CHNG VII NHNG TNH CHT PHN TCH CA CC NGUYN T

Khi nghin cu phng php xc nh mt hp cht ha v c bt k cn thit phi ch ti tt c nhng cu t c th c mt trong mu phn tch. V phn ng gia thuc th hu c vi cc hp cht v c l khng c trng (ch tr mt s ngoi l) nn vn nu trn l rt quan trng. gii quyt vn l c th s dng nhng tnh cht c bit no ca cc cu t t c la chn cao, trong chng ny chng ti s nu ln mt cch ngn gn mt s tnh cht quan trng nht ca cc nguyn t (khng cp ti mt s vn nh borhydrit, ferroxen, cu to ca silicat, phc cacbonyl) Tt c cc nguyn t s ln lt c nu theo th t cc ch cai, tr hydro, cacbon, cc kh tr, cn cc nguyn t rt him c cp ti trong phn lantan v cc thnh phn thip theo ca dy actinit c nghin cu trong phn amrixi. Hy vng rng nhng iu trnh by trong chng ny s c ch cho bn c c trong nhng trng hp thiu nhng d kin chnh xc. V d nh Pb(II) trong dung dch trung ha hoc ammoniac to vi galloxyanim (c cng thc cu to)

Kt ta mu xanh cha r thnh phn. C th to thnh hai loi hp cht ni phc. Trong mt loi kim loi lin kt vi nguyn t nit v nguyn t oxy ca nhm cacboxyl; Cn trong mt loi khc th nhm OH v nguyn t y bn cnh tham gia vo vic to thnh lin kt. Nhng nu ch ti nhng tnh cht ca ion ch nu trong phn Ch th thy rng gi thuyt v s to thnh hp cht loi I l c u th nhiu hn. ASEN As c th c ha tr III hoc V nhng ha tr II bn vng hn. Khi kh nhng hp cht ca As trong HCl hay H2SO4 ta thu c asin trng thi kh iu chng t rng nguyn t ny to nhng lin kt cng ha tr. Phn ng nu trn c s dng xc nh As, AsCl3 cng c c tnh cng ha tr nn c th chit hp cht ny bng CCl 4 hoc l cu t dung dch HCl nng cao c cht kh. AsBr3 b chit ng k vi dung dch HBr 4,5M bng diety ete. Cng c th ct hp cht ny t dung dch HBr c. AsBr5 cng l hp cht bay hi. Ngi ta cn cha chng minh c s tn ti ca ion As3+ trong dung dch nc. Asen to nhng lin kt bn vi lu hunh, do c th kt ta As(III) v As(V) di dng As2S3 v As2S5 t nhng dung dch axit. Trong mi trng axit v c n to nhng phc bn vi dietylamoni diety1ditiocacbamat v Kali etylxantogenat. Nhng phc ny b chit bng Clorofoc. Trong phn t asen trioxyt As4O6 nhng nguyn t oxy phn b theo hnh t din xung quanh nguyn t asen. Khi ha tan hp cht ny trong nc ta thu c axit yu (axit asen) v asenit l nhng cht rt d b oxy ha. Bng cch gin tip ngi ta iu ch c Pentaoxyt asen. l cht oxy ha, rt d tan trong nc to thnh axit.

Hin nay cha c thuc th hu c tt xc nh asen. Nhng phng php trng thng xc nh As l da trn c s to gng asen v xanh molybden. (Kh hp cht d a asenomolydat bng hydrazine sunfat hoc SnCl2. C th lm giu lng vt As trong dung dch bng cch s dng hydroxyt Fe (III) lm cht gp hoc l kh n trng thi nguyn t bng thy ngn mt clorua rn trong dung dch axit. ACTINI Ion Ac l ion c hot tnh phng x mnh, c cu hnh in t ca kh tr radon. Theo tnh cht ha hc, actini rt ging La3+ ch khc l n c tnh baz ln hn m thi. Bn knh ion ca chng hu nh bng nhau. Tnh baz ca Ac 3+ th hin trong tnh cht b hp th mnh hn bi Oationit v b chit yu bng tributylphotphat t cc dung dch axit nitric. ALUMINI(Nhm) Nhng tnh cht ha hc ca ion Al3+ c quyt nh bi in tch cao, bn knh nh v cu hnh in t kh tr neon ca n. Trong dung dch nc Al 3+ hydrat ha mnh v chc l tn ti di dng (Al(H2O6)3+). Ion ny trong mi trng trung ha hoc axit yu b thy phn mnh v d dng kt ta di dng Al2O3 ngm nc. Ngi ta li dng tan nh ca hydroxyt nhm trong dung dch ammoniac trung ha v mui photphat ca n pH= 5-5,5 tch Al khi Mg, Ca, Sr v Ba. Nu trong dung dch ch c mt lng nhm khng ng k th c th s dng hydroxyt Zr(IV), Fe(III) hoc photphat Fe(III) lm cht gp. Trong dung dch kim, aluminat Al(OH)4 c to thnh. Phc ca nhm c th c cu hnh t din hoc bt din. Phc t din thng l anion mt in tch v d nh AlBr4, hoc l thng gp hn l loi hp cht trung ha in to thnh do s cng hp hp cht AlX3 vi nhng cht cho in t loi ammoniac, amin, ete, ru, xeton, photphin v tioete. Anion nh nh F- to phc bt in AlF63- rt bn. Nhng AlCl4 trong dung dch nc khng c ngha ngay c trong HCl 12M. Trong HCl nhng phc anion ca nhiu kim loi b hp th trn ct anionit cn Al th khng b hp th. Khi Al to phc c cu hnh bt din, nhng phn t anion 1 rng cha oxy c u th hn nhng amin trung ha in v nhng phn t phn cc khc. Do nhng dixton, Pyrocatesin v axit dicacboxilic to phc bn 1:3 vi Al. Do nguyn nhn khng gian m phc 1:3 ga Al vi 8oxyquinaldin khng to thnh v cng do nguyn nhn nn Al ch c khuynh hng to phc yu vi dietylditiocacbonat. Ngi ta s dng nhng thuc th ny chit nhiu cation cn tr ra khi dung dch cha Al3+. Phc ca Al vi 8-oxyquinolin (nhng khng phi l vi 1,10phenantrolin) l phc rt c ch i vi phn tch. Trong a s trng hp ngi ta thng s dng aurinticacboxylic axit (aluminion), eriocromxianim R v alizarinsunfonic axit lm thuc th o mu xc nh Al. Tc dng ca cc thuc th ny da trn c s lin kt Al vi cc nhm cacboxylic, phenol hoc l vi cc nguyn t oxyquinoit. AMERIXI V NHNG THNH PHN XA HN CA DY ACTINIT Trng thi oxyha v quang ph hp th ca nhng nguyn t dy ny c xc nh bi mc in t 5f cha hon thnh. Do nhng nguyn t dy ta ang xt rt ging cc latanit (cc nguyn t t him) l nhng nguyn t c mc in t 4f cha hon thnh. Trng thi ha tr cao nht quan st thy trong trng hp Np v Pu gy nn bi nhng qu o 5f v 6d ca chng bng nhau v nng lng. Nhng trong trng hp nhng thnh phn khc ca dy ny th khi s in t 5f tham gia to
3+

lin kt ln hn i hi phi tiu th nng lng rt ln v in tch ht nhn tng v bn knh gim. Trong dung dch nc, trng thi ha tr 3 ca Am, Cm v ca nhng thnh phn tip theo ca dy rt bn. Kh nng ca beckli tn ti di dng Bk(IV) c gii thch nh sau: Bk(III) c 8 in t chim 7 qu o 5f; nng lng cn thit chuyn mt trong s nhng in t ln qu o 6d cn li 7 in t trn 7 qu o 5f mt phn c b tr nh s c li v mt nng lng trao i do tnh bn c bit ca mc in t f mi ch c hon thnh mt na to nn so snh vi 5 in t 3d trong Fe3+, v 7 in t 4f trong Tb4+. Nhng tnh cht tng t ch r kh nng tn ti ca Cf(V) v gii thch s chuyn dch f-f trong nhng nguyn t f7 ca gadolini v curi i hi nng lng ln v do nhng chuyn dch nm vng di sng ngn hn so vi nhng thnh phn khc ca dy ny. Hot tnh phng x ca phn ln cc nguyn t ny gy tr ngi cho vic nghin cu tnh cht ha hc chng. C th cng kt nhng cation 3 in tch vi RaF3, La(OH)3, CeF3, KLa(SO4)2 v sau tch amerixi bng cch oxy ha bng hexon t dung dch HNO3 6M hay bng dietylete t dung dch HNO3 1M bo ha NH4NO3. Thng ngi ta tch nhng actinit ha tr 3 bng oationit v ra phn on tip theo hoc l bng anionit v chit. Nhng phc 1:3 trung ha in ca Np(III) v Pu(III) b chit bng tenoiltrifloaxetat, xylen t nhng dung dch axit va phi, trong khi th phc ca Am(III) b chit t dung dch pH:4 v cao hn. Cng c th chit An(II) bng tributylphotphat 30% t nhng dung dch axit yu bo ha amoni nitrat. Cm(III) b chit bng tributylphotphat t dung dch HNO 3 16M cn Am(III) t dung dch HCl 0,05M sau gii hp n bng oxyisobitirat amoni. Ngc li trong dung dch Liti clorua 20M, Am(III) to phc anino b hp th trn anionit v sau b gii hp bng HNO3 8M. D on nh lng nhng tnh cht nh vy ta s gp kh khn v hu nh hon ton khng c nhng d kin v hng s bn cn thuyt tng phi t th mi ch c pht trin cho nhng kim loi chuyn tip cn i vi actinit v lantanit th cha c nghin cu. pht trin l thuyt ny cn phi bit nhng tnh cht xc nh v ha lp th ca cation trong nhng phc ca n. Tng t nh cc kim loi chuyn tip c th cho rng Am(III) qua cc tiu Cm(III) v tng n cc i khc Md(III) hoc No(III) (1018,2) v Cm(1018,4) n Cf(1019,1) khng pht hin thy cc tiu no c nhng c th cho rng l hu qu ca lc trng phi t yu. Mt cch nh tnh, c th ni rng nhng thuc th to vng cng bit, to phc vi actinit u ch yu thuc v nhm thuc th to lin kt bng nguyn t oxy. Nhng thuc th l xitrat, tactrat, lactat, glykolat, -oxyisobutirat, teoniltrif1axeton v EDTA; chng u to trng phi t yu. Ngi ta cha tm c nhng thuc th mu cho nhng cation ny. Hin nay, ch yu da vo cc phng php phng x v vo mauu kh nht ca mt s ion xc nh actinit. ANTIMON Anitimon c tnh baz mnh hn asen mc d Sb2O3 tan trong cc dung dch kim to ion antimonut(V). Do tnh tr ca nhng in t 5s2 ca antimony thng c ha tr 3. Ngi ta bit ch yu l nhng mui ca ion antimonyl SbO+ v nhng mui ca ion Sb3+. Cu hnh in t ca antimony ([Kr]4a105s25p3) to iu kin thun li cho s to lin kt cng ha tr do khi cho H2S qua dung dch axit th Sb2S3 kt ta (nu antimony(III) ch tn ti trong

dung dch lng khng ng k th phi dng ng sunfua ln cht gp). Sb 3+ to phc vi nhng phi t cha oxy to nhng anion loi Sb(SO4)2, Sb(C2O4)2 v Sb(OH)2C4H4O6 (ion antimonyltactrat) cn trong nhng dung dch trung tnh hoc kim yu th to nhng phn t trung ha nh:

tan hn ch ca phc anitmon vi pyrogallol l do s to phc a nhn nh nhm oxy khng lin kt trong cu to nu trn c kh nng phi tr vi nguyn t antimon khc. Cu to cho php lin kt c 3 nguyn t oxy ca pyrogallol vi mt nguyn t antimony khng th chp nhn c v mt ha lp th. Bismut cng to nhng hp cht trung ha in tng t. Khi c mt nhng cht oxy ha mnh nh Ce(VI) trong HCl c Sb(V) to phc anion b hp th mnh trn ct anionit do c th tch n khi nhng kim loi nh Pb Ion Cloroantimonat to nhng ion i khng tan trong nc, b chit bng nhng dung moi hu c, vi nhng baz c th tch ln c bit l vi metyl tm. Rodanion B, lc brilliant, v antraquinon -1-azo-4dima-tylanilin. Ion iodantimonat cng phn ng tng t vi pyridine v triphenylmetyl asonic. Ngi ta s dng nhng ion i ny o mu xc nh Sb. C th chit phc clorua ca Sb(V) trung tnh bng nhng dung mi cha oxy t mi tng axit mnh (v d bng diizopropyl ete t HCl 6,5M 8,5M). Trong nhng iu kin nh vy Sb(III) b chit kh yu. Nhng phc bromua ca Sb(V) v Sb(III) trong HBr 4,5M ging cc phc clorua v tnh cht b chit. Sb(III) b chit nh lng bng diety1 ete t dung dch HI 6,9M di dng iondantimonit c mu vng m. Cng c th chit SbI3 bng benzene t dung dch H2SO4 5M cha iodua khong 0,01M v cht kh. ASTATIN ng v sng lu nht ca astatin c chu k bn hy l 8,3 gi. Do nhng hiu bit v tnh cht ha hc ca n hon ton da trn c s cht ch th. Nhng tnh cht ging tnh cht ca iotn v rt gn vi nhng tnh cht da trn c s ngoi suy tnh cht ca nhng halogen. AZOT(Nit) Nhng hp cht ca nit c c tnh cng ha tr. Nguyn t ngy thng to thnh 3 lin kt chnh; i in t khng phn chia cn li cho php nguyn t ny tham gia vo s to phc vi chc nng nguyn t cho Nit cng to nhng lin kt kp, v d nh trong nhng hp cht azo (-N=N-) v trio (-NO2). S lai ha sp3 khi to thnh NH4+ tng t nh s lai ha trong trng hp CH4 dn ti s phi tr cc i 4 l cu to t din. Nhng amin cng c ha lp th tng t, i in t khng phn chia chim qu o nh hng xc nh trong khng gian. C th m t qu o ny nh qu o S vi s ng gp mt cch ng k ca qu o p lm tng nhiu tnh cht cho in t ca phn t. C th rt ra kt lun tng t i vi hydrazine N2H4 - trong phn t ny mi nguyn t nit c mt i in t khng phn chia. Kh nng nng phn cc ca nguyn t nit v lc trng phi t ln ca nhng phi t to lin kt qua nguyn t nit gip ta gi thch tnh bn vng nht ca nhng phc

amin ca nhng ion nhng dy kim loi lin tip hoc l ca nhng ion d y . Bn knh ca ion amoni bng bn knh ca Ion K+ v Rb+ v c 3 ion ny to mui c tan gn nhau. Tnh cht i xng qua ng thng ca ion azit N3- kh gn vi tnh cht ca ion halogen. Ha lp th ca nhng oxyt nit v ca nhng oxyt axit rt l khc nhau. V d nh ion nitrat c cu to phng v i xng. Cu to tng ng vi s to thnh 3 lin kt ca nguyn t nit vi s ng dng nh qu o lai ha sp2 ng thi nhng qu o pz ca nit v ca 3 nguyn t oxy c th lin kt vi nhau to thnh qu o phn t cha 2 in t. bn ca nhng h nh vy lm yu khuynh hng to phc ca ion nitrat vi chc nng phi t mt rng. BC Bc thng trng thi ha tr mt nhng trong nhng phc ngi ta bit Ag(II) v Ag(III). Ag+ c cu hnh in t d10 o xu hng to phc ch yu vi nhng phi t phn cc c bit l trong nhng trng hp m lin kt ngc c to thnh. Chnh v l do m bn ca nhng phc Ag(I) ging bn ca nhng phc Cu(I) gim theo th t I>Br>Cl>F. Cng c th l do s lai ha nhng qu o Ag2+ v S vi s cho in t nh trong trng hp ca Cu(I) nn trong cc phc ca n Ag(I) c s phi tr ch yu l 2 v do cu hnh phc c dng thng hng. Cng v l do nn nhng thuc th to phc vng cng to nhng phc a nhn. Ha lp th khng thun li v nhng lin kt c to thnh nh nhng nhm cacboxy gii thch tnh khng bn ca phc bc vi EDTA. Nh tnh cht ny nn EDTA c dng lm thuc th cn khi xc nh bc. Nh s to phc thng hng trong lin kt c nhiu c tnh cng ha tr nn ngi ta s dng p-dimotyl-, pdiotyl amio bonzylidonro-danin, 2-tio-5-xto-4-cacbtxy-1,3dihydropimidin v focmazyl cacbonic in t mnh ca phi t sau cng nn phc ca n vi Ag(I) c cu hnh t din. iu cng ng i vi phc ca bc vi ditizon l phc b chit khi trong dung dch khng c mt lng ln halogonua bng tetraclorua cacbon t mi tng axit mnh. Phc ca bc vi ditio-3-izoindigo, b chit bng ru butilic. C 2 phc ny u c s dng o mu xc nh bc. Bc cng kt vi tollua, Hg(I) clorua v di dng sunfua cng vi sunfua ng v Hg(II) (ging plladi), Ag(I) to nhng mui khng tan vi cc halogonua, xyanua, v tioxyanat, nhng mui ny tan trong cc dung dch c d cht to phc, to cc phc anion, Ag(I) cn to cc phc cation vi cc monoamine. Nhng phc ca Ag(II) c cu hnh phng vung v ng hnh vi nhng phc ca Cu(II). C th nu cc ion phc [AgPy4-]2+[Ag(biPy)2]2+ v [Ag(o-phen)2]2+ c to thnh khi oxy ha Ag + bng persunfat trong dung dch c phi t tng ng lm v d. Cng trong nhng iu kin nh vy phc ca Ag(III) vi etylendibiguanidin c thnh phn 1:1 c to thnh. BERILII Kch thc khng ln ca Be cho php n nm trong t din to bi 4 phn t nc lin kt vi nhau bng lin kt hydro. Nh vy l ion berilli hydrat ha xut hin tng tc ion lng cc mnh v ion d dng mt i mt hay mt s proton to thnh phc a nhn vi cu oxo(Be-O-Be) hoc l hydroxo (Be-OH-). Hydroxyt borilli kt ta khi thm ammoniac vo (c th dng mui Al3+ v Fe3+ lm cht gp) nhng trong dung dch kim anion berillat c to thnh. V c kch thc nh do t s in tch trn bn knh cao, Be 2+ biu l khuynh hng to lin kt cng ha tr (t nht l lin kt cng c mt phn cng ha tr) cao hn Mg 2+, Sr2+, Ca2+ hoc Ba2+.
2+

S to thnh nhng lin kt nh vy i hi phi ghp i 2 in t 2s to thnh nhng qu o lai ha sp thng v s phi tr 2. Nhng s phi tr 4 vn chim u th hn v t c hoc l do s trng hp nhng cuu M hoc l do s ht in t t nhng phi t cho to thnh, cu trc gn vi cu trc t din. Phc bis ca Be vi axetylaxeton l v d cho loi hp cht th 2 cn halogenua berilli khng ngm nc (BiX2)n (X=F,Cl,Br) l v d cho loi hp cht th nht. i vi berilli, oxy l nguyn t mnh hn nit do phn ln nhng thuc th dng o mu v o hunh quanh xc nh Be l nhng thuc th loi morin, oxyanthraquinon th v aurintricacboxylic axit (aluminon). Cng theo lun im trn, hp cht ni phc ca berilli vi axetyl, axeton bn vng v b chit bng benzene cn khuynh hng to phc ca n vi cuphenron v 8-oxyquinolin th li yu i nhiu. 8-oxy quinolidin to vi berilli phc 2:1 tan trong colorofoc; c th s dng phc ny xc nh Be khi c c Al. xc nh o mu Be, ngi ta ngh mt lot thuc th c nhm O-oxyazo trong c Thoron v P-nitro-benzena zorosocsin. C th nng cao la chn ca cc phng php phn tch bng cch kt ta Be trc di dng hydroxyt hoc l di dng phtphat pH 4,4 (s dng pht pht Fe3+ hoc Al3+ lm cht gp). Cn c vo cc ti liu cng b theo nhy cng nh la chn ca cc phn ng mu, nhng hp cht O,O-dicyazo v nhng hp cht tng t loi berillon II v III l nhng thuc th c trin vng nht xc nh Be bng phng php o mu. BISMUT Bismut to 2 loi mui tng ng vi nhng ion BiO+ v Bi3+. Nhng mui ca bismutyl thng khng tan trong nc cn ion Bi3+ th c khuynh hng to lin kt cng ha tr rt r rt vi nhng phi t phn cc cha lu hunh v nit. i vi nguyn t tr 6s2 lm gim mt cch ng k lin kt i ngc do khuynh hng to phc vi nhng phi t loi ion xyanua biu l yu hn so vi trng hp v d nh ca ion ng vi Ditionzon, Cupheron, dietylditiocacbanmat l nhng thuc th in hnh ca bismuth. Bi b chit bng tetraclorua cacbon di dng hp cht vi dithizon t dung dch xytrat bo ha bng clorofoc di dng hp cht vi cupheron t dung dch axit nitric 1M v bng CCl4 di dng hp cht vi dietylditiocacbamat pH=11-12. Thioure v ion thioxyanat cng to phc mu vi Bi3+ trong mi trng axit. Nhng phi t chnh oxy v d nh xyatrat, tactrat v EDTA lin kt vi bismut yu v do c th s dng lm thuc th cn. Xylen da cam l thuc th o mu xc nh Bi. Hin nay cha nhm to phc metyliminodiaxotat ging nh trng hp ca EDTA, li to phc kh bn vi bismuth (phn ng ra trong dung dch H2SO4 0,15N) Oxyt Bi2O3 v hydroxyt Bi(OH)3 l nhng baz, trong khi nhng dn xut tng ng ca Ag(III) v Sb(III) li lng tnh. Tnh baz ln gy nn khuynh hng to phc anion nh v kh nng b chit bng cc dung mi hu c yu. C 2 hiu ng ny u kh quan trng. BiI 3 b chit bng benzene t dung dch bismut 5M i vi trng hp H2SO4 v 0,01M i vi trng hp ion iodua. Axit HBiI4 c mu t vng n da cam b bin t mi trng axit bng nhng dung mi cha oxy v d nh ru amylic cn mui bruxin ca axit ny th c th b chit bng clorofoc. Do to phc cnh tranh vi clo v flor nn chng cn tr phn ng ny. Trong dung dch HCl bismuth to phc anion b hp ph trn c anionit.

C th kt ta Bi di dng photphat hoc sunfua (trong trng hp ny dng ng hay cadimi sunfua lm cht gp) t dung dch axit v c long. Cng c th kt ta Bi di dng Bi(OH) 3 pH 9 bng amoniac dng Al(OH)3 hay Fe(OH)3 lm cht gp. BOR Nhng hp cht ca bor c to thnh ch yu bng nhng lin kt cng ha tr, v tnh cht v phn ng ca chng tng t vi cc hp cht ca nhng phi kim loi c bit l sillic. Nhng hp cht ca bor vi 3 lin kt cng ha tr bao gm lai ha sp 2 dn ti s to thnh cu to phng. i vi trng hp ca halogenua mt phn c n nh ha bi s lin kt ca nhng qu o p c in t ca halogen vi qu o p cha y in t ca bor. Gi tr ca lin kt gim theo trt t sau BF3 BCl3 > BBr3. S thiu in t trong nhng hp cht BX 3 lm cho n tr thnh cht nhn in t mnh do nguyn t bor c th phi tr nhng cht loi anin, photphin, ete v sunphit vi s to thnh phc 1:1 t din. S phi tr nh vy c trng nht BBr3, km c trng nht BF3 v do c th cho rng trong rng hp ny s khc nhau v lin kt l quan trng hn nhng hiu ng lp th v tnh in. Bor c i lc rt ln i vi oxy, to thnh nhng oxyt Bor, axit boric v nhng borat m do s to thnh nhng cu oxo (B-O-B) c th c cu to vng, hoc a nhn thng. Nhng este ca Bor vi ru t nguyn t cacbon d bay hi nn c th s dng tch Bor khi nhng nguyn t khc. Ngi ta s dng ion tetraphenyl borat xc nh nhng ion kim loi kim theo phng php trng lng. Bor to nhng phc t din bn vi nhng anion-oxy hu c. C th nu nhng phc 1: 2 ca bor vi ion salisilat v pyrocatesin lm v d. S to phc vi nhng phi t cha oxy c ngha ln trong chun v xc nh o mu axit boric v ion borat. Thuc th azometyl II, c s dng xc nh o mu bor da trn s lin kt bn ca bor vi oxy v tnh cht cho in t ca nhng nguyn t nit. Hp cht ni phc mu vng to thnh c cu to nh sau:

BRM Nhn thm mt in t, brm a s in t ngoi ca mnh ti 8 vi s to thnh lin kt cng ha tr hoc ion bromua. Ngay c nhng hp cht ca brm c c tnh ion, nhng lin kt ca n cng c tnh cng ha tr ln hn so vi nhng lin kt tng t ca clo. iu c gii thch l ion Br- ln, d b phn cc. Trong nhng Bromua ca cc kim loi c mc d y hoc hu nh y in t, nhng qu o trng ca brm tng i d dng tham gia vo s to thnh lin kt cho. Nhng i in t ca brm biu l tnh cho rt mnh. Hai c im gii thch xu hng ng vai tr cu ca brm khi to phc a nhn v quyt nh tan nh ca nhiu brmua. iu biu l mc ln nht i vi nhng bromua ca nhng cation mt in tch vi mc d bo ha to phc c s phi tr 2: Cu, Ag, Au, Hg, Tl, BiO v SbO. Nhng bromua ca Pt(II) v Pd(II) cng khng tan. BrO- v BrO3- l nhng anion oxy duy nht quan trng ca brm. BrO- thu c khi ha tan brm trong nc. Ion ny khng bn, nhanh chng phn hy thnh nhng ion bromate v brmua. Nhng cht oxy ha, v d nh ion hypo-clorit, oxy ha bromua n bromate trong mi trng axit yu.

Ngi ta thng xc nh brm bng phng php trng lng di dng bromua bc. tan thp ca mui ny l c s ca nhiu phng php chun . Mt s phng php chun da trn s to thnh HgBr2 khng phn ly v s dng ch th xc nh bc nhy nng ca ion thy ngn hai im cui. Nhng phng php o mu xc nh brm da trn c s phn ng th vi s tham gia ca cc phn t hu c hoc l da trn kh nng oxy ha ca brm. CADIMI Ion Cd kh ging Zn nhng c tnh baz, khuynh hng to ion cadimat ca Cd kh yu. Nhng im khc nhau c bn gia Cd v Zn l d, bn knh ln ca ion Cd 2+ gy nn v cng chnh v l do nn Cd to phc ion km bn hn nhng phc cng ha tr li bn hn so vi Zn. Cu hnh in t ([Kr]4d10) ca Cd2+ quyt nh tnh mm ca ion ny v khuynh hng to phc vi amin, xyamua, sunfit ca n. Cd(OH)2 khng tan trong kim nhng tan trong amoniac c do to phc amin. Nhng anion cha oxy nh xitrat, tactrat lin kt yu vi cadimi. Do khi c mt nhng cht ngi ta c th chit phc to thnh ga Cd v ditizon trong CCl 4 (hoc di--naphtyltiocacbazon trong CHCl3) t mi trng kim. S dng HCl 0,01M c th ti chit cadimi vo tng nc cng c th cht phc cadimi vi dietyldithioncacbamat t cc dung dch kim. Ngi ta cn dng CHCl3 tch phc ca cadimi vi 2 mecaptobenzethiazol t mi trng ammoniac. Cd khng to phc bn vi Cupheron. C l rng trong trng hp ny phc to thnh l do nhng nguyn t oxy. Nhng phc halogenua ca Cd bn hn nhng phc tng ng ca Zn v bn ca chng tng theo trt t F < Cl < Br < I. Nhng halogenua ca Cd tan trong nhng dung mi cha oxy. V d nh phc iodua ca Cd b chit bng dietyl ete t dung dch HI 6,9 M. Trong cc phc ca Cd ngi ta khng quan st thy s n nh ha bi trng tinh th. Nu phi t l anion th nhng phc c cu hnh t din v d nh CdBr42+ cn trong tt c nhng trng hp khc cu hnh thng l bt din. Axit phc to bi cadimi vi ion thioxyanat b chit tt hn phc ca Zn do c th tch Zn khi Cd bng cch dng hn hp ru amylic v dietyl ete chit t dung dch HCl 0,6 M c cha amonitio-xyanat. c tnh cng ha tr ca lin kt gy nh hng kh nng kt ta sunfua Cd, t mi trng axit yu. Trong trng hp cn thit c th s dng sulfua Cu, Hg(II) v Zn l cht gp. CANXI, STRONI, BARI V RADI Tt c nhng cation 2 in tch ny c cu hnh in t ca kh tr. Do tt c nhng tnh cht l ha hc ca chng u bin i theo s tng kch thc. Nhng ion ny khng c kh nng phn cc r rt v khng c cc i hp th trong vng t ngoi v nhn thy. Tnh tan d ca cc mui clorua v nitrat canxi khng ngm nc, trong ru, te, axetn, v trong nhng axit cacbonic khng ngm nc cho php gi nh rng lin kt canxi trong nhng mui ca n c th c c tnh cng ha tr n mt chng mc nht nh. Mc d rng nhng cation nhm ny c u th to phc vi nhng phi t anion cha oxy (v d nh axit rodizonic, murexit, O-cresolphtanloin complexon) vn c th xc nh bng ph trc quan canxi (v magi) nh nhng thuc th cha nhng nhm nit cha bo ha v oxy phenol nh Eriocromden T v 8-oxyquinolin. Khng ph thuc vo loi phi t, trong tt c mi tng hp, nhng phng php o mu u da trn c s chuyn cc i hp th ca phi t di tc dng ca cation. Ngoi phn ng ca canxi vi canxicrome phn ln nhng thuc th u khng c trng v do cn tch cc nguyn t ra khi canxi.
2+ 2+

C th tch canxi bng kt ta di dng oxalate (Mg cng kt ta) phtphat, molybdat hoc l khi hm lng vt th kt ta dng oxinat v dung oxin d lm cht gp. Ngi ta kt ta bari di dng sulfat hay cromat. Kt ta bari cromat c dng lm cht gp cho Ra. C th s dng ct trao i ion tch phn on. Mt khc, c th xc nh ring bit nhng cation trong hn hp bng cch chun complexon min l la chn iu kin cho cn thn. Trong thi gian gn y ngi ta ngh nhng thuc th mi xc nh cc cation nhm ny. Dng ortanilic S [bis-(2-sunfobenzen)-(1,1-bisazo-2,7)-1,8-,aphtalin-3,6-disulnitormazo) c th xc nh Sr v Ba khi c mt Ca, nhng cation ha tr mt, Pb, Fo,Ti, Zn v Ta. bn ca cc phc to thnh bin i theo trt t Ba > Sr > Ca > Mg. Trong trng hp ca Clophosphoazo III th trt t thay i nh sau: Ca > Sr > Ba. Thuc th azoazooxy BN cho php ngi ta tch (v sau xc nh) canxi ra khi mui Sr v Ba. CH Tnh tr kh ln ca nhng in t 6s2 ca ion Pb2+ lm cho trng thi ha tr 2 ca ch trong cc hp cht bn hn rt nhiu so vi trng thi ha tr 4. Do tnh cht nn nhng hp cht loi tetra axtat ch u l nhng cht oxy ha mnh. C th da vo tnh cht ny xc nh gin tip ch bng cch o mu sinh ra khi oxy ha hp cht hu c thch hp(v d nh tetrametyl diamiodiphenylmetan vi nhng hp cht Pb(IV)). Tnh lng tnh ca Pb2-(IV) yu hn rt nhiu so vi Sn(IV) do ion plumbat Pb(OH)6 ch c to thnh trong dung dch kim mnh. Cu hnh in t [Xe] 4f14 5d10 6s2 ca Pb(II) ch r rng ion ny d bin dng ngay c khi nhng in t 6s2 lm gim mc to lin kt i ngc gia kim loi v phi t. Cu hnh in t cho php d on rng Pb(II) cn phi to nhng phc bn vng nht vi nhng phi t phn cc mnh. iu c xc nhn trong thc t. V d nh Pb(II) ch tng tc yu vi Cupheron trong axit nitric 0,01M, khi chit ch di dng ditizonat bng clorofoc hoc tetraclorua cacbon t mi trng kim, cn trong nc c th tn ti nhng anion cha oxy nh xitrat hoc tactrat. S h thp mc lin kt ngc v s vng mt hiu ng n nh ha bi trng phi t trong cc phc ca Pb(II). Ni chung nhng phc ca Pb(II) km bn hn nhng phc ca Cu(II) v ditizonat ca n phn li trong cc dung dch axit v c long. Dietylditiocacbamat ch b chit t dung dch m xitrat c pH = 7 bng hn hp ru amylic-toluen, b phn hy khi lc vi HCl 0.5M Ngoi nitrat v axetat, phn ln mui ca Pb(II) khng tan trong nc do vic tch n khi nhng kim loi khc khng gp kh khn. CLO Lin kt thm mt in t, clo hon thnh lp in t ngoi v c cu hnh in t ca kh tr argon. S nhn thm in t c th t c nh s to thnh anion hoc lin kt cng ha tr nh trong trng hp TiCl4. Nhng in t 3s v 3p c th tham gia vo s to lin kt cho vi nhng cht thiu in t, ngoi ra cn c th to nhng lin kt cho nh nhng qu o 5d trng ca clo. Do ion clorua d to phc clorua vi nhiu ion kim loi. iu cng c th dn ti s to thnh cu clo trong cc phc v phc a nhn hnh thnh c bit l trong trng hp ca nhng kim loi c cc qu o d y hoc gn y . Nhng tnh cht ca Clo tng t tnh cht ca brm nhng yu hn. Do nhng clorua ca nhng ion mt in tch nh Ag, Cu, Hg, BiO v SbO tan khng tt nh bromua.

Cng c th ch rng trong cc anion cha oxy nh ClO -, ClO2-, ClO3- v ClO4-, lin kt c thc hin nh s chuyn in t t clo n oxy ng thi vi lin kt ngc ca nhng in t p ca oxy vi nhng qu o d trong clo. Ion peclorat c khuynh hng to phc rt yu vi cc cation. COBAN Coban to hai loi mui v phc cht tng ng vi Co(II) v Co(III). Co(II) l trng thi bn trong cc mui cn Co(III) th ch yu tn ti trong cc phc bt din spin thp c bit l trong cc phc c nit tham gia vi chc nng ca nguyn t cho (theo nhng iu kin tnh in nhng phi t anion cng to nhng lin kt bn vi Co3+). V d nh phc 1:3 ca Co(III) vi 2-nitrozo-1-naphtol rt bn v khi to thnh cc lin kt kim loi- phi t c s tham gia ca ch nng nhm to mui. Do hiu ng n nh ha kh ln ca cu hnh in t d6 spin thp nn nhng phi t to trng mnh thng c u th to phc vi Co(III). Cng v l do nn nhng phc ca Co(II) trong trng hp ny d dng b oxy ha n phc ca Co(III). Cu hnh d6 spin thp gy nn tnh tr ng hc ca phc. V d nh phc 1:3 ca 2-nitrozo-1naphtol sau khi c to thnh trong dung dch axit yu chit c bng dung mi hu c nh clorofoc rt kha phn ly ngay c khi lc vi HCl c. Trong nhng iu kin , phn ln cc kim loi chuyn t tng hu c vo tng nc. Dietyl-ditiocacbamat, mono-oxim, di-1-naphtylxeton, to phc 1:3 d b chit bng cc dung mi hu c vi coban. Dimetylglyoxim, ,, tripyridin v mt s nhng dn xut nitrozophenol cha nhm:

Trong mui nitrozo R to phc tan trong nc vi coban Nhng thuc th ny u l nhng ligan phn cc v c x dng xc nh Co(III). Nhng hp cht ca Co(III) c th c cu hnh vung phng, t din hoc bt din. Nhng ion CoX42- v [CoX3(H20)] trong X= Cl, Br, I, SCN l nhng phc cht t din. Phc (NH4)2 [Co(SCN)4] nu xanh b chit bng nhng dung mi cha oxy t nhng dung dch amoni tioxyanat kh c c dung dch m khong pH = 3,5. nhng iu kin nh vy coban c tch khi niken khi c mt nhng cation ln loi tetra-phenylasonium v triphenylmetyl-asonium c th chit ion phc tioxyanat coban bng clorofoc. Phc clorua l anion ca coban sinh ra trong HCl b hp ph trn ct anionit. C th li dng tnh cht ny tch n khi mt s ion khc. CROM Crm c th tn ti trng thi s oxy ha II,III, VI nn d dng tch n khi cc nguyn t cn. V d nh: oxy ha bng H2O2 hoc brm, Cr(III) n Cr(VI) trong dung dch natri hydroxyt v sau lc th c th tch nhiu kim loi khi crm. Vic tch tip theo (v d dung dch Natri hydroxyt v natri cacbonat d to Cr(OH)3 khng tan. Nu nh crm tn ti lng khng ng k th c th kt n vi hydroxyt st ba. CrO3, CrO42- (u l nhng cht oxy ha mnh) v CrO 2Cl2 bay hi u l nhng hp cht ca Cr(VI). xc nh trc tip crm ngi ta s dng tnh hp th ca CrO 42- trong dung dch kim 366nm. Phn ng gia Cr(VI) v Cis-diphenylcacbazit trong mi trng axit l phn ng nhy nht xc nh crm nhng bn cht ca cation mu tm to thnh b chit bng cc dung mi hu c cn

cha c nghin cu. C th l cation ny l hp cht ca Cr(III) vi diphenylcacbazon. Hin nay iu ny c xc nhn. Ngoi nhng hp cht ca Cr(VI) c cu hnh t din, phn ln nhng phc ca crm c cu to bt din v trong trng hp ca Cr(II) cu hnh b bin dng do hiu ng Jahn-Teller. Nhng hp cht ca Cr(II) (d4) thu c khi kh nhng hp cht ca Cr(III) (bng Zn). Nhng hp cht ny d b oxy ha n Cr(III) v d nh bng oxy ca khng kh. S n nh ha bi trng phi t to iu kin thun li cho s to phc vi nhng phi t nh , dipyridin, etylendiami, ion tioxyanat v xyanua. Nhng phc ca Cr(III) rt nhiu v c tnh tr ha hc c bit (nhng h d) v do c th iu ch nhng hp cht ring bit loi [Cr(H 2O)6)]Br v [Cr(H2O)4Br2]Br. Oxyt ngm nc ca Cr(III) lng tnh to thnh Cr(H2O)63+ trong mi trng axit cn trong mi trng kim to thnh ion Cr(H2O)63-. NG ng to 2 loi mui v phc, nhng phc ca Cu(I) thng c (ty thuc vo bn cht ca phi t) cu to thng hng hoc t din cn nhng phc ca Cu(II) thng c cu hnh phng vung, hoc bt din bin dng do hiu ng Jahn - Tellerr. Cn bng oxy ha kh trong nhng dung dch mui ca Cu(I) v Cu(II) tr thnh phc tp do s oxy ha kh d dng ca Cu(I) thnh Cu(0) v Cu(II), do nhng phc ca Cu(I) thng ch c to thnh trong trng hp khi chng khng tan (v d nh CuCN v CuI) hoc l nu lin kt kim loi phi t c c tnh ch yu l cng ha tr v nhng yu t khng gian thun li. V c in tch thp v cu hnh in t 3d 10 nn Cu(I) to nhng phc bn vng nht vi nhng phi t phn cc mnh v c bit l trong trng hp khi m lin kt i ngc c th thc hin. C th nu nhng dn xut ca ,-dipyridin v 1, 10-phonantrolin lm v d. Trng thi thng thng ca Cu l ha tr 2 v Cu(II) to nhiu phc bn vng. Cu hnh d 9 lm cho ion Cu2+ d b bin dng v nh n to lin kt bn vi nhng anion cha lu hunh nh dietylditiocacbamat, etyl-xantogenat, ditizon to nhng phc tan trong dung mi hu c. bn ca nhng phc kim loi chuyn tip phn b theo trt t sau Mn < Fe < Co < Ni < Cu > Zn. S khc nhau ln nht v tnh cht ca cc nguyn t c quan st thy khi s dng nhng phi t phn cc ln. iu to iu kin thun li cho s tch Cu khi cc nguyn t khc ca dy ny. C th chit Cu bng ditionzon trong CCl4 t nhng dung dch axit v c 0, 1-1N trong khi th phn ln nhng kim loi khc trong nhng iu kin nh vy lin kt kh yu vi thuc th, Cu(II) cng to phc vi nhng phi t cha oxy c bit l trong dung dch kim v nhng phc ny thng l a nhn. Dung dch Feling l mt v d v loi tng tch ny. Khuynh hng to lin kt cng ha tr ca Cu(II) c minh ha bng s to kt ca ng sunfua khng tan khi cho H2S qua dung dch Cu(II) trong axit long (Ngi ta s dng phn ng tch Cu v trong trng hp cn thit c th dng PbS lm cht gp). Trong HCl v HBr nng cao, Cu(II) to nhng phc mu clorua v bromua. Khi c mt nhng baz hu c hoc nhng cation hu c nng, Cu(II) to nhng phc thioxyxyanat v b chit. FLO

Lin kt F-F trong phn t flo yu hn rt nhiu so vi nhng lin kt tng t trong nhng phn t ca nhng halogen khc bi v di lin kt ngn do lc y gia nhng in t khng lin kt ln. S y trong trng hp ca nhng halogen khc c gim i mt phn nh s s dng nhng qi o d trng bn ngoi. Flo l nguyn t m in nht v c kh nng phn ng nht trong s cc nguyn t. Ha phn tch ca nguyn t ny hu nh hon ton gn lin vi ion florua v vi hidro florua. V ion florua nh hn cc ion halogen khc nn, nhng florua c c tnh ion ln nht. Do lin kt vi nhng cation ca nhng phn nhm chnh ca nhm I v II yu dn theo th t F- > Cl- > Br- > I- cn i vi nhng cation phn cc mnh (v d nh Zn 2+, Cd2+ v Hg2+) thi th t trn li ngc li. Xt v chc nng ca cht cho in t th florua thua km nhiu so vi nhng phi t cha oxy v cha nit. Ngi ta cn cha bit r lin kt trong ion biflorua [FHF]- c phi l lin kt hydro hay khng. Cng c th gii thch lin kt xut pht t gi thuyt v s tng tc tnh in mnh hoc l bng s to lin kt 3 trung tm nh 2 qu o ca flo v qu o 1s ca hydro trong 2 in t trn qu o lin kt v 2 in t trn qu o khng lin kt. C s ca hu nh tt c nhng phng php o mu, o hunh quang, o in th, o th tch xc nh florua l s to phc florua bn hoc khng tan lm phn ly nhng phc kim loi, vi nhng thuc th v c v hu c c mu. Tnh bay hoi ca hp cht H 2SF6 c ngha ln i vi vic tch ion florua khi nhng cht cn tr. GALI Theo tnh cht ha hc ca mnh, ion Ga khc bit vi Al3+ ch yu bi kch thc ln v iu quan trng hn l n c 1 in t ngoi chim cc qu o 3d. Ging nh Al(III), Ga(III) lng tnh, trong mi trng kim to nhng phc anion hydroxo cn trong nhng dung dch trung ha hoc axit yu mui ca n thy phn mnh gali ch yu to phc bt din nhng ngi ta cng bit mt s phc t din v d nh GaCl4- v nhng sn phm cng hp gia Ga+3 vi nhng phi t cho in t trung ha in. Axit t do HGaCl4 b chit t dung dch HCl 6M bng dietyl hoc diisoproyl ete. Cng trong nhng iu kin nh vy HGaCl4 to ion i c mu v pht hunh quang vi rodamin B, b chit bng hn hp clobenzen v tetraclorua cacbon theo t l 3:1 v th tch. Phc thioxyanat ca Ga b chit bng dietyl ete t dung dch Ga cha amoni thioxyanat 7M v HCl 0,5M. Do in tch cao, Ga3+ to nhng phc bn vng nht vi nhng phi t anion c bit l nhng phi t cha oxy. l nhng phc 1:3 vi Cuphenon, quializarin v phc vi aluminon. Nhng phi t anion to phc vng cng do lin kt trc tip vi ion Ga3+ v lin kt qua nguyn t nit trung ha in. V d nh anion 8-oxiquinolin to vi Ga phc 1:3 pht hunh quang vng b chit bng clorofooc. C th lm giu lng vt Ga trong dung dch bng cch kt ta cng vi hydroxyt nhm. GECMANI Dioxyt gecmani c tnh axit yu v tnh baz ca n yu hn. Ngi ta bit nhng meta v octo gecmanat tng t nh nhng silicat tng ng, cn trong dung dch kh m c; hp cht cng ha tr GeCl4 c to thnh. C th ct gecmani clorua (si 860C) t dung dch 6M hay t hn hp H2SO4 v HCl hoc l c th chit n t tetraclorua cacbon hay bng nhng dung mi khng phn cc t dung dch HCl 8 -9 M. Ge4+ thy phn nhanh trong nc. Trong dung dch ammoniac hoc kim yu gecmani cng kt nh lng cng vi hydroxyt st ba v nhm.
3+

Ging nh Sn(IV) v Zn, Ge to phc mu t tan vi cc phi t cha oxy v d nh vi quinalinzarin; 2,3,7, trioxy-phenyl-6-flouron v cht tng t 9-(4-dimetylsminphenyl). Tt c nhng thuc th ny l o-diphenol. Phn ng vi hp cht 9-(4-dimetylsminphenyl) thc hin trong HCl 1M, l phc bt din c t l 1:2, dng phc to thnh Ge(OH) 2L2 phc ny d chit bng tetraclorua cacbon. HAFNI Hafni v Ziriconi c bn knh ion v nguyn t hu nh ng nht. Chng rt gn nhau v tnh cht ha hc v ging in t. Trng hp nhng ion ha tr 4 nhng cu hnh in t c dng sau: i vi Zr l[Kr] 4f14 v i vi Hf l [Xe] 4f14. Trong ion Hf nhng in t 4f nm qu su gy nh hng r rt n tnh cht ha hc. Nhng phng php ha hc xc nh Zr cng c dng xc nh Hf ch tr mt ngoi l l trong dung dch HCl kh c Zr v Hf to vi axit rufigalic nhng hp cht c mu khc nhau. C th l hin tng mt phn gy nn bi tnh baz ca Hf. Mt cch l thuyt, ngi ta c th nghin cu nhng phng php tch phn tch Hf v Zr da trn nhng bin php nh kt tinh phn on, kt ta phn on, ct, trao i ion hoc chit bng nhng dung mi hu c. Trong nhng nm gn y nhng phng php vt l nh phn tch quan ph, pht x, h quang v tia in hoc l phn tch quanq ph rnghen dng nh chim u th. INI In(III) khc vi Ga(III) v Al(III) ch l oxyt v hydroxyt ca n, khng lng tnh. Nhng tng t nh Ga v Al mui ca n thy phn mnh trong dung dch v ging nh Ga, In to phc vi cc halogen, iu kin chit In cng khc. V d nh Ga b chit (nhng In khng b chit) bng dietyl ete t dung dch HCl 6M cn khi lc dietyl ete mt s ln vi dung dch HBr 3M th In b chit (ch yu di dng HInBr4) nhng Ga khng b chit. Mt cch tng t, t dung dch HI (hoc l KI v H2SO4) 0,5-2M c th chit phc iodua ca In v hp ph In trn anionit di dng phc clorua t dung dch HCl 4-5M v gii hp bng HCl 0,1M. C th cho rng ion i c to thnh gia nhng phc anion vi nhng cation hu c loi rodamin B v c s dng xc nh In. Nhng kh nng ny cn cha c nghin cu. In (III) to phc bt din c bit l i vi nhng phi t anion. Nh cu hnh in t 4d 10 ca In c khuynh hng to lin kt cng ha tr n mt chng mc nht nh. Trong mi trng axit yu Indi to sunfua khng tan, pH 3,2-4,5 n to vi 8-oxyquinolin phc c t l 1:3 to mu vng v b chit bng clorofoc. Ngoi ra ngi ta c th chit In t mi trng kim yu bng dung dch ditizon trong clorofooc. Tng t nh phc ca Ga, phc ca In vi 8-oxy quinolin cng pht hunh quang Indi to phc nhng rt khng bn vi nhng phi t anion cha oxy nh xitrat, tactrat. IOD Do in tch nh, kch thc ln nn ion I d b phn cc v do n d dng to lin kt cng ha tr. Nu lin kt kim loi, halogenua v c bn l cng ha tr th bn ca phc tun theo trt t: I > Br > Cl > F cn trong nhng phc m lin kt c c tnh ion l ch yu th trt t v bn s theo chiu ngc li. Trong dung dch kim iod nhanh chng t oxy ha t kh (ion IO- khng bn) thnh iodat v iodun. Iod cng to axit iodic v nhng perclorat l nhng cht oxy ha mnh. Peiodat l dn xut ca axit H5IO6 c nhiu tnh cht chung vi tellurat sinh ra t H6TeO6. IRIDI
-

Mc d rng Ir to phc florua tng ng vi trng thi ha tr cao, ha hc ca nguyn t ny vn ch yu lin quan vi trng thi ha tr III v IV ca n m nhng phc bt din l i din. Trong nhng phc cation trung ha v anion ca Ir(III) ging Rh(III) nhng trng thi ha tr cn t c ng dng trong phn tch. Ir(IV) ly IrO2(H20)x lm i din, l kt ta thu c khi trung ha nhng dung dch axit cha bromate (cht oxy ha) v IrX62- (X: F,Cl,Br) bng bicacbonat natri. Mc d rng Ir(IV) l h d nhng phc ca n l phc spin thp v ging nh nhng phc trung ha v cation ca Ir(III), chng l nhng cht tr ng hc. Trng thi spin thp bo m cho nhng phc bt din ca In vi nhng amin c c s n nh ng k trong trng phi t. C th x dng tnh cht cc phc ca Ir(IV) b hp th trn amionit tch n khi nhng kim loi khc. C th chit cloroiridat ca tetraphenyl photphonic mu hung bng clorofoc t dung dch HCl long. Ngi ta cn xc nh gin tip Ir nh kh nng oxy ha ca n i vi nhng hp cht hu c thch hp nh p-nitrozodimetylanilin, o-anizidin, benzindin, baz leuco ca tm tinh th v baz leuco ca luc malachite to thnh sn phm mu. ITTRI V tnh cht ho hc, itrri ging scandi v cc lantanit. Ittri c cu hnh in t ca Kr v theo gi tr bn knh th n trong dy lantanit. Tng t nh nhng lantanit, itri to nhng phc bn vng nht vi nhng phi t cha oxy. C th tch ittri khi scandi bng cch chit scandi di dng phc vi thioxyanat bng dietyl ete. Ngy nay, ngi ta s dng nhng phc mu ca ittri vi nhng thuc th hu c nh quinallzanin, alizarin S, pyrocatechin tm xc nh n bng phng php ph trc quang. C th s dng nha cationit v gii hp bng nhng phi t anion nh triclotraxetat tch cc nguyn t cn tr khi ittri. KM Trong cc mui v phc ch mt mnh km tn ti trng thi ho tr 2. Ion Zn 2+ c cu hnh in t [AI] 3d10: Nh c im ca nhng qu o d nn Zn2+ d bin dng v c kh nng to nhng phc cng ho tr bn vi nhng phi t phn cc v d nh amoniac, amin v xyanua. Khi to cc phc km c cc mc d hon thnh) do nhng phi t c th to lin kt xui ngc. c im cng ho tr kh ln ca nhng lin kt trong cc halogennua km biu hin ch l chng tan c trong ru, axton v nhng dung mi tng t. Trong cc dung dch clorua km to nhng phc anion do c th tch n khi nhng nhng kim loi khc nh nha anionia. Nh s to thnh nhng ion i nn dung dch metyl dioxylamin trong triclor etylen chit c phc clorua km t HCl 2M. Thioxyanat km chit nh lng bng dietyl ete t dug dich amonithioxynat 1-5M v HCl 0,5M. nng thp ca thioxyanat th Zn(SCN)2 b chit cn nng cao th (NH4)2Zn(SCN)4 b chit. Khi xc nh ph quang k km s dng ion i to thnh gia nhng phc anion thioxyanat ca km vi mt baz hu c nh metyl xanh, pyridin v rodamin B chit bng nhng dung mi khng trn ln. Hydroxyt km lng tnh v tan trong cc dung dch kim to thnh ion zincat [Zn(OH) 3(H2O)3]- hoc l [Zn(OH)3H2O]-. Hiu ng n nh ho bi trng phi t khng xut hin trong cc phc nh vy ch ph thuc vo kch thc v vo trong nhng hp phn tnh in v cng ho tr ca lin kt. Nhng phc ca km c th l t in trong trng hp [Zn(OH)4]- hoc l bt in trong trng hp [Zn(NH3)6]2+.

Km to nhng phc kh yu vi nhng phi t loi xitrat, tactrat cha cc nguyn t oxy lm chc nng nguyn t lin kt. Hu nh khng c ngoi l no i vi tt c nhng thuc th hu c tt ca km iu lin kt vi kim loi nh nguyn t lu hunh hoc nit (hoc ng thi c 2 nguyn t ny). V d nh nhng thuc th quan trng nht hin nay l ditizon v dinaphtyl di thtiocacbazon c s dng chit km v xc nh ph quang k n u to cc hp cht nhng ni phc nh lu hunh v nit. Nhng ngay c nhng phc ny cng phn li v b ti chit t clorofoc, tetraclorua cacbon khi lc vi cc dung dch axit long trong nc. S to thnh phc vi zineon bao gm s cng hp vo kim loi 2 nguyn t nit v 2 nguyn t oxy anion dn ti s xut hin phc 4 rng. Trong cc phc ca km vi 8-oxyquinolin v indoxin lin kt cho vi nguyn t nit d vng c to thnh. iu t c kh nng xy ra i vi phcca km vi 1-anino-2naptol-4sunfoaxit. Km cng to nhng phc b chit vi natri dietyldithiocacbamat v vi dietylamoni dietyldithiocacbamat. LAMTAN V NGUYN T T HIM Ion La3+ c cu hnh in t ca kh tr Xe. Nhng khc bit nhau mt cch ng k ca nhng ion lantanit 3 in tch t Ce n Lu l do s tng lin tc (n 14) ca nhng in t 4f. Nhng in t ny nhng nm kh su trong cation nn trong s to nhng lin kt ho hc chng c ngha khng ln. Nhng s tng in tch ht nhn t La n Lu dn ti s gim bn knh nguyn t v ion. Bn knh ion gim t 1.5 n 0.8A. V nhng lin kt c u th ion nn khi bn knh gim i t La n Lu thi hng s bn ca phc cc lantanit tng dn. V cng do nguyn nhn y tnh baz ca nhng hydroxyt Me(OH)3 gim t La n Lu. Nhng Lantanit to nhng mui c trng vi cc axit. Trong cc mui nhng oxalat t tan c d axit oxalic nhng mui florua rt t tan khi c HF. S to phc biu l mnh nht trong trng hp phi t l anion cha oxy nh xitrat, tactrat v trong EDTA v NTA. Kch thc ca nhng ion hydrat ho tng t La3+ n Lu3+ (so vi t Os+ n Li+) do chng lin kt vi nhng nha trao i ion yu dn theo trt t . Tnh cht ny c s dng tch cc nguyn t t him da trn s hp ph chng trn ct catonit gii hp cn thn bng nhng cht to phc thch hp v d nh dung dch m xitrat. i khi ngi ta s dng s khc nhau v kh nng chit phc tch cc nguyn t ny: ch ti s khc nhau v tan ca mui sunfat kp vi natri sunfat ngi ta c th chia nhng nguyn t t him ra thnh 2 nhm chnh: Mui ca nhm La-Eu t tan trong natri sunfat cn mui ca nhm Gd-Lu v Y li tan ng k. Nhng thuc th o mu xc nh nhng nguyn t t him thng l nhng anion lin kt vi kim loi nh nhng nguyn t oxy. Nhng thuc th ny l alizarin S, quinalizarin, sunfosaxilic axit, xylen da cam, pyrocatechin tm v brom pyrogallon . Ngi ta cn ngh mt s thuc th m tc dng to phc da trn lin kt kim loi bng nhng nguyn t nit v bng nhng anion oxy mc d rng v nguyn tc nhng thuc th loi ny km thun li hn. C th k asenazo I, PAN l nhng thuc th to vi nhng nguyn t t him kt ta b chit bng dietylete. Ngi ta cn s dng n vo mc ch o mu. C th chit nhng phc to thnh clorofoc. Nhng nguyn t trong nhm ny thng trng thi ho tr 3 nhng trong 1 s trng hp nhng ion ho tr 1 hoc 2 c th c to thnh c bit l khi trng thi d to cu hnh in t f0, f7 hoc f14 cu hnh f7 to phc h c thm bn ph do 7 qu o f ch cha trn mi qu o 1 in t.

Trng thi ho tr 4 ch quan trng trong trng hp ca Ce(IV) (f0). Tnh cht ho hc ca n ging Hf(IV) va Zr(IV). tch Ce khi nhng lantanit ho tr 3 ngi ta oxy ho Ce(III) n Ce(IV) bng pesunfat hoc l natri bromat trong HNO3 9M hoc l bng nhng cht oxy ho mnh khc sau kt ta photphat, hydroxyt hoc iodat. S dng cc i hp th 320nm, c th xc nh Ce(IV) bng phng php ph quang trc. S dng tc dng ca oxy ho ca nhng dung dch axit ca Ce(IV) i vi nhng cht hu c nh axit anthranilic, benzidin, bruxin, mocfin, axit sunfanilic ngi ta c th xc nh o mu gin tip Ce(IV). Ce(IV) to nhng hp cht c c tnh cng ho tr hn so vi nhng ion ho tr 3 do mui ca n rt d b chit bng cc dung mi hu c nh dietyl ete hoc metylizo-butylxeton chit c H2Ce(NO3)6 t HNO3 8M. Phc ca Ce(IV) vi tenoil trifloaxeton b chit bng xylen t dung dch H2SO4 1N. Trong s nhng ion ho tr 2 th Eu(II) (f7) c gi tr ln nht, c th iu ch Eu(II) bng cch kh dung dch Eu(III) bng in hoc cc kim loi Al, Mg, Fe hoc Zn. Theo tnh cht ho hc Eu 2+ ging Ba2+ v khc vi nhng latanit khc ch l n c kh nng to hydroxyt tan v photphat, sunfat khng tan. LITI Kch thc nh v cu hnh in t loi kh tr ca Li + to nn nhng tnh cht ho hc quan trng nht ca ion ny. Do kch thc nh nn Li+ c kh nng phn cc ln so vi bt k ion kim loi kim no khc v khuynh hng solvat ho to nhng lin kt cng ho tr ca n cng tng ln r rt. Chnh v vy m liti clorua tan trong cc dung mi hu c loi etanol hoc dietyl ete. Trong cc dung dch kim Li+ to vi dipivaloimetan hp cht ni phc b chit bng ete, axit uramyl-diaxetic cng to phc vng cng kh bn vi Li+ nhng c 2 thuc th ny ch c ng dng hn ch trong phn tch. Trong dung dch kim mnh cha 70% axeton, Li + to phc mu vng vi Toron1-(2acsonophenylaze)-2-naphtol-3,6-disunfo axit. Phn ng c nhy cao nhng la chn rt thp do cn phi tch khi phn ln cc cation khc. Mt trong cc bin php tch l s dng nha cationit. Trt t hp ph trn nha ca cc ion kim loi kim hydrat ho l nh sau Li+ < Na+ < K+ < Rb+ < Cs+. S d c trt t l v Li+ l cation c kh nng hydrat ho mnh nht v theo chiu tng ca s th t nguyn t mc hydrat ho kim loi yu dn. Ngi ta cho rng t c kh nng tm c nhng thuc th hu c nhy v la chn c th xc nh trc tip vt Li. Phng php tt nht xc nh Li+ hin nay l phng php quang ph o mu ngon la v cc phng php gin tip. Gn y ngi ta mi cng b cng trnh xc nh Li + bng phng php o mu nh thuc th quinolin-azo. Thuc th ny vt tn c v nhy ( = 12.840) ln la chn. LU HUNH Nhn thm 2 in t, lu hunh c cu hnh in t ca kh tr Ar nhng anion 2 in tch to thnh ln n mc (bn knh bng 1.84A) l n rt d b cc cation lm phn cc v to lin kt cng ho tr c bit l khi cc cation ny li d bin dng. So snh ion O 2- vi S2- ta nhn thy rng bn knh nh ca ion u tin to iu kin thun li cho lin kt vi cc cation cng nh Na + v Mg2+ v Al3+ mang tnh cht mnh hn cn tnh cht cho in t ca S2- th li ln hn. Do oxy to vi kim loi nhng lin kt c tnh cng ho tr ln hn. iu cng ng i vi oxy v luu hunh

trong cc hp cht trung ho in v d nh cc ete v thioete. Trong nhng iu kin thun li nhng qu do 3d trng ca luu hunh c nng lng thp c th to lin kt ngc nh s chuyn ln nhng qu o y nhng in t ca nhng nguyn t kim loi c mc d hon thnh hoc gn nh hon thnh. Nhng lin kt kp cng c th l kt qu ca tng tc d-p gia oxy v lu hunh nh trong trng hp SO42-. Vic s dng nhng qu o d gii thch nguyn nhn ca vic lu hunh c th to 6 lin kt phi tr nh trong FS6 . Nhng s phi tr khng phi l bnh thng i vi lu hunh bi v nng lng cn thit lu hunh t trng thi c bn [Ne] 3s23p4 sang trng thi [Ne] 3s13p33d2 thng rt ln v nng lng to thnh 6 lin kt phi tr khng b tr. Kh nng kh cc ion lu hunh c gii thch bng tnh d cng hp thm mt nguyn t oxy qua lu hunh hon thnh s phn b in ca 8 in t 3s v 3p (nhng in t phn b tng i mt). Vic thay th nhng nguyn t oxy trong cu hnh phi tr nh vy s thu c ion S 2O32(tng t nh SO42- nhng km bn hn) v nhng ion khc cha 2 hoc 1 s nguyn t l hunh ln hn. Nhng anion ln loi SO42- c kh nng to phc tng i yu vi nhng ion kim loi nhng nh s c mt ca nguyn t lu hunh khng trung tm tnh cht li biu l 1 cch r rng trong nhng anion loi S2O32- khi tng tc vi nhng cation nh Cu2+. Lu hunh to lin kt hydro kh yu, do tan trong nc ca nhng phi t cha lu hunh v d nh kh sunfat thnh sunfit, oxy ho sunfit n lu hunh hoc sunit n sunfat. Do c th s dng phng php xc nh sunfit c hiu qu cao xc nh sunfat. C th s dng tinh oxy ho ca lu hunh lm c s cho nhng phng php nh tnh c xc nh nguyn t ny. MAGGIE Bn knh ion nh v in tch dng hai ca Mg2+ to cho n khuynh hng to lin kt cng ho tr kh mnh nhng yu hn so vi Ba2+. MgBr2, MgI2, vaf Mg(ClO4)2 tan trong ru, xeton, ete. Nhng alkyl magie v nhng hp cht Grignard to phc vi nhng phn t cha oxy ng vai tr cht cho Mg2+ v Ca2+ mc yu hn, u to phc kh bn vi nc v thng kt tinh di dng hydro kh bn. Magie to vi nhng phi t anion cha oxy nhng phc bn vng nht nhng kh nng to phc ca n khng ln lm. Do nhiu ion kim loi cn tr s xc nh Mg. Li dng s khc nhau v hng s bn ca phc vi nhng thuc th khng la chn nh dietyldithiocacbamat, 8oxyquinolin, cupheron v axetylaxeton, ngi ta c th tch cc nguyn t cn tr ra khi Mg bng cch chit hoc kt ta. Khi c mt cc nguyn t cn tr, c th xc nh Mg nng thp bng cch o ph quang k phc ca n vi 8-oxyquinolin 400nm. Ion i to bi butylamin v phc 1:3 ca Mg vi 8-oxyquinolin pH= 10.5-13.6 b chit bng clorofoc. Khi butylxellosol chim cc v tr phi tr cn li ca phc bt in ca Mg pH=10-12 th ngi ta c th chit phc 1:2 ca n vi 8-oxyquinolin. Khuynh hng to lin kt cng ho tr ca Mg gii thch v sao trong cc dung dch kim mnh (pH > 12) Mg2+ (hoc l 1 cch chnh xc hn l Mg(OH) 2 b hp ph trn mt s cht mu cha nhm azo to thnh sn mu). Vng titan, vng briliant, 4-(P-nitrophonylazo),-resocsin v 4-(Pnitrophonylazo)-1-naphal thuc loi nhng cht mu trn. S to sn vi quinaliazarin, cupheron, eriocrom xiamin R cng tng t nh nhng lin kt c thc hin nh nguyn t oxy ca Mg vi eriocrom den T.

 nng tng i cao ngi ta c th xc nh Mg2+ mt cch thun li bng cch chun complxon. MANGAN Trng thi II, III, VII l nhng trng thi ho tr c bn ca mangan. Mn 2+ c cu hnh in t d5 v do c tnh i xng cu nn phc ca n khng c n nh ho bi trng phi t. Mn 2+ c nhiu tnh cht chung vi Mg2+. S phn tch trn y dn ti kt lun l Mn(II) ch yu to nhng lin kt ion v do n c khuynh hng to phc yu vi nhng phi t trung ho. Ngay c hng s bn ca phc Mn2+ vi nhng anion cha oxy cng rt nh. Axit v c 0.1N cng ngn cn c s to thnh v s chit phc ca Mn2+ vi 8-oxyquinolin i hi pH=9. Ngi ta bit mt s khng nhiu phc spin thp ca Mn2+ l Mn(CN)64-, [Mn(CN)5NO]3- v Mn(CNR)62+ (RNC l izonitril). Mn2+ to nhng ion t in loi MnCl42- nhng phn ln nhng phc ca n c cu hnh bt in. Mn(II) l trng thi bn vng nht ca mangan trong nhng dung dch axit hoc trung ho. Ngi ta bit nhng hp cht ca Mn(III) nhng phn ln nhng hp cht ny khng bn vng trong cc dung dch nc. S n nh ho bi trng phi t ch c ngha quan trng trong nhng phc spin thp. Phc Mn(CN)63- d c to thnh khi oxy ho phc ca Mn(II) bng oxy ca khng kh ch l trng hp duy nht ta bit. bn ca phc ca Mn(III) du yu nhng c xc nh bi yu t tnh in ngha l lc ht gia cation ho tr 3 v anion phi t. Nhng phc ca Mn(III) bit l florua hydrat ho, phc 1:3 vi axetylaxeton v phc mu hung Mn(CH 2NO)3, focmaldioxim. Ngoi ra phc 1:3 ca Mn(III) vi dietyldithiocacbamat phn li d dng v b chit bng clorofoc t nhng dung dch axit yu. Thng thng ngi ta kt ta Mn (nu vic kt ta l cn thit) t cc dung dch kim yu di dng MnO(H2O)x, dng st hoc magie lm cht gp ri sau oxy ho n Mn(VII). C th tch mangan bng cch ct axit manganic. Ngi ta iu ch pemanganat bng cch oxy ho nhng hp cht ca mangan bng peiodat trong HNO3 hoc H2SO4 nng hoc l bng ion persulfat trong hn hp H3PO4 v HNO3 si c cha vt bc. Sau c th xc nh trc tip pemanganat bng cch o quang k hoc l xc nh gin tip vi nhy cao hn theo phn ng oxy ho cc cht loi benzydin bazoleuco ca lc malasit, o-toludin hoc l 4,4-tetrametyl diaminotriphenylmetan to thnh cc sn phm mu. MOLYBDEN Molybden tn ti nhiu trng thi ho tr v nhng hp cht ca n c nhng cu hnh lp th rt khc nhau. Nhng trng thi ho tr quan trng nht ca molybden l III, IV, V v VI. Trioxyt MoO3 tan trong kim to thnh MoO42-. Khc CrO42- , MoO42- biu l tnh oxy ho rt yu. Khi axit ho v yn dung dch molybdat axit molibdic MoO 3.2H2O kt ta. Nhng nhng dung dch km axit hn b trng hp ho to thnh izopolybdat loi ion paramolybdat Mo7O24. Khi axit ho nhng dung dch molybdat c cha nhng anion nh PO 43-, SiO44- v nhng cation tng t ca As(V), Ge(IV), Ti(IV), Zr(IV), Ce(IV), Th(IV), Pt(IV), Mn(IV), Te(IV), I(VII), Co(III), Al(III), Cr(III), Fc(III), Rh(III), Ni(II) th nhng d a molybdat d b chit bng nhng dung mi hu c c to thnh. Nhng axit d a tan trong nc nhng mui ca n vi nhng cation hu c ln khng tan. Trong nhng anion d a mi nguyn t Mo l mt trung tm ca bt in gm 6

nguyn t oxy. Nhng nguyn t ny li lin kt vi nhau to t in hoc l nhng cu hnh khc c d nguyn t. Trong tc dung dch HCl nng cao, Mo(IV) to nhng phc clorua v d nh MoO 2Cl2 l phc b chit bng nhng dung mi hu c cha oxy v sau b chit li bng nc. axit ti thch chit bng etyl ete l HCl 6M, chit bng tributylphotphat l HCl 1-2M. Nhng phc bromua tng ng ch b chit mt phn bng dietyl ete t dung dch HBr 6M. Trong cc axit v c Mo(IV) phn ng chm vi toluen-3,4-ditriol (mui Fe(II) xc tc cho phn ng ny) to phc 1:3 mu lc sm, trung ho, it tan, b chit bng nhng dung mi phn cc v khng phn cc. Khi thc hin phn ng vi s c mt ca axit limonic th Volphram khng cn tr. Lc u l nhng ion MoO22+ hnh thnh v sau theo mc phi tr vi nhng nguyn t lu hunh nhng nguyn t hydro dn dn c tch ra. Ion MoO22+ tn ti phc 1:2 vi axetylaxeton, MoO2(axax)2 trong MoO2F42- v trong MoO2SO4 (sn phm ho tan MoO3 trong H2SO4 c. Chc chn l chnh cation ca Mo(VI) tng tc vi nhng thuc th vng cng trong dung dch axit. S to to thnh nhng phc khng tan trong nc b chit bng clorofoc vi ,-benzoyloxim v cuphoron trong nhng iu kin nh vy c gii thch bng i lc molybden i vi nhng phi t anion cha oxy. xc nh Mo ngi ta ngh Tairon, morin, clorannilic axit, dietyldithiocacbamat v tioglycolic axit. Mo(IV) khng to phc rt bn vi nhng thuc loi ditizon. Trong HCl 1M cha ion thioxyanat v c Fe(II) hoc Fe(III), SnCl2 kh Mo(VI) to to thnh mt lot phc ca Mo(V). MoO(SCN)3 kh Mo(VI) to thnh mt lot phc ca Mo(V). MoO(SCN)3 sn phm ch yu nng thioxyanat cao l hp cht c gi tr nht. C th n nh ho phc mu h phch bng cch thm axeton vo dung dch hoc chit n bng dung mi hu c cha oxy nh ru izoanilic. Phc thioxyanat mang in tch m c th to ion i tng ng vi ion tetraphenyl asenium b chit bng clorofoc. Khi khng c st hoc ng, SnCl2 kh Mo(VI) n Mo(IV) v sau n t oxy ha kh thnh Mo(III) v Mo(V). Mo(V) cn to nhng phc khc nh MoF6, MoOX5(X= Cl, Br, CNS) v MoOBr4. Khi trung ho nhng dung dch phc ny th MoO(OH) 3 kt ta. Nhng phc ho tr thp ca molybden l Mo(CN)84- v MoX3- (X l nhng halogen hay halogen gi). Nhng phc ca Mo(III) l nhng cht kh mnh. Molybdat ch v sunfua molybden l nhng hp cht khng tan ca molybden. C th tch sunfua molybden t dung dch khi s dng Cu hoc Sb(V) lm cht gp v khi c mt axit tactric th kt ta khng b ln vonfram. NATRI, KALI, RUBIDI V XEDI Nhng cation ca dy ny c cu hnh in t ca kh tr (t neon n xeon) do cu tnh i xng cu v kh bin dng. bn ca nhng cu hnh in t nh vy gy nn tnh khng mu ca nhng cation ny bi v kch thch in t ln nhng qu o cha hon thnh c nng lng cao i hi nng lng rt ln. Nhng tnh cht ho hc ca nhng cation ny c quyt nh ch yu bi cc tng tc tnh in. T Li-Cs theo chiu tng ca kch thc ion ngi ta quan st thy nhiu bin i c trng v tnh cht. V d nh t s bn knh v nng lng mng li tinh th m bo cho nhng cation ln to mui bn vng hn vi nhng anion ln. Cation cng ln th mui to thnh cng t tan. Nhng

lin kt ca nhng cation ny thng c c tnh ion thm ch ngay c trong 1 s phc vng cng ca nhng cation ny vi nhng ligan anion cha oxy nh salysilaldehyd v benzoilaxeton. Nhng hng s bn ca nhng phc ny hu nh lun lun qu nh nn khng th s dng chng vo mc ch phn tch. V d chit CS bng dung dch dipycrilamin trong nitrobenzen. xc nh nhng nguyn t ny tt nht l dng quang ph hp th nguyn t, o mu ngn la Nhng phng php phn tch ho hc cc nguyn t ny thng da trn c s to nhng mui t tan. C th xc nh cc mui ny bng phng php trng lng hoc l nu hp cht th c th s dng c nhng phng php o mu. C th nu phn ng kt ta kali di dng K2AgCo(NO2)6 (s dng cobantinitrit-bc) rubidi v xesi di dng mui ca chng vi Bi(NO2)63-, xesi di dng Cs3Bi2I9 (nh iodobismutic axit) v silicovonframat xedi. NEPTULI trng thi kh, nguyn t neptuli c cu hnh in t [Rn] 5f46s26p67s2 hay [Rn]5f56s26p67s2. Nhng s khc nhau v nng lng ca nhng qu o 5f v 6d kh nh nn c th cho php nhng in t 5f chuyn ln qu o 6d v tham gia vo s to thnh nhng lin kt ha hc. V vy, trng thi oxy ha bn vng nht ca Np l Np(V). Trong vng ph t ngoi Np(III) c 2 cc i (h s hp th phn t l 2295 v 1593) tng ng vi s chuyn dch f-d. Nhng cc i ny c nhy ln hn nhiu so vi nhng cc i mnh trong vng nhn thy do s chuyn dch f-f b ngn cm. trng thi ha tr 3 Np c nhiu tnh cht chung vi nhng latanit cn Np4+ th li ging Zr4+ v Th4+. trng thi ha tr cao neptuli ging uran trong mi quan h l to nhng ion oxo NpO2+ v NpO22+. S tng t v loi cation neptuli v bn cht cht gp dng lm giu n cng kh r rng. V d nh, NpO22+ cng kt vi natri uranyl-axetat cn pht pht Ziriconi th c dung lm cht gp cho Np4+, LaF3, Th(C2O4)2 v KLa(SO4)2 y c Np3+ v NpO22+ ra khi dung dch. S d dng chuyn trng thi oxy ha to iu kin thun li cho vic tch neptuly bng bng nha trao i ion, bng cch to phc, cng kt v chit. bn vng ca cc phc to thnh gim theo trt t Np4+ > NpO22+ > Np3+ > NpO2+. Theo l thuyt tnh in n gin, cc anion phn b theo trt t CO32- > C2O42- > SO32- > SO42- > F- > NO3- > Cl- > Br-3 > I- > ClO4- cng l trt t gim dn bn ca phc neptuly. Np(IV) d dng to phc anion, do khi c mt cht kh nh sunfat st hai, semicacbazid (kh c Pu v cc thnh phn xa hn ca dy chuyn tip n trng thi ha tr 3), Np(IV) b hp ph trn ct anion baz mnh t dung dch HCl hay HNO3 v sau c th gii hp bng sunfat xeri 4. Trong nhng dung dch HCl hay HNO3, Np(IV) to phc trung tnh vi tenoyltrifloraxeton b chit bng xylen. Dung dch mono-(2-etylhexyl)-octophotphoric axit trong toulen tch c Np(IV) t nhng dung dch HCl nng cao. C th chit phc ca nitrat neptuli vi tributylphotphat v hexen bng cc dung mi hu c. tch Np t hn hp sn phm tch uran c th s dng phng php chit nitrat neptuli di dng phc tetrapropyl amoninitrat bng hn hp tenoyltrifloraxeton, axetonxylen. Trong tt c mi trng hp, c th tch nhng phc ny t tng hu c ra bng cch lm thay i trng thi ha tr ca kim loi. Phc rt bn ca Np(IV) vi EDTA khng b chit. Tng t vi Th, Np(IV) to phc my vi Toren trong cc dung dch c pH 1- 4. Asenazo I cng phn ng trong nhng iu kin chng nh vy, nhng trong nhng dung dch trung ha th nhng phc ny ca Np(V) v Np(VI) c to thnh 1-nitrizo-2-naphtol pH 9-10 to phc mu vi

Np(V) b chit bng ru izoamilic. Nhng thng thng nht ngi ta xc nh Neptuli bng nhng phng php ha phng x NIKEN Niken c ho tr bn vng bng 2 nhng ngi ta cng bit mt s phc ca Ni(III) v Ni(IV). Hydroxyt Ni(OH)2 c c tnh baz v ngi ta cng bit nhiu mui ca Ni(II). Ni(II) c th to c phc t in v bt in v d nh NiCl4, Ni(H2O)62+, Ni(NH3)62+ v Ni(BPy)2+. Nhng khi ligan c trng mnh n thng to phc phng vung. Nu nh trng phi t yu nh trong trng hp ca nhng thuc th cha oxyt loi axetylaxeton th phc bt in c to thnh. Ngi ta bit mt s v d nu ln nh hng kh r nt ca nhit n qu trnh chuyn t cu hnh phng vung spin thp ti cu hnh bt in. Ion Ni2+ l h d8. bn vng ca nhng phc ca n c xc nh c nh hng ca s n nh hn bi tinh th v bng kh nng to lin kt cho phi t vi nhng in t d ca kim loi. C th s dng nhng phc bn to bi cc phi t anion cha lu hunh nh dietyldithiocacbamat, dithioexalat , -mecaptopropionat, -izothioure idopropionat v nhng anion 2 in tch ca rubeanic axit v quinoxalin-2,3-ditiol lm v d cho loi hp cht m hiu ng th 2 quan trng hn. S n nh ho bi trng phi t l yu t quyt nh khi to phc 1:2 gia Ni(II) vi cc dioxim v d nh vi dimetylglyoxim. Nhng phc ny c s dng trong nhng phng php trng lng v o mu quan trng nht xc nh Ni. Nhng lin kt trong nhng phc ny c to thnh nh 4 nguyn t nit v trng mnh ca chng gy nn nng lng n nh ho ng k cho nhng phc phng vung. Khuynh hng lp y nhng v tr cn li xung quanh nguyn t kim loi rt yu gii thch tnh b chit ca nhng phc ny bi nhng dung mi khng phn cc loi clorofoc. Nh ngi ta c th tch Ni khi ion loi Co2+ to nhng phc bt in. Nhng phc ca Ni(III) v Ni(IV) khng c trng. Chng ch c to thnh trong nhng trng hp khi m s oxy ho phc Ni ho tr 2 dn ti s to lin kt phi t kim loi bn vng hn. Phi t trong nhng trng hp ny thng l anion. NIOBI Trng thi ho tr thc t quan trng ca Nb l trng thi ho tr 5. trng thi ho tr ny Nb ging photpho v asen. Nhng halogen NbX5 (X=F, CL, Br, I) NbOCl3 v NbOBr3 c c tnh cng ho tr bay hi v d b thu phn ngay c trong mi trng axit. Khi hydrat oxyt Nb2O5(H2O)x khng tan c to thnh c th tan trong kim mnh to thnh nhng phc floro khng tan NbF6, NbF7 v NbOF5. Trong HCl m c Nb(IV) tn ti di dng ion NbCl6 v c th chit n dng hp cht HNbCl6 bng diizopropylxeton. Dung mi ny cng c th tch niobi t hn hp H2SO4 6M v HF 9M. Kh nng chit HNbCl4 v H2NbOCl5 ca dung dch tribenzylamin trong clorofoc c gii thch bng s to thnh ion i. Ngi ta c th iu ch Nb nhng trng thi ho tr thp khng bn v d nh bng cch kh in axit niobio. Kh dung dch axit mnh cha thioxyamat ta thu c phc Nb(III) mu vng b chit bng ete. C th s dng phn ng ny o mu xc nh niobi. Niobi khng c nhng tnh cht ho hc cho phn ng ca n c trng. Tng t nh Ta ( v nhiu nguyn t khc) niobi c i lc vi nhng nhm vixynal, phenol nn to kt ta vi morin, querxetin v to phn ng mu vi quinalzarin, pyrocatachin, pyrogallon, tribromgallon v xylen da

cam. Mt trong nhng phng php tch Nb v Ta tt nht l phng php kt ta phn on axit niobilic v tantalic t nhng dung dch oxalat dng phc hp th vi tanin. Vic s dng nhng benzoyl-N-phenylhydroxylamin lm cht kt ta Nb v Ta chng t khuynh hng to phc ca chng vi nhng phi t cha oxy. Niobi v tanta to nhng phc tan vi cc axit tactric, xitric, oaxlic v ascocbic, Nb (Ta khng cho phn ng ny) to phc tan mu vng vi tairon trong HCl 1.6M, cn pH=5.8 th phc mu xanh bin vi brompyrogallo o c to thnh v khi c mt nhng amin thch hp th c th chit phc ny bng cc dung mi hu c. C th lm cho phn ng ny tr thnh la chn hn bng cch s dng dung dch m tractrat cha ETAD v xianua lm cht cn. 5-(2-pyridinnaz) resoesin l thuc th nhy khc thuc loi ny. Phc ca Nb vi 8-oxyquinolin khng bn lm d thu c phc ny tan trong clorofoc cn lm vic pH~9. Hin nay ngi ta thng s dng nhng hp cht o,o-dioxyazo lm thuc th nhy v la chn xc nh Nb ta c th nu ra l 2,4-nitrosunfophenol S v picramin R lm v d. Ngi ta cng s dng PAN xc nh Nb trong Ta. Nc oxy ga to phc peroxo vi Ta v Nb v trong dung dch H2SO4 nng cao axit photphomolybdic to mu xanh molybden vi niobi sau khi kh bng clorua thic hai. Trong dung dch H2SO4 c Nb v Ta to sn phm mu vng vi hydroquinon. OSMI Nhng phc bt in tng ng vi ho tr IV, VI v oxyt osmi(VIII) bay hi, OsO4 l nhng hp cht thng thng nht ca osmi. C th chit oxyt ny bng tetraclorua cacbon v clorofoc t dung dch axit. l phn ng c la chn cao, cho php tch Os v Ru ra khi cc kim loi platin. bn ln ca nhng trng thi ho tr cao ca Os so vi Ru c nu ln lm v d v tnh cht c trng i vi nhng cp nguyn t ca dy chuyn tip th 2 v th 3 trong dung dch axit nitric c 5M. Ttrong nc nhng hp cht ca Os b oxy ho n OsO4 d b ct khi dung dch trong khi thi Ru khng b oxy ho n RuO4. Trong cc dung dch axit RuO4 b kh bi Fe2+ nhanh hn nhiu so vi OsO4. C th xc nh Os theo sn phm mu to thnh khi cho OsO4 tc dng vi cc cht loi o-toludin, benzydin v tetrametyl-p-phenylendiamin. Trong cc dung dch axit OsO4 tc dng vi kali thioxyanat to phc mu xanh b chit bng ete hoc ru anylic. Ho tr ca Os trong nhng hp cht c th thp hn 8. Thioure tc dng vi OsO4 hoc ion cloroosmat trong mi trng axit to phc tan mu ca Os(III) l Os(H2NOSNH2)63+. Nhng dn xut ca thioure nh o,o-ditelyticure v 1-4-diphenylthiosmicacbazid cng phn ng tng t nhng trong trng hp sau cn thit phi s dng cht kh v d nh SnCl2. Os(IV) c to thnh mt cch chm chp khi cho OsO4 phn ng vi Fe2+ trong mi trng axit. Os(IV) to phc bn OsX62- (X=F,Br,Cl) v trong ion i vi ion tetraphenylasonium [(C6H5)4As]2OsCl6 b chit bng clorofoc. Ngi ta bit osmi ho tr 3 trong cc phc Spin thp vi amoniac, dipyrindin v vi nhng phi t cha oxy loi axetylaxetonat, oxalat, nitrit ([Os(NO2)5]2-). OXY hon thnh lp in t ngoi oxy cn 2 in t. Do nguyn t oxy c th tn ti di dng anion 2 in tch, anion 1 in tch loi OH- hoc di dng hp cht trung ho loi R-O-R (lin kt cng ho tr). Trong c 3 trng hp oxy l cht cho in t v trt t gim hiu ng cho in t

nh sau: O2- > OH- > R-O-R. Nhng oxyt c th c c tnh t u th ion (v d Ba-O) n u th cng ho tr (nh trong CO2 v OsO4). Ion O2- khng bn trong cc dung dch nc, to thnh ion hydroxyl. Trong nhng ion v phn t oxy thng to nhng lin kt cho bng mt i in t m thi bi v s phn b li in tch n c th cho c i in t th 2 i hi mc tnh in rt ln. Tnh cho in t ca oxy rt quan trng. Mt trong nhng h qu ca tnh cht ny l s to lin kt hydro rt mnh trong cc dung dch nc. H qu th 2 l s solvat ho mnh cc cation trong nc (thng c coi nh tng tc tnh in ca nhng ion lng cc). Khi to phc nhng anion oxy tun theo kh tt nhng i hi ca l thuyt tnh in n gin. Chng to nhng lin kt ln bn vng nht vi nhng cation c kch thc nh v din tch ln. C 2 yu t c ngha ln hn so vi loi cu hnh in t ca cation. PALLADI Pd(II) thng c s phi t 4 trong cc phc v to phc phng vung v d nh Pd(NH3)42+. Khuynh hng to phc vung phng ca palladi phn bit n nhng kim loi chuyn tip khc. Clorua palladi d dng phi tr nhiu vi phi t loi amin, photphin, sunfit, nhng phi t ny chim 2 v tr phi tr nguyn t kim loi. V d nh 2 phn t p-aminoaxetophenol phi tr (qua nhm amino) trong PdCl2 to phc khng tan trong nc c thnh phn [(NH2C6H4COCH3)2PdCl2] trong khi nhng kim loi to phc bt din cn phi tr thm nhng phn t nc v do tan c. V mt ny platinin tng t nh Pd. Phc bis loi Pd[NOC6H4N(CH3)2]Cl2 to bi p-nitrozoanilin v nhng dn xut ca n trong mi trng axit c s dng o mu xc nh Pd. C th chit phc vi nitrozodiphenylamin bng cc dung mi hu c nh ru butylic. Khuynh hng to phc vi nhng phi t phn cc c trng mnh (c bit l nu c th to lin kt i ngc) rt c trng i vi Pd(II) v c th thy r rng v d ca nhng thuc th s dng tch v o mu xc nh n. Ta c th k dithizon (to phc b chit bng CCl4 t dung dch HCl 1M vi Pd) ion thiozyanat (to phc H2Pd(SCN)4 b chit bng ru butylic hoc izoamilic) thioure thioglycolic axit 2-meccapto-4,5dimetytlzaol v nonditylditiocaebanat (to phc b chit bng benzen). Palladi cn to phc khng tan trong nc vi dietylamino-benyliderodamin, 1-nitrozo-2-naphtol v 2-nitrozo-1-naphtol (c th chit nhng phc ca nitrozonaphtol bng toluen). Tng t nh Ni, Palladi to vi dimetylglyoxim phc 1:2 khng tan b chit bng clorofoc. Nhng dioxim khc cng cho phn ng nhng -furyldioxim l thuc th tt nht. Pd cn to phc mu vi salisilaloxim. S khc nhau c bn gia nhng phc tng ng ca Pd(II) v Ni(II) l ch phc ca Pd(II) c tnh tr ng hc ln. Pd cng to phc bt in PdX62- (X = F,Cl,Br) nhng chng khng c gi tr ln. C th kt ta Palladi di dng sunfat ng thi dng ch lm cht gp. N cn d dng kt ta vi toluen nu thm toluarit vo dung dch ri sau kh bng axit sunfur hay clorua thic 2. Ngoi ra c th kh n Pd v hp ph trn Hg2Cl2 khi lc Hg2Cl2 vi dung dch Pd(II). PHOTPHO Photpho cng nh nit to nhng hp cht cng ho tr c trng. Nhng s d dng lai ho nhng qu o 3d cha hon thnh to cho photpho kh nng c s phi tr n 6, v d nh trong trng hp phc bt in PF6. Oxyt v nhng oxy axit l nhng loi hp cht quan trng nht ca photpho. Trong nhng hp cht ny cng nh trong nhng hp cht m lin kt p-s c hnh thnh

c th l nhng qu o d ca photpho c s dng to lin kt d-p vi nguyn t oxy (hoc lu hunh) lc ny lin kt bi c hnh thnh. Photpho khng c khuynh hng to nhng lin kt p- p. Cu to ca oxyt v oxytxit ca photpho s phn b bt in cc nguyn t xung quanh nguyn t photpho. Nh s to thnh nhng lin kt gia nguyn t oxy v 2 nguyn t photpho nhng thnh phn li lin kt vi nhau thnh nhng photpho ngng kt c th c cu to thng hoc vng. PLATIN Tnh cht ho hc ca Pd v Pt rt gn nhau ngoi tnh cht l phc ca Pt(IV) v bn hn phc ca Pd(IV), nhng phi t d phn cc v c t trng mnh thng to nhng lin kt i ngc vi kim loi l nhng phi t c th to phc phng vung vi Pt(II). Khi dng clorua thic hai kh Pt(IV), dithizon tc dng vi Pt(II) trong HCl 4M to phc b chit bng tetraclorua cacbon. Pt(IV) khng b chit di dng dithizonat, p-nitrozodimetyl anilin, p-nitrozodiphenylamin v ion dietylditiocacbamat l nhng thuc th c th s dng cho c Pd(II) v Pt(II) (2 thuc th sau to phc b chit bng cc dung mi hu c). Platin trng thi ho tr 4 to mt s ln phc bt in loi [PtLxX6-x] trong x bin i t 0 - 6; L= NH3, N2H4, NH2OH hoc (en) v X = Cl, Br, SCN hoc NO2. Tng t nh nhng phc ca Pt(II) v Pd(II) nhng phc ca Pt(IV) c tnh tr ng hc. Ion iodoplatin(IV) PtI62- mu c s dng tnh cht ca nhng anion loi ny tch Pt khi nhiu kim loi khc bng trao i ion. Khi oxy ho Pt n Pt(IV) pH=8 bng ion bromat v sau un si th ton b lng paladi tn ti trong dung dch b kt ta di dng oxyt hydrat cn Pt(IV) th cn li trong dung dch. Trong nhng trng hp khc nhng phng php kt ta Pd t dung dch c ng dng cho Pt, Thiosemicacbazid v phenylthiosemicacbazid trong mi trng axit yu to phc mu vi Pt (IV). Phc ca Pt(IV) vi phenylthiosimicacbazid b chit bng etylaxetat. PLUTONI Nhng tnh cht ho hc ca Pu (nguyn t trng thi kh c cu to [Rn] 5f6 6s2 6p6 7s2 rt gn ging nhng tnh cht ca Np trng thi ho tr tng ng. in tch ht nhn ln do cc qu o b thu nh li gy tr ngi cho s chuyn in t 5f ln 6d v s tham gia ca chng vo s to thnh lin kt. iu dn ti kt ta l trng thi oxy ho bn vng nht ca Pu l Pu(IV) (ngc li i vi Np li l Np(IV). Nhng ion Pu3+, Pu4+ v PuO22+ tng t nh nhng ion ca neptuli nhng PuO22+ trong cc dung dch axit yu lng phn v Pu3+, Pu4+ b oxy ho kh khn hn Np3+ v Np4+. Cho n nay phi t ngoi ca Pu3+ cha c m t r nhng c l nhng cc i mnh tng ng vi s chuyn dich f-d nm trong vng bc sng ngn hn so vi Np3+. Do bn knh nh nn nhng ion plutini to phc bn hn so vi nhng ion neptuli tng ng. Phc ca Pu(IV) vi EDTA kh bn nn c th chun ngc bng thori nitrat. Nhng cht cng kt ca Pu cng l nhng cht cng kt ca Np do l nhng mui ca zcon vi nhng axit hu c v d nh benzen sunfinat v phenyl asenat Zr u tch c Pu(IV). Ngi ta cn s dng photphat bismut lm cht gp cho Pu(III) v Pu(IV) trong cc dung dch axit sunfuric v nitric nng va phi. Kh nng to phc ca nhng ion Pu gim theo trt t Pu4+ >PuO22+ > Pu3+ > PuO2+. S phi tr vi cc phn t tributylphotphat, benoyltrifloraxeton v tri-nhng-oxtyllamin cng yu dn

theo trt t . Ngi ta dng nhng thuc th ny chit Pu t cc dung dch axit. Vic chit Pu4+ trong h TBP-HNO3 di dng Pu(NO3)4.2TBP c ngha ln. Nu dung mi ch phi tr yu v d nh trng hp ca dietyl ete v hexan (nhng dung mi c s dng tch phn tch) th ta c dy sau Pu(VI) >, Pu(IV) >> Pu(III )> Pu(V). Cng c th tch Pu bng trao i ion. Mun vy ngi ta hp th n trn cationit v sau gii hp bng HCl di dng phc clorua hoc l s dng nha anionit hp ph nhng anion phc clorua hoc nitrat ri sau kh v gii hp. V d nh hp th Pu(IV) trn ct anionit t dung dch HCl 12M th kh n Pu(III) v do b gii hp. Ho phn tch ca Pu tr thnh phc tp thm nhiu v nhiu nguyn t i km theo n trong qu trnh phn chia ht nhn. Th oxy ho kh ca cp Pu(III)/Pu(IV) trong HCl 1M bng 0.97V, trong HClO4 1M bng 9.8V v trong H2SO4 1M l 0.75V. Dng phc ca Fe(II) vi 1,10-phenantrolin lm ch th c th chun Pu(III) bng xeri(IV) sunfat. o mu xc nh Pu(IV) c th s dng nhng thuc th nh alizarin sunfonat natri ( pH=3 v 530nm, = 9870), toron ( =11.000 540nm) v asennazo I (phc 1:1 trong HNO3 0.1M 580nm =21000). Pu(III) ( pH=5.6-5.6) Pu(IV) v Pu(VI) ( pH=8.59.5) cng to phc mu vi asenazo I. Khng mt thuc th no trong s nhng thuc th k trn l la chn nn cn phi tch cc nguyn t cn tr trc v c mt s anion. POLONI S phng x mnh khi phn hu ht nhn poloni gy tr ngi cho s nghin cu ho hc nguyn t ny. Poloni c c tnh kim loi, tnh tr ca nhng in t 6s2 thng khng cho php n biu hin ho tr cao hn 4. Nhng lin kt ho hc ca nguyn t ny c nhiu tnh cht cng ho tr do tetrahalogenua polini bay hi nhit cao hn 1500C v tan trong cc dung mi hu c Nhng tetrahalogenua ny rt ging nhng hp cht tng t ca tellua. Nhng hp cht ny c to thnh khi ho tan PoO2 trong nhng axit halogenohydric chng d to thnh nhng anion phc loi PoBr62- b kt ta di dng mui khng tan vi nhng cation ln nh cation xesi v tetretylamoni. Dioxyt poloni biu l tnh axit yu hn nhiu so vi dioxyt tellua. Poloni to nhng mui suniat, nitrat, photphat, oxalat v axetat v c mt s baz ging nhmui tellua tng t. Vic s dng thuc th hu c xc nh poloni cng cha c nghin cu. PROTACTINI Protactini l thnh phn u tin ca dy actinit dy ca cc nguyn t ging actini. Tng t nh nhng lantanit, nhng actinit tn ti l do s hon thnh dn nhng qu o f (trong trng hp ny l qu do 5f) l nhng qu o ch ng vai tr khng quan trng trong s to thnh lin kt tt c cc thnh phn ca dy ny (ngoi thnh phn u tin). Vic hon chnh mc f kt thc No v Lr. Protactin c cu hnh in t [Rn} 5f2 6d1 7s2 hoc l [Rn] 5f1 6d2 7s2 v chnh v nng lng in t ca nhng qu o 5f, 6d, 7S trong nguyn t ny khc nhau rt t nn c th thc hin lin kt lai ha cng ho tr vi s tham gia ca cc in t 5f do dn ti mc oxy ho IV v V. Pa(V) ging Nb(V) v Ta(V) nhng c khuynh hng thu phn mnh hn. Pa(V) to nhng phc anion vi florua, clorua, nitrat, sunfat tioxyanat, xitrat v khng tn ti di dng cation n gin.Khi kh bng sunfat titan (III) hoc l hn hng km th thu c Pd(IV) rt d b oxy ho bi oxy ca khng kh.

 lm giu protactin ngi ta s dng phng php chit n vi N-benzoitl-ophenylhydroxylamin. Pa(V) to vi asenazo III mt phn ng hu nh la chn tuyt i trong H2SO4 7-8N ( ~ 22.000) RENI Nhng trng thi ho tr nh bin mt ca reni l III, IV, V, VII. Nhng phc ca Re(III) v Re(IV) thng l spin thp. Oxyt Re2O7 bay hi nn c th ct n t cc dung dch axit sunfuric. C th chit axit renic tng ng vi n t nhng dung dch axit bng ru butilic hoc izoamilic. Anion ca axit ny ReO4- bn trong cc dung dch nc v thu c kh oxy ho nhng hp cht ca reni bng cc dung dch HBr v HI th ngc li xy ra qu trnh kh ion RoO4-. tan ca nhng mui perrenat ging tan ca mui perclorat v d nh khc vi phn ln nhng hp cht ca Re(VII) d tan trong nc. Li dng tnh cht ngi ta tch Re ra khi Mo bng cc chit perrenat tetraphenylasenium bng clorofoc. Re(VII) c i lc ln i vi lu hunh, H2S kt ta sunfua Re2S7 t dung dch HCl 4-6 M hoc H2SO4 3M (dng asen 3 lm cht gp). Re(VII) to phc mu vi toluen-3,4-ditiol v vi 4-oxy-3-meccaptatoluen. Khi un si axit renic vi 2,4diphenyltisemicacbazid trong HCl 5-7M ta thu c sn phm mu b chit bng clorofoc. Bn cht ca phn ng ny cn cha r. Kh Re(VII) bng clorua thic 2 hoc clorua titan 3 c mt thioure hoc diphenylthioure ta thu c nhng phc mu ca Re(V) loi ReO2L4+. Khi c mt ca ion thioxyanat thic (II) clorua kh axit renic trong cc dung dch axit to thnh phc mu vng ca Re(V) c cu to ReO(SCN)3 hoc ReO(SCN)4- (xem molybden). C th chit phc ny bng dietyl ete. Nu khng dng ion thioxyanat m dng dimetylglyoxim (hoc tt nht l dng furyldioxim) th phc mu do b chit bng clorofoc ca Re(IV) di dng ReOL6. Trong HCl c nng, nu ch ho phc iodua tng ng bng kali xyanua trong metanol thi ion [Re(CN)8]3- bn v tan trong nc c to thnh trong khi th TeI62- to ion [Te(CN)6]2- d thu phn trong nc. Khi kh Re(VIII) trong HCl 10M nng bng crom (II)clorua ta thu c nhng hp cht ca Re(III). RODI Rodi khng to nhng anion oxy v nhng oxyt ha tr cao. Ha hc ca nguyn t ny ch yu lin quan vi trng thi ha tr III v IV trong trng thi ha tr III bn vng hn. Nhng phc ca Rh(III) cng nh ca Rh(IV) thng c cu hnh bt din. C th tch Rodi di dng Na3RbCl6 khi paladin, platin v iridi bi v khc vi phc nu trn, nhng hp cht loi Na2MeCl6 ca cc nguyn t ny (Me = Pd,Pt,Ir) tan trong etanol. Rh(H2O6)3+ ging Co3+aq to nhng mui sunphat, perclorat v clorua. Rodi l nguyn t chuyn tip th 2 v th 3 to cation 3 in tch c trng v hon ton bn vng. Khi a pH ca cc dung dch mui v d nh ca Rb2(SO4)3 .14H2O n gi tr ln hn 6 th Rb2O3 ngm nc b kt ta. Trong cc dung dch axit yu mui ca Rb(III) b thy phn to phc hydroxo. Tng t nh Coban, Rb(III) to phc loi (Me(CN)6)3- v (Me(NO2)6)3- nhng khc vi coban, Rb(III) khng to cc phc (RbX6)3- v (RbX5.H2O)2- (X = Cl,Br v SCN). Tt c nhng phc v mui ca Rb(III) c c tnh spin thp v v chng l h d nn nng lng n nh ha bi trng phi t cao, c bit l trong trng hp ca nhng phi t nh CN-, etylendiamin v , dipyridin.

Cation ba in tch Rh3+ to nhng phc bn vi nhng phi t anion. 1-nitrozo-2-naphtol,2meccaptobenxoxa-zol, 2-meccaptobenztiazol, thionalid v thiobarbituric axit l nhng thuc th in hnh c s dng kt ta Rh3+. Vic s dng nhng phi t lin kt vi kim loi qua lu hunh ch khng phi qua oxy s lm tng s ng gp ca trng phi t vo bn ca phc. Phng php o mu xc nh Rodi ph bin nht, da trn c s kh Rh(III) bng clorua hoc thic (II) iodua ch l phng php thc nghim v bn cht nhng sn phm ca phn ng cn cha bit. Khi un nng Rb(III) vi 2-meccapto-4,5-dimetyltiazol trong dung dch axit th mu h phch ca phc Rb(C4H6NSCS)2 ca Rb(III) xut hin, 2-meccaptobenzoxazol v 1-nitrozo-2naphtol l nhng thuc th o mu khc xc nh Rodi. Ngi ta cn s dng c phc 1:2 vi sim diphenylcacbazol trong metanol hoc l trong N,N-dimetylformamid RUTENI Trng thi ha tr thng gp ca Ruteri l II ,III v IV v phc ca n thng ch yu c cu hnh bt din. Trong trng thi ha tr VIII ch tn ti trong oxit bay hi RuO4, c to thnh khi un nng dung dch axit cha nhng hp cht ca Ru vi cht oxy ha mnh. Tng t nh OsO4, RuO4 b chit t mi trng axit bng tetraclorua cacbon hoc clorofoc v chnh nh tnh cht ny m ngi ta c th tch mt cch thun li Os v Ru khi nhng kim loi khc ca nhm platin. Khi lc phn chit vi cc cht kh nh HNO2 th c th chuyn Ru vo tng nc. Nhng anion RuO4- v RuO42ging MnO4- v MnO42-. Ion perrutonat c to thnh khi un nng chy hp cht ca Ruteni vi kim v cc cht oxy ha, trong dung dch kim ion rutenat li bn vng hn. Ru(IV) to nhng phc v d nh RuX62-(X = F,Cl,Br) nhng chng d b thy phn Phn ln nhng phn ng phn tch quan trng ca ruteni l phn ng ca Ru(III). Mc d rng Ru(III) l h d5 tt c nhng phc ca n u c c tnh spin thp. Ru(III) to nhng phc bn vi nhng phi t d phn cc loi ammonia v c vi nhng anion c bit l nhng anion cha lu hunh. Trong cc dung dch HCl nng cao, RuCl3 phn ng vi nhng anion mt in tch ca thioure v nhng dn xut ca n trong c thiosemicacbazid to nhng hp cht mu v d nh Ru(HNOSNH2)2+ v Ru(HNOSNH2)3, dithioxamid cng to phc mu. Cn phc 1:3 vi 2,4 diphenylthiosemicacbazic th b chit bng clorofooc, Ru(III) cn to phc vi cc halogenua v thioxyanat v trong mi trng axit yu. N to phc vi p-nitrozodimetylanillin nh phi tr vi nhm nitrozo, 8-oxyquinolin phn ng vi Ru(III) to phc khng bn lm do ngi ta iu ch phc trong cc dung dch m axetat v chit bng clorofoc. Tng t nh Fe(II), Ru(II) cng hp chm vi , dipyridin hoc 1,10-phenantrolin to phc mu 1:3 spin thp c tnh tr ng hc. ST St thng trng thi ha tr hai v ba. N thng to phc bt din nhng cng tn ti c phc t din, v d nh trng hp FeCl4- v FeCl42-. Ngi ta bit nhiu mui v phc ca st trng thi ha tr II. Tr nhng trng hp khi m nhng phc ny c to thnh bi nhng cht c kh nng n nh ha Fe(III). Nhng phc bn ca st hai l phc to thnh bi nhng phi t c trng phi t mnh ghp i in t trn nhng qu o 3d. Tnh tr ng hc ca nhng phc to thnh cng c gii thch bng iu ny. Thc t ch loi phi t no m lin kt c thc hin nh nhng nguyn t nit nh trong trng hp nhng nhm thuc th phn tch c ch nht m 1,10-phenantrolin v dipyridin l i din l c kh nng to thnh nhng trng hp nh vy.

Nhng phi t anion cha oxy (to phc st hai spin cao) lin kt vi Fe(II) km bn hn nhiu. Do c th dung EDTA lm thuc th cn khi xc nh Fe(II), v d bng 1,10-phonantrolin. C th cho rng nhng phi t anion loi mui nitriso-nitrozoaxotephenol v slixilaldoxim c tnh cht trung gian c th l trong mt s trng hp to spin thp. Fe(III) c khuynh hng to nhng hp cht c c tnh cng ha tr. Do Feaq3+ rt d b thy phn, trong dung dch pH < 1 tn ti phc hydroxo. Fe(III) thng to phc anion. Phc cloro ca n to thnh trong mi trng HCl b hp ph trn nha anionit. Ngi ta thng chit axit HFeCl4 bng metylisobutyxeton, dietylete v mt s dung mi cha oxy khc t dung dch HCl 5-7M. Fe(III) cng c nhng tnh cht tng t trong dung dch HBr 5M Ph hp th ca phc Fe(III) vi ion clorua gy nn bi s chuyn din tch t c dng xc nh Fe3+. Phc tng t vi ion thioxyanat c s dng rt rng ri. Mun xc nh Fe(III) cn dng phi t nng cao. Mt lot phc khc nhau v cc i hp th v cng mu c to thnh nn iu quan trng l phi tiu chun ha iu kin. S to phc s c tng cng khi thm axeton hay nhng dung mi trn ln vi nc c hng s in mi thp khc vo hoc l chit bng nhng dung mi hu c cha oxy, c th chit phc anion ca Fe(III) vi ion thioxyanat di dng ion i vi nhng cation hu c ln v d nh triphenylamin v tributymetylamoni. Hu nh trong tt c cc phc ca mnh, Fe(III) trng thi spin cao. iu c gii thch bng s thun li v mt nng lng ca qu o i xng ch cha 1 in t trong cu hnh in t spin cao d5 (ch tr mt s ngoi l l trng hp phc ng hc spin thp Fe(CN)63- v phc 1:3 ca Fe(III) vi 1,10-phenantrolin v dipyridin). Chnh v th nn Fe(III) rt t ging nhng ion kim loi chuyn tip khc v cng chnh v th nn n to nhng phc bn vng nht vi nhng phi t anion khng cha nit. Nhng phi t dng o mu xc nh Fe(III) c th lin kt n bng hai anionoxy(nh trong pyrocatechin, Tairon v trong axit thioglycolic, axit thiosalilic) bng nguyn t oxy v anion oxy (nh trong 8-exyquinolin, ferron v salyxilaldoxim). Fe(III) to phc rt bn vi EDTA c th x dng axit xitric, oxalic v tactric cn st hoc l gi n trong nhng dung dch axit yu hoc trung ha. Fe(III) cng to phc vi ion flo v pyrophotphat. Khi phi t n nh ha trng thi st ha tr hai th c th xc nh st ba theo tc dng oxy ha dimetyl-p-phenylendiamin ca n to ra hp cht c mu hng SELEN m in c selen nh hn rt nhiu so vi m in ca oxy do n ch yu to nhng lin kt cng ha tr. Tnh cht ha hc ca lu hunh v selen rt gn nhau. Nhng trng thi ha tr quan trng nht ca selen l IV v VI v di tc dng ca cht kh mnh th thu c hp cht bay hi H2Se. Nhng cht oxy ha v d nh HNO3 v brom chuyn selen thnh oxyt bay hi SeO2, d tan trong nc to thnh axit selenic OSe(OH)2 axit ny l cht oxy ha mnh va phi b cc thuc th nh st II sunfat, thic II clorua, hydrazin v glycose kh n selen. Di tc dng ca cc cht oxy ha mnh hn, axit selenit chuyn thnh axit selenic v ion selenat SeO42-. Axit selenic mnh bng axit sunfuric v b kh kh hn SeO2 SILIC

Theo tnh cht ha hc silic thc th l phi kim. S phi tr ca n thng bng 4. Do thnh phn cu to c bn ca silic dioxit v ca nhng anion trng hp ca axit silixic gm 4 nguyn t oxy phn b xung quanh nguyn t silic. Nhng n v cu to lin kt vi 2 nguyn t silic. Zeolit c s dng lm cht trao i ion v li phn t l b xng trng hp 3 c nhiu l nh ca nhng t din AlO4 vi SiO4 ng thi trung ha in tch ca nhm cn 1 proton hoc l mt in tch. Do nhng qu o 3d ca silic trng nn n cn c th to phc bt din nh s lai ha sp3d2 nh trong trng hp SiF62- v trng hp phc 1:3 vi axetylaxeton SCANDI Scandi to mui v phc ch trng thi ha tr ba. Ion Sc3+ cu hnh in t ca argon v bn knh ca n ch nh hn mt cht so vi bn knh ca nhng thnh phn sau cng ca nhm latanit l nhng nguyn t m n rt ging v tnh cht ha hc. Nguyn t ny c tnh baz hn nhm nhng km cc latanit do n to nhng oxyt hydrat ha ScO3(H2O)x v ScO(OH) nhng khng to c Sc(OH)3. C th cng kt oxyt hydrat scandi cng vi hydroxyt coban bng amoniac. S dng khuynh hng to phc ln ca scandi trong c Sc(SCN)3 ( b chit bng ete), c th tch n khi cc lantanit. Cng c th tin hnh tch tng t bng cch chit scandi di dng phc clorua bng tributylphotphat t cc dung dch HCl nng cao. Khc vi cc lantanit ha tr 3. Scandi c kh nng to cc sunfat kp khng tan trong dung dch kali sunphat. Scandi triflorua khng tan trong nc nhng tan khi c d ion florua to thnh ScF63-. Cng c th tch scandi khi nhm bng cch kt ta di dng phc 1:3 vi 8-oxyquinaldin. Khc vi nhm, ion scandi ln c th b qua tng tc khng gian gia cc phi t to phc 1:3. Phc tng ng ca n vi 8-oxyquinaldin kt ta t cc dung dch hu nh trung ha v b chit bng clorofoc hoc benzen C th xc nh nng scandi trong phn chit bng cch o mu trong vng ph t ngoi Sc3+ to nhng phc bn vng nht vi nhng phi t anion cha oxy. V d nh phc 1:3 ca n vi tenoyl trifloraxeton b chit pH = 1,5-2,0 bng benzen cha lng d thuc th. Nhng hp cht to sn vi Sc nh alizarin S v quinalizarin l nhng thuc th khc o mu xc nh nguyn t ny. Ngi ta cn s dng querxetin v antrarufin-2,6-disunfuaxit lm thuc th o mu xc nh scandi. Mt hp cht tng t l merin cng c s dng o hunh quang xc nh scandi. Nhng thuc th ny rt khng la chn do ph thuc nhiu vo hiu qu ca ng tc tch trc scandi khi cc kim loi khc nh bng trao i ion TALI Trong cc dung dch nc, trng thi ca Tl(I) bn hn rt nhiu so vi Tl(III). Tl+ ging Rb+, l ion c bn knh rt gn vi n, kh nng to baz mnh tan trong nc v mt s mui ng hnh vi mui ca kim loi kim. V c cu hnh in t [Xe]4f145d106s2, Tl+ b bin dng rt d dng v trong nhiu mi quan h n gingAg+. Nhng trong cc phc ca bc, s to lin kt cho c ngha ln cn i in t tr 6s ca Tl(I) tng ng vi trng thi ha tr thp li lm gim mt cch ng k khuynh hng chuyn nhng in t 5d ca Tl+ ln nhng qu o thch hp ca phi t to lin kt cho cc phc ca n. Chnh v vy Tl(I) to nhng phc km bn vng hn rt nhiu so vi nhng phc ca Ag(I); ch c th kt ta nhng phc ca Tl(I) vi xyanua v sunfua t nhng dung dch trung tnh hoc amoniac (trong khi sunfua bc kt ta t mi trng axit). chit phc ca

Tl(I) vi dithizon bng tetraclorua cacbon v to nhng phc khng tan ca n vi thionalid u cn mi trng kim yu (pH 9-12). C th nng cao la chn ca phn ng sau bng s dng nhng ion tactrat v xyanua lm thuc th cn. Tl(I) lin kt cc kim loi khc t dung dch cha Tl(I) c th s dng cc cht to phc nh cupheron, 8 oxyquinolin. Khi thm vo dung dch HCl ca tali ha tr 1 nc brom hay clo th Tl(I) b oxi ha n Tl(III), Tl(III) l cht oxy ha yu, b iodua kh n Tl(I). Cng c th xc nh Tl(III) bng cch o mu sn phm oxy ha ca n to vi nhng dn xut azo ca axit cromotropic v vi p-aminophenol c th chit Tl(III) d dng. C th chit Tl(III) t cc dung dch HCl bng cc dung mi hu c cha oxy c bit l diisopropyl ete. Trong nhng iu kin nh vy Tl(I) ch b chit mt phn. Chit Tl(III) t cc dung dch HBr 0,1-1M bng dietyl ete cho php ngi ta tch n khi Fe(III) v phn ln cc kim loi khc ngoi Au(III). Khc vi phc clorua, cc phc bromua ca Tl(I) b chit nh lng bng dieteyl ete t cc dung dch HBr 1-4M. Nhng phc iodua ca Tl(I) v Tl(III) cng b chit bng dietyl ete t cc dung dch HI 0,5-2,5M. Nhng ion i ca TlCl4 vi Pdimetylaminoazobenzen v metyl da cam u khng tan. Nhng ion i tng ng vi rodamin B, metyl tm v lc malakhit cng khng tan trong nc nhng b chit bng nhng dung mi hu c khng phn cc v d nh benzen. Do nhng hp cht ny c s dng trong nhng phng php o mu xc nh Tali. Nhng ion i ca TlBr4- vi tm tinh th v vi lc brilian b chit bng amilaxetat cng c s dng xc nh tali TANTAL Tnh cht ha hc ca Ta v Nb rt gn nhau ch tr tnh cht l nhng hp cht ca Ta c c tnh axit yu hn. Nhng hp cht ca Ta b thy phn ngay c trong mi trng axit to ra Ta2O5(H2O)x khng ta nhng tan trong cc baz mnh to thnh tantalat v trong HF to thnh cc phc florua TaF72- v TaF83-. Nhng phc oxo NbOF52- v NbOF63- cn cha c m t trong cc ti liu nhng ngi ta bit nhng hp cht TaOCl3 v TaOBr3. Phc ca Ta d b chit bng cc dung mi hu c loi diisopropylxeton hn phc ca Nb. Tng t nh Nb, Ta to phc tan vi tactrat v phc mu vi thuc th nh morin, pyrogallol, axit gallic v dn xut ca fluoron. Tt c thuc th ny u cha nhm phenol vixynal. Gn y ngi ta tm thy ng dng trong phn tch Ta ca asenazo I; 2,3,7-trioxy-9-phenyl-6-fluron v querxetin. C th tch Ta khi Nb bng cch chit la chn bng ru butylic phc ca n vi pyrocatechin pH 3 v c mt oxalat. Phc halogen ca Ta to kt ta mu vi rodamin B, lc builliant, tm gentian v metyl xanh. C th chit phc ny bng dung mi hu c v o mu phn chit. TELLUA Tellua c tnh kim loi c trng hn selen v c tnh axit, tnh baz yu. Oxyt ca n TeO2 biu l tnh axit yu hn SeO2, tuy vy n vn to nhng mui tan vi nhng hydroxyt ca kim loi kim v rt d b kh n nguyn t. Axit tolluric Te(OH)6 l axit rt yu. Ngi ta iu ch axit bng cch oxy ho Te hoc TeO2 bng nhng cht oxy ho mnh nh axit cromic. Tellua cng to nhng phc anion loi TeBr62-. Ngi ta iu ch phc ny bng cch cho TeO2 phn ng vi axit hogenohydric. S phi tr thng gp ca Te trong cc phc ca n l 6. TECNETI

Tecneti ging mangan nhng bn ca nhng trng thi ho tr cao tng khi s th t nguyn t trong mt nhm ca bng tun hon tng do trong trng hp ny trng thi ho tr quan trng nht l IV v VIII. Ngi ta tch tecneti t nhng cht thi phng x cha nhng sn phm phn hu bng cch cng kt tetraphenylasonium pertecnemat (Ph, As) TcO4 tan trong ru v tch trn ct anionit. Oxyt Tc2O7 bay hi do bng cch lm bay hi dung dch axit cha TcO4- ngi ta c th tch n khi Re. Axit tecnetic v perocnetat to thnh trong dung dch khi oxy ho nhng hp cht ca tecneti bng nhng cht oxy ho mnh nh axit nitric hoc nc oxy gi. Tng t nh ReO4, TcO4 b kh bi HCl, HBr v HI. Axit tecnetic l axit mnh tan ca cc mui ca n tng t tan ca perelorat. C th xc nh Tc(V) di dng phc thioxyanat nh tnh cht l n ging molybden cn Tc(VII) to nhng phc bn vi axit thioglycolic v toluen 3,4-ditiol. THIC Thic to 2 cation: Sn2+ ([Kr] 4d105s2]) v Sn4+ ([Kr] 4d10). S tn ti ca Sn2+ l kt qu tnh tr ho hc ca cc in t 5s2 v chuyn dng Sn(II)-Sn(IV) l kt qu ca s tch ra v np vo ca cc in t ny. Sn(II) ch yu c tnh baz (mc d n thu phn mnh trong dung dch v c th to nhng stanat cha anion [Sn(OH)6]2- tng t nh [SnX6]2- (X = F, Cl, Br, I) v to phc SnCl4. Trong cc phc ca Sn(II) v trong phn ln cc phc ca Sn(IV) lin kt c nhiu c im cng ho tr. Do c th chit thic bng dietylete di dng phc bromua t dung dch HBr 4M cn Sn(II) th b chit di dng phc iodua t HI 6.9M. Benzen chit c SnI4 t dung dch axit sunfuric cha 1 lng ln iodua. Cng c th chit nh lng Sn(IV) bng dietylete di dng phc thioxyant t dung dch amoni thioxyanat 1-10M v HCl 0,5M. c th ct d dng halogenuaca Sn(IV) nh SnBr4 v SnCl4 khi thm vo dung dch H2SO4 hay HClO4 nng cha thic, axit halogenohydric tng ng. Ngoi ra c th tch thic khi nhng kim loi khc bng cch kt ta n di dng sunfua t dung dch axit mnh v dng ng lm cht gp. C th phn bit Sn(II) v Sn(IV) theo c im ca phi t m chng to phc bn vng nht. i in t tr trong cc phc ca Sn(II) lm gim bn lin kt i ngc ca kim loi trong mt mc ng k. Cc qu o d hon thnh ca Sn(II) to iu kin cho n phc bn vng nht vi nhng phi t phn cc v s vng mt hiu ng n nh ho bi trng phi t (v Sn(II) l h d10 ) dn ti h qu l c in tch cao hn nu hiu ng tnh in ln hn v do c kh nng to phc vi nhng phi t anion cha oxy losipyrocatechin tm. Dung dch dithizon chit c thit II nhng khng chit thic (IV). iu ny c gii thch trc ht l do dithizonat trung ho in khng th c to thnh (tng ng vi s phi tr thp ca Sn(IV) ) v nhng kh khn khng gian. Sn(II) to phc 1:2 khng tan mu vi toluen-3,4-ditiol phc ny b chit bng cc dung mi hu c. Ngi ta s dng phn ng ny o mu xc nh thic trong nc c dng keo bo v. Dithiopyrocatechin v 1-clo-3,4-dimecaptobenzen cng phn ng tng t. dung dch dietylamonidietylditiocacbamat trong clorofoc chit c Sn(II) t mi trng axit nhng khng chit c Sn(IV). Ngc li Sn(IV) to phc mu t tan vi nhng thuc th loi galloin, hematoxylin, morin phenyl fluoron v quinalizarin v to phc pht hunh quang vi axit cacminic v pupurin.

Cupheronat Sn(IV) kt ta t dung dch HCl hoc H2SO4 1M b chit bng clorofoc. Sn(IV) cn to phc vi 8-oxyquinolin ( pH = 2.5-5.5) b chit bng clorofoc v to phc vi dietyldithiocabamat. Tnh cht oxy ho kh ca h Sn(II)-Sn(IV) trong mt chng mc nht nh hn ch s thuc th hu c dng xc nh thic v ngc li tnh kh ca Sn(II) li c s dng xc nh n. C th nu s xut hin mu tm ca cacotelin (dn xut nitro ca bruxin) v s to hp cht pht hunh quang xanh khi kh 6-nitro-2naphtinlamin-8-sunfo axit trong mi trng amoniac l v d. Di tc dng ca thic II clorua mu lc diazin to thnh khi tng hp N,N-dimetylanilin vi safranin diazo ho b kh tr li n safranin. Mu trong phn ng nhy ny bin i t xanh lc nht n tm hoc . THORI Trng thi ho tr quan trng duy nht i vi ho hc ca nguyn t ny l IV. Th c cu hnh in t ca kh tr radon. Trong cc phc thori c s phi tr 8 Th4+ to mui vi cc axit v c, nhng pH > 3 cc mui u b thu phn to thnh nhng hp cht a nhn cha cu hydroxo v oxo. Hydroxyt ca n b kt ta bi amoniac hoc hexametylen-ciamin (pH~5) khi dng hydoxxyt Al hoc Fe lm cht gp. tch thiori khi nhng nguyn t khc c th s dng tnh cht florrua, iodat, oxalat v photphat u khng tan ca n ngay c trong mi trng axit mnh. Thori nitrat tan tt trong nc, tan c trong cc dung mi cha oxy c bit l trong ru, este, ete, xeton. C th chit thiori t mi trng axit nitrit bng tributylphotphat, tenoyltrifloaxeton trong tetraclorua cacbon, xyclohexanon, oxyt mozityl, metyllisobutylxeton v nhng dung mi tng t mnh khc. Phc nitrat ca thori phi tr c dung mi. Cn ch l khc vi tt c nhng thuc th nu trn, tenoyltrifloraxeton to hp cht nhng ni phc, c th trnh nh hng ca nhiu cht to phc bng cch thm d nhm nitrat. Thori to vi nhng phi t polyanion cha oxy nhng phc bn vng nht, lc ny hp cht ni phc 2 c to thnh. o mu xc nh thori ngi ta s dng morin (to phc 1:2 trong mi trng axit yu), alizarin S, querxetin, quinializarin v pyrocatosin tm. Thorin [1-(2asonophenylazo)-2-naphtol-3,6-disunfoaxit] v o-aseno-phenylazocromotropic axit to vi thori phc 4 rng nh s phi tr ca 2 nguyn t oxy ca anion nhm aseno 2 in tch ca nguyn t oxy phenol v ca nit ca nhm azo. Do s nng cao bn ca cu trc nh vy nn phc tng ng c th c to thnh ngay c trong dung dch axit v do la chn ca php xc nh c nng cao. Asenazo (nistoron) l thuc th nhy v la chn i vi thori. xc nh thori ngi ta s dng c nhng thuc th loi khc nh mui nitroso R, 8 oxyquinolin v indoxin mc d nghin cu l thuyt ch php rt ra kt lun l nhng thuc th ny km gi tr. Asonazo III cho phn ng la chn v nhy nht (~14000) vi thori. THY NGN Thu ngn kim loi bn vng i vi tc dng ho hc hn l Zn hoc Cd (xem 2 gi tr th ion ho th nht v th hai). S d c tnh cht l v i in t 6s ca n tr v mt ho hc. C th s dng tnh tr gii thch v sao trng thi hi thu ngn dng n nguyn t. Cu hnh in t [Xe] 4f145d10, trong Hg2+ lm gim mt cch ng k bin dng ca cation v xut hin khuynh hng to lin kt cng ho tr rt ln. V vy, c th chit d dng HgBr2 t nc v H2HgI4 t dung dch HI 6.9M bng dietyl ete. Trong dung dch axit, Hg(II) to sunfua khng tan. xc nh

Hg2+ ngi ta s dng tnh hp th ca phc iodua tan trong ru isoamilic trong vng t ngoi v ca phc thioxyanat trong nc hoc trong ru butylic. Nhng alcaloit loi stricnin to iodomercurat khng tan. C th suy lun rng Hg(II) cn phi to nhng phc rt bn vi nhng phi t phn cc mnh m bo lin kt cho ditizon, cht tng t di--naphtyl ca n v diphenyl-cacbazon l nhng thuc th o mu xc nh Hg(II). Hg(II) to phc rt bn vi dithizon mu da cam nhy v chit bng clorofoc hay tetraclorua cacbon t nhng dung dch axit 1N. Khi s dng EDTA v ion thioxyanat lm thuc th cn th c th thc hin phn ng trong dung dch m axetat. kim tra vic o ph quang k phc dithizon vi Hg(II) trong dung mi hu c c th ph phc d dng sau khi o bng cch lc phn chit vi dung dch KI 6% trong hn hp m c pH=4, hng s bn ca HgI42- ~1030. S to thnh phc ca ion Hg2+ c th l do s chuyn dch qu o dz2 v s to phc thng hng loi O3I-Hg-IO3. Orgel cng gii thch s to phc thng hng ca Cd(I) nh vy trong nhiu trng hp do tnh bn ca nnh nn nhng hp cht ca Hg2+ khng tan trong nc. Nhiu cht Hg2 2+ Hg + Hg2+ to phc cng ho tr nh xianua v sunfit lm chuyn dch cn bng sang phi (s lng phn ca Hg2 2+) . Nu lin kt c c tnh ion nhiu hn v d nh trong oxalat, sixunat pyrophotphat th phc ca Hg22+ bng nhng nguyn t lu hunh v nit ng vai tr kh quan trng. C th nu nhng phc khng tan vi p-dimetylaminonenzylidonrodaniz; 4,4-bis(dimetylamino) thiobenzophenon, thiobenzophenon v thiobenzamid cng nh phc dithizon mu vng b chit t cc dung dch axit 1M lm v d. nng thp ngi ta c th tch thu ngn t dung dch bng cch kt ta di dng sunfua v dng Cd, Cu hoc As lam cht gp hoc cng kt vi tellua khi s dng nhng cht kh mnh. TITAN Ho tr thng gp ca titan l IV v hp cht ca Ti(IV) c c tnh cng ho tr. TiCl4 l cht lng c th ct c v d b thu phn bi tc ng ca nc. Ngi ta cn cha bit Tiaq4+. Trong cc dung dch nc tn ti dng thu phn v d nh Ti(OH)3+ v TiCl62-. Khi thm natri hydroxyt vo dung dch Ti(IV) th thu c kt qu hydroxyt Ti(OH)4. Cc cht kh mnh chuyn Ti(IV) thnh Ti(III) ng thi ngi ta bit rng r rng ion [Ti(H2O)6]3+ c tnh baz mnh hn nhiu so vi Ti(IV). Do khng c nhng in t nn Ti(IV) to nhng phc bn vng vi nhng phi t anion cha oxy. C th chit cuphoronat mu vng ca n t cc dung dch axit long bng clorofoc. Nhng thuc th dng o mu xc nh Ti(IV) c c tnh phenol. Ta c th nu nhng hp cht to sn phm mu vng hoc , da cam sau y: alizarin S, axit cromotropic, 1,8-di-oxynaphtalin, phenylfluron, pyrocatesin, sunfosalisilic axit v taizon. Trong mt s trng hp do s to phc tng nc nn mu ph thuc v gi tr pH ca mi trng ng thi phc cao c to thnh axit thp nht ca dung dch. Titan phn ng vi axit ascorbic to phc mu vng. Phn ng ny khng khng la chn v do cn tch trc. Phc ca titan vi sunfosalixilic axit to ion i vi anion tributylamin b chit bng clorofoc. Trong mi trng axit, Ti(IV) to mu vng vi H2O2. Mc d rng phn ng ny km nhy ngi ta vn s dng xc nh titan. Thuc th tt nht o mu xc nh titan hin nay l diantipyrimetan (phn ng xy ra trong dung dch HCl 3M ( = 60000).

URAN Hp cht ca uran tn ti tn ti trong dung dch nc 3 trng thi ho tr: U(III), U(IV) v U(VI) trong U(VI) l quan trng hn c. i vi nguyn t ny qu trnh to phc v thu phn c trng, qu trnh thu phn tng theo trt t U3+ < UO2+ < U4+. Uran ([Ra] 5f36d17s2) ging nhng nguyn t t him do nhng thuc th cha oxy nh cc ion xitrat , tactrat, axetylaxeton, tenoyltrifloaxeton u to vi n (thng di dng UO22+) nhng phc bn vng hn nhng phc vi nhng phi t cha nit. Nng lng cn thit chuyn in t t nhng qu o 5f ln 6d ca uran bng nng lng to lin kt ho hc do nhng in t 5f c th tham gia vo s to phc. Hp cht ca uran trongng cc gc ca mui (c bit l mui ca florua) c tnh pht hunh quang rt nhy. Khi dng Al3+ v Fe3+ lm cht gp, ion photphat hoc amoniac c th kt ta U(VI). Qu trnh to phc chim u th trong ho hc ca uran. V d nh U(IV) to nhng phc tan vi ion cacbonat d trong khi nhiu kim loi khc b kt ta. Ion urayl to vi nitrat phc d b chit bng cc dung mi hu c cha oxy do kh nng phi tr vi UO22+ nh l phi t mt rng, nhng dung mi nh vy l dialkyl ete, xeton, este, trialkylphotphat (phi tr bng nhm photphokyl P O ca mnh) v oxyt trialkylphotphin. Ngi ta la chn dung mi da trn tnh cht nh tan trong nc thp, hng s in mi tng i cao, bn vng v trong trng hp ca nhng hp cht photphoril ngi ta cn ch n baz ca nhng hp cht photphoril. Vic chit UO22+ s thun li hn khi a nhng nhm cho in t nhng hp cht c photpho. Trong mt s trng hp v d khi s dng tributylphotphat, s to thnh phc v s chit xy ra hiu qu n ni l mui nng cao la chn cn thit phi s dng cht pha long nh etedu ho cng cn phi ch ti bn cht ca anion tn ti trong dung dch : c th chit Fe(III) bng dietylete di dng phc clorua nhng khng chit c U(VI) cn trong trng hp ca anion nitrat th ngi ta quan st thy tnh hnh ngc li. Khi kh nhng phc uranyl trong tng hu c n U(IV) th uran b ti chit vo tng nc. Ion uranyl UO22+ solvat ho nhng nguyn t O-U-O nm trn mt trc cn 6 phi t (bao gm tt c cc anion v c) th phn b quanh uran trong mt phng thng gc vi trc nu trn. Trong trng hp ca nhng phn t ln (trong co tributyl photphat) khng c kh nng phn b quanh nguyn t uran mt s phi t hu c cn thit hon ton bao quanh n. Do phc loi UO2(TBP)(NO3)2 hnh thnh. Ho lp th nh vy khng thun li cho s phi tr ca EDTA v do phc UO22+-EDTA c hng s bn khng ln. Li dng tnh cht ngi ta s dng EDTA lm thuc th cn cc cation khc rt thun li ca qu trnh xc nh Uran. bn vng ca nhng phc anion trong c phc florua cho php ngi ta tch nhng cation cn tr php xc nh uran bng cch cho dung dch tng ng qua ct cationit. Trong mi trng axit phc ca Cupheron vi U(IV) kt ta nhng phc vi U(VI) khng kt ta c th chit phc ny bng dietylete hay clorofooc. Cng c th tch cc nguyn t cn tr bng cch chit cc cupherat ca chng t dung dch U(IV) ri sau dng cht kh chuyn thnh U(IV) vi tenoyltrloraxeton v U(IV) vi axetyaxeton l nhng hp cht khc c s dng tch chit uran. Uran to nhng phc mu vi nhiu thuc th hu c nhng nhng phn ng khng c trng. Nhng phc bn vng nht c to thnh khi uran lin kt vi nhng nguyn t oxy cnh nhau trong c t nht mt nguyn t l anion. Nhng thuc th nh vy ta c th k

dibensoilmetan, cromotrople axit, tairon, salixilic axit, sunfosalixilic axit, alizarin S, toron, morin. Khi khng c Cr(VI) (nu c cn phi kh) v cc halogenua lm cho nhng ion khc b chit th c th lm cho phn ng dibenzoilmetan vi uran tr thnh la chn bng cch chit n trc. Mun vy c th chit phc tetrapropylamonitrinitrat bng metyl isobutylxeton t nhng dung dch axit va phi cha nitrat nhm amoni. Nu thm vo phn hu c tch ring dibenzoilmetan trong m etanopyridin th trong s t nhng ion b chit ch c UO22+ to phc mu. Khi hm lng uran ln th c th o trc tip mu phc ca n vi tetrapropylamonitrinitrat. Ion tioxyanat to nhng phc [UO2SCN]+, UO2(SCN)2 v [UO2(SCN)3]- mu vng cng l thuc th c s dng rng ri. Ngi ta thng thc hin phn ng trong dung dch nc. Ion azit cng to phc mu vng vi U(IV). Tng tc ca uran vi H2O2 trong mi trng kim to peruranat mu vng cng l phn ng hay c s dng. o mu xc nh uran ngi ta ngh mt lot thuc th trong c t nht mt lin kt kim loi phi t trong t nht mt lin kt kim loi phi t c thc hin khng phi qua nguyn t oxy (mc d rng nhng thuc th ny km la chn). Vic s dng nhng thuc th ny thng i hi phi tch uran(VI) ra khi nhng ion c kh nng phn ng ln. Nhng thuc th l asenazo I; (2-(2-asononazo)-2-naphtol (PAN), salyxyl-hydroxamic axit, toglycolic axit, salixyldoxim, 8-oxyquinolin, 1-nitrozo-2-naphtol v tiocacbamat cng phn ng vi uran(VI) to nhng phc mu b chit bng nhng dung mi hu c. VANADI Khi nung nng chy nhng hp cht ca vanadi vi natri cacbonat c bit l khi c mt cc cht oxy ha ta thu c vanadat tan. Hp cht ca V(V) c to thnh l do kt qu ca s mt i dn dn nhng proton ca V2O5 ngm nc. Nhng anion to thnh c th lin hp nh nhng cu oxy. Trong dung dch a ion pervanadil VO2+ l ion chim u th. Nhng dung dch nh vy l nhng cht oxy ho mnh va v c th xc nh V(V) bng cch o mu xut hin khi n oxy ho nhng baz hu c v d nh diphenyldimetylnaphtidin, strienin v variamin. V(IV) l trng thi oxy ho bn vng nht. Do khng kh c th oxy ho V(III) n V(IV) v kh nh nhng cc vanadat v d bng SO2 dn ti s to thnh cc hp cht ca V(IV) loi hypovanadat. Hu nh tt c cc phc ca V(IV) u cha ion vanadi ho tr 3 V(H2O)63+ v mui hydrat ho ca n loi VX3(H2O)6 (X = F, Cl, Br , I). V(III) to phc vi nhng phi t cha oxy cng nh cha nit. Ion ny cng to mu vng vi ion thioxyanat trong dung dch axit trong axeton phn ng cn c ng dng trong ho phn tch. Trong dung dch kim vanadi tc dng vi ion sunfit to thnh ion thiovanadat c mu. Phn ng ny khng nhy lm. Phn ln nhng phng php xc nh vanadi(V) c thc hin trong mi trng axit hay axit yu lc ny ch yu tn ti cc dng cation VO2+ v VO(OH)2+. Nhng ion ny to phc bn vng nht ca mnh vi phi t anion. Trong vng pH=3-5, V(V) to vi cuphoron, 8-oxyquinolin v dietylditiocacbamat nhng phc b chit bng clorofoc c s dng tch v xc nh vanadi-salisin hydroaxmic axit v benzoilphenylhydroxylamin l nhng thuc th o mu khc ca nguyn t ny. Trong mi trng axit hn V(V) to sn phm mu vi hydro perooxyt v tng tc vi axit photphoro vonframic to axit photphoro vonphramovanadic tan, mu vng.

Ion vanadil VO2+ to phc mu vi pyrocatechin trong dung dch c pH = 4.5-6. V(IV) phn ng vi formaldoxim to phc mu vng trong dung dch kim. VNG Trong dung dch nc ion n gin Au+ t oxy ha t kh n Au v Au(III), do Au(I) ch bn vng di dng nhng phc cht loi Au(CN)2- v AuCl2- hoc l di dng cc cht ho tan rt km nh AuCN v AuI l nhng kt ta thu c khi thm ion xyanua hoc ion iodua vo dung dch Au(III). Trong dung dch axit yu vng to vi p-dimetylaminobenziliderodamin phc mu t tan trong Au(I) lin kt qua nit d vng. C th chit phc bng hn hp benzen-clorofoc. Au+ c cu hnh in t d10 v c u th to phc thng hng. S to phc xy ra mt cch u th vi nhng phi t phn cc c bit l trong trng hp khi m lin kt cho c th hnh thnh. Au(III) tn ti ch yu di dng phc, l cht oxy ho mnh. Do c th xc nh gin tip vng bng cch o mu sn phm oxy ho cc cht hu c loi o-toludin baz leuco ca lc malachit v o-dianizidin ca Au(III). Ngc li Au(III) c th tch vng bng cch lc dung dch ca n vi Hg2Cl2 rn. Mt khi dng SnCl2 lm cht kh th TeCl4 b kh n Te v Te mi b kh c dng lm cht gp Au. Au(III) to nhng phc c trng vi cc ion halogenua. C th chit HAuCl4 bng cc dung mi hu c cha oxy. V d nh etylaxotat t cc dung dch HCl c nng ln hn 0.3M. Ion i c mu to bi axit ny vi rodamin B b chit bng disiopropyl ete hoc benzen. Mt cch tng t c th chit HAuI4 t dung dch HI 6.9M v HAu(NO3)4 t HNO3 8M bng dietyl ete. Au(III) c khuynh hng to lin kt cng ho tr rt mnh. VOLFRAM Tnh cht ho hc ca Volfram v molybden kh gn nhau ch tr ngoi l l trng thi ho tr cao ca volfram bn hn molybden v volfram c tnh baz ln hn (tnh axit yu hn). Trng thi ho tr quan trng nht ca volffram l IV, V v VI. Oxyt WO3 l i din cho W(VI), tan c trong kim to thnh ion volfram WO42-. Trung ho hoc axit ho dch th axit volfram trng hp s lng xung thnh kt ta trng. Tng t nh ion molybden, ion volfram cng c th to cho axit d a. Phng php tch W(VI) khi nhng nguyn t cn tr s xc nh u da trn c s ho tan trong kim oxyt ca n cng vi nhng cht cng kt nh Fe(OH)3, Al(OH)3 hoc l asenat ch kh trung ho bng amoniac hoc hexametylen tetramin. S khc nhau v bn ca nhng phc tactrat molybden v volfram cho php tch Mo khi W bng cch kt ta MoS3 t dung dch axit. Tng t nh molybden v volfram to kt ta vi n-benzoinoxim (b chit bng clorofoc) v cuphoron (b chit bng ru isoamilic). Trong dung dch HCl long rodamin B tc dng vi axit volframic lm cho mu ca dung dch chuyn t vng n tm. C th s dng phn ng ny trong phn tch bng cch o s gim cng pht huynh ca rodami B. Dithiol to vi W(VI) hp cht mu xanh lc b chit bng cc dung mi hu c. Trong phn ng ny phc 1:3 c to thnh. Trong dung dch axit sunfuric nng cao W(VI) (cng nh Mo(VI) v Ti(IV)) phn ng vi hydroquinon to nhng cht mu cha r cu to. Khi cho tng tc W(VI) vi cc phi t cha oxy, halogenua, thioxyanat v xyanua ta thu c nhm phc ln nht ca volftram. C th nu WOCl52-, WOCl4-, [WO2(C2O4)2]3- v [W(CN)8]3lm v d cho nhm phc ny. Mt trong nhng phng php xc nh volfram quan trng nht da trn s to phc thioxyanat. Trc khi trn ln nhng thuc th cn gi W(VI) trong dung dch kim

hay trong dung dch tactrat trnh to nhng hp cht keo hoc trng hp. C th o mu phc mu trc tip trong dung dch nc. ngi ta n nh phc bng axeton hoc l chit bng propyl ete hoc bng mt dung mi cha oxy khng trn ln vi nc khc. Kh axit volfram bng thic trong mi trng HCl ta thu c [W(CH)Cl5]2-. Mt phc khc ca W(IV) l W(CN)84- phc ny b Co(IV) hoc permanganat oxy ho n W(CN)83-. Cho n nay phc ca W(IV) vn cha c ng dng trong phn tch. ZIRCONI Trong cc phc ca mnh, Zr c ho tr 4, oxyt hydrat ho ca n ZrO2(H2O)x khng tan trong cc dung dch kim. Do kh tch 4 in t khi kim loi nn nhng lin kt to thng c tnh cng ho tr. V vy ZrCl4 ct c 3500C v bc khi trong khng kh m. Kch thc ca nguyn t Zr cho php n c th c phi tr 8 v d nh trong cc phc oxalat, tetraaxit axetylaxetonat. Do s thy phn ni phn t ca hp cht Zr nn ion Zirconyl ZrO2+ (to mt lot mui kt tinh) v nhng ion [Zr(OH)3]+, [Zr2O3]2+ c to thnh. Zr2+ c cu hnh in t ca kh tr kripton v do kh bin dng (hiu ng ny tng ln mt cch ng k khi tng in tch hnh thc ca cation). Zr to phc bn vng nht vi nhng phi t anion khc c bit l vi nhng anion florua, sunfat, photphat l nhng ion to lin kt c tinh ion nhiu hn tnh cng ho tr. Nhng ion loi ZrF62- v [Zr(SO4)4]4tan c trong nc. Nh tan thp ca zirconyl photphat trong HCl hoc H2SO4 1N m ngi ta c th tch Zr ra khi cc kim loi khc. Khi to phc vi hu nh tt c cc thuc th hu c Zirnori (di dng ZrO2+) to nhng vng cng su hoc nm thnh phn trong c kim loi lin kt vi 2 nguyn t oxy. C th nu trng hp cupheron kt ta zconi t mi trng axit mnh di dng phc tetraoxy b chit bng clorofoc v trng hp tenoyl trigloraxeton to phc b chit bng xylen t dung dch HCl 6M. Nh d on, EDTA v ion xyttrat, tactrat to phc rt bn vi zconi t hp cht vng 4 to thnh 2 nguyn t oxy ca nhm aseno tham gia to lin kt. Axit mindalnic v nhng dn xut brom, clo ca n l nhng cht kt ta c hiu qu khc. Chng to vi zirconi nhng phc tetraoxy khng tan c th cn hoc chun oxy ho. Cng c th l mi l mi anion ca phi t lin kt vi kim loi khng ch bng nhm cacboxyl m c bng nguyn t oxy ca nhm ru to hp cht ni phc. Trong nhng thuc th to sn mu m t tan nguyn t oxy phenol ng vai tr nguyn t hot ng. Nhng thuc th loi ny bao gm alizarin S, cloranilic axit, hematexylin morin (phn ng hunh quang) phenylfluoron, purpurin pyrocatesintin, v toron. Tnh cht ho hc ca Zr v Hf ging nhau n mc l ngi ta thng xc nh nhng kim loi ny cng vi nhau nh l Zirconi nu khng s dng nhng phng php vt l nh quang ph pht x hoc quang ph pht x tia la in. Gn y ngi ta cng b cch xc nh ring bit Zr v Hf bng xylen da cam hoc metyl xanh. Sau khi o ph quang k tng s phc ca Hf v Zr trong mi trng axit ngi ta thm nc oxy gi vo cn Zr. Ngi ta cng nghin cu thnh cng phng php tch phn tch Zr v Hf di dng phc sunphat trn nha anionit. Asenazo III v picramin R l nhng thuc th c mu xc nh Zr c trin vng nht. Dng asenazo III c th xc nh Zr khi c Cu, Mo, Nb v V, Th, Ti, U(IV) v nhng nguyn t t him cn tr php xc nh.

LI NI U
Thuc th h c l mt trong nhng lnh vc quan trng trong Ho hc phn tch. T phng php phn tch c in n phng php phn tch hin i u c s gp mt ca thuc th hu c trong vic tch, chit vi mc ch lm giu mu hoc ch th hoc lm tng nhy ca php phn tch. Hin nay, c rt nhiu thuc th hu c khc nhau, mi cht li c nhng tnh cht c trng ring v mu sc, nhit nng chy, kh nng ho tan v kh nng to phcV vy, 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. Ngoi ra, nu bit c tnh cht ca thuc th, nh phn tch cng c th nh hng tng hp cc thuc th mi u vit hn. Cun sch Thuc th hu c c ti bn ln th 2 c bin son b sung thm mt s phn v cu trc nh sau: Phn I: L thuyt ca thuc th hu c: 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, Tnh ton mt s hng s ca thuc th hu c v phc ca chng . Phn II: Cc v d v thuc th. Chng ti c gng bin son phn ny theo hng u tin lin kt, to phi tr ti cc nhm nh O-O, O-N, -N=N-ca

thuc th nhm gip ngi c nhn nh v vn dng l thuyt thuc th trong thc t. Phn III: Tnh cht phn tch ca cc ion ion kim loi. Phn ny cung cp thng tin v s phi tr, c im cu to cng nh cc thuc th thng dng ca ion kim loi. D rt n lc trong qu trnh bin son, nhng khng trnh khi thiu st. Chng ti trn trng cm n nhng kin ng gp ca cc bn c gn xa ln xut bn sau c hon chnh hn.
Chng ti xin cm n Nh Xut Bn i hc Cng Nghip Tp. H Ch Minh tch cc gip cun sch ny ra i kp thi n vi bn c CC TC GI