HA HC V C 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 (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. Trong v t (phn thch quyn) cc kim lo t 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 O Si Na Ca K C Mn S % nguyn t 58 20 2,4 2,0 1,4 (1,5.10-1) 3,2. 10-2 3,0. 10-2 % khi lng 47,20 27,60 2,64 3,60 2,60 (1. 9. 5: Nguyn t H Al Fe Mg Ti P N % nguyn t 3,0 6,6 2,0 2,0 2,5. 10-1 5. 10-2 (2,5. 10-2) % khi lng (0.15) 8,80 5,10 2,10 6. 10-1 8. 10-2 (1.10-2)

10-1) 10-2 10-2

Trong nc i dng, cc kim loi c hm lng cao nh 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. Nhng kim loi chim thnh ph n 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 (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). Cc kim loi t nhm IIIA n VIIA c s electron lp v ngoi cng l ns2np1 - 5. V d Al (3s2 3p1) ; At(6s26p5) Trong chu k 5, c 10 kim loi chuyn tip t 39 nhm IIIB(Y) n nhm IIB (Cd) c cu hnh lp ngoi cng l 4d1 - 10 5s1 - 2. V d (39) Y (48) Cd

4d1 5s2 4d10 5s2 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

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HA HC V C 2 1.2. Cu trc tinh th ca kim loi 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). (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 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). p 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. p kim kiu thay th c hnh thnh khi hai nguyn tkim lo 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 1,28 A0 u c th to ra hp kim c mng tinh th dng thay th (hnh 1la). A0 v

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 A0 c th xm nhp vo mng tinh th ca st c bn knh l 1,27 A0 , 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.

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HA HC V C 2

nh 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. c bit l cc kim lo d n ph p 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 1. 4. Lin kt kim loi (1) u trc kim loi l c c trng cho kim lo ng 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) i thch cc tnh cht ca kim loi l thuy 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 TRN TH MAI Page 3

HA HC V C 2 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. 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. c 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". c gii quy a thuyt Mo p d 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. (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

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HA HC V C 2 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). 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 (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. t 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. 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. 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) 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) TRN TH MAI Page 5

HA HC V C 2

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 59,0 Na 20,8 Ni 13,9 Co 9,9 Rb 7,7 Nb 4,8 Sb 2,5 Cu 56,9 Mo 20,0 K 13,6 Fe 9,8 Cr 7,3 Pb 4,6 Ga 1,7 Au 39,6 Rh 19,4 Cd 12,6 Pt 9,7 Ta 6,2 Re 4,6 La 1,6 Al 36,1 W 17,5 Li 11,2 Pd 9,6 Th 5,3 Sr 4,2 Ce 1,2 Mg 21,4 Zn 16,0 In 10,6 Ru 9,6 Be 5,2 V 3,7 Bi 0,8 Ca 20,8 Ir 15,7 Os 10,6 Sn 8,3 Cs 4,8 U 2,6 Ge 0,001 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~ 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) E 0 Trong mi trng trung tnh ([H+]=[OH-]=10-7M) th in cc = 0,41V, nhng kim loi no c th in cc thp hn gi tr Page 6

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HA HC V C 2

2H + / H2 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 : t0 3Na + AlCl3 = Al + 3NaCl Al gii phng Fc trong qu trnh tecmit: t0 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

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HA HC V C 2 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 Au + 3Zn = AuZn3 Au + Zn = Auzn 3Au + Zn = Au3Zn H = - 1 29.71 kj. H = - 16,74 kj H= - 46.02 kj 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: .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 TRN TH MAI Page 8

HA HC V C 2 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: t0 PbO + H2 = Pb + H2O t0 Cao + Hi = Cu + H2O t0 Mo2O3 + 3H2 = 2Mo + 3H2O t0 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 : t0 4FeS2 + 11O2 = 2Fe2O3 + 8SO2 t0 Fe2O3 + 3H2 = 2Fe + 3H2O vi Sunfua ca kim loi km hot ng c th nung trc tip trong oxi: t0 HgS + O2 = Hg + SO2 V nguyn tc, oxit kim loi c nhit to thnh cng thp th qu trnh kh 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: 20000 C MgO + C = Mg + CO 12000 C 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 : t0 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: t0 2RbCl + Ca = CaCl + 2Rb t0 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

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HA HC V C 2 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 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: 6000 c = 2NaClnc 2Na + Cl2 in phn Al2O3 trong criolit (NaAlF6) nng chy h nhit nng chy ca Al2O3 t 12000C n 9500C : 9500 c = 2Al2O3 4Al + 3O2 khi in phn Nb2O5 trong phc cht K2[NbF7] nng chy iu ch : t0 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 : t0 Ni(CO)4 = Ni + 4CO t0 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: t0 2HgO = 2Hg + O2 hoc khi nung iotua dng MI4 iu ch Ti, Zn, Hf tinh khit: t0 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.

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HA HC V C 2

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

1 8 18 18 18

1 8 18 32

1 8 1 18 8

Ha tr 1 1 1 1 1 1

(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. Di y l mt s c im ca cc nguyn t kim loi kim (bng 8). (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) 2.2. Trng thi thin nhin v thnh phn cc ng v TRN TH MAI Page 11

HA HC V C 2 (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 K2SO4.MgSO4.MgCl2.6H2O; xinvinit NaCl.KCl ; xinvin KCl.... KCl.MgCl..6H2O; kainit

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 % 1,5. 10 5 1,0353 Hm lng mg/l 0,150 10,354 Nguyn t Rb Cs % 2. 10"5 3,7. 10"8 Hm lng mg/l 0,2 3,7. 105

K 0,0387 387,5 87 (27,85%); ng v Rb 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 TRN TH MAI Page 12

HA HC V C 2 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) : t0 Na2CO3 + 2C = 2Na + 3CO t0 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
dpnc

= 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). (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: 7000 C 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 TRN TH MAI Page 13

HA HC V C 2 (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. (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 -5 1,2. 10 1,1. 10 -3 3,3. 10 3,0. 10-3 1,4. 10-3 1,5. 10-3 -6 3,4. 10 8,7. 10-6 0,1. 10-6 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) ng v, trong c hai ng v thin nhin l 6Li (7,52%) v 7Li(92,48%) v ng v phng x l 8Li vi chu k bn hy l 0,841 giy.
3 ng v 20 25 22 ng v phng x, ng v Na c chu k bn hy lu nht l

ng v

i l

2,6 nm. ng v
37

44

ng v

39

41

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%.
85 87 ng v ng v Rb 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.

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HA HC V C 2 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 : t0 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), K 2Sx, 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: Na3N + 3H2O = 3NaOH + NH3

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HA HC V C 2 (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 : t0 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 : t0 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) : 2Na + 2NH3 = 2NaNH2 + H2 sn phm b nc nng phn hy thnh amoniac do ion amiua phn ng vi H2O: NH2 + HOH = OH + NH3

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HA HC V C 2 (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: t0 2Na + H2S = Na2S + H2 t0 2Na + 2HCl = 2NaCl + H2 Oxit ca mt s kim loi v phi kim loi cng b kh bi cc kim loi kim : t0 SiO2 + 4K = Si + 2K2O t0 Bi2O3 + 6K = 2Bi + 3K2O t0 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 :
t0 = Ti+4NaCl

TiCl4 + 4Na
t0

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. 4500 C 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. 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 Page 17 CsH

Nhit to thnh TRN TH MAI

HA HC V C 2 (kJ / mol) di a ( A0 ) 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).

M20 M202 M02

Li20 trng Li202 trng

Na20 trng Na202 vng nht

K20 trng K202 vng da cam K02 vng thm

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: t0 2KNO3 + 10K = 6K2O + N2 (3) Peoxit M2O2 v supeoxit MO2. Khi t chy cc kim loi kim trong oxi d to nn cc cht : 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 TRN TH MAI Page 18

HA HC V C 2 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 : t0 2FeS2 + 15Na2O2 = Fe2O3 + 4Na2SO4 + 11 Na2O Hoc chuyn Cr(OH)3 thnh cromat: t0 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: 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 TRN TH MAI Page 19

HA HC V C 2 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 M21O4 ; 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 TRN TH MAI

LiOH 450 -

NaOH 328 1390

KOH 360 1324

RbOH 300 -

CsOH 275 Page 20

HA HC V C 2 ( C) Nhit to thnh (kj / mol 25 C)

- 485,3

-428

-424,2

423,4

-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

Nhit ha tan (kJ / mol) tan (mol/l) 15 C tan (mol / l) d 30 C

LiOH 20,08 5,3 5,4 29,8

NaOH 43,51 26,4 22,6

KOH 55,23 19,1 16,9

RbOH 61,53 17,9 20,2

CsOH 70,29 25,8

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): TRN TH MAI Page 21

HA HC V C 2 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 : t0 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.

Ngy nay ngi ta dng phng php in phn dung dch NaCl bo ha vi dng cc bng than ch v TRN TH MAI Page 22

HA HC V C 2 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 =dp 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 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 K+ Rb+ Cs+ ClO4 1,1.10-2 5,0. 10-3 4. 10-3 MnO4 2,9. 10-3 9,1. 10 -5 -4 -4 IO4 8,3. 10 5,5. 10 4,4. 10-3 2-6 -8 PtCI 6 1,4. 10 9,0. KT 3,0. 10 -8 CO(NO2)63- (1) 4,3. 10-10 1,48. 10-15 5,8. 10 -16 -8 B(C6H6)4- (2) 2,25. 10 (1) ion hexanitro cobantiat (2) ion tetra phenylborat. 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...

TRN TH MAI

Page 23

HA HC V C 2 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. Bng 10. tan ca cc halogenua kim loi kim (mol/l 180 C)

FLi Na+ K+ Rb+ Cs0,1 1,1 15,9 12,5 24,2 18,6 5,8 4,5 7,2 10,9

CI20,3 8,6 5,4 6,5 5,6

Br 12,2 11,8 8,6 7,2 2,8

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) Li+ 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

FClBrI-

Bng12 Nng lng hirat ha cc cation kim loi kim (kj / mol)

Li+ Bn knh ion ( A0 ) TRN TH MAI 0,60

Na+ 0,95 1,33

K+ 1,48

Rb+

Cs+ 1,69 Page 24

HA HC V C 2 Nng lng hirat ha (kJ / mol) 506 397 313 288 255 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): t0C 0 10 20 30 50 70 90 100 NaCI 35,6 35,7 35,8 36,0 36,7 37,5 38,5 39,1 KCl 28,5 32,0 34,7 37,4 42,8 48,3 53,8 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 phn ng trao i: AX +BX YZXZAY +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: NaI + RbCl YZXZ NaCl + RbI Bng 13. Nhit nng chy (Tnc) v nhit si (Ts) ca cc halogenua kim loi kim (0C) FLi+ Tnc Ts Tnc Ts Tnc Ts Rb+ Tnc Ts Tnc Ts Cl842 606 1676 1382 995 800 1702 1454 856 768 1505 1417 780 717 1410 1883 684 638 1251 1303 BrI549 453 1310 1170 740 610 1393 1300 728 682 1376 1330 681 642 1350 1305 627 621 1300 1280

Na+

K+

Cs+

(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. TRN TH MAI Page 25

HA HC V C 2 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... 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:

TRN TH MAI

Page 26

HA HC V C 2 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 Tnc (C) 735 Na2C03 852 K2C03 894 Rb2C03 837 Cs2C03 -

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: TRN TH MAI Page 27

HA HC V C 2 HCO3 + H+ = CO2 + H2O CO2 + 2H+ = CO2 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: t 0C 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 0 Na2CO3.H2OV n l07 C 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. TRN TH MAI Page 28

HA HC V C 2 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: 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

TRN TH MAI

Page 29

HA HC V C 2

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

0 105

25 113,5

100 156

(g/100gH2O) 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 TRN TH MAI Page 30

HA HC V C 2 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

10 8,24

20 16,4

30 28,9

32,38 33,2

40 32,5

50 31,8

100 29,8

tan(g/100gdd) 4,5

TRN TH MAI

Page 31

HA HC V C 2 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 Na2SO4.MgSO4.4H2O; glazcrit Na2SO4.2K2SO4.... khong cht glauborit Na2SO4.CaSO4; astracanit

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: t 0C tan(g/100gH2O) TRN TH MAI 0 7,35 10 9,22 20 11,11 30 12,97 40 14,76 50 16,50 100 24,1 Page 32

HA HC V C 2

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

20 51,4

40 67,3

100 121,6

tan(g/100gH2O) 36,3

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. TRN TH MAI Page 33

HA HC V C 2 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): NaNO3 1000C 0C 175 73 KCl 56,6 28,5 NaCl 39,1 35,6 13 KNO3 246

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 TRN TH MAI Page 34

HA HC V C 2 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:

Rb+ MCIO4 M2[PtCl6] MH[C4H4O6] 0,76 g (140 C) 0,028 g (200 C) 1,17g(250C)

Cs+ 1,17g(140C) 0,009 g (200 C) 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 K hiu Be Mg Ca Sr Ba S th t 4 12 20 38 56 Nguyn t khi 9,01 24,31 40,08 87,62 137,34 2 2 2 2 2 2 8 8 8 8 2 8 18 18 2 8 18 2 8 2 Phn b electron Ha tr II II II II II Page 35

TRN TH MAI

HA HC V C 2 Radi Ra 88 [236] 2 8 18 32 18 8 2 II

(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 tr haBn knh nguyn t Bn knh ion Th ion ha (eV) ( A0 ) 1,13 1,60 1,97 2,15 2,21 2,35
0 M2+(A

Be Mg Ca Sr Ba Ra

2s 4s 5s 7s

2 2

0,34 0,74 1,04 1,20 1,33 1,44

I1 9,32 7,69 6,11 5,96 5,21 5,28

I2 18,21 15,03 11,87 10,93 9,95 10,10

3s

2 2 2

6s

(5) Be v Mg kt tinh theo mng lc phng (hnh1).Vi Be (a = 2,268 A0 c = 3,594 A0 .

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 A0 ; c = 5,56 A0 ; 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 A0 (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 A0 . 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 a = 6,05 A0 v d = 4,27 A0 . TRN TH MAI Page 36

HA HC V C 2 Bari kt tinh theo mng lp phng tm khi c (a = 5,01 A0 . Mi nguyn t bao quanh bi 8 nguyn t khc, c khong cch d = 0,5 a 3 = 4,34 A0 (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 (2) thin nhin dng hp cht. Trong v qu t Ca v Mg thuc loi nguyn t ph bin nht v c phn b nh (3) Nguyn t Be Mg Ca Sr Ba % s nguyn t 1,2 .10 3 2,0 2,0 1,0. 10
-2

%khi lng 6 .10 -4 2,1 3,6 4. 5. 10-2 10-2

5,7. 10-2

Ra 9,0. 10-12 1. 10 -10 (4) (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 ... (5) (6) 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... (7) (8) 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.... (9) (10) Strontiv banric trong cc qung ch yu l strontianit SrCO3 ,viterit BaCO3 xelestin SrSO4; barit BaSO4 . (11) (12) 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): (13) Nguyn t Be Mg Ca % 6. 10
-11

Hm lng mg// 6. 1
-7

Nguyn t Sr Ba Ra % 8. 10
-4

Hm lng mg// 8,0 0,02 1. 10-10

0,1297 0,0408

1,297 408

2. 10-6 1. 10-14

(14) (15) (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. TRN TH MAI Page 37

HA HC V C 2 (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: Hm lng trung bnh (s gam /1 g mu Nguyn ) t Be Mg Ca Sr Ba Apollo-11 0,2. 10-5 0,045 0,080 17. 10-5 20. 10-5 Apollo-12 0,072 0,071 17. 10-5 42. 10-5 Luna -6 0,25. 10-5 22. 10-5 18,5. 10-5

(6) Be c bn ng v, trong ch c cn li l ng v phng x, ng v 2,5.106nm.

mt ng v thin n k bn hy lu nh

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 %), 134 Ba (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 TRN TH MAI Page 38

HA HC V C 2 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: TRN TH MAI Page 39

HA HC V C 2

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 Be Mg Ca Sr Ba Khi lng ring (g / cm3) 1,85 Nhit nng chy (TK, C) 1285 Nhit si (Ts, C) 2471 dn in (Hg =1) 5 cng (so vi kim cng = 10) 4 Th in cc (V) -1,85 (1) m in 1,5 (1) Theo Pauling. 1,74 651 1100 21 2,5 -2,37 1,2 1,60 851 1489 20,8 2,0 -2,87 1,0 4 -2,89 1,0 2,60 770 1880 3,75 710 1634 1,5 -2,90 0,9

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 l 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: TRN TH MAI Page 40

HA HC V C 2 Be Nhit thng hoa (kj / mol) Mg Ca Sr Ba

153

180

205

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: rZ = n = rCd = rHg 1,34 A 1,56 A 1,60 A

ra = 1,97 A rSr = 2,15 A rBa = 2,21 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 TRN TH MAI Page 41

HA HC V C 2 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.

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HA HC V C 2 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 oxit hirua florua 50 5 clorua bromua iotua sunfua nitrua

Be

287

235 -

117

93

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 TRN TH MAI Page 43

HA HC V C 2 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:

(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) 2552 Nhit si (C) 4200 MgO - 3925 2800 3100 CaO 3519 2570 3600 SrO 3314 2460 2500 BaO 3121 1925 2000

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 0,34 Bn knh ion M2+ ( A0 ) Nhit hidrat ha ca oxit MO (kJ/mol) 14,2

Mg 0,74 40,6

Ca 1,06 66,5

Sr 1,26 81,6

Ba 1,33 102,5

(3) Beo c iu ch bng cch nung hiroxit hoc mui ca berili nh mui

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HA HC V C 2 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

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HA HC V C 2 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:

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HA HC V C 2

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

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HA HC V C 2 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

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HA HC V C 2 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 Ba(OH)2 -48,5 -51,5 Sr(OH)2. 8H20 Ba(OH)2. 8H20 + 61,1 + 63,6

V vy, theo nguyn l chuyn dch cn bng, khi tng nhit th tan ca

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HA HC V C 2 Ca(OH)2 gim, cn tan ca cc octahirat li tng (g /100g H2O): 0C 20C 40C 80C 100C

Ca(OH)2 0,185 0,165 0,141 0,094 0,077 Sr(OH)2 0,35 0,81 1,76 8,25 28,4 Ba(OH)2 1,67 3,98 8,22 101,5 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. TRN TH MAI Page 50

HA HC V C 2 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 M2+ 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, 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). 3.9. Hiroxit ca kim loi kim th (2) 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: TRN TH MAI Page 51 190 8 290 8 229 3 Ca Sr Ba

1577 2611 2058

1431 2460 -

1289 2368 1866

HA HC V C 2

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 Ba(OH)2 -48,5 -51,5 Sr(OH)2. 8H20 Ba(OH)2. 8H20 + 61,1 + 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 20C 40C 80C 100C

Ca(OH)2 0,185 0,165 0,141 0,094 0,077 Sr(OH)2 0,35 0,81 1,76 8,25 28,4 Ba(OH)2 1,67 3,98 8,22 101,5 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 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]

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HA HC V C 2 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 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 TRN TH MAI Page 53

HA HC V C 2

Mg Nng Ing hidrat ha ca ion M2+ Nng Ing mng li ca mui MF2 Nng lng mng Ii ca mui Ml2 190 8 290 8 229 3

Ca

Sr

Ba

1577 2611 2058

1431 2460 -

1289 2368 1866

3.11. Halogenua ca cc kim loi kim th 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, Nhit nng chy v nhit si u cao, mt s cht nh SrBr2, BaBr2, SrI2, BaI2 b phn hy sau khi nng chy. 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 MgF2 Tt 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).

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HA HC V C 2

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:

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HA HC V C 2 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 -55 0 10 60 65 20 40 60 137 100 159 260 347

tan CaCI2 (g / 100g H20) 42,5

74,5 115

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

trong S gam CaCI2 H2O Nhit si (C) trong S gam CaCI2 H2O Nhit si (C)

100g 6,0 101 100g 101 130 137,5 140 178 150 222 160 268 170 292 175 305 178 11,5 102 16,5 103 21,0 104 25,0 105 41,5 110 69,0 120

Bng 20 Nhit ng c ca dung dch CaCl2

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HA HC V C 2

S gam CaCI2 trong 100g dung dch 0,1 1 5 10 Nhit ng c (C) - 0,051 -0,46 -2,44 -5,89 S gam CaCI2 trong 100g dung dch 20 25 30 32,5 Nhit ng c (C) -18,6 -29,9 -48,0 -51,0 (6) BaCl2 dng khan l nhng tinh th mu trng, t tan trong ru, nhng d theo nhit :

15 -10,96 tan trong nc, tan tng

t0c 0 10 20 50 100 tan BaCI2 g/100g H20 31,5 33 36 43,5 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: TRN TH MAI Page 57

HA HC V C 2

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:

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HA HC V C 2 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):

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HA HC V C 2 BeC03 Tt 1.10-3 MgC03 4.10 -5 CaC03 4,8.10 -9 SrC03 1.1.10 -10 BaC03 5,1.10 -9

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: MgC03 CaC03 SrC03 BaC03 t 0c 540 897 1290 >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 MC0 p sut ca CO2 (mm Hg) 3 400 C 450C 500C 540C 560C MgC0
3

600C

650C

700C 750C

0,1

6,8

100

740

MC03 800C 850C 897C TRN TH MAI

p sut ca CO2 (mm Hg) 900 1000 1100 1200 C C C C 1300C Page 60

HA HC V C 2 CaC03 BaC03 167 0 302 0 760 0 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... TRN TH MAI Page 61

HA HC V C 2 (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 :

BeS04 tan(g/100gH2O ) Tch s tan (Tt) 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. TRN TH MAI Page 62

HA HC V C 2 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 MgSO4. H2O bn trong khong t 48,30C n 680C bn trong khong cao hn 680C

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 TRN TH MAI Page 63

HA HC V C 2 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 SO42khc: 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.Gaylussac) v Tna (L.Thenard) tm ra nm 1808 khi dng kali kh oxit boric; nhng n u th k 20 mi TRN TH MAI Page 64

HA HC V C 2 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 2 2 3 8 8 8 8 3 18 18 18 3 18 32 3 18 2 Phn b electron Ha tr

III I, III I, II, III I, II, III I, II, III

114,82 204,39 2

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 25,15 18,82 20,43 18,79 20,32 I3 37,93 28,44 30,60 27,90 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. TRN TH MAI Page 65

HA HC V C 2 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 oC) Nhit si ( Ts oC ) Khi lng ring (g1cm3 ) m in (1) Th in cc (V): M3+ + 3e Mo M+ + 1e Mo (l) Theo Pauling.

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

(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 :

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HA HC V C 2 B Al Ga ln Tl 6 .10-4 6,6 4. 10
-4

3. 10-4 8,8 1,5. 10-3 1. 10-5 3. 10-4

1,5. 10-5 3. 10-5

(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 1. 10-6 Hm lng mg/l 4,6. 10
-6

Nguyn t Ga ln Tl

% 3.10-9 1.10-9 1.10-9

Hm lng mg/l 3.10-5 1.10-5 1.10-5

4,6 0,01

(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 0,2.10-5 0,056 0,45.10 3.10-9 0,6.10-9
-5

0,074 0,4.10 9.10-9 2.10-9

-5

0,44.10-5 0,45.10-5 0,17.10-5 2.10-9

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HA HC V C 2

(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 69Ga (60,2%) v 71Ga (39,8%), cn li u l ng v phng x , trong c 67Ga c chu k bn hy l 3,25 ngy m. In c 13 ng v t (95,77%).
l07

In n

119

In, trong c hai ng v thin nhin l

113

In (4,23%) v ng v

115

In

Tl c 16 ng v t 195Tl n 210Tl trong c ng v 203Tl (29,50 %) v nhin. NHM V HP CHT CA NHM 4.3. iu ch nhm

205

Tl (70,50 %) l ng v thin

(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 + OH- 2Al(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

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HA HC V C 2 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 them 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 (20500C) 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%. 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

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HA HC V C 2 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 H = - 3338 kJ Khi nung hn hp tecmit (gm bt Al + bt Fe3O4) nhit c th t n 24000C. 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.

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HA HC V C 2 (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+ 4OHkim mnh nh NaOH , KOH: Eo = - 2,35V (dd) (rn ) v vy nhm d tan trong dung dch

2Al + 6OH- + 6H2O = 2[Al(OH)6]3- + 3H2 dung dch amoniac cng n mn nhm kh mnh.

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HA HC V C 2 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.

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HA HC V C 2

(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

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HA HC V C 2 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

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HA HC V C 2 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 : TRN TH MAI Page 75

HA HC V C 2

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 179,5 192,6 ( 1700 mmHg) 97,5 255 381 Nhit nng chy Tnc (oC) 1290 Nhit si Ts (oC) Thng hoa trn Tnc 180 (thng hoa)

(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 S d c s to thnh ime nh vy l do nguyn t kim loi c khuynh

TRN TH MAI

Page 76

HA HC V C 2 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:

TRN TH MAI

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HA HC V C 2

(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 :

t 0C 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

TRN TH MAI

Page 78

HA HC V C 2 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

TRN TH MAI

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HA HC V C 2 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. Al2S3l 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:

TRN TH MAI

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HA HC V C 2

(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. CHNG 4. 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 sau in phn dung dch mui 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.

TRN TH MAI

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HA HC V C 2 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:

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HA HC V C 2

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. (2) 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 : (3)

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 TRN TH MAI

Mu sc

Nhit nng chy

Nhit si ( 0C ) Page 83

HA HC V C 2 0 GaF3 GaCl3 GaBr3 GaI3 mu vng 1000 77 122 212 950 ( thng hoa ) 200 279 346

InF3 lnCl3 lnBr3 lnl3

khng mu khng mu khng mu vng nht

1170 586 436 210

1200 498 ( thng hoa ) 371 (thng hoa ) -

TlF3 TlCl3 TlBr3 TlI3

mu vng mu en

550 25 -

thng hoa -

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. TRN TH MAI Page 84

HA HC V C 2 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 TRN TH MAI Page 85

HA HC V C 2 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 : 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 : 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 TRN TH MAI Page 86

HA HC V C 2 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 : 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 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. Gay- lussac) 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 C

K hiu

s th t 6

Nguyn t khi 12,01 2

Phn b electron 4

Ha tr II IV Page 87

TRN TH MAI

HA HC V C 2 Silic Gecmani Thic Ch Si Ge Sn Pb 14 32 50 2 28,09 72,60 118,70 207,21 2 2 2 2 8 8 8 8 4 18 18 18 4 18 32 4 18 4 II IV II IV II IV II IV

(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:

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 4s 4p 1,39 0,65 0,44 7,88
2 2

Sn 5s 5p 1,58 1,02 0,67 2,15 7,33

2 2

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 TRN TH MAI Page 88

HA HC V C 2

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: Hm lng trung bnh( s gam/1g mu ) Nguyn Apollo - 11 Apollo - 12 Luna - 6 Ge Sn Pb 0,6.10-6 1,2.10-5 4.10-6 1,25.10-6 3.10-6 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%); 114Sn ( 0,65%); 115Sn ( 0,34%); l16 Sn (14,24%); 117Sn (7,57%); 118Sn (24,01%); l19Sn (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
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

TRN TH MAI

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HA HC V C 2 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 ( C )

0

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 si ( C )
0

dn in (Hg = 1) cng (kim cng = 10)

nhit thng, gecmani c mu trng bc, cng v rt gin, cn ch th mm. Thic v ch u d dt thnh l mng.

TRN TH MAI

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HA HC V C 2 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.

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 TRN TH MAI Page 91

HA HC V C 2 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 : TRN TH MAI Page 92

HA HC V C 2 (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 -165 Tnc ( C) Ts (0C) -90 29 110 -52
0

Ge2H6 -109 -106

Ge3H8 -150

SnH4

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:

TRN TH MAI

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HA HC V C 2 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 45) , 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 :

TRN TH MAI

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HA HC V C 2 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 TRN TH MAI Page 95

HA HC V C 2 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 :

TRN TH MAI

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HA HC V C 2

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: 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:

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HA HC V C 2 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 trng

SnO2.xH2O nu 1.10-57

PbO2.xH2O 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:

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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 216 637 320 714 SnI2

(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: 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 : TRN TH MAI Page 99

HA HC V C 2

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: 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.

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HA HC V C 2 PbBr2 cng c kh nng to ra cc con phc [PbBr3]2- V [PbBr4]2- tng 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 : (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, TRN TH MAI Page 101

HA HC V C 2 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 (5s1) v stronti (5s2), cc electron tip tc xp vo cc obitan 4d, hnh thnh 10 nguyn t h d l cc nguyn t : 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 TRN TH MAI Ti 4B 22 23 V 5B 24 Cr 6B 25 Mn 7B 26 Fe 8B 27 CO 28 Ni 1B 29 Cu 2B 30 Zn Page 102

HA HC V C 2 39 Y 57 La Hf 89 Ac Rf 104 Zr 72 40 41 Nb 73 Ta 105 Ha 42 Mo 74 W [106] 43 Tc 75 Re [107] 44 Ru 76 Os [108] 45 Rh 77 Li [109] 46 Pd 78 Pt 79 Au 47 Ag 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

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HA HC V C 2 nm. 5.3. iu ch Ge, Sn, Pb (3) 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 :

(4) 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 ( C )

0

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 si ( C )
0

dn in (Hg = 1) cng (kim cng = 10)

nhit thng, gecmani c mu trng bc, cng v rt gin, cn ch th mm. Thic v ch u d dt thnh l mng.

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HA HC V C 2 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. 5.6. Tnh cht ha hc ca Ge, Sn, Pb (2) 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.

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 TRN TH MAI Page 109

HA HC V C 2 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 : TRN TH MAI Page 110

HA HC V C 2 (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 -165 Tnc ( C) Ts (0C) -90 29 110 -52
0

Ge2H6 -109 -106

Ge3H8 -150

SnH4

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:

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HA HC V C 2 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 46) , 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 :

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HA HC V C 2 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 TRN TH MAI Page 113

HA HC V C 2 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 :

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HA HC V C 2

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: 5.9. 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:

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HA HC V C 2 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 trng

SnO2.xH2O nu 1.10-57

PbO2.xH2O 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: TRN TH MAI Page 116

HA HC V C 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 ( C ) Ts ( 0C )
0

SnCl2 khng mu 247 650

SnBr2 vng 216 637 320 714

SnI2

khng mu 210 -

(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: 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 TRN TH MAI Page 117

HA HC V C 2 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: 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.

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HA HC V C 2 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]2- tng 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 : (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).

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HA HC V C 2 (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, 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 (5s1) v stronti (5s2), cc electron tip tc xp vo cc obitan 4d, hnh thnh 10 nguyn t h d l cc nguyn t : 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 : d) Nhm nguyn t chuyn tip chnh ( h d ) e) Nhm lantanoit ( h f) TRN TH MAI Page 120

HA HC V C 2 f) 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 Hf 89 Ac Rf 104 Zr 72 Ti 40 4B 22 23 V 41 Nb 73 Ta 105 Ha 5B 24 Cr 42 Mo 74 W [106] 6B 25 Mn 43 Tc 75 Re [107] 7B 26 Fe 44 Ru 76 Os [108] 8B 27 CO 45 Rh 77 Li [109] 28 Ni 46 Pd 78 Pt 1B 29 Cu 47 Ag 79 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

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Hp cht

Th s tan 9,8.10-13

Hp cht

Tch s tan 4.10-3

Tl2CrO4 Tl2S TlI TlBr TlCl 5.10

-21

Tl2CO3 TlBrO3 Tl2SO4 Tl2SO3 Tl3PO4 3,9.10-4 4.10-3 6,3.10-4 6,7.10-8 6,5.10-8 3,9.10-6 1,7.10-4

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)).

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