Hoa Vo Co ND Van t2

PGS.
NGUYN C VN
HO HC V C
TP 2 (CC KIM LOI IN HNH) (In ln th ba) Dng cho sinh vin cc trng i hc, cao ng v gio vin trung hc chuyn ngnh Ha
NH XUT BN KHOA HC V K THUT H NI
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"HA HC V C"- Tp 2 (Cc kim loi in hnh) c bin son theo chng trnh Ha hc V c - Khoa Ha hc - Trng i hc S phm H Ni, da trn c s cc bi ging m tc gi ging dy trong nhiu nm cho sinh vin Khoa Ha hc ti Trng i hc S phm v Ni. Ni dung cun sch cp n mt s kin thc c bn v kim loi ; v trng thi thin nhin, v phng php diu ch, tnh cht l, ha hc ca cc n cht v hp cht ca cc kim loi in hnh, ng thi cng l ni dung thng c ging dy trong chng trnh Ha hc V c cc Trng i hc v mt phn Trng Trung hc ph thng Nhng kim loi cn li khng cp n trong sch, tc gi s trnh by trong tp 3 "Cc kim loi chuyn tip". V vy ni dung sch khng ch dc s dng cho sinh vin ngnh Ha hc - Trng i hc S phm, m cn h tr cho gio vin mn Ha hc cc Trng Trung hc ph thng lm ti liu tham kho trong qu trnh ging dy. Ngoi ra cn c th gip ch cho sinh vin hc mn Ha hc V ca cc Trng i hc khc v cc Trng Cao ng. Chc chn rng cun sch khng trnh khi thiu st, tc gi xin trn trng cm n nhng nhn xt ng gp ca bn c. Tc gi
CHNG 1 I CNG V KIM LOI 1. 1. S phn b kim loi trong thin nhin. V tr kim loi trong bng tun hon (1) Mt trong nhng c tnh quan trng ca cc nguyn t ha hc l tnh ph bin trong thin nhin. Hu ht cc kim loi u c trong thnh phn v qu t, c trong nc i dng, trong c th sng vi mc nhiu t khc nhau. y Trong v qu t (phn thch quyn) cc kim loi Al, Na, Fe, Ca, Mg, K, Ti, Mn v mt s phi kim khc... l nhng nguyn t c ph bin ln nht. Trong bng 1 di y l thnh phn phn trm v s nguyn t v phn trm v khi lng ca cc nguyn t : Bng 1. Thnh phn cc nguyn t c ph bin cao trong thch quyn
Nguyn t % nguyn t % khi lng Nguyn t % nguyn t % khi lng O Si Na Ca K C Mn S 58 20 2,4 2,0 1,4 (1,5.10-1) 3,2. 10-2 3,0. 10-2 47,20 27,60 2,64 3,60 2,60 (1. 10-1) 9. 10-2 5: 10-2 H Al Fe Mg Ti P N 3,0 6,6 2,0 2,0 2,5. 10-1 5. 10-2 (2,5. 10-2) (0.15) 8,80 5,10 2,10 6. 10-1 8. 10-2 (1.10-2)
y Trong nc i dng, cc kim loi c hm lng cao nht l Na, Mg, K, Ca ng vi thnh phn nh sau: Na : chim 1,0354% (khi lng); 10,354 mg/l. Mg : chim 0,1297% (khi lng); l,297mg/l. K : chim 0,0388% (khi lng); 387,5 mg/l. Ca : chim 0,0408% (khi lng); 408,0 mg/l. y Nhng kim loi chim thnh phn cao trong cc c th sng, c thnh phn phn trm v khi lng nh sau :
Ca :5. 10-1% K :3. 10-1% Mg :4. 10 -2% Na : 2.10-2% Fe:1.10-2% Al:5.10-3% Ba : 3.10-3% Sr:2. 10-3% Mn: 1. 10-3% Zn:5. 10-4% Cu:2.10-4%
(2) Hu ht cc nguyn t ha hc l kim loi, chim hn 80% tng s nguyn t. Trong bng tun hon cc kim loi c xp phn bn tri v pha di ca bng v c th coi Be, Al, Ge, Sr, Po l nguyn t gii hn. Cn phn bn phi pha trn ca bng l cc nguyn t phi kim v gii hn l B, Si, As v Te.Vy gia kim loi v phi kim c mt ranh gii gn ng l ng thng nm
gia hai dy nguyn t nu trn. Cc nguyn t gii hn nm cnh ng ranh gii c xem l cc nguyn t bn kim. Tm li, cc nguyn t chuyn tip, cc nguyn t nhm la v IIA, cc nguyn t nng nhm IIIA, IVA, VA u l kim loi. Bng 2. V tr ca kim loi, bn kim loi v phi kim loi trong bng tun hon
1 H 3 Li 11 Na 19 K 37 Rb 55 Cs 87 Fr 88 Ra 56 Ba 38 Sr 12 20 Ca Mg 21 - 30 Sc - Zn 39 - 48 Y - Cd 57 - 80 La - Hg 31 Ga 49 In 81 Tl 82 Pb 50 Sn 83 Bi 4 Be 13 Al 32 Ge 51 Sb 84 Po 5 B 14 Si 33 As 52 Te 85 At 6 C 15 P 34 Se 53 I 86 Rn 7 N 16 S 35 Br 54 Xe 8 O 17 CI 36 Kr 9 F 18 Ar 10 Ne 2 He
(3) Xt v cu trc lp v electron th hu ht cc kim loi c t 1 n 3 electron lp v ngoi cng: Cc kim loi nhm la v IIA c s electron lp v ngoi cng l ns1 -2 (n l s th t chu k). V d vi Na (3s1); Ca (4s2). y Cc kim loi t nhm IIIA n VIIA c s electron lp v ngoi cng l 2 ns np1 - 5. V d Al (3s2 3p1) ; At(6s26p5) y Trong chu k 4, sau khi xy dng xong lp 4s. cc nguyn t t 21 nhm IIIB (Sc) n 30 nhm IIB (Zn) hp thnh dy kim loi chuyn tip th nht, c cu hnh electron ngoi cng l 3d1 - 10 4s1 - 2. V d : (21) Sc (30) Zn 1 2 3d10 4s2 3d 4s Trong dy ny c hai sai lch l Cr c cu hnh 3d54s1 khng phi l 4 2 3d 4s ; Cu c cu hnh 3d104s1 khng phi l 3d94s2. Hin tng sai lch l do s khc nhau rt t v nng lng cc phn mc nng lng (n - 1)d v ns cc nguyn t chuyn tip gy ra. y Trong chu k 5, c 10 kim loi chuyn tip t 39 nhm IIIB(Y) n 48 nhm IIB (Cd) c cu hnh lp ngoi cng l 4d1 - 10 5s1 - 2. V d (39) Y (48) Cd 1 2 4d10 5s2 4d 5s Nhng s sai lch v cu hnh electron trong chu k ny cng c mt ngun gc nh trn. Nh vy, cu hnh electron ca cc kim loi thuc hai dy chuyn tip trn c dng chung l: (n - l)d1 - 10 ns1 - 2
y Trong chu k 6, ngoi 10 kim loi h d c cu hnh nh trn, cn c 14 nguyn t kim loi h f t 58 (Ce) n 71 (Lu). Dy nguyn t ny khng ng vi dy nguyn t no cc chu k trn, c gi l cc nguyn t (kim loi) t him hay cn gi l cc nguyn t h lantan (lantanoit). Lp v electron cc lp ngoi cng l : 4f2-14 5d0-l 6s2 V d: (58) Ce (64) Gd (71) Lu 2 7 1 2 4f 5d 6s 4f14 5d1 6s2 4f 6s Nhng sai lch trong dy ny l do s khc nhau rt t v nng lng ca cc phn mc (n - 1)d v ns; (n - 2)f v (n - 1)d gy ra. Trong chu k 7, c 14 nguyn t kim loi thuc h f t 90 (Th) n l03(Lr) cng c lp v tng t. 1.2. Cu trc tinh th ca kim loi y trng thi rn, hu ht cc kim loi u kt tinh theo ba dng mng tinh th chnh l: mng lc phng (lp), mng lp phng tm din (lptd) v mng lp phng tm khi(lpth).
Hnh 1. Ba dng mng tinh th ca kim loi : (1) mng lc phng: (2) mng lp phng tm din; (3) mng lp phng tm khi. Mt s kim loi kt tinh mng hn hp ; mt s kim loi tu theo nhit m c dng khc nhau. V d coban kt tinh theo mng hn hp lc phng v lp phng; scani 250C tinh th c mng lp phng tm din, nhng nhit cao li c mng lc phng (hnh 1). Trong cc kiu mng tinh th, cc nguyn t ca cng kim loi c xem l nhng ht cu c kch thc nh nhau v xp c st vo nhau thnh tng lp, mi ht cu c bao quanh bi 6 ht khc, v nu ni tm ca cc ht cu bng cc on thng s c nhng hnh tam gic u dnh st hnh ny vi hnh kia (hnh 2). Nu xp mt lp ht cu th hai ln lp th nht, cho cch xp c kht nht cc ht cu lp th hai phi xp vo ch lm ca lp th nht, lc mt
phn s ch lm ny c che khut (1) s ch lm cn li khng b che khut (2) bi lp th hai (hnh 3).
Hnh 3. Cch xp lp ht cu th hai ln lp th nht:. (1) lm b che bi lp th hai : (2) lm cha b che bi lp th hai; (3) lm ca lp th hai. y Khi xp lp th ba ln lp th hai xy ra theo hai cch khc nhau. Cch th nht : Xp cc ht cu lp th ba vo cc lm (3) ca lp th hai, lc cc ht cu lp th ba ng trn cc ht cu ca lp th nht v ht cu lp th t ng trn lp th hai (hnh 4).
Hnh 4. Cch xp lp ht cu th ba ln lp th hai. y Nh vy, lp th nht v lp th ba tng ng vi nhau v c k hiu l

ABA. Nu tip tc chng thm, lp th hai tng ng lp th t, lp th ba tng ng lp th su... v c dy ABABAB. Cch sp xp ny to ra mng tinh th lc phng.
Trong mng lc phng (hnh 1 v hnh 5) cc ht cu chim 74% th tch ca kim loi, mi nguyn t kim loi c bao quanh bi 1 2 nguyn t kim loi khc (6 nguyn t cng lp, 3 nguyn t lp trn v 3 nguyn t lp di), v vy trong tinh th mng lc phng, nguyn t kim loi c s phi tr l 12. y Cch th hai : cc ht cu lp th ba xp vo cc lm ca lp th hai, che khut cc lm(2) (hnh 3), lc lp ny khng tng ng vi hai lp trc v cch sp xp c k hiu l ABC, ngha l ht cu lp th ba khng ng trn lp th nht (hnh 6).
Khi thm lp th t, th nm... ht cu lp th t chng ng trn ht cu lp th nht, th nm trn lp th hai...(hnh 7) v to ra dy ABCABC... cch sp xp ny to ra mng lp phng tm din, cc ht cu chim 74% th tch ca kim loi. Cng nh trong mng lc phng, trong mng ny mi nguyn t kim loi cng c bao quanh bi 1 2 nguyn t kim loi khc, nn nguyn t kim loi c s phi tr l 12.
y Cng cch sp xp nh trn nhng khi mi nguyn t kim loi ch c 8 nguyn t nm gn nht (thay cho 12 nguyn t) mc d y cn c 6 nguyn t ca lp tip theo nhng khong cch ln hn 15%. Cch sp xp ny ch bng 92% mt c th c ca cch sp xp lc phng v lp phng tm din, ngha l th tch ca kim loi ch chim 68% th tch kim loi to ra mng lp phng tm khi. S phi tr ca kim loi trong mng ny l 8. y S phn b ba dng mng tinh th ca cc kim loi trong bng tun hon c dn ra hnh 9.
Hnh 9. Cc kiu cu trc mng tinh th ca cc kim loi trong bng tun hon.
(lptd : lp phng tm din: lp: lc phng: lptk: lp phng tm khi : mt s k hiu lng vo nhau th ki hiu to nht l dng cu trc bn 250C : k hiu lp/lptd l cu trc dng hn hp).
Ni chung. a s kim loi khi kt tinh u theo mng lc phng v mng lp phng tm din vi s phi tr l 12; cc cu trc ca kim loi u khc mt t so vi cu trc tinh th l tng; c bit l cu trc lc phng. Ni cch khc, s phn b cc nguyn t kim loi hon ton ng theo kiu mng li khng gian nh nu trn, lp li mt cch tun hon cht ch theo
ba chiu trong ton b tinh th, ch c th xy ra trong trng hp l tng, khi m iu kin kt tinh khng gy ra s bin i no trong cu to ca n. Thc t, a s trng hp, do s hnh thnh tinh th lun lun din ra trong nhng iu kin lm cho hnh dng bn ngoi ca tinh th b bin i, hoc lm cho cu trc bn trong ca tinh th c s sai lch no v s phn b hnh hc hoc thnh phn ca tiu phn. C th c nhng trng hp sau: Mng tinh th c th thiu mt s nguyn t kim loi nt no ca mng [ gi l mng khuyt Stky (Schottky)] cng c th c nhng nguyn t kim loi nm khong gia cc nt no 1 [gi l mng khuyt Phrenken (Frenkel)]; ngoi ra cng c th nt b thay th bi mt nguyn t kim loi khc (hnh 10).
1.3. Thnh phn v cu trc tinh th ca hp kim (1) Hp kim l vt liu c tnh cht ca kim loi m thnh phn gm mt kim loi c bn v mt kim loi khc hoc mt phi kim no . V d : loi hp kim thp khng g c thnh phn 80,6% Fe, 18% Cr, 1% Ni v 0,4% C; hp kim Wood c 50% Bi, 25% Pb, 12,5% Sn, 12,5% Cd... Da vo thnh phn v cu trc ca tinh th ngi ta chia hp kim thnh cc loi l hp kim dung dch, hp kim d th v hp cht gia cc kim loi (cc metalit). (2) y Hp kim dung dch hay cn gi l dung dch rn l mt hn hp ng th m cc cu t phn b ng u nh khi nng chy. Nguyn t cht tan c th chim v tr ca kim loi dung mi (nt ca mng li) hnh thnh mng tinh th hn tp kiu thay th, hoc c th xm nhp khong gia cc nt ca mng li hnh thnh mng tinh th hn tp kiu xm nhp. y Hp kim kiu thay th c hnh thnh khi hai nguyn t kim loi c bn knh tng t nhau v c bn cht lin kt ha hc ging nhau. V d Ag v Au u c bn knh nguyn t l 1,44 ; Cu v Ni c bn knh tng ng l 1,24
0 0
A v
1,28
A u c th to ra hp kim c mng tinh th dng thay th (hnh 1la).
Khi hai kim loi c bn knh khc nhau vo khong 15% th ha tan ca kim loi ny trong kim loi kia s b hn ch. Trong kiu hp kim ny cc cu t thm nhp c bn knh cng ha tr b hn nhiu so vi bn knh ca nguyn t dung mi. in hnh cho loi cu t xm nhp ny l cc phi kim. V d, cacbon
c bn knh cng ha tr l 0,77 A c th xm nhp vo mng tinh th ca st c bn knh l 1,27 A , to thnh thp cacbon. Thp cacbon c mng tinh th hn tp kiu xm nhp lm cho hp kim cng hn, bn hn v do hn (hnh 11b). (3) Trong cc hp kim d th cc cu t u khng phn tn ng u. Chng hn trong qu trnh luyn thp to ra hn hp peclit c cha hai pha ring bit l Fe - v xementit Fe3C trn ln mt thit vo nhau v hp cht ostenit l hn hp gm Fe - ~ v Fe3C. Cc hn hp u l hp kim d th.
0
(4) y Bn cnh cc loi hp kim trn, mt s kim loi c kh nng tng tc vi nhau, hnh thnh tinh th hp kim kiu hp cht gia cc kim loi. Thnh phn v cu trc ca loi hp kim ny c th xc nh bng cch da vo nng electron trong mng tinh th. Nh bit, nng clcctron trong hp kim c mng lp phng tm khi l 1,5 ; cn trong mng lc phng l 1,75. Chng hn, hai kim loi Cu v Zn khi to ra hp kim mng lp phng tm khi th c thnh phn n gin l Cuzn, cn nu to ra mng lc phng th c thnh phn l CuZn3, v cu C mt electron ha tr (s1), cn Zn c 2 electron ha tr (s2). Bng cch c th cho thy cc metalit AgZn, AgMg, Cu3Al, Cu5Zn u c cu trc lp phng tm khi ; cn cc hp kim Ag5Al3, Ag13Sb3, Cd3Li, Cu3Si u C Cu trc lc phng. y Tuy nhin trong a s cc metalit c bit l cc kim loi d c phn phc tp hn, do thnh phn v cu trc ca chng khng th p dng qui tc trn m c xc nh bng phng php thc nghim. Chng hn trong mng tinh th ca Cu v Au, cc nguyn t Au chim nh ca hnh lp phng, cn cc nguyn t Cu li phn b tm ca mt gii hn; mi nguyn t Au c phi tr bi 12 nguyn t Cu, cn mt nguyn t Cu c phi tr bi 4 nguyn t Au, do cng thc n gin ca hp cht to thnh l Cu3Au (hnh 12). Thnh phn ca cc hp cht gia cc kim loi phn ln khng ph hp r rt vi ha tr ca nguyn t, v mi cp nguyn t to thnh khng phi mt m mt s hp cht gia kim loi. Th d Na to nn vi Sn v Hg cc hp cht sau: NaSn5, NaSn4, NaSn3, NaSn2, NaSn, Na4Sn, Na3Sn, Na2Sn, Na4Sn3; NaHg4, NaHg2, NaHg, Na3Hg, Na3Hg2, Na5Hg2, Na7Hg8 ; trong s ch c Na2Sn v Na4Sn l ph hp vi ha tr bnh thng ca
nguyn t.
Ngi ta cng nhn thy rng mt s kim loi khi nng chy to ra hn hp ng nht, nhng khi kt tinh li to ra hn hp tinh th ring bit ca tng kim loi, nh hp kim Sn v Pb. Mt s kim loi trng thi lng hu nh khng tan vo nhau nh cc cp : Ag - Fe Fe - Pb Cd - Al Na - Al Al - Ti K - Mg K - Al Ag - Cr Thng thng th nhng kim loi nng chy ch trn ln vo nhau mt phn v trong cc trng hp , ngi ta cng thy kim loi c nhit nng chy cao ha tan kim loi c nhit nng chy thp d hn so vi trng hp ngc li. 1. 4. Lin kt kim loi (1) y Nh nu trn, cu trc kim loi l cu trc c trng cho kim loi trng thi rn (v lng). Bn cht lin kt ha hc trong kim loi lin quan n hai tnh cht c bn l tnh dn in, dn nhit tt v iu kin thng l cht kt tinh c s phi tr cao. y T cc tnh cht , dn n kt lun rng trong tinh th ca kim loi phi c mt phn electron c kh nng di chuyn trong ton khi kim loi. Trong tinh th kim loi, cc nguyn t kim loi li rt ging nhau, nn khng th hnh thnh kiu lin kt ha hc nh trong hp cht ion! Mt khc, cng khng th hnh thnh kiu lin kt nh trong hp cht cng ha tr, v s electron ha tr ca nguyn t kim loi khng to nn lin kt hai electron vi cc nguyn t phi tr! (2) y L thuyt u tin gii thch cc tnh cht ca kim loi l thuyt "kh electroll". Theo thuyt ny th trong tinh th kim loi c mt phn electron ng thi lin kt vi nhiu nhn, nhng electron ny tch ra t cc nguyn t kim loi, di chuyn t nguyn t trung ha ny n nguyn t b ion ha khc, m khng thuc v mt nguyn t nht nh no. Khi khng c tc dng ca in trng
ngoi, nhng electron ny chuyn ng hn lon trong khi kim loi theo mi phng tng t nh chuyn ng nhit ca cc phn t kh trong mt th tch no (v vy gi l thuyt kh electron !). y Vy nhng electron no tham gia vo m kh electron?. l nhng electron d dng ri b nguyn t kim loi nht, tc l cc electron ha tr. Tuy nhin khng nht thit l tt c cc electron ha tr u tham gia vo m kh electron, thng thng th s electron t do ny bng s nguyn t kim loi. Trong qu trnh chuyn ng cc electron t va chm vo nhau v kch thc b, nhng khng ngng va chm vo cc nguyn t ion ha. y C th hnh dung rng trong tinh th kim loi, cc nguyn t khng trng thi trung ha vnh cu, m trng thi ion ha thng xuyn i mi, qu trnh bin i thng xuyn xy ra, nn trong tinh th kim loi lun lun c mt s electron c tnh di ng cao, lc no cng c nhng nguyn t kim loi d b ion ha, v ch ny hay ch kia trong mng tinh th c mt s trng thi trung ha. Chnh nh c tng tc gia m kh electron vi cc ion, gy ra lin kt kim loi, bo m tnh bn vng ca mng tinh th. Khi c tc dng ca in trng ngoi, m kh electron chuyn ng theo mt chiu, hiu ng ny gy ra dng in kim loi. Trong chuyn ng , cc electron va chm mnh vo cc ion kim loi, nn mt phn ng nng chuyn thnh nhit gy ra hiu ng Joule ca dng in. Khi nhit tng, chuyn ng nhit ca electron v ion kim loi c tng cng, lm ri lon chiu chuyn dch ca electron, kt qu dn in gim tc l in tr tng. Thuyt kh electron cng gii thch c ti sao kim loi dn in tt, ng thi cng dn nhit tt. Cc electron t do trong kim loi tham gia vo chuyn ng nhit, v nh c tnh di ng ln, nn d dng san bng nhit, ch nng chng chuyn ng mnh, c ng nng ln v khi n ch lnh hn, th qua va chm vi cc con kim loi, s nhng bt ng nng v bng cch s ti nhit t ch nng n ch lnh. (3) y Mc d thuyt kh electron gii thch nh tnh c nhiu tnh cht ca kim loi, nhng li gp kh khn ln nht l khng th gii thch c gi tr thc nghim v nhit dung nguyn t ca kim loi l xp x 6 cal/ mol. Gi tr thc nghim ch c gii thch bng cch loi b dao ng ca cc electron "t do"trong mng tinh th m ch k n nhng dao ng ca nguyn t v ion trong mng, nh vy cc electron "t do"- xem nh cc phn t kh - khng c vai tr gy ra nhit dung ca kim loi, iu mu thun vi thuyt "kh electron". y Mu thun c gii quyt trn c s ca thuyt Mo p dng cho h cha mt s ln nguyn t, ngha l coi kim loi nh mt h nhiu nhn m trng thi ca electron trong h ging nh trng thi ca electron trong phn t. Thuyt Mo coi mt mu kim loi l mt phn t. ti mt ca mng li c cc ion kim loi. cn cc m my electron ca cc electron ha tr bao quanh cc ion kim loi v lin kt vi chng, ngha l cc electron ha tr trong "trng chung" ca tt c cc ion kim loi.
y Nh bit, theo thuyt Mo th khi hai nguyn t tng tc vi nhau s c s xen ph cc obitan phn t lin kt v phn lin kt, lc mi mc nng lng nguyn t s tch ra thnh hai mc nng lng phn l. Nu h c bn nguyn t th mi mc nng lng nguyn t s tch ra thnh bn, ngha l hnh thnh bn obitan phn t. S nguyn t trong h cng ln th s Mo cng ln v mi Mo ng vi mt trng thi nng lng xc nh. Nh vy trong tinh th c N nguyn t s to nn N obitan phn t. V N rt ln (v d 1 cm3 tinh th kim loi c khong 1022 - 1023 nguyn t) nn N mc nng lng rt gn nhau to ra vng nng lng. S khc nhau v nng lng ca cc trng thi electron trong gii hn ca vng ch khong 10-22 eV, nn c th coi s bin thin nng lng ca electron trong vng l lin tc. Cc obitan ca vng nng lng cng xem nh l cc obitan nguyn t trong phn t, v cung tun theo nguyn l Phauli, l mi obitan cng ch cha hai electron, v s in electron vo cc obitan cng tun theo ng trt t mc nng lng t thp n cao. Nh vy s electron cc i trong vng sinh ra do s xen ph cc obitan nguyn t s, p, d, f s l 2N(vng s), 6N(vng d) v 14N (vng f).
Trong trng hp kim loi, nhng vng nng lng gn nhau c th tip gip vi nhau hoc cch xa nhau. Vng nng lng cha cc electron gy ra lin kt ha hc gi l vng ha tr. Vng t do c mc nng lng cao hn, phn b pha trn vng ha tr gi l vng dn. Ph thuc vo cu trc v mng tinh th m hai vng c th xen ph vo nhau hoc khng xen ph vo nhau, ngha l cch nhau mt khong nng lng E no , khong cch ny gi l vng cm. Trong tinh th kim loi xy ra s xen ph ca hai vng ha tr v vng dn, trong cht bn dn vng cm c XE vo khong 0,1 - 3 eV, cn trong cht in mi, E vo khong ln hn 3 eV. (4) Vy thuyt vng nng lng gii thch cc tnh cht c trng ca kim loi nh th no? Ni chung, cc tnh cht vt l c trng ca kim loi u gy ra bi cc electron vng ha tr. S electron xp trong vng ha tr ph thuc vo s electron ha tr ca nguyn t. Nu nguyn t c mt electron ns th vng nng lng s ch mi c xp mt na s electron ti a; nu nguyn t c hai
electron ns th vng nng lng s xp s electron; cn nu tt c cc mc nng lng trong mt vng u b electron chim ht, th cc electron khng th chuyn ng t do trong vng m ch c th chuyn ng gii hn trong phm vi cc obitan phn t ca chng (hnh 14 -3). Nu trong vng nng lng cn c nhng obitan phn t cn trng (cha b electron chim hon ton) th nhng electron no c nng lng gn nht vi nng lng ca obitan s chuyn ti chim cc obitan ny, cn cc v tr c ca cc electron di chuyn s c cc electron khc ti thay th ; nh vy electron c th chuyn ng hn lon trong vng nng lng khng b chim hon ton ny (hnh 14 - la). Khi cc electron b kch thch (v d tc ng ca in trng ngoi) s chuyn ng theo phng ca trng ngoi v pht sinh ra dng in (hnh 14 - 1b). Cc kim loi nhm IA, IB v cc kim loi chuyn tip c lp v
Hnh 14. S cc vng nng lng v vng cm trong cht c mng li kim loi: 1. vng dn; 2. vng nng lng b chim nhiu nht khi ~XE = 0: a) khi khng c n trng : b khi c in trng. (vng b chim v vng dn tip gip nhau); 3. vng nng lng b chim hon ton khi ~XE > 0 : a) cht bn dn : b) cht cch in. (vng b chim v vng dn cch nhau mt khong ~XE).
Ki hiu. Chiu chuyn dch hn lon ca electron. Chiu chuyn dch c hng ca electron. (11 - 1)d cha xp s electron (l nhng kim loi m trong mng tinh th c vng nng lng cha b chim hon ton) u l nhng cht dn in in hnh. Trong trng hp m vng ha tr b electron chim hon ton nhng li tip gip vi vng trng cha b chim, di tc dng ca trng ngoi cc electron s chuyn ng ln vng trng s lm cho vng b chim hon ton thnh vng dn in (hnh 14 - 2a, 2b). Cc kim loi nhm IIA, IIB - thuc trng hp ny - cng u l cht dn in in hnh. 1 5. Tnh cht l hc ca kim loi Nhng tnh cht l hc ca kim loi nh trng thi, mu sc, v sng, tnh do, tnh cng, khi lng ring, nhit nng chy, nhit si, tnh dn in, dn nhit... u ph thuc vo mng tinh th v vo bn cht lin kt trong kim loi, v vy mun so snh tnh cht vt l gia cc kim loi vi nhau ch c th so snh cc kim loi trong cng kiu mng li (hnh 9). Di y ch nu ln nhng nt tng qut v cc tnh cht nu trn. (1) iu kin thng tt c cc kim loi u trng thi rn, tr thy ngn trng thi lng v cng v do hin tng chm ng nn xezi (Tnc = + 280C) v gali (Tnc= + 300C) cng thng trng thi lng. trng thi t do a s kim loi u c mu trng bc, mt s kim loi c mu c trng ch yu l cc kim loi chuyn tip, chng hn Cu - mu , Au mu vng, Bi - mu nht, Pb - mu trng xanh. Mt s kim loi dng tm v dng phn tn (bt, vn) c mu sc khc nhau. Th d Cu tm c mu , nhng Cu bt c mu gch ; Pb tm c mu trng xanh nhng bt li c mu xm... Trong thc t, mu sc ca mt s kim loi c thay i t nhiu do s hnh thnh cc oxit trn b mt ca kim loi. (2) Tinh th kim loi to nn bi cc nguyn t c s electron ha tr t hn s obitan ha tr, nn lin kt trong kim loi c tnh bin v mnh, v do c im m mng tinh th ca kim loi c th b bin dng di tc dng ca lc c hc, nhng lin kt khng b ph hy, cc lp nguyn t trong mng d dng trt ln nhau gy ra tnh do, d rn, d dt mng, d ko si ca kim loi. Vng l kim loi do nht! (3) Ph thuc vo mng tinh th, vo bn knh ca nguyn t (tc l khong cch gia cc nguyn t ln cn) cc kim loi c cng khc nhau. Trong cc kim loi th cng nht l crom (Cr), v mm nht l xezi (Cs). Bng 3 nu ln cc gi tr v cng ca cc kim loi theo thang cng thp phn cn gi l thang cng khong vt. Theo thang ny cng ca mt cht c xc nh bng phn lc khi rch ln cht nn cng cn gi l thang cng theo phng php rch v ly cng ca hot thch (3MgO. H2O. 4SiO2) lm n v. Nhng kim loi
c cng di 2 c th rch c bng mng tay, c cng di 5 c th rch c bng dao thng v c cng di 7 rch c bng da. T bng 3 ta thy crom c cng gp 8,5 ln cng ca hot thch hay ch bng 85% cng ca kim cng. i cng kim loi 4) Khi lng ring ca cc kim loi cng ph thuc vo mng tinh th v khi lng nguyn t ca kim loi, bin i trong khong rng t 0,5 g/cm3 li n 22,6 g/cm3 osimi. Bng 3. cng ca kim loi theo thang khong vt (phng php rch)(1)
Cr W Re Os lr Ta Ru Ge
8,5 Ti 7,5 Mn 7,0 Nb 7,0 Rh 6,5 Be 6,5 Mo 6,5 Hf 6,0 Co
6 Zr 6 Pd 6 Fe 6 Ni 5,5 Pt 5,5 Cu 5,5 Sb 5,0 Th
5,0 4,75 4,0 4,0 3,5 3,0 3,0 3,0
Al Mg Zn Ag La Ce Au Bi
2,75 Cd 2,5 Ca 2,5 Ga 2,5 Sr 2,5 Sn 2,5 Hg 2,5 Pb 2,25
2 Ba 1,75 TI 1,5 Li 1.5 K 1,5 Na 1,5 Rb 1,5 Cs
1,25 1,0 0,6 0,5 0,4 0,3 0,2
(1) ( hot thch tc bt trc =1 : kim cng ~ 10: than ch = 0.5). Nhng kim loi c khi lng ring D < 5 g/cm3 c gi l kim loi nh v D>5 g/cm3 c gi l kim loi nng. Khi lng ring ca cc kim loi nu trong bng 4. Bng 4. Khi lng ring ca cc kim loi (g/cm3)
Os lr Pt Re Au W U 22,6 Ta 22,5 Hg 21,5 Rh 20,9 Ru 19,3 Pd 19,3 TI 18,3 Th 16,6 Pb 13,6 Ag 12,4 Mo 12,2 Bi 12,0 Cu 11,9 Co 11,5 Ni 11,3 Cd 10,5 Nb 10,3 Fe 9,8 Mn 9,0 In 8,9 Sn 8,9 Cr 8,7 Zn 8,6 Ce 7,9 Sb 7,4 Zr 7,3 La 7,3 V 7,2 Ga 7,1 As 6,9 Ge 6,6 Ti 6,5 Ba 6,2 Al 6,0 Sr 5,9 Cs 5,7 5,4 4,5 3,5 2,7 2,6 1,9 Be Mg Ca Rb Na K Li 1,8 1,7 1,6 1,5 1,0 0,9 0,5
(5) ~ Nhit nng chy ca kim loi ph thuc vo mng tinh th v lc tng tc gia cc tiu phn trong mng. Nhiu kim loi, khi chuyn sang trng thi nng chy, lc tng tc vn cn tn ti,nn nhit nng chy ca chng khng cao; nhng cng c nhiu kim loi li c nhit nng chy rt cao, v lin kt kim loi trong cc mng tinh th ca cc kim loi li rt bn vng. Cc kim loi chuyn tip c nhit nng chy cao hn v cc electron d tham gia vo lin kt kim loi, bn hn so vi electron s v p. Trong cc kim loi chuyn tip th kim loi gia mi dy c nhit nng chy cao nht. v cc nguyn t ny c nhiu obitan ha tr nht na s electron. Cc kim loi khng chuyn tip c nhit nng chy thp hn v bn knh nguyn t ln hn, do lin kt kim loi yu hn.
Trong cc nhm A - th d nhm kim loi kim - nhit nng chy gim t Li n Cs, v lin kt trong kim loi kim l lin kt yu ; khi bn knh nguyn t tng, lin kt li cng yu Gi tr v nhit nng chy ca kim loi nu trong bng 5. Bng 5. Nhit nng chy ca kim loi (Tnc, 0C)
w Re Ta Os Mo Ru Tr 3410 3170 3000 2700 2625 2500 2450 Nb Hf Rh Zr Cr Th Pt 2415 2230 1966 1900 1800 1800 1744 V Ti Pd Fe Co Ni Re 1735 1725 1555 1539 1495 1455 1284 Mn U Cu Au Ag Ge Ca 1250 1133 1083 1063 961 959 851 La As Sr Ba Al Mg Sb 826 814 770 704 660 651 631 Zn Pb Cd TI Bi Sn Li 449 327 321 303 271 232 186 In Na K Rb Ga Cs Hg 156 98 63 39 30 28 -39
(6) y Nhit si ca cc kim loi ph thuc vo lin kt kim loi v bn knh ca nguyn t Trong qu trnh un si kim loi, i hi phi ct t c lin kt gia cc tiu phn, do nhit si thng cao hn nhiu so vi nhit nng chy. y Ni chung, cc kim loi chuyn tip c nhit si cao hn cc kim loi khng chuyn tip. Cng nh nhit nng chy, nhit si ca cc kim loi gia dy c nhit si cao hn, v l do nh nu trng hp nhit nng chy. y Trong cc kim loi kim, nhit si gim xung theo chiu tng ca in tch ht nhn do lc lin kt kim loi gim xung khi bn knh nguyn t tng. Vi gn c nhit nng chy thp, nhng nhit si li cao hn nhiu, v lin kt kim loi mnh trong gali lng khng tng ln nhiu khi chuyn t trng thi lng sang trng thi rn. Hn na, mng li tinh th ca gali khng phi hnh thnh bng cc nguyn t nh cc kim loi khc m bng cc phn t hai nguyn t (d = 2,44 A), ti mt ca mng li l cc phn t Ga2, Phn t cng tn ti trng thi lng; khi si, phn t Ga2 chuyn thnh n nguyn t nn nhit si cao. Gi tr nhit si ca cc kim loi nu bng 6. Bng 6. Nhit si ca cc kim loi (Ts, 0C)
W Re Os Hf Ir Ta
5930 5870 5500 5300 5300 5300
Zr Ru Mo Rh Pt Pd
5050 4900 4800 4500 4400 4000
U V Ti Au Be Co
3500 3400 3260 2970 2970 2900
Ni Ge Cu Cr Sn Ag
2730 2700 2600 2500 2360 2210
Ga Al In La Pb Sb
2070 2060 2000 1800 1740 1635
Ba TI Ca Sr Li Mg
1540 1460 1440 1380 1336 1110
Na K Cd Rb Cs As
890 770 767 680 670 610
Th
5200
Nd
3700
Fe
2740
Mn
2150
Bi
1560
Zn
907
Hg
357
(7) Tnh dn in ca kim loi l tnh cht vt l quan trng nht ca kim loi. i i vi tnh dn in l tnh dn nhit. Nhng kim loi c tnh dn in tt nht nh Ag, Cu, Au, Al cng chnh l nhng kim loi c tnh dn nhit tt nht. Nu ly dn nhit ca Hg lm n v th Ag dn nhit gp 48,8 ln dn nhit ca thy ngn ; v nu ly dn in ca thy ngn lm n v th dn in ca Ag s ln hn dn in ca thy ngn l 59 ln. Trong bng 7 nu ln cc gi tr so snh . Qua bng 7 ta thy dn in cng nh dn nhit ca cc kim loi rt khc nhau. Tuy nhin, tt c cc kim loi u c mt c tnh chung l dn in gim xung kh nhanh khi nhit tng (hnh 15a). Bng 7. dn in v dn nhit ca kim loi (Hg = 1) dn nhit (Hg = 1)
Ag Cu Au Al
48,8 46,2 35,3 26,0
W Be Mg Mo
23,8 19,2 18,5 17,5
Na K Cd Rh
16,2 11,8 10,8 10,6
Fe Li Co Cr
9,5 8,5 8,3 8,3
Pt Pd Sn Ir
8,3 8,1 7,9 7,1
Ni Ta Tl Pb
7,0 6,5 4,7 4,2
In Sb Bi Hg
2,9 2,2 1,0 1,0
dn in (Hg = 1)
Ag Cu Au Al Mg Ca 59,0 56,9 39,6 36,1 21,4 20,8 Na Mo Rh W Zn Ir 20,8 20,0 19,4 17,5 16,0 15,7 Ni K Cd Li In Os 13,9 13,6 12,6 11,2 10,6 10,6 Co Fe Pt Pd Ru Sn 9,9 9,8 9,7 9,6 9,6 8,3 Rb Cr Ta Th Be Cs 7,7 7,3 6,2 5,3 5,2 4,8 Nb Pb Re Sr V U 4,8 4,6 4,6 4,2 3,7 2,6 Sb Ga La Ce Bi Ge 2,5 1,7 1,6 1,2 0,8 0,001
Hnh 1 5. s ph thuc dn in ca kim loi vo nhit

: a) s thay i dn in khi thay i nhit : b) s thay i dn in ca mt s kim loi gn khng tuyt i. Mt s kim loi li c tnh cht c bit l nhit rt thp, gn khng tuyt i, th khi h nhit dn in tng ln lin tc v sau tng t ngt n v cc ngha l chuyn sang tnh siu dn. S chuyn t trng thi dn in bnh thng sang trng thi siu dn ng vi mt nhit xc nh v khng phi bt k kim loi no cng u c tnh siu dn, th d Au, Cu... khng c tnh siu dn ; mt s kim loi nh Hg, Su, Pb... v nhiu hp kim... li c tnh siu dn (hnh 15b). 1.6. Tnh cht ha hc ca kim loi Tnh cht ha hc ca cc kim loi gy ra bi cc electron ha tr ca nguyn t kim loi lin kt yu vi ht nhn nguyn t, do cc kim loi c kh nng d nhng electron to thnh con dng: M - ne = Mn+ v vy cc kim loi u l cht kh, u c kh nng tc dng vi nhiu cht khc nhau nh tc dng vi n cht l cc phi kim, tc dng vi cc hp cht axit, mui v nhng cht oxi ha khc. Khi tc dng vi phi kim th sn phm to thnh vi hidro l hidrua, vi cc halogen l halogenua ; vi oxi gi l oxit ; vi lu hunh gi l snua; vi nit gi l nitrua; vi photpho gi l photphua ; vi cacbon v silic gi l cacbua v silicua... Cc phn ng to ra cc hp cht trn c nu chi tit trong cc chng sau. (2) Khi kim loi tc dng vi axit khng c tnh oxit ha th cht oxi ha l con H+, ion ny tip nhn electron ca nguyn t kim loi. Zn + 2H+ = Zn2+ + H2 Nhng kim loi hot ng mnh (Mg v trc Mg) trong dy th in cc y c hidro nhanh hn so vi nhng kim loi hot ng trung bnh, tuy nhin phn ng xy ra nhanh hay chm cn ph thuc vo kh nng ha tan ca mui to thnh, chng hn khi cho Pb tc dng vi H2SO4 Phn ng s chm dn, do to ra PbSO4 kh tan (T, = 1,6.10-8) bm vo b mt thanh ch. Nhng kim loi c th in cc cao hn hiro khng di c hiro t axit, tuy nhin c nhng trng hp vi phm cn bng t nhin ca phn ng di ch, chng hn Cu sau H2 nhng li gii phng H2 khi dung dch axit HCN l axit yu (K = 2. 10-4) v to ra ion phc xiano ca Cu(I) : 2Cu + 2H+ = 2Cu+ + H2 Cu+ + 3CN - = [Cu(CN)3]2hoc Ag cng y c H2 khi dung dch HI 1N : 2Ag + 2HI = 2AgI + H2~
do tch s tan ca AgI rt b (Tt = 8,3. 10-17). Vi nhng axit c tnh oxi ha nh HNO3, H2SO4 c th axit l cht oxi ha trong nguyn t trung tm gim s oxi ha. (3) Trong mi trng trung tnh ([H+]=[OH-]=10-7M) th in cc E
0 2H / H 2
+
= 0,41V , nhng kim loi no c th in cc thp hn gi tr
trn mi c kh nng y c H2 ra khi H2O. nhng v sn phm to thnh l hiroxit, nn kh nng ha tan ca kim loi trong H2O Cn ph thuc vo tan ca hiroxit. Na, K phn ng rt mnh vi H2O ; Ca phn ng chm hn; Mg phn ng rt chm vi nc lnh v to ra mng Mg(OH)). nhng nhanh hn vi nc nng ; Al phn ng rt chm v c lp mng Al2O3 nhng khi cho thm HgCl2 Phn ng y H2 li rt nhanh, do to ra hn hng ; Fe khng phn ng vi nc nhit thng nhng vi hi nc to ra Fe3O4. y Trong cc trng hp trn H2O l Cht oxi ha. (4) Nhng kim loi m hiroxil ca chng l lng tnh. chng hn nh Al, Cr, Zn, Su, Pb khng nhng tc dng vi axit m cn tc dng vi dung dch kim. Trong cc trng hp H2O l cht oxi ha, qu trnh phn ng to ra hiroxit tan c trong dung dch kim. (5) Kim loi c th in cc cng m th tnh kh cng mnh v tnh oxi ha ca ion cng yu v vy mi kim loi ng trc u y c kim loi xp sau trong dy th in cc ra khi dung dch mui, chng hn: Zn + Cu2+ = Cu + Zn2+ Khng nhng th, trng thi rn nng cng c phn ng di ch ca mt s kim loi nh nm y c Al khi AlCl3 nng chy : 3Na + AlCl3 = Al + 3NaCl Al gii phng Fc trong qu trnh tecmit: 8Al + 3Fe3O4 = 9Fe + 4Al2O3 Tuy nhin nhng phn ng thuc loi ny khng th gii thch trn c s ca th in cc ca kim loi nh trng hp phn ng xy ra trong nc, v rng th in cc ph thuc vo ba hiu ng nng lng l nng lng mng li, nng lng ion ha v nng lng hirat ha. trng thi nng chy mng li cua kim loi b ph v, li khng c qu trnh hirat ha nn tnh kh ca kim loi ch yu ph thuc vo nng lng ion ha ; kim loi no c nng lng ion ha thp hn s kh c kim loi c nng lng ion ha cao hn. (6) Ngoi cc n cht l phi kim, cc kim loi cn c kh nng phn ng vi nhau to thnh nhng hp cht ha hc gia cc kim loi gi l hp cht metalit. Cc metalit c th c to ra trc tip t cc n cht hoc gin tip t cc metalit khc trong dung mi khng nc (thng l amoniac lng) v
t0 t0
thng c to nn bi nhng kim loi in hnh v nhng kim loi yu. Trong mc l.3(4) gii thiu v thnh phn v cu trc ca tinh th cc loi hp cht ny, di y nu mt s phn ng v tnh cht ca loi hp cht ny. Thng thng phn ng to la metalil t cc kim loi u l phn ng pht nhit : H = - 83,68 kj K + 2Hg = KHg2 H = -75,31 kj Na + 2Hg = NaHg2 Na + 2Cd = NaCd2 H = - 1 29.71 kj. Au + 3Zn = AuZn3 H = - 16,74 kj Au + Zn = Auzn H= - 46.02 kj 3Au + Zn = Au3Zn H = - 100,42 kj Mt s mctalit to ra dng kt ta hoc c mu khc nhau, chng hn: 3Na + 7sb = Na3Sb7 (dung dch mu ) 3Na + 7Bi = Na3Bi7 (dung dch mu nu) hay khi cho Pb tc dng vi dung dch natri tan trong amoniac lng to ra kt ta trng, sau cho lng d Pb to ra dung dch mu xanh : 4Na + Pb = Na4Pb (trng) Na4Pb + 17Pb = 2Na2Pb9 (dung dch xanh) Metalit cng c th to ra khi cho kim loi lc dng vi mui trong amoniac lng, v d: 9Na + 4Zn(CN)2 = 8NaCN + NaZn4 V tnh cht, nhiu metalit c bn nhit rt cao, v i khi c nhit nng chy vt xa cc kim loi thnh phn, chng hn:
Tnc C
Li 480
Bi 271
LiBi 1145
bn.
Ni chung, nhng metalit to ra t cc kim loi in hnh nh KNa2 u t
Khi c metalit to thnh thng km theo gim dn in v to ra vng cm kh r rt. Th d magie v thic - to ra metalit Mg2Sn c tnh cht khc nhau:
Tnc C dn in (Hg=1) Vng cm (eV)
Mg 650 21 (khng c)
(3-Sn 271,8 8
Mg2Sn 795 0,1 0,34
cc metalit khng tan trong nc, nhng mt s metalit li tan trong amoniac
lng, lc cng in ly thnh con v cng c phn ng trao i kp nh: 2Ca(NO3)2 + K4Pb = Ca2Pb + 4KNO3 Khi in phn dung dch hoc trng thi nng chy cc metalit, th cc kim loi chuyn v cc cc khc nhau, kim loi no m in hn chuyn v anot; cn kim loi dng in hn chuyn v catot, th d khi in phn dung dch Na2Pb9 trong amoniac lng thu c natri catot v ch anot. Mt s hp kim to ra t nhng kim loi vn khng c t tnh nh hp kim Cu v Mn khi cho thm mt s kim loi khc nh Al, Su, As, Sb, Bi li c t tnh rt mnh. iu c lin quan n s to thnh metalit. 1.7. Tng quan v cc phng php iu ch kim loi Qui trnh iu ch cc kim loi ring bit, c nu chi tit trong cc chng sau, v vy trong mc ny chi nu mt s nt tng qut v vn trn. Nh bit, nguyn tc chung iu ch kim loi l kh cc ion kim loi Mn+ c trong thnh phn cc hp cht nh oxit, sunfua, halogenua... to thnh kim loi theo s : Mn+ + ne M0 Da trn nguyn tc , thc t p dng cc phng php sau : a - Phng php dng cht kh ha hc. b - Phng php in phn. c - Phng php nhit phn. (1). Trong phng php dng cht kh ha hc kh oxit kim loi khi nung nng th cht kh thng c dng th nghim l kh hiro, cn trong cng nghip l cacbon dng than cc hoc than g, di y l m(vi v d: PbO + H2 = Pb + H2O Cao + Hi = Cu + H2O Mo2O3 + 3H2 = 2Mo + 3H2O SnO2 + 2C = Sn + 2CO Khi hp cht ca kim loi l sunfua, th trc ht nung cc sunfua trong khng kh chuyn thnh oxit, sau dng cacbon hay hiro kh oxit, th d : 4FeS2 + 11O2 = 2Fe2O3 + 8SO2 Fe2O3 + 3H2 = 2Fe + 3H2O vi Sunfua ca kim loi km hot ng c th nung trc tip trong oxi: HgS + O2 = Hg + SO2 V nguyn tc, oxit kim loi c nhit to thnh cng thp th qu trnh kh
t0 t0 t0 t0 t0 t0 t0
cng d, do vy nhng kim loi c tnh dng in b hn Zn th oxit kim loi d b hiro v cacbon kh thnh kim loi, so vi cc kim loi c tnh dng in cao hn km.Vi nhng kim loi ny cn phi nhit cao, chng hn:
2000 0 C
MgO + C
=
0
Mg + CO
ZnO + C = Zn + CO Hn na, nhng kim loi c tnh dng in cao khi tc dng vi cacbon thng to nn cacbua, lm ngn cn qu trnh kh oxit. Trong cc trng hp ny, ngi ta thng dng cht kh l Al, Mg, Ca... thng gi l phn ng nhit kim loi, th d hn hp tecmit : 3Fe3O4 + 8Al = 9Fe + 4Al2O3 kh cc halogenua kim loi, thc t cn dng nam, kim, canxi lm cht kh. Halogenua ca cc kim loi nng cng d b kh bng hiro hoc cacbon oxit, chng hn: 2RbCl + Ca = CaCl + 2Rb FeCl2 + H2 = Fe + 2HCl PdCl2 + CO + H2O = Pd + CO2 + 2HCl (2) Phng php in phn dung dch trong nc kt ta kim loi c tm quan trng ln trong k thut iu ch kim loi tinh khit. Qu trnh ny thng p dng iu ch cc kim loi khng b H2O phn hy v thu c kim loi catot: 2ZnSO4 + 2H2O = 2Zn + O2 + 2H2SO4 Vi cc kim loi c dng in cao khng th iu ch bng phng php in phn dung dch trong nc v cng khng th iu ch bng cht kh ha hc, trong phng th nghim li dng phng php in phn dung dch khng nc, chng hn dung dch piriin. Trong qu trnh tinh luyn kim loi bng phng php in phn, ngi ta cn s dng phng php anot tan. trong kim loi cha tp cht lm anot, cn cht in phn l mui ca kim loi cn tinh luyn. in th t vo cc in cc c chn sao cho kim loi cn tinh luyn s b oxi ha v con chuyn vo dung dch, sau thu c kim loi catot; cn cc kim loi tp cht khng chuyn vo dung dch m lng xung khu vc anot di dng bn!. Qu trnh ny thng c s dng tinh luyn Cu, Ni, Pb, Ag v mt s kim loi khc; dng bn thu c nhiu khi c c kim loi qu. Ngoi phng php in phn dung dch, trong thc t cn dng phng php in phn cht nng chy. Cht in phn l oxit hoc mui clorua(mui ny c nhit nng chy thp hn cc mui khc). Phng php ny ch yu iu ch cc kim loi c tnh dng in cao nh Al, Na. Ca, Mg... Thc t thng cho thm cht ph (cht chy) lm gim nhit nng chy ca cht
t0 t0 t0
1200 C
chnh, ng thi cng lm tng dn in; chng hn khi in phn Nacl nng chy th cht chy l CaCl, lm gim nhit nng chy ca NaCl t 800 0C xung 6000C: 2NaClnc = 2Na + Cl2 in phn Al2O3 trong criolit (NaAlF6) nng chy h nhit nng chy ca Al2O3 t 12000C n 9500C : 2Al2O3 = 4Al + 3O2 khi in phn Nb2O5 trong phc cht K2[NbF7] nng chy iu ch : 2 Nb2O5 = 4Nb + 5O2 (3) Phng php nhit phn hy cc hp cht thng c dng iu ch kim loi c tinh khit cao, chng hn c niken v st c tinh khit cao trong thc t nung cc hp cht cacbonyl Ni(CO)4, Fe(CO)5 : Ni(CO)4 = Ni + 4CO Fe(CO)5 = Fe + 5CO Ngi ta cng nhit phn mt s hp cht khc nh oxit, halogenua ca cc kim loi nng, chng hn nhit phn HgO: 2HgO = 2Hg + O2 hoc khi nung iotua dng MI4 iu ch Ti, Zn, Hf tinh khit: TiI4 = Ti + 2I2. (4) iu ch kim loi rt kh bay hi ngi ta cn dng phng php Van Bolten vi nguyn tc l nung nng kim loi trong chn khng bng l din nhit cao, cc tp cht bay hi ht, cn li kim loi linh khit.
t0 t0 t0 t0 t0
0 600 c
0 950 c
CHNG 2 CC NGUYN T NHM IA (KIM LOI KIM) 2.1. Nhn xt chung v cc nguyn t nhm IA (1) cc kim loi kim thuc nhm IA ca bng tun hon gm cc nguyn t Li(lithium), Na (Naltrium hay Sodium), K (Kalium), Rb (Rubidium 1, Cs (Caesium) v Fr (Francium). Liti c nh ha hc Thy in l Acvetsn (Arfvedson) tm ra nm 1817 khi phn tch khong vt petalit LiAl[Si4O10]. Nm 1807, nh vt l kim ha hc ngi Anh l vi (H. Davy) iu ch c natri v kali dng tinh khit khi in phn NaOH nng chy v KOH nng chy. Rubii c hai nh bc hc ngi c l Bunzen (K. Bunsen) v Kichp (G. Kirchhoff) tm ra nm 1861; cn xezi cng c hai nh bc hc trn tm ra nm 1860 u bng phng php phn tch quang ph. Nguyn t franxi c pht hin chm hn vo nm 1939 do mt nh nghin cu ngi Php l Pery (M. Perey); nhng mi n u nm 1950 mi iu ch nhn to bng phng php chiu x urani
(2) Nguyn t khi, s th t nguyn t v s phn b electron nh sau :

Nguyn t Liti Natri Kali Rubidi Xezi Franxi K hiu Li Na K Rb Cs Fr S th t 3 11 19 37 55 87 Nguyn t khi 6,939 22,99 39,1 85,47 132,9 [223] Phn b electron 2 2 2 2 2 2 1 8 8 8 8 8 Ha tr 1 1 1 1 1 1
1 8 18 18 18
1 8 18 32
1 8 18
1 8
(3) Tt c u c mt electron ns1 nm ngoi lp v ca cc kh tr ng trc mi nguyn t v vy cc kim loi kim rt d mt clectron ha tr to thnh cc ion M1+, do cc kim loi kim u l nhng kim loi rt hot ng. Tnh kh tng dn t Li n Fr, nn Fr l kim loi c tnh kh mnh nht. Mc d trong cng nhm kim loi kim, nhng Li c mt s tnh cht khc vi cc kim loi kim cn li, v d hiroxit cc kim loi kim khc u d tan, nhng LiOH li l cht t tan (Tt = 4. 10-2), mt s hp cht khc LiF, Li2CO3, Li3PO4 Cng u kh tan tng t hp cht tng ng ca cc kim loi kim th. (4) Cc ion kim loi kim c lp v ngoi cng (n- 1)s2p6 nn u c tnh oxi ha yu. (5) Di y l mt s c im ca cc nguyn t kim loi kim (bng 8).
Bng 8. Mt s c im ca cc nguyn t kim loi kim

Nguyn t
Electron ha tr
Bn knh nguyn t o (A)
Bn knh ion
The ion hoa
o M+ (A) 1,55 1,89 2,36 2,48 2,68 2,80 0,68 0,98 1,33 1,49 1,65 1,75
I1 (eV) 5,39 5,14 4,34 4,18 3,89 3,98
Li Na K Rb Cs Fr
2 s1 3 s1 4 s1 5 s1 6 s1 7 s1
(6) V cu trc tinh th, cc kim loi kim u c cu trc mng lp phng tm khi. khong cch a gia hai ht nhn nguyn t (cnh ca hnh lp phng) nh sau :
Li o a (A)= 3,50 4,29 5,31 5,66 ( -10 C) 6,13 ( -10 C) Na K Rb Cs
2.2. Trng thi thin nhin v thnh phn cc ng v (1)Do c hot tnh ha hc cao nn cc kim loi kim khng tn ti trng thi kim loi t do trong thin nhin m ch dng ion. S phn b cc kim loi trong v qu t nh sau: Nguyn t 1% s nguyn l 1% khi lng
Nguyn t Li Na K Rb Cs % s nguyn t 1,9.10-2 2,4 1,4 7. 10-3 9,5. 10-5 % khi lng 6,5. 10'3 2,64 2,60 3,1. 10-2 7,0. 10-4
(2) Trong v qu t, khong vt chnh c cha liti dng alumosilicat nhng rt him, nh khong vt triphan hay spodumen LiAl(SiO3)2 ; petalit LiAl(Si2O5)2, hoc dng photphat nh triphilin LiFe (PO4), ambligonit LIAIF(PO4)... Hp cht thin nhin c cha natri l NaCl (c trong nc bin, m mui); Na2SO4.10H2O; xoa Na2CO3.10H2O; trong Na2CO3.NaHCO3.10H2O, trong mt s silicat khc... Khong vt cha km dng alumino - silicat nh phenspat
K2O.Al2O3.6SiO2; mutcovit KHAl3(SiO4)3; cacnalit KCl.MgCl..6H2O; kainit K2SO4.MgSO4.MgCl2.6H2O; xinvinit NaCl.KCl ; xinvin KCl.... Rubii v xezi l nhng nguyn t rt phn tn, thng gp dng tp cht ln trong qung ca cc kim loi kim khc, do khong vt dng khai thc rubii v xezi l mt s qung c cha liti v kali. Trong qung ca actini v urani c ln cc du vt franxi. V d trong mt tn qung uran c khong 1,34. 10-11 g franxi. (3) Trong c th ng vt, natri ch yu tp trung trong cc dch m (bch huyt v mu), cn kali c trong bn thn ca m. Kali c nhiu trong gan, l lch. Natri c nhiu trong bo thai ca ng vt. Kali rt cn cho cy trng nh la, ng, khoai ty... Rubii c trong c ci , trong cc loi nho... (4) Trong nc i dng, cc kim loi kim u dng ion M+ vi thnh phn trung bnh nh sau :
Nguyn t Li Na K % 1,5. 10 5 1,0353 0,0387 Hm lng mg/l 0,150 10,354 387,5 Nguyn t Rb Cs Hm lng % mg/l 5 2. 10" 0,2 3,7. 10"8 3,7. 105
(5)Hm lng ca cc kim loi kim c trong cc mu do cc tu Apollo 11-12 v Luna - 6 a t Mt Trng v ba vng khc nhau c gi tr nh sau :
Hm lng trung bnh (s gam /1 g mu ) Apollo -11 Apollo-12 -5 1,2. 10 1,1. 10-5 3,3. 10-3 3,0. 10-3 -3 1,4. 10 1,5. 10-3 3,4. 10-6 8,7. 10-6 -6 0,1. 10 0,32. 10-6
Nguyn t Li Na K Rb Cs
Luna - 6 1,08. 10-5 1,9. 10-6 0,09. 10-6
(6) y Li c ba ng v, trong c hai ng v thin nhin l 6Li (7,52%) v 7 Li(92,48%) v ng v phng x l 8Li vi chu k bn hy l 0,841 giy. y Na c 6 ng v t 20Na n 25Na trong 3Na l ng v thin nhin (100%), cn li l ng v phng x, ng v 22Na c chu k bn hy lu nht l 2,6 nm. y K c 8 ng v t 37K n 44k, trong ng v 39K v 41K l ng v thin nhin chim 93,08% v 6,91%. Ngoi ra trong cc ng v phng x th ng v 40K l ng v bn nht vi chu k bn hy l l,3.106 nm, ng v ny cng c trong thin nhin khong 0,0119%. y R c 21 ng v, cc ng v thin nhin l 85Rb (72,15%) v 87Rb
(27,85%); ng v 87Rb cng c tnh phng x nhng chu k bn hy l 6,2.1010 nm. Cs c n 24 ng v, nhng ch c 133Cs l ng v thin nhin (100%), cn li l ng v phng x. 2.3. iu ch cc kim loi kim (1) Nguyn tc chung iu ch cc kim loi kim l dng dng in hoc dng cht kh mnh kh cc con kim loi kim, tch cc kim loi ra khi hp cht ca chng, bng phng php in phn hiroxit hoc mui clorua nng chy; hoc dng cacbon tc dng vi mui cacbonat hoc hiroxit nhit cao. Trc khi c phng php in phn, ngi ta iu ch nam bng cch nung hn hp gm cacbon vi Na2CO3, hoc hn hp cacbon vi NaOH 1000C (phng php Castner, 1886) : Na2CO3 + 2C = 2Na + 3CO 6NaOH + 2C = 2Na + 3H2 + 2 Na2CO3 (2) Ngy nay, li c iu ch bng cch in phn mt hn hp LiCl + KCl c khi lng bng nhau vi anot bng than ch v catot bng st. C th in phn LiCl tinh khit nng chy v Tnc ca LiCl thp (6060C), nhng trong k thut ngi ta cho thm KCl lm gim nhit nng chy ca LiCl. 2LiCl = 2Li + Cl2 (3) Natri c iu ch bng phng php in phn NaCl nng chy hoc NaOH nng chy. Khi in phn NaOH nng chy (phng php Castner, 1 890) thu c nm nng chy khu vc cator bng st (hnh 16a). Na+ + 1e = Na natri c khi lng ring b hn nn ni trn b mt ca cht in phn nng chy. b mt catot bng st hoc bng niken xy ra qu trnh oxi ha ln OH : 4 OH - 4e = 2H2O + O2 cng vi O2, Phn ln H2O bay hi thot ra khu vc anot, tuy nhin mt phn H2O b phn hy v v vy catot cn c kh H2 thot ra. Natri iu ch bng phng php in phn NaCl nng chy (phng php Ciba, 1910) c thc hin trong nhng thng bng thp (hnh 16 b), pha trong lt bng gch chu nng vi anot bng than ch (A) v catot hnh vng bng st (K), gia hai in cc c mng ngn (2). Cht in phn khng phi l NaCl tinh khit (v c Tnc cao l 8000C) m l hn hp ca NaCl vi 25% NaF v 12% KCl ( lm gim nhit nng chy ca NaCl cho php in phn 610 6500 C). Kh do thot ra ng (l), natri t lai phn trn (3) ca vng catot sau theo ng (4) v t chuyn vo bnh thu (5).
dpnc
t0 t0
(4) Kili cng c iu ch bng phng php in phn KCl nng chy hoc KOH nng chy. Rubii v xezi c iu ch bng cch dng canxi kh mui clorua nhit cao trong chn khng: 2RbCl + Ca = CaCl + 2Rb iu ch Rb v Cs vi lng nh ngi ta cn nung nng hn hp hiroxit cc kim oi vi Mg trong lung kh H2 hoc vi can xi trong chn khng. (5) Cc kim loi kim u c bo qun trong cc bnh kn cha du ha trung tnh, hoc rong bnh kn di lp vazlin hay parafin. 2.4. Tnh cht l hc cc kim loi kim v ng dng (1) B mt ca cc kim loi kim c mu trng bc v c nh kim mnh, tr xezi (theo d kin ca Costeanu) trng thi tinh khit c mu vng ca vng (Au). Tuy nhin, nh kim ch tn ti trong chn khng hoc trong mi trng lnh, khi tip xc vi khng kh, b mt b m dn. Mt s hng s l hc quan trng c nu ra trong bng 9. Tt c cc kim loi kim u mm, mm nht l xezi v cng nht l liti; natri c ng gn bng photpho trng, cn xezi th mm nh sp. Nhit nng chy v nhit si u thp v gim dn t Li n Cs. Kt qu l do lin kt kim loi yu v cng yu dn khi bn knh nguyn t tng dn. Tnh mm ca cc kim loi kim cng do nguyn nhn . Cc kim loi kim u nh, liti ni trn du ha, cn natri v kali th ni trn nc. Bng 9. Mt s hng s l hc quan trng ca kim loi kim
Tnh cht Khi lng ring (g /
7000 C
Li 0,53
Na 0,97
K 0,86
Rb 1,53
Cs 1,87
cm3) Nhit nng chy (Tnc, C) Nhit si (Tnc 0C) dn in (so vi Hg =1) cng (so vi kirn cng = 10) Th in cc (V) m in(1)
(1)
180 1370 11 0,6 -3,01 1,0
98 883 21 0,4 -2,71 0,9
64 760 14 0,5 -2,92 0,8
39 700 8 0,3 -2,98 0,8
29 670 5 0,2 -2,92 0,8
Theo Pauling. Cc kim loi kim u c dn in cao ph hp vi thuyt vng ca kim loi v cc kim loi kim c vng s ch mi b chim bi mt na s elcctron. dn in cao hay thp cn ph thuc vo s nguyn t kim loi trong mng tinh th ngha l ph thuc vo s nguyn t trong 1 cm3 kim loi trng thi rn. (2) Nhit thng hoa ca cc kim loi kim c gi tr nh sau :
Nhit thng hoa (kj / mol)
Li 150,6
Na 108,8
K 92,1
Rb 87,8
Cs 79,5
trng thi hi, phn t cc kim loi kim hu nh ch n nguyn t; tuy nhin, bng phng php quang ph ngi ta thy trong hi ca cc kim loi c c phn t lng nguyn t, ngha l chng c th to ra lin kt cng ha tr. Nng lng lin kt trong phn t kh b v gim dn t Li n Cs.
Phn t Khong cch ht
0
Li2 2,67 108, 8
Na2 3,08 75,3
K2 22 50,2
Rb2 21 46,0
Cs2 19 41, 8
nhn ( A ) Nng lng lin kt (kJ / mol)
Hi ca cc kim loi kim c mu khc nhau. Hi ca natri c mu nu tng t mu cua dung dch thuc tm long, hi kali c mu xanh lc; hi rubii c mu xanh da tri... Khi t trong ngn la khng mu, cc kim loi kim trng thi t do cng nh cc hp cht d bay hi ca chng, u lm cho ngn la c mu c trng, Li c mu ta, natri c mu vng, kali - mu tm, rubii - mu tm hng v xezi - mu xanh da tri. S nhum mu ca ngn la l do trong ngn la cc clectron ca nguyn t hoc ion kim loi kim b kch ng t cc obitan c mc nng lng thp nhy ra nhng obitan c mc nng lng cao hn; sau cc electron ny nhy v chim cc mc nng lng ban u lc s pht ra nng lng hp th
di dng nhng bc x vng nhn thy. V d vch vng ca quang ph natri xut hin khi electron nhy t mc 3p xung mc 3s. (3) Cc kim loi kim c kh nng ha tan ln nhau.Hp kim Na v K (24% Na v 76% K) l mt cht lng. ng c - 12,60C. Cc kim loi kim u d tan trong thy ngn to ra "hn hng"(xem chng 8 mc 8.4). V d 1, hn hng "ca liti c thnh phn LiHg2, LiHg, Li2 Hg, Li3 Hg... Cc kim loi kim cng to ra hp kim vi nhiu kim loi khc. V d vi liti to ra LiMg2, LiAl, Li3Al...; natri to ra hp kim vi Sn nh NaSn6, NaSn4, NaSn2, NaSn, Na2 Sn, Na3 Sn2... Cc kim loi kim tan c trong amoniac lng to ra dung dch, trong cc kim loi c ion ha, v vy dung dch long ca natri dn in ging nh cht in li, ngi ta cho rng trong dung dch c cc ion sonvat ha [ Na(NH3)X ]+ v cc ion [(NH3)n]. Khi nng ca Na ln hn, dung dch c mu xanh m, c nh kim v c tnh dn in kim loi, t ngi ta cho rng ngoi cc electron kt hp vi cc phn t NH3 cn c th c cc "electron t do" trong dung dch. (4) Cc ion kim loi Li, Na, K khng c, nhng hiroxit ca chng c tc dng n mn da nn thng gi cc cht LiOH, NaOH, KOH l kim n da. (5) Cc kim loi kim u c nhiu ng dng trong thc t. Liti c dng ch to mt s hp kim. C nhiu ng dng quan trng l hp kim ca li vi Ag, Mg, Zn, Cd, Pb, Ca. V d hp kim ca Ai c 1% Li lm tng bn c hc v khng b n mn ; hp kim ca Cu c 2% li lm tng dn in; thm 0,4% liti vo ch, cng ca ch tng gp 3 ln ng dng quan trng nht ca li l ngun iu ch triti:
6 1 3 4 Li + n = H + He 3 0 1 2
Ngoi ra liti cn c dng lm cht mang nhit trong l phn ng ht nhn. Natri c dng nhiu trong phn ng nhit kim. Phng php nhit natri c dng iu ch titan, ziconi v mt s kim loi khc. Hp kim ca Na v K c dng nhiu trong cc phn ng tng hp hu c. Natri dng hn hng c dng lm cht kh mnh ; Na v hp kim Na K cn c dng lm cht truyn nhit trong l phn ng ht nhn v mt s thit b khc. Di tc dng ca tia t ngoi cc kim loi Na, K, Rb, Cs u c kh nng phng electron ra khi b mt kim loi nguyn cht, cng ca dng electron c phng ra t l vi cng ca tia sng c hp th. Li dng tnh cht ny ngi ta dng Rb v Cs lm t bo quang in dng trong v tuyn truyn hnh...
2.5. Tnh cht ha hc ca cc kim loi kim Kim loi kim l nhng kim loi c hot tnh ha hc cao, trong cc phn ng u l nhng cht kh mnh v tnh kh tng dn t li n xezi. (1) Khi un nng nh trong kh quyn hung, cc kim loi kim phn ng trc tip to ra cc hirua ton. V d : Li + H2 = 2LiH. Cc kim loi kim khc, phn ng cng xy ra tng t. (2) Cc kim loi kim phn ng mnh vi cc halogen. Chng bc chy trong kh do m nhit thng. Vi brom lng, K, Rb v Cs n mnh, cn Li v Na ch phn ng b mt. Vi iot cc kim loi kim ch tc dng mnh khi un nng. Trong tt c cc trng hp tng tc vi halogen, sn phm ca phn ng l mui halogcnua. (3) Cc kim loi kim tc dng mnh vi oxi. Rubii v xezi bc chy mnh trong khng kh hoc ngay trong lung kh oxi; cc kim loi kim cn li ch t bc chy trong khng kh kh hoc trong lung kh oxi khi un nng. Trong trng hp , liti to nn Li2O v c mt t Li2O2. Natri chy to ra peoxit Na2O2 ; cc kim loi kim cn li to ra supeoxit KO2, RbO2, CsO2 Liti t to ra peoxit v ion Li+ c kch thc b nn khng th lin kt bn vi cc anion ln hn ion O2(4) Cc kim loi kim tc dng trc tip vi bt S ngay nhit thng to ra monosunfua M2S: 2M + S = M2S Cng to ra cc polisunfua nh Li2S2, Na2Sx (X = 2 5), K2Sx, Rb2Sx,Cs2Sx (X = 2 6) bng phn ng gin tip. Cng tng t, selen v telu cng phn ng trc tip vi kim loi kim to ra monoselenua M2Se v monotelua M2Te. (5) Vi nit phn t, ch c liti l c phn ng trc tip to ra Li3N : 6Li + N2 = 2Li3N phn ng xy ra chm nhit thng, nhng 5000C phn ng xy ra mnh hn. Cc kim loi kim cn li cng to ra hp cht dng M3N khi cho hi kim loi tc dng vi "nit hot ng" trong trng phng in m : 6M + N2 = 2M3N Cc hp cht thng c iu ch bng phn ng gin tip khi nung hirua trong lung kh nit: 6NaH + N2 = 2Na3N + 3H2 Nitrua ca cc kim loi kim u c mu ( nhit phng c mu ), bn trong khng kh kh, nhng nhanh chng b phn hu khi tip xc vi H2O to ra amoniac:
t0
Na3N + 3H2O = 3NaOH + NH3 (6) Cc kim loi kim cng phn ng trc tip vi photpho nhng rt kh khn. Li3P to ra khi nung liti kim loi vi photpho , sn phm thu c c mu nu. Na3P l cht rn mu hung, to ra khi nung natri vi photpho 5000C. Rubii to ra hp cht c thnh phn Rb2P5 khi nung hn hp gm Rb v P trong chn khng 5000C ; cn xezi cng to ra Cs2P5 khi nung hn hp photpho vi xezi kim loi trong ampun hn 400 5000C trong thi gian 373 - 423 gi. Cc photphua u b phn hy trong khng kh m to ra PH3 : Na3P + 3H2O = 3NaOH + PH3 (7) Cacbon ch ha hp trc tip vi liti to ra cacbua Li2C2. Cht ny nhit cao b phn hy to ra n cht : 2Li + 2C = Li2C2 Nhng cacbua ca cc kim loi kim khc c iu ch bng phng php gin tip, chng hn cho kim loi tc dng vi C2H2 : 2Na + C2H2 = Na2C2 + H2 hoc bng cch cho kh axetilen qua dung dch kim loi kim trong NH3. Sn phm thu c u b nc phn hy: K2C2 + 2H2O 2KOH + CH CH Cc kim loi kim cng phn ng trc tip vi silic khi nung nng vi silic trong kh quyn agon. nhit khong 550 7000C. Liti lo ra Li4Si v Li2Si ; cc kim loi kim cn li to ra MSi. Cc silixua Li4S; v Li2Si tc dng mnh vi H2O to ra silan SiH4 t bc chy. Cc hp cht dng MSi; u khng bn trong khng kh, n mnh khi tc dng vi H2O, v b phn hy thnh nguyn t khi un nng trong chn khng. (8) Cc kim loi kim c th in cc rt thp, do chng phn ng rt mnh lit vi nc, gii phng H2 : 2M + 2H2O = 2MOH + H2 Trong qu trnh phn ng, vi Li v Na - hidro thot ra khng bc chy, vi K - hiro bc chy ; nhng vi Rb v Cs - xy ra phn ng n. Cc dung dch thu c u c cha ion hiroxit nng cao nn c gi l dung dch kim (m khng gi l dung dch baz). Cc dung dch m c ca chng u c tc dng n mn da tay nn gi l kim n da. Do phn ng mnh vi H2O nn ngi ta dng natri lm khan cc dung mi hu c, chng hn lm khan ete - l cht khng phn ng vi natri. (9) Khng nhng phn ng mnh vi H2O, m cn gii phng H2 ra khi ru : 2Na + 2C2H5OH 2C2H5ONa + H2 (10). Trong amoniac kh, cc kim loi kim to ra cc amiua. Natri phn ng 3500C to ra natri amiua (tc xoamit) :
t0 t0
2Na + 2NH3 = 2NaNH2 + H2 sn phm b nc nng phn hy thnh amoniac do ion amiua phn ng vi H2O: NH2 + HOH = OH + NH3 (11) Khng nhng ch phn ng vi cc axit mnh lo ra H2 m cn c th thay th hir trong cc axit hu c to mui ln nh NaCH3COO, C6H5COONa. Khi un nng hir sunfua hoc nung trong hir clorua, cc kim loi kim u to ra mui sunfua v clorua tng ng: 2Na + H2S = Na2S + H2 2Na + 2HCl = 2NaCl + H2 Oxit ca mt s kim loi v phi kim loi cng b kh bi cc kim loi kim : SiO2 + 4K = Si + 2K2O Bi2O3 + 6K = 2Bi + 3K2O Al2O3 + 6K = 2Al + 3K2O Mt s mui clorua cng b kh tng t to thnh nguyn t, hoc mt s ankyl halogenua to thnh hirocacbon : TiCl4 + 4Na = Ti + 4NaCl Becb + 2Na = Be + 2NaCl C2H5I + 2Na + I C2H5 C2H5 C2H5 + 2NaI 2.6. Hirua ca cc kim loi kim (1) Trong s hirua ca cc kim loi kim th LiH l bn hn c, bn tng t hirua ca cc kim loi kim th. Liti hirua l cht rn mu trng, nng chy 6800C v phn hy trong chn khng 4500C. 2LiH = 2Li + H2 v b H2O phn hy : LiH + H2O = LiOH + H2 trng thi nng chy, LiH dn in, v khi in phn thu c Li catot v H2 anot, chng t LiH l hp cht ion. (2) Hirua ca cc kim loi kim cn li cng c iu ch bng cch cho H2 tc dng trc tip vi kim loi nhng kh khn hn nhiu so vi LiH. bn nhit gim dn t NaH n CsH, nhit to thnh gim dn.
4500 C t0 t0 t0 t0 t0 t0 t0
Hirua cc kim loi kim khc u b H2o phn hy tng t LIH. Tt c u l cht rn, kt tinh theo dng tinh th mui n, c di a (khong cch gia ht nhn ca Li v H) trong tinh th nh sau:
LiH 90,37 NaH 53,55 KH 41,00 RbH CsH -
Nhit to thnh (kJ / mol)

0
di a ( A )
4,085
4,880
5,700
6,037
6,376
2. 7. Oxit ca cc kim loi kim (l) Khi ha hp vi oxi, cc kim loi kim to ra cc oxit thng (M21O), peoxit (M21O2 v Supeoxit (M1O2).
Li20 trng Li202 trng Na20 trng Na202 vng nht K20 trng K202 vng da cam K02 vng thm
M 20 M202 M02
Rb20 vng nht Rb202 nu ti Rb02 vng thm
Cs20 da cam Cs202 vng Cs02 vng thm
(2) Oxit thng M2O. Nh trn nu, nhit thng hoc khi nung trong khng kh hay trong oxi, lai to ra oxit thng Li2O, cn cc kim loi khc ch yu to ra peoxit hoc supeoxit. Li2O tinh khit c th c iu ch bng cch nung LiOH, Li2CO3, LiNO3 trong lung kh H2 8000C. Li2O c th b kh bi C, CO v H2 to ra li. Li2O ha hp chm vi H2O to ra LiOH. Na2O thng c to ra mt t ln vi Na2O2 khi t chy natri. dng tinh khit c iu ch bng cch nung Na2O2 hoc NaOH vi natri kim loi: Na2O2 + 2Na = 2Na2O 2NaOH + 2Na = 2Na2O + H2 Natri cng c to ra khi t lng d natri kim loi trong oxi, r rng ban u to ra Na2O2, sau Na2O2 phn ng vi lng natri d. N cng c to ra khi nung NaNO2 vi Na : 2NaNO2 + 6Na = 4Na2O + N2 Cc oxit Ca cc kim loi kim cn li cng c th iu ch bng cch un nng peoxil, hiroxit, nitrit, nitrat vi kim loi tng ng lng t Na2O, v d: 2KNO3 + 10K = 6K2O + N2 (3) Peoxit M2O2 v supeoxit MO2. Khi t chy cc kim loi kim trong oxi d to nn cc cht :
t0
Na2O2 KO2 RbO2 CsO2 Ni Chung, cc peoxit v supeoxit u bn vi nhit, khng b phn hy khi nung chy. Tt c u ht m mnh v b chy ra trong khng kh. Cc supeoxit u l cht d bay hi. Chng u tc dng mnh vi H2O hoc vi axit: M2O2 + 2H2O = 2MOH + H2O2 M2O2 + H2SO4 = 2M2SO4 + H2O2 vi Supeoxit cn to ra O2: 2MO2 + 2H2O = 2MOH + H2O2 + O2 2MO2 + H2SO4 = M2SO4 + H2O2 + O2 cc peoxit v supeoxit u l cht oxi ha mnh. (4) Na2O2 l Cht c nhiu ng dng trong thc t. Trong k thut c iu ch bng cch nung natri kim loi trong chn bng nhm 1800C vi oxi hay khng kh kh. L cht rn mu hi vng (do c ln tp cht). Nng chy 4600C v phn hy r rt gn 6000C. Na2O2 tc dng mnh vi H2O v pht nhiu nhit do to ra hirat Na2O2.8H2O v sau b thy phn to ra O2: 2Na2O2 + 2H2O = 4NaOH + O2 cn nhit thp hay trong dung dch long th b phn hy to ra H2O2 : Na2O2 + 2H2O = 2NaOH + H2O2 Na2O2 l Cht oxi ha mnh. Cc cht d chy nh rm, bng, bt than, bt nhm, lu hunh, b bc chy v gy n khi tip xc vi Na2O2. Cc Cht hu c nh ete, axit axetic, nitro benzen, glixerin c ln nc trn vi Na2O2 cng gy n mnh. Trong ha hc phn tch,dng ph qung sunfua bng cch nu nng chy qung vi hn hp gm Na2O2 v Na2CO3 trong chn bng bc : 2FeS2 + 15Na2O2 = Fe2O3 + 4Na2SO4 + 11 Na2O Hoc chuyn Cr(OH)3 thnh cromat: 2Cr(OH)3 + 3Na2O2 = 2Na2CrO4 + 2NaOH + 2H2O Phn ng vi CO to ra Na2CO3 v vi CO to ra O2 nhng vi dung dch CO2 to ra H2O2 : Na2O2 + CO = Na2CO3 2Na2O2 + 2CO2 = 2Na2CO3 + O2 Na2O2 + H2O + CO2 = Na2CO3 + H2O2 (5) Kim supeoxit KO2 l cht rn mu vng, ht m mnh nn chy ra trong khng kh, d b H2O, kh CO2 v axit long phn hy gii phng O2:
t0 t0
4KO2 + 2CO2 = 2K2CO3 + 3O2 2KO2 + H2SO4 = K2SO4 + H2O2 + O2 2KO2 + 2H2O = 2KOH + H2O2 + O Da Vo phn ng CO2 ngi ta dng hn hp Na2O2 V KO2 vi t l 1 : 2 v s mol lm ngun ti sinh O2 trong cc bnh ln v trong tu ngm: Na2O2 + 2KO2 + 2CO2 = Na2CO3 + K2CO3 + 2O2 Trong chn khng, KO2 b phn hy to ra K2O2 v sau to ra K2O: 4KO2 = 2 K2O2 + 2O2 2K2O2 = 2K2O + O2 KO2 l Cht xi ha mnh, tc dng mnh vi H2, C, CO, NO v cc cht hu c: 2KO2 + H2 = 2KOH + O2 4KO2 + 2C = 2K2CO3 + O2 2KO2 + CO = K2CO3 + O2 2KO2 + 3NO = KNO3 + KNO2 + NO2 Trc kia, supeoxit ca cc kim loi kim c xem nh l tetraoxit dng 1 M2 O4 ; tuy nhin vic kho st bng tia Rnghen (V. Caxatokin - 1936 v Klemm - 1939) cho thy mng li tinh th ca KO2 ging mng li tinh th ca BaO2 v ca BaC2 (hnh 17) ngha l hnh thnh bi nhng ion K+ v O2 Ion O2 c tnh thun t ngha l c mt electron c thn. Pauling gi thit trong ion O2 c mt lin kt n v mt lin kt ba electron: (6) Ngoi nhng hp cht peoxit, cc kim loi kim cn to ra cc hp cht oxit c cha ion O3- trong mng li tinh th, gi l cc ozollit. Ngi ta bit c cc ozonit nh KO3, RbO3 v ca amoni NH4O3 trong c nghin cu k hn c l KO3.
Kaliozonit c to nn khi cho kh O3 i qua KOH bt nhit thp t

- 50C n -100C , nc to ra lin kt vi KOH rn d : 4O3 + 6KOH = 4KO3 + O2 + 2KOH. H2O KO3 l cht tinh th mu da cam v l cht oxi ha mnh. nhit thng b phn hy : 2KO3 = 2KO2 + O2 Nc cng phn hy mnh KO3 to ra oxi : 4KO3 + 2H2O = 4KOH + 5O2 2.8. Hirox cc kim loi kim (1) Hiroxit cc kim loi kim u l cht rn mu trng, nng chy nhit tng i thp, to ra cht lng linh ng v trong sut. Nhit nng chy, nhit si, nhit to thnh t cc nguyn t nh sau :
Nhit nng chy ( C) Nhit si ( C) Nhit to thnh (kj / mol 25 C)
LiOH 450 - 485,3
NaOH 328 1390 -428
KOH 360 1324 -424,2
RbOH 300 423,4
CsOH 275 -419,6
trng thi nng chy, hiroxit kim loi kim n mn thy tinh, s v khi c mt cht oxi ha (ngay c oxi khng kh) n mn c c platin, palai to ra anion phc, v d K2[Pt(OH)6]; do khng dng chn platin nu chy cc hiroxit trn, trong phng th nghim dng chn bng bc, cn trong k thut dng dng c bng st. Khi un nng n nhit cao, khng b phn hy tr trng hp LiOH b mt nc gn 6000C : 2LiOH = Li2O + H2O iu c gii thch bng cch cho rng ion Li+ c kch thc b, li ch c hai electron, nn ht mnh oxi hn so vi nhng ion kim loi kim khc. Hiroxit cc kim loi kim u d tan trong nc v thot ra nhiu nhit, tr trng hp LiOH t tan hn. Qu trnh tan hu nh chng b phn ly hon ton theo phng trnh MOH = M+ + OH- nn chng u l nhng baz mnh nht trong tt c cc baz. Tnh baz tng t LiOH n CsOH. Tuy nhin trong cng mt cht, khi nng tng th in ly gim do lc gia cc ion
LiOH 20,08 5,3 NaOH 43,51 26,4 KOH 55,23 19,1 RbOH 61,53 17,9 CsOH 70,29 25,8
Nhit ha tan (kJ / mol) tan (mol/l) 15 C
tan (mol / l) d 30 C
5,4
29,8
22,6
16,9
20,2
Khi ha tan, cc hiroxit trn pht ra nhiu nhit l do qu trnh hirat ha cc ion kim loi kim. Hiroxit kim loi kim c th to nn cc hirat c th tch ra dng tinh th, chng hn LiOH, NaOH tch ra khi dung dch vi mt s phn t H2O. KOH tch ra dng KOH.H2O, KOH.2H2O, KOH.4H2O trong dng KOH . 2H2O bn nhit thng; NaOH dng NaOH.H2O, NaOH.2H2O. Cc hiroxit trn cng c kh nng tan trong ru. (2) L nhng cht kim mnh, tng tc vi mt s kim loi nh Zn, Ai, Sn : Zn + OH + H2O = HZnO2 + H2 HZnO2 + OH = ZnO22- + H2O 2Al + 2OH- + 2H2O = 2AlO + 3H2 Sn + OH + H2O = HSnO2 + H2 Tng tc vi mt s phi kim nh Si, C, P,S, halogen : Si + 2OH + H2O = SiO32- + 2H2 Cacbon kh NaOH nng chy to ra Na v mui cachonat: 6NaOH + 2C = 2Na + 2Na2CO3 + 3H2 Photpho trng (khng phi photpho ) phn ng vi dung dch kim c to ra photphin v nam hirophotphin (cc nguyn t khc trong nhm VA khng phn ng): 4P + 3OH + 3H2O = PH3 + 3H2PO2 Tc dng vi axit v oxit to thnh mui. Hp th CO2, SO2 to ra mui cacbonat hoc sunft : CO + 2OH = CO32 + H2O SO + 2OH = SO3 + H2O n mn s v thy tinh to ra silicat: SiO2 + 2OH = SiO32 + H2O Tc dng vi mt s mui to ra kt ta hiroxit ca cc kim loi nh Mg(OH)2, Cu(OH)2... hoc to ra nhng baz yu nh : NH4Cl + NaOH = NH3 + NaCl + H2O CH3NH3Cl + NaOH = CH3NH2 + NaCl + H2O (3) Khi cn mt lng nh hiroxit rt tinh khit ngi ta cho kim loi kim tc dng vi H2O: 2Na + 2H2O = 2NaOH + H2
Trong thc t, ngi ta dng phng php in phn dung dch mui clorua cc kim loi kim v thu c hiroxit tng ng khu vc catot, hoc dng phng php trao i kp gia mui ca kim loi kim v hiroxit kim loi kim th. Phng php ny khng ch iu ch NaOH m cn dng iu ch RbOH v CsOH : Rb2SO4 + Ba(OH)2 = BaSO4 + 2RbOH (4) Trong cc hiroxit ca cc kim loi kim th NaOH l quan trng nht c dng trong nhiu ngnh cng nghip do c sn xut vi qui m ln, chng hn dng sn xut x phng, dng trong ngnh sn xut giy, t nhn to, ch bin du m, phm nhum, dc phm.v.v... NaOH c iu ch trong cng nghip bng cch cho xoan tc dng vi nc vi : Ca(OH)2 + Na2CO3 = CaCO3 + 2NaOH Phng php ny cho php chuyn xt (xoa) thnh NaOH, nn NaOH c gi l xt n da hay xoa n da. NaOH iu ch bng phng php ny cn ln nhiu nc vi.
t0
Ngy nay ngi ta dng phng php in phn dung dch NaCl bo ha vi dng cc bng than ch v m cc bng thp. Kh H2 thot ra cc m v kh do thot ra cc dng, cn li trong dung dch thu c cc m l ion Na+ v OH: 2NaCl + 2H2O = 2 NaOH + Cl2 + H2 ngn khng cho kh ch tip xc vi dung dch NaOH, ngi ta dng mng ngn bng li st ph aming bao quanh cc dng. Dung dch thu c c cha 8% NaOH cn ln rt nhiu NaCl, v vy khi c dung dch, NaCl c ha tan b hn nn kt tinh trc, c lp nhiu ln thu c NaOH c hm lng cao. KOH cng nh NaOH, d tan trong nc, trong metanol v etanol. Trong k thut cng iu ch KOH bng cch cho K2CO3 tc dng vi nc vi hoc in phn dung dch KCl c mng ngn. Khi lm bay hi dung dch cng c th thu c KOH rn, nhng thng dng trc tip dung dch c khong 50%. Kili hiroxit c dng ch yu trong cng nghip sn xut x phng
dp
mm, lm kh cc kh. hp th kh CO2... 2.9. Mui ca cc kim loi kim (l). cc mui ca cc kim loi kim u khng c mu, tr trng hp anion c mu, v d mui KMnO4 c mu tm l mu ca con MnO4. i a s cc mui ca kim loi kim u d tan trong nc, tr trng hp mt s mui ca liti l tng i kh tan. Dung dch trong nc ca cc mui ny hu nh in li hon ton v u cha ion kim loi kim khng mu. Nhng mui t lan ca kim loi kim thng l nhng mui c cha anion c kch thc ln ca cc kim loi kim nng. Sau y l tch s tan ca mt s mui thuc loi : Tch s tan (Tt) ca mt s mui kim loi kim
ClO4 MnO4 IO4 PtCI2-6 CO(NO2)63- (1) B(C6H6)4- (2) (1) ion hexanitro cobantiat (2) ion tetra phenylborat. K+ 1,1.10-2 8,3. 10 -4 1,4. 10 -6 4,3. 10-10 2,25. 10-8 Rb+ 5,0. 10-3 2,9. 10-3 5,5. 10-4 9,0. KT-8 1,48. 10-15 Cs+ 4. 10-3 9,1. 10 -5 4,4. 10-3 3,0. 10 -8 5,8. 10 -16 -
Mt s mui kp kim loi kim li rt kh tan nh kali uranyl ascnat UO2KAsO4 (Tt = 2,5. 10-23) kim uranyl photphat UO2KPO4(Tt =7,8. 10-24); natri uranyl asenat (Tt =l,3.10-22); natri km uranyl axetat ZnUO2(CH3COO)9.6H2O kt ta hon ton trong dung dch axit axctic long. Khi kt tinh t dung dch, cc mui kim loi kim hu nh khng to ra dng hirat tinh th tr mt s mui ca li v nam nh LiCl.H2O, LiNO3.H2O, NaCl.2H2O... Cc mui ca kim loi kim thng c nhit nng chy cao v dn in khi nng chy. (2) iu ch cc mui ca cc kim loi kim ngi ta ch ha t cc khong cht c trong thin nhin. Cc mui natri v kali - ch ha t khong cht clorua; mui liti - ch ha qung chuyn thnh dng mui ccbonat, mui ny kh tan nn d thu c dng tinh khit v t dng axit phn hy thu c cc mui khc nhau. Rubii v xezi l nhng nguyn t phn tn ln trong qung ca liti hoc kali, do cc mui ca rubi v xezi thu c t nc ci ca qung xinvinit KCl. MgCl.6H2O. 2.10. Halogenua ca kim loi kim (1) Halogenua ca cc kim loi kim u l nhng cht dng tinh th khng mu. Tt c u l hp cht ion, tr LiI c mt phn cng ha tr v ion I c kch thc ln d b cc ha ng thi con Li+ li c kch thc b nn li c tc dng cc ha ln.
Tr LiF (T, = 3,8.10-3), cc halogenua khc u d tan trong nc (bng 10).
Bng 10. tan ca cc halogenua kim loi kim (mol/l 180 C)

F0,1 1,1 15,9 12,5 24,2 CI18,6 5,8 4,5 7,2 10,9 Br 20,3 8,6 5,4 6,5 5,6 I 12,2 11,8 8,6 7,2 2,8
Li Na+ K+ Rb+ Cs-
T bng trn nhn thy tan ca cc florua tng t LiF n CSF, cn cc halogenua cn li - nhn chung - tan gim. Ni chung, ha tan cc cht ph thuc hai yu t chnh l nng lng mng li ca cc cht v nhit hirat ha ca cation. Nng lng mng li ca cc halogenua kim loi kim v nhit hirat ha ca cc ion kim loi kim nu trong bng 11 ; 12 di y: Bng 11. Nng lng mng li cc halogenua kim lot kim (kj/mol)
FClBrILi+ 991,6 815,9 774,0 715,5 Na+ 891,2 753,1 719,6 669,4 K+ 786,6 686,2 656,9 623,4 Rb+ 753,1 661,0 636,0 598,3 Cs+ 728,0 635,9 610,8 581,5
Bng12 Nng lng hirat ha cc cation kim loi kim (kj / mol)
Li+
0
Na+ 0,95 397
K+ 1,33 313
Rb+ 1,48 288
Cs+ 1,69 255
Bn knh ion ( A ) Nng lng hirat ha (kJ / mol)
0,60 506
T trn, theo chiu tng t Li+ n Cs+ nng lng mng li gim v nng lng hirat ha cng gim xung. Trong cc ngha i t Li+ n Cs+, nng lng mng li gim xung nhanh chng nn ha tan tng; tri li trong cc halogcnua khc, ha tan cc mui li gim do nng lng hirat ha gim. tan cc halogenua kim loi tng khi tng nhit (hnh 19). Ngi ta li dng kh nng ny tch cc mui clorua khi hn hp. V d ha tan ca Nacl v KCI c gi tr sau (gam/100gam H2O):
t 0C NaCI KCl 0 35,6 28,5 10 35,7 32,0 20 35,8 34,7 30 36,0 37,4 50 36,7 42,8 70 37,5 48,3 90 38,5 53,8 100 39,1 56,6
Khi un nng n gn nhit si ca nc, ha tan ca KCl cao hn NaCl, nhng khi lm lnh ha tan ca KCl li b hn NaCl, nn c th tch KCl khi hn hp vi NaCl. Khi kt tinh t dung dch, a s cc halogenua u tch ra trng thi khan tr cc mui sau y dng hirat: LiCl.H2O, LiBr.2H2O, LiI.H2O, LiI.3H2O, NaBr.2H2O, KF.2H2O, KF.4H2O, RbF. 1,5H2O. Tnc v Ts ca cc halogenua kim loi kim u cao v gim dn (bng 13). Khi un nng chy hn hp gm hai halogenuakim loi kim bt k, s c ZZ X phn ng trao i: AX +BX YZ Z AY +BX, cn bng s chuyn dch v pha to ra hai mui trong c mt phn t gm cc ion nh hn v mt phn t gm cc ion ln hn. V d: ZZ X NaI + RbCl YZ Z NaCl + RbI Bng 13. Nhit nng chy (Tnc) v nhit si (Ts) ca cc halogenua kim loi kim (0C)
FLi+ Na+ K+ Rb+ Cs+ Tnc Ts Tnc Ts Tnc Ts Tnc Ts Tnc Ts 842 1676 995 1702 856 1505 780 1410 684 1251 Cl606 1382 800 1454 768 1417 717 1883 638 1303 Br549 1310 740 1393 728 1376 681 1350 627 1300 I453 1170 610 1300 682 1330 642 1305 621 1280
(2) Nam clorua (NaCl) l mui quan trng nht trong cc halogenua ca kim loi kim. NaCl l hp cht ion, tinh th c mng lp phng tm din. Trong thin nhin, NaCl c trong nc bin khong 2,7% theo khi lng; c trong mui m, nhng m mui ln c lp dy n 1000m hoc ln hn. Cng nh KCl, NaCl tinh th c trong sut cao i vi tia trng thy v tia hng ngoi nn c dng ch to mt s dng c quang hc . Khi nng chy, mt phn NaCl bay hi nhng mc km hn so vi KCl. Ngi ta xc nh c 8000C, p sut hi ca NaCl l 1 mmHg; cn KCl 8000C l 4,5 mmHg . Ngi ta khai thc mui n t nc bin bng cch un nng hoc bng cch phi nng; mui n cng c th khai thc t mui m bng phng php ngm , bng cch ha tan ngm sau bm dung dch ln ri kt tinh li. iu ch NaCl tinh khit t mui n k thut , ngi ta cho kh HCl sc qua dung dch mui n bo ha, v ha tan ca NaCl gim khi c mt ca NaOH, HCl, CaCl ... NaCl c v mn , dng lm thc n cho ngi v gia sc (nn gi l mui n). Mui n tinh khit khng ht m, nhng mui bin li b chy ra trong khng kh do ln tp cht nh MgSO4 , CaCl2... NaCl rt cn cho c th , trong huyt thanh ca ngi c cha khong 0,08 % NaCl. Trong y khoa dng dung dch NaCl 0,9 % (dung dch ng trng) trong cc trng hp chy mu nhiu, a chy mt nc ... v dung dch NaCl 10 - 20% (gi l dung dch u trng) trong cc trng hp i t mt nc qu nhiu, ngoi ra cn dng ra v p cc vt thng c m . v. v...
Trong cng nghip NaCl dng iu ch Na, Cl2, HCl, NaCl v trong nhiu ngnh khc nh nhum, thuc da... (3) Cc halogenua khc Kali clorua (KCl) tinh khit l cht khng mu; tinh th trong sut, khng ht m . Trong cng nghip, KCl c iu ch t cc khong cht cacnalit KCl.MgCl.6H2O bng Cch ha tan trong nc sau lm bay hi, KCl c tan b hn nn tch ra dng tinh th trc. Trong k thut, KCl cng c iu ch t khong cht xinvinit (NaCl.KCl) bng cch ha tan xinvinit trong dung dch bo ha mui n khi un nng, sau khi ngui KCI s kt tinh. KCl c gi tr ln v l thnh phn chnh ca phn kali . Lui clorua (LiCl) khng mu , bay hi r rt nhit nung nng . c iu ch bng cch cho axit HCl tc dng vi mui cacbonat: Rubii clorua (RbCl) v xezi clorua (CsCl) u kt tinh theo kiu lp phng v u c iu ch bng cch cho HCl tc dng vi mui cacbonat tng ng; hoc bng cch phn hy hp cht cloroplatinat ca chng. Kali bromua (KBr) tinh th khng mu , c dng lm thuc an thn, ng kinh. Kali iotua (K) cng l tinh th khng mu , d ht m , chy nc c mu vng nu. Dung dch Ki trong nc c kh nng ha tan c iot do phn ng:
2.11. Cacbonat ca kim loi kim (1) cc kim loi kim to ra hai loi mui l hirocacbonat MHCO3 v cacbonat M2CO3 Ngi ta bit c tt c cc hiro cacbonat ca kim loi kim trng thi rn tr liti hiro cacbonat ch c bit trong dung dch nc. Tt c cc hirocacbonat ca kim loi kim u d tan, trong NaHCO3 t tan. Dung dch ca chng c mi trng kim rt yu (hnh 20). Khi un nng dung dch, MHCO3 b phn hy dn thot ra CO2 v dung dch tr nn kim mnh: ngay nhit thng, nu khng kh khng cha CO2 , MHCO3 trong dung dch cng dn dn b phn hy. trng thi kh, MHCO3 l nhng tinh th nh khng ngm nc, bn
nhit thng, khi un nng chng d b phn hy to thnh mui M2CO3 nh nu trn. bn nhit tng ln r rt t Na n Cs (hnh 21).
Mui hirocacbonat c to ra khi cho kh Coi tc dng vi mui cacbonat: (2)' Cc mui cacbonat ca kim loi kim u tan , dung dch u c tnh kim mnh do Phn ng thu Phn ; ha tan tng theo s th t nguyn t; Li2CO3 t tan (T, = 3,98.10-3); nhit thng tan ca Li2CO3 l 0,17 mol/l v gim xung khi nhit tng. Cc mui cacbonat M2CO3 rt bn i vi nhit. nhit nng chy (trong kh quyn CO2) vn cha b phn hy:
Li2C03 Na2C03 735 852 K2C03 Rb2C03 894 837 Cs2C03 -
Tnc (C)
Nhng khi nung nhit cao hn, cc mui b phn hy thnh oxit v kh CO2:
bn vi nhit ca chng tng t Li2CO3 n K2CO3 v gim xung t K2CO3 n Cs2CO3 (hnh c hai loi mui hirocacbonat v cacbonat u b axit mnh phn hy to ra kh CO2: HCO3 + H+ = CO2 + H2O CO2 + 2H+ = CO2 + H2O
Dung dch mui cacbonat c tnh kim mnh hn nn khi tc dng vi mui ca mt s kim loi, mui cacbonat kim loi kim to ra mui cacbonat baz ca kim loi , cn mui hirocacbonat to ra mui trung tnh:
Trong cc mui cacbonat kim loi kim th Li2CO3 ging vi mui cacbonat kim loi kim th, c th c iu ch bng cch cho amoni cacbonat tc dng vi Li2SO4 hoc mt s mui khc: Cn cc mui kim loi kim khc iu ch bng cch cho Coi tc dng vi hiroxit: Trong thc t , mui NaHCO3 v Na2CO3 l c nhiu ng dng . (3) Natri hirocacbonat (NaHCO3 l cht bt tinh th mu trng gm nhng ion Na+ v HCO3 . Cc ion HCO3 lin kt vi nhau bng lin kt hiro . NaHCO3 tan trong nc to ra mi trng kim rt yu:
t0C tan (g/100gH2O) 0 6,9 10 8,15 20 9,6 30 11,1 40 12,7 50 14,5 60 16,4
Dung dch NaHCO3 c th lm thay i mu qu tm hoc metyl da cam nhng khng lm thay i mu ca dung dch phenollhtalein (00C): NaHCO3 b phn hy mnh 350 - 4000 C theo phng trnh: nhit phng, dung dch NaHCO3 cng b mt mt lng CO2 ng k, cn khi un nng dung dch trn 700c th phn hy mnh hn. NaHCO3 c th c iu ch bng cch cho kh CO2 tc dng vi dung dch NaOH: hoc cho kh CO2 qua dung dch lnh bo ha Na2CO3: NaHCO3 c dng trong y khoa cha bnh d dy v rut do tha axit, d tiu, gii c do axit, chng nn o . Cng c dng trong cng nghip thc phm lm cht gy xp cho cc loi bnh . (4) Natri cacbonat (Na2CO3) khan l cht bt mu trng m v nng chy
8520C . Cao hn 8520C, bt u b phn hy (hnh 22). D tan trong nc , qu trnh tan pht nhiu nhit do s to thnh hirat. T dung dch, nhit di 32,50C, nam cacbonat kt tinh dng Na2CO3.10H2O. Gia khong 32,5 37,50C, Na2CO3.10H2O mt nc kt tinh bin thnh dng heptahirat Na2CO3.7H2O ; trn 37,50C bin thnh monohirat Na2CO3.H2OV n l070C mt nc hon ton to thnh Na2CO3 khan (hnh 23). T hnh 23 cho thy tan ca Na2CO3 .10H2O tng ln theo nhit cn tan ca Na2CO3. H2O li gim xung. Na2CO3.10H2O ln hoa nhanh ngoi khng kh to thnh bt trng Na2CO3.5H2O. Khi tan trong nc Na2CO3 b thy phn lm cho dung dch c tnh kim: vi dung dch 6N c pa = 12,8; dung dch 1N c pH = 12,3; dung dch 0,1 N c pH = 10,9 .
Na2CO3.H2O l nhng tinh th trng dng hnh thoi, mt nc 470C ngoi khng kh. Na2CO3 tinh khit c iu ch bng cch nhit phn NaHCO3 Trong cng nghip ngi ta iu ch Na2CO3 bng phng php Xonvay(E. Sonvay, 1838 - 1922 - ngi B) ra nm 1864 bng phn ng: Thc cht phn ng trn l thun nghch , ha tan cc cht trn 200C c gi tr nh sau:
tan (g/100gH2O)
NaCl NH4HCO3 NaHCO3 36 21 9,6
NH4Cl 37,2
Nh vy NaHCO3 t rn hn nn cn bng chuyn sang phi. Trong thc t, ngi ta cho kh NH3 ri kh CO2 qua dung dch NaCl bo ha: Lc tch NaHCO3 ri nung nng chuyn thnh Na2CO3 khan. Kh CO2 thu c t qu trnh ny c a li vo qu trnh sn xut. Sn phm ph NH4Cl li cho phn ng vi vi ti ti sinh kh NH3 cng c a li qu trnh sn xut
Ngi ta cng iu ch Na2CO3 t Na2SO4 bng phng php L Blng (N.Le Blanc - 1791) khi nung chy hn hp Na2SO4 vi vi v than 10000C. Phn ng xy ra nh sau:
Na2CO3 tch ra khi hn hp vi CaS kh tan bng cch ch ha vi nc. CaS c th dng iu ch H2S v sau iu ch lu hunh. Trong phng php trn , Na2SO4 c ly t ngun thin nhin hoc mui m ri cho tc dng vi H2SO4 c: Ngi ta cng iu ch Na2CO3 t criolit Na3AlF6 ( M) theo nguyn tc nung hn hp Na3AlF6 vi CaCO3:
sau Na3AlO3 b phn hy bi H2O v CO2: Ngi ta cng khai thc Na2CO3 t Cc h mui cacbonat c trong thin nhin , bng cch lm lnh hoc bng cch cho nc bay hi, hoc khai thc t kt ta Na2CO3 tch t y h di dng khong cht trong Na2CO3.NaHCO3.2H2O S hnh thnh Na2CO3 trong thin nhin trong cc h mui l do s kh Na2SO4 thnh Na2S bi cc vi khun hoc cc cht hu c di tc dng ca nhit cao; sau Na2S di tc dung ca H2O v CO2 kh quyn to thnh Na2CO3 , theo s :
H2S to ra trng thi kh , hoc ha tan trong nc ngm , hoc lin kt vi cc hp cht ca st trong nc to thnh bn mu en FeS. (5) Kim cacbonat (K2CO3) Cn gi l potat, l tinh th khng mu , ht m. Khi lng ring l 2.29g/m3. Nng chy 8940C , cao hn nhit th b phn hy . Tan trong nc cho phn ng kim; tan tng theo nhit :
tc tan (g/100gH2O) 0 105 25 113,5 100 156
Khi ngui dung dch bo ha, thu c dng hirat K2CO3.2H2O ; mt nc kt tinh 1000C Trong cng nghip , potat c iu ch bng cch cho kh CO2 tc dng vi KOH c iu ch l dung dch KCl bng phng php in phn: Tuy nhin , K2CO3 thu c theo phng php ny cn ln KCl kh tch ra. Ngi ta cng iu ch bng cch da vo tan km ca mui kp KHCO3.MgCO3.4H2O (phng php Engel v Precht). Mui kp ny to ra khi cho kh CO2 tc dng vi dung dch KCl bo ha mt huyn ph MgCO3 . 3H2O: un nng n 600C , mui kp trn phn hy thnh K2CO3 v
MgCO3.3H2O: Ngoi hai phng php ch yu trn , ngi ta cn dng phng php fomiat (phng php Goldschmidt) bng cch cho hn hp ng phn t K2SO4 v vi ti ri cho bo ha kh CO 2000C v 30atm:
lc tch CaSO4 , lm kh dung dch KHCO2 , sau nung cht rn, thu c K2CO3: K2CO3 c dng trong cng nghip x phng v cng nghip thy tinh. 2.12. Sunfat cc kim loi kim (1) Axit H2SO4 l axit hai ln axit nn to ra vi kim loi kim hai loi mui . Mui trung ha tan trong nc cho mi trng trung tnh ; mui axit (hay mui hirosunfat) tan trong nc cho phn ng axit . Cc mui sunfat v hirosunfat cc kim loi kim u d tan trong nc v u kt tinh t dung dch di dng khng ngm nc. tr Li2SO4.H2O v Na2SO4.10H2O tch ra khi dung dch iu kin thng . Nhit nng chy ca cc sunfat khan u rt cao: Li2SO4 (8600C); Na2SO4(8850C); K2SO4 (10690C); Rb2SO4(10740C); Cs2SO4(10100C). Tnh bay hi v bn cng bin i tng dn t liti n xezi. (2) Natri sunrat (Na2SO4.10H2O) l nhng tinh th lng tr , khng mu , v ng , khi lng ring l 1,46 g / cm3 . Kt tinh trong dung dch nc di 32,3830C c thnh phn Na2SO4.10H2O. trong khng kh b ln hoa nhanh , tch nc kt tinh to ra cht bt mu trng. Khi un nng cao hn 320C, nng chy trong nc kt tinh to ra dng mui khan . Kh nng ha tan ca natri sunfat (gam /100g dung dch) ph thuc nhit :
t0C 0 10 8,24 20 16,4 30 28,9 32,38 40 33,2 50 100
tan(g/100gdd) 4,5
32,5 31,8 29,8
ha tan cc i 32,380C , l im chuyn

tip gia dng ecahirat v dng khan, cng l im chuyn tip gia dng rn v dung dch bo ha. Di nhit dung dch bo ha cn bng vi tinh th Na2SO4.10H2O tc l tn ti dng ecahirat , trn 32,380C natri sunfat tn ti dng khan . S d ng cong tan ca natri - sunfat c im chuyn tip nh vy l do Na2SO4.10H2O c nhit ha tan m (H = + 78,49 kj/mol) nn khi tng nhit , ha tan tng. 32,380C , dng hirat chuyn thnh dng khan. Nng lng mng li ln hn nng lng hirat ha ca ion Na+ v SO42, nhit ha tan c gi tr dng, qu trnh pht khit nn cn bng tan sau y: chuyn sang tri khi tng nhit , kt qu l ha tan gim . Mt lng ln Na2SO4 thu c l sn phm ph ca qu trnh iu ch HCl t Nht v H2SO4 Trong thin nhin NaiSO4 nng cc khong cht glauborit Na2SO4.CaSO4; astracanit Na2SO4.MgSO4.4H2O; glazcrit Na2SO4.2K2SO4.... Natri sunfat c dng lm cht sinh hn. Trong y khoa, Na2SO4.10H2O c dng lm cht nhun trng; mt lng ln c dng trong cng nghip thy tinh. (3) Natri hirosunfat (NaHSO4) l nhng tinh th khng mu, d tan trong nc. Khi nung nng s mt nc to ra natri pyrosunfat: Nu nung mnh hn b phn hy tch ra SO3: Ngi ta li dng tnh cht ny chuyn mt s cht kh tan thnh cht d tan. V d trang hn hp gm Na2S2O7 + Cr2O3 Chuyn Cr2O3 thnh Cr(SO4)3 d tan: v cng c dng lm sch cc chn platin. NaHSO4 c to ra khi un nng c mc hn hp gm mui n vi
H2SO4 c: nu un nng mnh s to thnh Na2SO4: (4) Kali sunfat v khu hirosunft (K2SO4 V KHSO4) Kali suntktt trng thi khan dng hnh thoi. 5870C cu cang dng lc phng . Khi lng ring 180C bng 0C, 67 g/cm3. tan trong nc nh sau:
t0C tan(g/100gH2O) 0 7,35 10 9,22 20 30 40 50 100 11,11 12,97 14,76 16,50 24,1
Trong cng nghip, K2SO4 c iu ch t cc khong cht mui kim v magie sunfat, v d t khong cht kainit KCl.MgSO4.3H2O hoc t KCl v khong cht kizenit MgSO4.6H2O. Trong dung dch nc , MgSO4 Phn ng vi KCl: sau , K2SO4 v MgSO4 s to ra mui kp kh tan: lc cht rn v ra bng dung dch KCl ,thu c K2SO4: Kali hirosunfat KHSO4 l nhng khi mt thoi , khi lng ring 2,36 g/cm3, tan trong nc cho phn ng axit . Nhit nng chy 2160C . Khi nung 160 : 1700C, mt H2O to thnh kali pirosunfat v sau chuyn thnh mui trung ha:
tan ca KHSO4 trong nc nh sau:

t0C tan(g/100gH2O) 0 36,3 20 51,4 40 67,3 100 121,6
KHSO4 c xem l sn phm ph trong qu trnh sn xut HNO3 t KNO3 v H2SO4 c: dng tinh khit , c iu ch bng cch un nng hn hp gm K2SO4
V H2SO4 c Cho n khi c mt khi trong sut , lm lnh cht lng, c nhng tinh th KHSO4:
2.13. Nitrat cc kim loi kim (1) Nitral ca cc kim loi kim u l nhng cht kt tinh, d nng chy v tan nhiu trong nc. Nhit nng chy: LiNO3 - 2520C ; NaNO3 - 3060C ; KNO3 - 3330C ; RbNO3 - 3130C ; CsNO3 - 4040C. Khi un nng cao hn, b phn hy theo s : Trn hnh 25 cho thy tan ca cc nitrat kim loi kim u tng theo nhit . Ring ng cong ca LiNO3 c cc im gy l do tan khc nhau ca cc dng hirat LiNO3.3H2O; LiNO3.1,5H2O; cc nitrat ca kim loi kim khc khng to thnh hirat tinh th nn khng c cc im gy. Vi nitrat ca K, Rb, Cs ngoi mui khan, cn to ra nhng sn phm kt hp vi HNO3 vi dng tng qut MNO3.HNO3, MNO3.2HNO3, do khi ha tan cc tinh th nhng mui ny u c rt d HNO3 t do. Trong cc nitrat kim loi kim th NaNO3 v KNO3 l c gi tr thc t. Ngi ta dng c hai mui lm phn bn. KNO3 cn dng ch thuc sng en (khng dng NaNO3 v ht m). (2) Nam nitrat NaNO3 l nhng tinh th t din khng mu thuc h lc phng, chy ra ngoi khng kh m; tan nhiu trong nc. Khi un nng b phn hy to ra NaNO2 v oxi, sau l hn hp gm oxi, nit, v NO2. Phn ln NaNO3 thu c l sn phm ph ca qu trnh sn xut HNO3 khi cho cc oxit nh hp th bi dung dch kim. (3) Kim nitrat KNO3 l nhng tinh th trong sut , khng mu, bn trong khng kh; d tan trong nc. Khi un nng trn nhit nng chy (3330C) , bt u b phn hy tch ra O2 v chuyn thnh KNO2. KNO3 c iu ch bng phn ng phn hy K2CO3 bi HNO3 hoc phn
ng trung ha KOH vi HNO3. Ngi ta cng iu ch KNO3 bng phn ng trao i gia NaNO3 vi KCl: Phng php ny da trn tan khc nhau ca cc mui trn (g/100g H2O): KCl NaCl KNO3 NaNO3 1000C 175 56,6 39,1 246 0C 73 28,5 35,6 13
Khi thm KCl vo dung dch nng bo ha NaNO3, cn bng trn chuyn dch sang phi, NaCl t tan hn s tch ra trc, dung dch cn li bo ha NaCl v KNO3. Khi lm lnh dung dch , KNO3 t tan hn s tch ra sau. KNO3 c dng lm phn bn v c dng ch to thuc n. Thuc n thng thng (thuc sng en) l hn hp gm 68% KNO3, 15% S v 17% C gn ng vi thnh phn 2KNO3 + 3C + S , ni chung t l ny c thay i tu theo loi ring bit . V cn bn phn ng chy ca thuc sng xy ra theo phng trnh: Ngoi ra, mt phn to thnh K2SO4, K2CO3, CO, SO2:
2.14 . Mui kh tan ca kim loi kim (1) Nam hiroxoantimonat Na[Sb(OH)6] cn gi l natri hiropiroantimonat l cht bt mu trng hi xanh , to ra dng vi tinh th khi cho mui kali tng ng tc dng mui natri trong mi trng trung tnh hoc kim yu: Phn ng trn dng trong phn tch xc nh natri. (2) Kali hirotactrat KH[C4H4O6] (KOOC - CHOH - CHOH - COOH) l mui kh tan ca kali. Trong 100 g H2O, mui trn ch ha tan c 0,57 g 00C v 6,9 g 1000C. tan ca mui gim mnh trong dung dch ru. Tri li , mui trung ha K2[C4H4O6] v mui hn tp KNa[C4H4O6].4H2O li rt d tan. Mui kali hexacloroplatinat K2[PtCl6] tng i t tan. 200C ha tan l 1,09 trong 100 g dung dch. Trong dung dch ru, thc t l khng tan . K2[PtCl6] l cht rn tinh th mu vng; khi un nng , mui b phn hy to ra
kim loi. Kali peclorat KClO4 cng l mui t tan ca kali, nhng tan ph thuc mnh v nhit . Trong 100 g nc, kim peclorat ch ha tan c 0,7 g 00C v 18,7 g 1000C. (3) Cc mui peclorat, hexacloroplatinat, bitactrat ca Rb v Cs u l mui kh tan. ha tan ca cc mui trn (s gam mui khan trong 100 g dung dch) nh sau: Cs+ Rb+ MCIO4 0,76 g (140 C) 1,17g(140C) M2[PtCl6] 0,028 g (200 C) 0,009 g (200 C) MH[C4H4O6] 1,17g(250C) 8,9 g (250 C) (4) Tri li , cc mui Li2[PtCl6], LiH[C4H4O6] li d tan , nhng mui LiF, Li2CO3 , Li3PO4 u l mui kh tan . tan (s gam mui khan trong 100g dung dch) cc mui nh sau:
CHNG 3 CC NGUYN T NHM IIA (KIM LOI KIM TH) 3.1. Nhn xt chung v cc nguyn t nhm IIA (1) cc kim loi kim th thuc nhm IIA ca bng tun hon gm cc nguyn t Be (Beryllium), Mg(Magnesium), Ca(calcium), Sr (Strontium), Ba(Barium) v Ra (Radium). Berili c nh ha hc ngi Php l Vclanh(L. Vauquelin) tm ra nm 1798 trong qu beng, nhng mi n 30 nm sau mi c Vol (F. Whler) ngi c v Buyxi (A. Bussy) ngi Php- c lp vi nhau - mi iu ch c bt bnh tng i tinh khit. Magie - ln u tin c nh ha hc ngi Anh l vi (H.Davy) iu ch nm 1808. Canxi cng c vi iu ch nm 1808 bng phng php in phn . Nm 1790, mt bc s ngi Sctlen (Scotlandl l Cng (A. Crouford) pht hin c khong vt cha sng , nhng n nm 1808 , vi l ngi u tin tch c tronti kim loi bng phng php in phn. Nm 1774 , nh ha hc Thy in l Sut K. Scheele) tm ra bao dng oxit v n nm 1808 , vi mi iu ch c ban kim loi. Rinh c nh ha hc ngi Php l Pie Curi (PieTTe Curie) v B mng (Bmont) pht hin c trong qung gian vo nm 1898; n nm 1910 c Mau Curi (Marie Curie) v bicn (A. Debieme), ngi Php, tch ra dng kim loi. . (2) Nguyn t khi, s th t nguyn t v s phn b electron nh sau:
Nguyn t Berili Magie Canxi Stronti Bari Radi K hiu S th t Nguyn t khi Be 4 9,01 Mg 12 24,31 Ca 20 40,08 Sr 38 87,62 Ba 56 137,34 Ra 88 [236] Phn b electron 2 2 2 2 2 2 2 8 8 8 8 8 Ha tr II II II II II II
2 8 18 18 18
2 8 18 32
2 8 18
2 8
(3) u c hai electron ha tr ns2 ngoi lp v ca cc kh tr ng trc mi nguyn t, nn cc kim loi kim th u d mt electron to thnh ion M2+ , do vy cc kim loi kim th u c tnh kh mnh v tnh kh tng dn t Be n Ra. Tuy nhin, so vi kim loi kim cng chu k th km hot ng hn v c in tch ht nhn ln hn v bn knh b hn. Cc ion M+ c lp v ca kh tr (n - 1)s2 p6 nn u th hin tnh oxi ha
yu. (4) Di y l mt s c im ca cc nguyn t ca cc kim loi kim th (bng 14). Bng 14 . Mt s c im ca cc nguyn t kim loi kim th
Nguyn t Electron ha Bn knh tr nguyn t
0
Bn knh ion
0
Th ion ha (eV) I1 9,32 7,69 6,11 5,96 5,21 5,28
(A ) Be Mg Ca Sr Ba Ra 2s 3 s2 4s2 5s2 6 s2 7s2

2
M (A ) 0,34 0,74 1,04 1,20 1,33 1,44
2+
1,13 1,60 1,97 2,15 2,21 2,35
I2 18,21 15,03 11,87 10,93 9,95 10,10

0
(5) Be v Mg kt tinh theo mng lc phng (hnh1).Vi Be (a = 2,268 A ;

0
c = 3,594 A . Mi nguyn t Be c bao quanh bi 12 nguyn t khc; 6 nguyn t nm trong cng mt mt phng c khong cch l a. Vi Mg c a = 3,22 A ; c = 5,56 A ; mi nguyn t Mg cng c bao quanh bi 12 nguyn t khc . Canxi kt tinh theo mng lp phng tm din (hnh li c cnh (a = 5,56 A (dng - Ca). Mi nguyn t Ca c bao quanh bi 12 nguyn t khc c khong cch gia hai nguyn t d: 0,5 a 3 = 3,94 A . 3000C , - Ca chuyn thnh dng th hnh - Ca c tnh i xng km hn; 4500C chuyn thnh dng th hnh - Ca c mng lc phng tng t Mg. Stronti, tng t canxi, kt tinh theo mng lp phng tm din c
0 0 0 0 0 0
a = 6,05 A v d = 4,27 A . Bari kt tinh theo mng lp phng tm khi c (a = 5,01 A . Mi nguyn t bao quanh bi 8 nguyn t khc, c khong cch d = 0,5 a 3 = 4,34 A (hnh 1). 3.2. Trng thi thin nhin v thnh phn cc ng v (1) Cng nh cc kim loi kim, cc kim loi kim th ch tn ti trong
0 0
thin nhin dng hp cht. Trong v qu t Ca v Mg thuc loi nguyn t ph bin nht v c phn b nh
Nguyn t Be Mg Ca Sr Ba Ra % s nguyn t 1,2 .10 3 2,0 2,0 1,0. 10-2 5,7. 10-2 9,0. 10-12 %khi lng 6. 10 -4 2,1 3,6 4. 10-2 5. 10-2 1. 10 -10
(2) Khong vt chnh ca berili l beryl BeAl2(SiO3)6 hay 3BeO.Al2O3.6SiO2. Mt s dng beryl trong sut c mu khc nhau do ln tp cht c gi l ngc. V d ngc bch c mu lc (tp cht l hp cht ca crom), lam ngc c mu xanh da tri ... Hp cht thin nhin c cha magie c dng cacbonat nh qung manhezit MgCO3; qung olomit MgCO3.CaCO3; dng clorua nh qung bisophit MgCl2.6H2O; Cacnalit KCl.MgCl2.6H2O; dng sunfat nh kizerit MgSO4.H2O; kainit KCl.MgSO4.3H2O; dng silicat hoc hirosilicat nh bt tale Mg3H2(SiO3)4 hay Mg2[Si4O10].Mg(OH)2; qung atbet CaMg3(SiO3)4... Khong vt c cha canxi dng cacbonat l dng canxit aragonit CaCO3 olomit CaCO3.MgCO3; dng sunfat nh thch cao (xelenit) CaSO4.H2O; anhirit CaSO4; xighenit K2SO4.CaSO4.H2O; gloherit NaI2O4.CaSO4, dng florua nh fluorit CaF2 apatit 3Ca3(PO4)2.CaF2 v.v.... Strontiv banric trong cc qung ch yu l strontianit SrCO3 ,viterit BaCO3 xelestin SrSO4; barit BaSO4 . Radi l nguyn t phng x, c trong cc qung ca gurn nh qung cacnotit K2(UO2)2(VO4)2.3H2O) Trong nc i dng , thnh phn trung bnh ca cc kim loi kim th nh sau (theo A.P. Vinogradov 1967): Nguyn t Be Mg Ca Hm lng mg// % -11 6. 10 6. 1-7 0,1297 1,297 0,0408 408 Nguyn t Sr Ba Ra Hm lng mg// % -4 8. 10 8,0 -6 2. 10 0,02 -14 1. 10 1. 10-10
(4) Canxi khng nhng lun lun c trong t, trong nc bin m c c trong c th ca ng vt v thc vt. Canxi c trong thnh phn cu to nn
xng v l thnh phn khng th thiu ca mu. (5) Hm lng ca cc kim loi kim th c trong cc mu do cc tu Apollo 11 - 12 v Luna - 6 a t Mt Trng v ba vng khc nhau c gi tr nh sau:
Nguyn t Be Mg Ca Sr Ba Apollo-11 0,2. 10-5 0,045 0,080 17. 10-5 20. 10-5 Hm lng trung bnh (s gam /1 g mu ) Apollo-12 Luna -6 0,25. 10-5 0,072 0,071 -5 17. 10 22. 10-5 42. 10-5 18,5. 10-5
(6) Be c bn ng v, trong ch c mt ng v thin nhin l 9Be (100%), cn li l ng v phng x, ng v 10Be c chu k bn hy lu nht l 2,5.106nm. M c su ng v t 23Mg n 28Mg trong c ba ng v thin nhin l 24 Mg(78,60%), 25Mg(10,11%), 26Mg (11,29%), cn li l ng v phng x. Trong cc ng v phng x th ng v 28Mg l bn hn c vi chu k bn hu 0,891 ngy m. Ca c 11 ng v t 39Ca n 49Ca. cc ng v thin nhin l 48Ca (96,97%), 42 Ca (0,64%), 43Ca (0,145%), 44Ca(2,06%),46Ca(3,3.10-3%, 44CaC(0,085 %); trong nm ng v phng x cn li th ng v 41Ca bn nht vi chu k bn hy l 1,1.105 nm. Sr c 16 ng v t 81Sr n 97Sr(khng c ng v 96Sr), trong c bn ng v thin nhin l 84Sr (0,56%), 86Sr(9,86%), 87Sr (7,2%), 88Sr (82,56%). Trong cc ng v phng x th ng v 90Sr l bn nht vi chu k bn hu l 28 nm. Ba c 19 ng v t 126Ba n l44Ba trong c by ng v thin nhin l 130Ba (0,101%), l32Ba (0,097 %), 134Ba (2,42 %), 135Ba (6,59%), 136Ba(7,81%), l37Ba (11,32%), l38Ba (71,66%). ng v phng x bn nht ca bari ng v 133Ba c chu k bn hy lu nht l 10 nm. Ra c 13 ng v l 213Ra v cc ng v t 219Ra n 230Ra tt c cc ng v u c tnh phng x v bn nht l 228Ra c chu k bn hy l 6,7 nm. 3.3. iu ch cc kim loi kim th (1) Nguyn tc chung iu ch cc kim loi kim th l dng dng in hoc dng cht kh mnh kh ton kim loi kim th to kim loi: bng phng php in phn mui clorua nng chy hoc dng cht kh nh C, Al, Si... (2) Berili c iu ch bng phng php in phn BeCl2 nng chy, hoc hn hp gm BeCl2 + NaCl hay hn hp BeCl2 + NaF trong thng bng niken vi cc dng bng than ch. Ngoi ra cn dng phng php nhit - magie
kh BeFl. (3) Trong cc kim loi kim th th magie c nhiu ng dng trong k thut. Trong cng nghip ngi ta iu ch ma gie bng phng php in phn MgCl tinh khit hoc cacnalit khan nng chy (MgCl2.KCl) hoc hn hp mui clorua tng ng nhit khong 700 - 7500C trong thng in phn bng thp ng thi l cc m. Cc dng l mt tr than ch t trong ng s xp c l nh cho kh clo thot ra ngoi (hnh 26). trnh khng cho magie lng tp trung phn trn cht in phn khng b khng kh oxi ha, ngi ta thi chm mt lung kh H2 trn b mt ca magie lng. c MgCl2 thm vo, ngi ta iu ch t manhezit MgCO3 hoc t olomit MgCO3.CaCO3 theo phn ng: Kh clo c ly t cc dng ca bnh in phn. Ngoi ra, ngi ta cng thu magie clorua bng cch ch ha nc bin khi cho tc dng vi vi hoc sa olomit, lc ly Mg(OH)2 ri cho tc dng vi axit HCl. Ngoi phng php in phn, phng php quan trng trong cng nghip hin nay iu ch ma gie l phng php nhit. Nguyn tc ca phng php ny l dng cc cht kh nh CaC2 hoc than (phng php nhit - cacbon), hoc dng silic (phng php nhit - silic) kh MgO. Qu trnh kh c thc hin bng cch nung nng hn hp gm MgO(t manhezit) vi than antraxit nghin nh trong l h quang theo phn ng: cn bng chuyn theo chiu thun trn 2000oC; ngn cn qu trnh nghch to li MgO, ngi ta lm lnh rt nhanh hn hp hi thot ra ti 150 - 2000C v cn bng khng kp chuyn sang bn tri. Magie kim loi lng xung dng bi c cha tp cht MgO v C, tip tc c nu li, thu c magie c tinh khit cao (99,97 %). Thay cho cacbon, ngi ta cn dng CaC2 lm cht kh trong l chn khng 12000C theo phn ng: Ngi ta cn dng silic dng fero - silic lm cht kh MgO vi nguyn liu l olomit nung. Hn hp MgO + CaO vi silic nung nng di p sut nhit 1200 - 1 3000C. Phn ng xy ra theo phng trnh: hi magie thu c c tinh khit khong 98 - 99 %.
iu ch ma gie tinh khit (99,999%) ngi ta thng hoa lp magie k thut trong chn khng. (4) Canxi c iu ch bng phng php in phn CaCl2 nng chy trong l lt than ch, y l c lm ngui bng nc chy pha di. Qu trnh in phn vi catot bng st v anot - than ch. Cht in phn l CaCl2 khan, in p vo khong 20 30V, cng dng in vo khong 3000A v nhit cng thp cng tt. Nh nhit thp, thnh l bng than ch lun lun c ph bng mt lp mui rn bo v. Canxi c tinh khit cao c iu ch trong cng nghip bng cch dng nhm kh CaCl2 nhit cao: AlCl3 to thnh s bay hi (thng hoa 1830C) cn li l Ca c chng ct trong chn khng hoc trong kh agon. (5) Stronti cng c iu ch bng cch in phn mui clorua nng chy; cn bari c iu ch bng cch kh BaO trong chn khng bi nhm hoc silic 12000C theo phn ng:
3.4. Tnh cht l hc cc kim loi kim th v ng dng (1) cc kim loi kim th u c mu trng bc hoc xm nht, tr Be v Mg vn gi c nh kim trong khng kh, cn cc kim loi cn li u b m nhanh chng, do b ph mt mng mng mu vng nht, gm oxit Mo, mt phn peoxit MO2 v nitrua M3N2 Bng 15 l mt s hng s l hc quan trng ca chng. Bng 15. Mt s hng s l hc quan trng ca kim loi kim th
Tnh cht Khi lng ring (g / cm ) Nhit nng chy (TK, C) Nhit si (Ts, C) dn in (Hg =1) cng (so vi kim cng = 10) Th in cc (V) m in
(1) 3
Be 1,85 1285 2471 5 4 -1,85 1,5
Mg 1,74 651 1100 21 2,5 -2,37 1,2
Ca 1,60 851 1489 20,8 2,0 -2,87 1,0
Sr 2,60 770 1880 4
Ba 3,75 710 1634 1,5
-2,89 1,0
-2,90 0,9
(1) Theo Pauling. Trn hnh 28 m t s bin thin mt s tnh cht l hc ca cc kim loi kim th. Nhn chung, a s tnh cht ca cc kim loi kim th u cao hn cc kim loi kim l do lin kt kim loi trong kim loi kim th mnh hn trong kim loi
kim. Nhit nng chy v nhit si cao hn v bin i khng u nh cc kim loi kim, v cc kim loi kim th c cu trc mng tinh th khc nhau, trong khi cc kim loi
kim li c cng mt loi mng tinh th; mt khc lin kt trong kim loi kim th mnh hn nn nhit nng chy Tnc v nhit si Ts cao hn. Mi nguyn t kim loi kim th u c hai electron s nn vng s c lp y, v nu vy cc kim loi kim th phi l cht cch in hoc bn dn in;
thc t chng li c dn in cao v gn tng ng cc kim loi kim ? iu c th c gii thch rng vng nng lng s v p c mc nng lng gn nhau nn d xen vo nhau, hai electron s c nng lng nm trong vng kh rng cha electron to ra cht cch in, nn chng u c dn in cao. Cc kim loi kim th c cng khc nhau, cng nht l beng. iu kin thng, Be gin, nhng khi un nng li do; magie do c th dt mng v c th ko di thnh si. (2) Vic chuyn cc kim loi kim th t trng thi rn sang trng thi hi cn tiu th nhng nng lng nh sau:
Be Nhit thng hoa (kj / mol) Mg 153 Ca 180 Sr 205 Ba
trng thi hi, cc kim loi kim th l n nguyn t; khng c kh nng to ra phn t hai nguyn t trng thi kh nh cc kim loi kim hoc nh cc kim loi Zn, Cd, Hg thuc nhm IIB. iu c gii thch nh sau: Mun to ra phn t hai nguyn t, cc nguyn t kim loi kim th phi thng xuyn trng thi kch thch ns2 sp, nng lng lin kt to ra khi hnh thnh phn t M2 khng b li cho nng lng cn cung cp gy ra trng thi kch thch. Vi cc kim loi kim th nguyn t ch c mt electron ns1, cc nguyn t khng phi thng xuyn trng thi kch thch nh nguyn t kim loi kim th, nng lng thot ra l nng lng lin kt. Vi cc kim loi Zn, Cd, Hg cng c hai electron ns2 nn cng thng xuyn trng thi kch thch s2 sp nhng bn knh nguyn t li b hn:
ra = 1,97 A rSr = 2,15 A rBa = 2,21 A rZn rCd rHg = = = 1,34 A 1,56 A 1,60 A
nng lng lin kt ln hn nng lng cn cung cp gy ra trng thi kch thch, v vy cc phn t Zn2, Cd2, Hg2 tn ti trng thi kh. Tr Be v Mg, khi t cc kim loi kim th cn li trng thi t do, hoc trng thi hp cht d bay hi ca chng, trong ngn la khng mu, u lm cho ngn la c mu c trng: canxi - mu da cam; stronti - mu son; bari - mu lc hi vng. Cch gii thch nh trong trng hp kim loi kim (chng 2 - mc 2.4). (3) Nng lng ln ha tng i thp v gim dn t Be n Ba, chng t tnh kim loi tng t Be n Ba. Nng lng ion ha th hai ln gp i nng lng ion ha th nht (bng 14), nhng thc t li d to ra ion M2+ hn l ion M+, v trong dung dch nc nng lng hirat ha ca cc ion kim loi kim th M2+ kh cao, b cho nng
lng ion cao lm cho cc ion M2+ d to ra. Cng do nng lng ion ha th nht thp hn nn cc kim loi kim th cng d mt mt electron ha tr to ra mc oxi ha +l, v d trong hp cht CaCl khi nung hn hp CaCl2 + Ca 10000C. (4) Berili l nguyn t c nhiu ng dng trong nhiu ngnh k thut, chng hn k thut hng khng v k thut nguyn t. Loi thp c cha 1% Be c tnh bn cao, khng mt tnh n hi ngay khi t nng . Berili ln vo ng lm tng cng, bn c hc v bn ha hc m khng lm gim dn in ca ng; hp kim ca ng c cha 2% berili c sc chng gy gp bn ln ng nguyn cht. Hp kim ca magie c nhiu ng dng trong cng nghip t, my bay v ch to my; trong hai hp kim quan trng l hp kim "manhali" v hp kim " electron"." Manhali" l hp kim ca nhm c cha 5 - 30 % Mg, rn v bn hn nhm nguyn cht, v cng d ch ha v d bo nhn hn. " Electron" cng l hp kim m thnh phn chnh l magie. ngoi ra cn c nhm, km, mangan; i khi cn c Cu, Be, Ti... Hp kim ny c tnh c hc tt, nh. Trong ngnh luyn kim ngi ta cn dng magie kh vanai, crom, titan...Phc cht c cha Mg ca vng pofirin l c s cu to ca phn t clorofin. Canxi, stronti, bari c s dng rt hn ch v hot tnh cao ca chng. Canxi c dng trong luyn kim mu, lm cht kh lin kt cc tp cht c hi nh S, P, C d. Stronti c dng trong k thut n in chn khng hp th khng kh cn st li v trong k ngh luyn ng thanh loi S, P, C khi kim loi. Mt lng nh bari cng c ng dng tng t trong luyn ng v ch kh oxi; lm sch kim loi khi lu hunh v cc kh. Cho thm bari vo ch tng cng ca hp kim in. Rai l nguyn t phng x u tin c dng vo cc mc ch thc t, ch yu trong y hc cha cc khi u v mt s bnh khc. 3.5. Tnh cht ha hc ca cc kim loi kim th cc kim loi kim th u c hot tnh ha hc cao, trong cc phn ng u th hin l nhng cht kh mnh v tnh kh tng t Be n Ba. (1) Tr Be khng phn ng trc tip vi hiro; Mg phn ng rt kh khn (xem mc 3.6), cc kim toi kim th cn li u phn ng trc tip vi hiro khi un nng trong lung kh H2 to ra hirua ion: vi canxi dng bt mn phn ng xy ra ngay 00C, cn dng khi phn ng xy ra 1 50 - 3000C, vi sng xy ra khong 300 - 4000C, cn vi ban xy ra 1 800C. (2) Tc dng mnh vi cc halogen khi un nng to ra cc halogenua, phn ng km dn khi chuyn t no n iot.
(3) Khi un nng trong khng kh, Be v Mg to ra oxit Mo, cn cc kim loi kim th cn li th ngay nhit thng to ra oxit MO, v c mt phn peoxit MO2 v nitrua M3N2. Vi lu hunh, khi un nng to ra sunfua dng MS. Cc kim loi kim th cng to ra vi selen v tu cc hp cht dng MSe v MTe nhng bng phng php gin tip. (4) Cc kim loi kim th phn ng trc tip vi nit to ra cc nitrua cc nhit khc nhau. Be3N2 to ra khi cho bt berili tc dng vi nit nhit khong 527 - 9270C; Mg3N2 780 - 8000C; Ca3N2 khong 500 - 6000C; Sr3N2 khong 400 5000C; Ba3N2 khong 260 - 6000C. Vi photpho cng c phn ng trc tip to ra Be3P2; Mg3P2 to ra khong 330 - 5300C trong ampun hn; Ca3P2 nhit khong 5730C; cn Ba3P2 nhit 400 - 4500C (5) Khi un nng vi cacbon trong chn khng hoc trong kh quyn hidro, berili to ra Be2C v BeC2 khong 1700 - 21000C. Nc phn hy Be2C to ra CH4, cn BeC2 - to ra C2H2. Phn ng xy ra trong iu kin tng t vi magie to ra Mg2C3 740 - 7600C v to ra MgC2 6000C. Nc phn hy Mg2C3 to ra C3H4, cn MgC2 to ra C2H2. Canxi, stronti v bari cng phn ng trc tip vi cacbon to ra CaC2, SrC2 v BaC2; nhng nhng hp cht thng iu ch bng cch nung oxit kim loi tng ng vi cacbon. Cc hp cht b thy phn cho axetilen.
silic cng c kh nng phn ng trc tip vi kim loi kim th; Mg to ra Mg2Si - l hp cht t bn, b H2O phn hy chm, vi axit - b phn hy nhanh hn; vi can xi to ra dng Ca2Si, cn stronti v bari to ra MSi v MSi2 (M l Sr v Ba). (6) Nhit to thnh cc hp cht trn, nu trong bng 16. (7) Do c th in cc thp, cc kim loi kim th u c kh nng tc dng vi H2O gii phng H2 V cng d dng y H2 ra khi dung dch axit. Tuy nhin, trong thc t Be hu nh khng tc dng vi H2O, Mg khng tan trong nc lnh v tan mt phn trong nc nng, do c hai kim loi u c lp oxit bo v ngn cn tc Bng 16 Nhit to thnh mt s hp cht ca cc kim loi kim th (kj / ng lng gam)
Nguyn t Be oxit 287 hirua florua 505 clorua 235 bromua iotua sunfua 117 nitrua 93
Mg Ca Sr Ba
305 318 295 279
96 88,3 85
547 605 605 599
316 399 413 429
254 339 357 377
177 267 285 323
176 239 231 214
80 72 64 62
dng ca kim loi vi H2O; tri li, magie dng "hn hng" li phn ng rt mnh vi H2O do khng cn lp oxit bo v: Khi nung nng sng, magie c th kh c hi nc to thnh oxit: Cc kim loi Ca, Sr, Ba phn ng vi H2O xy ra ngay nhit thng to ra hiroxit tng ng v H2 (8) Beng cn c th tan trong dung dch kim mnh hoc kim nng chy to ra mui berilat v H2:
Magie kim loi thc t khng tc dng vi kim, nhng vi Ca, Sr, Ba tan c trong dung dch kim do phn ng vi H2O. Tr Be, cc kim loi cn li c kh nng y hiro ra khi ru ngay nhit thng, ring Mg th phi un nng: (9) Cng nh kim loi kim, cc kim loi Ca, Sr, Ba tc dng vi amoniac lng to ra dung dch mu xanh thm. Khi lm cho dung mi bay hi, cn li tinh th mu vng ng l cc amoniacat c thnh phn khng i: [Ca(NH3)6] [Sr(NH3)6] [Ba(NH3)6] Hin nay ngi ta cha bit r lin kt gia kim loi vi cc phn t NH3 V cng cha gii thch mt cch chu o v tnh dn in cao ca cc hp cht ; ngi ta cho rng trong cc dung dch c cc cation [Ca(NH3)6]2+ hay [Ca(NH3)6]+ v anion l cc electron t do. Cng nh cc amoniacat ca cc kim loi kim, khi c mt ca cht xc tc, chng hn plalin - cc amoniacat kim loi kim th b phn hy dn to ra cc amiua: Khi un nng trong chn khng cc amiua ny b phn hy to ra cc imiua mu vng:
Cc amiua v imiua ca cc kim loi th ch bn dng tinh th, tng tc mnh vi H2O to thnh hiroxit v amoniac, v d: Khi tip tc un nng, cc amiua v imiua trong chn khng cao, s thu c cc pcnitrua dng M3N4 v d penitrua ca stronti - l cht bt tinh th mu nu. Cc penitrua b axit long phn hy thnh nit v mui amoni: Khi un nng cc kim loi kim th vi amoniac th tri li, phn ng to ra nitrua v hirua. (10) cc kim loi kim th phn ng mnh vi cc axit theo s : chng hn vi berili to ra con Be2+ m thc t l ion [Be(OH2)4]2+ theo phng trnh: Trong HNO3 v H2SO4 c ngui, berili cng b th ng ha nh nhm. Mg cng phn ng vi axit long tr cc axit to ra mui kh tan chng hn HF, H3PO4 v.v... (11) Nhiu hp cht c th b cc kim loi kim th kh n nguyn t. Chng hn, khi nung Mg c th kh c CO, CO2, NO, N2O, SO2, Al2O3, Cr2O3, TiO2...
V vy trong thc t ngi ta dng kim loi kim th lm cht kh trong luyn kim iu ch c nhiu kim loi him hoc kh nng chy. Chng hn:
3.6. Hirua ca cc kim loi kim th (1) Tt c cc kim loi kim th u c kh nng to ra hp cht vi hiro ng vi ha tr II ca kim loi (MH2). Tt c u l cht rn mu trng, bn tng t BeH2 n MgH2 sau gim dn t CaH2 n BaH2. (2) BeH2 khng iu ch c trc tip t cc nguyn t m bng phn ng trao i gia BeCl2 vi LiH trong ru hoc bng cch cho Be(CH3)2 tc dng vi AlLiH4:
BeH2 l cht rn mu trng, c tnh cht tng t AlH3. Nc v metanol phn hy BeH2 tch ra H2:
(3) MgH2 cng to ra t nguyn t khi un nng Mg trong kh H2 di p sut v c mt ca MgI2; ngi ta cng iu ch n bng cch nhit phn ietyl magie trong chn khng nhit 1750C: MgH2 l cht rn mu trng, dng bt mn th t bc chy trong khng kh, cn dng cc th bn hn. Khi un nng trong chn khng khong 2800C th b phn hy: B H2O V CH3OH phn hy tng t BeH2 (4) CaH2, SrH2, BaH2 l nhng hirua to mui. CaH2 nng chy 10000C v b phn hy nhit cao hn; SrH2 - nng chy 6500C v phn hy trn 8000C; BaH2 - nng chy v phn hy 6750C, l cht kh mnh, t bc chy trong khng kh. u b H2O phn hy tng t nh Mm.
3. 7. Cc oxit v peoxit ca kim loi kim th (1) Cc oxit MO ca kim loi kim th l cht dng bt hoc khi xp mu trng, khi nu chy ri ngui chng dng tinh th. BeO kt tinh theo mng lc phng kiu vuazit ( - ZnS) vi lin kt hnh t din, mi nguyn t Be c bao quanh bi 4 nguyn t oxi v ngc li mi nguyn t oxi cng c lin kt vi 4 nguyn t Be (hnh 29). Tinh th cc oxit cn li kt tinh theo mng lp phng kiu mui n (hnh 30).
(2) Do c nng lng mng li ln nn cc oxit trn u rt kh nng chy v rt bn i vi nhit c th bay hi m khng b phn hy:
BeO Nng lng mng li (kJ/mol) Nhit nng chy (C) Nhit si (C) 2552 4200 MgO CaO 3519 2570 3600 SrO 3314 2460 2500 BaO 3121 1925 2000
3925 2800 3100
Tr BeO thc t khng tan trong nc, MgO dng xp tan mt t v rt chm, cc oxit cn li u tc dng mnh vi H2O, pht nhit ln to ra hiroxit: Nhit hirat ha tng dn t BeO n BaO. Cc tnh cht nu trn thay i u t BaO n Bao do s tng lin tc bn knh ca ion M2+:
Be
0
Mg 0,74 40,6
Ca 1,06 66,5
Sr 1,26
Ba 1,33
Bn knh ion M2+ ( A ) Nhit hidrat ha ca oxit MO (kJ/mol)
0,34 14,2
81,6 102,5
(3) Beo c iu ch bng cch nung hiroxit hoc mui ca berili nh mui
cacbonat, sunfat, nitrat: Khi nung BeO trong l in vi than, BeO chuyn thnh Be2C tng t Al4C3: L cht lng tnh, BeO tc dng vi oxit axit v oxit baz khi nung nng chy: hoc khi un nng vi dung dch axit hoc baz:
Do trong tinh th c lin kt t din, cc nguyn t Be v O u trng thi lai ha sp3, nn tinh th BeO u bn vng. Khi nung BeO nhit cao, tnh bn vng v mt ha hc tng ln nn BeO tinh th rt kh tan trong axit. Do c tnh chu nng cao nn BeO c dng lm lp lt trong cc l in, lm chn nung. BeO cn c dng lm cht xc tc trong tng hp hu c v trong cng nghip thy tinh. (4) MgO c iu ch bng cch t Mg trong khng kh, hoc nung hiroxit, cacbonat, sunfat v mt s mui cha oxi khc ca magie: Trong cng nghip, ngi ta iu ch MgO bng cch nung manhezit thin nhin (MgCO3) hoc ch ha t nc bin bng cch cho nc bin tc dng vi sa vi chuyn ion HCO3 thnh kt ta CaCO3 sau khi lc tch CaCO3, nc lc li c x l thm bng nc vi vi t l thch hp kt ta ion Mg2+ dng Mg(OH)2:
V Mg(OH)2 kh lc nn ngi ta x l bng cch cho tc dng vi CO2 sau lc kt ta MgCO3.3H2O, ri nung nhit cao thu c MgO:
Phng php trn c dng iu ch mt lng MgO kh ln trong cng nghip (M). Ngi ta cn iu ch MgO (v SO t qung kizerit (MgSO4.H2O) khi nung nng vi than: MgO l cht mu trng, ty theo nhit iu ch m c khi lng ring trong
khong 3,19 - 3,71 g/cm3. Kh tan trong nc, 180C ch tan ti a 2.10-3g trong 100g H2O. Khi trn 10 - 12 phn H2O th sau mt thi gian s chuyn thnh mt khi Mg(OH)2 nh cho c MgO c kh nng ht m v CO2 ca khng kh; khng kh c lm kh trn MgO c cha 0,008 mg H2O trong 1l khng kh 250C. Khi nung nng tht mnh, MgO (cng nh BeO) thng hoa sau lng xung dng tinh th kh tan trong axit. MgO l cht rt chu nng, nn l nguyn liu ch to cc vt chu la nh ng nung, chn nung v mt s dng c chu nhit khc. Cng do vy, mt lng ln MgO c dng ch to gch chu la, vt liu xy dng nh xiolit, phibroxilit. MgO cn c dng iu ch Mg; dng trong y khoa cha chng dch v tng axit; thuc nhun trng, thuc gii c axit. (5) CaO, SrO, BaO u c iu ch bng cch nung mui cacbonat nhit cao. Qu trnh phn hy ph thuc vo bn ca cc mui cacbonat ; khi p sut ca kh CO2 t n p sut ca kh quyn (1atm) th phi nung CaCO3 n khong 8500C, SrCO3 khong 11000C, cn BaCO3 Phi nung cao hn 1 3000C:
v s nhit phn BaCO3 thc hin kh khn hn nhiu so vi CaCO3, nn ngi ta iu ch BaO bng cch nung cacbonat thin nhin vi than nhit cao: Ngi ta cng iu ch Cao bng cch tng t nh vy, nn ngoi sn phm Bao (v c CaO), cn thu c BaC2 v CaC2 l nhng cht c nhiu ng dng trong thc t:
Chng u l nhng cht rn mu trng, xp, trong thc t c mu xm l do ln tp cht nh C. dng v nh hnh c khi lng ring thay i, chng hn Cao c khi lng ring trong khong t 3,2 - 3,4; SrO - khong 3.93 - 4.61, BaO - khong 4,7 - 5,8. Dng tinh th c iu ch bng phng php cho nng chy, u kt tinh theo mng lp phng n gin [ mc 3.7(l)]. u c kh nng ht m mnh v hp th CO2 nh oxit ca kim loi kim. V d:
Khng kh m sau khi cho qua ng ng Cao ch cn cha 0,2 mg H2O / 1l khng kh; cn vi BaO ch cn 8,5. 10-6 mg H2O / 1 /, hn hn nhng cht lm kh thng thng nh CaO, CaCl2, alumogen (Al2O3 khan), H2SO4 c, KOH, NaOH... Phn ng mnh vi H2O to thnh hiroxit tng ng M(OH)2 ng thi thot ra mt nhit lng kh ln [ 3.7(2)]. Chng u l cc oxit baz, phn ng mnh vi axit to thnh mui. nhit cao c th b kim loi kim nhm hoc silic kh thnh kim loi [ mc 3.3(5)]. CaO cn gi l vi sng c dng trong cng nghip xy dng, lm phn bn, cht chy trong luyn kim, iu ch CaC2, CaCO3 cc oxit SrO, BaO c dng trong cng nghip ch to thy tinh. (6) Tng t cc kim loi kim, cc kim loi kim th cng to ra cc peoxit dng MO2 v supeoxit dng MO4. Cng tng t nh hiro peoxit v peoxit ca kim loi kim, cc MO2 u c cha nhm O22- v supeoxit MO4 c cha nhm O21-. Cc peoxit c iu ch bng cch cho hiroxit tng ng tc dng vi H2O2. V d: sn phm to ra l hirat tinh th c thnh phn MO2.8H2O, Sau cho cc hirat ny mt H2O khong 100 - 1300C to ra peoxit t do: Trong k thut MgO2 cn c iu ch bng cch cho H2O2 tc dng vi MgO: SrO2 cng c iu ch bng cch cho SrO kt hp trc tip vi O2 p sut cao; cng tng t SrO2, khi cho khng kh qua ng ng BaO ung nng to ra BaO2: Cc peoxit kim loi kim th u kh tan trong nc, dung dch ca chng u c phn ng kim v u c tnh cht ca H2O2 do phn ng: u d tan trong axit to ra H2O2. v d: Khi un nng, b phn hy thnh oxit v O2. chng hn nh: bn ca chng tng theo dng in ca kim loi, peoxit ca berili hon
ton khng bn, vi magie peoxit ch bit dng hirat ha; CaO2, SrO2, BaO2 u tch c dng khan. Nhit to thnh ca chng c gi tr nh sau:
CaO2 22,59
BaO2 56,48
BaO2 67,78
(kj/ mol
(7) BaO2 l cht quan trng hn trong cc peoxit nu. BaO2 l cht bt mu trng, nng chy 4500C v l hp cht nghch t. BaO2 kh tan trong nc, khng tan trong ru v ete, d tan trong axit long gii phng H2O2: vi H2O, ban peoxit to ra dng hirat BaO2.8H2O, nhng vi CO2 to ra hp cht BaCO3 v O2: Khi nung nng cao hn 6000C trong chn khng v cao hn 7000 trong khng kh, bari peoxit chuyn thnh oxit v tch ra oxi. Ngc li, khong 5000C, Bao kt hp trc tip vi oxi to thnh peoxit: da vo phn ng ngi ta c th dng BaO iu ch oxi t khng kh. BaO2 l cht c tnh oxi ha mnh, khi un nng BaO2 tc dng vi H2, S, C, NH3... V d:
vi HCl c gii phng kh Cl2: Bn cnh tnh oxi ha, BaO2 cn th hin tnh kh, c th kh c ion [Fe(CN)6]3- thnh [Fe(CN)6]4 -; cng nh mt s mui ca cc kim loi nng, th d mui HgCl2 theo phng trnh:
BaO2 c iu ch nh nu trn, hoc nhit phn Ba(OH), Ba(NO3)2, BaCO3 trong lung khng kh. Trong cng nghip iu ch bng cch nung Bao trong lung khng kh 5000C. BaO2 c dng lm cht xc tc trong phn ng cracking du m; dng iu ch H2O2... (8) Supeoxit (M11O4) cc kim loi kim th c to ra khi un nng cc peoxit di p sut cao ca oxi. Cc hp cht cng c to ra mt phn khi un
nng cc peoxit vi dung dch H2O2 30%. Chng l hp cht c mu vng, b H2O phn hy thnh peoxit v O2 Ngc li cc peoxit, bn ca supeoxit gim nhanh theo th t CaO4 - SrO4 - BaO4, trong khi CaO4 nung n 2700C cha b phn hy, th BaO4 Phn hy 50 - 600C. 3.8. Hiroxit ca kim loi kim th (1) Hiroxit M(OH)2 ca cc kim loi kim th dng v nh hnh l cht bt mu trng. Khi kt tinh t dung dch nc thng dng khng mu ngm nc: Be(OH)2 c iu Ch bng cch cho mui berili tc dng vi dung dch kim: hoc bng cch cho hp cht berilal ca kim loi kim tc dng vi dung dch axit: Mg(OH)2 cng c iu ch theo phng php nh trn: nhng Mg(OH)2 li khng kt ta hon ton khi cho mui magie tc dng vi dung dch amoniac, do phn ng thun nghch sau: trong dung dch bo ha mui amoni gii phng amoniac, ni cch khc, Mg(OH)2 tan trong dung dch mui amoni. V l magie kim loi tc dng vi dung dch mui amoni mnh hn vi nc nguyn cht (nhiu hiroxit ca kim loi khc cng c phn ng tng t chng hn Mn(OH)2. Cc hiroxit Ca(OH)2, Sr(OH)2, Ba(OH)2 c iu ch bng cch cho oxit tng ng tc dng vi H2O. (2)hiroxit cc kim loi kim th u t tan trong nc (Tch s tan:
Tt Be(OH)2 = 2.10-18;
M(OH)2 AHht, (kJ/ mol) M(OH)2. 8H20 AHht (kJ/ mol)
Ca(OH)2 -11,7
Sr(OH)2 -48,5 Sr(OH)2. 8H20 + 61,1
Ba(OH)2 -51,5 Ba(OH)2. 8H20 + 63,6
V vy, theo nguyn l chuyn dch cn bng, khi tng nhit th tan ca
Ca(OH)2 gim, cn tan ca cc octahirat li tng (g /100g H2O):

0C Ca(OH)2 Sr(OH)2 Ba(OH)2 0,185 0,35 1,67 20C 0,165 0,81 3,98 40C 0,141 1,76 8,22 80C 0,094 8,25 101,5 100C 0,077 28,4
Khc vi hiroxit cc kim loi kim, hiroxit cc kim loi kim th u khng bn vi nhit, bn nhit tng ln t Be(OH)2 n Ba(OH)2, to ra oxit v H2O: Be(OH) c th c lm kh n 1000C, nhng nhit cao hn th bt u b phn
v d: hy; Mg(OH)2 Phn hy trn 1500C; Ca(OH)2 b mt H2O trn 4000C, cn Ba(OH)2 Phi nung trn 10000C. bn nhit ca cc hiroxit c th hin trn hnh 31. Cc hiroxit M(OH)2 u l nhng baz v u l hp cht ion. Trong dung dch nc tnh baz tng dn t Be(OH)2 n Ba(OH)2; Be(OH)2 l mt baz yu, cn Ba(OH)2 l mt baz mnh. Tt c u d tan trong axit to thnh mui, ring Be(OH)2 cn c kh nng tan trong dung dch kim m c do to thnh hiroxo berilat: Be(OH)2 + 2NaOH = Na2[Be(OH)4] Cc mui bcrilat cc kim loi nhm IA b thy phn hon ton, khi khng c kim d.
do ch c th tch c cc mui t dung dch ln. Cc hiroxit M(OH)2 u c kh nng hp th CO2 Khi ha tan Cao trong dung dch NaOH ri chng kh thu c khi rn c gi l "vi ti xt", c dng trong phng th nghim hp th CO2, thnh phn vi ti xt vo khong 83% Ca(OH)2, 5% NaOH v 12% Trong cc hiroxit ca cc kim loi kim th th Ca(OH)2 c nhiu ng dng thc t, lm baz mnh trong k thut, lm cht
dnh kt trong cng nghip xy dng. 3.9 Mui ca cc kim loi kim th cng nh mui ca cc kim loi kim, cc mui ca cc kim loi kim th thng khng c mu. Mui to ra vi cc anion Cl, Br. I, NO3, S2, CH3COO u d tan; mui vi cc anion F (tr BeF2 d tan), CO32 ,CrO42, PO43-, SO42- (tr BeSO4, MgSO4 d tan) u kh tan. tan ca mt s mui quan trng iu kin thng c so snh trn hnh 32.
T hnh 32 ta thy i vi tng loi mui, tan bin i khc nhau, c cc i hoc cc tiu mui ny hoc mui khc. Nguyn nhn l do kh nng ha tan ca cc mui chu nh hng ca nng lng mng 'li ca mui v nng lng hirat ha ca catin. Ni chung nng lng mng li cng ln th ha tan gim v ngc li nng lng hirat ha cng ln th ha tan cng tng. Tuy nhin, nng lng mng li ph thuc vo bn knh ca cation, nn trong qu trnh ha tan nng lng mng li ng vai tr ln hn so vi nng lng hirat ha. Di y l nng lng hirat ha ca ion M2+ v nng lng mng li ca mui florua v iotua ca kim loi kim th (bng 17). Bng 17. Nng lng hirat ha ca ion M2+ v nng lng mng mui ca mui iotua v iotua ca kim loi kim th
Mg Nng Ing hidrat ha ca ion M

2+
Ca 1577 2611 2058
Sr 1431 2460
Ba 1289 2368 1866
1908 2908 2293
Nng Ing mng li ca mui MF2 Nng lng mng Ii ca mui Ml2
3.10. Halogenua ca cc kim loi kim th (1) Khc vi cc kim loi kim, tinh th cc halogenua khan ca cc kim loi kim th c cu trc khc nhau: BeF2 l cht v nh hnh; CaF2, SrF2, BaF2,
SrCl2 c cu trc mng
florit; MgF2, CaCl2, CaBr2 c cu trc mng rutin; MgBr2, MgI2 , CaI2 , SrI2 c cu trc mng bruxit. Trong tinh th mng florit, cc con Ca2+ to ra mng lp phng tm din, c s phi tr bng 8; cc ion F chim tm ca tm hnh lp phng nh (hnh 33). Tr cc florua MF2 t tan, cc halogenua cn li u d tan, tan trong dung dch bo ha c gi tr nh sau (bng 18). Bng 1B. tan cc MX2 250C (mol / l).
Mui MF2 MCI2 MBr2 Ml2 Mg 1,3.10-3 5,7 5,6 5,3 Ca 2,2.10 -4 7,4 7,5 7,0 Sr 9,7.10-4 3,5 4,2 5,4 Ba 8,3.10 -3 1,8 3,4 5,2
Nhit nng chy v nhit si u cao, mt s cht nh SrBr2, BaBr2, SrI2, BaI2 b phn hy sau khi nng chy. (2) Trong cc mui florua th BeF2 l d tan, kh tan nht l CaF2. Tch s tan (Tt,) cc hp cht c gi tr nh sau
Tt MgF2 6,5.10 -9 CaF2 4.10-11 SrF2 2,5.10 -9 BaF2 1,1.10-6
CaF2, SrF2, BaF2 kt tinh cng kiu mng tinh th, nng lng mng li gim, v kch thc ca ion M2+ tng nn bn lin kt vi ion F gim, do tan gim. Cc florua trn u c th iu ch bng cch cho M(OH)2 tc dng vi dung dch HF long hoc phn hy mui cacbonat bng axit HF. V d:
CaF2 trng thi khan l cht bt mu trng, khi tc dng vi hiro florua to ra mui axit d tan c thnh phn CaF2. 2HF.6H2O. Tc dng vi H2SO4 c nng tch ra hiro florua: cn trong dung dch long ca cc axit mnh khc hu nh khng tan. CaF2 thin nhin c nhiu ng dng thc t, c dng rng ri trong cng nghip gm, dng iu ch HF, dng lm dng c quang hc do tnh trong sut ca tinh th i vi tia t ngoi v hng ngoi. (3) Trong cc mui clorua th BeCl2 l hp cht cng ha tr, trng thi hi gm nhng phn t tuyn tnh Cl - Be - Cl trong berili c s phi tr 2; trng thi rn BeCl2 c cu trc polime dng si vi s phi tr 4, to ra cu hnh 4 mt do s lai ha sp3 ca nguyn t berili (hnh 34).
Hnh 34. Cu to mt on mch polime (BeCl2)n. Trong mch, mi nguyn t berili lin kt vi 2 nguyn t clo bng hai lin kt cng ha tr bnh thng v lin kt vi hai nguyn t clo khc bng hai lin kt "cho - nhn". BeCl2 c iu ch bng cch nung nng berili kim loi trong lung kh clo hoc HCl kh: cng c iu ch bng cch cho kh clo kh qua hn hp BeO v than nung 9000C: BeCl2 l cht rn, dng khan c Tnc = 4500C v Ts = 5500C c p sut hi cao, d tan trong dung mi hu c nh ru, benzen, ete. BeCl2 l cht ht m mnh nn d b chy ra trong khng kh m, d tan trong nc v khi tan pht nhiu nhit: Khi kt tinh t dung dch to ra tinh th dng tetra hirat BeCl2.4H2O hay [Be(OH2)4]Cl2 C Cu hnh bn mt, trong berili c trng thi li ha sp3. Hirat ny cng chy ra trong khng kh v khi un nng khng to ra mui khan m phn hy to ra BeO
(4) MgCl2 l cht c nhiu ng dng quan trng trong thc t so vi cc halogen khc ca beng v magie. Tinh th MgCl2 c cu trc mng lp phng. MgCl2 c trong nc bin, trong khong vt bisophit MgCl2.6H2O v mt lng rt ln trong cacnalit KCl.MgCl2.6H2O. V vy, trong cng nghip ngi ta iu ch bng cch tch MgCl2 t nc bin, t bisophit v t cacnalit. MgCl2 l sn phm ph khi ch ha cacnalit thnh KCl. Cacnalit nng chy trong nc kt tinh 1760C ng thi b phn hy, KCl kt ta gn nh hon ton, cn MgCl2.6H2O (nng chy l060C) tn ti dng lng. MgCl khan khng th iu ch bng cch cho bay hi trc tip dung dch do s thy phn. Trong phng th nghim ngi ta iu ch MgCl bng cch cho Mg tc dng vi Cl2 hoc HCl kh: hoc cho kh O. kh qua hn hp MgO + C nung nng nhit cao: ngoi ra cng iu ch c bng cch un nng dung dch MgCl2 vi NH4Cl to ra tinh th MgCl2.NH4Cl. 6H2O Sau un nng sn phm thu c MgCl2 khan: Trong dung dch nc, MgCl2 tn ti mt s dng hirat MgCl2. xH2O (x =2; 4; 6; 8; 12), bn hn c l dng hexahirat MgCl2. 6H2O, cht ny kt tinh c t dung dch nc nhit thng. Khi nung, nc kt tinh mt dn v cui cng to ra MgO:
MgCl2 l cht d tan trong nc, ht m mnh nn d chy ra trong khng kh; kt hp vi mui clorua kim loi kim hoc amoni to ra cc mui kp. V d: MgCl2 c dng iu ch Mg, dng trong y khoa, v dng sn xut ximng magie. Loi ximng ny to ra khi trn MgO nung trc vi dung dch MgCl2 c. Ximng magie c bn cao vi axit v kim, d mi trn, dng lt sn nh, mi... (5) CaCl2 khan l cht rn, mu trng, nng chy 7800C. Trong thin nhin, CaCl2 c trong nc bin, nc khong, trong mt s khong vt nh clorocanxit (CaCl2), tachirit CaCl2.2MgCl.12H2O. (CaCl2 l Sn phm ph ca nhiu qu trnh sn xut nh sn xut xoa bng phng php F. Solvay t nguyn liu ban u l NaCl v CaCO3; sn xut KClO3 t Cl2 V Ca(OH)2.CaCl2 tinh khit c th c iu ch bng cch ha
tan CaCO3 tinh khit trong axit HCl; cn CaCl2 khan c th thu c khi nung CaCl2.6H2O 2600C trong kh quyn hiro clorua. L cht d tan trong nc, qu trnh ha tan CaCl2 khan pht nhiu nhit do hnh thnh hirat (72,84 kj/mol), cn qu trnh ha lan cc dng hirat li l qu trnh thu nhit, do nguyn nhn nn ha tan ca CaCl2 tng khi nhit tng:
t0c tan CaCI2 (g / 100g H20) -55 42,5 0 60 10 65 20 74,5 40 115 60 100 137 159 260 347
Trong cc hirat tinh th ca can xi clorua th dng hexahirat l bn hn c, nng chy 30oc, khi un nng mt dn H2o kt tinh v n 260oC th khan hon ton: Ngoi nhng tnh cl t ca mt mui, CaCl2 cn c kh nng kt hp vi NH3, CH3OH, C2H5OH, to ra hp cht CaCl2.8NH3, CaCl2, 4CH3OH, CaCl2.6C2H5OH. Cng v nguyn nhn ngi ta khng dng CaCl2 lm kh kh amoniac. Do kh nng ht m cao, ngi ta dng CaCl2 khan lm kh cc cht CaCl2.6H2O cn c dng ch hn hp sinh hn, hn hp gm c CaCl2.6H2O v nc vi t l khi lng 1,44: 1 c th lm lnh n nhit ng vi im ng bng - 54,90C. Dung dch CaCl2 cn dng lm cht lng duy tr mt nhit nht nh ph thuc vo nng ca CaCl2 theo bng 19; 20 di y. Bng 19 Nhit si ca dung dch CaCl2
S gam CaCI2 trong 100g H2O Nhit si (C) S gam CaCI2 trong 100g H2O Nhit si (C)
6,0 101 101 130
11,5 102 137,5 140
16,5 103 178 150
21,0 104 222 160
25,0 105 268 170
41,5 110 292 175
69,0 120 305 178
Bng 20 Nhit ng c ca dung dch CaCl2

S gam CaCI2 trong 100g dung dch Nhit ng c (C) S gam CaCI2 trong 100g dung dch Nhit ng c (C)
0,1 1 - 0,051 -0,46 20 25 -18,6 -29,9
5 10 -2,44 -5,89 30 32,5 -48,0 -51,0
15 -10,96 -
(6) BaCl2 dng khan l nhng tinh th mu trng, t tan trong ru, nhng d tan trong nc, tan tng theo nhit :
t0c tan BaCI2 g/100g H20
0 31,5
10 33
20 36
50 43,5
100 59
T dung dch nc, bari clorua kt tinh dng ihirat BaCl2. 2H2O, bn trong
khng kh nhit thng. Khi un nng, chuyn thnh monohirat BaCl2.H2O Sau chuyn thnh mui khan. Trong k thut, BaCl2 c iu ch bng cch ha tan viterit (BaCO3) trong axit HCl: cng c iu ch bng cch dng than kh BaSO4 to ra BaS sau cho phn ng vi CaCl2 nhit cao:
Trong k thut, BaCl c dng lm mm nc v trong phng th nghim dng nh tnh v nh lng ln SO42- v iu ch mt s mui khc ca bari. (7) Cc mui halogenua khc ca kim loi Ca, Sr, Ba thng tch khi dung dch dng hexahirat hoc ihirat. Nhiu mui chy ra trong khng kh v tan nhiu trong ru. Nhit nng chy ca mui khan u cao. Ngi ta cng iu ch cc mui theo nguyn tc chung l trung ha hiroxit hoc cacbonat bng axit tng ng. V d:
Cc mui khan clorua, bromua, iotua u c khuynh hng kt hp vi NH3 to ra cc hp cht c thnh phn MX2. 8NH3. Theo chiu t Ca - Sr - Ba bn cc hp cht gim xung. Chng hn, p sut ca amoniac t n 50 mmHg i vi [Ca(NH3)8]I2 960C; vi [Sr(NH3)8]I2 620C; vi [Ba(NH3)8]I2 ch 200C. Trong dung dch nc, cc amiacat ny u b phn hy. Ngoi cc halogenua dng MX2, cc kim loi Ca, Sr, Ba cn to ra cc mui dng MX, chng hn CaCl, CaI, CaF, BaCl. Cc hp cht ny u bn nhit cao v c mu khc nhau. Tinh th CaCl c mu tm bn trn 8000C; tinh th Cai - mu nu bn trn 7800C; Cai mu vng da cam bn trn 14000C. Cc mui trn thng c to ra khi nung mui vi kim loi tng ng, v d: ngui chng b phn hy dn theo hng ngc li. B phn hy trong khng kh m theo phng trnh: BaCl cn c to thnh catot khi in phn BaCl2 nng chy, do vic iu ch Ba bng cch in phn BaCl2 nng chy xy ra kh khn hn nhiu so vi
qu trnh iu ch Ca v Sr. 3.11. Nitrat ca cc kim loi kim th (1) Nitrat ca cc kim loi kim th cng tng t cc mui nitrat khc l u d tan trong nc tr Ba(NO3)2 t tan (Tt = 4,5. 10-3). Da vo quang ph Rnghen, ngi ta xc nh c cu trc tinh th ca Ca(NO3)2, Sr(NO3)2, Ba(NO3)2 u c dng florit. Trong mng linh th, cc cation M2+ u to ra mng lp phng tm din, mi nhm NO3 c phn b trong tm hnh lp phng nh, nhng khng phn b tm hnh lp phng nh ion F trong mng florit (xem mc 3.10, hnh 33). (2) Be(NO3)2 c iu ch bng phn ng trao i gia BeSO4 v Ba(NO3)2 trong dung dch nc: Be(NO3)2 cng c iu ch bng cch ha tan Be(OH)2 trong HNO3. Tinh th tch ra khi dung dch nc dng trihirat Be(NO3)2 '3H2o. Khi un nng n 600C, tinh th nng chy ng thi tch H2O kt tinh; n 1000C bt u tch HNO3 v n 2000C b phn hy hon ton to ra BeO. (3) Mg(NO3)2 kt tinh t dung dch nc dng hexahirat Mg(NO3)2.6H2O Khi un nng n khong 900C bt u tch H2O kt tinh to ra Mg(NO3)2.2H2O; n 129,50C th nng chy ng thi tch HNO3 v sau khi tip tc nung n nhit cao hn mui b phn hy hon ton to ra MgO tinh khit. Mg(NO3)2 c iu ch bng ha tan kim loi, oxit, hoc cacbonat trong HNO3. Cng l cht ht m mnh v cng tng t mui clorua, to ra mui baz khi un nng nh dung dch. (4) Ca(NO3)2 cng c iu ch bng cch ha tan CaCO3 hoc Ca(OH)2 trong HNO3. Tinh th tch khi dung dch nc dng tetrahirat Ca(NO3)2.4H2O, nng chy trong nc kt tinh 400C. Khi un nng trn 1000C, dng tetrahirat chuyn thnh dng khan, rt ht m, rt d tan trong nc v trong ru. Khi un nng nhit cao hn nhit nng chy (5610C) bt u tch ra oxi v mui nitrit: sau nung mnh to ra CaO v cc oxit ca nit. Ca(NO3)2 c dng lm phn bn. (5) Sr(NO3)2 c iu ch bng phn ng trao i gia SrCl2 v NaNO3: phn ng da trn c s Sr(NO)2 c ha tan b hn SrCl2 v NaNO3.
Cng c iu ch bng cch ha tan SrCO3 trong HNO3 Tinh th tch ra khi dung dch dng tetrahirat Sr(NO3)2.4H2O. Khi nung nhit cao hn 1000C, H2O kt tinh tch dn v sau bin thnh dng khan Sr(NO3)2 Tnc = 6450C. Khi nung nhit cao hn nhit nng chy, bt u tch ra O2 v to ra mui nitrit: sau nung mnh to ra SrO v cc oxit ca nit. Ch nhit kh cao mi phn hy hon ton. Sr(NO3)2 c dng ch pho hoa, pho hiu mu . (6) Ba(NO3)2 c iu ch bng cch ha tan BaCO3 dng viterit trong HNO3 long. Mt phng php khc l dng phn ng trao i gia BaCl2 v NaNO3 hoc BaCO3 v Ca(NO3)2:
nhit thng, kt tinh trng thi khan Ba(NO3)2 c Tnc = 5720C. nhit di 120C tinh th tch ra dng ihirat Ba(NO3)2.2H2O. Ba(NO3)2 rt kh tan trong nc nng so vi cc nitrat ca cc kim loi kim th khc. Khng tan trong ru. Khi nung mnh Ba(NO3)2 bt u tch ra oxi chuyn thnh mui nitrit v ch khi nung tht mnh mi chuyn thnh oxit BaO v cc oxit ca nit: Ba(NO3)2 c dng iu ch oxit v hiroxit bari tinh khit. Cng c dng ch pho hoa, pho hiu mu lc. 3.12. Cacbonat ca kim loi kim th (l) Mui cacbonat ca cc kim loi kim th l nhng mui kh ph bin trong thin nhin cc dng khong vt khc nhau. Magie tn ti dng manhezit MgCO3; olomit CaCO3.MgCO3; hiromanhezit Mg(OH)2.3MgCO3.3H2O; t ph bin hn l cc khong vt stroxianit SrCO3, viterit BaCO3. Ph bin nht l khong vt cha canxi cacbonat nh canxit v aragonit. Thnh phn ha hc chnh ca hai loi khong vt l CaCO3. Canxit tn ti cc dng khc nhau nh Bng o, vi cm thch, phn. Bng o c nhiu Bng o thng gp di dng tinh th ln, trong sut, khng mu, c kh nng chit quang nn c dng lm dng c quang hc. vi l dng ph bin nht ca canxit, c dng sn xut CaO, CO2), lm vt liu xy dng... cm thch c to nn trong iu kin nhit v p sut cao; cm thch c nhiu mu khc nhau lm vt liu trang tr trong xydng. phn l dng mm ca vi nh cc loi v s, v hu, hn...Ngoi ra. CaCO3 cn c dng natrocanxit Na2CO3.CaCO3.5H2O; Uranotalit 2CaCO3.UO2(CO3). 10H2O. (2) Cc mui cacbonat ca kim loi kim th u l cht dng tinh th, u
kh tan trong nc. Tch s tan c gi tr nh sau (Tt):

BeC03 1.10-3 MgC03 4.10 -5 CaC03 4,8.10 -9 SrC03 1.1.10 -10 BaC03 5,1.10 -9
Tt
Trong dung dch c cha d kh CO2, cc mui cacbonat ca Ca, Sr, Ba li tan do to ra mui hirocacbonat M(HCO3)2: Phn ng trn gii thch hin tng n mn vi trong thin nhin, v do phn ng nn trong nc sng, nc ngm c cha mt lng ng k Ca(HCO3)2. Khi trong khng kh hoc khi un nng, cc mui u phn hy tch ra CO2: Phn ng trn gii thch s hnh thnh thch nh, sui ha , cn m, cn ni hi. Tri li cc mui trung ha BeCO3 v MgCO3 li tn ti trong dung dch cha lng d CO2, do chng b thy phn to ra kt ta l nhng mui cacbonat baz [M(OH)]2CO3. Mui baz ny lun lun c to thnh khi cho dung dch cachonat kim tc dng vi mui ca Be v Mg. (3) Cng nh mui cacbonat ca cc kim loi khc, cc axit(k c axit axetic) u phn hy cachonat kim loi kim th tch ra CO2; v d: Khc vi cacbonat ca kim loi kim M2CO3, cc mui MCO3 u b nhit phn hy, bn nhit tng t MgCO3 n BaCO3 ng vi nhit phn hy nh sau:
t0c MgC03 540 CaC03 897 SrC03 1290 BaC03 >1360
s ph thuc p sut ca CO2 vi nhit trong qu trnh nhit phn nh sau (bng 21) T bng 21 ta thy rng khi nhit phn CaCO3 trn 8970C th p sut ca CO2 bng p sut ca kh quyn; trong khi nung BaCO3 n 9000C, p sut hi ca CO2 mi ch t 0,2 mmHg. Bng 21. p sut phn hy ca MCO3
MC03 p sut ca CO2 (mm Hg) 400C MgC03 0,1 450C 6,8 500C 100 540C 740 560C 600C 650C 700C 750C
CaC03
0,1
0,4
1,8
6,9
22,2
63
MC03 800C CaC03 BaC03 0 167 850C 302 0 897C 760 0
p sut ca CO2 (mm Hg) 900C 1000C 1100C 1200C 1300C
0,2
2,7
17,7
92
382
(4) BeCO3 Ch c th kt ta trong dung dch khi c mt ng thi trong dung dch vi lng d kh CO2. Khi cho mui cacbonat kim loi kim tc dng vi dung dch mui berili to ra mui baz dng [Be(OH)]2CO3. Mui baz ny c th chuyn thnh mui trung ha khi un nng vi dung dch KHCO3 c. BeCO3 l cht rn mu trng, kh tan trong nc, nhng li d tan trong lng d cacbonat kim loi kim, c bit d tan trong dung dch c (NH4)2CO3 do to ra cc mui kp M2[Be(CO3)2]. BeCO3 kt tinh t dung dch dng tetrahirat BeCO3.4H2O, khi un nng n nhit 1000C chuyn thnh mui khan, khi un n nhit cao hn b phn hu tch ra CO2 (5) MgCO3 l cht rn mu trng kh tan trong nc (9,4 mg trong 100 g H2O 180C). Khi un nng dung dch, cng b thu phn to thnh mui cacbonat baz. Tan trong dung dch d cacbonat kim loi kim v trong dung dch (NH4)2CO3 m nhng kh hn BeCO3; qu trnh tan do to ra cc mui kp nh K2[Mg(CO3)2].4H2O, KH[Mg(CO3)2].4H2O. Amoniac cng to ra hp cht tng t, v vy khi cho dung dch (NH4)2CO3 m tc dng vi mui magie khng to ra kt ta. Tan trong axit to thnh mui magie. Mt khc khi cho kh CO2 qua cht lng c cha huyn ph MgCO3 huyn ph ny d tan do to mui bicacbonat: khi un nng, Mg(HCO3)2 b phn hu thnh MgCO3. Khi cho mui magie tc dng vi mui cacbonat ca kim loi kim to thnh mui baz theo phng trnh: v vy phn ng phi thc hin trong dung dch c lng d kh CO2. Mui cacbonat baz ca magie l cht bt mu trng t tan trong nc (0,02% 150C c thnh phn gn ng: Mg(OH)2.xMgCO3. nH2O (X =3; 4...;n = 3; 4; 5...). MgCO3 tinh khit c iu ch bng cch thi CO2 tinh khit ln b mt magie cacbonat baz un nng ti 150 - 2200C n khi bt trng xp to ra c khi lng khng i, sau c bo qun trong kh quyn CO2:
MgCO3 tch ra t dung dch nc dng tinh th MgCO3.5H2O 160C; cn nhit cao hn th dng trihirat hoc monohirat. (6) CaCO3 l Cht kt tinh mu trng, t tan trong nc, tan trong nc vo khong 1,4 mg /100 gH2O 250C, tan nhiu hn trong dung dch cha lng d NH4Cl. Khi un si CaCO3 vi dung dch NH4Cl, CaCO3 S b phn hy hon ton: CaCO3 c iu ch bng cch cho mui canxi tc dng vi mui cacbonat kim loi kim hoc amoni, cng c iu ch bng cch cho dung dch nc vi hp th CO2 T dung dch nng, CaCO3 kt tinh dng tinh th, cn nu l dung dch ngui li kt ta dng v nh hnh. Dng bt mn nhn to c dng ch x phng nh rng; dng trong y khoa cha bnh thiu canxi, bnh d axit trong dch v... (7) SrCO3 c iu ch bng cch cho mui stroni tan tc dng vi dung dch (NH4)2CO3: SrCO3 l cht rn mu trng, rt kh tan trong nc. Trong dung dch SrCO3 b thy phn mt phn to ra mi trng kim. Tan nhiu trong dung dch c cha CO2 do phn ng to ra hiro cacbonat. Khi nung nng, phn hy tch CO2 nhng kh hn so vi CaCO3. (8) BaCO3 l cht rn mu trng, t tan trong nc. Dung dch bo ha c phn ng kim do b thy phn. BaCO3 c iu ch bng cch cho dung dch Ba(OH)2 hp th CO2 hoc cho dung dch mui bari tc dng vi mui cacbonat kim loi kim:
Trong cng nghip BaCO3 c iu ch bng cch dng than kh BaSO4 khi nung hn hp 600 - 8000C to ra BaS, sau cho CO2 tc dng vi dung dch BaS to ra kt ta BaCO3:
Cng c th bng cch un nng huyn ph BaSO4 vi dung dch m c K2CO3: BaCO3 tan trong axit; tan mt t trong dung dch cha CO2 do to ra Ba(HCO3)2. cng lng t cc mui cacbonat kim loi kim th khc, BaCO3 cng tan mt phn trong cc dung dch mui amoni do to ra cc mui kp.
3.13. Sunfat ca kim loi kim th (1) cc mui sunfat ca kim loi kim th u l cht kt tinh mu trng. Hai mui BeSO4 v MgSO4 u d tan, cc mui cn li u kh tan, tan gim dn t BeSO4 trn BaSO4; 200C tan (g/ 100g H2O) nh sau :
tan(g/100gH2O) Tch s tan (Tt)
BeS04 39,9 -
MgS04 35,5 -
CaSO4 0,203 2,4.10-5
SrS04 0,015 3,2. 10-7
BaS04 2. 10-4 1,1.10-10
Mui sunfat ca cc kim loi kim th u to ra sunfat kp vi cc kim loi kim dng M21 M11(SO4)2. (Trong M1 l cc kim loi kim; M11 l kim loi kim th). (2) BeSO4 to thnh khi un nng Beo hoc Be(OH)2 trong H2SO4 d: tinh th BeSO4 tch ra dng tm mt khng mu BeSO4.4H2O, ngoi ra cn cc dng BeSO4.2H2O; BeSO4.H2O. Trong dung dch nc, BeSO4 b thy phn mt phn nhng mc thy phn km hn BeCl2. Khi lm bay hi dung dch khng cha H2SO4, tinh th tch ra dng mui baz. Khi nung tinh th hirat BeSO4.4H2O n 2300C chuyn thnh mui khan, nung nhit cao hn, bt u tch SO3 v sau chuyn thnh BeO tinh khit: (3) MgSO4 trng thi khan l cht bt mu trng. Tinh th mui tch ra - t dung dch nc - dng hirat. Ngi ta bit cc dng l; 2; 4; 5; 6; 7 v 12 phn t H2O, trong cc dng 2; 4; 5 phn t H2O l t bn; cn li u bn v quan trng hn c l monohirat MgSO4.H2O (kizerit) v dng hepta hirat MgSO4.7H2O long mui trng). Mt s dng hirat trn, bn trong khong nhit sau: bn trong khong t - 3,90C n 1,80C MgSO4. 12H2O bn trong khong t l,80C n 48,30C MgSO4. 7H2O MgSO4. 6H2O bn trong khong t 48,30C n 680C bn trong khong cao hn 680C MgSO4. H2O MgSO4 Cng c iu ch bng cch cho MgO tan trong H2SO4 30%: tinh th tch ra dng MgSO4.7H2O. Mun. iu ch dng khan MgSO4 cn un dng MgSO4.7H2O n 2380C. Nu nung nhit cao hn s tch dn SO3.
Trong thin nhin, MgSO4 dng khong cht kizerit (MgSO4.H2O) v dng mui ng (MgSO4.7H2O). Khong cht kizerit rt kh tan trong nc k c khi un nng. Kizerit thin nhin c dng iu ch MgO v SO2 khi nung vi than: " Mui ng" dng trong cng ngh si, giy v dng trong y khoa lm thuc ty, nhun trng, thng mt. MgSO4 to ra mui kp vi kim loi ha tr I trong ng ch l dng xenit c thnh phn M2[Mg(SO4)2].6H2O; quan trng l cht K2[Mg(SO4)2].6H2O i khi c dng lm phn bn. (4) CaSO4 l mui quan trng hn c trong cc mui sunfat kim loi kim th. L cht rn mu trng, t tan trong nc ( 200C n tan khong 203,6 mg trong 100 g H2O). tan tng chm khi tng nhit , nhng qu 500C tan gim dn. ng cong tan c cc i khong 30 - 400C. Trong dung dch mui sunfat ca kim loi khc, tan ca CaSO4 gim xung nhng trong H2SO4 c tan ca CaSO4 li cao hn nhiu v mt phn to ra cc hp cht kp nh CaSO4.H2SO4 v CaSO4.3H2SO4, nhng hp cht loi c tch ra trng thi t do. Vi sunfat kim loi kim, CaSO4 to ra nhng mui kh tan, nhng mui kp cng gp trong thin nhin, v d mui globe Na2SO4.CaSO4; mui sinvinit K2SO4.CaSO4.H2O. Trong dung dch (NH4)2SO4, tan ca CaSO4 li tng ln do to thnh mui phc: Ngi ta cng li dng tnh cht ny tch Ca ra khi Sr v mui tng t ca Sr li t tan hn. CaSO4 tinh khit c iu ch bng cch cho CaCl2 d tc dng vi dung dch (NH4)2SO4. Kt ta tch ra dng vi tinh th hnh kim ihirat CaSO4.2H2O di 660C. Nu nhit trn 660C li tch ra dng khan. Trong thin nhin tn ti dng CaSO4. 2H2O gi l thch cao. Thch cao c cu trc lp nn c th tch thnh l mng. Khi un nng n gn 1280C thch cao mt mt phn H2O kt tinh thnh hemihirat 2CaSO4.H2O (hay CaSO4. /2H2O) gi l thch cao nung: Thch cao nung l cht bt mu trng, sau khi trn vi mt t nc thnh h cho lng, c kh nng ng cng nhanh do cc vi tinh th CaSO4. 2H2O an xen vo nhau. Li dng kh nng ny ngi ta dng thch cao nn tng, lm khun c, lm vt liu xy dng, b chun hnh trong y hc, v d b xng gy... Khi nung trong khong 200 - 3500C thch cao nung chuyn thnh CaSO4 khan tan c trong nc:
Nung n gn 5000C, chuyn thnh dng khng tan trong nc, khng tng tc vi nc, v vy khng th lm vt liu dnh kt, gi l thch cao cht. Nung n khong 900 - 10000C l cht bt mu trng kh c kh nng ht m, nn c dng lm kh. Khng kh m, sau khi qua ng ng CaSO4 ch cn li khong 0,005 mg H2O trong mt lt khng kh. Nung n 12000C bt u phn hy to ra CaO: (5) SrSO4 thng gp trong thin nhin dng khong vt seletin, l nguyn liu ch yu dng iu ch cc hp cht ca stronti. SrSO4 rt t tan trong nc, 180C tan vo khong 11,4 m trong 100g H2O. vi mui sunfat kim loi kim, chng hn K2SO4, (NH4)2SO4, Stronti sunfat to ra nhng mui kp kh tan. Cng tng t CaSO4, SrSO4 Cng b nhit phn tch ra SO3 nhng nhit cao hn nhiu so vi CaSO4. (6) BaSO4 l Cht bt mu trng, hu nh khng tan trong nc, 180C -100g H2O ch ha tan c 0,22 mg BaSO4. Trong H2SO4 c ha tan ca BaSO4 tng ln do to ra phc cht. BaSO4 nng chy 15800C v tip theo l bay hi hon ton. Bari sunfat c iu ch bng cch kt ta t dung dch khi cho dung dch mui bari tc dng vi dung dch H2SO4 hoc dung dch cha ion SO42- khc: V bn i vi khng kh v mt s cc kh khc nn BaSO4 c dng rng ri trong cng ngh sn t. Mt khc, v khng tan trong nc v trong cc axit v c long nn BaSO4 khng c nh mt s cc mui khc ca bari trong c BaS, BaCl2, BaCO3 li rt c. BaSO4 li c tc dng cn quang, khng cho tia Rnghen i qua nn ngi ta cho bnh nhn ung mt t bt vi nc trc khi dng X - quang chiu hoc chp d dy, rut.
CHNG 4 CC NGUYN T NHM IIIA ( NHM - GALI - INI - TALI) 4.1. Nhn xt chung v cc nguyn t nhm IIIA (1) Nhm IIIA thuc bng tun hon gm cc nguyn t B (Borum), Al (Aluminium), Ga (Gallium), In (Inium) v Tl (Thallium ) . Bo c nh bc hc ngi Anh l vi (H.Devy) v hai nh ha hc ngi Php l Gay Luyxc (J.Gay-lussac) v Tna (L.Thenard) tm ra nm 1808 khi dng kali kh oxit boric; nhng n u th k 20 mi c mt nh ha hc ngi M l Ventrau (E. Weitraub) iu ch c dng tinh khit 99%. Nhm l nguyn t ph bin trong thin nhin , nhng ch n nm 1825 ln u tin mi c nh vt l ngi an Mch l xtet (J.C.Oersted) iu ch dng tinh khit . Gali c nh ha hc ngi Php Lecoq Boabrng (Lecoq de Boisbaudran) pht minh ra nm 1875 khi nghin cu qung sfalerit ( ZnS). Nm 1863 hai nh ha hc ngi c l Rai c (F.Raich) v Ricte (T. Richter) pht hin ra nguyn t mi trong ch phm km clorua. Mun hn cc nguyn t trn , v l nguyn t phn tn nn tali mi c tm ra gia th k th 19 (1861) khi nh khoa hc ngi Anh l Cruc (W . Crookes) nghin cu cht thi nh my sn xut axit sunfuric bng phng php phn tch ph . (2) Nguyn t khi, s th t nguyn t v s phn b electron nh sau :
Nguyn t Bo Nhm Gali Ini Tali
K hiu B Al Ga In Tl
S th t 5 13 31 49 81
Nguyn t t 10,82 26,98 69,72 114,82 204,39
Phn b electron 2 2 2 3 8 8 8 8
Ha tr III I, III I, II, III I, II, III I, II, III
3 18 18 18
3 18 32
3 18
Mc d u c ba electron ha tr l ns2np1, nhng ch c cc nguyn t B v Al cc electron mi nm ngoi lp v kh tr, ngha l lp v bn. Cc nguyn t cn li ng sau dy nguyn t chuyn tip trong mi chu k, nn lp electron pha trong st lp electron ha tr li l 18 electron, do tnh cht ca cc nguyn t nhm IIIA khng bin i u nh nhm IIIA khng bin
i u nh nhm IA v IIA. (4) Sau y l mt s c im ca cc nguyn t nhm IIIA. Bng 22 . Mt s c im ca cc nguyn t cc nguyn t nhm la
Nguyn t B Al Ga ln Tl
Bn knh nguyn t 0,83 1,26 1,27 1,44 -
Bn knh ion M3+ () 0,20 0,57 0,62 0,92 1,05 I1 8,30 5,95 6,0 5,8 6,1
Th ion ha ( eV) I2 I3 25,15 37,93 18,82 28,44 20,43 30,60 18,79 27,90 20,32 29,80
I1+I2+I3 71,38 53,21 57,03 52,49 56,22
Nhn chung nng lng ion ha ca cc nguyn t nhm IIIA bin i khng u nh cc nhm IA v IIA . Nng lng ion ha ca B tng i ln do B rt kh mt 3 electron to ra cation trong cc hp cht ion, m ch yu to ra hp cht cng ha tr ; trong khi s hnh thnh ion Al3+ li xy ra d hn do bn knh nguyn t tng, ng thi nng lng hirat ha ca ion Al3+ cng kh ln. Chnh iu cho chng ta hiu c ti sao tnh cht ca bo khc vi nhm v cc nguyn t cn li trong cng nhm; trong khi Al l kim loi cn B l phi kim, cc hp cht B2O3 V B(OH)3 C tnh axit, AI(OH)3 li c tnh baz. T Al n Ga - tng nng lng ion ha li tng ln chng t tnh kim loi hi gim xung. T Ga n In tnh kim loi li tng ln , nhng t In n Tl tnh kim loi li gim xung, th hin s thay i tng nng lng ion ha. S d c s bin i khng u l do Ga l nguyn t ng sau cc kim loi chuyn tip dy th nht, nn chu nh hng ca s co d; cn Tl ng sau cc lantanit nn chu nh hng ca s co lantanit (cof). (5) Cc nguyn t nhm IIIA c s oxi ha ch yu l +3, nhng v nng lng ion ha th nht b hn nhiu so vi tng nng lng ion ha th hai v th ba nn t Al n Tl Cn c kh nng to ra s oxi ha +1 , bn ca s oxi ha +1 tng ln t Al n Tl, Tl c nhiu hp cht Tl(I) bn hn cc nguyn t cn li. (6)Th in cc ca B khng xc nh c do B khng to nn cation trong dung dch, cn cc nguyn t cn li c th in cc ln hn cc kim loi kim th . Mt s hng s l hc quan trng ca cc nguyn t nhm IIIA nu trong
bng 23. (7) Ni chung , v nhiu mt, bo ging silic nhiu hn so vi nhm v cc nguyn t cn li , nh hp cht halogenua ca B v Si (tr BF3) u d b thu phn , trong khi Al halogenua ch b thu phn mt phn ; hp cht ca B v Si vi hir u l cht d bay hi v t bc chy cn nhm halogenua l cht rn polime (AlH3)n... (8) Gali c nhit nng chy thp l do trng thi rn, gali c mng li phn t Ga2 ; gali li c nhit si cao l do khi si phn t Ga2 phn hy thnh nguyn t. Bng 23. Mt s hng s l hc quan trng ca kim loi nhm IIIA
Tnh cht Nhit nng chy ( Tnc C) Nhit si ( Ts oC ) Khi lng ring (g1cm3 ) m in (1) Th in cc (V): M3+ + 3e Mo M+ + 1e Mo
o
B 2300 ~2550 2,33 2,0 -
Al 660 2270 2,70 1,5 - 1,66 -
Ga 29,8 ~2070 5,93 1,6 -0,53 -
ln0 157 ~2300 7,29 1,7 - 0,34 -
Tl 304 -1457 11,8 1,8 (+0,72) -0,335
(l)
Theo Pauling.
(9) Nhm kt tinh theo mng lp phng tm din vi khong cch gia hai nguyn t = 4,0414 (hnh 1). Tali c hai dng th hnh, trong c mt dng kt tinh theo mng lc phng, c hai dng bin i cho nhau 2350C. 4.2. Trng thi thin nhin v cc thnh phn ng v (1) Trong thin nhin , B v Al l nhng nguyn t kh ph bin. ph bin ca Al trong v qu t ng vo hng th t sau cc nguyn t O, H, v Si. Cn cc nguyn t Ga, In v Tl l nhng nguyn t him , t ph bin v rt phn tn . Trong v qu t s phn b nh sau :
Nguyn t
% s nguyn t
% khi lng
B Al Ga ln Tl
6 .10-4 6,6 4. 10-4 1,5. 10-5 3. 10-5
3. 10-4 8,8 1,5. 10-3 1. 10-5 3. 10-4
(2) Khong vt chnh ca B l borac (Na2B4O7.10H2O)- l khong vt c bit nhiu nht. Ngoi ra cc khong vt c ngha rt ln trong k thut l boraxit (2Mg3B8O15.MgCl2), kecnit (Na2B4O7.4H2O), kolemanit( Ca2B6Oll .5H2O), xaxolin (H3BO3) Phn ln nhm trong v qu t tp trung dng khong vt alumosilicat nh octhoclaz (K2O.Al2O3.6SiO2) mica (K2O.3Al2O3.6SiO2) nefelin ( Na2O.K2O.2Al2O3.4SiO2) caolinit (Al2O3 . 2SiO2 . 2H2O). Khong vt quan trng ca nhm l boxit ( Al2O3 . xH2O) v criolit (Na3[AlF6]). Vit Nam c nhiu m cha boxit cc tnh H Tuyn , Sn La, Lai Chu, Ty Nguyn... Ngi ta khng bit c cc khong vt ring ca gali, ini v tali. Cc nguyn t ny thng ln trong qung ca nhiu kim loi khc, c bit l qung Zn thng c ln cc kim loi trn dng hp cht . Tali cng thng c trong x ca qu trnh sn xut H2SO4 Gali cn c trong qung boxit (khong 3.10-3 % gali), trong tro ca mt s loi than . (3) Trong nc i dng , thnh phn trung bnh ca cc nguyn t nhm IIIA nh sau (theo A.P. Vinogradov 1967) :
Nguyn t B Al
Hm lng % mg/l -6 4,6 4,6. 10 -6 0,01 1. 10
Nguyn t Ga ln Tl
Hm lng % mg/l -9 3.10-5 3.10 1.10-9 1.10-5 1.10-9 1.10-5
(4) Hm lng ca cc nguyn t nhm IIIA c trong mu Mt Trng do cc trm gia cc hnh tinh Apollo 11 - 12 v Luna - 6 thu thp c ba vng khc nhau c gi tr nh sau :
Nguyn t B Al Ga Ln Tl
Hm lng trung bnh (s gam /1g mu ) Apollo - 11 Apollo -12 Luna - 6 -5 0,44.10-5 0,2.10 0,056 0,074 -5 -5 0,45.10 0,45.10-5 0,4.10 3.10-9 9.10-9 0,17.10-5 0,6.10-9 2.10-9 2.10-9
(5) B c nm ng v, 10B (18,45% - 18,98%) v 11B (81,02% - 81,55% ) u l ng v thin nhin, cn 8B v 12B u l ng v phng x . Al c su ng v t 24Al n 29Al, trong c ng v 27Al l ng v thin nhin chim 100%. Ga c 10 ng v t 64Ga n 73Ga, trong c hai ng v thin nhin l 69 Ga (60,2%) v 71Ga (39,8%), cn li u l ng v phng x , trong c 67 Ga c chu k bn hy l 3,25 ngy m. In c 13 ng v t l07In n 119In, trong c hai ng v thin nhin l 113 In (4,23%) v ng v 115In (95,77%). Tl c 16 ng v t 195Tl n 210Tl trong c ng v 203Tl (29,50 %) v 205 Tl (70,50 %) l ng v thin nhin.
NHM V HP CHT CA NHM 4.3. iu ch nhm (l) Ngi ta sn xut Al bng phng php in phn Al2O3 nng chy trong criolit Na3AlF6 ( hay AlF3 . 3NaF). Nguyn liu dng sn xut nhm l qung boxit v criolit cn nhiu tp cht, mt khc tinh ch Al khi cc tp cht rt kh khn, v vy vic tinh ch nguyn liu ban u li rt cn thit. Boxit thin nhin cha khong 40 - 60% Al2O3 V tp Cht ch yu l SiO2, Fe2O3... Ty theo loi qung m thnh phn tp cht c thay i, chng hn boxit trng cha SiO2 nhng hu nh khng c Fe2O3 ; boxit nu li c khong 27% Fe2O3. c Al2O3 C tinh khit cao (khng cha qu 0,2% SiO2) v 0,04% Fe2O3) ngi ta un nng bt boxit vi dung dch NaOH 40% 1500C di
p sut 5 - 6 atm, boxit tan trong dung dch kim: Al2O3 .xH2O + 2NaOH = 2NaAlO2 + (x+ 1 )H2O hoc Al2O3 + 2OH - + 3H2O 2[Al(OH)4]pha long dung dch bng nc, kt ta Al(OH)3 s tch ra v sau nung 12000C trong l quay s thu c Al2O3 tinh khit: [Al(OH)4]- Al(OH)3 + OH2Al(OH)3 = Al2O3 + 3H2O Ngi ta cng iu ch Al2O3 tinh khit bng cch ch ha nefelin hoc cao lanh, chng hn nung nefelin vi vi trong l quay 12000C: (Na2O.K2O.2Al2O3 .4SiO2) + 4CaCO3 = 4CaSiO3 + 2NaAlO2 + 2KAlO2 + 4CO2 nghin mn hn hp rn thu c, sau ngm vo nc ri cho kh CO2 (thu c t qu trnh trn) qua dung dch aluminat: NaAlO2 + KAlO + 4H2O = Na[Al(OH)4] + K[Al(OH)4] [Al(OH)4]- + CO2 = Al(OH)3 + HCO3 Nung kt ta thu c Al2O3. Phng php trn cn thu c NaHCO3, KHCO3 v CaSiO3 sn xut xi mng. (2) V d tr criolit tri t l c hn nn ngi ta tng hp ly criolit bng cch ha tan Al(OH)3 v Na2CO3 trong axit flohiric : 2Al(OH)3 + 3Na2CO3 + 12HF = 2Na3[AlF6] + 3CO2+ 9H2O (3) Qu trnh in phn c thc hin 9500C, vi in p khong 5V v cng dng khong 100000A. Thit b in phn l mt thng v st bn trong lt gch chu nng. Trn lp ny c bc mt lp than dng lm cc m; cc dng l nhng thi than cm vo thng in phn. B mt cht lng trong l c ph mt lp rn cht in li cho khi nng chy khi b ngui . Trong qu trnh in phn c kh O2 bay ra ant tc dng vi C to ra kh CO v CO2 ng thi c mt t flo cng bay ln, to ra mt t CF4, do vy dng cc b n mn dn, nn trong qu trnh in phn phi h thp dn cc dng xung. Qu trnh in phn c tin hnh lin tc, sau mt thi gian , ngi ta li cho thm
Al2O3 v mt t criolit mt cch tun hon; nhm t li khu vc catt v c tho ra ngoi. S thit b in phn m t hnh 35. Nhm nng chy 660oC, nhng Al2O3 nng chy nhit rt cao (2050 C) nn khi Al2O3 tan trong criolit nng chy, h nhit xung khong 10000C. Nhm thu c c tinh khong 99,5%. Sau khi tinh ch li c th t c tinh khit khong 99,998%.
0
sn xut 1000 kg nhm cn khong 4000 kg boxit( ~50% Al2O3 ) tc vo khong 1900 kg Al2O3 ; 70 kg criolit; 450 kg graphit lm ant; v cn mt nng lng khong 56.109J ( hay 15,5.103 kwh) 4.4. Tnh cht l hc ca nhm Nhm l kim loi mu trng bc, trong khng kh c mu xm do b mt ph mt mng oxit mng, trong iu kin thng mng oxit ny thng dy khong 1.10-5 mm bo v cho nhm. B mt Al nguyn cht c kh nng phn x n 90% tia sng ng u vi cc tia c bc sng khc nhau, nn c dng lm vt liu m ln knh vin vng; nhm cng phn x tt cc tia nhit nn c dng lm xitec bo m khng b t nng bi cc bc x mt tri. Nhm c dn nhit cao gn gp ba ln dn nhit ca st, nn c dng ch to my trao i nhit v lm dng c nu nng. Nhm li c dn in cao bng 0,6 ln dn in ca Cu, nhng li nh gp ba ln ca Cu nn c dng lm dy dn in thay cho Cu. nhit thng, nhm tinh khit kh mm, d dt mng v ko thnh si. 100 1500C , nhm c th dt thnh l mng dy 0,01mm c dng nhiu lm my t in v lm giy gi thc phm. 4.5. Tnh cht ha hc ca nhm (1) Nhm l kim loi c hot tnh ha hc cao nhng iu kin thng t
ra km hot ng v b mt nhm c mt mng oxit bn che ph. So vi Na v Mg cng chu k, Al c tnh kh km hn v th in cc dng hn; nhng so vi B th Al li l mt kim loi v Al c bn knh ln hn hn B. (2) L mt cht c tnh kh mnh, Al c kh nng phn ng trc tip vi phi kim . nhit thng hoc khi un nng, Al phn ng trc tip vi cc halogen : 2Al + 3X2 = 2AlX3 tr AlF3 l kh tan trong nc (0,56g/100g H2O 250C ) , cn li u tan v u b thy phn to ra mi trng axit. Ring phn ng vi I2 cn c nc lm xc tc. Nhm phn ng mnh vi oxi, nhit thng to ra lp mng oxit b mt. Khi t nng bt Al hoc l Al mng trong khng kh, nhm chy pht ra nh sng chi v mt lng nhit kh ln; nu t bt Al trong lung kh O2 c th to ra ngn la trn 30000C, phn ng to thnh oxit Al2O3 : 4Al + 3O2 = 2Al2O3 H = - 1670 kJ/mol ngha l khi t 1g bt Al ta ra khong 31 kJ. Tuy nhin, khi t dy Al hay l nhm dy, nhm khng chy m to thnh ti , bn trong l nhm chy lng, bn ngoi l oxit. Do phn ng kt hp vi oxi ta ra nhiu nhit v nhiu hn so vi nhiu kim loi khc, nn khi un nng bt Al vi oxit kim loi no , phn ng xy ra rt mnh lit v y kim loi t do ra khi oxit, chng hn: 8Al + 3Fe3O4 = 4Al2O3 + 9Fe
0
H = - 3338 kJ
Khi nung hn hp tecmit (gm bt Al + bt Fe3O4) nhit c th t n 2400 C. Phng php trn gi l phng pht nhit nhm, dng iu ch mt s kim loi kh nng chy nh Cr, Mn, Fe, V, Tl ... Vi nit, lu hunh , photpho, cacbon, Al cng ha hp trc tip cc iu kin khc nhau to ra AlN, Al2S3, AlP, Al4C3, nhng hp cht ny u b H2O thy phn to ra Al(OH)3 v hirua ca phi kim tng ng: AlN + 3H2O = Al(OH)3 + NH3 Al2S3 + 6H2O = 2Al(OH)3 + 3H2S AlP + 3H2O = Al(OH)3 + PH3 Al4C3 + 12H2O = 4Al(OH)3 + 3CH4 Nhm khng phn ng trc tip vi hir.
(3) Mc d th in cc ca Al trong mi trng axit l kh thp: Al3+(dd) + 3e = Alo(rn) Eo = - 1,66 V nhng do c mng oxit bo v b mt, nn nhm kh bn vi H2O v mt s axit k c khi un nng, chng hn nhm khng phn ng vi H2O , khng tc dng vi dung dch long ca CH3COOH, H3PO4. Nhm ch d tan trong HCl v H2SO4 nht l khi un nng. Phn ng chung xy ra theo phng trnh : 2Al + 6H3O+ + 6H2O = 2[Al(H2O)6]3+ + 3H2 Vi mt s axit khc phn ng cng xy ra tng t . Mc d vy, nhm nguyn cht kh bn trong HCl, cn nhm k thut li d b HCl n mn. Hnh 36 cho thy nh hng ca cc tp cht n tc ha tan nhm trong axit HCI. Nhm hu nh khng tc dng vi HNO3 rt long, nhng vi nng trung bnh d ha tan nhm hn. Trong dung dch c ngui, nhm khng nhng khng tan, m cn b th ng ha, ngha l sau khi ngm trong HNO3 m c, nhm li khng phn ng vi HCl hoc H2SO4 long na.
Qu trnh ngm trong cc dung dch nh vy (hoc mt s dung dch cht oxi ha khc nh K2Cr2O7...) to ra trn b mt ca nhm mt mng bo v c chiu dy khong 20 - 30.... (micromet) Trong mi trng kim, th in cc ca nhm kh thp: AlO2- + 2H2O + 3e = Al+ 4OHEo = - 2,35V (dd) (rn ) v vy nhm d tan trong dung dch kim mnh nh NaOH , KOH: 2Al + 6OH- + 6H2O = 2[Al(OH)6]3- + 3H2 dung dch amoniac cng n mn nhm kh mnh.
4.6. Hp kim ca nhm Nhm c kh nng to nn hp kim vi nhiu nguyn t khc, trong quan trng nht l hp kim uyara v silumin. Phn ln lng Al khai thc c u dng iu ch hp kim. uyara (hay uralumin) c thnh phn gm 94% Al, 4% Cu, 0,5% Mg, 0,5% Mn, 0,5% Fe, 0,5% Si; l loi hp kim cng v bn c dng trong cng nghip my bay, t. Silumin c thnh phn 85 - 90% Al, 10 - 14% Si, 0,1% Na; l hp kim rt bn v rt d c, dng sn xut ng c my bay, tu thy. Manhali l hp kim c thnh phn 90 - 98% Al v 10 - 2% Mg; c bn cao v nh. Nhng hp cht ca Al vi cc nguyn t h d - cc aluminit - u c kh nng chu nng n 12000C nh Ni3Al, NiAl, CoAl, Ti3Al, TiAl..v.v.. 4. 7. Nhm oxit A12O3 (1) Nhm oxit tn ti nhiu dng th hnh khc nhau, c cu trc tinh th khc nhau v ph thuc vo iu kin iu ch nh cc dng -,-, -,- ... trong dng - Al2O3 l bn hn c. Khi nung Al(OH)3 hoc mui nhm ca axit d bay hi to ra cht bt mu trng v nh hnh khng tan trong nc; nhng nu nung mnh n 10000C to thnh dng - Al2O3 khng nhng khng tan trong nc m cn khng tan trong axit. (2) -Al2O3 l cht rn tinh th hnh mt thoi (tc hnh romboet thuc h lc phng ).C th xem mng tinh th - Al2O3 l mng phn t, ti mt mng li l nhng phn t Al2O3. Trong mng tinh th mi nguyn t Al c bao quanh bi 6 nguyn t oxi v mi nguyn t oxi c bao quanh bi 4 nguyn t Al. Trong mi t bo nguyn t c phn b bi mt phn t Al2O3. Khong cch gia hai nguyn t Al l 1,36 A, cn khong cch gia nguyn t Al v O l 1,99 A (hnh 37 a , b). - Al2O3 c khi lng ring D = 3,99 g/cm3. Trong thin nhin thng gp dng khong vt c tn l corunum cha 90% oxit, thng cha tp cht nn u c mu. xaphia l corunum tinh khit cha Fe2+ , V4+; rutin (hng ngc) mu l corunum cha vt Cr3+ ( Qu Hp, Yn Bi). Hin nay cc loi hng ngc c iu ch nhn to bng cch nu chy Al2O3 ri cho thm tp cht thch ng, sau cho kt tinh thnh n tinh th. Loi ngc c iu ch bng cch nhn to ny c cht lng tt hn ngc thin nhin.
(3) Loi corunum thin nhin c nhit nng chy cao( 20500C) v rt cng, nn c dng lm mi. dng bt tn nh gi l bt nhm dng nh sch b mt kim loi; lm chn knh ng h, lm trc quay trong mt s my chnh xc. Corunum rt tr v mt ha hc , khng tan trong nc , trong axit , trong kim. Khi nung n 10000C, -Al2O3 Phn ng mnh vi hiroxit, cacbonat, hirosunfat, pirosunfat... ca cc kim loi kim nng chy: Al2O3 + 2NaOH = 2NaAlO2 + H2O cc nguyn t nhm IIIA Al2O3 + Na2CO3 = 2NaAlO2 + CO2 Al2O3 + 3K2S2O7 = Al2(SO4)3 + 3K2SO4 (4) Mt dng th hnh khc ca nhm oxit c dng tinh th lp phng l - Al2O3 . Dng ny khng tn ti trong thin nhin v to nn khi nung tinh th hiraglit Al(OH)3 hoc nung bemit, hoc nung Al(OH)3 v nh hnh khong 5000C. Khi nung n 10000C chuyn thnh dng - Al2O3. - Al2O3 l nhng vi tinh th khng mu, c khi lng ring l 3,4 g/cm3 , c kh nng ht m mnh, khng kh m qua ng ng - Al2O3 200C ch cn li 0,003 mgH2O/1l khng kh. Trong cng nghip Al2O3 c iu ch bng cch nung Al(OH)3 1200 14000C : 2Al(OH)3 = Al2O3 + 3H2O 4.8. Nhm hiroxit (l) Khi cho dung dch amoniac tc dng vi dung dch mui nhm s to ra kt ta dng keo v nh hnh mu trng ca nhm hiroxit, kt ta ny cha nhiu nc ng vi thnh phn Al(OH)3 .nH2O. Kt ta cng c biu din
dng hirat oxit Al2O3 .nH2O. Thnh phn v cu trc ca kt ta ph thuc vo iu kin iu ch v phng php duy tr kt ta, chng hn: Khi cho dung dch amoniac tc dng vi mui nhm khi lnh s to ra kt ta v nh hnh; nhng khi un nng n khong 2000C to ra hn hp gm nhng tinh th AIO(OH) tc Al2O3 . nH2O thng gi l bemit vi dng v nh hnh. Khi cho kh CO2 qua dung dch kim aluminat nu cho kt ta chm to thnh tinh th hiragilit a - Al(OH)3; nhng nu cho kt ta nhanh to thnh tinh th baeri - Al(OH)3 (2) Trong thin nhin , tinh th khong vt hiragilit c cu trc lp kh phc tp, cc lp xp song song nhau. Mi lp c xem l to ra t ba mt phng, cc nhm OH nm trong hai mt phng hai bn, cn nguyn t Al nm trong mt phng gia. Mi nguyn t Al c bao quanh bi 6 nhm OH to ra hnh 8 mt ( hnh 38)
Dng hiragilit c khi lng ring l 2,42 g/cm3 khc vi dng v nh hnh l rt kh tan trong axit. (3) Mt dng th hnh ca Al(OH)3 c trong thin nhin l dng tinh th iaspo0, khong vt ny cng c thnh phn nh bemit. Cc khong vt nu trn u c thnh phn ca cc loi boxit. Khi un nng hiragilit ~ 1500C s tch mt phn nc to ra bemit; sau un tip n 3000C, bemit chuyn thnh - Al2O3, vy bemit tn ti trong
khong nhit t 160 2800C. Mt khc, khi un nng iaspo khong 4200C to thnh corinon - Al2O3 ; - Al2O3 Chuyn thnh - Al2O3 khi nung 10000C.
(4) Nhm hiroxit l cht lng tnh tan trong axit v trong kim mnh theo phng trnh:
Vi axit, Al(OH)3 d to ra cc dung dch c cha ion hirat ha [Al(H2O)6]3+ khng mu, hnh thnh cc mui nhm. Mui ca a s axit mnh u d tan trong nc, nhng b thu phn mnh nn dung dch c mi trng axit ; cn mui ca axit yu nh Al2S3 thc t b nc phn hy hon ton. Khi cho dung dch mui nhm tc dng vi dung dch kim c xem l qu trnh thay th cc phn t H2O trong ion [ Al(H2O)6]3+ bng cc nhm OH- :
nu lng kim d s to nn cc ion [Al(OH)4(H2O)2]-, [Al(OH)5(H2O)]2- , [Al(OH)6]3-. Cc ion u c gi chung l ion hiroxialuminat. Khi lm bay hi dung dch natri hiroxialuminat thu c mui, thng biu din dng n gin l NaAlO2 v coi nh l mui ca axit mm - aluminic (c hng s axit l 4.10-13) HAlO2 hay AlO(OH) . Ngi ta cng biu din nhng hp cht dng phc cht , chng hn nh :
Nhng mui nh Ca3 [Al(OH)6]2 ; Sr3 [Al(OH)6]- cu trc tinh th c xc lp bng quang ph Rnghen. (5) Cc aluminat ca cc kim loi ha tr I u d tan trong nc v u b thy phn mnh nn ch tn ti khi kh d kim; cn cc aluminat t cc baz
yu b thy phn thc t l hon ton, v vy nhng loi hp cht ny u c iu ch bng phng php kh khi nu chy Al2O3 Vi Oxit kim loi tng ng . Nhng "aluminat khan" ny u c biu din dng tng qut MII(AlO2)2; cc hp cht in hnh thuc loi ny gp trng thi tinh th trong thin nhin l cc spinen nh Zn(AlO2)2, Mg(AlO2)2, Fe(AlO2)2... a s cc aluminat ny u khng tan trong nc. V Al(OH)3 c hng s phn ly axit rt b nn khi pha long dung dch aluminat hoc thi kh CO2 vo dung dch , s to ra kt ta Al(OH)3. Ngi ta cng iu ch Al(OH)3 bng cch cho mui nhm tc dng vi cc cht nh NaOH, KOH, NH., Na2 CO3 NaCH3COO...vi phn ng tm tt l :
4.9. Nhm halogenua ( 1 ) Trong cc halogenua ca nhm th nhm florua c cu to v tnh cht khc nhiu so vi cc hp cht nhm halogenua cn li. Nhm florua c kin trc ion, nng chy nhit cao, khng tan trong nc v t c kh nng phn ng; cc nhm halogenua cn li u c nhit nng chy thp, u d tan trong nc v u c kh nng phn ng cao; d hnh thnh hp cht c Al2X6 . Nhit nng chy v nhit si nh sau (bng 24). Bng 24. Nhit nng chy v nhit si ca nhm halogenua AlX3 AlF3 AlCl3 AlBr3 AlI3 Nhit nng chy Tnc (oC) 1290 192,6 ( 1700 mmHg) 97,5 179,5 Nhit si Ts (oC) Thng hoa trn Tnc 180 (thng hoa) 255 381
(2) Nhm florua c iu ch bng cch cho hiro florua tc dng vi Al hoc Al2O3 nhit cao :
Cng c iu ch bng cch nung nng criolit vi nhm sunfat, sau ha tan trong nc tch natri sunfat.
Nhm florua ngm nc c iu ch bng cch cho Al(OH)3 tc dng

HF, khi chng dung dch, cht rn thot ra dng hirat tinh th AlF3 .3H2O. AlF3 khan l cht rn mu trng, khng tan trong nc, trong axit v kim, kh tr v mt ha hc. Tuy nhin li c kh nng kt hp vi cc florua kim loi kim to ra cc hp cht floanuminat ng vi cc cng thc M31 AlF6, M21, AlF5, M1 AlF4; trong s quan trng nht l natri floaluminat (Na3AlF6) c dng trong cng nghip sn xut nhm. (3) Criolit (Na3AlF6) cn gi l bng thch l mt khong cht thin nhin, ngoi phng php iu ch nu trn, ngi ta cn iu ch bng cch nung hn hp gm canxi florua, kali
sunfat vi than to ra kali florua. Cho kali florua tc dng vi natri sunfat to ra natri florua v hon nguyn li kali sunfat; sau nung natri florua vi nhm sunfat thu c criolit :
Trong tinh th criolit, nhm c s phi tr 6, tinh th to ra bi ion Na+ v ion AlF63-, ion c dng hnh tm mt, mi nguyn t F chung cho c hai hnh tm mt bn cnh nhau (hnh 39). cc hp cht M21 AlF5 v M1 AlF4 dng polime ng vi thnh phn (AlF5)n2nv (AlF4)nn- (hnh 40).
Na3AlF6 tinh khit l nhng tinh th mu trng dng lp phng, c khi lng ring l 2,95g/cm3, nng chy 10000C. Rt kh tc dng vi axit nhng li d b phn hy khi un nng vi kim hoc sa vi. Mt lng ln xoda v Al2O3 c sn xut bng cch nung criolit vi CaCO3:
sau phn hy Na3AlO3 bng H2O V CO2 :
xoa v Al2O3 (t nhm hiroxit) c iu ch bng phng php ny kh tinh khit. Ngi ta cng tch c axit hexafloro aluminic t do ng vi Na3AlF6 trng hirat tinh th H3AlF6 .3H2O v H3AlF6 . 6H2O. (4) Nhm clorua khan c iu ch bng cch nung bt nhm trong lung kh ch 5000C, hoc nung bt nhm vi kh HCl cho AlCl3 vi cht lng cao :
Ngi ta cng iu ch bng cch cho kh clo qua hn hp gm Al2O3 V than nung nng :
Sn phm k thut thng c mu vng l do c ln FeCl3. tinh ch loi AlCl3 k thut ny ngi ta nung nng sn phm vi nhm kim loi trong ng hn kn 2000C, sau cho thng hoa sn phm, khi FeCl3 b kh thnh kim loi:
trng thi rn, AlCl3 c cu trc ion, n gn nhit thng hoa (180 C), nhm clorua ime ha thnh dng Al2Cl6 lc s phi tr ca nhm
0
thay i t 6 n 4. Nh vy, cu trc ime chim u th trong pha hi gn nhit si, khi un nng n 8000C xy ra s phn ly thnh monome :
Trong phn t ime, mi nguyn t Al lin kt vi bn nguyn t clo; v mi nguyn t clo trung tm (B) li lin kt vi hai nguyn t Al, to ra hai hnh t din c cnh chung. Cu trc khng gian nu trong hnh 41 . Hai lin kt to ra gia nguyn t clo trung tm vi 2 nguyn t Al, th c mt lin kt cng ha tr bnh thng do s ghp i cp electron gia mt nguyn t Al v nguyn t clo; lin kt cn li l lin kt cng ha tr- kiu cho - nhn, trong Al l "cht nhn". trng thi hi v trng thi ha tan trong dung mi hu c, khng nhng ch nhm clorua m c nhm bromua v iotua cng trng thi ime Al2Br6 V Al2I6 . Cu trc khng gian ca cc phn t ime cng c dng nh hnh 41, nhng khc nhau v di lin kt v gc ha tr (bng 25).
Qu trnh to thnh ime theo s 2AlX3 Al2X6 l mt qu trnh pht nhit vi Al2Cl6 l 121,3 kJ; Vi Al2Br6 l 110,8 kJ; vi Al2I6 l 94,1 kJ; nh vy nhm clorua d trng hp hn so vi nhm iotua.. Bng 25 . di lin kt v gc ha tr ca phn t Al2X6 (So Vi hnh 41) dAl - A Al2Cl6 Al2Br6 Al2I6 2,06 2,21 2,53 Khong cch gia cc nguyn t () dAl - B dA- B dAl - Al 2,21 2,33 2,58 3,56 3,78 4,24 3,41 3,39 3,24 Gc ho tr () BAlB AAlA 80 87 118 115 -
S d c s to thnh ime nh vy l do nguyn t kim loi c khuynh
hng h sung lp v electron bn ngoi ca mnh thnh octet. AlCl3 khan l nhng tinh th dng lc phng mu trng, khi lng ring 2,44g/cm3. trng thi rn dn in tt hn so vi trng thi nng chy do chuyn t kin trc ion sang kin trc phn t ime; khi nhm clorua lng kt tinh th th tch gim ng k do nhm clorua chuyn t kin trc phn t Al2Cl6 sang kin trc ion. AlCl3 khan ht m rt mnh, nn bc khi trong khng kh m do hin tng thy phn gii phng hir clorua:
do d iu ch bng bt k cch no, AlCl3 khan u phi c bo qun trong cc l kn v kh. AlCl3 khan cn c kh nng kt hp vi NH3 to ra cht bt mu trng AlCl3.6NH3 hp cht ny ch tch mt phn amoniac 1800C; cn hp cht AlCl3. NH3 thng hoa 400oC. Ngoi ra, cn c kh nng kt hp vi nhiu cht khc nh H2O, H2S, SO2 PCl3, POCl3 v nhiu hp cht hu c, v vy AlCl3 khan c s dng nhiu trong tng hp hu c. AlCl3 khan cng c kh nng kt hp vi mui clorua ca kim loi kim to ra clo- aluminat dng MlAlCl4, M31AlCl6 tng t AlF3. Ngi ta gii thch khuynh hng mnh to ra cc hp cht kp nh trn l do tnh phn cc mnh ca phn t AlCl3. AlCl3 d tan trong nc v trong nhiu dung mi hu c; khi tan trong nc li pht nhit mnh. ha tan (g/100gH2O) tng chm khi tng nhit nh nu bng di y:
t0C tan, S
0 43,8
10 44,9
20 45,9
30 46,6
40 47,3
60 48,1
80 48,6
100 49,0
Dung dch AlCl3 c phn ng axit mnh do b thy phn, v vy mun kt tinh dng hirat AlCl3 . 6H2O cn phi cho bo ha kh HCl dung dch nhm trong HCl. AlCl3.H2O l cht rn tinh th trng, rt ho nc, nn chy ra trong khng kh m. Khi un nng , khng mt nc kt tinh m b phn hy to ra Al2O3 ng thi mt H2O v h:
(5) Nhm bromua ( AlBr3) khan l nhng tinh th ng nh khng mu. Khi nng chy thnh cht lng linh ng trong sut. Bc khi mnh trong khng kh m, phn ng mnh lit vi H2O ng thi gii phng mt lng nhit kh ln lm tung te khi phn ng. Tan trong CS2 v axeton. AlBr3 khan c iu ch bng cch cho Al v bo hay Al ht (d) tc dng vi Br2 lng:
Chng ct AlBr3 lng khong 2600C, sau lm ngui c tinh th khan. AlBr3.6H2O l nhng tinh th khng mu, d tan trong nc. Khi un nng b phn hy :
(6) AlI3 cng c nhng tnh cht tng t AlBr3.C hai u c kh nng to ra hp cht kp vi mui kim loi kim dng MlAlBr4 v M1AlI4. C hai u l hp cht cng ha tr nn d tan trong dung mi khng cc nh benzen, trong dung dch chng u dng c Al2Br6 v Al2I6 .Khc vi AlCl3, trng thi rn AlBr3 V AlI3 khng dn in. 4.10. Nhm sunfat v phn nhm (1) Nhm sunfat khan Al2(SO4)3 l cht bt kt tinh mu trng. T dung dch nc kt tinh dng hirat ha mu trng Al2(SO4)3 .18H2O . c iu ch bng cch ha tan Al(OH)3 trong H2SO4 98% :
cng c iu ch t boxit hoc t st. (2) Al2(SO4)3 . 18H2O l nhng tinh th hnh kim, mu trng, d tan trong nc, ha tan tng khi tng nhit ; di y l tan (g/100 g H2O) Ca Al2(SO4)3 khan :
t0C tan
0 31,2
10 33,5
20 3,.4
30 4,.4
40 45,7
60 59,2
80 73,1
100 89,0
dung dch Al2(SO4)3 C phn ng axit mnh do b thy phn mt phn:
Khi nung nng tinh th , mui phng to bin thnh khi xp do mt dn nc kt tinh. un nng n 3400C bin thnh mui khan. Bt u phn hy 5900C, phn hy mnh 6400C v n 7800C th phn hy hon ton bin thnh Al2O3 :
Al2(SO4)3 c kh nng kt hp vi mui sunfat kim to ra mui kp gi l phn nhm. (3) Phn l loi mui kp c cng thc chung l M21SO4 . M2III(SO4)3.24H2O trong : M1 l cc kim loi Na, K, Rb, Cs, Tl, NH4+. MII l cc kim loi Ti, V; Cr, Mn, Fe, Co; Al, Ga, In ; Ra, Ir. Tr liti khng c kh nng to phn v ion Li+ c th tch qu b nn khng bo m tnh bn ca mng tinh th. Tinh th cc loi phn nh trn c dng hnh tm mt, khng mu hoc c mu, cu to t cc ion [M(H2O)6]+ [M(H2O)6]3+ v hai ion SO42- . Tinh th cc loi phn khc nhau u ng hnh vi nhau. Phn t tan hn so vi mi sunfat ring, nhng khi tng nhit , a s trng hp c ha tan tng. (4) Phn nhm - kali K2SO4 .Al2(SO4)3.24H2O l mt loi phn quan trng c nhiu ng dng trong thc t. Phn nhm - kali l nhng tinh th hnh tm mt, trong sut khng mu c v cht. Nng chy 920C trong nc kt tinh. Cng nh cc loi phn khc, ha tan ca phn nhm - kali thp hn so vi tan ca sunfat thnh phn, nhng li tan nhanh khi nhit tng; di y l tan ca phn nhm - kali (g/100 H2O) ph thuc nhit : Phn nhm - kali khng ln hoa ngoi khng kh, nhng nung n 1200C, phn mt nc kt tinh, bin thnh khi xp mu trng gi l "phn phi" d ht m v chy nc. Phn nhm - kali c iu ch bng phng php kt tinh t dung dch ng phn t K2SO4 v Al2(SO4)3 :
Cng nh Al2(SO4)3. 18H2O, phn nhm - kali c dng rng ri trong cng nghip nhum vi, dng lm cht cn mu; trong cng ngh thuc trng
da; trong cng ngh h giy; lm trong nc. Trong y khoa, dng lm cht st trng, nh mt, bi hng, cm mu chn rng. 4.11. Cc hp cht khc ca nhm (1) Nhm nitrat Al(NO3). 9H2O l cht rn dng tinh th, d tan trong nc v trong ru. tan 200C l 75,4 g Al(NO3)3 trong 100 g H2O. Ht m, nn chy ra trong khng kh. Dung dch nc c phn ng axit do b thy phn. Al(NO3)3 c iu ch bng cch ha tan Al(OH)3 trong axit HNO3 :
hoc bng phn ng trao i khi cho Al2(SO4)3 hoc phn nhm - kali tc dng vi Pb(NO3)2 hoc Ba(NO3)3 Al(NO3)3. 9H2O nng chy 700C, chuyn thnh dng Al(NO3)3. 6H2O; n 140oC to thnh mui baz v n 2000C b phn hy to thnh Al2O3.
(2) Nhm axetat Al(CH3COO thu c trong dung dch nc khi cho nhm sunfat tc dng vi ch axetat hoc ban,rihoc khi ha tan Al(OH)3 trong axit axetic . Al(CH3COCOO b thy phn mnh hn nhiu so vi cc mui khc ca nhm nn ch tn ti trong dung dch nc, m khng tch c trng thi rn. Khi un dung dch cho nc bay hi, to ra kt ta Al(OH)3 hoc mui axetat baz, lc mt phn axit axetic cng bay hi. Nhm axetat cng c dng lm cht cn mu trong cng ngh nhum vi... (3) Nhm hirua (AlH3)n l mt polime c iu ch bng cch cho AlCl3 tc dng vi dung dch hiro aluminat Li[AlH4] trong eete
(AlH3)n l cht rn v nh hnh mu trng, b phn hy nhit cao hn l05oC tch ra hiro; l hp cht thiu electron. Mi nguyn t Al c bao quanh bi 6 nguyn t Al dng hnh tm mt, hai nguyn t Al bn cnh nhau lin kt vi nhau qua nguyn t hiro Al - H - Al bng lin kt ba tm. (AlH3)n d dng to ra sn phm kt hp chng hn vi NaH trong dung dch ete to ra hiro aluminat:
Cc sn phm u l cht rn mu trng, d dng b H2O phn hy, u c tnh kh mnh, c dng nhiu trong qu trnh tng hp hu c v v c.
(4) Nhm sunfua Al2S3 c th c iu ch bng cch cho phn ng trc tip gia Al v lu hunh : 2Al + 3S = Al2S3 Phn ng xy ra khi nung nng hn hp, ng thi li ta ra nhit lng kh ln 589,7 kJ/ mol. Al2S3 l cht rn tinh th mu trng, nng chy 11000C. Khi t trong khng kh to ra Al2O3 V SO2 :
B H2O phn hy hon ton thnh Al(OH)3 V H2S:
(5) Nhm nitrua AlN c th iu ch trc tip t nhm v nit 8000C, ng thi pht ra nhit lng kh ln (267,7kJ/mol) . Trong cng nghip iu ch bng cch nung hn hp gm Al2O3 v than trong kh quyn N2 17000C :
Nhm nitrua tinh khit l cht bt mu trng, nng chy 22000C di p sut 4atm ca nit. Khi un nng di p sut thng b phn hy thnh nguyn t gn 20000C. B nc phn hy chm nhng vi dung dch kim b
phn hy nhanh hn thnh NH3; khi cho hi H2O nu qu, Al2O3 li c ti sinh :
AlN c dng iu ch NH3. (6). Nhm cacbua Al4C3 to ra t cc nguyn t nhit cao trong kh quyn hiro, pht ra nhit lng 167,4 kJ/mol. Ngi ta cng iu ch bng cch nung nng hn hp gm Al2O3 vi than 20000C :
Al4C3 tinh khit l cht bt mu vng chi, trong chn khng thng hoa 22000C m khng nng chy. B nc phn hu to thnh CH4. CC KIM LOI GALI - INI - TALI 4.12. iu ch Ga, In, Tl Nguyn liu chnh iu ch gali l qung boxit hoc cht b ca qu trnh ch ha qung km; cn nguyn liu chnh iu ch In v Tl l bi thu c khi t qung Sunfua c mt S kim loi nh km, ch, ng , st. T cc nguyn liu c chuyn thnh dng mui hoc dng oxit ri sau in phn dung dch mui ca chng, hoc dng hiro kh oxit cc kim loi trn. 4.13. Tnh cht ca Ga, In, Tl (l) u l nhng kim loi c mu trng bc, mm; thi ini khi vch ln t giy li nt en. C ba kim loi u c nhit nng chy thp, nht l gali, nhng li c nhit si cao (bng 23); gali lng li rt d chm ng, ngha l di nhit nng chy (~ 300C ) vn khng ha rn; do nhit nng chy thp, nhit si cao v dn n kh u, nn galic dng np vo cc nhit k dng nhit cao, c th o c n 12000C. Gali lng b ngoi ging thy ngn , nhng li d tm t b mt ca rt nhiu nguyn t phi kim loi, nn c dng trng ln b mt ca thy tinh c gng phn chiu rt tt ng u cc tia sng v chu c nhit rt cao. Ini cng c kh nng phn x cc tia sng nh vy nn cng dng trng gng, c bit gng trong knh thin vn. (2) Cng nh nhm, gali, ini v tali u d to ra cc hp kim vi nhiu kim loi, nht l nhng hp kim d nng chy, chng hn :
Hp kim gm 18,1 % In vi 41 % Bi ; 22,1 % Pb; 10,6% Sn v 8,2% Cd nng chy 470C dng trong y khoa b xng gy. Hp kim gm 75% Ga v 25% In nng chy 16oC v hp kim gm 90% Ga vi 8% Sn; 2% Zn nng chy 19oC nn c dng ch to thit b cha chy t ng. Tali c dng ch hp kim vi Pb, Sn c kh nng chu axit. c bit l hp kim c thnh phn 70% Pb, 20% Sn v 10% Tl Chu ng c hn hp axit H2SO4, HNO3 v HCl. (3) C ba nguyn t u c kh nng tc dng vi cc n cht v hp cht vi mc khc nhau. Khi trong khng kh, Ga v In khng bin i do c bo v bi mt lp oxit mu xm; cn tali th b oxi ha chm . Khi nung nng, c ba u ha hp mnh vi oxi v lu hunh; vi clo, brm phn ng xy ra ngay nhit thng, cn vi it th phi un nng. Tng t nhm, gali hon ton bn i vi H2O, cn ini v nht l tali b nc ph hy trn b mt khi c khng kh. Axit sunfuric v nht l axit clohiric ha tan d Ga v In; cn Tl tc dng vi HCl rt chm do to ra lp mui TlCl khng tan che ch b mt. Vi axit nitric, Ga phn ng chm, cn tali phn ng rt mnh lit. Tng t nhm, gali tan trong dung dch kim mnh.
cn ini v c bit l tali li bn trong dung dch kim khi khng c mt ca cht oxi ha. Ngoi ra, gali cn tan r rt trong dung dch amoniac. 4.14. Cc hp cht Ga(III), In (III), Tl(III) (l) Cc oxit M2O3 u l nhng cht rn c mu khc nhau, Ga2O3 mu trng, In2O3 mu vng v Tl2O3 mu hung. Khng tan trong nc, tan c trong axit v tan tng theo trt t t Ga2O3 n Tl2O3. bn vi nhit gim, Ga2O3 nng chy 17400C m khng b phn hy; 8500C In2O3 bin thnh In3O4; Cn Tl2O3 bt u mt oxi 900C, sau khi nung n trn 7500C th chuyn hon ton thnh Tl2O. Khi t trong khng kh, gali b oxi ha n Gao, ini to ra In2O3. Cn tali to ra hn hp Tl2O3 v Tl2O; V Vy iu ch cc hp cht trn ngi ta thng dng cc phng php nhit phn nitrua, sunfua, nitrat hoc hiroxit ca chng, chng hn :
Tl2O3 cn c iu ch bng cch dng ozon oxi ha Tl2O. (2) Cc hiroxit M(OH)3 u l nhng kt ta keo, thc t khng tan trong nc, c thnh phn khng xc nh v c mu khc nhau: Ga(OH)3, In(OH)3 c mu trng, cn Tl(OH)3 C mu hung . Tt c cc hiroxit u c iu ch bng cch cho dung dch mui M(III) tc dng vi dung dch kim.
u tan trong dung dch axit to thnh mui M(III):
Ga(OH)3 v In(oH)3 u tan trong kim mnh to ra cc ion hiroxigalat v hiroxiindat tng t nh aluminat:
Tl(OH)3 hu nh khng tan trong kim. V mc axit - baz ca M(OH)3 c khc nhau, Ga(OH)3 chc baz v chc axit gn bng nhau; In(OH)3 tnh baz cao hn tnh axit; cn Tl(OH)3 tnh axit th hin rt yu:
iu c lin quan n s tng kch thc v kh nng phn cc ca ion M3+ . bn nhit gim t Ga(OH)3 trn Tl(OH)3 ; Ga(OH)3 mt nc hon ton khi nung nng, cn Tl(OH)3 mt nc ngay nhit thng. (3) Cc mui M(III) ca chng vi a s axit mnh u d tan trong nc, nhng b thy phn mnh nn u c phn ng axit, mc thy phn gim dn t Ga3+ n Tl3+. Hng s cn bng thy phn :
Cc mui ca axit yu v tan c u b thy phn gn nh hon ton, chng hn cc sunfua, cacbonat, xianua, axetat... u d b phn hy khi tip xc vi nc. Cc mui khi kt tinh t dung dch nc u to ra dng hirat tng t cc
mui ca nhm. (4) Cc mui halogenua ca Ga3+ ; In3+ ; Tl3+ u d nng chy v d tan trong nc (tr mui florua) v u to ra dng MX3.6H2O khi kt tinh t dung dch. Mu sc, nhit nng chy, nhit si ca chng theo bng 26 . Bng 26. Nhit nng chy nhit si ca MX3 (M l Ga, In. Tl; X l halogen)
Hp GaF3 GaCl3 GaBr3 GaI3 InF3 lnCl3 lnBr3 lnl3 TlF3 TlCl3 TlBr3 TlI3
Mu sc mu vng khng mu khng mu khng mu vng nht mu vng mu en
Nhit nng chy

0
Nhit si ( 0C ) 950 ( thng hoa ) 200 279 346 1200 498 ( thng hoa ) 371 (thng hoa ) thng hoa -
1000 77 122 212 1170 586 436 210 550 25 -
Cc hp cht ini halogenua v c GaF3, TlCl3 u thng hoa khi un nng, nhit nng chy ch c xc nh di p sut. Cc mui TlCl3, GaCl3 khan cng bc khi mnh trong khng kh m ging nh AlO3. trng thi hi cc halogenua ca gali v ini cng tn ti dng c M2X6 (X l Cl, Br, I) tng t Al2X6 chng cng c cu to khng gian tng t cu to Al2Cl6 (hnh 41). (5) Cc mui sunfat ca Ga3+ ; In3+ ; Tl3+ u khng mu v d tan trong nc. Gali sunfat kt tinh dng Ga2(SO4)3. 18H2O, Cn ini sunfat kt tinh dng In2(SO4)3. 9H2O. Vi cc kim loi ha tr 1, cc mui sunfat ca Ga3+; In3+; Tl3+ to ra hp cht kp dng hirat M21SO4 . M2III(SO4)3.8H2O( MIII l Ga, In, Tl); nhng dng phn M2ISO4.M2III (SO4)3.24H2O th MIII ch l Ga v In; ngha l Tl3+ khng c
kh nng to ra phn. Cc loi sunfat , khi tan trong nc thc t phn ly hon ton thnh nhng ion to nn chng. (6) Cc mui nitrat ca Ga3+ ; In3+ ; Tl3+ u khng mu, u kt tinh t dung dch dng hirat tinh th : Ga(NO3)3.8H2O; In(NO3)3. 4,5H2O; Tl(NO3)3.3H2O. Cc hp cht u l sn phm khi cho oxit M2O3 tc dng vi HNO3 c:
(7) Cc sunfua ca Gali ; In3+ v Tl3+ u l nhng cht rn c mu khc nhau. Ga2S3 l cht kt tinh mu vng (Tnc = 125,50C) b H2O phn hy chm to ra H2S. In2S3 l cht rn mu vng (Tnc = 10500C) khng b nc phn hy, nn c th iu ch bng cch cho kh H2S qua dung dch axit yu ca mui In3+ Tl2S3 l cht rn mu en (Tnc = 2600C) khng tan trong nc v cc axit long; c iu ch bng phng php kh t cc nguyn t; khi cho kh H2S tc dng vi mui Tl3+ s kh ion Tl3+ to ra Tl2S mu en:
4.15. Cc hp cht M(I), M(II) (1) Ngoi nhng hp cht ha tr (III) , cc nguyn t Al - Ga - In, Tl u c kh nng to ra cc hp cht c ha tr thp hn l hp cht ha tr (II) v ha tr (I) . Chng hn, cc hp cht ca nhm ha tr 1 to nn theo s chung :
( X l halogen) trn 10000C , nhng khi lm lnh li b phn hy thnh cc sn phm ban u. Cc hp cht nh Al2S , Al2Se cng ch bn trng thi hi, cng c to ra nh AlX nu trn . Cc hp cht ha tr (II) cng c to ra , chng hn GaCl2 l nhng tinh th khng mu, nng chy 1700C v si gn 5350C. GaCl2 c to thnh khi nung GaCl3 vi gn kim loi :
GaCl2 b nc phn hu to ra H2. Ngi ta cng bit c sunfua GaS mu vng , khng tan trong nc v nng chy 9650C. Ngi ta cng bit c nhiu hp cht In(II) chng hn cc halogenua InX2, cc hp cht u b nc phn hy thnh In v InCl3 :
Ngi ta cng bit c mt s hp cht ca Ga(I) v In(I), chng hn Ga2O, Ga2S u l nhng cht rn mu en. Ga2O l Cht c tnh kh :
(2) Trong khi cc hp cht ca Ga v In ha tr thp l khng in hnh, th cc hp cht ha tr (I) ca tali li rt c trng. Trong khi cc hp cht ca Ga(I) v In(I) u rt t bn, th hp cht Tl(I) c iu ch kh phong ph. Trong dung dch nc, ion Tl+ bn hn ion Tl3+ :
bn knh ca ion Tl+ (1,54 ) gn vi bn knh ca ion K+ (134 ), ion Rb+ (1,48 ) v ion Ag+ (l,27 ), do cc hp cht ca Tl+ c nhng tnh cht ging hp cht kim loi kim hoc ca bc; ion Tl+ c th th ion K+ trong mt s men nn c th dng th kali; tinh th TIF c cu trc kiu NaCl; cn TlCl, TlBr, TlI li c cu trc dng KCl ngha l thng c s phi tr 6 hoc 8. Tl2O l cht dng bt mu en, nng chy 3000C v si l0800c. Ht m v tan trong nc v dung dch c phn ng kim mnh:
Khi un nng trong khng kh hoc trong O2 bin thnh Tl2O3 :
cng b H2 hoc CO kh thnh kim loi. Tl2O c iu ch bng cch phn hu TlOH 1000C trong iu kin khng c khng kh. TlOH l cht rn mu vng, l mt baz mnh nhng khc vi KOH , NaOH l TlOH d tch H2O khi nung nng. Mc d c yu hn KOH, nhng dung dch ca NOH cng hp th kh CO2 t khng kh. TlOH c th c iu ch bng cch ha tan Tl2O trong nc hoc cho Tl2SO4 tc dng vi mt lng Ba(OH)2 c tnh trc :
Cc mui Tl(I) phn ln u l hp cht ion nh mui ca cc kim loi kim, nhng nhiu mui ni li c tan b hn so vi mui kim loi kim. Mt khc, ging vi mui Ag+, tali florua tan trong nc, cn cc halogenua khc kh tan; ging vi AgCl, tali clorua cng nhy vi nh sng, ha sm di tc dng vi nh sng nhng li khng tan trong amoniac nh AgCl. Tch s tan mt s mui Tl(I) nh sau : Hp cht Tl2CrO4 Tl2S TlI TlBr TlCl Th s tan 9,8.10-13 5.10-21 6,5.10-8 3,9.10-6 1,7.10-4 Hp cht Tl2CO3 TlBrO3 Tl2SO4 Tl2SO3 Tl3PO4 Tch s tan 4.10-3 3,9.10-4 4.10-3 6,3.10-4 6,7.10-8
Khc vi cc hp cht Ga(I) v In(I) l nhng cht kh mnh, cc hp cht Tl(I) c tnh kh yu hn, ch chuyn thnh Tl(lll) khi tc dng vi cht oxi ha mnh; cc hp cht Tl(lll) l cht oxi ha mnh d dng chuyn thnh hp cht Tl(I)).
CHNG 5 CC NGUYN T NHM IVA (GECMANI - THIC - CH) 5.1. Nhn xt chung v cc nguyn t nhm IVA (l) Nhm IVA thuc bng tun hon gm cc nguyn t C (Carboneum), Si (Silicium), Ge (Germanium) , Sn (Stannum), Pb (Plumbum). Cacbon c con ngi bit n t thi xa xa, khng bit tn ngi tm ra cacbon v cng khng bit dng cacbon tinh khit no tm ra trc. Silic l nguyn t quan trng trong th gii v sinh, c Gay Luyxc (J. Gaylussac) v Tna(l. Thenard) tm ra nm 1811; nhng n nm 1825 mi c nh khong vt hc kim ha hc ngi Thy in l Beczeliut (I.Berzelius) tch ra c dng n cht khi nung kali flosilicat vi kali:
Gecmani l nguyn t c ph bin trung bnh nhng thng phn tn trong qung cc nguyn t khc, mi n 1886 mi c nh khoa hc ngi c l Vinkle (K. Winkler) tm ra. Hai nguyn t cn li ca nhm IVA l thic v ch c bit t thi xa xa cng vi nm nguyn t kim loi khc l vng, ng, bc, thy ngn, st. (2) Nguyn t khi, s th t nguyn t v s phn b electron nh sau :
Nguyn t Cacbon Silic Gecmani Thic Ch
K s th t hiu C 6 Si 14 Ge 32 Sn 50 Pb 2
Nguyn t khi 12,01 28,09 72,60 118,70 207,21
Phn b electron 2 2 2 2 2 4 8 8 8 8
Ha tr II II II II II IV IV IV IV IV
4 18 18 18
4 18 4 32 18
(3) Trong nhm IVA, cacbon l phi kim in hnh; silic cng l mt phi kim, nhng mt s tnh cht l hc li chng t l mt nguyn t bn - kim loi; gecmani c tnh cht gn vi silic mc d nhiu tnh cht ha hc chng t l mt kim loi; thic v ch l kim loi , c bit l trng thi ha tr II, c hai nguyn t ny u th hin tnh kim loi.
Cng nh cacbon v silic, gecmani, thic, ch u c lp v ns2np2 vi s electron ha tr bng s obitan ha tr, u to ra hp cht cng ha tr vi s oxi ha -4, +2 v +4. Tuy nhin khi chuyn t Ge n Pb th bn ca bc oxi ha +4 gim xung, cn bn ca bc oxi ha +2 tng ln. iu c gii thch l do khi chuyn t Ge - Pb, s th t nguyn t tng ln, th cc obitan d v f c nh hng n vic hnh thnh lin kt ha hc . Ngi ta cho rng khi chuyn t Ge n Pb, tnh tr ca cc cp electron ns2 tng ln, vai tr tham gia vo s hnh thnh lin kt ca cp electron ns2 gim xung, nn khuynh hng to ra mc oxi ha +4 gim xung v khuynh hng to ra mc oxi ha +2 tng ln. V d:
nh vy :
Bng 27 . Mt s c im ca nguyn t cc nguyn t Ge - Sn - Pb
Nguyn t Electron ha tr Bn kinh nguyn t () Bn kinh ton M2+ () Bn kinh ion M4+ () Bn kinh ion M4- ()
Ge 4s2 4p2 1,39 0,65 0,44 7,88
Sn 5s2 5p2 1,58 1,02 0,67 2,15 7,33
Pb 6s2 6p2 1,74 1,32 0,84 7,41
(4) V cacbon v silic l hai phi kim, nn s c trnh by chi tit trong gio trnh "Cc nguyn t phi kim" do di y ch nu cc c im nguyn t ca Ge - Sn - Pb (bng 27) . B ngoi, gecmani ging vi kim loi, nhng li c cu trc tinh th mng kim cng (hnh 43) vi a = 5,63 , mi nguyn t Ge cch bn nguyn
t gecmani khc trong hnh chp bn mt vi di l
a 4 3
2.43
Cng nh silic, gecmani khng to ra tinh th dng than ch v khng c kh nng to ra lin kt p - p nh cacbon. Thic ( - Sn) cng c cu trc mng kim cng vi 6,46 , di gia hai nguyn t trong hnh t din 2,8 . Khc vi gecmani v thic, ch c cu trc tinh th mng lp phng tm din vi khong cch gia hai nguyn t, cnh ca hnh lp phng a = 4,91 . 5.2. Trng thi thin nhin v thnh phn cc ng v (1) S phn b cc nguyn t Ge, Sn, Pb trong v qu t ng vi thnh phn thch quyn nh sau:
Nguyn t Ge Sn Pb
% tng s nguyn t 2.10-4 10-4 1,6.10-4
% khi lng 7.10-4 4.10-3 1,6.10-3
Khong vt ch yu ca gecmani l qung gecmanit (Cu2S. CuS. Ge2S ) v agiroit ( 4Ag2S.GeS ); hu nh ch gp thic dng caxiterit ( SnO2 ), cn galen (PbS) l qung ch quan trng nht trong cng nghip, ngoi ra cn gp ch trong qung xeruzit (PbCO3). nc ta c m caxiterit Tnh Tc (Cao Bng), Qu Hp (Ngh An), Lm ng. (2) Trong cht sng (ch yu l thc vt) c cha khong 10-4 mg gecmani; 5.10-5mg thic v 5.10-5 mg ch theo khi lng. (3) Trong nc i dng c 6.10-5 mg gecmani; 3.10-3 mg thic v 10-5 mg ch trong 11 nc bin.
(4) Trong cc mu ly c t Mt Trng do cc tu v tr a v Qu t th hm lng cc nguyn t nh sau: Nguyn Ge Sn Pb Hm lng trung bnh( s gam/1g mu ) Apollo - 11 Apollo - 12 Luna - 6 1,25.10-6 0,6.10-6 3.10-6 4.10-6 1,2.10-5 4.10-6
(6) Gecmani c 13 ng v , trong c nm ng v thin nhin l 70Ge (20,55%); 72Ge (27,37%); 73Ge (7,67%); 74Ge (36,74%); 76Ge (7,67%); cn li l ng v phng x, trong ng v 68Ge l ng v phng x bn nht vi chu k bn hy l 250 ngy m. Thic c 20 ng v, trong c 10 ng v thin nhin l 112Sn (0,95%); 114 Sn ( 0,65%); 115Sn ( 0,34%); l16Sn (14,24%); 117Sn (7,57%); 118Sn (24,01%); l19 Sn (8,58%); 120Sn (32,97%); 122Sn (4,71%); 124Sn (5,98%). Trong s cc ng v phng x th ng v 123Sn c chu k bn hy di nht l 136 ngy m. Ch c 18 ng v, c bn ng v thin nhin l 204Pb(l,48%); 206 Pb(23,6%); 207Pb (22,6%); 208Pb (52,3%); ng v phng x bn nht l 202Pb c chu k bn hy l 3. 105 nm. 5.3. iu ch Ge, Sn, Pb (1) Gecmani l nguyn t phn tn, nn trong thc t c xem l sn phm ph ca qu trnh ch ha mt s qung ca mt s kim loi khc, c cha gecmani, vi nguyn tc l chuyn cc qung thnh dng oxit GeO2, sau dng H2 hoc than kh nhit cao :
(2) Trong cng nghip, thic c sn xut bng cch dng than kh qung caxiterit 1300oC :
Trong thc t ngi ta cn thu hi thic t st ty (st trng thic) vi mt lng kh ln, bng cch dng dung dch kim tch thic khi st, sau dng phng php in phn iu ch thic kim loi. (3) T galen (PbS) hoc t xeruzit (PbCO3) chuyn thnh PbO sau ngi ta dng than kh nhit cao:
tinh ch Pb kim loi ngi ta dng phng php in phn dung dch PbSiF6 vi ant bng ch k thut, thu c ch nguyn cht n 99,99% catot. Ngi ta cng in phn Pb(NO3)2 thu c ch tinh khit loi thuc th. 5.4. Tnh cht l hc v ng dng (1) V mt tnh cht l hc th Ge - Sn - Pb l nhng kim loi, tnh kim loi tng dn t Ge n Pb. Bng 28 l mt s hng s l hc quan trng ca gecmani - thic - ch. Bng 28. Mt s hng s l hc quan trng ca gecmani - thic - ch
Tnh cht Khi lng ring (g/cm3) Nhit nng chy ( 0C ) Nhit si ( 0C ) dn in (Hg = 1) cng (kim cng = 10)
Ge 5,4 959 2700 0,001 6
Sns 7,31 232 2360 8,3 1,5
Pb 11,34 327,4 1740 4,6 1,5
nhit thng, gecmani c mu trng bc, cng v rt gin, cn ch th mm. Thic v ch u d dt thnh l mng. iu kin thng thic l kim loi mu trng ( thng gi l thic trng). Thic tn ti ba dng th hnh ph thuc vo nhit v bin i ln nhau:
Thic trng ( - Sn) tn ti nhit khong 13,2 1610C; thic xm( Sn) l dng bn di 13,20C ; nhit < 13,20C mt t, s chuyn ha t 13 Sn sang dng ( - Sn) vi vn tc rt b, tc chuyn ha li tng rt mnh khi h thp nhit v cc i - 330C , v vy vng lnh nhng vt bng thic chng b hng, do qu trnh bin i t thic trng sang thic xm xy ra nhanh nn lm tng th tch ca thic (n 25,6%) v vy thic vn ra
thnh bt mu xm. Chnh v nguyn nhn , thic hn ca nhng bnh ng nhin liu lng b ph hy m mt on thm him Nam Cc b hy sinh vo nm 1912. Khi cho - Sn tip xc vi - Sn bin ha thnh dng bt th s bin i 13 - Sn thnh - Sn li xy ra rt d dng, v vy nhng dng bng thic chng b ph hy khi ln vi bt thic - nn thng c gi l " bnh dch thic ". Ngy nay lm chm qu trnh ngi ta dng dng hp kim . nhit trn 1610C thic thng chuyn sang dng th hnh - Sn. Thic gin, nn thic nung trn 2000C d nghin thnh bt. Trong c ba dng th hnh ca thic th B - Sn c khi lng ring ln nht do cu trc tinh th c kht hn cc dng th hnh cn li . Ch l kim loi c mu xm v c khi lng ring ln nht do c cu trc lp phng. (2) Do s thay i v cu trc ca tinh th dn n s thay i nhiu tnh cht l hc, chng hn Ge v - Sn l cht bn dn; B - Sn v Pb l kim loi dn in. Mt lng ln thic ph ln b mt ca st chng g (st ty) dng trong cng nghip thc phm. L thic mng (giy thic) dng trong my t in . Ch c dng ch to cc bn cquy, v dy cp, u n, ng dn nc v dng ch to thit b bo v khi cc tia phng x . Ch v cc hp cht ca ch u rt c. Mt lng ch khi vo c th s tch ly li, thay th mt phn canxi trong Ca3(PO4)2 ca xng; tc dng c gy ra vnh xm li rng v s ri lon thn kinh. 5.5. Tnh cht ha hc ca Ge, Sn, Pb (1) Cc nguyn t Ge, Sn, Pb hnh thnh hai loi hp cht ng vi hai trng thi ha tr c trng l IV v II . Vi gecmani th hp cht ha tr bn l dng in hnh; vi thic th hai dng hp cht u c khc nhau , nhng iu kin thng th hp cht ha tr bn bn hn so vi cc hp cht ha tr hai, trong khi hp cht ha tr hai li in hnh hn so vi ha tr bn, v vy cc hp cht ha tr hai ca gecmani v ca thic c tnh kh mnh , c bit trong mi trng kim; cn vi ch th hp cht ha tr bn li c tnh oxi ha mnh, nht l trong mi trng axit , cn trong mi trng baz th hu nh khng th hin. Di y l th oxi ha - kh chun ca ba nguyn t trn : Phn ng in cc E0298
Ge4+ + 4e = Ge GeO + 2H+ + 2e = Ge + H2O GeO2 + 4H+ + 4e = Ge + 2 H2O HGeO3- + 2 H2O + 4e = Ge +5OHSn2+ + 2e = Sn Sn4+ + 2e = Sn2+ Sn4+ + 4e = Sn HSnO2 + H2O + 2e = Sn + 3OHPb2+ + 2e = Pb Pb4+ + 2e = Pb Pb4+ + 2e = Pb2+ PbO+ H2O + 2e = Pb + 2OHHPbO2- + H2O + 2e = PbO +3OHPbO2 + H2O + 2e = PbO + 2OHPbO2 + 4H+ + 2e = Pb2+ + 2H2O
+ 0,124 - 0,2 - 0,15 - 1,0 - 0,14 + 0,15 +0,01 - 0,91 - 0,13 + 0,84 +1,8 - 0,58 - 0,54 + 0,28 + 1,46
(2) Gecmani khng phn ng trc tip vi hiro phn t, nhng kh H2 ha tan trong gecmani nng chy to > 10000C ; thic tc dng vi hiro nguyn t khi c mt ca xc tc to ra SnH4 ; cn ch phn ng trc tip vi H2 8000C :
(3) iu kin thng , gecmani v thic khng tc dng vi oxi ca khng kh , cn ch th b oxi ha to ra mng oxit bo v cho kim loi khng b tip tc oxi ha. Khi un nng trong khng kh , gecmani v thic to ra GeO2 V SnO2. Cn ch b oxi ha dn n ht to ra PbO :
Khi nung nng c ba kim loi u c kh nng ha hp trc tip vi lu hunh to ra GeS, SnS, PbS :
Vi selen v telu hi cng c phn ng tng t to ra GeSe, GeTe, SnSe, SnTe, Pbse, PbTe. (4) C ba nguyn -t u tc dng trc tip vi cc halogen; gecmani,
thic to ra MX4, cn ch to ra PbX2 :
vi clo v brom , phn ng c th xy ra vi thic ngay nhit thng , cn vi tt th c th un nng nh. Vi gecmani phn ng xy ra kh hn so vi hai nguyn t cn li. (5) Gecmani v thic khng tc dng vi HO ngay c khi H2o trng thi hi . Do thic bn vi H2O v khng kh, nn c dng ch to st ty ( st trng thic) lm v hp trong cng nghip thc phm. Ch phn ng chm vi H2O khi c mt ca oxi to ra hiroxit : Lng kh CO2 ha tan trong nc cng nh hng mnh n tnh bn ca ch i vi nc. Ngi ta thy rng , vi nng thp, kh CO2 lm cho cc ng dn nc bng ch bn hn do to ra lp PbCO3 thc t khng tan ( tch s tan ca PbCO3 bng 1.10-13 ); nhng khi nng CO2 trong nc ln hn s to ra Pb(HCO3)2 d tan hn gy ra hin tng ng c ch khi ung loi nc c cha nhiu CO2 ? (6) Nhng axit mnh khng c tnh o xi ha ch n mn c thic v ch, cn gecmani c th in cc dng nn khng phn ng:
Thic tan chm trong dung dch HCI long do th tiu chun ca thic gn vi th tiu chun ca hiro; cn ch li to ra lp PbCl2 kh tan nn lm cho ch khng tan thm c na; tuy nhin vi HCI c , thic v ch li d tan hn v to hp cht d tan dng H2[MCl4] V H[MCl3] :
Tng t HCI, axit sunfuric long khng tc dng vi gecmani; vi thic phn ng xy ra kh khn to ra SnSO4: Ch ch tc dng trn b mt vi dung dch H2SO4 C nng thp hn 80% to ra lp mui kh tan, ngi ta li dng tnh cht ny ch to cquy ch . C hai nguyn t u phn ng vi H2SO4 c nng to ra SO2, ring
thic to ra Sn(SO4)2 : cn ch li d tan trong H2SO4 c hn, do to ra hp cht d tan Pb(HSO4)2 khng bo v c ch khi b axit tip tc tc dng :
Trong dung dch HNO3 c, gecmani v thic chuyn thnh axit gecmanic H2GeO3 (GeO2.xH2O) V axit stanic H2SnO3 (SnO2.xH2O) :
cn trong HNO3 long, thic li d tan hn : do dung mi tt nht ca thic l HNO3 long! Ch tc dng vi axit nc bt k nng no cng to ra Pb(NO3)2. Tuy nhin Pb(NO3)2 li kh tan trong HNO3 bc nn bo v cho kim loi khi b axit tc dng. Mt khc , Pb(NO3)2 li d tan trong nc nn ch d tan trong HNO3 long : Ch cng tan c trong axit axetic v mt s axit hu c khc khi c mt ca oxi : (7) Gecmani hu nh khng tc dng vi dung dch kim, nhng li d tan trong dung dch kim c khi c mt ca H2O2 : Thic v ch tan c trong dung dch kim c nng to ra stanit , plombit v H2 :
n gin hn c th vit dng Na2sno2 V K2pbo2' 5.6. Hirua ca gecmani , thic v ch Tng t cacbon v silic , cc nguyn t gecmani , thic v ch to ra cc hp cht hirua, ng vi bc oxi ha + 4 ch yu l cc hp cht MH4 c cu trc khng gian dng hnh bn mt, ng vi trng thi lai ha sp3 ca nguyn t trung tm M ( Ge, S, Ph. Hin nay ngi ta bit gecmani to ra mt dy hirua ng vi cng
thc GenH2n + 2 t GeH4 n Ge9H20 ; hai hirua ca thic l SnH4 v Sn2H6 v mt hirua ca ch l PbH4- a Do khuynh hng gim bn ca trng thi lai ha sp3 t Ge n Pb nn bn nhit ca cc hp cht gim nhanh chng t GeH4 n PbH4, v d GeH4 b phn hy 280-C , cn SnH4 150-C :
Cc hp cht GeH4, SnH4 v PbH4 u l cht kh , khng mu, d b chy to ra oxit v H2O : Di y l nhit nng chy v nhit si ca mt s cht : GeH4 Tnc (0C) Ts (0C) -165 -90 Ge2H6 -109 29 Ge3H8 -106 110 SnH4 -150 -52
Gecman (GeH4 ) v stanan (SnH4 ) u b H2O hoc dung dch axit , dung dch baz phn hy : Cc hp cht trn u c th c iu ch bng cch cho hp kim ca cc nguyn t trn vi Mg tc dng vi dung dch axit long hoc vi NH4Cl trong amoniac lng:
5.7. Oxitgecmani, thic , ch Cc nguyn t gecmani, thic , ch u to ra hai oxit chnh l MO v MO2. (1) GeO l cht rn mu en , c iu ch bng cch nung nng Ge vi GeO2 8000C: GeO hu nh khng tan trong nc, nhng tan c trong axit v trong kim mnh:
(2) SnO l cht rn c mu en hoc mu lc hay tm tu theo phng php iu ch. Khi nung nng chy mt hn hp gm SnCl2.2H2O v Na2CO3.10H2O :
sau khi ngui ra vi nc ho tan NaCl , cht rn thu c l SnO c mu en. SnO cng c iu ch bng cch un nng dung dch gm SnCl2 vi NaOH hoc vi dung dch NH3 trong iu kin khng c khng kh. Ban u to ra kt ta Sn(OH)2. Sau Cho thm SnCl2 to ra oxiclorua SnOHCl l cht d b phn hy:
axit HCI to thnh li phn ng vi Sn(OH)2 cho li SnOHCI. Sn phm SnO thu c theo phng php ny c mu lc hoc tm. SnO cn c iu ch bng cch nung mui oxalat Sn(II) trong iu kin khng c khng kh :
Tinh th SnO c cu trc lp phc tp , trong cng mt lp mi nguyn t Sn lin kt vi bn nguyn t oxi to ra nhm SnO hnh chp t gic ( hnh 44) , nhng chp ni vi nhau qua nguyn t oxi. SnO nng chy 10480C v si 17000C. Khi nung trong khng kh d dng chuyn thnh SnO) :
Nung trong khong 400 - l0400c b phn hy dn theo s :

Khi nung nng d dng b H2, C, CO kh n kim loi :
Hu nh khng tan trong nc, tan trong axit to ra mui Sn(II) v trong dung dch kim to ra stanit:
Trong dung dch kim c d phn ng tip tc to ra Sn v stanat:
(3) PbO c hai dng th hnh l - PbO mu v dng - PbO mu vng. Tinh th PbO c cu to lp phc tp , tng t cu to tinh th SnO ( hnh 44). Ch(II) oxit c iu ch bng cch nung cc hp cht hiroxit, cacbonat, nitrat:
Trong cng nghip ngi ta iu ch bng cch nung nng mnh hp kim Pb - Ao (phng php Cupen ) , ch trong hp kim chuyn thnh PbO mu . Ngi ta cng iu ch PbO bng cch nung ch(II) oxalat 300oC :
PbO l cht rn Tnc = 8800C v Ts = 14700C ; dng tinh th mu vng gi l maxicot; dng tinh th mu gi l litac Khi un nng "maxicot" trong khng kh n 400oC chuyn thnh Pb3o4 mu , v sau nung n 4700C chuyn thnh "litac":
Khi un nng "litac" trong lung kh H2, CO hoc hn hp vi cacbon,

PbO b kh thnh Pb:
PbO tan rt t trong nc, tan trong dung dch KOH , NaOH nng to ra plombit; tan trong HNO3 long to ra mui Pb(II); tan trong HCI to ra PbCl2 : PbO c dng lm nguyn liu trong cc nh my sn xut cquy ch ; trong cc nh my sn xut dng c quang hc, ch to thu tinh... (4) GeO2 - gecmani ioxit c iu ch bng cch nung nng mnh Ge hoc GeS trong lung kh O2 hoc bng cch cho Ge tc dng vi HNO3 c :
GeO2 l cht rn mu trng, Tnc = 11150C v Ts = 12000C. Ging vi SiO2, GeO2 rt bn i vi nhit v d chuyn sang trng thi thy tinh, nn GeO2 c tm quan trng ln trong cng nghip thy tinh quang hc, v khi thay th mt phn SiO2 s to ra mt loi thy tinh c kh nng khc x nh sng rt mnh. GeO2 t tan trong nc , c tnh lng tnh, nhng tnh axit ln hn tnh baz nn tan trong dung dch kim d hn trong dung dch axit. Khi tan trong kim , to ra hp cht dng hiroxi : cn khi phn ng vi kim nng chy to ra K2GeO3. GeO2 c th d dng b kh bi C, Co, H2, Mg, Al n kim loi .
(5) SnO2 c iu ch trong cng nghip bng cch nung chy thic trong lung kh O2 hoc khng kh:
c dng tinh khit ngi ta cho Sn tc dng vi HNO3 c nng , sn phm thu c dng hirat ha :
sau nung thu c SnO2:
Ngi ta cng iu ch bng cch cho SnCl4 tc dng vi NaOH, sau tc dng vi HCI to ra kt ta axit a - stanic , lm kh ri nung thu c SnO2 Ngoi cc phng php trn , SnO2 cng c iu ch bng cch nung Sn(OH)2 trong khng kh 800 - 9000C :
SnO2 l cht rn mu trng, nng chy 19000C . Khng tan trong nc. C tnh lng tnh, ch tan trong axit H2SO4 c nng; vi dung dch kim nng to ra dng hiroxi: cn khi nung vi kim rn to ra K2SnO3 :
SnO2 cng d dng b kh bi C, Co, H2, Ai thnh kim loi :
SnO2 c dng trong cng nghip gm ch to cc th men cng nh lm thy tinh m. (6) PbO2 khng iu ch c bng phng php trc tip t Pb v oxi m phi bng phng php gin tip. PbO2 c kt ta khi un si dung dch Pb(CH3COO)2 vi clorua vi trong mi trng kim: hoc dng hipoclorit oxi ha PbO: hoc cho kh clo tc dng vi Pb(CH3COO)2 trong mi trng kim : L cht rn mu nu thm, khi un nng PbO2 mt gn oxi bin thnh cc oxit c bc oxi ha thp hn:
v sn phm cui cng l to ra litac . Trong khi tnh o xi ha ca GeO2 v SnO2 l khng c trng th PbO2 li l cht oxi ha mnh. PbO2 oxi ha axit HCI c to ra kh clo: PbO2 v HNO3 c s oxi ha mui Mn(II) thnh axit pemanganic Oxi ha SO2 hoc S trong khng kh to ra PbSO4 :
Khi un nng vi H2SO4 c nng gii phng O2 : Mt khc , khi un nng vi kim mnh to ra plombat tng t stanat:
(7) Pb3O4 ( hoc 2PbO.PbO2) thng gi l minium l cht bt mu , c xem l mui Pb(II) ca axit orthoplombic (H2PbO4 ), tc l Pb(II) orthoplombat (Pb2PbO4 ) trong ch c s oxi ha l +2 v +4. Bn cnh hp cht trn cn c Pb2O3 mu da cam c xem l mui Pb(II) ca axit metaplombic (PbPbO3) Trong tinh th minium c mch gm nhng bt din PbO6 , cc bt din ny ni vi nhau bi hai nguyn t oxi v cc mch lin kt vi nhau qua nguyn t Pb(II) (hnh 45).
Minium c iu ch bng nung PbCO3 hoc PbO trong lung khng kh khong 4000C :
Khi minium tc dng vi H2SO4 long hoc HNO3 long to ra mui Pb(II) v PbO) :
nhng v Pb(OH)4 khng tn ti chuyn ha thnh PbO2:
cc phn ng chng t Pb3O4 l mui Pb(II) ca axit orthoplombic. Minium t tan trong nc. B phn hy khi nung khong 500oC to ra " litac ":
Khi tc dng vi H2SO4 c nng gii phng O2 : Pb3O4 l cht oxi ha mnh, oxi ha HCI to ra Cl2: Trong mi trng axit, oxi ha Fe(II) thnh mui Fe(iil); oxi ha H2O2 to ra O2: v c th b kh n kim loi khi nung vi cacbon hoc nung trong lung kh CO hay H2:
Pb3O4 c dng ch yu trong sn xut thy tinh, men s, v trong cng nghip ch to sn 5.8. Hiroxit gecmani, thic, ch (l) Cc hiroxit dng M(OH)2 ( M l Ge, Sn, Pb) c iu ch bng cch cho mui M2+ ca cc kim loi trn tc dng vi dung dch kim :
Hiroxit gecmani, thic, ch l nhng cht kt ta dng keo, kh tan trong nc. Ge(OH)2 Mu Tch s tan da cam Sn(OH)2 trng 6,3.10-27 Pb(OH)2 trng 1,1.10-20
Khi un nng, b phn hy thnh oxit Mo. Chng hn , vi Pb(OH)2 nung 1000C cha b phn hy, n 1300C bt u mt H2O V n 1450C mt H2O hon ton: u c tnh lng tnh, tnh baz tng dn t Ge(OH)2 trn Pb(OH)2. Hng s in ly baz ca Pb(OH)2 c gi tr K1 = 9,6. 10-4 v K2 = 3. 10-8 250C; cn hng s in ly axit K = 2,1. 10-16 ( 250C) , iu cng cho thy tnh baz ln hn tnh axit. Khi tan trong axit to ra mui ca M2+ :
Khi tan trong kim to ra gecmanit , stanit, plombit: u dng phc hiroxi K2[M(OH)4]. Cc hp cht ny u b thy phn mnh, nn ch bn trong dung dch kim d. Tuy nhin, nu dung dch c nng kim khng ln, trong dung dch dn dn xy ra phn ng phn hy , chng hn: do dung dch stanit lu ngy s c mu en. Khi d nhiu kim phn ng phn hy li xy ra theo phng trnh: do c nhng ht Sn rt nh xut hin trong qu trnh nn dung dch cng tr nn en. Vi dung dch gecmanit cng c phn ng tng t. Cc gecmanit , stanit, cng nh cc mui ca Ge(II) v Sn(II) u l cht kh mnh, cn cc hp cht ca Pb(II) khng th hin tnh kh. Chng hn, stanit c th kh c mt s mui thnh kim loi t do:
(2) Hiroxit ca Ge(IV) , Sn(IV) , Pb(IV) dng M(OH)4 thc t l dng hirat MO2.xH2O ( hoc nMO2.yH2O ) C thnh phn thay i, u l nhng cht kt ta keo , khng tan trong nc: GeO2.xH2O Mu Tch s tan trng 1.10-57 SnO2.xH2O trng 1.10-57 PbO2.xH2O nu 3.10-66
L nhng cht c tnh lng tnh, cc hiroxit ny tan trong kim d hn trong axit. Dng axit ng vi cc kt ta l axit gecmanic, axit stanic, axit plombic v mui tng ng l gecmanat, stanat v plombat. Thic to ra hai dng l axit - stanic v axit 13 - stanic . Khi cho SnCl4 tc dng vi kim to ra stanat, sau axit ha dung dch to ra kt ta axit a stanic:
Axit -stanic c iu ch bng cch cho Sn tc dng vi HNO3 c:
S thay i v thnh phn v cu trc ca axit stanic dn n s thay i v hot tnh ha hc. Chng hn axit - stanic d tan trong kim v c trong axit, cn axit - stanic ch phn ng vi kim khi nung nng chy. Khi cho dng tc dng vi HCI to ra SnCl4 cn ang hu nh khng thay i. Vi kim c hay long, dng d tan to ra stanat, cn dng th ngay c kim c cng khng tan. Ngi ta bit c cc mui gecmanat, stanat v plombat, chng hn metagecmanat ca kim loi kim M2GeO3 ( M l kim loi kim); mui orthogecmanat Mg2GeO4, orthostanat Ba2SnO4 ; Orthoplombat Ca2PbO4 ... Cc stanat v plombat ca kim loi kim kt tinh dng trihirat nh K2SnO3.3H2O, Na2SnO3.3H2O. Thc t nhng loi mui thng dng phc cht c cha cc ion [Sn(OH)6]2- , [Pb(OH)6]2-; khi un nng mt dn H2O chuyn thnh dng n gin , v d Na2[Pb(OH)6] 1100C mt H2O chuyn thnh Na2PbO3 v sau li d dng ha hp vi H2O chuyn ngc li thnh Na2[Pb(OH)6] :
5.9. Halogenua gecmani , thic, ch Cc nguyn t Ge, Sn, Pb u to ra cc hp cht halogenua vi tt c cc halogen. (1) GeX2 c iu ch cho hi GeX4 tc dng vi Ge khi un nng : hoc cho HX tc dng vi Ge(OH)2: Cc ihalogenua ca gecmani u l cht rn , GeF2 khng mu; GeCl2 nhit thng khng mu nhng khi un nng c mu da cam; GeBr2 hnh kim mu vng; GeI2 mu da cam. Cc hp cht trn u km bn v u c tnh kh mnh. Gecl2 d b oxi oxi ha v nhanh chng b clo chuyn thnh GeCl4:
Cc ihalogenua ca gecmam u tan trong nc v b thy phn mnh, b H2Ophn hy to ra GeO dng hirat ha ; khi un nng b phn hy :
(2) SnX2 c th c iu ch bng cch cho Sn tc dng vi axit halogenhiric : Cc hp cht thic (II) halogenua u l cht rn, c mu sc khc nhau v u d tan trong nc SnF2 Mu sc Tnc ( 0C ) Ts ( 0C ) khng mu 210 SnCl2 khng mu 247 650 SnBr2 vng 216 637 SnI2 320 714
(3) Trong s cc halogenua ca Sn(II) th SnCl2 c nhiu ng dng hn c. SnCl2 khan c iu ch bng cch un nng thic ht trong lung kh hiro clorua kh:
hoc un nng dng hirat SnCl2.2H2O 130 - 1450C thu c SnCl2 khan. Ngi ta cng iu ch bng cch gi SnCl2.2H2O trn H2SO4 c trong chn khng nhit phng trong khong 10 ngy. Thic (II) clorua ihirat SnCl2.2H2O c iu ch bng cch cho thic ht tan trong dung dch HCI c ( D = 1 , 14g/cm3 ) nng. Thic tan chm trong HCI nhng nu trong dng c platin th thic s ha tan nhanh hn ( do to ra cp ganvanic Sn - Pt). SnCl2 khan l cht rn tinh th trong sut , khng mu d tan trong nc , trong ru v trong e. Kt tinh t dung dch nc dng ihirat SnCl2.2H2O. Tinh th ihirat kt tinh dng hnh kim khng mu, nng chy trong nc kt tinh 400C; khi un nng nc kt tinh b mt dn. Sn(Il) clorua khan hoc hirat u b thy phn mnh to ra mui baz t tan. ngay c khi un nng dng ihirat cng to ra dng mui baz trn : v vy mun pha ch dung dch SnCl2 ngi ta khng ha tan vi nc m ha tan SnCl2.2H2O Vi trung dch HCI c! (4) Sn(II) clorua l cht kh mnh nhng km GeCl2. Khi trong khng kh , n b oxi ha chm bin thnh oxiclorua mu vng, b o oxi ha thnh SnCl4 :
Khi un nng SnCl2 bin thnh SnO2 :
Trong dung dch nc SnCl2 b oxi ha chm bi oxi ca khng kh theo phn ng : Vy ngi ta phi thm Sn ht vo dung dch SnCl2 trnh qu trnh oxi ha . L cht kh mnh nn c th kt ta c Au, Ag, Hg t dung dch mui ca chng:
SnCl2 c th chuyn dung dch mu vng nu ca mui Fe(ili) thnh xanh nht ca mui Fe(II) : kh c mui icromat mu da cam thnh mui Cr(III) mu xanh:
Ngoi ra, khi ha tan trong HCI c hoc trong dung dch c mui clorua kim loi kim, SnCl2 c kh nng to ra cc con phc [SnCl3]- v [SnCl4]2- . SnCl2 c nhiu ng dng quan trng, dng lm cht cn mu trong cng nghip in hoa trn vi, lm cht kh trong ha hc hu c (5) PbX u l cc halogenua kh tan nn thng c iu ch bng phn ng trao i. PbF2 c iu ch dng cht bt mu trng khi cho mui cacbonat hoc hirxit ch(II) tc dng vi dung dch axit flohiric : PbCl2 c iu ch bng cch cho dung dch long ca mui ch (II) tc dng vi dung dch c cha ton Cr : Cng c iu ch bng cch cho PbO hoc mui cacbonat baz chm) tc dng vi axit HCI:
Ngoi ra, PbCl2 cng c iu ch bng cch ha tan thic ht trong dung dch axit HNO3 long ri sau kt ta bng axit HCI:
PbBr2 cng iu ch vi cc phng php tng t phng php iu ch PbO2 ; PbI2 c iu ch bng cch cho mui Pb(II) axetat tc dng vi Ki : Cc halogenua ca chu) u l cht rn c mu khc nhau, t tan trong nc: PbF2 PbCl2 PbBr2 PbI2
Mu sc Tnc 0C ) Ts 0C ) Tch S tan
khng mu 855 1290 2,7.10-8
khng mu 500 954 1,6 .10-5
khng mu 373 916 9,1.10-6
vng 412 950 1,1.10-9
Hi ca cc halogenua trn u dng n phn t v u c cu trc tam gic; trong dung dch long , tt c chng u phn ly hu nh hon ton. Trong dung dch HCI khong 10% , tan ca PbCl2 gim , nhng nng HCI cao hn 10% th ha tan tng; iu c gii thch l do to ra cc con phc [PbCl3]2- v [PbCl4]2- . Cc ion phc trn u t bn, nn khi pha long dung dch PbCl2 bo ha trong HCI c th mt phn PbCl2 thot ra dng rn. PbBr2 kt tinh trong nc nng dng tinh th hnh kim, khi nng chy to ra cht lng mu , sau khi ngui , ng cng li to thnh khi trng ging nh sng. PbBr2 cng c kh nng to ra cc con phc [PbBr3]2- V [PbBr4]2tng t nh PbCl2 PbI2 dng tinh th l nhng l vng nh. Khi un nng , ban u bin thnh mu vng sau chuyn sang mu gch v cui cng bin thnh mu nu en, ngui li bin thnh mu vng ban u. Tan t trong nc, phn tan to ra dung dch c mu vng l mu ca phn t khng phn ly. Tan nhiu trong dung dch KI hoc NaI hoc HI hn l trong nc nguyn cht do to ra ion phc [PbI4]2- : Cng tng t cc con phc [PbPCl4] v [PbBr4]2- , ion [PbI4]2- t bn (K= 6.10-7) nn khi pha long cc dung dch c cha ion phc trn vi nc, PbI li kt ta xung. (6) Quan trng nht trong cc mui ng vi bc oxi ha +4 ca Ge, Sn, Pb l cc hp cht halogenua. Ngi ta bit c tt c cc halogenua ca cc nguyn t trn tr hai hp cht PbBr4 v PbI4 v u l hp cht cng ha tr. ' Cc halogenua MX4 trn c iu ch bng phn ng trao i hoc bng phng php oxi ha M hoc MX2 Vi GeX4 iu ch bng cch cho GeO2 tc dng vi HX hoc oxi ha Ge bng halogen :
Vi SnX4 c iu ch bng phn ng trao i :
hoc dng halogen oxi ha Sn hoc SnCl2:
PbF4 c iu ch bng cch cho PbF2 tc dng vi F2 2500C, cn PbCl4 th iu ch bng phn ng trao i gia PbO2 vi HCI c ngui:
V mt tnh cht l hc cc hp cht trn ( tr SnF4 v PbF4 ) u khng c xem l nhng mui in hnh m l nhng hp cht tng t hp cht ca C v Si. Trng thi, nhit nng chy v nhit si cc hp cht trn nh sau: GeCl4 kh. thng hoa 36.60C -150C -370C SnF4 tinh th >2000C thng hoa 7050C PbF4 tinh th 6000C GeCl4 lng -500C 830C SnCl4 lng -330C 1130C PbCl4 lng -150C GeBr4 lng 260C 1860C SnBr4 tinh th 300C 2030C GeI4 tinh th da cam 1440C 3770C SnI4 tinh th vng nu 1450C 3440C
Trng thi Tnc (0C ) Ts ( 0C ) Trng thi Tnc (0C ) Ts ( 0C ) Trng thi Tnc (0C )
T cc d kin trn, chng ta thy cc halogenua trn u c mng li phn t nn u d nng chy v u d bay hi. Khi chuyn t GeF4 n SnF4 v PbF4 nhit nng chy v nhit si tng, do tinh th chuyn t mng li phn t sang mng polime. Tinh th SnF4 v PbF4 c mng lp gm nhng nhm bt din SnF6 v PbF6 lin kt vi nhau qua nhng nguyn t F chung ( hnh 46).
Nh vy trong tinh th PbF4 nguyn t Pb trng thi lai ha sp3d2 , do PbF4 bn vng hn nhiu so vi cc halogenua cn li ca Pb(IV).
Tnh cht ha hc c trng nht ca cc tetrahalogenua l kh nng kt hp vi mt s cht v c hoc hu c to ra hp cht phc, chng hn to ra axit hexaflorogecmanic H2GeO6 :
vi ch cng c nhng hp cht tng t: Trong dung dch nc cc tetrahalogenua u b thy phn mnh. (7) Trong tt c cc tetrahalogenua MX4 th quan trng nht l SnCl4, c nhiu ng dng trong thc t nh dng lm cht cm mu trong cng nghip nhum vi, lm cht xc tc trong nhiu phn ng ha hu c... SnCl4 c iu Ch bng cch cho Sn nng chy trong lung kh clo kh; trong cng nghip cn c iu ch bng cch thu hi thic t v hp ; khi ch ha v hp ( st trng thic) 5500C kh clo kh khng phn ng vi st, nhng lp thic mng phn ng vi ch to ra Sna4. SnCl4 khan l cht lng khng mu, bc khi mnh trong khng kh m do b thy phn bi hi m trong khng kh . Trong dung dch nc b thy phn mnh to thnh axit : SnCl4 tan trong mt s dung mi khng cc nh CS2 v ng thi SnCl4 li l dung mi tt ha tan mt s cht khng in ly nh I2, P, S ... Khi un nng, SnCl4 b H2 kh n Sn kim loi:
C kh nng kt hp vi nhiu cht nh HCI: H2[SnO6] l mt axit mnh, kt tinh dng hexahirat H2[SnCl6].6H2O khng mu, nng chy 19,20C. Cng kt hp vi nhiu cht c cp electron " cho" nh NH3, PCl5 , PH3, POCl3... 5.10. Sunfua ca gecmani , thic , ch (l) cc monosunfua ( MS ) v isunfua ( MS2 ) ca cc nguyn t gecmani , thic , ch c th c iu ch trc tip t cc nguyn t ( tr PbS) ) hoc bng cch cho H2S tc dng vi dung dch mui tng ng; chng hn :
PbS cng c th iu ch bng cch nung n 3000C mt hn hp gm PbCO3 v S bt : (2) Cc sunfua trn u l cht rn c mu khc nhau : GeS nu Mu sc 0 Tch s tan (25 C) 3.10-35 SnS nu 1.10-25 PbS GeS2 SnS2 vng PbS2 hung -
en trng -27 2.5.10 -
Khng tan trong nc v trong dung dch axit long tr GeS, c tan mt t v b thy phn: cn PbS2 t phn hy ngay c nhit thng, di tc dng ca HCI c gii phng ra H2S2 nn PbS2 c xem nh l dn xut ca H2S2 vi ch ha tr II. Tan trong HNO3 v trong HCI m c :
PbS b H2O2 oxi ha to thnh PbSO4 mu trng.
phn ng dng phc hi li cc bc tranh c v bng bt trng ch [2PbCO3.Pb(OH)2 ] lu ngy ng mu en v mui ch b H2S trong kh quyn phn ng to ra PbS. SnS2 tan trong dung dch kim to ra thiostanat v stanat [Sn(OH)6] 2- : Mt tnh cht quan trng ca sunfua v isunfua ca cc nguyn t trn l s khc nhau v kh nng phn ng vi (NH4)2S. cc monosunfua khng tc dng vi (NH4)2S , Cn cc isunfua MS2 li d tan trong dung dch (NH4)2S to thnh mui thio ca axit thiostanic H2SnO3 V axit thiogecmanic H2GeO3 : V cc axit theo nu trn u khng bn nn khi cho cc mui thio tc dng vi axit s to ra cc isunfua v H2S : Mt khc, SnS v GeS b amoni polisunfua oxi ha thnh SnS, v GeS2 (v c d S) ri sau SnS2 v GeS2 tan trong amoni sunfua, cho nn SnS v GeS tan c trong amoni polisunfua. Tri vi SnS v GeS, PbS khng tan trong (NH4)2S2 :
da vo tnh cht ngi ta tch GeS v SnS ra khi PbS. Trong s cc sunfua trn th SnS) c cng dng thc t. Bt SnS2 c gi l " vng gi " c dng pha vo sn m vng. "Vng gi " l nhng vy vng trong sut , lp lnh mu v mm nh than ch. Khi un nng bin thnh mu thm , khi lm lnh tr li mu vng ban u, khi un nng rt mnh b phn hu thnh SnS v S :
"Vng gi " c iu ch bng cch un nng dn n khong 3000C mt hn hp gm hn hng Sn - Hg vi lu hunh hoa v NH4Cl . 5.11. Mt s mui khc ca thic v ch Ngi ta iu ch c nhiu mui cha oxi ca gecmani, thic , ch , trong c thiu ng dng quan trng l mui Pb(II). (1) Sn(NO3)2 c iu Ch bng cch cho Sn ht tan trong dung dch HNO3 rt long khng c kh thot ra), sn phm thu c cn c c Sn(IV) nitrat:
Dng tinh khit c iu ch bng cch cho SnO tan trong dung dch HNO3 30% lm lnh nhit thp - 200C, tinh th thu c c thnh phn Sn(NO3)2.2H2O. D b phn hy, dng mui baz Sn2O(NO3)2 bn hn so vi dng khan, un nng n 1000C mi b phn hy. (2) Sn(NO3)4 c iu ch bng cch cho dng hirat SnO2 tan trong dung dch HNO3 c : (3) SnSO4 c iu ch bng cch cho Sn ht hoc SnO tan trong H2SO4 long: SnSO4 l nhng tinh th hnh kim khng mu, tan trong nc, bn hn so vi thic(II) nitrat. Dung dch thic(II) sunfat d tch ra kt ta dng mui baz (SnOH)2SO4 SnSO4 c dng trong m in ( ph thic ln kim loi khc). (4) Sn(SO4)2 c iu ch bng cch cho dng hirat SnO2 tan trong dung dch axit sunfuric : hoc cho tng lng nh dung dch H2SO4 50% Vo thic(IV) clorua, sau lm bay hi hn hp . Thic (IV) sunfat kt tinh dng Sn(SO4)2.2H2O l nhng tinh th nh , tan trong nc axit ha, c tc dng ht m. (5) Cc mui tan ca chm) nh nitrat hoc axetat c iu ch bng cch cho "litac", hiroxit hoc mui cacbonat ca ch (II) tc dng vi axit long tng ng; cn cc mui khng tan ca ch (II) c iu ch bng phng php trao i ion trong dung dch. (6) Pb(NO3)2 dng tinh khit c th c iu ch bng cch cho ch ht tan trong dung dch axit nc 65% : Pb(NO3)2 l nhng tinh th trng hoc khng mu , d tan trong nc, trong nc nng tan nhiu hn, khng tan trong ru; khi nung nng b phn hy to ra PbO :
Ch(II) nitrat c dng ch yu lm nguyn liu iu ch cc hp cht khc ca ch(II).

(7) Pb(CH3COO)2 ( tc ng ch ) c iu ch bng cch ha tan ch(II) oxit trong axit axetic 50% : Kt tinh dng ihirat Pb(CH3COO)2.2H2O , l nhng tinh th khng mu trong sut, nhanh chng ln hoa khi ngoi khng kh. Trong chn khng mt nc kt tinh 400C. Nng chy trong nc kt tinh 750C , nu tip tc un nng s chuyn thnh cht bt mu trng, nng chy 2800C. Pb(CH3COO)2 l Cht d tan trong nc v rt c ! Ch(II) axetat c dng trong ngnh nhum v trong y hc. (8) PbSO4 c iu ch bng cch cho ch(II) nitrat tc dng vi axit sunfuric 15% : PbSO4 l cht rn mu trng, nng chy 11000C, kh tan trong nc (tch s tan Tt = 1,6.10-8 ). Tan trong dung dch kim to ra plombit, v trong dung dch amoniac ca amoni axetat. Trng ha phn tch ngi ta da vo tan b ca PbSO4 tm ra ch v nh phn ch. (9) PbCrO4 c iu ch bng cch cho ch(II) axetat tc dng vi dung dch natri icromat : Khi va mi kt ta l cht bt mu vng chanh, cn trng thi tinh th c mu hoc nu thm, nng chy 8400C chuyn thnh cht lng mu nu thm. PbCrO4 rt kh tan trong nc ( tch s tan Tt : 1,8.10-14 ) nhng li d tan hn trong dung dch HNO3 v c trong dung dch kim. Do kh nng ha tan b nn c dng nh phn ch. Ch (II) cromat c dng lm sn v c mu vng ( vng cromat). (10) PbCO3 c iu ch bng cch cho mui ch trung tnh nh Pb(NO3)2 hay Pb(CH3COO)2 tc dng vi dung dch natri cacbonat ngui v d: hoc cho Pb(NO3)2 tc dng vi dung dch natri hirocacbonat: Ch(II) cacbonat l cht bt mu trng , khi un si vi nc mt dn CO2 chuyn thnh mui baz. Rt t tan trong nc( tch s tan Tt = 1.10-13 ), tan trong dung dch HNO3,
trong dung dch axit CH3COOH v c trong dung dch kim. 300oC phn hy thnh PbO v CO2 : Khi cho dung dch mui ch (II) tc dng vi Na2CO3 trong kim d to ra cacbonat baz: Ch(II) cacbonat baz l cht bt mu trng , khng tan trong nc v trong ln , tan trong dung dch axit nc, axit axetic long v trong cc dung dch NaOH , KOH. Khi un nng n nhit cao hn 1800C th b phn hy thnh PbO:
Ch(II) cacbonat baz c dng lm sn du mu trng nn c gi l " trng ch ".
CHNG 6 I CNG V NGUYN T CHUYN TIP 6.1. V tr cc kim toi chuyn tip trong bng tun hon Trong bng tun hon mi chu k u c bt u t vic in electron vo obitan ns ( n l s th t chu k) v sau cc electron k tip s in vo cc obitan tip theo. (l) chu k th t, sau hai nguyn t kim (4s1) v canxi (4s2 ), cc electron bt u c xp vo cc obitan 3d. V nm obitan 3d c ti a l 10 electron nn c 10 nguyn t h d xut hin trong chu k th t, l cc nguyn t : Nhng nguyn t ny c gi l cc nguyn t (hay kim loi) chuyn tip dy th nht. (2) Cng tng t vy, trong chu k th nm, sau hai nguyn t rubii (5s ) v stronti (5s2), cc electron tip tc xp vo cc obitan 4d, hnh thnh 10 nguyn t h d l cc nguyn t :
1
Nhng nguyn t ny c gi l cc llgllyll khuy kim loi) chuyn tip dy th hai. (3) Trong chu k th su, sau khi electron xp vo obitan 6s xezi (6s1) v bari (6s2 ) v mt electron xp vo obitan 5d lantan , th cc electron ln lt xp vo 7 obitan 4f nn xut hin 14 nguyn t t 58 (Ce) n 71 ( Lu). V khng ng vi nguyn t no trong cc chu k trn, nn 14 nguyn t ny c xp chung cng mt vi nguyn t lantan, nn gi l cc nguyn t h lantan hay lantanoit ( thng gi l nguyn t t him). l cc nguyn t : Sau 14 nguyn t h lantanoit, cc electron li tip tc xp vo cc obitan 5d hnh thnh 10 nguyn t h d l cc nguyn t : c gi l cc nguyn t( kim loi ) chuyn tip dy th ba. (4) chu k th by, bt u hai nguyn t franxi v mi c cu hnh 7sl v 7s2, sau l nguyn t actini vi cu hnh 7s26dl , cc electron tip theo xp vo cc obitan 5f ( hoc 6d) hnh thnh 14 nguyn t xp vo cng mt vi actini nn c gi l cc nguyn t h actilloit, l cc nguyn t:
Sau cc actinoit , ngi ta ch mi bit c hai nguyn t h d chu k th by l nguyn t c s th t 104 l rzefoi Rf ( cn c tn l kursatovi Ku) v nguyn t c s th t 105 l hani Ha (cn c tn l ninxbori Ns). Nh vy cc nguyn t chuyn tip cc chu k di v c chia thnh ba nhm ln : a) Nhm nguyn t chuyn tip chnh ( h d ) b) Nhm lantanoit ( h f) c) Nhm actinoit ( h f). Cc nguyn t chuyn tip ( h d) c nu tm tt bng 29. Bng 29. Cc nguyn t chuyn tip h d trong bng tun hon 3B 21 Sc 39 Y 57 La 89 Ac 4B 22 Ti 40 Zr 72 Hf 104 Rf 5B 23 V 41 Nb 73 Ta 105 Ha 6B 24 25 Cr Mn 42 43 Mo Tc 74 75 W Re [106] [107] 7B 26 Fe 44 Ru 76 Os [108] 8B 27 CO 45 Rh 77 Li [109] 1B 28 29 Ni Cu 46 47 Ag Pd 78 79 Pt Au 2B 30 Zn 48 Cd 80 Hg
(5) Cng cn phi ni thm rng, nu xut pht t nh ngha "nguyn t chuyn tit l nhng nguyn t c ln V d (hocf) c in mt phn trng thi c bn l c nhng nguyn kh lp v d hoc f c in mt phim trong cc hp cht th iu c ngha l cc kim loi Cu, Ag, Au vn l cc kim loi chuyn tip, mc d c lp v (n 1)d hon chnh vi 10 electron, nhng, ion Cu(II) c cu hnh 3d9 , ion Ag(II) c cu hnh 4d9 v con Au(III) c cu hnh 5d8 ; cn cc kim loi Zn, Cd, Hg khng phi l cc kim loi chuyn tip, v cc nguyn t ny u c cu hnh (n- l)d10 ns2 ging nh cc nguyn t tip theo, hn na chng li khng to nn nhng hp cht c lp v ( n - 1 )d b ion ha, v d, trng thi c bn km c cu hnh 3d104s2 v con Zn2+ duy nht c cu hnh 3d10 ging nh con Ga3+ ng sau km. nh vy, c tt c 57 nguyn t chuyn tip ( k c nguyn t 104 v l05).
6.2. c im cu to nguyn t cc kim loi chuyn tip dy th nht (1) Nh trn nu cc kim loi chuyn tip dy th nht gm cc nguyn t t 21 (Sc) n 30 ( Zn) , nguyn t ca cc nguyn t ny c mt s c im nh nu bng 30. V cu hnh electron, tr mt vi ngoi l, cc nguyn t cn li u c cu hnh electron ngoi cng ca nguyn t u l 4s2 , do cc nguyn t ny u l kim loi,v chnh v vy bin thin tnh cht ca cc nguyn t h d theo chiu tng ca s Z khng r rt nh trong cc nguyn t s v p. (2) V kch thc nguyn t ca cc nguyn t chuyn tip dy th nht (v c cc dy khc) th s bin i ca bn knh nguyn t v con khng n gin nh cc nguyn t khng chuyn tip, ngha l khng bin i mt chiu m cn bin i t hn so vi cc nguyn t Bng 30 . Mt s c im nguyn t ca cc nguyn t chuyn tip dy th nht Ngu yn t Sc Ti V Cr Mn Fe Co Ni Cu Z cu Nguyn hnh t khi electro 3d14s2 44,956 2 2 3d 4s 47,900 3 2 3d 4s 50,942 3d44s2 51,996 5 2 3d 4s 54,938 6 2 3d 4s 55,847 7 2 3d 4s 58,933 8 2 3d 4s 58,700 10 1 3d 4s 63,546 3d104 2 65 380 Bn knh nguyn t () 1.61 1,45 1,36 1,28 1,31 1,27 1,25 1,24 1,28 1 33 Th ion ha th nht (ev) 6,56 6,83 6,74 6,764 7,432 7,90 7,86 7,633 7,724 9 391 m in (l) 1,3 1,5 1,6 1,6 1,5 1,8 1,8 1,8 1,9 16 Th tiu chun -2,08 -1,63 -1,18 -0,74 -1,18 -0,44 -0,277 -0,25 -0,337 0 763
(2) Cc tr S bn knh nguyn t trnh by trn ng vi mng li c s phi tr 12 thng thng nht i vi kim loi ( bn knh kim loi). Khi chuyn sang cc s phi tr 8: 6: v 4 cc bn knh nguyn t gim xung bng cch nhn cc tr s vi 0,97; 0,96; 0,88. khng chuyn tip. Nguyn nhn l trong cc nguyn t chuyn tip, electron
c thm dn vo cc obitan d, nhng obitan ny chn mnh in tch ht nhn bi cc electron ns lm cho kch thc ca nguyn t khng bin i bao nhiu. (3) V nng lng ion ha cng bin i t hn so vi cc nguyn t khng chuyn tip, nguyn nhn cng nh trong trng hp trn, l khi s lp electron ca nguyn t khng i, nh hng ca s tng in tch c b li bi mc chn ca cc electron c in vo cc lp trong. (4) Mc oxi ha ca cc nguyn t ny c trnh by hnh 47, trong mc oxi ha thng gp nht v quan trng nht c ghi bng vng trn ln. Nhn chung , ta thy mc oxi ha ca cc nguyn t ny thay i trong khong t +l Cu v +7 Mn, trong ph bin nht i vi tt c cc nguyn t l mc +2 v +3, ngoi l khng c mc +2 Sc v +3 Zn. Mi mc ox\i ha ng vi mt cu hnh electron nht nh chng hn vi crom c cu hnh :
T cu hnh electron , chng ta thy rng nhng nguyn t chuyn tip m cc obitan cha hoc xp mt na s electron s c s oxi ha ln nht trng vi s th t ca nhm tng ng ; cn vi nhng nguyn t m cc obitan d gn c hon chnh ( ngha l xp qu
5 electron ) th hu nh khng c khuynh hng to nn hp cht ng vi mc oxi ha cao. Chnh v vy , ta hiu c ti sao st , coban, niken khng c mc oxi ha +8 , cn Zn ch c mc o xi ha duy nht l +2.
Mc oxi ha +2 thng gp trong cc hp cht nh t v thng l hp cht ion, chng hn cc oxit MO u c tnh baz. Cc ion hirat ha [M(H2O)6]2+ u c bit trong dung dch cng nh trng thi tinh th ( tr ion Ti2+ ). cc ion V2+ , Cr2+ , Fe2+ d b oxi ha bi khng kh trong dung dch axit. Mu sc ca cc con hirat c a ra bng 31 . C th thu c cc ion hirat ha ny khi ha tan kim loi, oxit, mui cacbonat.v.v..ca cc kim loi tng ng trong axit cng nh khi in phn cc mui M3+. Nhng mui hirat ha m anion khng c kh nng to phc th thng cha cc ion [M(H2O)6]2+ . Chng hn nh
Khi thm kim vo dung dch mui M2+ s to thnh hiroxit , c trng hp c th to ra dng tinh th nh Fe(OH)2 Ni(OH)2 c cu trc tinh th dng Mg(OH)2. Khi thm HCO3- s to ra kt ta cacbonat ca mangan, st, coban, niken v ng. Vi mc oxi ha +3 cng l mc c trng cho cc nguyn t ang xt. Ring vi Cu ch mi bit c mt t hp cht ca CU(III) v thng l khng bn vi tc dng ca nc. Cc florua MF3 , cc oxit M2O3 thng l hp Cht ion , cn cc hp cht khc nh cc clorua, bromua, sunfua... c c tnh cng ho tr ng k. Cc nguyn t t Ti n Co to thnh ion hirat ha tm mt [M(H2O)6]3+ , mu sc ca cc ion ny dn ra bng 31 . Trong dung dch nc cc ion d b thy phn , th d: Cc loi phn nh Cs.Ti(SO4)2.12H2O, K.V(SO4)2 .12H2O Cng cha cc ion hexahirat ca cc kim loi . Bng 31. Th tiu chun (V) v mu sc ca con hirat ha [M(H2O)6]2+ v [M(H2O)6]3+
6.3. Tnh cht l - ha hc ca cc kim loi chuyn tip dy th nht Tnh cht l - ha hc c th ca cc kim loi v cc hp cht ca chng c trnh by c th trong cc chng sau, y ch nu mt s nhn xt chung. (l) Tt c u l nhng kim loi , ng nh, mt s c mu, nh coban c mu lam nht, ng c mu nht. u l nhng cht rn c cng cao (tr Cu); khi lng ring ln; dn in dn nhit tt; kh nng chy v kh bay hi. Mt s tnh cht nu trn c trnh by cc bng 2; 3; 4; 5; 6 chng 1. (2) Tr S v Zn , cc nguyn t cn li u a ho tr, to ra cc hp cht u c mu. Tr mangan v st rt d tham gia phn ng, cc kim loi cn li nhit phng t c kh nng phn ng , u bn vi s n mn. Khi t nng u phn ng vi oxi, halngen, lu hunh v cc phi kim khc. u phn ng mnh vi cc dung dch axit nh HF, HCl, HNO3, H2SO4 Cc nng v nhit khc nhau. Cc phn ng vi cc n cht v hp cht c trnh by c th trong cc chng sau. (3) Mt trong nhng tnh cht quan trng ca cc nguyn t chuyn tip l tnh thun t. Nh bit, da vo tc dng ca t trng, cc cht c chia ra lm hai nhm l cc cht thun t v cc cht nghch t (hay phn t). Nhng ion, nguyn t, hay phn t bt k c mt s electron cha ghp i ( c s l electron) u gy nn tnh thun t, v t ra c mt electron trong s c t trng cha khp kn , bt k vt liu no c cha cc tiu phn u b t
trng ht. Ngc li, cc cht khng c electron c thn ( tc c s chn electron ) - tr mt s ngoi l - u l cht nghch t. Vic nghin cu t tnh ca cc cht l phng php hiu nghim pht hin s electron khng ghp i trong cc nguyn t ha hc v trong cc hp cht ca chng. n v dng nghin cu t tnh ca nguyn t, ton v phn t l manheton Bom (8 ) v gi s mmen t hon ton gy ra bi n electron khng ghp i ca nguyn t hay ion s c tnh theo phng trnh: ( trong S l sm tng cng ca tt c cc electron khng ghp i). Mmen t ca nguyn t v ion c t mt n nm electron khng ghp i tnh theo phng trnh ( 1 ) c nu bng 32 . minh ho chng ta ly dn chng CUSO4.5H2O V MnSO4.4H2O lm dn chng. T thc nghim , mmen t o c ca CUSO4.5H2O l 1,95 B gn vi tr s l thuyt (l,73B); v ca MnSO4.4H2O l 5,86 B Cng gn tng ng vi tr s l thuyt (5,92 B ). T nhng kt qu , c th kt lun rng trong phn t CuSO4.5H2O C Cha ion Cu2+ ng vi cu hnh [Ar].3d9 vi mt electron khng ghp i. Bng 32. Mmen t ca nguyn t v ion tnh theo phng trnh(1) s etectron khng ghp S Mmen t ( , B ) 1 1/2 1.73 2 1 2.83 3 3/2 3.87 4 2 4.90 5 5/2 5.92
Cng tng t , trong phn t MnSO4.4H2O C mt ca ion Mn2+ ng vi cu hnh [Ar].3d5 vi 5 electron c thn. Trn hnh 48 so snh gi tr mmen t tnh theo l thuyt (ng nt lin) v gi tr thc nghim (cc chm en) i vi cc con kim loi chuyn tip dy th nht. S chnh lch gia tr s thc nghim v tr s l thuyt nh nu trong hnh 48, c gii thch bng cch cho rng c l l do nh hng ca cc mmen t gy ra bi s chuyn ng obitan ca electron.
Ni tm li, nguyn t v ion cc nguyn t h d u c tnh thun t v c bit ba nguyn t Fe, Co, Ni v hp cht ca chng - ngay nhit thng - li c tnh thun t c bit mnh, nn c gi l cc cht st t. Tnh cht ny gy ra do cc nguyn t hay ton thun t rt gn nhau, xut hin tc dng hp lc vi nhau lm cho tnh thun t tr nn rt mnh. Khng nhng b nam chm ht , m cc cht st t di tc dng ca dng in - li tr thnh nam chm. Nhng cht c tnh st t khng nhiu lm m li cn ph thuc vo nhit , chng hn Gd c tnh st t di 160C ; cn Fe (7600C) , Co (l0750C), Ni (3620C) , trn nhit - tnh st t s mt. 6.4. Nhn xt chung cc nguyn t dy chuyn tip th hai v th ba Dy chuyn tip th hai v th ba gm nhng nguyn t thuc chu k 5 v 6 tng ng. Cc nguyn t ny c mt s c im khc vi cc nguyn t dy chuyn tip th nht ( bng 33). Bng 33. Mt s c im nguyn t ca cc nguyn t chuyn tip dy 2 v 3
(1) Bn knh ca cc kim loi u ln hn so vi bn knh nguyn t ca cc kim loi dy chuyn tip th nht. Tuy nhin, bn knh ca cc nguyn t dy th ba khc nhau khng nhiu so vi bn knh ca cc nguyn t dy th hai cng nhm, mc d s lp electron tng ln , iu c gii thch l do hin tng co lantanit. (2) Khc vi cc nguyn t dy mt khng to ra mc oxi ha +8; cn cc nguyn t chuyn tip dy 2 v dy 3 c s oxi ha thay i t +l n +8 nh nu trong hnh 49.
Cc hp cht ng vi bc oxi ha cao li bn hn nhiu so vi dy chuyn tip th nht. Chng hn, W, Re, Ru, Pt c kh nng to ra cc hp cht nh WCl6 , ReF7, RuO4, PtF6; trong khi nhng hp cht tng t khng hnh thnh cc nguyn t chuyn tip dy th nht. (3) u l nhng cht rn c nhit nng chy cao, nht l W (Tnc = 3410 C ) v Re (Tnc = 31700C ) . Mt s tnh cht khc nh cng, khi lng ring, nhit nng chy, nhit si, dn in dn nhit c trnh by chng 1 ( cc bng 3; 4; 5; 6).
0
(4) So snh th ion ha v m in cho ta thy tnh kh ca cc kim loi thuc hai dy ny thay i khng nhiu so vi cc nguyn t chuyn tip dy th nht trong cng nhm. (5) c bit cc nguyn t thuc dy hai v dy ba to ra claste nhiu hn so vi cc nguyn t dy th nht .
Claste l hp cht m trong c tn ti lin kt ha hc gia cc nguyn t ca cc nguyn t chuyn tip h d. V d hp cht cacbonyl hai nhn dng claste ca mangan [Mn(CO)5]2:
Trong cacbonyl hai nhn trn c lin kt to ra trc tip gia 2 nguyn t Mn do hai electron cha ghp i ca hai nguyn t mangan:
Ngi ta bit c kh nhiu claste v chia ra lm hai nhm : a) Cc halogenua thp v mt s oxit. b) Cc cacbonyl a nhn (6) Nhm th nht ch yu to ra bi cc kim loi Tc v Re , Mo v W, Nb v Ta. Nhng claste hai nhn c nghin cu k l Mo2Cl93- , W2Cl93cng nh Re2Cl82-. D kin thc nghim cng thit lp c rng trong ton Re2Cl2- (hnh 50) c di lin kt Re-Re l 2,24 b hn 0,5 so vi lin kt Re - Re trong tinh th kim loi mng lc phng ( bn knh kim loi ca Re bng 1,37 ). Khong cch ngn hn c gii thch l do s to thnh lin kt bn Re - Re trong c mt lin kt , 2 lin kt v mt lin kt . Claste ba nhn nh polime ReCl4 gm cc mnh Re3Cl23- nh nu trong hnh 51 .Trong hp cht ny c khong cch d ( Re Re ) = 243 - 250 b hn khong cch gia hai nguyn t Re trong cu trc tinh th mng lc phng ca reni l 0,3 - 0,25 ..
Mt v d v claste tm mt l MoCl2 mu vng. Nhng d kin phn tch Rnghen cho thy MoCl2 ng vi cng thc [Mo6Cl8]Cl4 . Trong ion phc Mo4O84+ cc nguyn t clo nm gc ca hnh lp phng , cn cc nguyn t molipen chim tm mt ca hnh lp phng ( hnh 52) .
Trong trng hp ny, cc mnh claste M6X8 u kh bn khng b bin i khi chuyn thnh hp cht khc, chng hn khi cho MoCl2 tc dng vi kim to ra mui baz [Mo6Cl8](OH)4, hp cht ny khi tc dng vi axit li to ra ion [Mo6Cl8 ]4+ . Claste a nhn khc c dng M6X12 trong phn t [Nb6X12]Cl2.7H2O v [Pt6X12]PtCl2 nh minh ha hnh 53. (7) Nhm claste th hai ch yu to ra bi cc kim loi Mn, Tc, Re, Co, Rh... Ni chung, cc nguyn t h d c s l electron ha tr u c kh nng to ra cc hp cht cacbonyl hai nhn dng claste nh [Tc(CO)5]2, [Re(CO)5]2 , [Co(CO)4]2 , [Rh(CO)4]2... Trong phn t nhng cacbonyl ny u tn ti lin kt to ra gia hai nguyn t M-M do electron cha ghp i ca hai nguyn t kim loi nh nu trng hp [Mn(CO)5]2, Nhng claste ny u l cht kt tinh, d tan trong dung mi hu c v cc k c .
Nhng cacbonyl c dng iu ch kim loi tinh khit bng phng php nhit phn; ngoi ra cn dng lm cht xc tc trong cc qu trnh tng hp hu c ... Ngoi nhng cacbonyl hai nhn nu trn, mt s kim loi chuyn tip h d cn to ra nhng cacbonyl d nhn v a nhn khc, chng hn nh MnRe(CO)10 :
Cc cacbonyl a nhn khc nh Fe3(CO)9 l tinh th mu vng, im nng chy l 1000C; Fe3(CO)12 l tinh th mu xanh en, nng chy 140 1500C ; Rh4(CO)12 l Cht rn mu nu nng chy 1500C. Phng php chung iu ch cacbonyl l kh hp cht kim loi vi s c mt ca CO, thng thng cn p sut cao( 200-300atm );trong nhiu trng hp CO cng ng vai tr l cht kh ; v d :
nhng thng c mt cht kh no nh hiro hoc kim loi nh natri , nhm, magie:
(8) Mt trong nhng tnh cht c trng ca kim loi h d l kh nng to phc vi cc phi t trung ho nh cacbon oxit ( nu trn ) , photphin, asin, stibin, nh oxit, v c nh phn t (N2) Cht u tin ca phc cht no phn t l [Ru(NH3)5N2]Cl2. S to thnh phc cht cha nit phn t ng vai tr quan trng trong qu trnh c nh nit kh quyn trong cc cy h u , cng nh trong qu trnh xc tc tng hp amoniac. (9) Cc kim loi h d to phc vi nhiu phi t l hp cht hu c , trong c c cc phn t hu c mch vng , th d hp cht ibenzcrom Cr(C6H6)2 ( Tnc = 2840C ) v hp cht feroxen Fe(C5H5)2 ( Tnc = 1730C ). C hai u l cht tinh th bn, u c tnh nghch t; ibenzocrom c mu nu ti, cn feroxen c mu da cam. Phng php Rnghen cho thy rng trong cc phn t nguyn t kim loi nm kp gia hai mt phng song song ca hai phn t hu c mch
vng ( hnh 54). Nhng phn t c cu trc nh vy gi l cu trc bnh kp hay l hp cht kiu xan uch. Lin kt ha hc trong phn t ibenzocrom to ra theo c ch cho nhn do 18 electron (6 electron ca nguyn t Cr v 12 electron n ca hai phn t C6H6) vi cc obitan t do ca nguyn t crom v hai phn t benzen; 18 electron ny trong trng ca mi ba tm ( mt nguyn t Cr v 12 nguyn t C ca hai vng benzen).
Phn t feroxen cng c 18 electron ( 8 electron ca nguyn t Fe v 10 electron pi t hai phn t C5H5 ) chuyn ng trong trng 11 tm ( mt nguyn t Fe v 10 nguyn t C hai vng C5H5 )
CHNG 7 CC NGUYN T NHM IB ( NG - BC - VNG ) 7.1 . Nhn xt chung v cc nguyn t nhm IB (l) Cu (Cuprum), Ag(Argentum) v Au(Aurum) l cc nguyn t gn cui cng thuc h d trong cc chu k 4; 5; 6 thuc bng tun hon. C ba kim loi u l nhng nguyn t bit t thi k c i , trong vng l mt nguyn t him, theo quan nim ca cc nh gi kim thut th vng l " vua kim loi " do v b ngoi gy n tng lun lun sng chi, bn vi a s cc cht phn ng. Nguyn t khi , s th t v s phn b electron nh sau :
Nguyn t ng Bc Vng K hiu Cu Ag Au ST Ngyn t T khi 29 63,546 47 107,868 79 196,966 Phn b electron 2 2 2 8 8 8 18 18 18 1 18 32 Ha tr I, II, III I, II. III I, III
1 18
(2) V cu trc electron trng thi c bn , th ng l cu trc hai lp ngoi cng ca ba nguyn t ny phi l (n - 1)d9ns2 (n l s th t chu k tng ng), nhng lp (n - 1)d gn hon thnh , nn vic chuyn mt electron phn lp ns2 sang phn lp (n - 1)d s thun li hn v mt nng lng, do cu trc cc lp electron ngoi cng ca ba nguyn t Cu, Ag, Au s l (n l)d10ns1 . (3) Nh vy, c ba nguyn t ny u c mt electron lp ngoi cng tng t nh cc kim loi kim; nhng lp th hai t ngoi vo (lp n - 1) li c 18 electron , cn cc kim loi kim ch c 8 electron (tr Li). Chnh iu gy ra s khc nhau v kch thc nguyn t , dn n s khc nhau v tnh cht ca cc nguyn t ca hai phn nhm. Bng 34 so snh s khc nhau v bn knh nguyn t, th ion ha v i lc electron ca chng. (4) T bng 34 , ta thy th ion ha gim t Cu n Ag sau li tng ln n Au ; cn i lc electron li tng t Cu n Ag sau li gim n Au. So vi cc kim loi kim, bn knh nguyn t ca Cu, Ag, Au b hn cc kim loi kim Bng 34 . Bn knh nguyn t . th ion ha v i lc electron ca Cu. Ag. Au
Nguyn Bn kinh t nguyn t ( ) Cu 1,28 Ag 1,44 Au 1,44
Th i lc Nguyn t ion electro ha I1 n (ev) 7,724 2,4 K 7,574 2,5 Rb 9,224 2,1 Cs
Bn knh nguyn t ( ) 2,36 2,53 2,74
Th i lc ion electron ha I1 (ev) 4,339 0 82 4,176 3,893 -
cng chu k, nn th ion ha ca Cu, Ag, Au cao hn, ng thi i lc electron cng cao hn nhiu so vi kim loi kim v ln hn c oxi (1.465 ev), lu hunh (2,07 eV), nit (0,05ev), photpho( 0,77 eV). V vy, Cu, Ag, Au kh b oxi ha so vi cc kim loi kim. v con ca chng d b kh hn cc con kim loi kim. (5) Do c mt electron ns1 lp ngoi cng nn c kh nng hnh thnh phn t hai nguyn t nh cc kim loi kim( Cu2, Ag2, Au2). Nng lng phn ly ca Cu Ag2, Au2 l 174,3 ; 157,5; 210 kj/mol; (ca K2, Rb2, Cs2, vo khong 40 kJ/mol). Nng lng phn ly tng i ln so vi phn t M2 ca cc kim loi kim cng chu k, do phn t Cu2, Ag2, Au2 bn hn kim loi kim, l do c to ra hai lin kt n b sung c hnh thnh do c ch " cho " gy nn (cc cp electron d t do v cc obitan d cn trng) . (6) Vi Cu v Au th mc d phn lp d c in y , nhng cu trc cha phi hon ton bn vng, do nguyn t c th b kch thch chuyn thnh trng thi (n-l)d94slpl, kt qu to ra ba electron khng cp i v nh vy c mt hoc hai electron d tham gia vo qu trnh hnh thnh lin kt :
Do cc nguyn t phn nhm ng ng vi cc mc oxi ha +l, +2, +3. Vi Au th trng thi oxi ha +3 l c trng, y c hai electron u tham gia vo qu trnh hnh thnh lin kt. Vi Cu th trng thi c trng l +2 , cn vi Ag l +l. Tnh bn vng ca trng thi +l Ag l do cu hnh 4d10 c tnh bn vng tng i, v rng cu hnh c hnh thnh t nguyn t ng trc bc l palai (Pa) : 4s10 5s0. Cng t cu trc chng ta hiu c ti sao nng lng ion ha ca Ag li b hn ca Cu. (7) T s v th in cc di y chng ta c th so snh mc oxi
ha - kh ca cc hp cht ng vi cc trng thi oxi ha ca chng trong mi trng axit:
(8) V cu to tinh th , c ba kim loi u kt tinh theo mng lp phng tm din.
7.2. Trng thi thin nhin v thnh phn cc ng v (1) s phn b cc kim loi nhm IB trong v qu t ( ng vi thnh phn thch quyn) nh sau : % s nguyn t 3.6.10-3 1.6.10-6 5.0.10-8 % khi lng 1.10-2 1. 10-5 5.10-7
Cu Ag Au
Trong v qu t ngi ta gp ng ch yu dng hp cht sunfua ln

vi cc kim loi khc. Quan trng l qung cancopirit CuFeS, cancozin Cu2S , qung cuprit Cu2O, malachit Cu2(OH)2CO3 , tenorit cao. Vi bc , thng gp dng khong cht acgentit Ag2S hn hp vi qung sunfua ch. Ngoi ra cn c trong cc loi qung nh naumanit Ag2Se; prustit Ag3AsS3 Vi vng, thng gp dng khong cht calaverit AuTe2 ; sinvanit AgAuTe4 hoc petxit Ag3AuTe2. (2) Tuy nhin, dng thng thng hn gp trong thin nhin l vng t do, nm ri rc trong cc nham thch , trong ct. Cng ging nh vng, trong thin nhin , ngi ta cng gp ng v bc trng thi t do. (3) Trong nc ca i dng (tnh trong mt lt nc bin) c 3.10-3 mg ng dng Cu2+ ; 3.10-4 mg bc dng AgCl21- , AgCl32- ; 4.10-6 mg vng dng AuCl41(4) Trong cht sng gm ng vt v thc vt (tnh theo phn % khi lng) th c 2.10-4 % ng . ng l mt trong nhng nguyn t rt c bit v mt sinh vt hc . Nhiu loi cy nu c bn thm mt lng thch nghi cc hp cht ca ng th nng sut thu hoch thng tng ln; trong s cc ng vt th mt s loi nhuyn th nh hu , bch tuc c cha nhiu ng nht. C th ngi v cc ng vt khc , ng ch yu tp trung gan. Mi ngy c th ngi cn khong 5 mg ng, nu sinh vt b thiu ng, th qu trnh ti to hemoglobin s gim, gy ra bnh thiu mu. Trong cc loi thc n th sa c cha nhiu ng. (5) Vic xc nh hm lng cc nguyn t him trong cc mu Mt Trng ( do cc tu Apollo - 11 , - 12 v Luna - 6 a v Qu t ) trong ba vng khc nhau , ngi ta thy Mt Trng cc nguyn t ng , bc , vng c hm lng nh sau: Nguyn t Cu Ag Au Hm lng trung binh( s gam /1 g mu ) Apollo - 1 1 Apollo - 12 -5 1.1.10 -9 5.10-9 8. 10 4.10-11 2.10-9
Luna - 6 3,7.10-5 2,8.10-7 2,8.10-9
(6) Cu c 11 ng v t 58CU n 68CU, trong c hai ng v thin nhin l 63Cu ( Chim 69, 1 %) v 65Cu (Chim 30,9%) cn li l ng v phng x. Trong s cc ng v phng x, c hai ng v bn hn c l 57Cu ( Chu k
bn hy l 2,2 1 ngy - m) v 64Cu (Chu k bn hy l 0 541 ngy - m ) , cn ng v km bn nht l 58Cu ( Chu k bn hy l 3 giy). Ag c 19 ng v , trong c hai ng v thin nhin l 107Ag ( chim 5 1 ,35%) v l09Ag ( chim 48,65% ), cn li l cc ng v phng x t l02Ag n 115Ag, trong ng v phng x bn nht 110Ag ( chu k bn hy l 270 ngy - m ). Au c rt nhiu ng v t 183Au n ng v thin nhin l 197Au ( chim 100% ).
204
Au nhng trong ch c mt
7.3. iu ch Cu, Ag, Au ( 1 ) ng c sn xut ch yu t qung cancopirit CuFeS2 bng phng php nhit luyn. Trc ht ngi ta nung qung trong khng kh tch bt lu hunh ra khi qung. giai on ny mt phn st chuyn thnh FeO v mt phn ln lu hunh chuyn thnh SO2. Qung sau khi nung , c trn vi SiO2 v than cc ri tip tc c nu nng chy . Phn tp cht v mt phn st chuyn thnh FeSnh FeSiO3 dng x ; cn li l hn hp cc sunfua trong c cha Cu vi hm lng ln dng Cu2S.FeS v cc nguyn t khc nh Au, Ag, Ni, Se, Te... trng thi nng chy . Thi khng kh qua trng thi nng chy ny tip tc chuyn lu hunh thnh SO2, st chuyn vo x, cn li l Cu: sn phm thu c cha khong 95 - 98 % Cu. T loi ng thu c trn , tip tc tinh ch bng phng php nhit hoc phng php in phn c th thu c loi ng c hm lng 99,7% Cu. Sn phm ph thu c l SO2 Nu luyn Cu t qung oxit hay qung cacbonat ngi ta dng phng php kh bng than . Ngoi phng php luyn Cu nhit cao , ngi t cn dng phng php thy luyn bng cch ch ha qung ng trong cc cht lng khc nhau ( thng l H2SO4 long, dung dch amoniac ...). t dung dch thu c , ngi ta tch Cu bng st hoc bng phng php in phn . (2) Phn ln lng Ag khai thc c ( khong 80% ) u c luyn t qung a kim nh qung acgentit l qung Ag2S V PbS . sau khi kh qung , kim loi thu c dng nng chy cha Ag, Pb v Zn, t y bng phng php chng ct thu c Ag. (3) tch vng t sinh c trong bt qung ngi ta dng cc phng
php i (ra qung bng nc ) , ha tan vng trong thy ngn lng ( phng php thy ngn ) to ra hn hng Au - Hg , sau cho hn hng thng hoa , thy ngn bay hi, cn li Au. Phng php tt nht tch vng ra khi qung l phng php xianua. Bn cht ca phng php ny l ha tan vng c trong bt qung bng dung dch NaCN long (0,03 - O,2%), ng thi cho khng kh li qua, Au chuyn vo phc cht : sau cho dung dch phc cht tc dng vi Zn, Au c tch ra :
7.4 . Tnh cht l hc ca Cu, Ag , Au v ng dng (l) trng thi n cht , Cu tm c mu , Cu vn c mu gch ; Ag tm c mu trng nhng Ag vn c mu xm; cn Au trong nh sng phn chiu c mu vng , nhng trong nh sng xuyn qua ( cc l vng mng) c mu xanh lc. Bng 35 l mt s hng s l hc quan trng ca chng. Bng 35 . Hng s l hc quan trng ca Cu. Ag. Au Tinh cht Khi lng ring ( g/ cm3 ) Nhit nng chy ( Tnc , 0C ) Nhit Si ( Ts, 0C) cng ( so vi cng ca kim cng = 10) dn in ( so vi Hg = 1 ) dn nhit ( so vi Hg = 1 ) Cu 8.93 1083 2600 3 57 46 Ag 10,49 961 2210 2,7 59 49 Au 19,30 1063 2970 2,5 40 35
(2) C ba kim loi u c khi lng ring kh ln ; u c nhit nng chy Tnc v nhit si Ts cao. (3) cng tng i thp, v vy d dt mng v d ko di thnh si; lo Au c th ko thnh si di 3 km, v c th dt mng thnh l vng c chiu dy 1.10-4 mm. (4) C ba kim loi u dn in v dn nhit tt, c bit l Ag, Au c kh nng dn in ln nht . ng tinh khit c dn in cao, nhng dn in ca ng gim xung rt mnh khi c cc tp cht ; tu thuc vo bn cht v
lng ca tp cht m dn in ca ng thay i. V d c khong 0,03% mi tp cht sau y th dn in tng i so vi Cu nguyn cht l:
Ngy nay , ngi ta iu ch c nhng vt liu c dn in cao cha Cu nh YBa2Cu3O7 ( Siu dn ); YBa2Cu3O6 ( bn dn ). (5) Cu, Ag, Au d to hp kim vi nhau v vi nhiu kim loi khc. Di y l thnh phn gn ng ca mt s hp kim thng gp m Cu l kim loi chnh (%) : Tn hp kim Bronz ng thau ng en Mayso Thanh - ng (hp kim speculum) Hp kim Devarda Constantan Hp kim Denta Cu 80-90 70-80 90 80 67 50 59 55 Sn 5-10 Zn 2-10 3020 10 Mn Ni Al Fe
20 33 1 5 40 41 4 40
(6) Trong thc t, Cu c dng trong hai ngnh ch yu l k thut in v luyn kim. Trong k thut in , ng dng ch to dy dn ( dng tinh khit). Trong luyn kim dng ch to cc hp kim vi ng dng khc nhau. V d ng thau dng trong ngnh ch to ng c, v c do cao li bn hn ng. Hp kim thanh - ng bn hn Cu nguyn cht v ng thau li d n khun nn dng c trong cng ngh ch to my. Hp kim Devarda dng lm cht kh c th gii phng hiro ra khi nc ngay khi ngui. Hp kim constantan c in tr cao, c dng ch to cc dng c t nng. (7) Bc dng ch yu trng gng soi, dng trong gia nh. Dng c tin ( tin bc l hp kim c khong 50% bc , 40% Cu, 5% Ni, 5%zn);
dng lm trang sc (hp kim vi 7,5% Cu); mt s hp cht ca bc dng trong cng nghip nh v trong y khoa , chng hn AgNO3 dng cha bnh co tht , vim hng ... lm thuc tra mt ... Ion Ag+ c tnh tit trng rt mnh . Nc trong cc bnh bng bc c th hng thng m khng thi, do c mt lng rt nh ion Ag+ chuyn t thnh bnh vo dung dch tit trng. (8) Vng c dng lm trang sc , dng m ln cc kim loi khc . L kim loi ch yu m bo cho vic lu thng tin giy. Tin vng l hp kim cha 90% Au v 10% Cu. H tin t Vit Nam trong cc th k trc l tin ng, ch yu l hp kim ca Cu v Zn; c loi pha thm vng; c loi pha thm st nh tin thi Vng triu Mc. (9) Tt c cc hp cht tan ca Cu, Ag, Au u c ! 7.5. Tnh cht ha hc ca Cu, Ag, Au Hot tnh ha hc ca nguyn t ny tng i nh v gim nhanh theo chiu t Cu n Au. (1) C ba kim loi u khng phn ng vi H2 ngay c nhit cao, tuy nhin kh H2 c kh nng ha tan trong Cu, Ag nng chy p sut cao; ring hiro phn t khng tan trong vng. Hiro nguyn t tc dng vi Ag to ra AgH (bn ) v vi Au to thanh km bn hn. (2) Vi oxi , ch c Cu l phn ng trc tip . Khi nung trong iu kin thiu khng kh to ra Cu2O mu gch ; nu d khng kh to ra CuO mu en.
Ag v Au khng phn ng trc tip vi o xi, nhng nhit cao, c bit trng thi nng chy , cc kim loi hp th o xi vi lng kh ln , v d 9600C bc nng chy hp th n 20 th tch O2. Trong khng kh Ag v Au khng b bin i; trong khng kh kh Cu cng khng b bin i, nhng trong khng kh m c cha kh CO2 th Cu b bao ph mt lp mng mu xanh ca mui cacbonat baz Cu2(OH)2CO3. (3) Cu v Ag u phn ng trc tip vi lu hunh . Khi nung hn hp bt mn Cu v S (c khi nn p sut cao) to ra Cu2S, ng thi cng to ra CuS:
Phn ng cng tng t nh trn to ra Ag2S: Au khng phn ng trc tip vi S. (4) Cu, Ag, Au cng ha hp trc tip vi Se, Te khi nung cc n cht trong ampun hn kn. Thnh phn ca cc hp cht to thnh kh phc tp , trong c Cu2Se; CuSe, Ag2Se ; Cu2Te; Ag2Te v AuSe3 ; AuTe2 l n gin hn c. (5) Vi cc halogen, phn ng vi Cu, Ag, Au d dng hn cc nguyn t khc. Cu ha hp vi flo to ra CuF2 ngay c nhit thng , tuy nhin tc dng b hn ch do to ra lp hp cht florua che ph , lm cho kim loi khng tip tc b tc dng na. Do trong thc t Cu rt bn i vi flo ( khi khng c mt ca H2O). Ag Cng phn ng trc tip vi flo nhng chm hn , cn Au ch tc dng vi flo nhit cao. Sn phm phn ng l CuF2, AgF , AuF3. Khi cho kh clo qua Cu, Ag , Au , nung nng to ra mui clorua tng ng: CuCl2, AgCl , AuCl3. Trong dung lch nc clo , Au tan d dng hn, nhng vi Ag phn ng li chm hn v c lp AgCl che ph :
(6) Nit khng phn ng trc tip vi Cu , Ag , Au; nhng photpho th c phn ng trc tip vi Cu, Ag, Au nhit cao to ra cc hp cht c thnh phn Cu3P, AgP2, Au2P3 : (7) C ba kim loi u khng phn ng trc tip vi cacbon . Ag v Au khng phn ng trc tip vi silic, nhng khi nung Cu vi Si nhit cao th c phn ng to ra nhiu sn phm nh Cu6Si, Cu5Si , Cu4Si ,Cu3Si , ......,Cu15Si4 ... (8) Trong dy th in cc, c ba nguyn t u sp xp bn phi hiro,
nn u c tnh kh yu C ba kim loi u khng b H2OV hi H2O n mn. Ring Cu ch phn ng vi hi nc nhit nung nng trng . (9) Cu v Ag khng phn ng vi kim ngay c kim nng chy, v vy, trong phng th nghim ngi ta dng chn bc nu nng chy cc cht kim nhit cao; cn Au b kim nng chy n mn. (10) C ba kim loi u khng phn ng vi cc axit khng c tnh oxit ha, ngha l khng phn ng vi cc con hironi H3O+ trong dung dch axit. Trong cc axit l cht oxi ha nh HNO3 , H2so4 c nng , Cu v Ag u d tan cn Au ch tan trong axit c tnh oxi ha mnh lit, chng hn H2SeO4 khan nng. Cu v Ag khi tc dng vi HNO3 c to ra nh ioxit, cn HNO3 long va phi ( khong 50% ) to ra nit oxit, sn phm to thnh cn c mui nitrat v H2O:
Phn ng vi Ag cng xy ra tng t . Ag tc dng vi H2SO4 c to ra Ag2SO4 V kh SO2: vi Cu, H2SO4 c nng cng b kh to ra SO2 v H2O , Cn Cu b oxi ha n CuSO4 mc d Cu2S Cng c hnh thnh dng cht bt mu en (l) : Nh trn ni, Au khng tc dng vi HNO3 V H2SO4, nhng li tan trong H2SeO4 khan nng ( nhng khng ha tan c platin) , Ag cng ha tan tng t ( nh H2SO4 ) : (11) Dung mi tt nht ca Au l nc cng thy ( hn hp gm IV HNO3 c + 4VHClc ) do tc dng ca chlomi sinh , to ra axit cloroauric H[AuC4]:
hay Ag khng tan trong nc cng thy v AgCl khng tan . (12) Trong khng kh, H2SO4 n mn Cu to ra CuSO4 do s c mt ca O2 trong mi trng
Trong khng kh , Cu cng tan trong HCI c to ra dung dch mu xanh ti ca phc cht :
Ag v Au khng c phn ng nh trn . V nguyn tc Ag khng phn ng vi cc dung dch axit long, nhng Ag c kh nng y c H2 khi axit HI , v to ra AgI kh tan (Tt (AgI) = 8,3.1017 ): Khi un nng Ag trong kh quyn hiro clorua xy ra phn ng thun nghch:
Phn ng trn ph thuc vo nhit , p sut kh quyn , khi un nng n 6000C hn hp kh thu c gm 92,8%V l HCI v 7,2%V l H2, cn 7000C - 95% HCI v 5%H2. Trong iu kin nh trn , Cu cng c phn ng tng t. (13) Trong dung dch kim, Cu cng b oxi ha khi c mt ca oxi (E O2+2H2O/4OH- = +0,4v ) nn Cu phn ng vi dung dch amoniac to ra [ Cu(NH3)4]2+ :
0
(14) Cu, Ag v Au u phn ng vi dung dch KCN khi c mt ca oxi v to ra phc cht :
Trong cc loi hp cht ca Cu, Ag, Au th Cu to ra ch yu l cc dn
xut ha tr I v II, trong bn v c nhiu ng dng quan trng l cc hp cht Cu(II). Bc cng to ra cc dn xut ha tr 1 , ha tr II, nhng quan trng l hp cht Ag(I) . Vng to ra hp cht ha tr I v III trong quan trng l cc hp cht Au(III). 7.6. Cc hp cht vi s oxi ha +1 Oxit (l) Cu2O l hp Cht gp trong thin nhin dng qung ng (qung cuprit), l cht rn c mu gch ; rt bn i vi nhit . un nng n Tnc = 12350C m khng b phn hy; ch phn hy r rt khi nung n Ts = 1 8000C :
Trong thc t , ngi ta iu ch Cu2O bng cc cch sau: t Cu trong iu kin hn ch khng kh :
Nung nng CuO n 11500C hoc nung CuO vi bt Cu :
D hn, l dng cht kh nh anehit , glucoz kh cc hp cht Cu(II) trong mi trng kim nng. Chng hn khi un nng fomalin vi CuSO4 khi c mt ca NaOH : Hoc khi cho CuSO4 tc dng vi Na2SO3 khi; c mt NaCl to ra dung dch khng mu c cha ion phc CuCl32- :
sau thm t t dung dch borac nng vo , Cu2O S Xut hin : Cu2O l oxit c tnh baz l ch yu , khng tan trong nc. un nng trong khng kh, Cu2O b oxi ha thnh CuO v b H2 hoc CO ( hoc hn hp vi C ) kh thnh kim loi :
Vi dung dch H2SO4 long , to ra Cu v CuSO4: Nhng nu l H2SO4 nng ch to ra CuSO4: HNO3 oxi ha Cu2O to thnh Cu(NO3)2 v nit oxit : Trong iu kin khng c khng kh , Cu2O ha tan trong axit HCI to ra dung dch khng mu c cha cc ion phc CuCl32- hoc CuCl4 : nhng trong iu kin c khng kh li to ra CuCl2 : Trong dung dch nc c phn ng kim yu : Cu2O kh tan trong nc, nhng d tan trong dung dch amomac v dung dch amoni sunfat do to ra phc cht : Cu2O cng c kh nng tan trong dung dch kim c : Cng dng c bit ca Cu2O l dng ch to my chnh lu. Dung dch Cu2O trong axit clohiric dng hp th kh CO v dung dch trong amoniac dng hp th C2H2 :
(2) Ag2O l cht rn.c mu hung sm . Mc d Ag khng phn ng trc tip vi O2 p sut thng ngay c khi un nng, nhng khi nung n 3000C trong oxi di p sut cao, Ag li ha hp trc tip to ra Ag2O :
Trong thc t ngi ta iu ch cht bt mu hung sm ny bng cch cho dung dch kim n da vo dung dch AgNO3:
Ag2O bn di 1000C , nn c th lm kh 800C. Trn 1000C bt u phn hy v n 3000C th phn hy hon ton thnh kim loi : Trong dung dch nc, to ra mi trng kim yu, c kh nng i mu qu tm, do Ag2O l Oxit baz, nn c kh nng hp th CO2 trong khng kh to ra cacbonat : L cht oxi ha, Ag2O b H2 V H2O2 kh thnh kim loi :
Ag2O Cng c th kt ta t dung dch amoniac, nhng kt ta li tan trong amoniac d to ra baz phc [Ag(NH3)2]OH c phn ly gn bng NaOH : phc cht ny lu s hnh thnh cht kt ta mu en l AgN ( bc nitrua hay bc fuminat ) l cht n ! (3) Au2O l Cht rn c mu tm xm; t c nghin cu, v c to ra khi cho dung dch Aucl tc dng vi NaOH hoc KOH. Khng tan trong nc, v d dng b nhit phn hy to ra kim loi : Hiroxit (4) Ngi ta cha bit c CuOH! Khi cho dung dch mui Cu+ tc dng vi dung dch kim mnh to ra kt ta mu vng, ngi ta cho rng kt ta l dng hirat ha ca Cu2O . (5) AgOH c hnh thnh khi cho dung dch KOH trong ru tc dng vi AgNO3 -300C . Mt khc , khi cho Ag2O tc dng vi lng nc ln , dung dch thu c c tnh kim, c kh nng kt ta c hiroxit ca nhiu kim loi , chng t trong dung dch c cha AgOH vo khong 2.10-4 mol/l. Qu trnh phn ly trong dung dch :
(6) Khi kim ha dung dch AuCl to ra kt ta mu tm l Au2O khng phi l AuOH, l dng hirat ha ca Au2O. Cc mui halogenua Cc mui halogenua Cui c iu ch bng cch sau :
(7) CUF : Cho HF tc dng vi Cucl nhit cao hn 10000C to ra CuF, sau lm ngui t t thu c tinh th mu thm . (8) CuCl : c to ra khi nung Cu trong kh clo c hn ch hoc cho kh hiro clorua kh qua Cu nung nng :
Cng c th thu c khi kh CuCl2 bng Zn ( dng bi phn )hoc bng SO2:
Trong phng th nghim c iu ch bng cch nung nng dung dch c cha CuCl2 ( thng dng l hn hp gm CuSO4 + NaCl ) vi axit HCI c vi Cu. Ngi ta khuy dung dch cho n khi mu dung dch chuyn t xanh lam sang mu vng rm sng, giai on ny to ra phc cht :
sau ngi ta cho thm mt t dung dch Na2SO3 to ra mi trng khng c tnh oxi ha, lc kt ta trng CuCl xut hin : (9) CuBr iu ch bng cch nung nng mnh CuBr2 trong khng kh : (CuCl2 Cng phn hy theo phn ng tng t ) (10) CuI c iu ch bng cch cho dung dch Ki tc dng vi CuSO4 to ra CuI Ngi ta gii thch rng ban u to ra CuI2, sn phm trung gian ny b phn hy thnh CuI mu trng v iot:
(11) Cc halogenua ca cui u l cht rn. Phng php o t khi hi cho thy trng thi hi Cu(I) clorua v bromua c dng nh phn Cu2Cl2, Cu2Br2, cn iotua ch dng n phn CuI. Mt vi hng s l hc nh sau : CuF CuCl CuBr CHI
Mu sc Tnc( 0C ) Ts (0C) Tch s tan (T1 )
thm 908 1100 (thng hoa) Khng tan
trng 422 1366 1.2.10-6
trng 504 1345 5,25.10-9
trng 605 1290 1.1.10-12
Tt c u bn i vi nhit , hu nh khng tan trong nc, nhng tan trong dung dch amoniac (tr CUF) to ra phc cht khng mu dng ion [ Cu(NH3)2]+ : Cc halogenua Cu(I) cng tan trong axit halogenhiric m c tng ng khi un nng to thnh cc axit phc. V d : Cc dung dch khng mu trong amoniac hoc trong axit HCI , khi ngoi khng kh s nhanh chng chuyn thnh mu xanh lc do ton Cui oxi ha thnh Cu2+: (12) Cc hp cht halogenua Ag(I) c iu ch bng cch sau : AgF to ra khi ha tan Ag2CO3 hoc Ag2O trong axit HF:
(13) AgCl c iu ch bng cch cho axit HCI hoc mui clorua tc dng vi dung dch AgNO3 : (14) AgBr, AgI cng c to ra tng t nh iu ch AgCl. (15) Mt vi hng s l hc ca cc halogenua Ag(I) nh sau :
Khc vi cc halogenua khc , AgF tan trong nc . N tch ra khi dung dch dng tinh th khng mu AgF.H2O hoc AgF.2H2O ; Cn trong dung dch HF c li thot ra dng axit phc H[AgF2] hoc H2[AgF3]. Cc halogenua Ag(I) cng tan trong axit halogenhiric c tng ng
v cc mui kim loi tng ng to ra cc axit phc hoc mui phc , chng hn khi cho AgI tc dng vi Hi v KI to ra axit phc H[AgI2] V cc mui phc khng mu nh K[AgI2] , K2[Agl3]. Cc halngenua bc cng c kh nng tan trong HNO3 c nng to ra cc mui kp AgNO3.AgCI; AgNO3.AgBr; AgNO3.AgI . Trong dung dch amoniac ha tan d dng AgCl; AgBr t tan hn, cn AgI khng tan : ng thi cng c kh nng hp th c kh amoniac to ra AgCl.3NH3; 2AgCl.3NH3 Cc halogenua Ag(I) cng tan trong dung dch natri thiosunfat v kali xianua
Khi nung nng chy Na2CO3 Vi AgCl, n s b kh n kim loi AgCl cng b kh khi nung nng trong lung kh H2 hoc bng dung dch H2SO4long vi Zn ( to ra hiro mi sinh ) :
Tr AgF , cc halogenua cn li u b nh sng phn hy thnh bc kim loi v halogen t do, v d : Ngi ta bit rng s phn hy ch xy ra vi cc lia vng xanh tm, cn nhng tia th khng c tc dng , v vy trong cc phng ra nh ngi ta thng dng nh sng mu . Nhit cng thp , qu trnh phn hy cng gim. (16) Cc mui halogenua Au(I) c iu ch bng cch un nng nh cc halogenua Au(III) tng ng : Di y l mt vi tnh cht ng ch ca cc halogenua Au(I): AuF AuCl AuBr AuI
Mu sc Tch s tan Nhit phn hy
vng 2.10-13 2900C
vng xm 5.10-17 1150C
vng nht 1,6.10-23 1200C
Khc vi cc halogenua ca Cu(I) , Ag(l) ; cc halogenua ca Au(I) tc dng vi dung dch amoniac to ra kt ta khng mu AuCl.NH3, AuBr.NH3, AuI.NH3 : Cng tan trong axit halogenhiric tng ng to ra cc axit phc hoc mui kim ca axit phc :
Cng b H2O phn hy : Hp cht xianua (17) CuCN : thu c khi cho mui Cu(II) tc dng vi dung ch cha ion CN- to ra kt ta Cu(CN)2, nhit thng kt ta ny nhanh chng phn hy thnh CuCN v kh xianogen :
AgCN : thu c khi cho mui Ag+ tc dng vi dung dch cha CN- : AuCN : ngi ta cho Au tan trong dung dch KCN khi c mt ca khng kh to ra K[Au(CN)2] ( hoc thay th O2 bng H2O2 ) dng trong k thut m vng :
un nng phc cht vi HCI 50oC to ra AuCN : (18) CuCN mu trng ( Tt = 3,2 .10-20 ); AgCN mu trng (Tt = 2,3.10-16 ); AuCN mu vng . CuCN nng chy 4750C ( trong kh quyn nh 1 v sau b phn hy khi tng nhit ; cn AgCN v AuCN b phn hy khi cha t n trng thi nng chy . C ba mui hu nh khng tan trong nc v trong cc axit long ,
nhng li d tan trong dung dch KCN to ra phc cht bn:
Hp cht sunfua (19) Cu2S trc iu ch bng cch nn mnh hn hp bt mn Cu v S di p sut hng ngn atmotphe :
Ag2S to thnh khi cho H2S tc dng vi Ag c hi m v khng kh : v vy cc dng bng Ag lu ngy trong khng kh b ha en . Cng c th iu ch bng cch cho H2S tc dng vi dung dch mui Ag(I): . Khi nung trong khng kh to ra Ag v SO2: Au2S c iu ch bng cch cho dung dch bo ha H2S tc dng vi dung dch K[Au(CN)2] : (20) Di y l mt vi tnh cht ng ch ca cc hp cht trn:
Hp cht hirua , nitrua , cacbua (21) CuH : Hp cht hirua ny c to ra khi un nng mt dung dch gm 2mol axit hipophotphor ( H3PO2) vi lmol CuSO4 trong khong t 40 500C to ra kt ta mu nu c thnh phn ng vi cng thc CuH. CuH d b oxi ha v khi un nng b bc chy do phn hy to ra hiro . AgH : Khi cho hiro nguyn t tc dng ln Ag kim loi to ra bc hirua mu trng , bn trong kh quyn hiro , nhng li b H2O phn hy : AuH : cng c to nh AgH. B nhit phn hy 1000C : (22) Cu3N mu lc thm , to ra khi cho lung kh NH3 kh 250 270 C qua Cu2O hay CuO Cng c th cho qua CUF2. H2O . Trn 3000C phn
0
hy thnh Cu v N2. Ag3N cht bt mu en, to ra khi cho hi Ag tc dng vi NH3 12800C. Cng c to ra cho dung dch amoniac trong ru hoc axeton tc dng vi Ag2O. Khng tan trong nc lnh , tan mt phn trong nc nng. Tan trong HNO3 v cc axit v c khc . (23) Cu2C2 mu hung ; Ag2C2 mu trng c to ra khi cho axetilen CH - CH qua dung dch amoniac ca cc mui CuCl , AgNO3 : Nhng cacbua ny khng tan trong nc v trong dung dch kim nhng tan trong HCI to ra C2H2 . Trong khng kh , dng kh , d dng b phn hy gy n ! Cc hp cht khc ca Ag(I) (24) Trong cc hp cht cn li ca Cu(I), Ag(I), Au(I) th thc cht quan trng l cc hp cht ca Ag(I). Hn na, Ag(I) li to ra c nhiu mui bn hn so vi Cu(I) v Au(I) . Mt trong cc mui quan trng ca Ag(I) l AgNO3. Mui ny c iu ch bng cch cho Ag tan trong HNO3 v sau kt tinh li t dung dch : Tnc = 208,50C v b phn hy khi nung . AgNO3 khng b phn hy di tc dng ca nh sng nu khng c mt ca cht hu c . Khi c mt ca cht hu c n s ha en, v vy, AgNO3 li cc vt trn trn da tay. AgNO3 rt tan trong nc ( nhit thng c kh nng tan c 13mol trong 1 lt H2O) v trong glixerin. Khi nung nng n b phn hy : Nhit phn hy ca AgNO3 cao hn ca Cu(NO3)2 , v vy ngi ta dng phng php ny tch Cu(NO3)2 tp cht khi AgNO3. Khi nung , Cu(NO3)2 b phn hy trc thnh CuO ha tan trong nc thu c AgNO3. (25) Ag2SO4 c to ra bng cch cho Ag tc dng vi H2SO4 c nng hoc ha tan Ag2Ohay Ag2CO trong H2SO. Ag2SO l cht t tan trong nc ( Tt = 1,6.10-5 ), nhng d tan hn trong H2SO4 V HNO3 long . Ag2SO4 b phn hy nhit cao hn 9000C : Tng t kim loi kim, Ag cng to ra c AgHSO4
(26) Ag2CO3 c kt ta t dung dch AgNO3 v Na2CO3 hoc thi kh CO2 vo dung dch mui nitrat amoniacat Ag(I) :
N l cht rn mu vng , t tan trong nc ( Tt = 8,2.10-12 ). Ni chung , cc mui ca bc u kh tan v c mu, di y nu vi d kin v mu sc v tch s tan ca mt s mui thng gp : Anion CH3COOC2O42CrO42Cr2O72Mu trng trng nu Tt 4.10-3 1.10-11 1.1.10-12 1.10-10 Anion Fe(CN)63Fe(CN)64MnO4PO43Mu da cam vng tm en vng Tt 1.10-22 1.5.10-41 1,6.10-3 1,3.10-20
7. 7 . Cc hp cht vi s oxi ha +2 Trong s cc hp cht ng vi bc oxi ha +2 th cc hp cht ca Cu(II) c nhiu gi tr thc t nn di y ch nu cc hp cht ca Cu(II) . Cc oxit CuO c iu ch bng cch nhit phn Cu(NO3)2 , cacbonat baz CuCO3.Cu(OH)2 hoc Cu(OH)2; trong cng nghip iu ch t malachit:
CuO l mt poli me c cu trc cng ha tr, mu en hi nu ( Tnc= 1148 C ). un nng n 11500C th b phn hy :
0
Khng tan trong H2O, d tan trong axit long to ra dung dch mui Cu2+ : Khi nung nng , b kh bi H2, CO , C v cht hu c to ra Cu :
CuO c dng to mu xanh ca thy tinh v ca men s.

Ngi ta cng iu ch c Ag2O2 khi cho dung dch AgNO3 tc dng vi hn hp gm Na2CO3 + K2S2O8 ; v cng iu ch c Au2O2 m thc cht l mui AuI[AuIIIO2]. Hiroxit Cu(OH)2 l cht kt ta keo mu xanh khi cho dung dch mui Cu2+ tc dng vi dung dch NaOH hay KOH : Nu un nng dung dch n 90 - 1000C s to ra hirat, chng hn 4CuO.H2O, lc kt ta chuyn sang mu en . Dung dch amoniac tc dng vi dung dch mui Cu2+ to ra kt ta mui baz mu xanh thm hn , kt ta ny tan trong amoniac d :
hoc vit dng :
Cu(OH)2 tan trong axit to ra dung dch mui Cu2+ ; cng tan trong lng d dung dch c kim mnh to ra mui cuprit mu xanh Na2CuO2 hay Na2[Cu(OH)4]: Tuy nhin Cu(OH)2 c tnh baz mnh hn hn tnh axit, th hin tnh d thy phn ca Na2CuO2. Cc halogenua CUF2: c iu ch bng cch cho axit HF tc dng vi CuO un nng : CuCl2 : iu ch bng cch cho kh Cl2 tc dng vi Cu nung nng; hoc nung tinh th hirat CuCl2. 2H2O , ri cho lung kh hiro clorua i qua 1500C; hoc cho tinh th CuCl2 .2H2O tc dng vi H2SO4 m c :
hoc cho CuO hay CuCO3, Cu(OH)2 tc dng vi axit HCI , sau cho bay hi thu c tinh th . CuBr2 : cho CuO tc dng vi HBr trong chn khng . CuI2 : hin nay cha bit c CuI2 v khng bn, b phn hy thnh CuI
v I2. Di y l mt s tnh cht ca cc Cu(II) halogenua : dng hirat ha CuF2.2H2O C mu lam , khi nung nng trong lung kh HF to ra tinh th mu trng ( Tnc = 9500C ) ; t tan trong H2O lnh (4,7 g /100g H2O 200C ). CuBr2 l cht rn mu en , d b chy ra , trong dung dch nc c mu nu ; khi kt tinh ph thuc vo nhit to ra CuBr2. 2H2O hoc CuBr2. 4H2O . D tan trong nc (126,8 g CuBr2. 4H2O / 100g H2O 200C ). Khi nung nng, mt phn brom tch ra. CuCl2 khan l cht rn c mu vng nu , Tnc = 4980C , khi nung n 9930C b phn tch to ra CuCl. D b chy ra trong khng kh . D tan trong nc ( 72,8g CuCl2. 2H2O / 100g H2O 200C ). Khi tan trong nc mu sc thay i dn. T dng hirat ha CuCl2 . 2H2O mu xanh l cy , khi c du vt ca nc chuyn thnh mu xanh thm , khi thm t nc chuyn thnh hung thm , nu pha long thm chuyn thnh mu lc v cui cng dung dch long c mu lam. Hin tng thay i mu sc nh trn c lin quan n s hnh thnh cc ion phc ; mu xanh lam gy ra bi cc ion [Cu(H2O)6]2 + v mu thm gy ra bi cc ion CuCl3- V CuCl42- , Chng hn theo phng trnh : Cc dung dch m c ca CuCl2 v CuBr2 hp th NO to ra cc ion phc [Cu(NO)Cl3]- v [Cu(NO)Br3]- mu xanh tm. V mt cu trc , CuCl2 v CuBr2 dng khan l nhng polime cng ha tr c cu to mt phng :
Trong mt phng , mi nguyn t Cu lin kt vi hai nguyn t clo vi lin kt cng ha tr bnh thng v vi hai nguyn t clo khc bng lin kt "cho - nhn " , trong clo l "cht cho" . trng thi hirat ha CuCl2 . 2H2O l nhng nhm phng c dng :
Ngi ta cng iu ch c AgF2 bng cch cho flo tc dng vi Ag . L cht bt mu en , b nc phn hy : Khi cho Au bt tc dng vi clo kh to nn hp cht mu ng vi cng thc AuCl2. Cc loi mui khc (4) CuCO3 Cha iu ch c , nhng iu ch c dng phc cht K2[Cu(CO3)2] mu xanh en. Trong thin nhin , gp di dng mui baz malachit mu xanh l cy Cu(OH)2 . CuCO3 V dng agurit mu xanh lam Cu(OH)2 . 2CuCO3 . Khi cho dung dch Na2CO3 hoc NaHCO3 tc dng vi dung dch mui Cu2+ th thu c cht bt mu xanh l cy :
(5) Cu(NO3)2 khan c mu trng , dng hirat ha Cu(NO3)2.3H2O C mu xanh thm. iu ch bng cch cho kim loi, oxit, hiroxit hoc cacbonat baz tan trong dung dch HNO3. Khi nung nng dng Cu(NO3)2.6H2O hoc Cu(NO3)2.3H2O th ban u mt H2O kt tinh sau to ra CuO, NO2 v O2 Cu(NO3)2 l cht d tan trong nc ( 55,6 g Cu(NO3)2 khan / 100 g H2O 20 C ); Tnc =114,50C .
0
(6) Cu(CH3COO)2. H2O l Cht rn mu lc pha lam thm. Khi ngm nhng l ng trong dung dch gim n c mt ca khng kh : thng thu c dng Cu( CH3COO)2. Cu(OH)2. Ngi ta cng iu ch bng cch cho CuO tc dng vi CH3COOH to ra tinh th Cu(CH3COO)2.H2O. Cu( CH3COO)2 ( Tnc = 1150C ), tan trong nc , c dng lm cht cm mu trong y khoa v lm thuc bo v thc vt . (7) CUSO4.5H2O l mui quan trng nht ca ng. c iu ch bng cch cho CuO tan trong H2SO4 long ; hoc cho Cu tc dng vi H2SO4 c nng. Trong cng nghip , bng cch cho Cu tan trong dung dch H2SO4 long c mt ca khng kh [ xem 7.5(12) ] hoc bng cch nung hn hp gm mt Cu vi S trong lng d khng kh:
Dng CuSO4 khan c mu trng, dng thng gp c mu xanh lam CuSO4.5H2O, trng ny khi phi trong khng kh thnh dng CuSO4.3H2O; un nng n 1000C to ra dng CuSO4.H2O ; 2500C th ha khan CuSO4. Khi nung n 650 - 7000C to thnh CuO:
Trong phn t dng CuSO4.5H2O C phn t H2O ng vai tr cu ni gy ra bi lin kt hiro gia con SO42- v ion [ Cu(H2O)4]2+ :
Ngoi cc hirat nu trn ngi ta cn iu ch c c dng heptahirat CuSO4.7H2O gng hnh vi FeSO4.7H2O . Cu(II) sunfat c nhiu ng dng. CuSO4 khan c mu trng rt d ht H2O nn dng lm cht pht hin du vt H2O. Trong nng nghip , dng lm cht dit nm, mc cng nh su b ph hoi cy nho. Hn hp Booc ( dung dch CuSO4 vi vi ) dng phun vo khoai ty dit nm Phytophthora. Trong cng nghip , dng lm cht m ng. Trong y khoa, lm thuc st trng , ty u nh ca, dung dch 0,3 - 1 % lm thuc cha au mt ht ; lm thuc cha bng do photpho gy ra , hoc kh photpho d trong cc dng c th nghim : 2P + 5CuSO4 + 8H2O = 2H3PO4 + 5H2SO4 + 5Cu (8) CuS c iu Ch bng cch nung Cu bt vi lu hunh hoa hoc bng cch cho H2S qua dung dch mui Cu(II) c axit ha :
CuS l cht kt ta mu en khng tan trong nc ( Tt = 6,3.10-36 ) ; khng tan trong axit tr HNO3, trng thi m dn dn b khng kh oxi ha thnh CuSO4. (9) Nhn chung tt c cc dung dch mui Cu(II) u c mu xanh do ion
hirat ha ca Cu2+ . cc mui u c th b kh thnh Cu bi cc kim loi , tr Ag, Au v kim loi h platin c dng in thp hn. To ra kt ta Cu(II) hiroxit vi dung dch kim , cn vi dung dch amoniac; th ban u cho kt ta hiroxit sau tan trong lng d amoniac hnh thnh ion [ Cu(NH3)4]2+ . Vi hiro sunfua to ra kt ta mu en CuS, cn tc dng vi kali feroxianua K4[Fe(CN)6] to ra kt ta dng keo mu nu - socola ca Cu(II) feroxianua Cu4[Fe(CN)6]trong mi trng axit yu hoc trung tnh. Trong khi cc hp cht Cu(I), Ag(I) , Au(I) d dng b phn hy khi un nng nh hoc khi chu tc dng ca nh sng, nn phi bo qun trong cc chai mu ti, th cc hp cht ca Cu(II) li bn . Tuy nhin niotuav xianua ca Cu(II) li km bn hn CuI v CuN v cc ion I v CN- u c hot tnh kh cao.
-
7.8 . Cc hp cht vi s oxi ha +3 Trong cc hp cht c s o i ha +3 th c trng hn c l i vi Au. (1) Au2O V Au(OH)3 Khi cho dung dch AuC3 tc dng vi dung dch NaOH hoc un nng dung dch ri cho thm Na2CO to ra kt ta mu vng thm . Sau khi lm kh kt ta bng P2O5 thu c cht bt mu nu c thnh phn l Au(OH)3 .H2Ohay Au(OH). un nng cn thn n 140 - 1500C kt ta chuyn thnh cht rn mu nu en l Au2O . Tuy nhin Au2O li d gng tch o i ngay c khi va mi c to thnh v d 1600C b phn hy . Au2O V Au(OH)3 l nhng cht lng tnh in hnh, tan trong HaClv cc axit v c khc to ra cc phc cht :
v tan trong dung dch kim nng : hay NaAuO2 . 2H2O . (2) Ngi ta cng iu ch c Cu2O3 dng bt mu khi cho dung dch nam cum tc dng vi Na2O2: nung Cu2O3 n 1000C mt dn oxi, nn 4000C chuyn thnh CuO :
Cu2O3 l Cht lng tnh , tan trong HCI v trong kim to ra cuprat mu
Ngi ta cng iu ch c oxit Ag( III ) dng Ag2o3 ' 2Ago mu en . (3) Cc halogenua Au(III) Ngi ta iu ch c cc hp cht AuF3 mu da cam; AuCl3 mu ; AuBr3 mu nu thm ; AuI3 mu lc thm, khng tan trong nc (Tt = 10-46). Trong dung dch nc ch c AuF3 b phn hu hon ton, cn li thu phn theo phng trnh: dung dch ny c mu hung , khi cho tc dng vi Ag+ to ra kt ta khng tan l Ag2[ AuOCI3] , kt ta khng phi l AgCl, chng t ion [ AuOCI3]2+ c bn cao. Cc hp cht AuCl3, AuBr3 v AuI3 u d b nhit phn ; vi AuO3 bt u b nhit phn 2000C ; AuBr3 1500C ; cn Aul3 nhit thng. V d :
Chng d dng to phc vi axit hoc halogenua tng ng. V d : K[AuCl4] mu vng ; K[AuBr4] mu v K[AuI4] mu en. (4) Cc hp cht khc ca Au(III) Au(NO3)3 V Au2(SO4)3 khng tch c trng thi rn ch bit c trong dung dch c ca HNO3 v H2SO4 tng ng. Khi pha long vi H2O s b thy phn to ra Au(OH)3 ( Tt = 10-53 ) . Au2S3 iu ch c bng phng php gin tip nhit thp trong mi trng ru khi cho Li[ AuCl4 ] tc dng vi H2S kh. Au2S3 l cht bt mu en b phn hy 2500C thnh Au v S; b H2O phn hy thnh :
CHNG 8 CC NGUYN T NHM II B (KM - CAIMI THY NGN) 8.1 . Nhn xt chung v cc nguyn t nhm IIB (l) Zn ( Zincum), Cd (Cadmium), Hg ( Mercurius hay Hydrargyrum) l cc nguyn t cui cng h d trong cc chu k 4; 5; 6 thuc bng tun hon . Km v thy ngn bit t thi c i, cn caimi l mt nguyn t him c nh ha hc ngi c l Stromai ( F. Stromeyer) tm ra nm 1817. Nguyn t khi , s th t v s phn b electron nh sau : Nguyn t Km Caimi Thy ngn K hiu Zn Cd Hg S th t 30 48 80 Nguyn t 65,37 112,41 200,59 Phn b electron 2 2 2 8 8 8 18 18 18 2 18 32 Ho tr II II 2 I, II
2 18
(2) V mt cu trc electron c ba nguyn t ny u c lp v (n - l)d10 ns2 ( n l s th t chu k tng ng ). Lp ( n - 1 )d hon ton bn vng vi 10 electron. (3) C ba nguyn t ny u c hai electron s nm ngoi v d nn ging vi cc nguyn t nhm II A , u to nn cation hai in tch dng M2+ , nhng khc vi nhm II A , cc nguyn t II B c lp v ( n - 1)d10 li d b bin dng hn so vi lp v kh tr ( n - 1 )s2p6 ca cc ion nhm II A , v vy kh nng phn cc ca Zn2+ , Cd2+ , Hg2+ ln hn . Bng 36 nu mt s c im nguyn t ca cc nguyn t trn . Bng 36. Mt s c im ca nguyn t cc nguyn t Zn , Cd,. Hg Nguyn t Electron ha tr Bn kinh nguyn t () Bn knh ton M2+ ( ) Th ln ha I1 ( ev ) Zn 3d104s2 1,39 1,74 9,391 Cd 4d10 5s2 1,56 0,97 8,991 Hg 5d106s2 1,60 1,10 10,431
4) Do tnh bn c bit ca cu hnh 6s2 nn th ion ha ca Hg rt cao v

cao hn c cc nguyn t d cn li , iu gy ra tnh cht khc bit gia Hg vi Zn v Cd . Cc hp cht ca Zn v Cd bn hn , cn cc hp cht ca Hg t bn hn . S khc bit cn thy ch Hg to ra cc hp cht cha nhm Hg22+ , trong hai nguyn t Hg lin kt vi nhau bng lin kt cng ha tr - Hg - Hg - cng do cu hnh 6s2 . (5) Th in cc chun ca Hg rt cao, tri li Zn v Cd li c gi tr thp . Hai kim loi ny xp trc Hg , th hin tnh kim loi mnh hn nhiu so vi Hg. Sau y l s th in cc chun ca chng trong mi trng axit :
(6) V cu trc tinh th , Zn v Cd c cu trc mng lc phng m mi nguyn t lin kt c vi 12 nguyn t khc.
Vi Hg : khi ha rn to ra tinh th hnh tm mt ng, nhng vn l cu trc lc phng. Trong mng tinh th ca Hg c dng c bit hn : mi mt nguyn t Hg c bao quanh su nguyn t Hg vi khong cch l 3,005 v 6 nguyn t cn li vi khong cch l 3,477
8.2 . Trng thi thin nhin v thnh phn cc ng v (l) S phn b ca cc kim loi nhm II B trong v qu t ( ng vi thnh phn thch quyn ) nh sau : Nguyn t Zn Cd Hg % s nguyn t 1.5.10-3 7.10-6 7.10-7 % khi lng 5.10-3 5.10-5 7.10-6
(2) Trong v qu t, km dng cc khong vt ch yu l qung blen km ( ZnS ), calamin (ZnCO3) , Phranclinit hay ferit km ( Zn(FeO2)2 ) , ngoi ra cn c zincit ZnO. Trong thin nhin , cc khong vt ca Zn u c ln khong vt ca Pb, An v Cd. Vi Cd , khong vt ch yu l qung grinokit (CdS). Trong qung blen km v calamin c cha khong 3% caimi . Vi Hg , khong vt quan trng l qung xinaba ( cinnaba ) thnh phn chnh l HgS (cn gi l Thn sa hay Chu sa). (3) Trong c th ca ng vt hoc thc vt c cha Zn vi hm lng b , trong s hn c khong 12% ; trong c th ngi c khong 0,001% c nhiu rng , h thn kinh v tuyn sinh dc . (4) Trong nc ca i dng ( tnh trung bnh vi 1l nc bin ) c 1.10-2 mg km dng Zn2+ (ZnSO4) ; 1,1.10-4 mg caimi dng Cd2+ (CdSO4) ; cn thy ngn c hm lng 3.10-5 mg dng HgCl42- v HgCl3-. (5) Hm lng trong cc mu Mt Trng do cc tu Apollo -11 , -12 v tu Luna - 6 a v cho thy cc kim loi Zn, Cd , Hg c hm lng nh sau ba vng khc nhau : Nguyn Zn Cd Hg Hm lng trung bnh ( s gam 1 1 g mu ) Apollo - 1 Apollo - 12 Luna - 6 -5 -6 5.4.10 3,34.10-5 1,5.10 4.10-8 4.10-8 5,2.10-7 0,4.10-5
(6) Zn c 15 ng v, trong c cc ng v thin nhin l 64Zn (48,89%); 56Zn(27,8 1 %) ; 67Zn(4, 1 1 % ); 68Zn( 1 8,56% ) ; 70Zn(o,62% ) . Trong cc ng v phng x th bn nht l ng v 65Zn c chu k bn hy l
245 ngy m; cn ng v 61Zn chu k bn hy ch c l 90 giy . Cd c 19 ng v , trong tm ng v bn gp trong thin nhin 106Cd (l,215% ); 108Cd ( 0,875 % ) ; 110Cd 12,39 % ) ; 111C( 12,7 % ) ; 112C( 24,07 % ) ; 113 Cd(12,26 % ) ; 114Cd (28,86% ) v 116Cd (7,58% ) . Trong cc ng v phng x th ng v 100Cc chu k bn hy 470 ngy m l bn nht . Hg c 24 ng v trong c by ng v thin nhin l 196Hg (0,04 % ); 198Hg (10,02%) ; 199Hg (16,84%) ; 200Hg (23,13%) ; 201Hg (13,22% ); 202 Hg(29,80%) ; 204Hg(6,85% ). Trong cc ng v phng x c ng v 194Hg c chu k bn hy l 130 ngy m . 8.3 . iu ch Zn, Cd , Hg (1)Ni ta luyn Zn t cc qung blen km (ZnS ) hoc t qung calamin (ZnCO3). Cc loi qung c lm giu bng cc phng php khc nhau, chng hn phng php t hc tch oxit st ; phng php i ni ... T loi qung c lm giu, qu trnh luyn km c tin hnh bng phng php nhit luyn, qua hai giai on : giai on u l nung qung trong khng kh , cc loi qung u chuyn thnh oxit :
Giai on hai l kh oxit bng than : Di y nu tm tt qu trnh trn:
Ngi ta trn than vi qung lm giu ri cho vo cc ngn nung (A) trong l. Dng kh t l khong 12000C , qung s b phn tch thnh oxit , cacbon s kh oxit to thnh Zn. Km lng s t li trong cc khoang ngng (B),
mt phn Zn chuyn thnh bi t li thng (C) gn vi khoang ngng , c lm ngui bng khng kh. Lng km th thu c c cha khong 97 - 98 % Zn, tp cht l Pb , Fe; cn bi km c cha 80 - 90 % Zn , tp cht l Cd, Pb , Fe v c c Sb v As ... (2) Trong cc qung blen v calamin c cha CdS . V vy trong qu trnh luyn Zn cn thu c caimi . V Cd d bay hi hn Zn nn phn ln Cd cha trong bi Zn. tch Cd , ngi ta ha tan bi trong H2SO4 long , sau dng Zn kh ion Cd2+ : tinh ch Cd , ngi ta dng phng php in phn . (3) V bn ca HgO km hn nn thu c Hg t HgS theo phn ng : ngi ta cng dng Fe hay vi sng iu ch Hg t HgS :
Ngng t hi Hg , thu c Hg lng. 8.4. Tnh cht l hc Zn, Cd , Hg v ng dng (l) dng n cht c ba kim loi u c mu trng bc , nhng trong khng kh m b ph mt lp oxit mng. Mt s hng s l hc c nu bng 37 : Bng 37. Mt s hng s l hc quan trng ca Zn, Cd, Hg Tnh cht Khi lng ring ( g / cm3 ) Nhit nng chy ( Tnc , 0C ) Nhit Si ( Ts , 0C ) dn in ( so vi Hg = 1 ) m in Zn 7,14 419 907 16 1,6 Cd 8,64 321 767 13 1,7 Hg 13,55 -39 357 1 1,9
C ba kim loi ny u c khi lng ring ln, c Tnc v Ts thp hn so vi cc kim loi nng , v vy u c bay hi cao. Vi Zn , 3530C (gn vi Tnc = 4190C ) c p sut hi l 1,57.10-2
mmHg; vi Cd, c p sut hi l 3,13.10-2 mmHg 2910C ( gn vi Tnc = 3210C ). Ring i vi Hg th 200C c p sut hi l 1,33.10-3 mmHg. V iu kin thng Zn kh gin , nn khng ko di c , nhng khi un nng n 100 - 1500C li do v dai, khi un nng n 2000C li c th tn c thnh bt . Tri li, Cd c th rn v ko di c . (2) V c tnh, Zn trng thi rn khng c, nhng hi ca ZnO li rt c , cn cc hp cht khc ca Zn li khng c. Vi Cd, dng kim loi khng c , nhng cc hp cht ca Cd li rt c . c bit , thy ngn rt c , cc mui ca thy ngn nh clorua , nitrat cc k c c tnh ca thy ngn gy ra tc hi lm t lit h thn kinh , gim tr nh, vim lot li rng .... Lng thy ngn cho php cc i trong khng kh cc nh my l 10-5 mg/lt. (3). C ba kim loi u c kh nng to ra hp kim vi nhau v vi cc kim loi khc , c bit l hp kim ca thy ngn gi l " hn hng " . Hn hng thng l nhng hp cht ca thy ngn v kim loi ha tan trong thy ngn . Mt s hn hng trng thi lng, mt s trng thi rn hoc nho. Hn hng ca Na hoc K l cht rn tinh th ; hn hng ca Sn dng trng gng ... Nhiu kim loi d to ra hn hng nh Au , Ag , Cu , Sn , Na, K ... mt s khng to ra hn hng nh Mn, Fe , Ni ... bng phng php trc tip khi ho tan cc kim loi trong thy ngn , v vy ngi ta dng bnh bng st ct tr thy ngn . Mc d qu trnh to ra hn hng l qu trnh pht nhit , nhng cc kim loi trong hn hng khng thay i tnh cht ha hc ca n . V d hn hng natri khi tip xc vi H2O vn to ra H2 v NaOH nhng m du hn : Mt khc, trong hn hng, c tn ti cc hp cht ca Hg vi kim loi. V d : Vi Li c cc hp cht Li6Hg , Li3Hg , LiHg , LiHg2 , LiHg3. Vi Na c cc hp cht Na3Hg , Na3Hg2 , NaHg , NaHg4 , Na7Hg8. Vi Ca c cc hp cht CaHg3 , CaHg5 , CaHg10. Gc NH40 cng to ra hn hng vi thy ngn , khi cho hn hng natri tc dng vi dung dch m c mui amoni . V d : Gc t do NH40 trong hn hng ny bn hn trng thi t do v phn hy chm hn:
(4) Mt lng ln Zn c dng m ln st bo v cho st khi g, trn b mt ca lp m c ph mt lp mng cacbonat baz ( ZnCO3.3Cu(OH)2 ) bo v cho kim loi . Mt phn Zn dng iu ch hp kim nh hp kim vi Cu. Mt s hp cht ca km dng trong y khoa nh ZnO dng lm thuc gim au dy thn kinh, cha eczema, cha nga ... ZnSO4 dng lm thuc gy nn, dng lm thuc st trng; dung dch 0,1 - 0,5 % lm thuc nh mt cha au kt mc . Zn cn dng sn xut cc pin kh . Loi ph ny gm mt v ngoi bng Zn ng thi l ant ; gia pin l mt tr bng than ch ng vai tr ca catot. gia Zn v tr than cha hn hp h nho gm MnO2 , NH4Cl v bt than . Phn ng xy ra trn b mt in cc khi phng in nh sau : ant : Zn - 2e = Zn2+ (5) Caimi dng iu ch mt s hp kim d nng chy chng hn hp kim Wood nng chy 680C gm 50% Bi, 25% Pb , 12,5 %Sn v 12,5% Cd. Mt lng Cd pha ln vo Cu lm tng tnh bn ca Cu nhng khng lm gim tnh dn in . Mt phn Cd dng lm cquy Ni - Cd . Loi cquy ny tt hn cquy kh l khi phng ht in c th np li nh cquy ch . Trong loi pin ny, Cd ng vai tr ca ant , cn NiO2 ng vai tr ca catot . Khi phng in , b mt in cc xy ra cc qu trnh sau :
Khi cquy Ni - Cd phng in c dng vi th khong 1,2 - 1,3V. (6) Mt lng ln Hg dng trong k thut in , k thut nh sng , n thy ngn cao p , n thy ngn thch anh ... Dng iu ch cc hn hng c nhiu ng dng thc t nh hn hng c cha 5,8% tali ha rn - 600C nn dng ch to nhit k c nhit thp . Dng trong y khoa cha mt s bnh . Qung xinaba ( cinnabar ) thnh phn chnh l HgS, l mt loi Trung Quc nn gi l Chu sa ( hay an sa , Thn sa ) dng cha bnh mt ng , cha tnh hong ht ; cc hp cht HgCl2 , HgI2 , HgO, HgCN ch yu cha bnh giang mai v st trng . Tt c u l thuc c bng A.
8.5. Tnh cht ha hc ca Zn , Cd , Hg (1) Hot tnh ha hc ca cc nguyn t trong nhm II B gim dn khi khi lng nguyn t tng . Trong dy th in cc Zn v Cd ng trc hiro , cn Hg sau hiro . Km l nguyn t kim loi trung bnh , cn Cd th km hn . Mc d l kim loi ng sau hung , nhng li c hot tnh ha hc cao l do Hg trng thi lng lm cho phn ng xy ra d dng hn . (2) C ba kim loi u khng phn ng vi H2 , nhng H2 c kh nng tan trong Zn nng chy to ra dung dch rn . (3) Khi tip xc vi khng kh kh nhit thng , Zn , Cd v Hg u khng b bin i , nhng khi nung nng th Zn v Cd b chy nhanh hn , cn Hg th chm hn . Tt c u to ra oxit : ZnO , CdO , HgO . C ba kim loi u phn ng trc tip vi lu hunh, vi Zn v Cd th phi un nng, cn vi Hg xy ra ngay nhit thng khi nghin S bt vi Hg ; phn ng to ra ZnS , CdS v HgS. Vi Se v Te cng c phn ng trc tip to ra selenua v telurua tng ng : MSe v MTe ( M l Zn , Cd , Hg ). (4) Phn ng trc tip vi cc halogen to ra cc halogenua mu trng tr HgI2 c mu . (5) C ba kim loi u khng phn ng trc tip vi Ni , cc hp cht nh Zn3N2 , Cd3N2 , Hg3N2 Ch iu ch c bng phng php gin tip . Khi un nng c ba kim loi cng vi P trong ampun chn khng , th Zn phn ng trc tip vi P 400 - 4500C to ra Zn3P2 ; Vi c 450 - 5000C to ra Cd3P2 ; vi Hg nhit thp hn 275 - 3000C to ra Hg3P2. (6) Zn , Cd v Hg khng phn ng vi C , Si , B v khng to ra hp cht , tuy nhin cacbon ha tan mt t trong Zn v Cd nng chy , khi ngui cacbon thot ra dng than ch . (7) V mt nhit ng , Cd khng y c H2 ra khi H2O nguyn cht , nhng Zn li c kh nng khi so snh th in cc chun ca Cd, Zn vi. E0 + = 0, 413V . Thc t, kh nng ca Zn li khng xy ra v trn 2H (pH=7) H2 b mt bao ph mt mng oxit . Khi nung Zn trong lung hi nc to ra oxit km : (8) Tr Hg v Cd khng phn ng vi dung dch kim , cn Zn tan trong dung dch kim c nng to ra zincat:
Cc zincat ch tn ti trong dung dch kim d v Na2ZnO2 b thy phn mnh nh Na2SnO2 hay NaAlO2 , do trong dung dch nc khng phi l Na2ZnO2 m l NalZn(OH)3], Na2[Zn(OH)4] , Ba2[Zn(OH)6] . Cc hp cht ny tch c trng thi rn. (9) Zn v Cd tan trong axit khng c tnh oxi ha nh HCI , H2SO4 long to ra H2; cn Hg khng phn ng . Zn nguyn cht phn ng rt chm vi axit loi trn , nhng nu cho thm mt vi git dung dch CuSO4 hoc trong Zn c tp cht l nhng kim loi km hot ng hn th phn ng vi axit xy ra nhanh hn . Nguyn nhn l ban u hiro thot ra trn b mt ca Zn nguyn cht to ra mt lp mng mng cch ly km vi cht lng. Khi c tp cht, s hnh thnh nguyn t Ganvani nn H2 thot ra ti cc m tp cht . Khi nhng mt thanh km k thut ( c cha tp cht ) v mt thanh kim loi khc (v d Cu ) vo dung dch H2SO4 long hnh thnh mt pin in , thanh Zn s b axit n mn ngay c khi pin hot ng. khc phc iu , ngi ta hn hng ha b mt thanh km ; vi thanh Zn b hn hng ch thc s n mn khi pin hot ng , do electron chuyn t thanh Zn sang thanh Cu qua dy dn. (10) Vi axit c tnh oxi ha , c ba kim loi u b n mn. Vi H2SO4 m c v nng , Zn v Cd s phn ng to ra SO2 v S , cn vi H2SO4 c ngui c th to thnh H2S :
Hg tc dng vi H2SO4 c nng to ra HgSO4 nu axit d , khi Hg d to ra Hg2SO4:
Vi HNO3 c tc dng vi Zn ngoi NO2 hay NO cn to ra N2O ; nu l HNO3 long to ra mui amoni :
ion NO3- ng vai tr l cht oxi ha trong mi trng axit (H+) to ra ion
NH4+ Cn trong mi trng kim , ion NO3- s b Zn kh thnh amoniac : hay Vi Hg , khi tc dng vi HNO3 long to ra Hot thut khi Hg d; cn khi axit c d to ra Hg(II) nitrat :
(11) Km cn tan c trong dung dch amoniac , nhm khng c kh nng ny , do cc qu trnh sau :
hoc Khng nhng th , Zn cn tan c trong dung dch mui amoni c do qu trnh thy phn mui amoni to ra sn phm ph hy mng bo v ! 8.6. Cc hp cht vi s oxi ha + 2 (1) Km v caimi to thnh cc hp cht ha tr II , cn thy ngn ngoi ha tr II cn to ra nhng hp cht ha tr I . S phi tr c trng ca Zn (II) l 4 v ca Cd (II) l 6 , tng ng vi obitan lai ha sp3 ( phn b lin kt dng hnh bn mt ) v sp3d2 (dng tm mt):
V d cc hp cht nh K2[ZN(OH)4]; [ZN(OH2)4]SO4; ZN(NH3)4]Cl2; [ZN(NH3)2Cl2]; ZNO, ZNS, CdS, HgS u c cu hnh bn mt ng vi dng lai ha sp3 (hnh 58). Cn cc hp cht nh [Cd(NH3)6(NO3)2; [Cd(NH3)2Cl2]; CdO, CdBr2, CdI2 u c cu hnh tm mt ng vi dng lai ha sp3d2 ( hnh 59).
Hnh 59. Cu trc lp lin kt dng hnh tm mt ca MX2: (1) nguyn t kim loi M; (2) (3) nguyn t X; X phn b pha trn v di mt phng cha nguyn t M. Vi cc hp cht ca Hg(II) c dng hnh tuyn tnh ng vi dng lai ha sp, chng hn nh Hg(CN)2, [Hg(NH3)2]Cl2...
Sau y xt mt s hp cht quan trng ca Zn(II), Cd(II), Hg(II). (2) Cc oxit MO ZnO c iu ch bng cch nung mui cacbonat, nitrat, ferit km, hoc nung bt km trong khng kh
CdO c to ra khi nung bt Cd trong lng kh O2, to ra tinh th mu nu. HgO c iu ch bng cch nhit phn mui nitrat Hg(II):
Hoc bng cch trn dung dch nng HgCl2 vi K2CO3 hay Na2CO3: un nng Hg trong khng kh n gn nhit si ( Ts = 357oC ) cng to ra HgO : Hg thu c t cc phn ng u c mu . Khi cho dung dch kim d tc dng vi dung dch clorua hoc nitrat Hg(II) to ra dng HgO mu vng : Cc oxit ZnO, CaO, HgO u bn vi nhit, bn gim t ZnO n HgO. Khi un nng, t ZnO mu trng, n 250oC chuyn sang mu vng chanh, khi ngui li tr v mu trng ban u. Nung n 1950oC th b phn hy thnh nguyn t. CdO b thng hoa khong 700oC, n 1813 oC th b phn hy. Khi un nng HgO cng c hin tng chuyn mu. V d khi un nng HgO mu , s chuyn mu vng, ngui - tr li dng mu ban u. Nung n 400oC HgO b phn hy thnh n cht : C ba oxit hu nh khng tan trong nc, ring HgO c tan nhiu hn so
vi ZnO v CdO; khi tan, HgO to ra mi trng kim yu : ZnO l cht lng tnh, trong dung dch axit to ra cc mui clorua, sunfat km, cn trong dung dch kim d to ra zincat :
Khi nung hn hp gm ZnO v BaO 1100oC to ra oxit kp Bao, ZnO hay BaZnO2 : CaO v HgO l nhng oxit baz. ZnO, CdO u b H2 hoc C kh thnh kim loi :
(3) Cc hiroxit M(OH)2 Zn(OH)2 to ra khi cho dung dch kim tc dng vi dung dch mui km; kt ta tan trong kim d: Cd(OH)2 cng c iu ch tng t, khng tan trong kim d: Hg(OH)2 rt khng bn, cn bng sau y chuyn dch mnh sang phi : V vy khi cho mui Hg(II) tc dng vi dung dch kim, to ra HgO : Zn(OH)2 v Cd(OH)2 u l cht kt ta mu trng, khng tan trong nc; c tch s tan nh sau :
Khi nung Zn(OH)2 trn 100oC th bt u b phn hy thnh ZnO v H2O; vi Cd(OH)2 Sn phm thu c sau khi nung c mu sc khc nhau ph thuc vo nhit .V d nung 350oC thu c oxit mu vng xanh, cn 800oC l oxit mu xanh en. Zn(OH)2 c tnh lng tnh, tan trong axit v kim :
Bn cht lng tnh ca Zn(OH)2 c th m t theo s :
Cd(OH)2 cng th hin tnh axit nhng rt yu; d tan trong dung dch axit, cn trong kim c khi un si lu mi to ra caimat : sn phm phn ng tch c dng rn c thnh phn Na2[Cd(OH)4]. Zn(OH)2 v Cd(OH)2 tan trong dung dch amoniac do to ra phc cht :
t gi tr hng s khng bn ca ion phc [ Zn(NH3)4]2+ v [ Cd(NH3)4]2+ tng ng l 3.10-10 v 8.10-8 cho thy amoniacat ca km bn hn. Zn(OH)2 cng tan mt phn trong dung dch mui amoni. C ch phn ng nh sau : Khi c mt ca Zn(OH)2 cn bng trn s chuyn sang phi : hay Nhng amoniacat nh trn cng c to ra khi cho cc mui Zn2+ hay Cd2+ tc dng vi dung dch amoniac, chng hn : nhng vi [Hg(NH3)4]2+ ch c to ra khi c lng rt d NH3 v phi c mt ca mui amoni. V d hp cht [Hg(NH3)2]Cl2 to ra dng tinh th trng khi cho HgCl2 tc dng vi dung dch amoniac d v dung dch NH4Cl m c. (4) Cc halogenua Trong cc mui halogenua ca km, caimi, thy ngn th c ng dng rng ri nht l ZnCl2 v HgCl2. ZnCl2 khan c iu ch bng cch hay nht l un nng mui kp ZnCl2.3NH4Cl trong lung kh hiro clorua kh : hoc bng cch cho lung kh do hay HCl kh qua Zn nung nng, hoc bng cch cho Zn ha tan trong axit HCl, sau lm bay hi dung dch trong lung
HCl ( kh ) trnh hin tng thy phn : Cc mui halogenua khc ca km cng iu ch tng t. CdCl2 c iu ch bng cch nung Cd trong lung kh clo; cn CdBr, cng iu ch tng t trong hi brom, hoc bng cch cho Cd tc dng vi nc brom nng. Ngi ta cng c th iu ch CdI2 bng cch cho CdO, CdCO3 tan trong dung dch HI long. HgCl2 c iu ch bng cch cho Hg tan trong nc cng thy hoc cho HgO tc dng vi HCl un nng : Trong cng nghip iu ch bng cch un nng hn hp gm HgSO4 vi NaCl: HgI2 l cht bt mu to ra khi nghin Hg vi I2. Cng c th to ra khi cho mui Hg(NO3)2 hay HgCl2 tc dng vi dung dch KI : HgI2 tan trong lng d KI nn lng KI phn ng phi c tnh ton trc : Cng v l do , HgO cng phn ng vi dung dch KI : Cc mui halogenua ca km, caimi, thy ngn u kt tinh dng khng mu, tr HgI2 mu , a s tan trong nc. Di y l ha tan (mol / l H2O) ca cc halogenua iu kin thng: F Cl Br I -5 Zn 5.10 27 21 14 Cd 0,3 7 4 2,5 Hg 0,3 0,017 1,3.10-4 Cc mui florua t tan trong nc, chng t cu trc ca ZnF2 v CdF2 u c nng lng mng li cao. Cc mui clorua c tan ln nht v c bit vi ZnCl2 li c tnh ht m mnh. Cc halogenua ca Hg(II) u l nhng cht in ly yu, in ly ca HgCl2 vo khong 0,1%. V lin kt, florua l cht c lin kt ion, do u nng chy nhit cao, cn cc halogenua khc u c bn cht cng ha tr.
Cc halogenua ca Zn(II), Cd(II), Hg(II), nht l cc clorua, bromua, iotua khi tc dng vi ion halogenua to ra phc halogenua tng ng. V d :
Trong dung dch cc mui halogenua ca caimi u c cha cc con Cd , CdX+, CdX2o, CdX3-... Trong s cc phc halogenua , c nhiu cht rt bn,v d [HgBr4]- v [HgI4]2- c hng s khng bn l 2.10- 22 v 5. 10- 31 tng ng. Khi cho dung dch KI vo dung dch HgCl2 n khi kt ta HgI2 tan ht, sau cho thm KOH, thu c dung dch mu vng gi l thuc th Nette ( Nessler ) dng nhn bit amoniac v cc mui amoni to ra kt ta mu nu :
2+
Dung dch ZnCl2 c phn ng vi H2O to thnh axit phc : v vy ngi ta dng dung dch thu c sau khi cho Zn tc dng vi HCl (dung dch ZnCl2 c) trong k thut hn thic ty lp oxit trn b mt ca kim loi. Phn ng xy ra theo v d sau : Khi tip tc nung nng ch hn, nc bay hi, kim loi c ph mt lp mui nng chy, ngn cn s oxi ha kim loi, lm cho s tip xc gia thic hn vi kim loi c tt hn. Cc mui ca Hg(II) u c tnh oxi ha. Trong dung dch, HgCl2 b phn hy chm to ra Hg2Cl2 mu trng v clo : Cng b bin i tng t khi tc dng vi cht kh :
(5) Cc sunfua ZnS l cht rn mu trng, c to ra khi cho H2S qua dung dch mui km trong mi trng kim, hoc bng cch cho dung dch mui amonisunfua tc dng vi dung dch mui km:
Kt ta ZnS khng c hnh thnh khi cho H2S tc dng vi dung dch mui km ca axit mnh ( v d HCl ), v ZnS tan trong axit mnh. ZnS khng tan trong CH3COOH nn c th cho Zn(CH3COO)2 tc dng vi H2S : CdS cng c iu ch bng cch cho H2S tc dng vi dung dch mui caimi. CdS c mu vng chanh hoc vng ty theo iu kin kt ta. HgS c bit di hai dng : en v . Dng mu en c to ra khi nghin Hg vi S hoc khi cho H2S i qua dung dch mui Hg(II). Kt ta ny mu trng sau chuyn thnh mu v cui cng chuyn thnh mu en. Khi HgS en thng hoa chuyn thnh dng HgS l dng thng gp trong thin nhin. tan ca cc sunfua rt nh. Di y l gi tr tch s tan ca chng : - ZnS -ZnS CdS HgS HgS en Tch s tan Tt 2.10-25 3.10 - 2 5 1.10 -27 5. 10-54 2.10-53 tan trong nc gim dn t ZnS n HgS. tan trong axit cng gim tng t: ZnS tan trong axit mnh, khng tan trong axit yu. CdS khng tan trong HCl long, nhng tan trong trong HCl c, trong HNO3 long, trong H2SO4 long nng. HgS ch tan trong HCl c si. Tan trong nc cng thy to ra HgCl2; tan trong dung dch kim ca natri hoc kali sunfua to ra mui thio : HgS en tan trong HNO3 to ra mui nitrat. Khi un nng trong khng kh to ra thy ngn v SO2 : ZnS c dng ch to sn khong mu trng, thng c dng hn hp vi BaSO4 gi l litopon. Loi sn ny khng b ha en bi H2S v c iu ch theo phn ng : Khi nung ZnS v nh hnh trong lung kh H2S to thnh ZnS tinh th. Dng ny khi c ln vi mt lng nh kim loi khc (nh Cu) th c tc dng pht ln quang, ngha l sau khi chiu sng, n tip tc pht sng trong bng ti. (6) Cc xianua Cc xianua Zn(CN)2, Cd(CN)2, Hg(CN)2 c to ra khi cho dung dch
cc mui M2+ tc dng vi dung dch xianua ca kim loi kim. V d : Vi Hg(CN)2 ngoi phng php trn cn c th ha tan HgO trong dung dch HCN: Zn(CN)2, Cd(CN)2 thc t khng tan trong nc nn lng xung dng kt ta mu trng, cn Hg(CN)2 tan nhiu trong nc, nhng khng to ra ion Hg2+ v in ly ca Hg(CN)2 v cng nh; v vy ngi ta c th dng mt mui Hg(II) ha tan nhng mui xianua khng tan. V d : Khi un nng n 320oC, Hg(CN)2 b phn hy thnh xian : Cc xianua trn u d to thnh phc cht, phn ln cc phc cht u d tan trong nc v u bn dng [ M(CN)4]2-. V d :
(7) Cc nitrat Zn(NO3)2 c iu ch bng cch cho Zn ht, hoc ZnO tan trong HNO3 long: kt tinh trong nc nhit thp hn - 18oC v nng chy +36,5oC. To ra bn dng hirat vi 2; 4; 6; 9 phn t H2O. Dng hirat bn nht l Zn(NO3)2,. 6H2O. Cd(NO3)2 dng tinh khit c iu ch bng cch cho CdCO3 tan trong HNO3 long : nhit thng, tch ra dng tinh th hirat ha Cd(NO3)2.4H2O (cng tn ti dng 2; 9 phn t H2O). Hg(NO3)2 c iu ch bng cch cho Hg tan trong HNO3 d hoc cho Hg2(NO3)2 tc dng vi HNO3 long :
sau khi lm bay hi dung ch, mui tch ra dng hirat Hg(NO3)2.H2O. Hg(NO3)2 ch bn trong dung dch khi c mt ca HNO3 trnh hin tng thy phn. Trong dung dch long, hon ton b phn hy :
C ba mui u kt tinh mu trng, u d tan. ha tan trong 100 g H2O 20oC vi Zn(NO3)2.6H2O l 118,4 g, cn vi Cd(NO3)2.4H2O l 153 g. (8) Cc sunfat ZnSO4 c iu ch bng cch cho v bo km tan trong dung dch H2SO4 long, hoc nung ZnS trong khng kh :
Khi lm bay hi di 39oC, tinh th tch ra dng ZnSO4.7H2O. Tinh th mu trng, d tan trong nc. 20oC, ha tan l 54,4 g ZnSO4.7H2O trong 100 g H2O. trong khng kh dn dn b ln hoa. 39oC nng chy trong nc kt tinh to ra dng ZnSO4.6H2O. Mt nc kt tinh 250 - 270oC. Khi nung nng , b phn hy: CdSO4 c iu ch bng cch ha tan Cdhay CdCO3 trong H2SO4 long :
T dung dch trong nc, thu c tinh th hirat CdSO4.7H2O; CdSO4.H2O. CdSO4 tan trong nc. Vi sunfat ca kim loi kim, CdSO4 to ra mui kp, c cng thc l : M2SO4.CdSO4.6H2O (M l kim loi kim). Khi nung n 700oC, bt u thng hoa, ng thi bt u phn hy. 1000oC phn hy r rt thnh CdO v SO3: HgSO4 c iu ch bng cch un nng rt cn thn H2SO4 c vi Hg hoc bng cch ha tan HgO trong H2SO4 :
dng khan c dng hnh vy trng, khi c nc to thnh tinh th hirat HgSO4. H2O khng mu. Khi un nng lc u bin thnh mu vng, sau chuyn thnh mu nu, ngui mu s bin mt. Khi nung n nhit nng to thy ngn : HgSO4 tan t trong nc lnh, nhng khi un nng dung dch n 25oC, to ra tinh th mui baz mu vng v H2SO4 t do:
(9) Mui cacbonat ZnCO3 c iu ch bng cch cho dung dch lnh KHCO3 hay NaHCO3 bo ha CO2 tc dng vi dung dch mui km hoc cho lung kh CO2 qua huyn ph Zn(OH)2 trong nc to ra kt ta trng :
Nu li cho dung dch cacbonat ca kim loi kim tc dng vi mui km th to ra mui cacbonat baz, kt ta mu trng : Thnh phn ca kt ta ph thuc iu kin phn ng nh ZnCO3.Zn(OH)2.H2O; 2ZnCO3.3Zn(OH)2.H2O Mui cacbonat khng tan trong nc nhng b phn hy dn thnh mui cacbonat baz. Khi un nng n 150oC, mui ZnCO3 kh bt u phn hy thnh CO2. CdCO3 c iu Ch bng cch cho dung dch mui caimi tc dng vi dung dch cacbonat kim loi kim hoc amoni : Kt ta dng v nh hnh mu trng, khng tan trong nc (Tt = 5,2.10 ). Mun chuyn thnh dng tinh th ngi ta un nng dng v nh hnh vi dung dch amoni cacbonat n 170oC v sau lm lnh t t. Khi un nng CdCO3 b phn tch thnh CaO v CO2 :
12
HgCO3 cha iu ch c. Khi cho K2CO3 vo dung dch mui Hg(II) to ra kt ta nu HgCO3.2HgO. (10) Cc hp cht khc Km hirua (ZnH2) g c iu ch bng cch cho ZnI2 hoc Zn(CH3)2 - imetyl km - tc dng vi LiAlH4 : ZnH2 l cht rn, mu trng, un nng n 90oC b phn hy thnh Zn v H2; vi H2O - to ra Zn(OH)2 :
ZnH2 cng c iu ch bng cch cho ZnI2 tc dng vi LiH trong ete : Cng bng phng php tng t, ngi ta tng hp c caimi hirua CdH2 v thy ngn hirua HgHz :
Qu trnh tng hp cc hp cht trn u c thc hin nhit thp, c bit vi HgH2. Cht ny nhit - 125oC b phn hy. CdH2 v HgH2 u l cht rn mu trng, d b phn hy hn so vi ZnH2. Km nitrua Zn3N2 c iu ch bng cch nung km trong lung kh amoniac 527 - 627oC cung nh khi nhit phn km amit Zn(NH2)2 nhit 227oC :
Zn3N2 l cht bn dn in, dng ht mu xm nung nng trong chn khng b phn hy thnh Zn v N2 350oC, bn trong khng kh, b H2O phn hy : Caimi nitrua Cd3N2 cng c iu ch bng cch nung caimi amit Cd(NH2)2) trong chn khng 180oC : Cd3N2 l cht bt mu en, b H2O phn hy v n, phn ng tng t nh trn. Thu ngn nitrua Hg3N2 li c iu ch bng cch cho lung kh NH3 nng 120 - 170oC lin tc qua HgO vng : Hg3N2 l cht bt mu nu thm, b phn hy gy n. Km cacbua ZnC2 v caimi cacbua CdC2 c to thnh khi un nng kim loi trong lung kh axetilen, cn thy ngn cacbua HgC2 thu c khi cho C2H2 qua dung dch mui thy ngn. 8.7. Hp cht thy ngn (I) Nhng hp cht ca thy ngn m trong thnh phn phn t c cha nhm - Hg - Hg - hoc trong dung dch c cha ion phc tp Hg22+ gi l hp
cht thy ngn (I). Khong cch Hg - Hg bin i trong khong t 2,5 - 2,7. Km v caimi cng to ra cc ion Zn22+ v Cd22+ nhng hon ton khng bn. Ngi ta bit c nhiu hp cht Hg(I) nh Hg2O, cc halogenua Hg2X2 v nhiu mui khc. V ion Hg22+ khng mu nn a s cc hp cht Hg(I) u khng mu. Hu ht u kh tan trong nc, ch c Hg2(NO3)2 l d tan nn thng dng lm cht ban u iu ch cc hp cht Hg(I) khc. Cc cht d tan th in li mnh v b thy phn to ra mui baz. V d khi pha long Hg2(NO3)2 s c phn ng : v vy phi axit ha dung dch Hg2(NO3)2 bng HNO3. Ty theo iu kin phn ng, m cc hp cht Hg(I) th hin tnh oxi ha hoc kh. V d :
Cc hp cht Hg(I) c khuynh hng t hy thnh Hg v hp cht Hg(II) tng ng, ngha l c cn bng : chng hn xianua Hg(I) khng tn ti, v Hg(CN)2 l cht in ly rt yu nn : Cng chnh v vy, cc hp cht Hg2(CN)2 v Hg2S khng th iu ch bng phn ng trao i do qu trnh t phn hy nn xy ra theo phng trnh :
Di y nu phng php iu ch v mt vi tnh cht ca mt s hp cht Hg(I) : Oxit Hg2O c to ra khi dung dch Hg2(NO3)2 hay calomen Hg2Cl2 tc dng vi dung dch kim mnh s hnh thnh cht bt Hg2O mu en. Tuy nhin bng phng php phn tch tia X l hn hp gm HgO v Hg ( HgO.Hg). Hg2O thc t khng tan trong nc. Khi un nng hoc khi chiu sng mnh, phn hy theo phng trnh : Hg2(NO3)2 c iu ch bng cch ha tan khi un nng thy ngn d trong HNO3:
Cng c th thu c bng cch cho thy ngn tc dng vi dung dch Hg(NO3)2 trong nc : Kt tinh t dung dch trong nc to ra tinh th hirat Hg2(NO3)2.2H2O khng mu. trong khng kh mt dn nc kt tinh v n 70oC th bt u phn hy. Rt d tan trong nc, trong dung dch long b thy phn chm khi lnh, v nhanh hn khi nng to ra mui baz HgNO3.HgO hay Hg2(OH)(NO3) c mu vng chanh. Dung dch Hg2(NO3)2 c tnh kh mnh, trong khng kh b oxi ha thnh Hg(NO3)2: V vy dung dch Hg2(NO3)2 c bo qun trong cc l c cha mt t thy ngn. Thy ngn (I) nitrat b phn hy khi un nng thnh HgO v sau HgO phn hy tip thnh Hg:
Hg2Cl2 ( calomen ) c iu ch bng cch cho SO2 qua dung dch HgCl2 un si, hoc bng phn ng trao i ca Hg2(NO3)2 vi NaCl: C th bng cch nghin HgCl2 vi Hg trong ci bng st : Cng iu ch bng cch ha tan Hg trong H2SO4 nc mui sunfat, sau un nng vi mui n v Hg :
Cng c iu ch bng cch ha tan Hg trong HNO3 long to ra thy ngn (I) nitrat sau cho thm NaCl hoc axit HCl. Hg2Cl2 l cht bt mu trng, hu nh khng tan trong nc (2,1 m trong 1 l H2O 18oC). Ha tan trong HNO3 v trong nc cng thy. Di tc dng ca nh sng, calomen sm li dn do phn hy mt phn thnh HgCl2 v Hg. Khi un nng n 383oC th thng hoa khng nng chy, nhng khi nung trong ng hn kn th nng chy 525oC ( c phn hy mt phn thnh HgCl2 V Hg ) to ra cht lng mu nu .
Khi un nng vi C hoc Na2CO3 th b kh n thy ngn kim loi :
Mt trong nhng phn ng quan trng ca Hg2Cl2 ( Cng nh cc mui Hg22 + khc) l phn ng phn hy Hg22+ do NH3 lm cho cn bng Hg22+ Hg2+ + Hg chuyn dch mnh sang phi gn nh tc thi, to ra hp cht amiua khng tan trong nc, cn Hg thot ra dng mu en :
Ni chung, cc mui halogenua ca Hg(I) u kh tan trong nc. Tch s tan ng vi qu trnh sau y c gi tr :
Hg2F2 tan nhiu hn v b thy phn. Hg2Cl2 V Hg2Br2 khng mu, cn Hg2I2 c mu vng m; cn khi mi kt ta t dung dch Hg2(NO3)2 vi KI th c mu vng xanh : nu KI d, kt ta s to thnh ion phc : Ni chung cc halogenua ca Hg(I) u t bn, bn gim t Hg2Cl2 n Hg2I2 Hg2SO4 c iu ch bng cch cho lng d Hg tc dng vi H2SO4 c hoc bng cch cho Hg2(NO3)2 tc dng vi H2SO4 long : Hg2SO4 l cht rn mu trng, kt ta hu nh khng tan trong nc v trong H2SO4 long. Trong dung dch long (d H2O), Hg2SO4 b thy phn to ra mui baz sunfat khng tan mu vng xanh. Hg2CO3 to ra khi cho lng d dung dch Na2CO3 tc dng vi dung dch mui Hg(I). Hg2CO3 l cht kt ta mu vng, un nng n 100 - 130oC hoc chiu sng, b phn hy :
CHNG 9 CC NGUYN T NHM VIB (CROM - MOLIPEN - VONFRAM)
9.1. Nhn xt chung v cc nguyn t nhm VIB (1) Ba nguyn t Cr ( Chromium ); Mo ( Molibdenium ); W ( Wolframium ) l cc nguyn t thuc h d trong cc chu k 4; 5; 6 thuc bng tun hon. Crom c nh ha hc ngi Php l Vclanh (N. Vauquelin ) tm ra nm 1779; nm 1782 - nh ha hc Thy in l Hienm (P. Hjelm) iu ch c molipen; cn vonfram li do nh ha hc Thy in l Sao (K. Scheele) v cc nh ha hc Ty Ban Nha l anh em luia ( d' Elluyar ) tm ra ng thi vo cui th k 18 vo khong cc nm 1781 - 1783. Nguyn t khi, s th t nguyn t, s phn b electron v trng thi ha tr ca ba nguyn t nh sau :
Nguyn t K Nguyn S TT hiu t khi 24 42 74 51,996 95,940 183,850 2 2 2 Phn b electron 8 8 8 13 18 18 1 13 1 32 12 2 Ha tr I, II, III, IV, V, VI, II, III, IV, V, VI II, III, IV, V, VI
Crom Cr Molipen Mo Vonfram W
Lp (n - 1)d cha hon chnh nn c nhiu trng thi ha tr. Bc oxi ha dng cao nht l +6 tng t nh nguyn t nhm VIA. c bit l crom - nguyn t in hnh ca nhm VIB - c nhiu tnh cht ging lu hunh, c hai u to ra oxit XO3 (CrO3 v SO3), u l oxit axit v u c axit tng ng l H2SO4 v H2CrO4; C hai cng u to hp cht SO2Cl2 v CrO2Cl2 u c bn cht cng ha tr. C hai nguyn t u to ra mui dng M2X2O7 l mui isunfat (v d Na2S2O7) v icromat (Na2Cr2O7). Ngoi ra, crom cng c nhiu tnh cht ging nhm v st, chng hn crom v nhm to ra oxit v hiroxit lng tnh; mui Cr(II) tng t mui Fe(II) v d CrCl2 v FeCl2; c crom v st u to ra mui c mu, v d ferat K2FeO4 mu ; cromat K2CrO4 c mu vng. Nhng tnh cht ging nhau, to ra hp cht tng t nhau, u c lin quan n bn knh ca ion trung tm = 0,35; r = 0,83; r = 0,84; r = 0,57 (hoc ( r = 0,34 ; r Fe S Cr Cr Al (2)
6+ 6+ 2+ 2+ 3+
0,62); r = 0,67; r = 0,64). Fe Cr (3) Mc d c mt s tnh cht ging vi nguyn t nhm VIA, nhng v c ba nguyn t ny u c mt electron s nm ngoi v d ( c 2e vonfram ) nn c tnh dng in hn v lp v ( n - 1)d cng d bin dng hn so vi cc nguyn t nhm VIA. Mt s c im nguyn t ca ba nguyn t trn nu ra bng 38. Bng 38. Mt s c im ca Cr - Mo - W Cr Mo W 5 1 5 1 3d 4s Electron ha tr 4d 5s 5d56s2 Bn knh nguyn t () 1,27 1,39 1,40 2+ Bn knh ton M () 0,83 Bn knh ton M3+ () 0,64 4+ Bn knh ton M () 0,68 0,88 6+ Bn knh ton M () 0,35 0,65 0,65 Th ion ha l1 (eV) 6,704 7,10 7,98
3+ 3+
(4) T bng 38, ta thy bn knh nguyn t tng t Cr - Mo, nhng hu nh khng i khi chuyn t Mo n W. iu c gii thch l do hin tng nn lantanit ca cc nguyn t h lantan pha trc W. Do vy, molipen v vonfram c tnh cht gn nhau hn so vi crom. Cng chnh do s co lp v electron, nn th ion ha tng, c bit tng mnh khi chuyn t Mo n W. (5) Khi so snh th in cc chun c th thy c crom v molipen u l kim loi c hot tnh trung bnh. Crom ng sau mangan v trc st, cn molipen ng trc thic. Di y l s th in cc ca crom v molipen: Trong mi trng axit :
Trong mi trng baz :
(6) V mt cu to tinh th, c ba kim loi Cr - Mo - W u kt tinh theo kiu lp phng tm khi( hnh 60 ) : Vi Cr : : 2,8846 Mo : = 3,1464 W : = 3,1650
Hnh 60. Cu to tinh th ca Cr - Mo - W.
9.2. Trng thi thin nhin v thnh phn cc ng v (1) s phn b cc nguyn t nhm VIB trong v qu t ng vi thnh phn thch quyn th sau : Nguyn t % tng s nguyn t % khi lng 6. 10-3 Cr 6.10-5 3. 10-4 1.10-5 6. 10-4 W Trong v qu t, khong vt ch yu ca crom l qung st cromit [FeCr2O4 hay FeO.Cr2O3; Fe(CrO2)2] v qung croisit hay ch cromat (PbCrO4); ca molipen l qung molipenit ( MoS2); cn vonfram l qung vonframit ( FeWO4 v MnWO4), qung silit (CaWO4), qung tonsit (PbWO4), i khi cn gp trioxit WO3 t do trong qung tungstit. Vit Nam c khong sn cromit C nhh (Thanh Ha ). (2)Trong c th sng, ch yu l thc vt c cha khong 10 - 4 % crom (theo khi lng) v 1.10-5 molipen (theo khi lng). (3) Trong nc ca i dng( mg/1l nc bin ), c 5.10-5 mg crom; 0,01 mg molipen dng MoO42- ; cn vonfram chim 1.10-4 v dng WO42-. (4) Trong mu Mt Trng, cc kim loi Cr, Mo, W c hm lng nh sau :
Nguyn t Cr Mo W
Hm lng trung bnh ( s gam /1 g mu ) Apollo - 11 Apollo -12 Luna - 6 -3 -3 2,1. 10 2,8.10 5,3.10-6 0,5. 10-6 0,3. 10 -6 -
(5) Crom c 10 ng v, cc ng v thin nhin l 50Cr (4,31%); 52Cr (83,76%); 53Cr (9,55%); 54Cr (2,38%). Trong cc ng v phng x th ng v 51 Cr c chu k bn hy l 28 ngy m, v ng v km bn nht l 47Cr c chu k bn hy l 0,4 giy. Molipen c 16 ng v, by ng v bn gp trong thin nhin l 92 Mo(15,86%); 94Mo (9,12%); 95Mo (15,7%); 96Mo (16,5%); 97Mo (9,45%); 98 Mo(27,75%); 100Mo(9,62%). Trong cc ng v phng x th 93Mo bn nht vi chu k bn hy ln hn 2 nm; cn ng v km bn nht l 91Mo c chu k bn hy l 66 giy. Vonfram c nm ng v thin nhin l 180W(0,135%); 182W(26,4%); 183 W(14,4%); 184W(30,6%); 186(8,4%). ng v phng x bn nht l 181W vi chu k bn hy l 145 ngy m. 9.3. iu ch Cr, Mo, W Trong thc t, thng c luyn thnh cc hp kim vi st c giu cc kim loi , nh hp kim ferocrom (cha 30-60% crom); hp kim feromolipen (cha 50-75% Mo) v hp kim ferovonfram (cha 50 - 80% W). iu ch hp kim cacbon - ferocrom ngi ta dng cacbon kh trc tip qung cromit trong l in hoc l Xi men Mactanh (Siemens Martin): iu ch kim loi tinh khit, th nguyn tc chung l chuyn cc loi qung trn thnh oxit, sau dng Al hoc hiro kh nhit cao. iu ch crom tinh khit ngi ta nung nng chy qung cromit st - (sau khi lm giu) - vi NaOH hoc K2CO3 v oxi ha bng oxi chuyn Cr(III) thnh CrO42- 1000 - 1300oC:
Ha tan hn hp trong nc ri axit ha to ra bicromat, sau dng cacbon kh natri bicromat to thnh Cr2O3:
oxit to thnh c kh n crom bng phng php nhit nhm; H2 khng kh c Cr2O3 : Qung molipenit sau khi lm giu c khong trn 70% MoS2. chuyn thnh oxit MoO3 ngi ta t chy qung theo phng trnh : hoc nung qung vi xoa trong l la to ra natri molipat : chuyn ha natri molipat thnh axit H2MoO4 khng tan, sau nung kt ta H2MoO4 to thnh MoO3 :
sau kh MoO3 bng hiro hoc bng than: T qung vonframit FeWO4 ngi ta cng iu ch c vonfram bng cch nung qung vi xoa sau cho tc dng vi HCl to ra axit vonframic mu vng :
sau khi nung kt ta, kh WO3 bng hiro hoc bng than : Qu trnh thot ra mt nhit lng rt ln, lm cho vonfram nng chy, sn phm thu c dng bt. 9.4. Tnh cht l hc ca Cr, Mo, W v ng dng (1) trng thi n cht, crom, molipen, vonfram u l nhng kim loi mu trng bc. Mt s hng s l hc ca Cr, Mo, W c trnh by trong bng 39. C ba kim loi u c khi lng ring rt ln, rt kh nng chy v kh bay hi. Dn in km trong crom dn in km nht ch bng 10% dn in ca Au v 6,8% dn in ca bc. Cc kim loi Cr, Mo, W v cc hp cht ca chng u c c bit cc hp cht c bc oxi ha cao nh cromat, icromat, trioxit ca molipen v cc
molipat, cc dung dch vonframat. (2) C ba kim loi u c kh nng to thnh hp kim c bit vi st to ra cc loi thp c bit. Bng 39. Mt s hng s l hc quan trng ca Cr. Mo. W Cr Mo W 3 7,2 10,2 19,3 Khi lng ring (g/cm ) 1875 2620 3380 Nhit nng chy (Tnc,oC) o 2430 4800 6000 Nhit Si ( Ts, C ) dn in (so vi Hg = 1) 4 20 18 m in 1,6 1,8 1,7 Crom c dng m cc dng c bng kim loi cn c sc chu ng tt, thng dng phng php in phn vi lp m c chiu dy khong 0,5 mm. Thp crom ch to bng cch cho hp kim ferocrom vo thp; loi thp ny cng hn v do hn so thp thng, dng ch to cc dng c quay nhanh; thp khng g (stainless - steel) cha 12% crom v 0,7% niken. Thp crom niken (nichrome) cha 6% ni ken, 25% st v 15% crom c nhit nng chy cao, dn in cao, khng b oxi ha bi khng kh, c dng trong cng nghip in. Molipen kim loi c dng trong k thut in chn khng, ch to chn bng n in. Vonfram c nhit nng chy cao nn c dng lm dy tc bng n in; dng ch to hp kim rt cng sn xut cc loi dng c ct gt, khoan. v.v.. 9.5. Tnh cht ha hc ca Cr, Mo, W Hot tnh ha hc ca cc kim loi nhm ny gim t crom n vonfram, do kh nng phn ng vi cc cht gim dn. (1) C ba kim loi u khng phn ng trc tip vi H2, nhng to ra dung dch rn cc nhit khc nhau. (2) iu kin thng khng phn ng vi oxi, nhng khi t trong khng kh th crom to ra Cr2O3; molipen v vonfram to ra MoO3 v WO3. Khi nung hn hp gm bt crom vi bt lu hunh trong ampun thu cc sunfua c thnh phn khc nhau nh CrS, Cr2S3, Cr3S4, Cr5S6, Cr7S8. Cng tng t, khi nung Mo v W vi S sn phm to ra l Mo, MOS3 v WS2, WS3. Vi Selen v telu cng c phn ng trc tip. Sn phm ca phn ng tng hp t cc nguyn t c thnh phn ng vi cc bc oxi ha khc nhau ca
ba kim loi : Vi Cr to ra CrSe, Cr2Se3, CrSe4, CrTe. Vi Mo to ra MoSe, MO2Se3, MoSe2, MoSe3, Mo2Te3, MoTe3. Vi W to ra WSe2, WSe3, WTe2. Tt c cc hp cht trn - tr hp cht ca crom - u bn trong dung dch axit long v axit khng c tnh oxi ha nhit trong phng. (3) Vi cc halogen, phn ng xy ra c mc khc nhau ph thuc vo hot tnh ca cc kim loi v cc halogen; c ba kim loi u phn ng trc tip vi flo ngay c khi ngui; vi clo phi un nng; molipen khng phn ng vi iot; cn vonfram khng phn ng vi c brom v iot. (4) Khi nung bt crom trong kh quyn nit to ra Cr2N 900oC v CrN 1200oC. Vonfram tc dng vi ng khi nung 2800oC to ra WN3. Photpho cng phn ng trc tip vi ba kim loi khi nung trong chn khng, trong ampun bng thch anh to ra cc hp cht nh CrP, MoP, WP; Cr3P, Mo3P; CrP2, MoP2, WP2... (5) Phn ng trc tip vi cacbon to ra Cr2C3; Mo2C, W2C; MoC, WC khi nung cc kim loi vi cacbon nhit cao; vi silic to ra CrSi, Cr3Si, CrSi2; Mo3Si, MoSi2; W3Si, WSi3... cng nhit cao. (6) V trn b mt c lp oxit c hot tnh ha hc km rt mng v bn vng che ch cho kim loi, nn nhit thng, crom rt bn v mt ha hc. Khi nung n nhit nng , crom kh c H2O to ra hiro : Mo v W cng c kh nng . Crom ha tan trong HCl v H2SO4 long nng to mui Cr(II) mu xanh lam, sau mui Cr(II) b oxi ca khng kh oxi ha to ra mui crom(III) mu xanh l cy :
H2SO4 c ha tan crom to ra mui Cr(III) v SO2 : HNO3 c hoc long v nc cng thy - khi ngui - khng tc dng vi crom, khi un nng tc dng yu, khi un si phn ng xy ra mnh to ra mui crom (III) :
Nguyn nhn gy ra tnh bn ca crom trong cc loi axit trn l do to ra lp oxit bo v b mt kim loi nn gy ra " tnh th ng " ca crom. Tc dng vi dung dch mui ca nhng kim loi c th tiu chun cao hn to thnh mui Cr(II) : (7) iu kin thng, molipen khng phn ng vi axit long, nhng khi un nng li tan dn : Molipen cng b " th ng ha" bi HNO3; cng tan trong H2SO4 c v si, tan mnh trong nc cng thy v trong hn hp gm HF v HNO3. Molipen khng tan trong dung dch kim nhng phn ng rt chm vi kim nng chy khi c mt ca cht oxi ha : (8) Vonfram rt bn i vi axit, do tnh th ng ca W, ngay c HNO3 c hoc nc cng thy cng ch phn ng c trn b mt. Tan chm trong hn hp gm axit HF v HNO3. Vonfram phn ng mnh vi NaNO3 trong NaOH nng chy :
9.6. Cc hp cht vi s oxi ha +2 Nh nu 9.1, crom - molipen - vonfram c cc bc oxi ha t 1 n 6, trong crom to ra nhng hp cht bn v c nhiu ng dng thc t l cc dn xut Cr(III) v Cr(VI); cn vi Mo v W l cc dn xut ca Mo(VI) v W(VI). Ngi ta ch bit c mt s t cc hp cht ng vi bc oxi ha +2 nh CrO mu en; Cr(OH)2 mu vng; CrS mu en, CrCl2 mu trng... (1) Trong dung dch, ion Cr2+ c mu xanh nht. Cc hp cht ca Cr(II) u c tnh kh, d b oxi ha thnh Cr(II), do u l tc nhn kh tt. Ion Cr2+ c tnh kh mnh n mc c th kh c ion H+ theo phng trnh : Trong dung dch ion Cr2+ dng [ Cr(H2O)6]2+ vi cu trc tm mt.
(2) Crom(II) oxit (CrO) c iu ch bng cch phi hn hng crom trong khng kh, nhng khng th thu c khi nung crom (II) hiroxit Cr(OH)2. Hiroxit ny to ra khi cho mui Cr(II) tc dng vi dung dch kim trong iu kin khng c khng kh :
trong khng kh dn dn chuyn thnh Cr(OH)3 mu xanh ru : Khi un nng CrO vi lng oxi d to thnh Cr2O3, cn khi nung Cr(OH)2 to ra Cr2O3 v H2 : CrO v Cr(OH)2 u tan trong axit khng c tnh oxi ha to thnh mui Cr(II); khng tan trong kim, chng t ch c tnh baz. (3) Crom(II) clorua ( CrCl2) khan c iu ch bng cch un nng crom trong kh quyn hiro clorua : hoc nung CrCl3 trong lung kh hiro 600oC : CrCl2 dung dch c iu ch bng CrCl3 bng hiro mi sinh (hn hp gm Zn + HCl). Khi cho dung dch CrCl2 c tc dng vi natri axetat to ra kt ta Cr(II) axetat : CrCl2 d b oxi ca khng kh oxi ha, nn ngi ta thng dng dung dch CrCl2 trong HCl hp th oxi : Khi khng c mt cht oxi ha, CrCl2 b H2O phn hy : CrCl2 khan l cht kt tinh mu trng, Tnc = 824oC, rt ht m v tan trong nc thnh dung dch mu xanh da tri. T dung dch, CrCl2 c th tch ra dng hirat kt tinh CrCl2.4H2O mu xanh c cu hnh tm mt, trong bao quanh Cr(II) l 4 phn t H2O v 2 nguyn t clo :
Ngi ta cng iu ch c CrF2 mu xanh ( Tnc = 1100oC); CrBr2 mu vng nht ( Tnc = 842oC); CrI2 mu ( Tnc = 195oC ), bng phng php kh (t crom trong kh hiro halogenua ). Tr CrF2 t tan, cn li u d tan trong nc. (4) Crom(II) sunfat ( CrSO4 ) c iu ch bng cch ha tan crom hoc Cr(II) axetat trong H2SO4 long trong iu kin khng c khng kh : To ra hai dng hirat ha CrSO4.4H2O v CrSO4.7H2O ng hnh vi FeSO4.7H2O. Trong tinh th CrSO4.4H2O th nhm (SO4) ng vai tr cu ni gia 2 nguyn t Cr(II); cn trong tinh th CrSO47H2O th c mt phn t H2O ng vai tr cu ni do to ra lin kt hiro :
Khi kt tinh vi sunfat ca kim loi kim, CrSO4 cng c kh nng to ra dng mui kp K2SO4.CrSO4.6H2O. V c tnh kh, nn dung dch CrSO4 trong H2SO4 long cng dng hp th oxi, theo phng trnh tng qut : hay (5) Ngi ta bit c kh t cc hp cht ca Mo(II) v W(II). Molipen (II) clorua (MoCl2) l cht bt mu vng khng tan trong H2O nhng tan trong ru v ete; cng thc phn t l Mo3Cl6. Khi un nng trong lung kh H2, n b kh n molipen kim loi. Vonfram (II) clorua (WCl2) dng bt mu xm, khng bn trong khng kh. c iu ch bng cch dng hiro kh WCl6 ( nu nhit cao c th kh n kim loi) : cng c iu ch bng cch nhit phn WCl4 trong lung kh CO2 kh. WCl2
l cht kh mnh, khi tc dng vi H2O gii phng kh H2 : Vonfram bromua (WBr2), cng c tnh cht tng t. Vonfram iotua, WI2, cht rn mu nu, thu c khi cho hi I2 tc dng vi W di tc dng ca nh sng. Khng tan trong nc lnh, tan trong nc nng v b phn hy. 9.7. Hp cht vi s oxi ha +3 Nh nu nhn xt trn, cc hp cht ca Cr(III) c nhiu gi tr thc t. Trong cc hp cht Cr(III) c s phi tr l 6, ng vi dng lai ha d2sp3 :
(1) Crom(III) oxit ( Cr2O3 ) l Cht bt mu xanh thm, cn trng thi tinh th c mu en v c nh kim. Cr2O3 l Cht rt kh nng chy (Tnc=265oC). Cr2O3 c cu trc ion dng corinon ( - Al2O3). Cr2O3 c iu ch bng nhiu cch khc nhau. + t bt crom trong khng kh, crom chy theo phng trnh : + Nung ( NH4)2Cr2O7 ( hay hn hp K2Cr2O7 + NH4Cl ): + Dng than g hoc lu hunh kh K2Cr2O7 nhit cao:
Cr2O3 khng tan trong nc, tan rt chm trong axit to thnh mui Cr(III), v khi nung vi kim trong khng kh hoc vi cht oxi ha khc nh KNO3 to ra cromat :
hay Ngi ta c th chuyn Cr2O3 khng tan thnh mt cht d tan hn bng cch nung vi kali isunfat to ra Cr2(SO4)3 d tan hn : Cr2O3 cng c th thnh cht tan c trong nc bng cch nu nng
chy vi Na2CO3 v NaNO3 to ra natri cromat : Ngoi ra, natri peoxit, kali pemanganat, ch(IV) oxit, bt ty... u c th oxi ha Cr2O3 thnh cromat. (2) Crom hiroxit (Cr(OH)3) l kt ta keo mu xanh nht, to ra khi cho dung dch kim tc dng vi dung dch mui Cr(III). Thc cht ca kt ta keo l dng hirat ha Cr2O3.xH2O.Cr(OH)3 l mt polime a nhn trong nhm OH v H2O ng vai tr phi t v ng vai tr cu ni l nhm -OH. Thnh phn v cu trc ph thuc vo iu kin iu ch, v d c cu trc lp nh sau :
Khi x = 3 Cr2O3.3H2O tc l dng Cr(OH)3 Kt ta thu c khng tan trong nc (Tt = 1.10-32) nhng d tan trong axit v kim, lc c xy ra s ct t lin kt gia cc lp,v d :
Qu trnh to ra cation v anion phc c th tm tt nh sau :
Cr(OH)3 cng b oxi ha to ra cromat mu vng khi cho tc dng vi Na2O2, Br2 trong dung dch kim, bt ty, nc Javen, PbO2...
(3) Crom(III) clorua (CrCl3) dng khan c iu ch bng cch cho kh Cl2 qua crom nung nng : hoc cho kh clo qua hn hp gm Cr2O3 v Cacbon nung nng : Dng hirat ha CrCl3.6H2O c iu ch bng cch cho Cr(OH)3 tan trong dung dch HCl, sau cho kt ta t dung dch nc. Ph thuc vo cc nhit , nng v pH ca dung dch m thnh phn ca cation phc aquo thay i, do mu sc ca CrcC3.H2O s thay i t tm n xanh. V d :
CrCl3 khan c cu trc ca polime, c mu tm , khc vi mu ca dng hirat ha nu trn. S khc nhau v cu trc gy ra s khc nhau v tnh cht, v d CrCl3 khan khng tan trong nc, cn CrCl3.6H2O li d tan trong nc. Trong dung dch, c ba dng hirat ha u dn dn bin thnh hn hp dng mu xanh thm v dng xanh tm. Bc chuyn ko di t 10 - 40 ngy ph thuc vo iu kin bn ngoi, v d 25oC sau 15 ngy trong dung dch c cha khong 42% dng xanh tm v 58% dng xanh thm. Khi nung nhit cao trong lung kh clo, CrCl3 thng hoa nhng khng c clo th phn hy : Khi nung trong khng kh chuyn thnh oxit : v khi tc dng vi hp cht cha hiro th clo trong phn t c thay th :
(4) Crom (III) sunfat (Cr2(SO4)3) c iu ch bng cch khuy bt nho Cr(OH)3 trong H2SO4 c. Tinh th thu c c mu tm Cr2(SO4)3.18H2O hoc Cr2(SO4)3.6H2O c mu lc. Khi ng kt tinh vi mt mui sunfat ca kim loi ha tr 1 (Na+, K+, NH4+, Rb+, Cs+, Tl+) tch ra tinh th phn crom mu tm thm c thnh phn [M2SO4.Cr2(SO4)3.24H2O] trong phn kali d tan trong nc v c nhiu ng dng thc t nh dng trong cng nghip dt, cng nghip thuc da. Phn crom - kali l nhng tinh th hnh tm mt, mu tm thm, khi cho nh sng truyn qua c mu ta. Phn crom - kali c iu ch bng cch kh K2Cr2O7 trong dung dch c axit ha bng H2SO4. Tc nhn kh tt nht l SO2 hoc C2H5OH; phn ng xy ra theo phng trnh :
ngoi khng kh, phn b ln hoa, ph mt mng mng mu tm. Khi un nng n 100oC, phn c mu xanh lc do mt mt phn H2O kt tinh. Nc kt tinh mt hon ton 350oC, v khi nung qu 350oC mui c mu vng lc khng cn c kh nng ha tan c na. Bng phng php phn tch tia X cho thy rng cu trc ca phn gm I [M (OH2)6][Cr(OH2)6].(SO4)2. Nh vy phn l mt mui kp. (5) Crom(III) nitrat (Cr(NO3)3) c iu ch bng cch ha tan Cr(OH)3 trong axit nitric. Dung dch trong nh sng phn chiu c mu tm xanh da tri, cn trong nh sng i qua li c mu . Khi un nng, c mu xanh lc, ngui tr li mu tm ban u. Khi kt tinh t dung dch nc, hm lng nc kt tinh thay i ph thuc vo iu kin iu ch. Cr(NO3)3 c dng lm cht cm mu trong k thut in hoa vo vi. (6) Crom(III) sunfua (Cr2S3) l cht rn mu en, khng tan trong nc v b nc phn hy chm. Tng t nh nhm sunfua, Cr2S3 khng th to ra khi cho dung dch mui Cr(III) tc dng vi mt sunfua tan m to ra hiroxit do qu trnh thu
phn : iu ch Cr2S3 c th bng cch nung hn hp bt crom vi bt lu hunh trong ng kn : hoc bng cch cho hi H2S qua CrCl3 nung : Cr2S3 b thy phn to ra Cr(OH)3: Cng tng t, khng th iu ch Cr(III) cacbonat bng cch cho xoa tc dng vi dung dch mui Cr(III) :
(7) Crom (III) xianua (Cr(CN)3) to ra khi cho dung dch mui Cr(III) tc dng vi dung dch xianua ca kim loi kim. Kt ta Cr(CN)3 tan trong axit v tan trong dung dch xianua d to ra M3I[Cr(CN)6] :
K3[Cr(CN)6] l cht mu vng ti, ng hnh vi K3[Fe(CN)6] mu mu. (8) Trng thi ha tr +3 ca Mo v W t c bit n, ngi ta bit mt s hp cht nh Mo2O3 mu en, Mo2S3 mu xm; MoCl3 mu thm; cng tch c cc mui kp nh 2WCl3, 3KCl... 9.8. Cc hp cht vi s oxi ha +6 Trong dy cc hp cht ca Cr(VI) - Mo(VI) - W(VI) bn tng dn. (1) Crom(VI)oxit (CrO3) mu thm, c iu ch bng cch cho axit H2SO4 c tc dng vi dung dch bo ha kali icromat hoc kali cromat : CrO3 tch ra dng tinh th hnh kim (Tnc = 196oC). CrO3 l mt anhirit axit in hnh, ht m mnh v d tan trong nc to ra axit cromic : CrO3 rt c v l cht oxi ha mnh. Khi nung nng n 196oC to ra cht lng mu thm; n 250oC to ra crom(IV) ioxit v cui cng 420oC to ra crom(III) oxit:
Anhirit cromic oxi ha c rt nhiu cht gy ra hin tng n, phn ng mnh vi nhiu cht hu c, chng hn ru, giy u b bc chy khi tc dng vi CrO3. Tuy nhin, CrO3 li tan trong axit axetic m khng gy ra hin tng g. (2) C ba oxit u l nhng cht kt tinh c mu khc nhau : MoO3 - mu xanh (Tnc = 791oC); WO3 - mu vng (Tnc = 1473oC). Tinh th MoO3 v WO3 c cu trc hnh tm mt; cn CrO3 c cu trc hnh bn mt :
Hnh 61. Cu trc tinh th tm mt ca MoO3 v WO3 : - Mo hay W; O - oxi.
Hnh 62. Cu trc tinh th bn mt ca CrO3 : - crom : O - oxi.
Khi un nng, MoO3 v WO3 thng hoa khng b phn hy, chng t bn t CrO3 - MoO3 - WO3 tng ln. Khc vi CrO3, MoO3 v WO3 khng tan trong nc nn khng to thnh axit nh CrO3. Tnh axit ca MoO3 v WO3 th hin khi tan trong kim to thnh mui molipat v vonframat :
(3) Axit cromic( H2CrO4) v mui cromat ( CrO42-). Khi ha tan CrO3 vo nc to ra axit cromic l mt axit trung bnh, ch tn ti trong dung dch, khng tch c trng thi t do; trong dung dch nc tn ti cn bng :
Nh vy trong dung dch tn ti c hai dng ion CrO42- v Cr2O72- : Nhng cromat tan quan trng l kali cromat K2CrO4 v natri cromat Na2CrO4.10H2O. Nhng Cromat khng tan quan trng l ch(II) cromat PbCrO4; bc cromat Ag2CrO4; v bari cromat BaCrO4. Kali cromat (K2CrO4): l nhng tinh th t phng, mu vng, bn ngoi khng kh; Tnc = 968oC. Tan trong nc cho dung dch mu vng m, c phn ng trung ha vi qu. Khi cho thm axit, dung dch c mu vng da cam do phn ng : Khi un nng n 670oC, K2CrO4 chuyn thnh mu , ngui tr li mu vng ng hnh vi K2SO4. Ngi ta iu ch K2CrO4 bng cch cho Na2CO3 hoc KOH tc dng vi dung dch K2Cr2O7 :
Natri cromat (Na2CrO4) c iu ch bng cch cho natri icromat tc dng vi Na2CO3 : Trong cng nghip iu ch bng cch nung hn hp gm Fe(II) cromit vi Na2CO3 trong khng kh : Khi kt tinh t dung dch nc, to ra tinh th ngm nc. S phn t H2O kt tinh ph thuc vo nhit . 19,5oC to ra tinh th Na2CrO4.10H2O; khong 19,5-25,9oC l Na2CrO4.6H2O; khong 25,9-62,8oC to ra Na2CrO4.4H2O. Khi kt tinh trn 62,8oC to ra mui khan. Tt c cc dng tinh th u c mu vng. Mui khan c Tnc = 792oC. Amoni cromat ((NH4)2CrO4) l nhng tinh th hnh kim vng nh, d tan trong nc. ngoi khng kh hay phi kh b mt mt phn amoniac v bin thnh (NH4)2Cr2O7. (NH4)2CrO4 khi un nhanh, b phn hy v bc chy : Dng tinh khit c iu ch bng cch cho dung dch (NH4)2Cr2O7 tc dng vi dung dch amoniac sau cho kt tinh +5oC : Bc cromat ( Ag2CrO4 ) l cht bt v nh hnh mu t tan trong nc, Tt = 1,110-12; nhng li tan c trong axit nitric v trong dung dch amoniac :
Dng tinh khit c iu ch bng cch cho dung dch AgNO3 tc dng vi K2CrO4 : Ch cromat (PbCrO4) khi mi kt ta l cht bt mu vng chanh; tinh th , trong sut hay nu thm. Tnc = 844oC, khng tan trong nc, tan trong dung dch HNO3 v dung dch kim (Tt = 8,3.10-12). Dng tinh khit c iu ch bng cch cho ch axetat tc dng vi dung dch Na2Cr2O7 : PbCrO4 tan trong dung dch kim l do to ra hp cht hiroxoplombit: Nhng nu lng kim t li to ra cht kh tan l ch(III) cromat baz PbCrO4.Pb(OH)2 : Nu lng cromat Pb(II) nhiu hn th to ra hp cht mu thm PbCrO4.PbO : Bari cromat (BaCrO4) l cht bt mu vng, khng tan trong nc, Tt = 1,2.10-10. Dng tinh khit c iu ch bng cch cho dung dch K2Cr2O7 tc dng vi hn hp gm natri axetat v BaCl2 : (4) 'Theo trt t H2CrO4.H2MoO4.H2WO4 tnh bn tng, trong khi H2CrO4 ch bit c trong dung dch, th H2MoO4 v H2WO4 l nhng cht bt mu trng (H2MoO4 ) hoc mu vng (H2WO4) hu nh khng tan trong nc. Khi un nng c hai axit ny u mt H2O, v d: Cng theo trt t H2CrO4.H2MoO4. H2WO4 th mnh ca axit gim dn, tnh baz tng dn. Chng hn H2MoO4 v H2WO4 cng tc dng vi axit: Hng s ion ha ca H2CrO4: K1 = 1,8.10-1; ca H2MoO4 : K1 = 1,2.10-2. Mui cromat, molipat v vonframat ca cc kim loi kim v ca magie u d tan.
(5) Axit icromic (H2Cr2O7) v mui icromat ( Cr2O72-) Axit icromic ch bit c trong dung dch c cu to tng t H2SO7. Trong cc mui ca axit H2Cr2O7 th c bit l mui K2Cr2O7 v Na2Cr2O7.2H2O l nhng mui quan trng, thng lm cht u iu ch cc hp cht khc ca nguyn t . Kali icromat (K2Cr2O7) c iu ch bng cch cho KCl tc dng vi dung dch c Na2Cr2O7 : ( tan ca Na2Cr2O7.2H2O l 180g/100 g H2O 20oC). Lm bay hi dung dch thu c tinh th khan mu da cam. K2Cr2O7 tan trong nc; un si dung dch c mu thm; nng chy 395oC. Khi nung K2CrO7 nhit nng trng phn hy theo cc giai on:
cui cng l: Amoni icromat ((NH4)2Cr2O7) c iu ch bng cch cho dung dch amoniac tc dng vi dung dch CrO3. (NH4)2Cr2O7 l cht rn kt tinh mu da cam, tan nhiu trong nc t bc chy 168oC to thnh Cr2O3: Bc icromat (Ag2Cr2O7) c iu ch bng cch un si dung dch K2Cr2O7 v HNO3 sau cho tc dng vi dung dch nng AgNO3: ngui, tinh th mu tch ra. Khi un si vi H2O to thnh Ag2CrO4, ngui li tr li tinh th Ag2Cr2O7 ban u. N t tan trong nc Tt = 2.10-7, 25oC tan nhiu trong HNO3. (6) Cc hp cht cromat u c tnh oxi ha mnh. Khi tc dng vi cht kh ty theo mi trng m to ra sn phm khc nhau, t Cr(VI) chuyn thnh Cr(III). Trong mi trng trung tnh to ra Cr(OH)3: Trong mi trng axit to ra ion [Cr(OH2)6]3+: Trong mi trng kim to ra aon phc [Cr(OH)6]3-:
Tnh oxi ha ca icromat th hin mnh trong mi trng axit. Trong mi trng axit, cc mui icromat oxi ha c Fe2+ Fe3+; I- I2; SO32SO42-..v.v... Tnh oxi ha ca cc hp cht Mo(VI), W(VI) ch th hin khi tc dng vi cht kh mnh. (7) Ion icromat c cu to nh hnh 63.
n = 131o CrOCr
dO-O(a) = 1,78 ; dCr-O(b) = 1,61. Nh nu trn, trong dung dch, v tr ca cn bng: s chuyn dch ph thuc vo pH ca dung dch: + pH > 6 trong dung dch tn ti ion CrO42-. + 2 pH 6 ion HCrO4- v ion Cr2O72 - nm cn bng vi nhau. + pH < 1 ch yu tn ti cc phn t H2CrO4 (hng s axit ca H2CrO4: K1 = 1,8. 10-1; K2 = 3,2. 10-7; ca H2Cr2O7: K2 = 2,3.10-2). Ch c axit HNO3 v HClO4 mi lm thay i cn bng. Nu s dng HCl s to thnh clorocromat: cn trong H2SO4 s to ra phc cht sunfat: Cn bng trn cng thay i khi cho thm cc cation c kh nng to ra cromat khng tan nh ion Ag+, Pb+, Ba2+, th s kt ta cromat m khng phi l icromat. Vi Cr(VI) c kh nng to ra mt dy hp cht gi chung l policromat c cng thc tng qut K2[CrO4(CrO3)n-1], V d K2Cr2O7 - icromat; K2Cr3O10 tricromat; K2Cr4O13 - tetracromat. (8) CroMyl clorua (CrO2Cl2) l mt trong nhng hp cht c trng ca Cr(VI). L cht lng mu to ra khi cho CrO3 kh tc dng vi kh HCl: hoc khi un nng icromat vi hn hp gm mui clorua kim loi kim trong H2SO4 c: Cromyl clorua c Tnc = -95,6oC v Ts = 117oC, l cht oxi ha mnh lit
cc hp cht hu c. CrO2Cl2 b thy phn to ra CrO42-: Vi MoO2Cl2 (molipenyl clorua) v WO2Cl2 (Vonframyl clorua) cng b thy phn nh trn, nhng cn bng chuyn dch v pha tri. C ba kim loi cng to ra hp cht tng t vi flo v brom. (9) Cc hp cht ca Cr(VI) c tnh cht tng t nh S(VI). CrO3 c cu to tng t SO3 v u c tnh oxi ha, u phn ng vi H2O to ra axit tng ng. Cc mui cromat kt tinh ng hnh vi mui sunfat: Na2CrO4 . 10H2O Na2SO4 . 10H2O tan K2CrO4 K2SO4 tan PbCrO4 PbSO4 khng tan BaCrO4 BaSO4 khng tan
Cc axit icromic v axit isunfuric c cu to tng t v u to ra mui tng ng:
Crom v S u to ra ion policromat v ion polisunfat tng ng:
Crom to ra cromyl clorua v lu hunh to ra sunfuryl clorua c tnh cht tng t nhau.
CHNG 10 CC NGUYN T NHM VII B (MANGAN - TECNEXI - RENI)
10.1. Nhn xt chung v cc nguyn t nhm VIIB (1) Ba nguyn t Mn(Manganum), Tc(Technecium), Re(Rhenium) thuc h d cc chu k 4; 5; 6 thuc bng tun hon. Mangan c Sil (K.Scheele) tm ra nm 1774. L nguyn t nhn to, Tecnexi c tng hp vo nm 1937 do cc nh khoa hc Italia l Prie (C. Penier) v Sgr (E.Segr) khi chiu chm teri vo bn molipen. Reni c pht hin vo nm 1925 lin quan n tn tui ca cc nh bc hc c l W. Noddak, I. Noddak v O. Berg. Nguyn t khi, s th t nguyn t, s phn b electron v trng thi ha tr ca ba nguyn t nh sau:
Nguyn t Mangan Tecnexi Reni K S Nguyn t hiu TT khi Mn Tc Re 25 43 75 54,938 [99] 186,210 2 2 2 Phn b electron 8 8 8 13 18 18 2 13 32 Ho tr I, II, III, IV, V, VI, VII IV, VI, VI 2 I, II, III, IV, V, VI, VII
2 13
(2) C ba nguyn t c s electron phn b hai lp ngoi cng l: (n - 1)d5ns2
Mn, Tc, Re l nhng nguyn t a ha tr, gy ra bi cc electron hai lp ngoi cng. Bc oxi ha c trng ca mangan l +2, +4 v +7, ngoi ra cn to ra nhng hp cht ng vi bc oxi ha +3, +4 v +6. Bc oxi ha c trng ca tecnexi v reni l +7. Khi theo chiu tng ca bc oxi ha, khuynh hng to ra anion phc tng ln, cn khuynh hng to ra cation phc gim xung. (3) Tng t cc halogen - c bit l vi clo - mangan v reni to ra hp cht Mn2O7 v Re2O7 c tnh cht tng t Cl2O7; cc mui pemanganat (MnO4-), renat (ReO4) ng hnh vi mui peclorat (ClO4-); c hai axit pemanganic (HMnO4) v axit pecloric(HClO4) u l axit n chc v u c tnh oxi ha mnh. Trong s cc hp cht ca mangan, c mt s ging vi hp cht ca
crom v ca st. Mangan v crom to ra oxit thp (tnh baz) v trioxit (tnh axit). Mui cromat (CrO42- ) ng hnh vi mui manganat (MnO42-). Mangan cng to nn phn tng t nh phn st K2SO4.Mn2(SO4)3.24H2O; hoc dng mui kp nh (NH4)2SO4. MnSO4.6H2O tng t mui kp ca st (II). Ngoi ra mangan cng to ra cc oxit MnO, Mn2O3.Mn3O4( MnO.Mn2O3) tng t cc oxit ca st. (4) Bng 40 l mt s c im ca ba nguyn t Mn, Tc, Re. Bng 40. Mt s c im ca Mn, Tc, Re
Electron ha tr Bn knh nguyn t () Bn knh ion M2+ () Bn knh ion M3+ () Bn knh ion M4+ () Bn knh ion M7+ () Th ion ha l1 (eV) Mn 3d54s2 1,30 0,91 0,70 0,52 0,46 7,43 Tc 4d55s2 1,36 0,95 0,72 0,57 7,23 Re 5d56s2 1,37 0,72 0,57 7,87
Bn knh nguyn t tng t Mn n Re, nhng khng ng k, c bit khi chuyn t Tc n Re; do Tc v Re c tnh cht gn nhau hn so vi Mn. (5) Di y l s th in cc ca mangan v reni: Trong mi trng axit:
Trong mi trng kim:
(6) V mt cu to, cc dng th hnh ca mangan u kt tinh theo kiu lp phng; cn reni kt tinh theo kiu lc phng. V d dng hnh th - Mn tn ti 1070 - 1130oC c dng cu trc mng lp phng tm din c cnh = 3,862 , theo dng cu trc ca Cu. Cn dng th hnh - Mn theo dng - Fe, ngha l kt tinh theo kiu lp phng tm khi c cnh = 3,081. 10.2. Trng thi thin nhin v thnh phn cc ng v (1) Khong vt ch yu ca mangan l pirolusit (MnO2); ngoi ra mt s khong vt khc c cha mangan nh bronit (Mn2O3); manganit Mn2O3.H2O; v cc sunfua nh MnS; MnS). Tecnexi l nguyn t nhn to. Lng reni trong v qu t c rt t. Qung giu reni nht l cc molipenit cng ch cha khong 2.10-3 % v khi lng. (2) Trong c th ngi, mangan c khong 4. 10-4 % cha trong tim, gan v tuyn thng thn, nh hng n s trng thnh ca c th v s to mu. Trong nc i dng c cha rt t mangan, nhng y su ca i dng c mt lng rt ln mangan. (3) Hm lng cc kim loi trn Mt Trng do cc tu v tr Apollo v tu Luna thu thp c c gi tr sau: Hm lng trung bnh ( s gam / 1 g mu ) Nguyn t Mn Tc Re Apollo -11 1.9.10-3 -0,01.10-6 Apollo - 12 1.9.10-3 Luna - 6 -
(4) Mangan c nhiu ng v t 49Mn n 57Mn, trong ch c 55Mn l ng v thin nhin chim 100%. ng v phng x bn nht l 53Mn c chu k
bn hy l 140 nm v km bn nht l 49Mn c chu k bn hy l 0,4 giy. Tecnexi l nguyn t nhn to, cc ng v u c tnh phng x 1 trong s ng v 99Tc bn nht c chu k bn hy l 2,12.105 nm. Reni c 14 ng v.Cc ng v thin nhin l 185Re (37,07%); 187Re (62,93%); cn li l cc ng v phng x. 10.3. iu ch Mn, Tc, Re (1) Mangan c iu ch bng phng php nhit nhm t cc oxit MnO hoc Mn3O4: Cng c th iu ch bng phng php nhit silic: Trong cng nghip mangan c iu ch bng cch dng cacbon kh oxit mangan trong l in. Cng c iu ch bng phng php in phn dung dch mui sunfat. Mangan tinh khit c iu ch bng cch in phn dung dch MnCl2 vi catot bng thy ngn. Mangan ha tan trong thy ngn to ra hn hng Mn Hg. Chng ct hn hng trong chn khng, tch c Mn v thu hi li Hg. (2) Ngi ta iu ch mt lng nh tecnexi (vi mg) trong l phn ng ht nhn khi bn ph oxit molipen bng ntron
Cng iu ch trong l phn ng ht nhn khi phn hch urani. (3) Ngi ta iu ch reni bng cch dng H2 kh amoni renat nhit cao:
10.4. Tnh cht l hc ca Mn, Tc, Re v ng dng (1) Ty theo phng php iu ch, mangan to ra bn dng th hnh. Mangan iu ch bng phng php nhit nhm, tn ti hai dng Mn v - Mn. Dng - Mn tn ti nhit thng c khi lng ring l 7,21g/cm3. Dng - Mn tn ti nhit cao (742 - 1070oC) c khi lng ring l 7,29 g/cm3. Nu mangan c kt ta bng phng php in phn, mangan tn ti
dng - Mn, bn trong khong 1070 - 1130oC; c khi lng ring l 7,21g/ cm3. Dng th hnh tn ti nhit cao hn 1130oC l dng - Mn: - Mn - Mn - Mn - Mn o o o Tn ti: ( t thng ) ( 1070 C) ( 1130 C) (> 1130oC) Cc dng - Mn v - Mn u cng v gin; dng - Mn th mm v do. Mn v Re c mu trng bc, cn Tc c mu xm. Mt s hng s l hc ca Mn, Tc, Re nu ra bng 41. Bng 41. Mt s hng s l hc quan trng ca Mn, Tc, Re Tnh cht Mn Tc Re Khi lng ring (g/cm3) Nhit nng chy (Tnc, oC) Nhit si (Ts, oC) m in 7,4 1244 2120 1,5 11,5 2700 4900 1,9 21 3180 5670 1,9
(2) Mt lng kh ln mangan c dng iu ch hp kim fero mangan (60% - 90% Mn v 40% -10% Fe) khi kh hn hp st v qung mangan. Loi hp kim ny rt bn v cng, thng dng lm bi, cc b phn my nghin, lm ng ray xe la. Ngi ta cng dng hp kim ca mangan iu ch trc tip gang trng trong l cao. Hp kim bronz - mangan (95%Cu v 5% Mn) c bn c hc cao. Reni c dng trong cng nghip in v c dn in cao (ln hn Hg 4,5 ln v thp hn vonfram ) l nguyn liu rt tt lm dy tc bng n in, bn hn vonfram. Hp kim Re v Pb dng lm pin nhit in. Ngoi ra, reni lm cht xc tc cho nhiu phn ng ha hc hu c. 10.5. Tnh cht ha hc ca Mn, Tc, Re Hot tnh ha hc ca kim loi trong nhm gim dn t Mn n Re do kh nng phn ng vi cc cht gim dn. (1) Mangan v reni khng phn ng trc tip vi hiro, nhng kh H2 tan c trong mangan nng chy (70 - 100 cm3 H2 trong 100 g Mn nhit 1244oC). Reni khng ha tan c H2. (2) Trong khng kh, mangan dng khi rn, khng b oxi ha, ngay c khi un nng v c bao bc bi mt lp oxit mng bo v cho kim loi; nu trng thi vn li d b oxi ha hn; nhng ni chung mangan rt kh phn ng vi oxi, to ra Mn3O4 940oC:
Khi un nng bt reni trong kh quyn oxi 300oC to ra oxit Re2O7. Mangan v reni u phn ng trc tip vi lu hunh, selen, telu to ra cc hp cht nh MnS, MnSe, MnSe2, ReSe2, MnTe, MnTe2... (3) Mangan ha hp trc tip vi nit to ra Mn3N2 nhit khong 600 - 1000oC khi cho bt mangan tc dng vi nit: Mangan v reni phn ng trc tip vi photpho khi nung trong ampun hn to ra cc cht Mn3P2, MnP, ReP... (4) Mangan ha hp trc tip vi cacbon v silic to ra cc hp cht Mn3C, Mn7C3; Mn3Si, MnSi... (5) C mangan v reni u phn ng mnh vi cc halogen to thnh mui dng MX2, v d: (6) Mangan c th in cc ng trc Zn, nn khi un nng phn hy c H2O, c bit khi c tp cht nh cacbon, mangan d b nc v khng kh m n mn: Tecnexi v reni khng c kh nng . Mangan tan trong cc axit long khng c tnh oxi ha nh HCl, H2SO4 to ra H2: Tecnexi v reni khng c kh nng . Mangan tan trong H2SO4 c to ra SO2, nu H2SO4 c ngui phn ng xy ra rt chm, nhng khi un nng phn ng xy ra rt nhanh. Vi HNO3 to ra kh NO: Mangan khng th hin tnh th ng khi ngm trong HNO3 c. Tecnexi v reni phn ng mnh vi HNO3 v H2SO4 c to ra hp cht ng vi ha tr bn ca Tc(VII) v Re(VII) l:
(7) Mangan khng phn ng vi kim.
10.6. Cc hp cht vi s oxi ha +2 (1) Mangan v reni to ra c cc hp cht ng vi cc s oxi ha th n +7, ring tecnexi c cc s oxi ha +4; +6; +7. Trong , mangan c cc hp cht quan trng ng vi s o xi ha+2; +4; +7; cn tecnexi v reni to ra hp cht bn nht ng vi s oxi ha+7. Di y ch nu cc hp cht Mn(II). S phi tr c trng ca Mn(II) l bng 6 ng vi dng lai ha sp3d2 vi s phn b lin kt tm mt. Cc hp cht Mn(II) u c tnh thun t v u c nm electron c thn. Cu to ca phc cht tm mt spin cao ca Mn(II) tng ng vi cu hnh electron nh hnh 64. S phi tr ca Mn(II) trong tinh th bng 6. Mt s hp cht lng t u d kt tinh, c tnh ng hnh chng hn MnO v MnS c cu trc dng NaCl...
Hnh 64. S phn b electron theo cc obitan trong phc cht Mn(II) tm mt spin cao
a s cc mui u d ha tan trong nc v u l mui bn nht ca Mn(II). Khi tan trong nc, cc mui Mn(II) phn ly to ra phc - aquo [Mn(OH2)6]2+ v dung dch c mu hng. Mt s hp cht khng tan trong nc nh MnO, MnS, MnF2, Mn(OH)2, MnCO3, Mn3(PO4)2. (2) Mangan(II) oxit (MnO) c iu ch bng cch nhit phn Mn(II) oxalat hoc cacbonat khi khng c khng kh (nung trong lung kh H2 hoc N2):
Cng dng H2 hoc Co kh oxit bc oxi ha cao nh MnO2, Mn3O4:

MnO l cht tinh th, mu xanh xm, Tnc = 1780oC. Khng tan trong nc, khng phn ng vi nc. trng thi tinh th hon ton bn trong khng kh, nhng dng bt d b oxi ha to thnh cc oxit cao: ngoi ra cn to ra MnO2, Mn2O3. MnO b H2 kh thnh kim loi nhng phi nhit rt cao: MnO tan trong cc axit to thnh mui Mn(II): (3) Mangan (II) hiroxit (Mn(OH)2). Tng t nh Fe(OH)2, khi cho kim tc dng vi dung dch mui Mn(II) to ra kt ta mu trng: Mt s phc amoniacat ca Mn(II) nh [Mn(NH3)6]Cl2, [Mn(NH3)6](ClO4)2 cng d dng b nc phn hy to thnh Mn(OH)2: V vy cc loi phc trn ch tn ti trng thi rn hoc trong dung dch nhng phi c lng d NH3 rt ln. Mn(OH)2 trong khng kh dn dn b ha nu v b oxi ha theo phng trnh:
Mn(OH)2 khng tan trong nc (Tt = 4,5.10-13), l mt baz, d tan trong axit to thnh cc mui Mn(II). Trong mi trng kim, Mn(OH)2 s b oxi ha, ngay c O2 ca khng kh: (4) Mangan(II) clorua (MnCl2.4H2O) c iu ch bng cch cho kim loi, oxit, hiroxit, cacbonat tc dung vi axit HCl v kt tinh t dung dch nc: Trong cng nghip, iu ch bng cch un nng MnO2 vi axit HCl cho n khi khng cn kh clo thot ra:
Trong tinh th hirat ha, mt s phn t H2O ng vai tr phi t. trng thi khan to ra tinh th hnh phin mu hng. Nng chy 650oC, v trong lung kh H2, MnCl2 bay hi 1190oC; H2 khng kh c MnCl2 nhng khi un nng trong lung kh O2 hoc trong hi nc chuyn thnh Mn2O3. (5) Mangan(II) sunfat ( MnSO4). Phng php iu ch MnSO4 tng t nh MnCl2 l cho kim loi, oxit, hiroxit, mui cacbonat tan trong dung dch H2SO4: Trong cng nghip, MnSO4 c iu ch bng cch cho pirolusit (MnO2) tan trong HlSO4 c nng, hoc nung hn hp MnO2 vi FeSO4:
trng thi khan hu nh l mu trng. Khi kt tinh t dung dch nc to ra tinh th c mu hng khc nhau ph thuc vo hm lng nc kt tinh: MnSO4.H2O; MnSO4.4H2O; MnSO4.5H2O; MnSO4.7H2O. Trong tinh th cc sunfat , nhm SO4 ng vai tr cu ni gia cc nguyn t Mn(II):
T dung dch MnSO4 v mui sunfat ca kim loi kim c th tch ra nhng tinh th mui kp dng M2SO4.MnSO4.nH2O ( n = 2; 4; 6). Khi tc dng vi cht oxi ha, MnSO4 th hin tnh kh ph thuc vo mi trng: Trong mi trng kim mnh Mn2+ MnO42-. V d: Trong mi trng axit, Mn2+MnO4-, khi tc dng vi cht oxi ha mnh, v d PbO2: (6) Mangan(II) nitrat (Mn(NO3)2) c iu ch bng cch cho kim loi, oxit, hiroxit, cacbonat tc dng vi HNO3 long to ra dung dch mu hng nht:
nhit thng, tinh th tch ra dng Mn(NO3)2.6H2O; nu cao hn 25 C - dng Mn(NO3)2.3H2O. D tan trong nc, khi nung nng tch ra NO2 v MnO2:
o
y l phng php iu ch MnO2 nguyn cht. (7) Mangan (II) cacbonat - MnCO3 - c iu ch bng cch cho mui Mn(II) tc dng vi dung dch cacbonat. Nu tc dng vi dung dch mui cacbonat s thu c mui cacbonat baz: Nu tc dng vi dung dch hiro cacbonat bo ha kh CO2 to ra kt ta mu trng MnCO3.H2O: MnCO3 l cht bt mu trng, mn nh lng t, khng tan trong nc (Tt = 1.10-10 25oC). Khi un nng n 100oC, MnCO3 b phn hy: Khi trong khng kh m d b oxi ha chuyn thnh mu thm li do to ra Mn2O3. (8) Mangan (II) sunfua (MnS). Khi cho mui mangan (II) tc dng vi mui sunfua tan to ra kt ta mu hng thm. Mu ca kt ta thay i ty theo iu kin to kt ta. Khi lu (khng c khng kh) to ra dng khan MnS mu xanh. trong khng kh, b oxi ha chuyn dn thnh mu nu: Khng tan trong nc (Tt = 2,5.10-10). 10.7. Cc hp cht vi s oxi ha +4 (1) cc mui n gin ca Mn(IV) u khng bn. a s cc mui u c bit dng mui phc axio nh M2I[MnF6], M2I[MnCl6], cn dng MnF4, MnCl4 u khng bn, d b phn hy. Vi mangan(IV) th bn nht l MnO2 v Mn(OH)4 hay MnO2.2H2O. (2) Mangan(IV) oxit (MnO2) l thnh phn chnh ca khong cht piroluzit. MnO2 tinh khit c iu ch bng cch un nng Mn(NO3)2 n 200oC: Cc dung dch mui mangan (II) cng u b oxi ha bi bt ty,
hipoclorit, KMnO4, v nhng tc nhn oxi ha khc u to ra MnO2 trong mi trng kim:
MnO2 l cht bt mu nu en, khng tan trong nc. Khi un nng b phn hy: v khi un nng vi H2SO4 c nng to ra O2: MnO2 v hiroxit Mn(OH)4 u c tnh lng tnh. Tc dng vi H2SO4 c to ra mui Mn(SO4)2 khng bn, cn khi nung nng chy vi kim to ra cc hp cht M2IMnO3 v M4IMnO4:
MnO2 c tnh oxi ha mnh v c c tnh kh. Oxi ha HCl c to ra kh clo: Trong mi trng axit, MnO2 oxi ha mui Fe(II) thnh mui Fe(III), oxi ha axit oxalic thnh CO2:
Oxi ha axit sunfur thnh Mn(II) ithionat; oxi ha H2O2 thnh O2:
Khi tc dng vi cht oxi ha mnh hn, MnO2 th hin tnh kh. Khi cho MnO2 trn vi dung dch KOH 5% un nng 250oC ri cho khng kh i qua s to ra K2MnO4 mu lc:
Trong mi trng axit, to ra dung dch mu tm: (3) Ngi ta cng bit c cc hp cht ha tr IV ca tecnexi v reni nh TcO2, ReO2, cc halogenua nh ReCl4, M2IReCl6... (4) MnO2 l hp cht c nhiu ng dng trong thc t. Dng trong cng nghip thy tinh oxi ha cc hp cht sunfua v cc hp cht ca st; dng
trong cc mt n phng c trnh cacbon oxit. Dng lm cht oxi ha trong pin kh hiro; dng trong cng ngh ch to dim. Ngoi ra, MnO2 c dng lm cht oxi ha trong mi trng axit, lm cht xc tc cho qu trnh nhit phn KCIl3... l 10.8.Cc hp cht vi s oxi ha +6 (1) Cc hp cht ng vi s oxi ha +6 u khng bn. Vi mangan, c bit r nht l mui manganat MnO42-; trong dung dch nc tn ti cn bng sau: v vy cc mui manganat bn trong mi trng kim, cn mui pemanganat bn trong mi trng axit. Cc mui TcO42-, ReO42- trong dung dch nc cng tn ti cn bng nh trn. (2) Kali manganat (K2MnO4). Nh trn nu, nu nung nng hn hp gm MnO2 vi NaOH hoc KOH khi c mt ca khng kh hoc mt tc nhn oxi ha khc nh clorat, nitrat to ra manganat: Ha tan sn phm vo nc to ra dung dch mu xanh l cy, v khi lm bay hi trong chn khng thu c tinh th mu xanh l cy l K2MnO4 hoc Na2MnO4.10H2O, ng hnh vi cc mui sunfat. Khi axit ha dung dch K2MnO4 to ra axit H2MnO4 nhng li khng bn, phn hy ngay theo phng trnh: Khi un nng dung dch K2MnO4 to ra dung dch mu tm v kt ta mu nu en: Cc mui K2MnO4, Na2MnO4 u d tan trong nc; BaMnO4 t tan (Tt = 2,5.10-10) Ni chung, tt c cc dn xut ca mangan (VI) u c tnh oxi ha mnh. Trong mi trng kim s b kh n MnO2, cn trong mi trng axit to ra mui Mn(II):
V Mn(VI) ng vi s oxi ha trung gian, nn khi tc dng vi cht oxi ha mnh, cc manganat c th b oxi ha to thnh pemanganat MnO4-. V d:
(3) Ngi ta bit c mt s hp cht ca Re(VI) nh ReF6 c mu vng nht; ReCl6 c mu xanh; ReOCl4, ReOF4; ReO3 c mu . Cc hp cht u c tnh axit. Tr ReO3, cn li d dng b nc phn hy:
Reni trioxit khng tc dng vi H2O v vi axit, cn trong kim xy ra qu trnh t oxi ha kh: Cc dn xut ca Re(VI) th hin tnh kh, d dng b oxi ha, ngay c oxi ca khng
10.9. Cc hp cht vi s oxi ha +7 (1) Theo dy cc hp cht Mn(VII), Tc(VII), Re(VII) th bn tng dn. Chng hn, vi Mn(VII) ch c bit Mn2O7 v oxoflorua MnO3F, cn vi Re (VII) iu ch mt dy hp cht ReF7, ReOF5, ReO2F3, ReO3F, Re2O7; v d: Tnc = 5,9oC. Mn2O7 c mu xanh thm Tnc = 296oC Re2O7 mu vng Trong cc dn xut ca Mn(VII) th quan trng nht trong thc t l KMnO4. (2) Axit pemanganic (HMnO4) v anhirit penanganic (Mn2O7). Khi un nng mt dung dch gm mui Mn(II) vi PbO2 v HNO3 to ra axit pemanganic: Khi lm lnh mt dung dch c KMnO4 v AgNO3 thu c kt ta mu AgMnO4 (Tt = 1,6.10-3). Nu cho BaCl2 vo dung dch c cha AgMnO4 th AgCl s kt ta (Tt = 1,78.10-10), cn li Ba(MnO4)2 trong dung dch: T dung dch bari pemanganat, cho thm mt lng H2SO4 cn thit, sau khi tch kt ta BaSO4, dung dch cn li c cha HMnO4: Axit pemanganic l mt axit mnh tng ng HCl v HNO3; dung dch ch c th c c n 20%, sau bt u b phn hy:
Anhirit tng ng vi HMnO4 l Mn2O7.Mn2O7 l cht lng, mu xanh thm thu c khi cho H2SO4 c 90% tc dng vi KMnO4: Khi bay hi, to ra hi mu tm cng vi hi nc. Khi un nng b phn hy: V vy Mn2O7 l cht oxi ha rt mnh, ete, ru v nhiu cht hu c khc bc chy khi tip xc vi Mn2O7. Tc dng vi nc to ra HMnO4: (3) Kali pemanganat ( KMnO4) l mt mui quan trng nht ca axit pemanganic. iu ch KMnO4 c th bng cch cho K2MnO4 tc dng vi H2SO4: Lc tch MnO2, sau c dung dch nc lc. Kali pemanganat c ha tan b hn kali sunfat nn kt tinh trc. Cng c th iu ch bng cch cho clo tc dng vi K2MnO4: hoc cho kh CO2 tc dng vi dung dch K2MnO4:
KMnO4 trng thi rn l nhng tinh th hnh thoi, d kt tinh mu tm gn nh en, c nh kim. Tan trong nc c mu tm m; dung dch long c mu . trng thi rn kt tinh ng hnh vi KClO4. Khi nung nng b phn hy 200oC: v khi un si vi dung dch kim to ra K2MnO4 v O2: Kali pemanganat l cht oxi ha mnh c nhiu ng dng thc t trong phng th nghim. Tnh oxi ha ca KMnO4 ph thuc vo mi trng ca dung dch, mnh nht l mi trng axit. V d: Trong mi trng axit: Trong mi trng trung tnh:
Trong mi trng kim: Phn ng to ra K2MnO4 Phi c nng kim cao v cht kh t, hn na cc phn ng trn thng xy ra trong dung dch long, do sn phm kh trong mi trng kim hay trung tnh thng l MnO2. Trong dung dch, KMnO4 oxi ha c cc mui Fe(II) thnh mui Fe(III); axit H2SO4 thnh H2SO4; sunfit thnh sunfat; axit oxalic to ra CO2 v H2O (60oC); iotua thnh iot; axit halogenhiric thnh halogen tng ng; nitrit thnh nitrat; hiro mi sinh thnh H2O; hiro sunfua thnh lu hunh; thiosunfat thnh sunfat; amoniac v mui amoni thnh nit; mui stanit thnh mui stanat... V d:
Trong mi trng axit, oxi ha c c H2O2: KMnO4 oxi ha c mui Mn(II) thnh MnO2: (4) Ngi ta cng bit cc mui kim loi kim khc nh LiMnO4.3H2O d tan; NaMnO4.3H2O d tan; RbMnO4 t tan (Tt = 2,9.10-3), CSMnO4 kh tan (Tt = 9,1.10-5); mui pemanganat ca kim loi kim th, kim loi nng nh Ca(MnO4)2.5H2O d tan; Ba(MnO4)2 tan; AgMnO4 t tan (Tt = 1,6.10-3); (5) Cc hp cht Tc(II), Re(VII) tng t cc hp cht ca Mn(VII). Cc oxit Tc2O7 v Re2O7 cng c iu ch bng cch un nng cc axit HTcO4 v HReO4:
Cng c th thu c khi un nng bt Tc hay Re trong lung kh oxi:
C hai u l cht rn mu vng, v u d tan trong nc to ra axit tng ng:
Cc axit HTcO4 v HReO4 (axit petecnexic v axit perenic) u l nhng

axit mnh. Phng php iu ch ch yu l cho kim loi tng ng tc dng vi HNO3 30%: Cc dung dch long HTcO4 v HReO4 u khng c mu v khi un nng b phn hy thnh anhirit tng ng. Cc mui petecnat v perenat u khng c mu (nu cation khng mu). a s u d tan trong nc, mt s mui perenat kh tan KReO4 (Tt = 1,9.10-3); RbReO4(Tt = 9,6.10-4); CsReO4(Tt = 4.10-4); AgReO4(Tt = 7,9.10-5); Ba(ReO4)2 (Tt = 5,3.10-2). (6) So snh vi cc dn xut ca Mn(VII) th cc dn xut ca Tc(VII) v Re(VII) bn hn. Chng hn: Mn2O7 trng thi lng; H298 = - 743 kJ/mol. Tc2O7 trng thi rn; H298: - 1117 kJ/mol. Re2O7 trng thi rn; H298 = - 1243 kJ/mol. HMnO4 ch c c n 20%, cn HTcO4 v HReO4 c th c dung dch n kh. Cc axit u c tnh oxi ha mnh v tnh axit mnh, nhng tnh oxi ha v tnh axit gim dn t HMnO4 n HReO4. Mui perenat rt bn khi nung nng, v d KReO4 nng chy 555oC v n 1370oC vn cha b phn hy; trong khi KMnO4 b phn hy 200oC. Ngi ta cha bit c hp cht khng cha oxi ca Mn(VII) nhng iu ch c cc hp cht ca Re(VII) nh Re2S7, HReS4... (7) Vi mangan, to ra cc oxit v cc hiroxit ng vi bc oxi ha t thp n cao v s bin i bc oxi ha nh hng n tnh cht ca chng:
Tnh axit tng theo dy trn cng c th gii thch trong khun kh s tng quan in tch v bn knh ca cc ion. Khi chuyn t Mn(II) - Mn(VII), bn knh ca ion gim dn, in tch ca ion tng dn, nn kh nng tch ion H+ tng dn theo chiu t Mn(OH)2 n HMnO4. bn ca ion MnO4- ln hn bn ca ion MnO42- cng c gii thch trong phm vi ca thuyt obitan phn t nh sau: Trong ion phc hnh 4 mt, chng hn nh MnO4-, CrO4-, MnO42-... th cc obitan ca cht to phc tham gia hnh thnh lin kt gm 5 obitan (n-1)d;
mt obitan ns v ba obitan np, vi cc obitan p ca bn phi t. Trong ion MnO4- c 24 electron ha tr gm 7 electron ca nguyn t Mn (3d54s2), 16 electron ca 4 nguyn t oxi O (2p4) v 1 electron do tch in ca ion. Trong ion MnO42- c 25 electron ha tr tham gia hnh thnh lin kt. S phn b electron trong cc obitan phn t (MO) trong ion MnO4- v ion MnO42- c cu hnh nh sau (hnh 65 ). MnO4-: (lk )(lk )10 ()6
lk 8 lk 10 6 plk l MnO42-: ( ) ( ) () ( )
Nh vy, trong ion MnO4- c mt electron ha tr chim MO phn lin kt, do ion MnO4- km bn hn ion MnO4. Tng t nh vy, trong cc ion MnO43-; MnO44- c 2 v 3 electron chim MO phn lin kt nn cng km bn, v v vy chng ta hiu c tnh khng bn ca s phi tr 4 trong hp cht Mn(IV) v cng hiu c v sao cc ion MnO43-, MnO44- khng tn ti.
Hnh 65. Cc mc nng lng ca phc cht bn mt vi lin kt ~
CHNG 11 CC NGUYN T NHM VIII B (ST - COBAN - NIKEN V H PLATIN)
11.1. Nhn xt chung v cc nguyn t nhm VIIIB (1) Nhm VIIIB gm 9 nguyn t thuc h d cc chu k 4; 5; 6 thuc bng tun hon. St (Ferrum) c bit t thi k c i. Coban (Cobaltum) c mt nh khoa hc Thy in l Bran(G.Bandt) tm ra nm 1775. Niken (Niccolum) c tm ra nm 1751 bi nh ha hc kim khong vt hc ngi Thy in l Cronstet (A. Cronstedt) v n u th k th 19 mi c nh ha hc ngi c l Richte (J. Richter) nghin cu k v tnh cht ca niken kim loi. Ruteni (Ruthenium) do nh ha hc ngi Nga l Claox (K.Klaus) tm ra nm 1843; hai nguyn t roi (Rhodium) v palai ( Palladium) u tm ra nm 1803 do pht minh ca nh ha hc ngi Anh l Volastn (W. Wollaston); osmi (Osmium) v irii ( Iriium) do nh ha hc ngi Anh l Thenn (S. Tennant ) tm ra nm 1804, cn platin ( Platinium) bit t thi c i. (2) Khi so snh tnh cht l hc v ha hc c bn ca cc nguyn t nhm VIIB, ngi ta thy cc nguyn t st, coban v niken c tnh cht tng t nhau, nn c xp chung thnh h st; cc nguyn t cn li c tnh cht ging nhau theo chiu thng ng, nn c xp chung thnh h platin. Ni cch khc, khi kho st cc tnh cht ca cc nguyn t nhm VIIIB, ngi ta khng xem nhm ny l mt nhm thng nht nh cc nhm khc, m xem l nhng b ba chuyn tip gia cc nguyn t nhm VIIB (Mn, Tc, Re) v nhm IB(Cu, Ag, Au). Tm tt nh sau:
H PLATIN
43 44 45 46 47
Tc 75
Ruteni 76
Rodi 77
Paladi 78
Ag 79
Re
Osmi
Iridi
Platin
Au
(3) Nguyn t khi, s phn b electron v trng thi ha tr ca cc nguyn t nh sau:

Nguyn t Sat Coban Niken Ruteni Rodi Paladi smi Iridi Platin K hiu Fe Co Ni Ru Rh Pd Os Ir Pt Nguyn t khi 55,847 58,933 58,710 101,070 102,905 106,400 190,200 192,220 195,090 2 2 2 2 2 2 2 2 2 8 8 8 8 8 8 8 8 8 Phn b electron 14 15 16 18 18 18 18 18 18 2 2 2 15 16 18 32 32 32 Ha tr I, II, III,IV, VI I, II, III, IV I , II , III, IV II, III, IV, V, VI, VII, VIII I, II, III, IV, VI II, III, IV II, III, IV, VI, VIII I, II, III, IV, VI I, II, III, IV, VI
1 1 0 14 15 17
2 2 1
(4) V tnh cht , cc nguyn t thuc nhm VIIIB c nhng nt chung nh sau: u c tnh cht ca kim loi, mu sc t xm n xm trng; rt kh nng chy v rt kh bay hi; th tch nguyn t thp. Tt c u c kh nng hp th hiro trn b mt t hoc nhiu v gy ra hot tnh cao ca hiro (hiro hot ng). Tt c u c tc dng xc tc cho phn ng ha hc v c hoc hu c. u c khuynh hng to phc, c trng nht l phn ng to phc vi NH3, vi CO v c vi NO. C kh nng to ra nhiu hp cht c ha tr khc nhau v c th d chuyn ha t trng thi ha tr ny n trng thi ha tr khc. u to ra hp cht c mu ngay c trng thi t do( dng hirat ha ). Hiroxit ca chng u c tnh baz yu, hoc axit yu, hoc c tnh lng tnh. C i lc yu i vi oxi v gim dn t tri sang phi; nhng li c i lc mnh vi lu hunh v tng dn t tri sang phi. V mt ny, cc nguyn t nhm VIIIB tng t nhm IB. (5) V cu hnh elcctron, nguyn t nhm VIIIB u thuc h d m nguyn t lp y dn cc obitan d lp (n - l) - (n l s th t ca chu k). (6)Tinh th cc kim loi c cu trc theo mng nh sau: Co Ni Fe
Mng lap phng tm khi
0
Mng lc phng
0
Mng lp phng tm din

0
a = 2,8664 A
a = 1,5063 A
a = 3,5238 A
c = 4,0795 A
Ru
Mng lc phng
0
Rh
Mng lap phng tm din
0
Pd
Mng lp phng tm din
0
a = 2,7085 A
0
a = 3,8044 A
a = 3,8907 A
c = 4,2816 A
Os
Mng lc phng
0
Ir
Mng lp phng tm din
0
Pt
Mng lp phng tm din
0
a = 2,7353 A
0
a = 3,8938 A
a = 3,9239 A
c = 4,3191 A
CC KIM LOI H ST 11.2. Nhn xt chung v kim loi h st (l) C ba kim loi st, coban v niken - trng thi kim loi cng nh trng thi hp cht u c nhng c im ging nhau v tnh cht. C ba kim loi u to ra cc mui c s oxi ha +2 ; ngoi ra st to ra cc mui c s oxi ha +3; coban(II) d dng chuyn thnh Co(III) nhng thng gp trong cc hp cht phc; vi niken th ch yu to ra hp cht Ni(II). Khuynh hng to ra hp cht ha tr I tng t st n niken; niken d dng to ra hp cht ha tr I tng t ng. Ha tr cc i ca st l Vi ( trong ferat FeO42- ) tng t mangan; trong khi ha tr ca coban v niken l (IV) trong cc hp cht ca ioxit d dng b phn by tch ra oxi. (2) Bng 42 l mt s c im nguyn t ca ba nguyn t trn . Bng 42. Mt s c im ca Fe - Co - Ni
Electron ha tr
0
Fe 3d64s2 1,26 0,80 0,67 7,90

0 0
Bn kinh nguyen tuf A Bn kinh ion M2+ ( A ) Bn kinh ion M3+ ( A ) Th ion ha I1 (eV)
Co 3d7s2 1,25 0,78 0,64 7,86
Ni 3d64s2 1,24 0,74 7,63
(3) Th in cc : tm tt theo s sau : Trong mi trng axit:
(4) V cu to tinh th : St c bn dng th hnh, c cu to nh hnh 66.
iu kin thng n 770oC tn ti dng - Fe c mng lp phng tm khi ; 7700C dng - Fe chuyn thnh dng - Fe, mng tinh th khng thay i nhng di gia hai nguyn t tng ln; n 910oC chuyn thnh dng y Fe, mng tinh th thay i thnh mng lp phng tm din; n 1390oC li chuyn thnh mng lp phng tm khi l dng - Fe. Coban c hai dng th hnh. iu kin thng n 417oC tn ti dng a - Co c mng lc phng (a : 2,5063 A , c - 4,0795 A ); n ~4800C tn ti dng - Co c mng lp phng tm din (a : 3,5441 A ). Niken tn ti hai dng th hnh. Thp hn 250oC dng - Ni c mng lc phng (a = 2,65 A , (c = 4,32 A ); cao hn 250oC chuyn thnh dng - Ni vi mng lp phng tm din (a = 3,5238 A ).
0 0 0 0 0 0
11.3. Trng thi thin nhin v thnh phn cc ng v (1) St thuc cc nguyn t ph bin nht cu to nn v qu t. Khong vt ch yu ca st l manhetit (Fe3O4), hematit (Fe2O3), hematit nu [Fe2O3.2Fe(OH)3]. Ngoi ra, mt lng st kh ln dng khong cht xierit (FeCO3) v c trong qung vi lu hunh, asen nh pirt FeS2 ... tuy nhin pirit khng phi l cht dng iu ch st m dng iu ch H2SO4. Hm lng ca coban trong v qu t t hn nhiu so vi st. Khong vt quan trng ca coban l cobantin ( CoAsS). Coban ln vi cc kim loi khc nh Cu, Ni, Ag, Fe, Mn trong cc qung a kim. Hm lng ca niken trong v qu t nhiu hn coban. Khong vt ch yu ca niken l penlait l qung sunfua ca ni ken, ng v st. Ngoi ra cn c cc loi qung khc nh gacnierit ( NiSiO3.MgSiO3 ), qung smantit l qung arsenua ca Ni, Co, Fe. (2) Trong cc thin thch c khong 5,15%Fe; 0,01%Co; 0,14%Ni(% nguyn t), nhng trong cc thin thch st c n 90%Fe; 8,5Ni; 0,5%Co cng vi mt t tp cht khc. Hng nm c n trn 1000 thin thch ri xung tri t ch yu l thin thch st. Thin thch st ln nht nng 60 tn pht hin nm 1920 Ty Nam chu Phi. Trong c th ng vt , st c trong hemoglobin, chc nng chnh ca phc cht ny l lin kt oxi phn t v chuyn oxi vo cc m. Ngoi ra, cn c trong mioglobin l cht protein d tr oxi trong c bp; c trong phc cht feritin cng l protein c chc nng to nn nhng hp cht khc cha st cn cho c th ca sinh vt . Gan v l lch l b phn giu st nht trong c th. Coban thuc s nguyn t quan trng i vi con ngi, vitamin B12 hay cobanamin l phc cht ca coban c cha 4,5% Co v khi lng , dng cha bnh thiu mu. (3) Trong nc i dng, cc nguyn t h st, coban, niken dng Fe(OH)3 ; Co2+ , CoSO4; Ni2+ , NiSO4 [ theo D. Golldberg ( 1963)] ng vi thnh phn ha hc trung bnh nh sau ( theo A.P. Vinogradov -1967) :
Nguyn t %
Hm lng mg/l
Fe 1. 10-6 0,01 -8 5. 10 Co 0, 0005 -7 2. 10 Ni 0, 002 (4) Hm lng ba nguyn t trong cc mu Mt Trng c cc hm lng nh sau:
Nguyn t Fe Co Ni
Hm lng trung bnh (s gam/ 1g mu ) Apollo - 11 Apollo -12 Luna - 6 0,134 0,132 -5 -5 2,5.10 4,2.10 4,1.10-6 2.10-4 1,171.10-4
(5) St c bn ng v bn l 54Fe (5,84%); 56Fe (91,68%); 57Fe (2,17%); 58 Fe (0,31%); trong s cc ng v phng x th ng v 55Fe l bn hn c , c chu k bn hy l 2,9 nm. Coban c tm ng v t 54Co n 61Co nhng ch c 59 Co l ngv thin nhin (100%) , s ng v cn li u l ng v phng x trong bn nht l 60Co c chu k bn hy l 5,2 nm, km bn nht l 54Co Vi Chu k bn hy l 0,18 giy. Niken c 11 ng v t 56Ni n 66Ni , trong c nm ng v thin nhin l 58Ni (67,76%); 60Ni (26,16%); 61Ni (l,25%); 62Ni (3,66%); 64Ni (l,16%). Trong cc ng v phng x th ng v 59Ni c chu bn hy l 7,5. 104 nm bn nht, v ng v 65Ni km bn nht c chu k bn hy l 0,108 ngy m. 11. 4. iu ch Fe, Co, Ni (1) St tinh khit c iu ch bng cch dng H2 tinh khit kh oxit st tinh khit :
Qu trnh kh xy ra khong 175 - 270oC; nhit , sn phm thu c l loi st t chy khi tip xc vi khng kh loi st ny s b oxi ha nhanh v nng ln. thu c sn phm c bn cao i vi khng kh, qu trnh kh phi thc hin nhit cao hn khong 550 - 6500C; iu kin , st thu c dng bt mn khng cn c kh nng t chy. Qu trnh kh xy ra theo tng giai on, ban u to ra Fe3O4, sau mi to thnh Fe:
Nu nung 5730C th to ra oxit FeO:
Nu qu trnh kh xy ra khi tng nhit n khong 700 - 10000C khng thu c dng bt mn m dng st rn tc l dng khi chy. C th iu ch bng phng php nhit phn Fe(CO)5 st pentacacbonyl:
St rt tinh khit c th iu ch bng phng php in phn dung dch mui Fe(II) chng hn nh FeSO4. FeCl2, vi dng cc l tm Fe - Cr, cn m cc l st tinh khit. Qu trnh in phn ph thuc vo cc yu t nh pH ca dung dch , nng ca cht in phn , mt dng ca anot v catot. (2) Coban tinh khit c iu ch bng cch dng H2 kh coban(II) oxit CoO hoc cc oxit khc :
Khi nung n 1200C qu trnh kh bt u xy ra , n 2500C thu c (coban t (hay. Nu nung n khong 4000C, sn phm thu c dng bt hon ton bn i vi khng kh kh. Sn phm thu c ph thuc vo nhit , chng hn 4500C thu c dng th hnh - Co (mng lp phng), nhit thp hn 450oC s thu c dng - Co (mng lc phng). Coban tinh khit c th iu ch bng phng php in phn dung dch CoSO4 trong nc vi dng cc bng thp khng g c x l b mt v m cc bng tm ch tinh khit ha hc. Sn phm thu c c cha 99,1% 99,2% coban, tp cht cn li l niken. (3) Niken tinh khit cng c iu ch bng cc phng php nh trn. Khi dng H2 kh oxit NiO:
nu nung 270 - 280oC thu c niken t (hay, cn 350 - 400oC hoc cao hn thu c niken bt, hon ton bn i vi khng kh. Niken bt cng c iu ch bng phng php in phn dung dch NiSO4 trong nc vi dng cc bng cc l ( Fe - Ni ), cn m cc bng Ni; pa ca dung dch cht in phn khong t 4 - 4,5 . (Niken tinh khit cng c th iu ch bng cch nhit phn niken
tetracacbonyl Ni(CO)4 :
(4) Ngoi cc phng php nu, cc kim loi trn u c th iu ch bng phng php nhit nhm thu c kim loi khi nng chy :
Cc phn ng ta ra mt lng nhit kh ln cho cht phn ng nng chy. Sn phm thu c khng tinh khit. (5) Nh trn nu , cc kim loi Fe, Co, Ni trng thi bt rt nh tch ra t cc hp cht c kh nng t chy, ngha l t bc chy trong khng kh ngay nhit thng. Bt t chy ca st cng c th iu ch bng cch nung cn thn Fe(II) oxalat:
Cc ht st iu ch bng cch c ng knh khong 5.10- 8 cm do b mt tip xc rt ln nn lm tng tc oxi ha, tuy nhin nguyn nhn quan trng l do cu trc mng tinh th ca cc ht so vi kin trc bn ca kim loi . 11. 5. Tnh cht l hc ca Fe, Co, Ni v ng dng (1) C ba nguyn t l nhng kim loi mu trng c nh kim ; Fe v Co c mu xm, cn Ni c mu trng bc. Mt s hng s l hc ca Fe, Co, Ni nu ra bng 43. Bng 43. Mt s hng s l hc quan trng ca Fe, Co, Ni
Tnh cht Khi lng ring (g / cm3) Nhit d nng chy ( Tnc , C ) Nhit si ( Ts, C ) dn in (Hg =1 ) dn nhit (Hg =1 ) m in <1>
(1)
Fe 7,9 1539 2740 10 10 1,8
Co 8,9 1495 2900 10 8 1,7
Ni 8,9 1455 2730 14 7 1,8
Theo Pauling.
St v niken d rn, d dt mng; coban cng v gin. (2) iu kin thng , khc vi tt c cc kim loi, ba nguyn t Fe, Co,
Ni u l cht st t tc l cht b nam chm ht. Tuy nhin, trong bn dng th hnh ca Fe, ch c - Fe mi c tnh st t, ngha l tnh st t ca st ch nhit n 770oC, trn nhit tnh st t ca st bin mt, mc d mng tinh th khng i, st ch cn li tnh thun t. Coban c tnh st t nhit l0750C, cn niken - 3620C; trn nhit tnh st t ca coban v niken s mt. Mt s hp cht ca cc nguyn t trn cng c tnh st t, do ngi ta lm giu qung st bng phng php t hc. Ngoi tnh cht b nam chm ht , di tc dng ca dng in cc cht st t s tr thnh nam chm . Tuy nhin, st nguyn cht ch tc dng nh mt nam chm khi chu tc dng ca dng in, cn thanh thp khi nam chm ha th sau vn tc dng nh mt nam chm vnh cu. (3) St l kim loi quan trng nht i vi cc ngnh k thut v cng nghip hin i. C ba kim loi c dng ch yu to ra cc hp kim c bit l cc loi thp. Nhiu hp cht ca st c ngha quan trng trong thc t nh FeCl3 dng lm cht ng t khi lm sch nc, lm cht cm mu, lm cht xc tc trong ha hc hu c. Cc mui ferit ca kim loi ha tr hai dng trong k thut my tnh. Cc oxit ca st khng nhng l ngun iu ch nhiu hp cht ca st m cn l ngun nguyn liu quan trng ca ngnh luyn kim en. (4) Hn 3/4 lng coban c sn xut dng ch to thp v hp kim c bit. Coban truyn cho thp tnh cng v tnh chu mn nn loi thp c cha coban dng ch to cc dng c ct gt khc nhau. Mt s hp kim ca coban dng trong k thut quc phng v k thut tn la. Coban l vt liu st t, nhiu hp kim ca co ban cng c tnh st t. Hp cht gia cc kim loi ca coban v samari ( SmCo5 ) v mt s kim loi t him khc c dng lm vt liu ch to nam chm vnh cu mnh. 60 Co c iu ch theo phn ng: ng v 27
c dng rng ri trong y khoa cha bnh ung th. (5) Niken c nhiu ng dng hn coban, c nhiu ng dng trong nhiu ngnh kinh t quc dn, hn 80% lng ni ken c sn xut, dng trong ngnh luyn kim. Thp c cha niken c bn cao v mt ha hc v c hc; niken c
dng m ln b mt cc sn phm lm bng vt liu d b n mn. Hp kim Monen ( A. Monel l gim c mt cng ty Canada ch to ra loi hp kim ny) c bn cao vi mi trng n mn, c s dng nhiu trong ngnh ch to my cho cng ngh ha hc , ng tu... Mt s hp kim khc ca niken c dng sn xut cc loi tin thay cho bc. Niken v hp kim ca n c dng trong k thut hng khng v v tr , trong cng nghip ha cht dng lm cht xc tc. (6) Mt iu cn ch l khi ni n tnh cht l hc ca st cn n thnh phn tp cht c trong st vi hai loi : St c tinh khit cao c cha di 0,001% tp cht, c t tnh tt v d hn, nhng tnh cht c hc khng cao, bn km hn nhiu so vi gang v cc loi thp; khng th dng trong vt liu ch to. St tinh khit k thut cn gi l thp in k thut c cha 0,02 - 0,04% cacbon, ngoi ra cn c cc tp cht khc nh oxi , nh, lu hunh, photpho cng c t tnh tt v d hn, c tnh c hc cao, dng lm vt liu ch to. 11.6. Tnh cht ha hc ca Fe, Co, Ni Fe, Co, Ni l nhng kim loi hot ng trung bnh. Tc dng c vi nhiu n cht v hp cht. Hot tnh ha hc gim dn t Fe n Ni. Chng hn, Fe d dng b oxi ha trong khng kh m; Co bn iu kin thng, un nng n 300oC th b oxi oxi ha; cn niken bt u b oxi ha 5000C. (1) C ba kim loi u khng phn ng trc tip vi hiro, nhng trng thi bt nh v nhit cao u hp th hiro vi lng kh ln. Cc hp cht vi hiro ca chng u khng c thnh phn xc nh v iu ch bng phng php gin tip. Cc hirua u bn nh : FeH, FeH2, FeH3; CoH, CoH2 ; NiH, NiH2 ha tan ca hiro trong st nng chy ph thuc vo dng th hnh ca st. dng - Fe l dung mi tt hn c so vi cc dng th hnh khc, 15400C c th ha tan c 18gH2 trong 100g Fe; ngi ta cng nghin cu thy rng s gii hp th bt u 150 - 3000C. Coban hp th hiro km hn nhiu. 12000C ,100g coban hp th c 5,46 cm3 hiro. Coban in phn hp th km, cn coban tm hu nh khng hp th hiro. c bit l niken hp th mnh hiro, kh nng cho php dng niken lm cht xc tc trong qu trnh hiro ha cc cht hu c. ha tan ca hiro trong niken c khc nhau ph thuc vo trng thi rn
hay lng. 1600oC, 100g niken ha tan c 43cm3 hiro. (3) iu kin thng st, coban v niken u bn vi khng kh v nc. Khi nung bt Fe trong khng kh hoc trong oxi to ra Fe3O4 :
nhit nng trng, coban b oxi ha to ra CO3O4:
Cn niken b oxi ha chm hn, bt u 5000C to ra NiO:
(4) Trong khng kh m, st c ln cc tp cht s b g, tc l b n mn trn b mt. Lp g to nn c thnh phn ch yu l Fe2O3. XH2O, lp g ny xp v gin nn khng bo v c cho st. Phn ng to g ch yu theo Phng trnh:
Tc to ra g st ln nht cc u mt, ch b cong c bit cc vt ct ; cn phn phng ca tm st b n mn mc nh. (5) C ba kim loi u phn ng mnh vi cc halogen. Khi un nng st kim loi vi cc halogen thu c Fe(III) halogenua khan FeX3; v d:
Tuy nhin khi nghin bt tt vi bt st to ra sn phm c thnh phn l Fe3I8 ( hay 2FeI3 .FeI2 ).
ngha l hn hp c c iotua Fe(III) v Fe(II). Ni cch khc, FeI3 ch bn trong cn bng vi lng d kh ln FeI2
Coban v niken tc dng trc tip vi cc halogenua to ra mui ng vi s oxi ha +2 ca kim loi. V d: khi t chy coban hay niken trong lung kh ch to ra CoCl2 v NiCl2 ; tng t nh vy vi brom.
nhng vi flo, coban to ra hn hp COF2 + COF3 (6) Khi nung hn hp gm S vi cc kim loi h st to ra cc sunfua :
Co v Ni cng c phn ng tng t to ra COS v NIS. Selen v tu phn ng trc tip vi Fe, Co, Ni: Vi Fe to ra : Fese, FeSe2 ; FeTe, FeTe ; trong Fese v Fese2 l cht bn dn. Vi Co to ra : CoSe, CoSe2 ; CoTe, CoTe2. Vi Ni to ra : Ni Se, Nise2 ; Nhe, NiTe2 (7) C ba kim loi u khng phn ng trc tip vi nit. Cc hp cht nh Fe2N, Fe4N; Co2N, Co3N, Co3N2; Ni3N, Ni3N2 u c iu ch bng phng php gin tip v u t bn. Tc dng vi photpho trong cc ampun hn to ra dung dch rn ng vi cc hp cht c thnh phn Fe3P, Fe2P, FeP, FeP2 ; Co2P, CoP, CoP3; Ni3P, Ni2P, NiP3. (8) Fe, Co, Ni to ra hp cht vi cacbon ng vi thnh phn M3C v M2C, trong quan trng nht l Fe3C:
Fe2C c iu ch bng cch nung Fe vi C 2500C. Cc hp cht ng vi thnh phn nh trn ca Co v Ni c iu ch bng phng php gin tip, chng hn khi nung coban bt vi CO:
Fe to ra cc xilixua quan trng nh FeSi2, FeSi, Fe3Si2 v Fe2Si c trong thnh phn ca ferosilic. Coban to ra cc hp cht Co3Si, Co2Si , CoSi, CoSi2 trc tip t cc nguyn t, nng chy nhit trong khong t 1200 - 14000C ; v d :
Niken cng phn ng trc tip vi silic to ra cc silixua Ni3Si, Ni2Si, NiSi , NiSi2; chng hn:
Nng chy trong khong t 1000 - 12000C (9) Fe, Co, Ni u phn ng trc tip vi B : Nung nng bt Fe vi B 1300 - 14000C trong bu kh tr to ra FeB v FeB2 :
Khi nung Co vi bt B v nh hnh trong ng thch anh hn kn to ra cc

hp cht Co3B , Co2B , COB , COB2. Cng tng t cch iu ch nh trn, niken to ra cc hp cht Ni3B, Ni2B, NiB, Ni3B2, Ni4B3. (10) Nc khng cha khng kh ha tan hu nh khng n mn st nhit thng, v trn b mt d to ra lp mng Fe(OH)2 bo v cho kim loi . Nhng khi cho hi nc qua Fe nung to ra Fe3O4 :
Co v Ni khng b H2O n mn nhit thng, nhng khi cho H2O qua Ni nung to ra NiO:
(11) Vi dung dch kim, iu kin thng thc t khng tc dng vi c ba kim loi. Tuy nhin, khi un si bt st kh vi dung dch NaOH 50% , trong iu kin khng c khng kh, thu c dung dch natri hipoferit:
(12) Trong dy th in cc, Co v Ni ng gia Fe v Sn nhng gn Sn hn nn c hai kim loi tan trong axit long chm hn Fe. St tc dng vi axit khng c tnh oxi ha to ra mui Fe(II) v H2 :
st kh c cc ion kim loi ng sau st trong dy th in cc :
H2SO4 c ngui gy ra tnh th ng cho st , nhng vi H2SO4 c nng s oxi ha st to ra mui Fe(III) v ng thi b kh n So):
Hnh 67 cho thy st ha tan mnh nht trong dung dch H2SO4 khong
50%. Khi nhng thanh st vo HNO3 bc khi mt thi gian, sau nhng vo dung dch cha ion Cu2+ hoc dung dch axit long nh HCI, H2SO4 st s mt kh nng phn ng, ngha l st b th ng ha bi HNO3 bc khi, HNO3 long , lnh ho tan st to ra st(II)nitrat :
(13) Trong dung dch axit long nh HCl, H2SO4, coban kh tan hn so vi st, to ra H2 :
Coban phn ng vi H2SO4 c nng to ra SO2 :
Coban tan trong HNO3 long, v cng tng t nh st, coban cng b th ng ha bi HNO3 c. (14) Cc axit v c long tc dng vi niken chm hn st to ra H2:
nhng d tan trong HNO3 long :
Tng t Fe v Co, Ni cng b th ng ha bi HNO3 bc khi. 11.7. Hp cht cacbonyl ca Fe, Co, Ni Cng tng t nh cc nguyn t Mn, Cr, V, Ti, cc nguyn t Fe, Co, Ni cng c kh nng phn ng vi ccbon oxit to ra cc hp cht cacbonyl m trong cc nguyn t trung tm ny mang s o xi ha " 0 ". (1) Khi un nng bt st trong ng cha CO 150 - 2000C p sut khong 100atm to ra stpentacbonyl:
Fe(CO)5 l cht lng mu vng nht (Tnc = - 200C ; Ts = l030C) c cu to hnh chp kp vi nguyn t Fe trung tm [d(Fe - C) = 1,84 A ; d(C - O) = 1,15 A ] , ng vi obitan lai ha dsp3 ca nguyn t st (hnh 68 ).
0 0
Khi t chy hi Fe(CO)5 trong khng kh to nn Fe2O3 :
B nhit phn hy 1400C to thnh st kim loi:
Ngi ta dng phn ng ny iu ch st tinh khit ha hc. Fe(CO)5 khng tan trong nc, tan trong ete v benzen, trong dung dch ete Fe(CO)5 phn ng vi H2SO4 theo phng trnh :
iu chng t st trong hp cht c tc dng nh l st kim loi. Fe(CO)5 c tnh cht oxi ha v kh. Chng hn trong amoniac lng, tc dng vi natri kim loi th hin tnh oxi ha:
v tc dng vi dung dch kim trong ru th hin tnh kh:
Cc hp cht M21[Fe(CO)4] d ang b thy phn to ra hirocacbonyl H2[Fe(COl4] c tnh axit:
Gc [Fe(CO)4]-2 c th xem l dn xut ca st ( - 2) . (2) Khi un nng bt coban trong kh quyn cacbon oxit 150 - 2000C v 250atm to ra coban octa cacbonvl:
Co2(CO)8 l hp Cht hai nhn, trong nguyn t coban to ra su lin kt - . Bn lin kt to ra bi bn cp electron ca bn phn t CO t vo bn obitan t do ca coban; lin kt th nm to ra t mt cp electron d t vo obitan ca phn t CO. Lin kt gia Co - Co to ra do s ghp i bi hai electron c thn ca hai nguyn t coban:
Co2(CO)8 l tinh th c mu da cam, bt u b phn hy 600C:
Khi un nng di p sut ca kh hiro to ra hp cht hidrua cacbonyl:
Cht ny c mu vng, Tnc = - 330C, tan trong dung dch kim to thnh mui nh K[Co(CO)4] , NH4[Co(CO)4]. (3) bit c nikell tetracabonyl Ni(CO)4 l hp cht ca Ni(0) c cu hnh bn mt ng vi dng lai ha sp3 ( hnh 69 ).
Ni(CO)4 l cht lng khng mu ( Tnc = 19,30C ; Ts = 430C ) d dng iu ch bng cch cho CO tc dng vi bt niken 60 - 800C:
Ni(CO)4 khng tan trong nc, khng phn ng vi axit long, kim long, d tan trong cc dung mi hu c.
Khi un nng khong 180 - 2000C, Ni(CO)4 b phn hy to ra Ni nguyn cht:
Phn ng trn dng iu ch ni ken tinh khit. CC HP CHT VI S OXI HA +2 S phi tr ca Fe(II), Co(II) v Ni(II) l bng 6 v 4 ng vi cu hnh tm mt v bn mt hoc mt phng vung . (1) S phi tr 6 ca Fe(II) trong cc hp cht nh FeO (hnh 70); FeF2 (hnh 71); FeCl2 v a s cc ion phc nh [Fe(OH)2]62+ ; [Fe(OH)6]4- ; [Fe(CN)6]4- .... Mt s phc bn mt ng vi s phi tr 4 ca Fe(II) nh [FeCl4]2- , [Fe(NCS)4]2-...
(2) S phi tr 6 ca coban trong cc phc sm cao nh [Co(OH)2]62+ ; [Co(OH2)6]2+; [CoF6]4- hoc trong cc phc spin thp [Co(CN)6]4- , [Co(NO2)6]4.... CoO u c cu trc dng NaCl. Mt s phc bn mt ng vi s phi tr 4 nh [CoCl4]2- , [CoBr4]2-, [Co(NCS)4]2a s cc hp cht ca Co(II) u c tnh thun t. (3) Cc hp cht lng t ng vi s phi tr 6 ca Ni chng hn nh NiO c cu trc tinh th dng NaCl (hnh 70); NiF2 - c cu trc dng tun (hnh 71) NiCl2, NiBr2, NiI2 c cu trc lp. 11.8. Cc ox FeO, CoO, NiO Nh trn nu, cc oxit trn u kt tinh theo mng tinh th nh NaCl vi a(FeO) = 4,29 A ; a(CoO) = 4,24 A ; a(NiO) = 4,17 A (hnh 70) (l) St (II) oxit l cht bt mu en, c iu ch bng cch dng H2 kh Fe2O3 3000C
0 0 0
Hoc bng cch nhit phn Fe(II) oxalat ( cht rn mu vng) trong iu kin khng c khng kh:
Hm lng ca st trong FeO thng b hn so vi hm lng ca nguyn t ng vi cng thc phn t, v cc nguyn t Fe chim khng hon ton cc mt ca mng li tinh th, ng vi cng thc Fe0,95O. FeO khng tan trong nc, nhng c phn ng vi H2O c bit khi un nng. Sau khi nung nng mnh, FeO tr nn tr, ngha l mt hot tnh ha hc cao. FeO d tan trong axit , khng tan trong dung dch kim, l oxit baz. Khi tan trong axit long to ra ion [Fe(OH2)6 ]2+:
(2) Coban(II) oxit l oxit baz. CoO l cht rn mu xanh, to ra khi nung Co(OH)2, CoCO3 hay Co(NO3)2 trong bu kh tr hay trong chn khng:
nu nung trong khng kh s chuyn thnh Co3O4:
Khi nung rt mnh, tt c cc oxit ca coban u chuyn thnh CoO , v khi nung trong lung kh H2 tt c cc oxit u b kh thnh kim loi:
Mu sc ca CoO khan cng khc nhau, ph thuc vo cch sp xp nguyn t trong tinh th, ngoi mu xanh cn c cc mu vng, xm, hung, hoc en, tuy nhin cho n nay ch mi bit c dng lp phng, cha bit c dng th hnh khc. (3) Niken(II) oxit l cht rn mu xanh, c to ra khi nhit phn Ni(OH)2, NiCO3, Ni(NO3)2.
Thc t khng tan trong nc, nhng d tan trong axit. Hiro d dng kh NiO thnh kim loi:
Khi nung mnh, NiO chuyn thnh dng hnh tm mt ng, mu en xm, c v sng kim loi, lc NiO mt kh nng ho tan trong axit. NiO c dng lm cht to mu xm cho thy tinh, lm cht xc tc cho cc phn ng hu c. 11.9. Cc hiroxit Fe(OH)2, Co(OH)2, Ni(OH)2 Phng php chung iu ch cc hiroxit trn l cho mui tc dng vi dung dch kim mnh :
(l) Fe(OH)2 kt ta mu trng, hp th mnh O2 , mu sc xanh thm dn v cui cng thnh mu nu ca Fe(OH)3 :
Cn ch rng amoniac khng th kt ta hon ton Fe(OH)2, v khi c mt lng ln mui amoni, kt ta Fe(OH)2 hu nh khng xy ra do s to thnh phc cht amoniacat ca Fe(II):
nng ion OH- khng th tng rt ln vt qu gii hn , v khi tng nng OH- ng thi li gim nng Fe2+ nn nng cc ion khng t n tch s tan Tt = [Fe2+ ][OH-]2 . Phc cht amoniacat Fe2+ ch bn trng thi rn, trong dung dch nc d dng b thy phn:
Fe(OH)2 tan trong dung dch axit long khng c khng kh; tan trong dung dch kim c to ra hipoferit :
khi lm lnh dung dch, tinh th hipoferit tch ra dng mu xanh - nu. Khi tan trong nc b phn hy. Khi cho Sr(OH)2 hay Ba(OH)2 tc dng ln Fe(OH)2 cng to ra cc hipoferit tng t Sr2[Fe(OH)6] v Ba2[Fe(OH)6] (2) Co(OH)2 tn ti hai dng th hnh : xanh v hng. Khi tc dng
dung dch kim vi mui Co(II), lnh, to ra dng th hnh mu xanh; khi un nng, kt ta Co(OH)2 chuyn thnh dng mu hng:
Trong khng kh , Co(OH)2 b oxi ha chm chuyn thnh Co(III) hiroxit mu hung.
Co(OH)2 c tnh lng tnh, nhng nng v tnh baz. D tan trong axit, tan trong dung dch kim c nng to thnh cobantit mu tm - xanh
Cng tng t, cc hp cht Sr2[Co(OH)6] v Ba2[Co(OH)6] cng c hnh thnh dng tinh th mu tm - . Khi cho dung dch amoniac d tc dng vi mui Co(II) to ra phc cht amoniacat:
Phc cht ny bn hn amoniacat Fe(II) , nhng cng b H2O phn hy:
Ni(OH)2 kt ta mu xanh qu to, khng b oxi ha trong khng kh. C tnh baz, tan trong axit to thnh mui tng ng. Tan trong dung dch amoniac d v trong dung dch mui amoni do to ra phc cht amoniacat :
Cng tng t nh cc amoniacat ca Fe2+ v Co2+, amoniacat ca Ni(II) cng b nc phn hu mt Phn :
Khi d amoniac v mui amoni , cn bng trn chuyn sang tri d hn trng hp ca Fe2+ v Co2+ . Nh vy , dung dch amoniac kt ta khng hon ton cc hiroxit trn. 11.10 Cc halogenua ca Fe(II), Co(II), Ni(II) (l) St(II) ngha v clorua khng th iu ch trc tip t cc n cht. C hai mui trn dng khan c iu ch bng cch cho hiro halogenua tc
dng vi st nung nng:
FeCl2 cng c th iu ch bng cch nung mui kp FeCl2.2NH4Cl hay (NH4)2 FeCl4 trong iu kin khng c khng kh:
Cng c th iu ch bng cch dng H2 kh FeCl3 nung nng:
FeCl2 l cht kt tinh mu trng. 15000C ng vi cng thc FeCl2, nhit thp hn ng vi cng thc Fe2Cl4. Tinh th hirat ha FeCl2.4H2O to ra khi lm bay hi dung dch sau khi cho st tc dng vi axit HCl. Tinh th mu lam. ngoi khng kh c mu lc v b oxi ha mt phn. Khi un nng nh hoc trn H2SO4 c Chuyn thnh FeCl2.2H2O . FeCl2 b oxi ha thnh Fe2O3 v FeCl3 khi un nng trong khng kh:
(2) St(II) bromua v iotua c iu ch trc tip t st v cc halngen.
nu d im to ra Fe3I8 (hay FeI2. 2FeI3 ) FeBr2 l nhng vy c mu vng lc, ht m. Khi un nng n 300oC chuyn thnh Fe2O3 (3) Coban (II) clorua khan c iu ch bng cch nung coban trong lung kh clo:
Dng khan l cht bt mu xanh l, hp th mnh hi H2O to ra CoCl2.6H2O. Tnc = 7220C, d tan trong nc. Mui CoCl2 . 6H2O b mt mt phn nc kt tinh km theo s thay i mu sc kh r rt :
Khi cho H2O tc dng ln CoCl2 khan qu trnh li xy ra ngc li. S thay i mu sc c dng trong cc m k xc nh m ca khng kh. Khi un nng dung dch CoCl2 hay mui coban khc cng c s thay i mu sc. Mu hng ca dung dch CoCl2 long s chuyn thnh mu xanh khi un nng hoc khi tng nng , hoc khi cho thm cc cht nh HCl c, CaCl2, lm ph v s hirat ha ca Co2+, thay th cc phn t H2O trong cu ni bng ion Cr-:
Ngc li , mt dung dch CoCl2 trong ru c mu xanh khi cho thm Zncb hay HgCl2, li chuyn thnh mu hng do phn ng:
(4) Coban(II) ngha v bromua c iu ch bng cch cho coban(II) cacbonat tc dng vi axit tng ng :
cn coban(II) iotua li c th iu ch trc tip t cc n cht :
(5) Niken(II) clorua c th iu ch bng cch cho niken tc dng vi nc cng thy hoc cho tc dng vi niken nung nng: hay (6) Niken(II) bromua v iotua c iu ch bng phn ng trc tip t cc n cht :
cn niken florua c iu ch bng cch nhit phn florua kp niken v amoni. (7) Ni chung cc mui halogenua ca Fe2+ , Co2+ , Ni2+, iu hin thng phn ln u kt tinh vi su phn t H2O ( tr florua ), u d tan trong nc v trong ru. trng thi khan, u c mu khc nhau do chu nh hng ca anion: FClBrIFe2+ Co2+ Ni2+ khng mu nht vng nht khng mu xanh nht hung vng
vng lc nht lc hung sm
hung en en
11.11 Cc sunfua ca Fe(II), Co(II), Ni(II) (1) Cc sunfua FeS, CoS, NiS c iu ch bng cch nung cc kim loi tng ng vi lu hunh, hoc bng cch cho (NH4)2S tc dng vi dung dch mui ca cc kim loi , to ra kt ta mu en, thc t khng tan trong nc. ( Tt(FeS) = 5. 10-18 ; Tt( -Co S) = 2,0. 10-25 ; Tt( - Ni S) = 1.10-24 ). Ngay sau khi kt ta, c ba sunfua u d tan trong axit long k c axit yu nh axit axetic . lu trong dung dch, CoS v NiS chuyn sang dng kh tan trong axit. V cu trc tinh th, c ba sunfua u kt tinh theo kiu NiAs ( hnh 72 ; 73 ).
Kiu kin trc ging nh kiu NaCl, u c s phi tr 6, nhng khong cch t mt tiu phn n cc tiu phn khc bao quanh n l hon ton khc nhau (bn tiu phn sp xp gn hn hai tiu phn kia).
Do kin trc theo kiu NiAs nn c s gim khong cch trong mng li so vi tng bn knh hiu dng ca cc con , v d vi FeS c d = 2,45 A trong khi bn knh hiu dng ca ion Fe2+ = 0,83 A v ca S2- = 1,74 A , iu c gii thch bng s bin dng tng h ca hai ion. Mt iu cn ch l trong tinh th, v d FeS, mt phn nguyn t st c th thay th bi cng mt s nguyn t lu hunh m cu trc v bn ca tinh th khng thay i. Trong ba sunfua trn th FeS c nhiu ng dng thc t, c dng lm nguyn liu iu ch H2S. FeS thc t khng tan trong nc, nhng tan c trong axit long to ra H2S. Trong khng kh m, kt ta FeS dn dn b oxi ha thnh sunfat v cui cng to thnh Fe2O3 :
0 0 0
(2) St(II) isunfua FeS2 thng gp trong thin nhin dng qung git st v qung maccasit. FeS2 c th c iu ch bng cch nung nng FeS vi S:
Trong khng kh m, FeS2 b oxi ha chm to ra FeSO4; nhit cao tch ra lu hunh v thun nghch r rt khong 550 - 7000C; khi nung trong khng kh to ra Fe2O3 V SO2 :
C hai dng pirit v maccasit u c mu vng ng thau, u c v sng kim loi, v c cu to mng tinh th khc nhau. 11.12. Cc xianua ca Fe(II), CO(II), NI(II) (1) Cc hp cht xianua trn u to ra dng kt ta v nh hnh mu vng (Fe), mu (Co) v mu xanh (Ni) khi cho KCN tc dng vi cc mui. Xianua ca st (II) dng tinh khit cha c bit. Khi cho ion Fe2+ tc dng vi ion CN- , kt ta lng xung ban u s nhanh chng to thnh anion phc [Fe(CN)6]4 - :
bit c nhiu mui dng M41[Fe(CN)6] v thng kt tinh dng hirat ha, trong quan trng nht l kali feroxianua K4[Fe(CN)6] tch ra t dung dch dng hirat tinh th K4[Fe(CN)6].3H2O C mu vng, mt nc kt tinh 870C, thng c gi l mui vng - mu ( v trc kia ngi ta iu ch cht ny t mu b ). Cc feroxianua ca kim loi kim v kim th u d tan trong nc, tr bari feroxianua Ba2[Fe(CN)6] l kh tan. Trong dung dch nc, khng c phn ng ca con Fe2+ v CN- ban u v con [Fe(CN)6]4- rt bn ( Kkb 10-37 ):
Ni chung, cc hp cht u bn vi khng kh, vi axit, vi kim, tuy nhin khi nung nng b phn hy v khi tc dng vi H2SO4 c nng to ra CO:
(2) Khi cho HCl c tc dng vi dung dch m K4[Fe(CN)6] to ra kt ta trng H4[Fe(CN)6] :
L axit mnh hai chc u, cn s phn ly tip theo th yu hn ( K3 = 1.10 ; K4 = 5.10-5 ). D tan trong nc v trong rn. Khi un nng vi axit long to ra HCN ( Ts = 260C ) t do:
-3
cn khi tc dng vi CuSO4 to ra kt ta mu nu socola Cu2[Fe(CN)6] :
(2) Khi cho KCN tc dng vi dung dch mui coban (II) hnh thnh kt ta mu nu coban(II) xianua Co(CN)2 :
Co(CN)2 tan trong KCN d to ra dung dch mu vng , sau dn v cui cng to ra tinh th mu tm c thnh phn K4[Co(CN)6] ( kim cobantoxianua):
Hp cht ny bn trong iu kin khng c khng kh, d tan trong nc cho dung dch mu , nhng khi un nng dung dch s b H2O oxi ha ( khng c khng kh):
(3) Khi cho KCN tc dng vi mui niken(II) to ra Ni(CN)2 kt ta mu xanh sng. Khi cho d KCN, kt ta ban u s tan to thnh phc cht mu vng K2Ni(CN)4] , kt tinh dng monohirat K2Ni(CN)4].H2O mu da cam.
Hp cht ny d mt nc v tan nhiu trong nc, b axit mnh phn hy gii phng Ni(CN)2 Khi thm nhiu KCN vo dung dch cha ton [Ni(CN)4]2- mu ca dung
dch t vng chuyn thnh mu , do s to thnh con [ Ni(CN)4 ]4- :
11.13. Cc sunfat ca Fe(II), Co(II), Ni(II) (1) St(II) sunfat l mui quan trng nht trong thc t, dng lng tinh th c thnh phn FeSO4.7H2O. Trong cng nghip c iu ch bng cch dng O2 ca khng kh v H2O oxi; ha pirit Fe(II) nhit thng:
Trong phng th nghim iu ch bng cch ha tan st tinh khit trong H2SO4 long:
Kt tinh t dung dch nc to ra tinh th mu xanh lam [Fe(OH2)6]SO4.H2O. Khi nung nng to ra mui khan mu trng v khi nung nng mnh to ra Fe2O3 :
Phn ng trn c dng iu ch Fe2O3. Nhiu kim loi khc cng kt tinh ng hnh vi FeSO4 vi cng thc tng qut:
Trong : M l Fe, Zn, Cd, Mn, Cr, Co, Ni FeSO4 to ra dung dch mu nu ti khi tc dng vi kh NO do to ra phc cht nitrozo Fe(II) sunfat:
Cng nh cc mui Fe(II) khc, FeSO4 b oxi ha chm khi trong khng kh. Trong mi trng axit to ra mui Fe(II); cn khi khng c mt axit to ra mui baz:
FeSO4 l cht kh tt, kh c mui Ag+ v mui Au3+ thnh kim loi:
Kh c HgCl2 ( hp cht cng ha tr ) thnh Hg2Cl2:
FeSO4 hnh thnh mui kp vi kim loi kim hoc amoni:
(2) Coban(II) sunfat c iu ch bng cch cho kim loi , oxit, hiroxit tan trong H2SO4 .v d:
CoSO4 kt tinh t dung dch dng COSO4.7H2O hay [Co(OH2)6]SO4.H2O mu son. trong khng kh khng h b bin i, nhng khi nung mnh th ban u mt nc kt tinh tr thnh dng khan CoSO4 mu v sau b phn hy thnh Co3O4 :
CoSO4 d tan trong nc nhng khng tan trong ru. Trong dung dch nc 40 - 500C kt tinh dng CoSO4.6H2O. CoSO4 cng to thnh mui kp vi kim loi kim v amoni, v d amoni coban(II) sunfat mu :
ng hnh vi mui amoni magie sunfat. Coban(II) sunfat to ra dng mui baz : dng mu xanh c thnh phn CoSO4. 3Co(OH)2 v dng mu tm c thnh phn 2CoSO4 . 3Co(OH)2 .5H2O. (3) Ni ken (II) sunfat c iu ch bng cch ha tan niken, oxit hoc hiroxit trong
Kt tinh t dung dch nc nhit thp hn 320C to ra tinh th NiSO4.7H2O hay [Ni(OH2)6]SO4.H2O mu xanh. Trn 320C khong 31,5 53,30C kt tinh dng NiSO4.6H2O mu xanh, cn khi kt tinh trn 53,30C to ra dng NiSO4.6H2O mu lc. Tc dng vi kh NH3 to thnh amoniacat :
nhng vi (NH4)2SO4 th to mui kp mu lc xanh:
c dng lm cht m niken. NiSO4 cng to ra mui kp vi cc kim loi kim, v d nh K2SO4 . NiSO4.6H2O. 11.14. Cc nitrat ca Fe(II), Co(III), Ni(II) (l) St(II) nitrat to ra khi ha tan st trong HNO3 long, lnh:
Tt nht l bng phn ng trao i gia FeSO4 v Pb(NO3)2 :
Kt tinh dng hexahirat Fe(NO3)2.6H2O mu xanh sng nhit thng, cn - 100C kt tinh dng nonahirat Fe(NO3)2. 9H2O Khi un nng dung dch st(ll) nitrat b phn hy to thnh mui baz st(III). (2) Coban(II) nitrat c iu ch bng cch ha tan coban, oxit Co(II), Co(OH)2. CoCO3.6H2O trong axit HNO3 long :
Kt tinh trng tinh th hexahirat Co(NO3)2.6H2O mu thm. Chy ra ngoi khng kh m, khi gi nu trn H2SO4 s mt mt phn t H2O. Khi un nng s nng chy gn 550C ri mt nc kt tinh, sau b phn hy.
(3) Niken(II) nitrat c iu ch bng cch ha tan niken kim loi , NiCO3 trong HNO3:
Kt tinh dng hexahirat Ni(NO3)2.H2O mu lam ngc bch, ng hnh vi mui coban tng ng. Niken(II) nitrat d ln hoa trong khng kh kh, v chy ra nhanh trong khng kh m. Nng chy trong nc kt tinh 57oC, tip tc un nng cao hn 85,40C mt dn nc kt tinh, v n 3000C phn hy cn li Ni2O3 v NiO :
Ni2O3 l Cht bt mu xm hoc en, do ngi ta dng Ni(NO3)2 to mu xm trong cng nghip gm. 11. 15. Mui cacbonat ca Fe(II), CO(II), Ni(II) (1) St(II) cacbonat gp trong thin nhin thnh nhng m ln dng khong cht xierit. c iu ch bng cch cho dung dch mui Fe2+ tc dng vi dung dch mui cacbonat trung tnh chng hn Na2CO3
FeCO3 l cht rn mu trng khng tan trong nc, nhng tng t nh CaCO3 tan r rt trong nc c cha CO2 v to nn mui hiro cacbonat :
Fe(HCO3)2 cng d b phn hy khi un nng. Trong nc thin nhin thng c st dng st(II) hirocacbonat cng vi Ca(HCO3)2 v Mg(HCO3)2 trng thi m, nhanh chng tr thnh mu lc v sau chuyn thnh nu khi trong khng kh, do qu trnh thy phn dn dn v qu trnh oxi ha to thnh Fe(OH)3:
Khi un nng , FeCO3 b phn hy:
p sut hi khi phn hy l 1atm 2820C. Fe(HCO3)2 cng b oxi ha thnh Fe2O3 :
(2) Coban(II) cacbonat; niken(II) cacbonat kt ta dng hirat tinh th CoCO3. 6H2O ( mu ) l NiCH2. (mu hng nht ) khi cho cc hirocacbonat ca kim loi kim tc dng vi mui ca CO(II) v NI(II):
Khc vi cch iu ch FeCO3 nu cho cc mui CO(II) , Ni(II) tc dng vi Na2CO3 th sn phm thu c li l mui cacbonat baz kt ta COCO3. nCo(OH)2 (mu xanh); NiCO3.mNi(OH)2 mu lc sng. Mui khan CoCO3 v NiCO3 c th iu ch bng cch un nng dng hirat tinh th trong ng hn kn 1400C.
CoCO3 thc t khng tan trong nc ( Tt = 8.10-13 250C ) , cn NiCO3 c tch s tan Tt = 6,6. 10-9 nhng NiCO3. mNi(OH)2 li c tch s tan Tt = 1,7. 10-7 CC HP CHT VI OXI HA +3 Nh nu mc 11.2 hp cht ng vi s oxi ha +3 ca niken l khng c trng, nn trong phn ny ch yu trnh by cc hp cht ca Fe(III) v Co(III). S phi tr ca Fe(III) l bng 6 v 4 ng vi s phn b tm mt v bn mt. Chng hn FeCl3 trng thi hi ng vi cng thc Fe2Cl6 ( dng Al2Cl6 ) cn khi ha vo nc to ra phc cht tm mt [Fe(OH2)6]3+ . S phi tr c trng ca Co(III) l bng 6, chng hn cc ion Co(OH2)6]3+, [Co(NH3)6]3+. Mu Sc Ca cc hp cht st (III) ph thuc vo bn cht ca anion. V d FeCl3 - mu nu en; Fe(CNS)3 - mu mu; Fe2S3 - mu en; Fe(NO3)3. 6H2O - mu tm sng. Cc hp cht ca Fe(III) u c tnh oxi ha; trong dung dch cc mui Fe(III) b kh n mui Fe(II).
11.16. Cc oxit Fe2O3, Co2O3, Fe3O4, Co3O4 (1) St (III) oxit to ra ba dng th hnh l - Fe2O3 dng thun t , dng - Fe2O3 l dng st t v dng - Fe2O3 c cu trc kiu corinon. Khi nung st (III) hiroxit, ni ng hn l oxit b hirat ha Fe2O3. nH2O , nhit thp hn 6500C to ra cht rn dng bt mu nu, nhng nu nung nhit cao hn to thnh tinh th mu xm en khng cn kh nng tan trong axit, tng t nh Cr2O3, Al2O3 dng tinh th :
Fe2O3 Cng c th iu ch bng cch nung FeSO4.7H2O ; FeO hoc mt mui st (II) ca axit d bay hi khc :
Ngoi ra trong cng nghip c iu ch bng cch nung qung pirit m thnh phn chnh l FeS2
Fe2O3 nng chy 15650C v thng hoa 20000C.

Fe2O3 tan trong axit to thnh ion phc [Fe(OH2)6]3+ khng mu ; mu nu ca dung dch mui st (III) l do mu ca sn phm phn ng thy phn, tc l mu ca cc con phc hiroxo - aquo :
Bn cnh tnh cht ch yu l tnh baz, Fe2O3 cn c tnh axit to thnh mui ferit mu vng hoc , khi nung hn hp Na2CO3 + Fe2O3 :
Khi nung vi C, hoc nung trong lung kh CO, H2 hoc kh than , Fe2O3 s b kh thnh Fe:
(2) Coban(III) oxit c iu ch bng cch nhit phn Co(NO3)2 :
Cng c iu ch dng tinh khit bng cch nung Co(OH)2 trong l in 350 - 3700C trong chn s:
c sn phm tht tinh khit ngi ta dng phn ng sau:
Co2O3 l Cht bt mu nu sm, nung n gn 6000C to thnh CoO4 l cht bt mu
Nung 13000C phn hy tip to ra 4CoO. Co2O3 v cui cng l CoO :
Co2O3 cng b hiro kh n kim loi :
tan trong axit HCl to ra Cl2 v vi H2SP4 to ra O2:
(3) Niken(III) oxit to ra khi nung trong khng kh mui cacbonat hoc
nitrat niken(II) 3000C :
tuy nhin thnh phn ca sn phm thu c t cc phn ng c hm lng oxi thp hn so vi cng thc Ni2O3. L cht bt mu en hoc xm, cng nh Co2O3, Ni2O3 l cht oxi ha mnh, chng hn tan trong HCl to ra kh Cl2 :
(4) St(II, III) oxit ( Fe3O4) c thnh phn ng vi khong cht oxt st t c iu ch bng cch nung nng Fe2O3 nhit trn 14500C :
Khi nung st trong khng kh to ra Fe3O4 ( Cng vi cc sn phm khc):
Fe3O4 cng to ra khi cho lung hi H2O hoc CO2 qua st nung :
Cng c th iu ch bng cch cho hn hp hiro v hi nc i qua Fe2O3 nung
Ngoi ra iu ch dng tinh khit ngi ta cho dung dch FeSO4 v Fe2(SO4)3 tc dng vi dung dch KOH, un si thu c kt ta Fe3O4 :
lm kh kt ta trong kh quyn H2 thu c sn phm vi thnh phn Fe3O4 .2H2O. Fe3O4 l cht bt mu en, nng chy 15400C; nung nhit cao hn , mt mt phn oxi to ra FeO:
trng thi m, d b oxi ha ngoi khng kh to ra Fe2O3:
Khi tc dng vi t axit to ra Fe2O3 V dung dch mui st (II) , sau thm tip axit n d, s tan hon ton to nn mui st(II) v st(III):
Fe3O4 b (Al, H2), CO kh thnh kim loi:
Oxit st t thin nhin (manhetit) khng tan trong kim v axit, li c dn in cao nn i khi c dng lm in cc trong mt s qu trnh in ha ,nh in phn mui clorua kim loi kim... Ngi ta cng xem Fe3O4 nh l mt mui ca axit fer HFeO2 v Fe(OH)2
(5) Coban(II, III) oxit (Co3O4) c to ra khi nung coban(II) nitrat:
Cng c to ra khi nung CoO trong khng kh:
Co3O4 l Cht bt mu en, b H2 kh thnh kim loi khi nung nng:
tc dng vi axit HCl to ra mui Co(II) v ch:
Khc vi Fe3O4, trong mng tinh th c ion kim loi ha tr II v ha tr III, trong Co3O4 c ion kim loi ha tr II v ha tr IV, v c xem l mt mui ca Co2+ tng t Mn3O4 : CO2II[CoIVO4] 11.17. Cc hiroxit Fe(OH)3, Co(OH)3, Ni(OH)3 (1) St (III) hiroxit l cht kt ta mu nu c to ra khi cho mt tc nhn kt ta nh kim, amoniac, dung dch cacbonat tc dng vi mui Fe(III):
Thc ra, dng kt ta keo mu nu v nh hnh l dng Fe2O3. nH2O, vi hm lng nc khc nhau. Trong cng thc thng vit Fe(OH)3 chnh l Fe2O3 .3H2O; trong thin nhin, dng hematit nu Fe2O3 .H2O hay l FeO(OH). Fe(OH)3 kh l nhng cc xp, khi lng ring thay i trong khong t 3,4g/cm3 n 3,9g/cm3 . Hu nh khng tan trong nc ( Tt = 4.10-38 ).
Kh nng ha tan trong axit ph thuc vo "tui" ca kt ta. Kt ta va mi iu ch d tan trong axit v c v hu c, nhng lu mt thi gian th li kh tan. Khi un nng n 500 - 7000C s mt nc hon ton bin thnh Fe2O3:
Bn cnh tnh cht ch yu l tnh baz, Fe(OH)3 cn th hin tnh axit yu ( axit fer HFeO2) nn khi cho Fe(OH)3 tc dng vi kim c nng hoc bng cch nu chy vi Na2CO3 hay K2CO3 to thnh cc mui ferit NaFeO2 hay KFeO2 :
NaFeO2 hay cc ferit khc u b thy phn n kim v Fe2O3:
Ngi ta cng li dng phn ng trn iu ch NaOH trong cng nghip bng cch nung hn hp Na2CO3 v Fe2O3 11000C:
sau cho NaFeO2 thy phn nh trn. Ngoi cc ferit ca kim loi kim, ngi ta cn bit mt s ferit khc nh Mg(FeO2)2 Zn(FeO2)2 .v.v.. (2) Coban(III) hiroxit l cht bt mu nu en, to ra khi oxi ha Co(OH)) bng oxi ca khng kh tng t Fe(OH)2 hoc oxi ha nhanh cc mui Co(II) khi cho tc dng vi cc cht nh NaOCl , Cl2, Br2, H2O :
Co(OH)3 l cht khng tan trong nc ( Tt : 4.10-45 ), tan trong axit to thnh mui CO(III), trong kim c d to ra mui hiroxo, v d : K3[Co(OH)6]. (3) Niken(III) hiroxit l cht bt mu en, to ra khi oxi ha Ni(OH)2 bng oxi khng kh hoc bng brm trong mi trng kim to thnh oxit b hirat ha NiO(OH), thng vit dng Ni(OH)3. Qu trnh oxi ha cng c thc hin bng cch oxi ha in phn trong mi trng kim. Ngi ta li dng tnh oxi ha ca Ni(OH)3 ch to cquy kim ( Acquy Edisen). Khc vi cquy ch , cquy kim gm mt in cc bng Fe, v mt in cc c ch to bng bt oxit Ni(III) ngm nc vi
cht in ly l KOH. S vn hnh ca loi cquy trn theo s :
Nhc im ca loi cquy ny l h s hiu dng thp. Cc mui Fe(III), Co(II) Cc mui Fe(III) c iu ch bng cch oxi ha cc mui Fe(II) hoc Fe(OH)2 bng axit tng ng. V d ha tan Fe(OH)2 trong HNO3:
Dung dch ca cc mui Fe(III) khng c axit d, c mu thay i t vng - nu n nu thm, mu sc khng phi l mu ca ion Fe3+ m do dng keo ca mui baz gy ra bi phn ng thy phn. Bn thn ca ion Fe3+ khng mu, trong dung dch dng hirat ha [Fe(OH2)6]3+ mu vng nht, mu vng m dn do qu trnh:
Trong mi trng axit d, mu ca dung dch li ph thuc vo bn cht ca anion v axit thm vo. V d dung dch FeF3 khi thm axit HCl c mu hng , cn dung dch FeCl3 c mu vng. Cc mui Fe(III) u d b kh n mui Fe(II) bi cc cht nh hiro mi sinh , SO2, SnCl2, H2S, KI v mt s kim loi m in hn nh Zn... V d :
Tr oxit Co(III) v cc phc cht, ni chung cc mui Co(III) u km bn v u c tnh oxi ha. 11. 18. Cc halogenua ca Fe(III), Co(III) (1) St (III) ngha c iu ch khi ha tan Fe(OH)3 trong axit HF, sau khi lm bay hi trn ni cch thy thu c tinh th FeF3. 3H2O. Tinh th hirat ha c mu hng nht; dng khan c mu hi xanh. (2) St (III) clorua thu c khi cho kh clo kh qua bt st nung nng to ra FeCl3 khan :
Khi ha tan st trong axit HCl, sau cho kh clo qua dung dch, t dung
dch ny tinh th hexahirat FeCl3. 6H2O s tch ra:
FeCl3 khan l nhng tinh th mu hung en dng vy hoc phin, c mu lu trong nh sng truyn qua v c mu lc trong nh sng phn chiu. Nng chy 3000C thnh cht lng linh ng mu . Si v phn hy mt phn 3170C. 4400C, t khi hi ng vi cng thc kp Fe2Cl6 (hnh 74 ); 7500C ng vi cng thc ln FeCl3; trn 7500C ng vi s phn hy FeCl3 thnh FeCl2 v Cl2 :
Trong khng kh, FeCl3 d b chy ra, nhng khi nung FeCl3 trong khng kh hoc cho lung hi nc i qua s chuyn thnh Fe2O3 :
FeCl3 d b kh n FeCl2 nh nu trn. (3) Fe(III) bromua mu hung, cng c iu ch tng t FeCl3:
Dng khan c mu nu ; dng hirat ha FeBr3.6H2O l nhng tinh th c mu lc thm. C hai dng u d tan trong nc. Khi nung nhit cao FeBr3 b phn hy d hn so vi FeCl3 :
(4) St (III) iotua khng bn ngay nhit thng, ch bn trong cn bng vi lng d ln FeI2
do khng th tch ra dng nguyn cht. Khi nghin I2 vi bt st to nn sn phm c thnh phn Fe3I8 ( tc 2FeI3. FeI2). Khi nung sn phm ny vi K2CO3 to ra KI:
Phn ng trn dng iu ch Ki trong k thut t rt t do. (4) Coban(III) florua bn nht trong halogenua ca Co(III) . CoF3 l cht bt mu hung lc c th iu ch bng cch cho flo tc dng vi CoF2 3000C:
Cng c iu ch dng hirat CoF3.3,5H2O khi in phn vi in cc platin mt dung dch bo ha CoF2 trong dung dch HF 40%, thu c tinh th mu lc ti anot. Nc tinh khit phn hy COF3 thnh Co(OH)3:
Khi un nng n 3000C trong lung CO2, CoF3 b phn hy thnh CoF2 v F2. (5) Coban(III) clorua rt khng bn. Khi cho Co(OH)3 tc dng vi HCl khng thu c CoCl3 do phn ng:
nhng c th iu ch bng cch cho Co2O3 tc dng vi hiro clorua trong bng ti - 50C di lp ete kh. 11.19.Cc sunfat ca Fe(III), Co(III) (1) St (III) sunfat c iu ch bng cc cch sau y : Ha tan hiroxit st(III) trong H2SO4 :
un nng FeSO4 vi H2SO4 c:
un nng FeSO4 vi HNO3 v H2SO4 c theo phng trnh:
Ch ha Fe2O3 vi axit sunfuric c :
trng thi khan l cht bt mu trng hoc vng nht, ht m mnh, ngoi khng kh s chy ra thnh cht lng mu hung. To nn vi nc mt s dng hirat ha nh Fe2(SO4)3. 9H2O v Fe2(SO4)3.l0H2O. C hai dng ny cng gp trong thin nhin. Khi tan trong nc c kh nng to thnh dung dch rt m c, nhng qu trnh tan kh
chm. Tan trong ru , nhng khng tan trong H2SO4. Dung dch nc c mu nu do b thy phn mnh, nhng nu cho thm H2SO4, phn ng thy phn b hn ch v dung dch hu nh khng mu. Khi un si dung dch long, mui baz s kt ta:
Khi un nng, s mt dn nc kt tinh to ra Fe2(SO4)3 khan v sau b phn hy:
St(III) sunfat c kh nng to ra mui kp dng MI. Fe(SO4)2. 12H2O c gi l phn - st. Quan trng hn c l phn st - amoni NH4. Fe(SO4)2. 12H2O v phn st - kali K.Fe(SO4)2.12H2O, c dng lm cht cm mu vi. trng thi tinh khit cc loi phn st ny u khng mu, nhng thng c mu tm nht l do c du vt ca mangan(III) sunfat. Phn c iu ch bng cch oxi ha dung dch FeSO4.7H2O bng HNO3, c dung dch n trng thi bo ha th thm mt lng ng phn t amoni sunfat hoc kali sunfat:
330C phn - st amoni bin thnh mu nu; nng chy khong 40 410C, n 1500C mt 23 phn t H2O v 7500C to thnh phn khan. (2) Coban(III) sunfat c iu ch bng cch in phn dung dch c CoSO4 trong H2SO4, thu c tinh th mng hnh kim mu xanh nht, anot lm lnh n 00C, c dng hirat ha Co2(SO4)3. 18H2O; b H2O phn hy, nhng trong dung dch H2SO4 long li khng b phn hy. H2O phn hy Co2(SO4)3 to ra oxit
Vi sunfat kim loi kim v amoni , Co2(SO4)3 to ra phn - coban , v d phn coban - kali c iu ch khi lm lnh dung dch ng phn t K2SO4 v Co2(SO4)3. Phn K2SO4 . Co2(SO4)3 . 24H2O l nhng tinh th tm mt mu xanh thm, b H2O phn hy nhit phng to ra O2. Phn coban- rubii v phn coban - xezi cng c mu xanh thm nhng kh tan hn nhiu so vi phn coban - kali. Phn coban - anloni (NH4)2SO4.Co2(SO4)3 .24H2O cng thu c khi in phn dung dch gm (NH4)2SO4 v CoSO4
11.20. St (III) nitrat c to ra khi ha tan v bo st trong HNO3 long gn 25% to ra Fe(III) nitrat v hn hp cc oxit no khc nhau. nhit thng , ph thuc vo nng , mui c th kt tinh dng khng mu hnh lp phng c thnh phn Fe(NO3)3. 6H2O hoc dng n t mu tm c thnh phn Fe(NO3)3 . 9H2O. St(III) thut tan trong nc to ra dung dch mu nu do thy phn, mu s mt dn khi cho thm HNO3. Trong cng nghip , st(III) thut c dng lm cht cn mu. 11.21. Cc sunfua ca Fe(III) v Co(III) (1) Fe(III) sunfua ( Fe2S3 ) c to ra dng kt ta mu en khi cho H2S hoc (NH4)2S tc dng vi mui Fe3+ trong mi trng trung tnh hoc kim yu(amoniac). trng thi m, Fe2S3 b phn hy nhanh chng trong khng kh to thnh Fe(OH)3 v lu hunh t do:
Fe2S3 thc t khng tan trong nc , tan trong dung dch HCl long:
Tuy nhin, ngi ta nghi ng kt ta c phi l hon ton l Fe2S3 khng, hay l mt hn hp gm FeS v S to ra do phn ng :
Khi nung st vi S khng to ra st(III) sunfua. Trong thin nhin gp dng mui kp Cu2S. Fe2S3 v 3Cu2S. Fe2S3 (2) Coban(III) sunfua ( Co2S3 ) ch to ra khi nung nng chy mui Co2+ vi S V Na2CO3; sn phm thu c l nhng tinh th mu xm, khng tan trong nc v rt kh tan trong axit c 11.22. Phc cht xianua ca Fe(III) v Co(III) (1) Kali ferixianua ( K3[Fe(CN)6]) c iu ch bng cch oxi ha km feroxianua K4[Fe(CN)6] bi cc cht nh Cl2, KMnO4, HNO3 hoc H2O2:
Hp cht ny khng th iu ch bng phng php nh khi iu ch
K4[Fe(CN)6] , ngha l khng th cho mui Fe3+ tc dng vi dung dch KCN , v s to ra kt ta Fe(OH)3 do s thy phn KCN to ra mi trng kim. K3[Fe(CN)6] l cht kt tinh mu - gch, khi nghin nh chuyn thnh cht bt mu vng, tan trong nc cho dung dch mu vng. Trong dung dch nc, khng c phn ng ca ion Fe3+ v ion CN- v ion [Fe(CN)6]3- rt bn ( Kkb 10-44) :
K3[Fe(CN)6] l cht oxi ha mnh, c bit hot ng trong mi trng kim, kali ferixianua c th oxi ha PbO thnh PbO2 ; hp cht Cr3+ thnh Cro42; H2S thnh S:
Khi cho HCl c tc dng vi dung dch bo ha K3[Fe(CN)6] to ra tinh th mu nu l axit ferixian hiric H3[Fe(CN)6] :
un nng K3[Fe(CN)6] vi dung dch KOH c ( vi t l l: 1 to ra K4[Fe(CN)6] v O2:
Vi mui Fe2+, dung dch K3[Fe(CN)6] to ra kt ta mu "xanh Tuabun" (Tumbull) :
Ngc li, cc mui Fe3+ li tc dng vi dung dch kim feroxianua K4[Fe(CN)6] to ra kt ta mu " xanh Ph" cn gi l " xanh Beclin" hay " xanh Pht Prussian):
Trong ion [Fe(CN)6]3- c 17 electron ha tr (12 electron ca 6 nhm CNv 5 electron ca ion trung tm), c cu hnh :
nhng mun c cu hnh bn [n(d)]6 cn phi thm mt electron, do ion [Fe(CN)6]3- l cht oxi ha mnh; tnh oxi ha ca ion [Fe(OH2)6]3+ cng gii thch tng t; tuy nhin, [Fe(CN)6]3- c tc dng oxi ha mnh trong mi trng kim, cn ion [Fe(OH2)6]3+ - trong mi trng axit. (2) Kali cobantixianua ( K3[Co(CN)6) l nhng tinh th mu vng, thu
c khi cho mui Co2+ tc dng vi KCN trong iu kin c cht oxi ha:
Nu mui tc dng vi HNO3 hay H2SO4 S thu c tinh th khng mu l axit cobantixian hiric :
Axit cng c th iu ch bng cch cho K3[Co(CN)6] tc dng vi CuSO4 to ra kt ta mu xanh l Cu3[Co(CN)6]2 Sau cho phn hy vi H2S:
Axit cobantixianhiric l axit mnh ba ln axit, kt tinh dng hirat ha H3[Co(CN)6].5H2O , trong dung dch nc ch bn di 500C. Khi un nng lu n 1200C to ra Co(CN)3 mu xanh:
(3) St(III) thioxianat ( Fe(NCS)3 ) hay st(III) sunfoxianua c to ra khi cho mui Fe3+ tc dng vi KNCS hay (NH4)NCS :
l cht mu mu, c th tch ra t dung dch dng hirat tinh th Fe(NCS)3. 3H2O mu thm, d tan trong nc. Mu mu ca dung dch chnh l mu ca ion [FeNCS]2+.
HP CHT CA ST VI S OXI HA +6 Hp cht gp dng ion FeO42- to ra khi oxi ha kim loi Fe hoc hp cht ca Fe(III) bng cht oxi ha mnh trong mi trng kim mnh. Khi nu chy Fe2O3 vi KNO3 v KOH to nn mui K2FeO4 theo phn ng :
hoc khi nu chy Fe2O3 vi Na2O2 :
hoc cho clo tc dng vi huyn ph Fe(OH)3 trong kim c:
Cc ferat c mu sm, t bn trong dung dch nc, khi un nng nh gii phng ra oxi
Cho tc dng vi BaCl2 to ra kt ta mu tm ca bari ferat:
Cc ferat u l cht oxi ha mnh, v d oxi ha amoniac iu kin thng dn n nit t do:
TI LIU THAM KHO 1 . Bernard M . Comparative Inorganic Chemistry - Edward Arnold , New York 1991 2 . Brown L .T Lemay E . H Bursten EB . Chemistry : The Central Science Prentice Hall, Englewood Chiffs , New Jersay , 1991 . 3 .Frederick Presscott - Intermediate Chemistry Inorganic and Physical University Tutoral Press LTD . London 1947. 4 . Graham Lappin - Redox Mechanisms in Inorganic Chemistry, Ellis Horwood New York - 1994 . 5 . John Burgess , M.A - Metal Ions in Solution - Ellis Horwood Limited - New York - 1978 . 6 . William.L. Jolly - Modern Inorganic Chemistry - Second Edition - McGraw Hill, Inc . New York 1991 . 7 . H.C. . . , 1981. 8. . . . , 1963. 9. . . , , 1968. 10. .., . . . , 1969. 11. ., . . . , 1971,( I). 12. . . . . . , 1968. 13. .. . -e () - - 1965. 14. .. . . . . , 1967. 15. B. V. Nhekraxop. Gio trnh ha hc i cng (bn dch ting Vit). Nh xut bn Gio dc-H Ni, 1967. 16. F. Cotton - G. Wilkinson . C s ha hc v c (Bn dch ting Vit ). Nh xut bn H v THCN, H N i 1984. 17. T.U.V. Kariakin - I.Z. Angelop Thuc th ha hc tinh khit (Bn dch ting Vit). Nh xut bn H v THCN, H Ni 1984 . 18. Hong Nhm - Ha hc v c, Tp 2 - Nh XBGD, H Ni 1994 .
MC LC
Li ni u .............................................................................................................................. 2 CHNG 1 I CNG V KIM LOI 1. 1. S phn b kim loi trong thin nhin. V tr kim loi trong bng tun hon
3
1.2. Cu trc tinh th ca kim loi .................................................................................... 5 1.3. Thnh phn v cu trc tinh th ca hp kim ........................................................ 9 1. 4. Lin kt kim loi ......................................................................................................... 11 1 5. Tnh cht l hc ca kim loi ................................................................................... 15 1.6. Tnh cht ha hc ca kim loi ................................................................................ 19 1.7. Tng quan v cc phng php iu ch kim loi .............................................. 22 CHNG 2 CC NGUYN T NHM IA (KIM LOI KIM) 2.1. Nhn xt chung v cc nguyn t nhm IA .......................................................... 25 2.2. Trng thi thin nhin v thnh phn cc ng v............................................... 26 2.3. iu ch cc kim loi kim ....................................................................................... 28 2.4. Tnh cht l hc cc kim loi kim v ng dng................................................. 29 2.5. Tnh cht ha hc ca cc kim loi kim .............................................................. 32 2.6. Hirua ca cc kim loi kim ................................................................................... 34 2. 7. Oxit ca cc kim loi kim ...................................................................................... 35 2.8. Hirox cc kim loi kim ........................................................................................ 38 2.9. Mui ca cc kim loi kim ...................................................................................... 41
2.10. Halogenua ca kim loi kim................................................................................. 41 2.11. Cacbonat ca kim loi kim ................................................................................... 46 Na2CO3 tinh khit c iu ch bng cch nhit phn NaHCO3 .......................... 49 2.12. Sunfat cc kim loi kim ......................................................................................... 52 2.13. Nitrat cc kim loi kim .......................................................................................... 55 2.14 . Mui kh tan ca kim loi kim........................................................................... 56 CHNG 3 CC NGUYN T NHM IIA (KIM LOI KIM TH) 3.1. Nhn xt chung v cc nguyn t nhm IIA ........................................................ 58 3.2. Trng thi thin nhin v thnh phn cc ng v............................................... 59 3.3. iu ch cc kim loi kim th................................................................................ 61 3.4. Tnh cht l hc cc kim loi kim th v ng dng ......................................... 63 3.5. Tnh cht ha hc ca cc kim loi kim th ....................................................... 66 3.6. Hirua ca cc kim loi kim th ............................................................................ 70 3. 7. Cc oxit v peoxit ca kim loi kim th ............................................................. 70 3.8. Hiroxit ca kim loi kim th ................................................................................ 76 3.9 Mui ca cc kim loi kim th............................................................................... 78 3.10. Halogenua ca cc kim loi kim th .................................................................. 78 3.12. Cacbonat ca kim loi kim th ............................................................................ 85 3.13. Sunfat ca kim loi kim th.................................................................................. 89 CHNG 4 CC NGUYN T NHM IIIA ( NHM - GALI - INI - TALI) 4.1. Nhn xt chung v cc nguyn t nhm IIIA ....................................................... 92 4.2. Trng thi thin nhin v cc thnh phn ng v............................................... 94
NHM V HP CHT CA NHM 4.3. iu ch nhm ............................................................................................................. 96 4.4. Tnh cht l hc ca nhm ........................................................................................ 98 4.5. Tnh cht ha hc ca nhm ..................................................................................... 98 4.6. Hp kim ca nhm .................................................................................................... 101 4. 7. Nhm oxit A12O3 .................................................................................................... 101 4.8. Nhm hiroxit ............................................................................................................ 102 4.9. Nhm halogenua ........................................................................................................ 105 4.10. Nhm sunfat v phn nhm .................................................................................. 110 4.11. Cc hp cht khc ca nhm ................................................................................ 112 Nhm nitrat. .................................................................................... 112 Nhm axetat ................................................................................... 112 Nhm hirua ................................................................................... 112 Nhm sunfua ................................................................................ 113 Nhm nitrua .................................................................................. 113 CC KIM LOI GALI - INI - TALI ........................ 114 4.12. iu ch Ga, In, Tl ................................................................................................ 114 4.13. Tnh cht ca Ga, In, Tl ......................................................................................... 114 4.14. Cc hp cht Ga(III), In (III), Tl(III) ................................................................. 115 4.15. Cc hp cht M(I), M(II) ...................................................................................... 118 CHNG 5 CC NGUYN T NHM IVA (GECMANI - THIC - CH) 5.1. Nhn xt chung v cc nguyn t nhm IVA .................................................... 121
5.2. Trng thi thin nhin v thnh phn cc ng v............................................. 123 5.3. iu ch Ge, Sn, Pb .................................................................................................. 124 5.4. Tnh cht l hc v ng dng ................................................................................. 125 5.5. Tnh cht ha hc ca Ge, Sn, Pb.......................................................................... 126 5.6. Hirua ca gecmani , thic v ch ......................................................................... 129 5.7. Oxitgecmani, thic , ch ........................................................................................... 130 5.8. Hiroxit gecmani, thic, ch .................................................................................... 136 5.9. Halogenua gecmani , thic, ch .............................................................................. 139 5.10. Sunfua ca gecmani , thic , ch .......................................................................... 145 5.11. Mt s mui khc ca thic v ch ..................................................................... 146 CHNG 6 I CNG V NGUYN T CHUYN TIP 6.1. V tr cc kim toi chuyn tip trong bng tun hon ...................................... 150 6.2. c im cu to nguyn t cc kim loi chuyn tip dy th nht (1) ...... 152 6.3. Tnh cht l - ha hc ca cc kim loi chuyn tip dy th nht ................ 155 6.4. Nhn xt chung cc nguyn t dy chuyn tip th hai v th ba ................ 157 CHNG 7 CC NGUYN T NHM IB ( NG - BC - VNG ) 7.1 . Nhn xt chung v cc nguyn t nhm IB ....................................................... 164 7.2. Trng thi thin nhin v thnh phn cc ng v............................................. 166 7.3. iu ch Cu, Ag, Au................................................................................................. 168 7.4 . Tnh cht l hc ca Cu, Ag , Au v ng dng ................................................ 169 7.5. Tnh cht ha hc ca Cu, Ag, Au ........................................................................ 171 7.6. Cc hp cht vi s oxi ha +1 .............................................................................. 175
Oxit M2O ... ..175 Hiroxit MOH .......................................................................................................... 177 Cc mui Halogenua MX......178 Hp cht xianua ....................................................................................................... 181 Hp cht sunfua MCN ............................................................................................ 182 Hp cht hirua , nitrua , cacbua .......................................................................... 182 Cc hp cht khc ca Ag(I) ................................................................................. 183 Tng t kim loi kim, Ag cng to ra c AgHSO4 ........................................ 183 7. 7 . Cc hp cht vi s oxi ha +2 ........................................................................... 184 Cc oxit Hiroxit
......................................................................................................... 184 .......................................................................................................... 185
Cc halogenua .................................................................................................... 185 Cc loi mui khc ............................................................................................ 187 7.8 . Cc hp cht vi s oxi ha +3............................................................................. 189 Au2O V Au(OH)3.................................................................. 189 Cc halogenua Au(OH)3 CHNG 8 CC NGUYN T NHM II B (KM - CAIMI THY NGN) 8.1 . Nhn xt chung v cc nguyn t nhm IIB ..................................................... 191 8.2 . Trng thi thin nhin v thnh phn cc ng v ........................................... 193 8.3 . iu ch Zn, Cd , Hg ............................................................................................... 194 8.4. Tnh cht l hc Zn, Cd , Hg v ng dng .......................................................... 195 8.5. Tnh cht ha hc ca Zn , Cd , Hg ...................................................................... 198
... ..190
Au(NO3)3, Au2(SO4)3, v Au2S3 ...190
8.6. Cc hp cht vi s oxi ha + 2............................................................................. 200 Cc oxit MO............................................................................ 202 Cc hiroxit M(OH)2.............................................................. 203 Cc halogenua ......................................................................... 204 Cc sunfua............................................................................... 206 Cc xianua............................................................................... 207 Cc nitrat ................................................................................. 208 Cc sunfat................................................................................ 209 Mui cacbonat......................................................................... 210 Cc hp cht khc ................................................................... 210 8.7. Hp cht thy ngn (I) ............................................................................................. 211 CHNG 9 CC NGUYN T NHM VIB (CROM - MOLIPEN - VONFRAM) 9.1. Nhn xt chung v cc nguyn t nhm VIB ..................................................... 216 9.2. Trng thi thin nhin v thnh phn cc ng v............................................. 218 9.3. iu ch Cr, Mo, W .................................................................................................. 219 9.4. Tnh cht l hc ca Cr, Mo, W v ng dng .................................................... 220 9.5. Tnh cht ha hc ca Cr, Mo, W ......................................................................... 221 9.6. Cc hp cht vi s oxi ha +2 .............................................................................. 223 Crom(II) oxit (CrO) hiroxit ....................................................... 224 Crom(II) clorua ................................................................................ 224 Crom(II) sunfat ................................................................................ 225 Molipen (II) clorua ........................................................................ 225 Vonfram Clorua ...226
Vonfram bromua .............................................................................. 226 9.7. Hp cht vi s oxi ha +3 ..................................................................................... 226
Crom(III) oxit ................................................................................... 226 Crom hiroxit (Cr(OH)3) .................................................................. 227 Crom(III) clorua (CrCl3).................................................................... 228 Crom (III) sunfat (Cr2(SO4)3)........................................................... 229 Crom(III) nitrat (Cr(NO3)3). ............................................................. 229 Crom(III) sunfua (Cr2S3) .................................................................. 229 Crom (III) xianua (Cr(CN)3)............................................................. 230 9.8. Cc hp cht vi s oxi ha +6 .............................................................................. 230 CHNG 10 CC NGUYN T NHM VII B (MANGAN - TECNEXI - RENI) 10.1. Nhn xt chung v cc nguyn t nhm VIIB ................................................ 237 10.2. Trng thi thin nhin v thnh phn cc ng v .......................................... 239 10.3. iu ch Mn, Tc, Re .............................................................................................. 240 10.4. Tnh cht l hc ca Mn, Tc, Re v ng dng................................................. 240 10.5. Tnh cht ha hc ca Mn, Tc, Re ...................................................................... 241 10.6. Cc hp cht vi s oxi ha +2 ........................................................................... 243 10.7. Cc hp cht vi s oxi ha +4 ........................................................................... 246 10.8.Cc hp cht vi s oxi ha +6............................................................................. 248 10.9. Cc hp cht vi s oxi ha +7 ........................................................................... 249 CHNG 11 CC NGUYN T NHM VIII B (ST - COBAN - NIKEN V H PLATIN) 11.1. Nhn xt chung v cc nguyn t nhm VIIIB ............................................... 254 11.2. Nhn xt chung v kim loi h st ...................................................................... 256 11.3. Trng thi thin nhin v thnh phn cc ng v .......................................... 258
11. 4. iu ch Fe, Co, Ni ............................................................................................... 259 11. 5. Tnh cht l hc ca Fe, Co, Ni v ng dng ................................................. 261 11.6. Tnh cht ha hc ca Fe, Co, Ni ........................................................................ 263 11.7. Hp cht cacbonyl ca Fe, Co, Ni ...................................................................... 267 CC HP CHT VI S OXI HA +2 11.8. Cc oxit FeO, CoO, NiO ....................................................................................... 270 11.9. Cc hiroxit Fe(OH)2, Co(OH)2, Ni(OH)2 ........................................................ 272 11.10 Cc halogenua ca Fe(II), Co(II), Ni(II) .......................................................... 273 11.11 Cc sunfua ca Fe(II), Co(II), Ni(II) ................................................................. 276 11.12. Cc xianua ca Fe(II), CO(II), NI(II) .............................................................. 277 11.13. Cc sunfat ca Fe(II), Co(II), Ni(II)................................................................. 279 11.14. Cc nitrat ca Fe(II), Co(III), Ni(II)................................................................. 281 11. 15. Mui cacbonat ca Fe(II), CO(II), Ni(II) ...................................................... 282 CC HP CHT VI OXI HA +3 11.16. Cc oxit Fe2O3, Co2O3, Fe3O4, Co3O4 .............................................................. 283 11.17. Cc hiroxit Fe(OH)3, Co(OH)3, Ni(OH)3 ..................................................... 286 11. 18. Cc halogenua ca Fe(III), Co(III) .................................................................. 288 11.19.Cc sunfat ca Fe(III), Co(III) ............................................................................ 290 11.20. St (III) nitrat ......................................................................................................... 292 11.21. Cc sunfua ca Fe(III) v Co(III) ..................................................................... 292 11.22. Phc cht xianua ca Fe(III) v Co(III) .......................................................... 292 HP CHT CA ST VI S OXI HA +6 TI LIU THAM KHO ............................................................................................ 296
PGS. NGUYN C VN
HA HC V C
Tp 2 (CC KIM LOI IN HNH)
Chu trch nhim xut bn Bin tp Sa ch bn V ba
: PGS. TS. T NG HI : ThS. NGUYN HUY TIN : QUANG HUY : HNG LAN
NH XUT BN KHOA HC V K THUT 70 THN HNG O - H NI
In 800 cun, kh 19 x 27cm ti Xng in NXB v2n ha Dn tc Quyt nh xut bn s: 136 - 2006/CXB/70.2-06/KHKT - 12/4/2006 In xong v np lu chiu qu III nm 2006.

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PGS.

NH XUT BN KHOA HC V K THUT H NI

Hnh 4. Cch xp lp ht cu th ba ln lp th hai. y Nh vy, lp th nht v lp th ba tng ng vi nhau v c k hiu l

A u c th to ra hp kim c mng tinh th dng thay th (hnh 1la).

8,5 Ti 7,5 Mn 7,0 Nb 7,0 Rh 6,5 Be 6,5 Mo 6,5 Hf 6,0 Co

6 Zr 6 Pd 6 Fe 6 Ni 5,5 Pt 5,5 Cu 5,5 Sb 5,0 Th

5,0 4,75 4,0 4,0 3,5 3,0 3,0 3,0

2,75 Cd 2,5 Ca 2,5 Ga 2,5 Sr 2,5 Sn 2,5 Hg 2,5 Pb 2,25

2 Ba 1,75 TI 1,5 Li 1.5 K 1,5 Na 1,5 Rb 1,5 Cs

1,25 1,0 0,6 0,5 0,4 0,3 0,2

5930 5870 5500 5300 5300 5300

5050 4900 4800 4500 4400 4000

3500 3400 3260 2970 2970 2900

2730 2700 2600 2500 2360 2210

2070 2060 2000 1800 1740 1635

1540 1460 1440 1380 1336 1110

890 770 767 680 670 610

48,8 46,2 35,3 26,0

23,8 19,2 18,5 17,5

16,2 11,8 10,8 10,6

9,5 8,5 8,3 8,3

8,3 8,1 7,9 7,1

7,0 6,5 4,7 4,2

2,9 2,2 1,0 1,0

Hnh 1 5. s ph thuc dn in ca kim loi vo nhit

= 0,41V , nhng kim loi no c th in cc thp hn gi tr

Ni chung, nhng metalit to ra t cc kim loi in hnh nh KNa2 u t

Tnc C dn in (Hg=1) Vng cm (eV)

Mg2Sn 795 0,1 0,34

(2) Nguyn t khi, s th t nguyn t v s phn b electron nh sau :

Bng 8. Mt s c im ca cc nguyn t kim loi kim

Bn knh nguyn t o (A)

The ion hoa

I1 (eV) 5,39 5,14 4,34 4,18 3,89 3,98

Luna - 6 1,08. 10-5 1,9. 10-6 0,09. 10-6

180 1370 11 0,6 -3,01 1,0

98 883 21 0,4 -2,71 0,9

64 760 14 0,5 -2,92 0,8

39 700 8 0,3 -2,98 0,8

29 670 5 0,2 -2,92 0,8

Nhit thng hoa (kj / mol)

Li2 2,67 108, 8

Na2 3,08 75,3

nhn ( A ) Nng lng lin kt (kJ / mol)

Nhit to thnh (kJ / mol)

Rb20 vng nht Rb202 nu ti Rb02 vng thm

Cs20 da cam Cs202 vng Cs02 vng thm

Kaliozonit c to nn khi cho kh O3 i qua KOH bt nhit thp t

Nhit nng chy ( C) Nhit si ( C) Nhit to thnh (kj / mol 25 C)

LiOH 450 - 485,3

NaOH 328 1390 -428

KOH 360 1324 -424,2

RbOH 300 423,4

CsOH 275 -419,6

Nhit ha tan (kJ / mol) tan (mol/l) 15 C

Tr LiF (T, = 3,8.10-3), cc halogenua khc u d tan trong nc (bng 10).

Bng 10. tan ca cc halogenua kim loi kim (mol/l 180 C)

Li Na+ K+ Rb+ Cs-

Na+ 0,95 397

Rb+ 1,48 288

Cs+ 1,69 255

Bn knh ion ( A ) Nng lng hirat ha (kJ / mol)

NaCl NH4HCO3 NaHCO3 36 21 9,6