu c, 54% trong benzene v 66% trong chloroform. Disulfodiantipyrylmethane(bis(1psufophenyl2,3dimethylpyzazol5onyl) methane): Thuc th cho Fe v Ti. Dithioantipyrylmethane (4,4methylenebis(1,5dimethyl2phenylpyrazolin3 thione): Thuc th cho Au, Bi, Mo, Te, Tl(III).
XI.8. NATRI TETRAPHENYLBORATE

CTPT: C24H20BNa. KLPT = 342,22.
-
Na+
1. Tn gi khc Tetraphenylboron, mui natri, Na-TPB, Kalignost, Kalibor. 263

2. Ngun gc v phng php tng hp Thuc th ny ph bin trn th trng. N c tng hp t phn ng gia phenylmagnesium bromide vi BF3, sinh ra bi s thu phn khi c NaCl. 3. ng dng Nh l mt thuc th kt ta cho ion kim loi kim nng (K, Rb, Cs) v ion NH4+, bao gm cc cht hu c c bn. 4. Tnh cht ca thuc th dng tinh khit l nhng tinh th khng mu, d tan trong nc (30g/100ml) to ra dung dch trong sut. N cng tan trong methanol, ethanol, acetone v ether. Tuy nhin, trong thng nghip mu b h hng th c mu nu nht v cho dung dch c khi tan trong nc. Thuc th rn tinh khit tng i bn v c th gi c vi thng m khng b phn hu khi c lu trong kho ti v mt. Thuc th km tinh khit th b phn hu nhanh, cho mi t trng ca phenol v biphenyl v. dng dung dch th bn pH = 7, nu bo qun trnh nh sng trc tip (phn hu 0,1% sau 9 tun ti pH = 9,9), nhng rt d b phn hu trong mi trng acid v anion TPB th b proton ho to thnh phenol, biphenyl v acid boric. 5. Phn ng vi cc cation Ion TPB phn ng to kt ta trng vi cc ion kim loi ho tr mt c bn knh ion ln (K, Rb, Cs, Tl(I) v Ag) v ion NH4+, bao gm nhng amin v ion amoni bc bn, nhng mui ca Li v Na th d dng tan trong nc. Nhng ion kim loi a ho tr khng cho kt ta vi anion TPB, nhng Cu(II) th b kh thnh Cu(I) v kt ta vi anion TPB di dng Cu(I)TPB. Nhng hp cht Onium khc khng phi ion NH4+ nh PH4+, AsH4+, SbR4+, BiH4+, =NN, SR4+, cng b kt ta bi anion TPB. Li-TPB tan t trong ether v chloroform nhng Na-TPB khn tan. tan tng khi nhit gim. Cc kt ta kim nh K-TPB th b ha tan trong dung mi hu c phn cc nh acetone (60mg/ml trong acetone 95%; 42mg/ml trong acetone 100%; 28oC), dioxane, DMF, acetonitrile v pyridine. 6. Tinh ch thuc th Thuc th phn tch th c tinh khit t 99,5% tr ln. Thuc th rn khng tinh khit c th c tinh ch bng vic cho ti kt tinh t chloroform hoc acetone, nhng hiu sut thp. i vi dung dch pha th em lc vi keo nhm hydroxide. 7. ng dng trong phn tch S dng nh mt thuc th kt ta cho kali. Kt ta ca mui TPB cng c th c chit vo dung mi hu c nh l nitrometan, nitrobenzene v MIBK. Tnh chit v gi tr logD (pha nc l NaClO 264
0,1M, v NaTPB 0,01M) trong h nitrobenzene/nc tng, nh K (0,89), Rb (1,60), v Cs (2,48). Ion TPB trong dung dch, cng ngy cng thp dn 10-5 n 10-6M, c th xc nh bng cch quan st s thay i ph ca phm nhum cationic nh l Rhodamin 6G bc sng 525nm (cht dng nhum len, la) hc Crystal Violet bc sng 590nm, n c to thnh bi cp ion gia anion TPB v thuc nhum cation. Cch s dng khc NaTPB c s dng nh l mt thuc th Nepherometric cho K v nhng cation c ha tr 1 khc trong nhiu mu khc nhau, bao gm nguyn vt lu sinh hc v t. iu kin cho kt qu xy ra (thuc th phi tinh khit, nng K ln, nhit , thm nhng thuc th khc, tiu chun v thi gian, v nhng nguyn giao thoa): tt c c nhiu nh khoa hc tm ra. Phn ng kt ta vi ion TPB th qu nhym NaTPB c th c s dng pht hin cc cation khc nhau. Mt vi v d c cho trong bng XII.8.1. KTPB cng c xut nh l hp cht hot ng to thnh trong in cc chn lc ion. Bng XII.8.1 : S PHT HIN CA CATION CA TPB Cation Ag+ Cs+ Hg+ Hg2+ K+ NH4+ Rb+ Tl+ GH pht hin (mg) 0,20 0,3 1,1 1,4 0,13 0,11 0,38 1,5 Gii hn pha long 1:210,000 1:100,000 1:40,000 1:30,000 1:320,000 1:400,000 1:110,000 1:28,000 Cation Aniline n-Butylamine di-n-Butylamine metylpyridylnium iod pyridyl quinoline tetrametylamonium iod tetraphenylasonium chloride GH pht hin (mg) 2,9 2,6 0,54 0,15 1,3 0,97 0,32 0,32 Gii hn pha long 1:14,000 1:16,000 1:78,000 1:28,000 1:32,000 1:43,000 1:130,000 1:130,000
8. Thuc th khc vi mi quan h cu trc Tetrakis(4fluorophenyl)borate, mui natri(2), X = F, Y = H, C24H16BF4Na, KLPT = 414,19.
265
X Y Y X Y Y X Y B Y Y Y X Na+
N thng c cung cp mt dihydrate (NaL.2H2O, KLPT = 450,22). Hydrate l mt tinh th bt trng d tan trong nc, acetone v methanol. N c s dng nh mt tc nhn kt ta cho nhng cation ha tr 1 nh l: K+, Cs+, Pb+, Ag+ v Tl+. N c bit hu dng cho vic xc nh s c mt ca Cs trong khi lng ln Li+, Na+, NH4+. Tnh tan ca mui Cs+ (g/100ml nc x 103) ty vo s khc nhau ca nhit c hin th nh sau: 1,5g (5oC), 1,8g (20oC), 5g (40oC) v 43g (50oC). Thuc th ny c s dng nh mt tc cht phng x Cs+ trong nhng mu thuc v mi trng v nh l mt php chun 2 pha s chun ca nhng cht hot ng b mt khng thuc ion. Tetrakis(4chlorophenyl)borate, mui natri (3), KTCPB, X = Cl, Y = H, C24H16BCl4K, KLPT = 496,11. Dng bt mu xm nht, khng ha tan trong nc nhng tan trong methanol. y l mt trong nhng anion ha tr mt in hnh v c xem nh l mt anion trong mi trng trung tnh mang lai mng in cc ion. N cng c s dng trong chun 2 pha, php chun ca nhng cht hot ng b mt khng thuc ion. Tetrakis [3,5bis(trifluoromethyl)phenyl] borate, mui natri, dihydrate (4), thuc th Kobayashi, TFPB; X = H, Y = CF3, C32H12BF24Na.2H2O, KLPT = 922,24. Loi bt tinh th mu trng d tan trong nc, acetone, dietylether v methanol. Ngc li vi ion tetraphenylborate, anion TFPB th rt n nh trong dung dch acid, n c th gi c 20 ngy trong H2SO4 0,05M. Cng vi thi gian ny, TFPB c sc ht ln hn cc cht khc trong nhm ca chng. Chit khng i ca alkali tetraryl borate c tng hp bng XII.8.2. TFPB th c xem nh l ion trung tnh. Lai in cc ion chn la, n rt tt trong vic chuyn i pha xc tc trong phn ng hu c. Ion tetraphenylborate trong dung dch ngy cng thp dn, t 10-5 n 10-6M, c th xc nh c bng cch quan st s thay i quang ph ca cationic phm nhum nh l Rhodamin 6G bc sng 527nm hoc tinh th tm bc sng 590nm n c to thnh bi cp ion gia anion ATTB v thuc nhum cationic. Bng XII.8.2: HNG S CHIT CA ALKALI TETRARYLBORATE GIA 266
NC V TOLUENE Thuc th Li Na K Rb (1) 0,31 0,20 > 50b 550b (2) 0,35 23 1,0b 1,3b (4) 2,5.103 1,3.103b - b - 10b
XI.9. CC CHUI ALKYLAMINE MCH DI

1. Nhn xt chung Cc cation ammonium c c t nhng amin bc 2 v bc 3, c thay th vi nhm cht bo th quan trng cho vic tch, chit cc kim loi. Thng thng cc kim loi thng c tch t dung dch acid nh cc phc anion ha tan vo trong dung dch ca alkylamine ln trong dung dch dung mi ca oxy ha nh MIBK. Ion kim loi, nh Ag, Au, Bi, Cd, Co(II), Fe(III), Ga, In, Ir(IV), Pt v Zn, th tch t vic ha tan dng MClnn-m dng phc anion. Ly v d, trng thi cn bng lin quan trong vic to phc ca Fe(III) t vic ho tan trong dung dch HCl trong mi trng dung mi ca cc amin bc 3 c th c vit di dng sau: R3N.HCl R3N.HCl + + FeCl4FeCl4' ' {R3NH}+ {FeCl4}- + Cl{R3NH}+ {FeCl4}-. R3N.HCl + Cl-
HCl nng cao, h s tch chit c th gim hnh thnh dng R3NHCl.HCl hoc R3NHCl2-. Nh trng hp trn cc dng mui kim chlorua c cng vo gc Cl-. Vic ha tan HNO3, ion kim loi nh Np(IV), Pu(IV,VI), TH, U(VI) v kim loi t him, c th tch dng phc M(NO3)nn-m. Vic tch, chit bng cc dung dch khc nh H2SO4 hay hn hp HClHF cng tng t nh trn. H s tch, chit b nh hng bi nhiu yu t. S n nh ca phc anion kim loi v in tch trn phc anion l nhng tc ng chnh cho s khc bit trong kh nng to phc ca kim loi. C nhng gi thuyt cho rng vic tch ca anion l s tng kch thc ban u v gim in tch. Kh nng tch cc kim loi khc nhau cng ph thuc vo bc amin v dung mi. Ni chung, cc amine bc 1 v bc 2 th kh nng tch km hn so vi amine bc 3, cng nh vy kh nng to phc s tng theo di chui mch ca nhm alkyl v gim vi cc nhnh ca cc chui alkyl. Kh nng to phc cng ph thuc vo bn cht ca dung mi. Mc d khng c nhiu h thng thc nghim khi qut y mi quan h gia tnh cht t nhin ca dung mi v kh nng to phc ca chng, nhng kt qu sau bo co v tch ca Th t dung dch HNO3 6M ha tan 0,1M Trinoctylamin trong cc dung mi khc nhau: CHCl3, D = 0,03; benzene: 0,04; toluene: 0,47; nitrobenzene: 0,60; CCl4, 1,0; n hexane: 3,7; kerosene: 4,6; cyclohexane: 4,8. * Trinotylamine: TOA, TNOA, KEXL83. CTPT: C24H51N. KLPT = 353,67.
267
CH3(CH2)7 CH3(CH2)7 CH3(CH2)7
y l cht du nht khng mu v khng tan trong nc, nhng d tan trong cc dung mi thng thng. Hm lng vt (ppmppb) ca TOA tan trong nc c th c xc nh bng chit cp ion vi ion dichloromate t H2SO4 ha tan trong chloroform, xc nh bng phng php trc quang ca Cr(VI) trong hp cht hu c vi diphenylcarbazide. Cht cung cp nh Alamine 336 l hp cht ca amine bc 3 vi chui alkyl mch thng (thnh phn chnh l octyl v decyl) v cha 90 95% amine bc 3, khi lng phn t trung bnh l392. Vic chit ion kim loi vi TOA t nhng acid khc nhau cho cc kt qu khc nhau v c trnh by Bng XII.9.1. * Triisooctylamine, TIOA CTPT: C24H51N. KLPT = 353,67.
CH3 H 3C CH3 CH3 CH2 N 3 H
C CH2 C
y l cht du khng mu. Cht mang tnh thng mi l hp cht amine bc 3 ca dimethylhexyl ( 3,5; 4,5 v 3,4), methylheptyl v mt s chui alkane khc. Ging vi TOA, TIOA c s dng chit ion kim loi t dung dch acid khc nhau. C ch hot ng ca ion kim loi vi 5% TIOA trong xylene t 0 n 12N HCl (28 29) 0 n 15N HNO3 (4.22) v 0,1N H2SO4 (4.23) c nghin cu t m tng chi tit nh. Mt vi kt qu 5% TIOA trong h thng xyleneHCl c tng kt bng XII.9.2. Nhng v d in hnh ca vic tch ca kim loi bi vic chit TIOA c lit k trong bng XII.9.3. * Cc chui mch di amine bc 2:
268
R2 R1 C HN CH2 CH CH R3 CH3 CH2 C CH3

2
R1=R2=CH3 CH3 CH3 R3 CH2 C CH3 n=2 Amberlite LA-1

n
CH3
Amberlite LA1 (D25 = 0,840) v LA2 (D25 = 0,830) l nhng cht c mu h phch v nht ging du. Nhng cht ny u c th mua c nh nhng gc amine t do v c bo co l nhng hn hp ca cc amine trung bnh chui di, n c tng s cc phn t Carbon ca R1, R2 v R3 l t 11 14. Khi lng phn t trung bnh 372 (LA1) v 374 (LA2). Hai cht ny d tan trong cc dung mi hu c khc, nhng khng tan trong nc, kh nng tan trong dung dch acid H2SO4 1N l 15 n 20 mg/L cho LA1 v gn bng 0 vi LA2. Kh nng tch ion kim loi vi 10% Amberlite LA1 trong dung mi xylene t HCl, HNO3, H2SO4 c kim tra y cc mc (28, 29, 30, 39, 42) mt s kt qu trnh by ti Bng XII.9.4. Nhng amine cn c th c dng c nh b mt cho sc k phn b v sc k giy.
L cht du nht c mu h phch (D25 = 0,845). L hn hp ca alkylamine mch 269

di, c tng s carbon ca 3 gc: R1 + R2 + R3 t 17 n 23 v phn t lng trung bnh t 311 n 315. D tan trong cc dung mi hu c nhng khng tan trong nc. Kh nng ha tan trong H2SO4 1N l l50mg/L. Hot ng tch ion kim loi vi 10% Primene JMT trong xylene t dung dch acid HCl hay H2SO4 c bo co y chi tit. nhng ion kim loi c th c chit t dung dch HCl l : Au(III) ( 1 8M), Fe ( 8 12M), Sb(IV) ( 4 12M), v Pa, Se(IV) (12M), Cd, Hg(II), Tl v Zn (2 4M); t dung dch H2SO4 l: In, Y (0,05M), Am, Bi, Ce, Eu, Hf, In, La, Lu, Mo, Nb, Np, Pa, Pm, Ru, Sc, Tb, Tc, Th, U, W v Zr (0,05 0,5M) v t dung dch HNO3 l Sn v U(IV). Bng XII.9.3: MT S V D V CHIT KIM LOI VI TIOA. Ion kim loi Am(III) Hng dn 10-3N HCl, 11,8M LiCl 410N HCl hay HBr (X = Br hay Cl) Dung mi Xylene hay methylene chloride CCl4 Dng tch lantanides Kh nng tch v ch gii
Au
Mo(VI)
0,010,1N HCl, 6M NaCl 4N HNO3 HCl 46 N hay HBr 4N HCl 68M LiCl hay 4N HBr, 10HBr
Dichloroethane 6M hay CCl4 Xylene CCl4 CCl4
Np(IV) Pd
Pt Pu(VI) Ti(IV)
4N HCl 68M LiCl hay 4N HBr 6,4N HCl, 0,01 M, K2Cr2O7. 1,87N H2SO4, 2,7.10-2 M H2C2O4(x) +
CCl4 Xylene Toluene
Tch 9697% nhng kh nng tch ca Ce, Eu, Pr, Th, Y thp (nhit 20oC 35%) Ir, Rh Chit 100, dng Au(X)4(TIOA)3, max (vi Cl-) 325nm; = 5,8.103, max (vi Br -) 300nm; = 4.104. Dng tch: MoO2Cl4(TIOA)2 hay Mo4O13(TIOA)2, tch 100%. Ir, Rh Tch 90% (25oC) Ir, Rh Tch 100%, Au, Pt gy tr Pt ngi, max (vi Cl-) 467nm; = 1,4.103, max (vi Br-) 345nm; = 9.104. Pt khng tch c khi c s hin din ca LiCl 10M, vi 30% tch c trong s hin din ca KBr 10M. Ir, Rh Tch 100%, khng tch c khi c s hin din ca LiCl hay KBr. Tch 99,8%. Th hay sn phm phn chia Dng tch : Ti(Y)3(X)(TIOA)36
270
U(VI) Zn
0,270,54M gallic 35 acid (Y) 4-3710N HCl 1 383N HCl
Xylene hay MIBK MIBK
Th hay sn phm phn chia Ba, Co, Ir, Mn, Nb, Sb
max = 400nm Chit 9699%, cn tr bi Ag, Cd, Fe, In, Sn.
271
CHNG XII:
XII.1. CURCUMIN
CTPT: C21H20O6. KLPT = 368,39.
THUC TH HU C CHO ANION
OCH3 CH CH O C O C CH2 CH CH OH CH3 OH
1. Tn gi khc Mu vng ngh, curcumagelb, diferulonymethane, 1,7bis(4hydroxy3 methoxyphenyl)1,6heptadien3,5dione. 2. Ngun gc Trn thng mi, n c trong curcuma, the rhizome ca curcuma longa L.Zingiberaceae. 3. ng dng Pht hin ra: B, Ba, Ca, Hf, Mg, Mo, Ti, V, W, Zr. Phn ng o sng ca B, cch s dng nh xt ln t giy sc k. 4. Tnh cht ca thuc th L bt mu vng cam, nhit si 183oC, khng tan trong nc, tan t trong ether, d tan trong methanol, ethanol, acetone, v acid acetic bng. N phn ng vi dung dch kim cho mu vng. Mc d thuc th c diketonemoiety trong cu trc ca n,nhng khng d liu no ph hp cho hng s phn ly ca enolic proton. Hnh 1 minh ho ph hp th ca curcumin iu kin mt vi dung dch khc nhau.
Hnh 1 272
5. Phn ng to phc cht v cu trc phc cht Curcumin c 2 dng phc tp v mu sc: Rosocyamin (1) v Rubrocurcumin (2), vi acid boric, ph thuc ch yu vo s c mt acid oxalic.
Khi khng c mt acid oxalic, acid boric phn ng vi curcumin, khi b proton bi acid v c to thnh dng phc mu (1). Phn ng kh chm v mc d tt nhin mt lng nc cn thit cho giai on tt ca phn ng, nhng phn ng pha trn phi c bay hi cho kh phn ng hon ton. Hay l phn ng to mu c thc hin trong t nhng acid khan, nh acid sulfuricacid acetic bng, ni m nc tn ti c th ph hy bi phn thm vo ca propionyl anhydriceoxalyl chloride. Dung dch (1) s tr v mu xanh en, khi n to bi cht kim. Mc d curcumin cng phn ng vi Fe(II), Mo, Ti, Ta, v Zn, nhng phc cht s khng chuyn sang mu en trong iu kin dung dch kim. Dung dch ethanol ca (1) th c th n nh hon ton 273
v c th gi trong 5 ngy m khng c s thay i quang ph khi gi nhit 0oC. Khi c mt acid oxalic, mu 2:2:2 phc (2) c hnh thnh, s bay hi ca phn ng trn ln n kh th vn cn cho s pht trin mu sc l ln nht. S c mt ca nc lm tr hon phn ng, nu acid v c c mt th s hnh thnh ng thi ca (1) cng c mong i. Quang ph hp thu ca (1) v (2) c minh ha trong hnh 2, hp th phn t ca (2) c ghi nhn l 9,3.104 550nm.
Hnh 2 6. S tinh ch v phn ng tinh khit Sn phm thng mi th hu ht tinh khit, bng s kt tinh li t ethanol cho ti khi im tan ti 183oC. Th v thay ngun gc tng hp curcumin c ghi nhn sai vi mu phn ng vi acid boric. 7. ng dng trong phn tch Curcumin c s dng rng ri nh mt thuc th mu trong phng php so mu xc nh hm lng vt Bo trong nhng vt liu khc nhau. S hnh thnh phc mu (1) hoc (2) c s dng trong phng php so mu. Phng php rosocyanin (1) c nhy cao nhng mu sc phn ng ph thuc rt nhiu vo iu kin phn ng. Phng php rubrocurcumin c nhy thp nht so vi cc dng khc, nhng sn phm ca n khng bao qut. Phng php rosocyanin: nhy ca phng php ny caonhng ph thuc vo s c mt ca nc v lng d ca curcumin vn li trong trng thi proton. Theo n rt quan trng loi b nc v s hp th ti thiu khng vt qu gii hn ca phn ng. Vic sn xut m cn thit c pht trin bi Uppstrom, nc th loi b bi vic s dng cc anhydratpropionic v proton curcumin d th c loi tr bng ion acetat. + Dung dch thuc th: Dung dch curcumin: dung dch phi c tng hp tinh khit trc 1 tun bng cch ho tan 0,125g curcumin trong 100ml acid acetic bng v phi ng trong bnh nha. Dung dch sunfuricacid acetictrn bng nhau nng (H2SO4 98% v acid acetic bng). Dung dch mtrn 90ml C2H5OH 95%,180g CH3COONH4 v 135ml acid acetic bng, nh mc thnh 1l vi nc. 274
Anhydric propionie. Oxaly chloride. + Sn xut: Chuyn 1ml dung dch mu nc cha 0,2 1g Bo vo cc nha, thm 2ml acid acetic bng, 5ml anhydric propionic v trn u. Thm 0,5ml oxalyl chloride v cho php phn ng trong 30 pht, nhit phng v thm khong 4ml sunfuricdung dch acid acetic v 40ml dung dch curcumin, trn u, v yn trong 45 pht. Thm 20ml dung dch m, trn u v lm lnh ti nhit phng. o hp th bc sng 545nm. - Phng php Rubrocurcumin: Phng php ny c nhy km hn so vi phng php khc, nhng phn ng mu nhanh v n khng cn H2SO4. Phng php ny thch hp cho mu sau khi pha long. + Dung dch thuc th: dung dch acid curcuminoxalic: ho tan 0,4g curcumin v 50g acid oxalate trong ethanol (> 99%) v nh mc thnh 1l tr trong chai nha, dung dch phi c gi nhit phng khong mt tun trc khi s dng. + Sn xut: t 2ml mu dung dch cha 0,1 ti 2,0g Bo vochn platin. Sau thm 4ml dung dch acid curcuminoxalic v trn u. S bay hi ca nc khong 52 58oC, thm 25ml C2H5OH, lm kh hon ton v trn k.Sau b phn cht khng tan sau khi lc hoc ly tm, chuyn phn dung dch vo cuvet 1cm v o hp thu ti bc sng 550nm.
XII.2. MONOPYRAZOLONE V BISPYRAZOLONE

O C N H2C H3C C N
(1)
O N C
C N CH CH C N N C CH3 CH3
(2)
C10H10N2O KLPT: 174,20 1. Tn gi khc (1) 3Metyl1phenyl5pyrazoline5one.
C20H18N4O2 KLPT: 346,39
(2) 3,3dimethyl1,1diphenyl4,4bispyrazolin5,5dione. 2. Ngun gc v phng php tng hp Trong thng mi, pyrazoline c tng hp t phenylthydrazine v acetoacetic ester nh l 1 sn phm trung gian ca thuc nhum. Bispyrazolone thu c bng cch cho chy ngc dung dch ethanol ca Monopyrazolone vi Phenylhydrazine. 3. ng dng 275
Hn hp ca Monopyrazolone v Bispyrazolone c dng nh 1 thuc th trc quang c nhy cao vi CN- v thng khng nhy vi SCN- v OCN-. 4. Tnh cht ca thuc th Monopyrazolone: L mt cht bt tinh th khng mu, nhit si 128 130oC. Nhng mu thng mi c mu vng nht nhng c th dng nh thuc th cho CN-, hu nh n khng tan trong nc, nhng tan kh tt trong Alcohol nng, chloroform, pyridine v cc acid. N hnh thnh dng phc mu vi Ag, Co, Cu v Fe. Bispyrazolone: L mt cht bt tinh th khng mu hoc c mu vng xm, nhit si > 300oC v hu nh khng tan trong nc v trong dung mi hu c ni chung ngoi tr pyridine, cn trong thuc th th tan kh tt. 5. Phn ng vi ion CNTrong vic xc nh ion CN- bng phng php Pyrazolone, dung dch mu c x l bng chloramine T, sau bng phn ng vi monopyrazolone v bispyrazolone trong pyridine cho ra dung dch mu xanh o quang. Phn ng lin tc cho n khi ln mu c trnh by hnh 1. Kt qu thuc nhum mu xanh c th chit trong n butanol c nhy cao. Vai tr ca bispyrazolone khng chc chn, nhng n khng th thiu trong qu trnh ln mu ti a. T s ca hn hp khong 12,5:1 th c khuyn dng. Mi ca Pyridine kh ngi nn c th b loi tr v thay th bng DMF c cha acid isonicotinic. Thiocyanur v ammonia gy cn tr nghim trng, chng b oxy ha bi chloramine T cho ra CNCl v NHCl2 tng ng. Sn phm sau cng cng c cho phn ng vi monopyrazolone cho thuc th tm (max = 545nm), cht ny c th chit vi trichloethane sau khi acid ha dung dch nc (mu vng, max = 450nm).
276
CNChloramine T
CNCl
Pirydine
N+ CN
H2O
CH2 HC
CHO
CH CHO
Monopyrazolone
O N HC H 2C HC HC HC N CH3 CH3 N N O
Thuc nhum mu xanh (max = 620 - 630nm) Hnh: S chuyn mu ca Pyrazolone vi ion cyanide
6. ng dng trong phn tch c khuyn dng cho vic xc nh CN- nh sau: Thuc th: Dung dch Pyridine pyrazolone: thm Monopyrazolone t 125ml dung dch nc nng to thnh dung dch bo ha. Lm lnh v lc. lc c, thm 25ml Pyridine chng ct li c cha 25mg bispyrazolone. Dung dch pyridine v pyrazolone tinh khit, c trn ln v chun b trc khi s dng. Dung dch chloramine T 1%: chun b mi mi ngy. m phosphate (pH = 6,8; 14,3g Na2HPO4 v 13,6g KH2PO4 trong 1l nc). Dung dch Cyanide chun: Cch lm o quang trc tip: Chuyn t 1 10ml dung dch CN- tiu chun c chia thnh cc phn bng nhau vo ng o th tch n vch 50ml. Thm 5ml dung dch m v 0,3ml dung dch chloramine T, trn v yn 1 pht. Thm 15ml dung dch pyridine pyrazolone, pha long n th tch, trn v yn 30 pht. Quan st hp th bc sng 620nm. i vi mu c cha 1 n 10g CN-, trung ha n v pH = 6 7 bng CH3COOH hay NaOH v x l nh cch trn. Chit trc quang theo di cch lm trn cho ti khi ln mu y . Chuyn lng mu cng dung dch sc ra cho ti 125ml vo phu chit c cha chnh xc 277
10ml nbutanol v lc vi pht. Sau khi c s phn chia pha, quan st hp th ca lp hu c bc sng 630nm. Thiocyanate cn tr nghim trng. Phng php ny c th ng dng trong vic xc nh thiocyante (620nm, 0 4ppm trong dung dch), cyanate (450nm, 0 5ppm trong CCl4), v ammoniac (450nm, 0 0,5ppm trong trichloroethylene), nh nhng anion ny c tin hnh nh cyanate. Nitrat c th c xc nh sau khi kh t ammoniac bng alkaline FeSO4. Vic xc nh Vitamin B12 (Cyanocobalamine) bng phng php ny c tin hnh. Monopyrazolone cng c th c s dng nh mt cht th cho Ag v Cu. 7. Mi quan h cu trc vi thuc th khc Phenazone (2,3dimethyl1phenylpyrazolin5one) va c nghin cu nh mt cht th i vi NO3-.
XII.3. 2AMINOPERIMIDINE
CTPT: C11H9N3.HCl. KLPT = 219,67.
H N C NH2 . HCl N
1. Ngun gc v phng php tng hp Sn c trn th trng l hydrochloride v hydrobromide. Cho 1,8 diaminonaphthalene phn ng vi NH4SCN. 2. ng dng Thuc th kt ta v o c ion sulfate. 3. Tnh cht thuc th L cht bt tinh th mu trng hi xm. Tan t trong nc khong 0,5% nhit phng nhng d dng tan trong nc nng. Thuc th d b oxy ho, thuc th dng rn t bn nn phi c gi ni mt v ti. Thuc th dng dung dch th n nh trong mt vi ngy nu c gi trong chai kn v ti. Thuc th c th tinh ch bng cch un si dung dch bo ho vi than, lc v loi b hydrochloride kt tinh. 4. Phn ng vi ion sulfate Cho dung dch c cha ion sulfate vo dung dch thuc th (bo ho ti nhit phng, 0,5%) th ngay lp tc hnh thnh kt ta snh vn la mu trng ca amine sulfate. Tnh c trng ca kt ta ny l thng khng c nhng ht c nh (< 2m). 2 aminoperimidinium sulfate c tan thp, iu l tng s dng thuc th trong phng php o c cho ion sulfate. Trong bng XIII.3.1, 2aminoperimidine sulfate c kh nng ho tan ti thiu gia cc amine sulfate khc nhau. 1ppm sulfare 278
kt ta c th quan st c v c th thc hin c 0,05ppm sulfate vi th tch o l 10ml. Dung dch 2aminoperimidine hydrochloride c minh ho hnh 1 dng phng php ph hp th UV. Nu vng rng hn ti 305nm ( = 7,23.103) c th s dng phng php trc quang xc nh cation 2aminoperimidine trong phn dung dch sau khi kt ta ion sulfate vi lng d thuc th bit. iu ny lm c s cho phng php so mu gin tip xc nh ion sulfate (4120ppm SO42-). Toei ngh s dng thuc th mu, 6(pacetylphenylazo)2aminoperimidine (pH = 3,4 4,1; max = 480nm ; = 6,1.103) cng tng t, nhng vng nhn thy c ca phng php trc quang nng sulfate t 0 ~ 10ppm.
Hnh XIII.3.1 5. ng dng trong phn tch Phng php ny xc nh nng sulfate t 0 ~ 5ppm. Chuyn 1,0 n 5,0ml dung dch chun sulfate 10ppm vo 5 bnh nh mc. Pha long vi khong 5ml nc thm 4ml dung dch thuc th 2aminoperimidine hydrochloride 0,5%. Trn u v loi b huyn ph trong khong t 5~10 pht chuyn vo trong ng o c v o tn x nh sng ca mi dung dch. Dung dch mu cng lm tng t. T 0 n 1ppm hay 0 n 0,5ppm ca sulfate, qu trnh thc hin chnh xc vi cng mt cch thc nhng phi s dng dng c o c nhy cao. Cng nh sng truyn qua ti bc sng 600nm cng quan st c thay v o bng tn x nh sng c cng mnh. Nhng anion gy nh hng c gii thiu bng XIII.3.2. Bng XIII.3.1: TAN KHC NHAU CA AMINE SULFATE Benzidine 1,8-Diaminonaphthalene 279
0,098 0,222
4-Amino-4-chlorobiphenyl 0,155 4,4-Diaminotoluene 0,059 2-Aminoperimidine 0,020 Bng XIII.3.2: NH HNG CA NHNG ANION NHIU NO310 - 100ppm khng b nh hng Br t 10ppm tr ln khng b nh hng, nhng 100ppm b sai l 20% I 10100ppm b sai l 10% F-, SiF41ppm F- b sai l 10%, nhng 10ppm b sai l 15% PO431ppm b sai l 25% Cl 10ppm khng b nh hng, nhng 100ppm b sai t 515%
280
TI LIU THAM KHO 1. Nguyn Trng Hiu, T Vn Mc - Thuc th hu c - NXB KHKT, 1978 Handbook
of organic reagents in inorganic analysis.
2. C s l thuyt ha phn tch (Creskov) NXB KHKT. 3. Thuc th hu c - T Vn Mc, Hong Trng Biu NXB KHKT. 4. Lm Ngc Th - Thuc th hu c -, H Ni 2000. 5. Hand book of Organic Analytical Reagents-K. Ueno; Toshiaki Imamura; K.L Cheng.
CRC Press. 2000.
6. Springer,C.S., Kr., Meek, D. W., and Sievers,R.E., Inorg.Chem.,6,1105,1967. 7. H Flaschka, G. Schwarzenbach (Lm Ngc Th v o Hu Vinh dch) - Chun
phc cht - NXB KHKT, 1980.
8. Sekine, T. and Ihara,N., Bull. Chem. Soc. Jpn., 44, 2942, 1971. 9. C. Saclo (T Vng Nghi, o Hu Vinh dch) - Cc phng php ha phn tch NXB H&THCN, 1987.
10. Yu.X. Lialikov (C Thnh Long, Ng Quc Qunh dch) - Nhng phng php ho l
trong phn tch - NXB KHKT, 1970.
11. H Vit Qu Cc phng php phn tch quang hc trong ha hc NXB HQG H
Ni, 1999.
12. Phm Gia Hu - Ha phn tch H Dc H Ni, 1998. 13. A.P.Kreskov (T Vng Nghi v Trn T Hiu dch) - C s ho hc phn tch, tp 1,2
NXB H&THCN, 1990.
14. Nguyn Tinh Dung Ho hc Phn tch, tp 1, 2, 3 NXBGio dc, 1981. 15. L Xun Mai, Nguyn Th Bch Tuyt - Ha phn tch- NXB HQG TpHCM, 1990. 16. L Xun Mai, Nguyn Th Bch Tuyt - Gio trnh phn tch nh lng NXB
HQG Tp. HCM, 2000.
17. Hong Minh Chu - C s ha hc phn tch NXB KHKT, H Ni, 2002. 18. T Vng Nghi - Ha hc phn tch - NXB HQG H Ni, 2000. 19. Melia, T. P. and Merrifield, R., J. Inorg. Nucl. Chem., 32, 1489, 2573, 1970. 20. Schwarberg, J. E., Sievers, R. E., and Moshier, W., Anal. Chem., 42, 1828, 1970. 21. Chattoraj, S. C. Lynch, C. T., and Mazdiyasni, K. S., Inorg. Cem., 7, 2501, 1968. 22. Richardson, M. F. and Sievers,R.E., Inorg.Chem., 10, 498, 1971. 23. Dilli, S. and Patsalides, E., Aust. J. Chem., 29, 2369, 1976. 24. Shigematsu, T., Matsui, M., and Utsunomiya, K., Bull. Chem. Soc. Jpn., 41, 763,
1968.
25. Shigematsu, T., Matsui, M., and Utsunomiya, K., Bull. Chem. Soc. Jpn., 42, 1278,
1969.
26. Honjo, T., Imura, H., Shima, S., and Kiba, T., Anal. Chem., 50, 1547, 1978. 281
27. Heunisch, G. W., Mikrochim. Acta, 258, 1970. 28. Holzbecher, Z., Divis, L., Karal, M., Sucka, L., and Ulacil, F., Handbook of Oganic
Reagents in Inorganic Analysis, Ellis Horwood, Chichester, England, 1976.
29. Dhond, P. V. and Khopkar, S. M., Talanta, 23, 51, 1976. 30. Solanke, K. R. and Khopkar, S. M., Fresenius Z. Anal. Chem., 275, 286, 1975. 31. Savrova, O. D., Gibalo, I. M., and Lobanov, F. I., Anal. Lett., 5, 669, 1972; Chem.
Abstr., 78, 1138n, 1972.
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MC LC CHNG I: I.1. I.2. I.3. I.4. I.5. II.1. II.2. II.3. II.4. II.5. II.6. II.7. II.8. II.9.

CHNG V: V.1. V.2. V.3.

TNH TON CC HNG S CA THUC TH V PHC ............ 72

CHNG I: PHN LOI THUC TH HU C

S BT HP L CA CCH PHN LOI TRONG HO HU C

Phn ng vi hydroxide magie trong mi trng kim cn cht mu

PHN LOI THEO YOE

PHN LOI THEO FEIGL

PHN LOI THEO WELCHER

CHNG II: L THUYT V LIN KT PHI TR

NH3 H3N Cu NH3 NH3

H3N NH3 H3N Ni NH3 H3N NH3

(2.4) (2.5) (2.6) (2.7) (2.8)

[Cu (OH 2 )2 ]2 + 4 : NH 3 [Cu (: NH 3 )4 ]+2 + 4 H 2 O

(2.11) (2.12) (2.13)

6d 5f 7s 6p 5d 4f 6s 5p 4d 5s 4p 3d 4s 3p 3s 2p 2s 1s Hnh 2.1: S mc nng lng ca nguyn t

Hnh 2.4: Hnh dng khng gian ca qu o s z z y z y y

Hnh 2.5: Hnh dng khng gian ca qu o p.

PHNG PHP LIN KT HA TR (VB)

L THUYT V TRNG TINH TH

ec Nng lng 0,6 0 0 0,4 0 t2

Ion kim loi t do (Ti4+)

Phc gi thuyt vi cc qu o d suy bin

Phc bt din [(TiF6)2-]

Qu cu bng bt bin (ion kim loi t do)

Qu cu bng bt bin di p lc ca lp v hnh cu (phc gi thuyt)

Qu cu bng bt bin di p lc tc ng vo nhng hng xc nh (phc cht).

trong ion kim loi 1 2 3 4 5 6 7 8 9 10

1,6 2,0 2,4 1.8

dx2y2 Nng lng dx2-y2dz2

T gic lng chp

Phc spin cao

Phc spin thp

0 0 0.2 0.6 0.4 di nh sng () 0.8 1 (x 104)

THUYT QU O PHN T (MO)

Tr xen ph Qu o A phn lin kt Cng xen ph Qu o lin kt P P Tr xen ph Qu o Cng xen ph A

Hnh 2.16: Biu mc nng lng qu o phn t ca phn t H2 AO MO AO

Nng lng thot ra khi to thnh phn t AB a+b A 2a+b

1s2 1s2 1s22s1 1s2 1s2 1s22s1 1s22s2

0 1s2 1s2 1s22s1 1s22s2 1s22s2 1s22s2

Lin kt Fe-CN Hnh 2.20: Lin kt v lin kt trong phc [Fe(CN)6]4-.

HNH DNG HNH HC CA CC HP CHT PHI TR

CO CO CO Fe CO Tam gic lng chp F F

Thay i t gic Thay i t gic Khng thay i Khng thay i

d3, d8 d4, d9 d5,d10 Spin thp d6 d

Thay i t gic mnh Khng nh bng thc nghim

Khng thay i Thay i t gic mnh

Khng nh bng thc nghim Phc di dng vung phng

CNG TRNG PHI T

CU TRC PHN T V TAN

II.10. PHC CHELATE (VNG CNG)

II.11. S N NG KHNG GIAN V CHN LC

II.12. BN CA HP CHT PHI TR

[ MY ] [ M'][ Y'] Y M [ MY ] [ M'][ Y']

II.13. NG HC CA PHN NG TRONG THUC TH HU C.

NHM CHC PHN TCH V NHM HOT TNH PHN TCH

III.1. NHM CHC PHN TCH

V nhng dn xut ca rhodamine c cu to tng qut

Bozoncenckun cho rng mui bc to thnh trong phn ng c cu to V hoc VI.

Nhng axyloinoxim c cng thc tng qut

Chnh v vy nn nhng oxim ca methylacetonylcarbinol v chloracetophenol cha nhm nguyn t.

Do ngi ta cng nhn 2 cu to nhm chc phn tch ca Cu(II)

Nm ngoi nhm thm

Nm trong nhm thm