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05 Hoa-hoc-vo-co-Nguyen-Duc-Vant PDF
05 Hoa-hoc-vo-co-Nguyen-Duc-Vant PDF
NGUYN C VN
HO HC V C
TP 2
(CC KIM LOI IN HNH)
(In ln th ba)
Dng cho sinh vin cc trng i hc, cao ng v
gio vin trung hc chuyn ngnh Ha
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Li ni u
"HA HC V C"- Tp 2 (Cc kim loi in hnh) c bin son
theo chng trnh Ha hc V c - Khoa Ha hc - Trng i hc S phm
H Ni, da trn c s cc bi ging m tc gi ging dy trong nhiu nm
cho sinh vin Khoa Ha hc ti Trng i hc S phm v Ni.
Ni dung cun sch cp n mt s kin thc c bn v kim loi ;
v trng thi thin nhin, v phng php diu ch, tnh cht l, ha hc ca
cc n cht v hp cht ca cc kim loi in hnh, ng thi cng l ni dung
thng c ging dy trong chng trnh Ha hc V c cc Trng i
hc v mt phn Trng Trung hc ph thng Nhng kim loi cn li khng
cp n trong sch, tc gi s trnh by trong tp 3 "Cc kim loi chuyn
tip".
V vy ni dung sch khng ch dc s dng cho sinh vin ngnh Ha
hc - Trng i hc S phm, m cn h tr cho gio vin mn Ha hc cc
Trng Trung hc ph thng lm ti liu tham kho trong qu trnh ging dy.
Ngoi ra cn c th gip ch cho sinh vin hc mn Ha hc V ca cc
Trng i hc khc v cc Trng Cao ng.
Chc chn rng cun sch khng trnh khi thiu st, tc gi xin trn
trng cm n nhng nhn xt ng gp ca bn c.
Tc gi
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CHNG 1
1. 1. S phn b kim loi trong thin nhin. V tr kim loi trong bng tun
hon
(1) Mt trong nhng c tnh quan trng ca cc nguyn t ha hc l tnh
ph bin trong thin nhin. Hu ht cc kim loi u c trong thnh phn v qu
t, c trong nc i dng, trong c th sng vi mc nhiu t khc nhau.
y Trong v qu t (phn thch quyn) cc kim loi Al, Na, Fe, Ca, Mg, K,
Ti, Mn v mt s phi kim khc... l nhng nguyn t c ph bin ln nht.
Trong bng 1 di y l thnh phn phn trm v s nguyn t v phn trm v
khi lng ca cc nguyn t :
Bng 1. Thnh phn cc nguyn t c ph bin cao trong thch quyn
Nguyn t % nguyn t % khi lng Nguyn t % nguyn t % khi lng
O 58 47,20 H 3,0 (0.15)
Si 20 27,60 Al 6,6 8,80
Na 2,4 2,64 Fe 2,0 5,10
Ca 2,0 3,60 Mg 2,0 2,10
K 1,4 2,60 Ti 2,5. 10-1 6. 10-1
C (1,5.10-1) (1. 10-1) P 5. 10-2 8. 10-2
Mn 3,2. 10-2 9. 10-2 N (2,5. 10-2) (1.10-2)
S 3,0. 10-2 5: 10-2
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gia hai dy nguyn t nu trn. Cc nguyn t gii hn nm cnh ng ranh
gii c xem l cc nguyn t bn kim.
Tm li, cc nguyn t chuyn tip, cc nguyn t nhm la v IIA, cc
nguyn t nng nhm IIIA, IVA, VA u l kim loi.
Bng 2. V tr ca kim loi, bn kim loi v phi kim loi trong bng
tun hon
1 2
H He
3 5 6 7 8 9 10
Li 4 Be B C N O F Ne
11 13 14 15 16 17 18
Na 12 Mg Al Si P S CI Ar
19 20 21 - 30 31 32 33 34 35 36
K Ca Sc - Zn Ga Ge As Se Br Kr
37 38 39 - 48 49 50 51 52 53 54
Rb Sr Y - Cd In Sn Sb Te I Xe
55 56 57 - 80 81 82 83 84 85 86
Cs Ba La - Hg Tl Pb Bi Po At Rn
87 88
Fr Ra
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y Trong chu k 6, ngoi 10 kim loi h d c cu hnh nh trn, cn c 14
nguyn t kim loi h f t 58 (Ce) n 71 (Lu). Dy nguyn t ny khng
ng vi dy nguyn t no cc chu k trn, c gi l cc nguyn t (kim
loi) t him hay cn gi l cc nguyn t h lantan (lantanoit). Lp v
electron cc lp ngoi cng l :
4f2-14 5d0-l 6s2
V d:
(58) Ce (64) Gd (71) Lu
2 7 1 2
4f 6s 4f 5d 6s 4f14 5d1 6s2
Nhng sai lch trong dy ny l do s khc nhau rt t v nng lng ca
cc phn mc (n - 1)d v ns; (n - 2)f v (n - 1)d gy ra.
Trong chu k 7, c 14 nguyn t kim loi thuc h f t 90 (Th) n
l03(Lr) cng c lp v tng t.
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phn s ch lm ny c che khut (1) s ch lm cn li khng b che khut
(2) bi lp th hai (hnh 3).
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ABA. Nu tip tc chng thm, lp th hai tng ng lp th t, lp th ba
tng ng lp th su... v c dy ABABAB. Cch sp xp ny to ra mng
tinh th lc phng.
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y Cng cch sp xp nh trn nhng khi mi nguyn t kim loi ch c 8
nguyn t nm gn nht (thay cho 12 nguyn t) mc d y cn c 6 nguyn
t ca lp tip theo nhng khong cch ln hn 15%. Cch sp xp ny ch
bng 92% mt c th c ca cch sp xp lc phng v lp phng tm
din, ngha l th tch ca kim loi ch chim 68% th tch kim loi to ra mng
lp phng tm khi. S phi tr ca kim loi trong mng ny l 8.
y S phn b ba dng mng tinh th ca cc kim loi trong bng tun hon
c dn ra hnh 9.
Hnh 9. Cc kiu cu trc mng tinh th ca cc kim loi trong bng tun hon.
(lptd : lp phng tm din: lp: lc phng: lptk: lp phng tm khi :
mt s k hiu lng vo nhau th ki hiu to nht l dng cu trc bn
250C : k hiu lp/lptd l cu trc dng hn hp).
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ba chiu trong ton b tinh th, ch c th xy ra trong trng hp l tng, khi
m iu kin kt tinh khng gy ra s bin i no trong cu to ca n. Thc
t, a s trng hp, do s hnh thnh tinh th lun lun din ra trong nhng
iu kin lm cho hnh dng bn ngoi ca tinh th b bin i, hoc lm cho
cu trc bn trong ca tinh th c s sai lch no v s phn b hnh hc
hoc thnh phn ca tiu phn. C th c nhng trng hp sau:
Mng tinh th c th thiu mt s nguyn t kim loi nt no ca mng
[ gi l mng khuyt Stky (Schottky)] cng c th c nhng nguyn t kim loi
nm khong gia cc nt no 1 [gi l mng khuyt Phrenken
(Frenkel)]; ngoi ra cng c th nt b thay th bi mt nguyn t kim loi khc
(hnh 10).
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0
c bn knh cng ha tr l 0,77 A c th xm nhp vo mng tinh th ca st
0
c bn knh l 1,27 A , to thnh thp cacbon. Thp cacbon c mng tinh th
hn tp kiu xm nhp lm cho hp kim cng hn, bn hn v do hn (hnh
11b).
(3) Trong cc hp kim d th cc cu t u khng phn tn ng u.
Chng hn trong qu trnh luyn thp to ra hn hp peclit c cha hai pha ring
bit l Fe - v xementit Fe3C trn ln mt thit vo nhau v hp cht ostenit
l hn hp gm Fe - ~ v Fe3C. Cc hn hp u l hp kim d th.
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nguyn t.
Ngi ta cng nhn thy rng mt s kim loi khi nng chy to ra hn
hp ng nht, nhng khi kt tinh li to ra hn hp tinh th ring bit ca tng
kim loi, nh hp kim Sn v Pb.
Mt s kim loi trng thi lng hu nh khng tan vo nhau nh cc cp :
Ag - Fe Fe - Pb Cd - Al Na - Al
Al - Ti K - Mg K - Al Ag - Cr
Thng thng th nhng kim loi nng chy ch trn ln vo nhau mt
phn v trong cc trng hp , ngi ta cng thy kim loi c nhit
nng chy cao ha tan kim loi c nhit nng chy thp d hn so vi trng
hp ngc li.
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ngoi, nhng electron ny chuyn ng hn lon trong khi kim loi theo mi
phng tng t nh chuyn ng nhit ca cc phn t kh trong mt th tch
no (v vy gi l thuyt kh electron !).
y Vy nhng electron no tham gia vo m kh electron?. l nhng
electron d dng ri b nguyn t kim loi nht, tc l cc electron ha tr. Tuy
nhin khng nht thit l tt c cc electron ha tr u tham gia vo m kh
electron, thng thng th s electron t do ny bng s nguyn t kim loi.
Trong qu trnh chuyn ng cc electron t va chm vo nhau v kch thc b,
nhng khng ngng va chm vo cc nguyn t ion ha.
y C th hnh dung rng trong tinh th kim loi, cc nguyn t khng
trng thi trung ha vnh cu, m trng thi ion ha thng xuyn i mi,
qu trnh bin i thng xuyn xy ra, nn trong tinh th kim loi lun lun
c mt s electron c tnh di ng cao, lc no cng c nhng nguyn t kim
loi d b ion ha, v ch ny hay ch kia trong mng tinh th c mt s
trng thi trung ha. Chnh nh c tng tc gia m kh electron vi cc ion,
gy ra lin kt kim loi, bo m tnh bn vng ca mng tinh th.
Khi c tc dng ca in trng ngoi, m kh electron chuyn ng theo
mt chiu, hiu ng ny gy ra dng in kim loi. Trong chuyn ng , cc
electron va chm mnh vo cc ion kim loi, nn mt phn ng nng chuyn
thnh nhit gy ra hiu ng Joule ca dng in. Khi nhit tng, chuyn ng
nhit ca electron v ion kim loi c tng cng, lm ri lon chiu chuyn
dch ca electron, kt qu dn in gim tc l in tr tng.
Thuyt kh electron cng gii thch c ti sao kim loi dn in tt, ng
thi cng dn nhit tt. Cc electron t do trong kim loi tham gia vo chuyn
ng nhit, v nh c tnh di ng ln, nn d dng san bng nhit, ch nng
chng chuyn ng mnh, c ng nng ln v khi n ch lnh hn, th qua va
chm vi cc con kim loi, s nhng bt ng nng v bng cch s ti
nhit t ch nng n ch lnh.
(3) y Mc d thuyt kh electron gii thch nh tnh c nhiu tnh cht
ca kim loi, nhng li gp kh khn ln nht l khng th gii thch c gi
tr thc nghim v nhit dung nguyn t ca kim loi l xp x 6 cal/ mol. Gi tr
thc nghim ch c gii thch bng cch loi b dao ng ca cc electron
"t do"trong mng tinh th m ch k n nhng dao ng ca nguyn t v ion
trong mng, nh vy cc electron "t do"- xem nh cc phn t kh - khng c
vai tr gy ra nhit dung ca kim loi, iu mu thun vi thuyt "kh
electron".
y Mu thun c gii quyt trn c s ca thuyt Mo p dng cho
h cha mt s ln nguyn t, ngha l coi kim loi nh mt h nhiu nhn m
trng thi ca electron trong h ging nh trng thi ca electron trong phn
t. Thuyt Mo coi mt mu kim loi l mt phn t. ti mt ca mng li c
cc ion kim loi. cn cc m my electron ca cc electron ha tr bao quanh
cc ion kim loi v lin kt vi chng, ngha l cc electron ha tr trong
"trng chung" ca tt c cc ion kim loi.
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y Nh bit, theo thuyt Mo th khi hai nguyn t tng tc vi nhau s
c s xen ph cc obitan phn t lin kt v phn lin kt, lc mi mc nng
lng nguyn t s tch ra thnh hai mc nng lng phn l. Nu h c bn
nguyn t th mi mc nng lng nguyn t s tch ra thnh bn, ngha l hnh
thnh bn obitan phn t. S nguyn t trong h cng ln th s Mo cng ln v
mi Mo ng vi mt trng thi nng lng xc nh. Nh vy trong tinh th c
N nguyn t s to nn N obitan phn t. V N rt ln (v d 1 cm3 tinh th kim
loi c khong 1022 - 1023 nguyn t) nn N mc nng lng rt gn nhau to ra
vng nng lng. S khc nhau v nng lng ca cc trng thi electron trong
gii hn ca vng ch khong 10-22 eV, nn c th coi s bin thin nng lng
ca electron trong vng l lin tc.
Cc obitan ca vng nng lng cng xem nh l cc obitan nguyn t
trong phn t, v cung tun theo nguyn l Phauli, l mi obitan cng ch cha
hai electron, v s in electron vo cc obitan cng tun theo ng trt t
mc nng lng t thp n cao. Nh vy s electron cc i trong vng sinh ra
do s xen ph cc obitan nguyn t s, p, d, f s l 2N(vng s), 6N(vng d) v
14N (vng f).
Trong trng hp kim loi, nhng vng nng lng gn nhau c th tip
gip vi nhau hoc cch xa nhau. Vng nng lng cha cc electron gy ra lin
kt ha hc gi l vng ha tr. Vng t do c mc nng lng cao hn, phn b
pha trn vng ha tr gi l vng dn. Ph thuc vo cu trc v mng tinh th
m hai vng c th xen ph vo nhau hoc khng xen ph vo nhau, ngha l
cch nhau mt khong nng lng E no , khong cch ny gi l vng
cm. Trong tinh th kim loi xy ra s xen ph ca hai vng ha tr v vng dn,
trong cht bn dn vng cm c XE vo khong 0,1 - 3 eV, cn trong cht in
mi, E vo khong ln hn 3 eV.
(4) Vy thuyt vng nng lng gii thch cc tnh cht c trng ca
kim loi nh th no?
Ni chung, cc tnh cht vt l c trng ca kim loi u gy ra bi cc
electron vng ha tr. S electron xp trong vng ha tr ph thuc vo s
electron ha tr ca nguyn t. Nu nguyn t c mt electron ns th vng nng
lng s ch mi c xp mt na s electron ti a; nu nguyn t c hai
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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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Ki hiu.
Chiu chuyn dch hn lon ca electron.
Chiu chuyn dch c hng ca electron.
(11 - 1)d cha xp s electron (l nhng kim loi m trong mng tinh
th c vng nng lng cha b chim hon ton) u l nhng cht dn in
in hnh.
Trong trng hp m vng ha tr b electron chim hon ton nhng li
tip gip vi vng trng cha b chim, di tc dng ca trng ngoi cc
electron s chuyn ng ln vng trng s lm cho vng b chim hon ton
thnh vng dn in (hnh 14 - 2a, 2b). Cc kim loi nhm IIA, IIB - thuc
trng hp ny - cng u l cht dn in in hnh.
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c cng di 2 c th rch c bng mng tay, c cng di 5 c th
rch c bng dao thng v c cng di 7 rch c bng da.
T bng 3 ta thy crom c cng gp 8,5 ln cng ca hot thch
hay ch bng 85% cng ca kim cng.
i cng kim loi
4) Khi lng ring ca cc kim loi cng ph thuc vo mng tinh th v
khi lng nguyn t ca kim loi, bin i trong khong rng t 0,5 g/cm3
li n 22,6 g/cm3 osimi. Bng 3. cng ca kim loi theo thang khong vt
(phng php rch)(1)
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Trong cc nhm A - th d nhm kim loi kim - nhit nng chy
gim t Li n Cs,
v lin kt trong kim loi kim l lin kt yu ; khi bn knh nguyn t tng,
lin kt li cng yu
Gi tr v nhit nng chy ca kim loi nu trong bng 5.
Bng 5. Nhit nng chy ca kim loi (Tnc, 0C)
w 3410 Nb 2415 V 1735 Mn 1250 La 826 Zn 449 In 156
Re 3170 Hf 2230 Ti 1725 U 1133 As 814 Pb 327 Na 98
Ta 3000 Rh 1966 Pd 1555 Cu 1083 Sr 770 Cd 321 K 63
Os 2700 Zr 1900 Fe 1539 Au 1063 Ba 704 TI 303 Rb 39
Mo 2625 Cr 1800 Co 1495 Ag 961 Al 660 Bi 271 Ga 30
Ru 2500 Th 1800 Ni 1455 Ge 959 Mg 651 Sn 232 Cs 28
Tr 2450 Pt 1744 Re 1284 Ca 851 Sb 631 Li 186 Hg -39
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Th 5200 Nd 3700 Fe 2740 Mn 2150 Bi 1560 Zn 907 Hg 357
(7) Tnh dn in ca kim loi l tnh cht vt l quan trng nht ca kim
loi. i i vi tnh dn in l tnh dn nhit. Nhng kim loi c tnh dn in
tt nht nh Ag, Cu, Au, Al cng chnh l nhng kim loi c tnh dn nhit tt
nht.
Nu ly dn nhit ca Hg lm n v th Ag dn nhit gp 48,8 ln
dn nhit ca thy ngn ; v nu ly dn in ca thy ngn lm n v th
dn in ca Ag s ln hn dn in ca thy ngn l 59 ln. Trong bng 7
nu ln cc gi tr so snh .
Qua bng 7 ta thy dn in cng nh dn nhit ca cc kim loi rt
khc nhau.
Tuy nhin, tt c cc kim loi u c mt c tnh chung l dn in
gim xung kh nhanh khi nhit tng (hnh 15a).
Bng 7. dn in v dn nhit ca kim loi (Hg = 1) dn nhit (Hg = 1)
dn in (Hg = 1)
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:
a) s thay i dn in khi thay i nhit :
b) s thay i dn in ca mt s kim loi gn
khng tuyt i.
Mt s kim loi li c tnh cht c bit l nhit rt thp, gn khng
tuyt i, th khi h nhit dn in tng ln lin tc v sau tng t
ngt n v cc ngha l chuyn sang tnh siu dn. S chuyn t trng thi dn
in bnh thng sang trng thi siu dn ng vi mt nhit xc nh v
khng phi bt k kim loi no cng u c tnh siu dn, th d Au, Cu... khng
c tnh siu dn ; mt s kim loi nh Hg, Su, Pb... v nhiu hp kim... li c
tnh siu dn (hnh 15b).
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do tch s tan ca AgI rt b (Tt = 8,3. 10-17).
Vi nhng axit c tnh oxi ha nh HNO3, H2SO4 c th axit l cht oxi
ha trong nguyn t trung tm gim s oxi ha.
(3) Trong mi trng trung tnh ([H+]=[OH-]=10-7M) th in cc
0
E +
= 0,41V , nhng kim loi no c th in cc thp hn gi tr
2H / H 2
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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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 :
K + 2Hg = KHg2 H = - 83,68 kj
Na + 2Hg = NaHg2 H = -75,31 kj
Na + 2Cd = NaCd2 H = - 1 29.71 kj.
Au + 3Zn = AuZn3 H = - 16,74 kj
Au + Zn = Auzn H= - 46.02 kj
3Au + Zn = Au3Zn H = - 100,42 kj
Mt s mctalit to ra dng kt ta hoc c mu khc nhau, chng hn:
3Na + 7sb = Na3Sb7 (dung dch mu )
3Na + 7Bi = Na3Bi7 (dung dch mu nu)
hay khi cho Pb tc dng vi dung dch natri tan trong amoniac lng to ra
kt ta trng, sau cho lng d Pb to ra dung dch mu xanh :
4Na + Pb = Na4Pb (trng)
Na4Pb + 17Pb = 2Na2Pb9 (dung dch xanh)
Metalit cng c th to ra khi cho kim loi lc dng vi mui trong
amoniac lng, v d:
9Na + 4Zn(CN)2 = 8NaCN + NaZn4
V tnh cht, nhiu metalit c bn nhit rt cao, v i khi c nhit
nng chy vt xa cc kim loi thnh phn, chng hn:
Li Bi LiBi
Tnc C 480 271 1145
Ni chung, nhng metalit to ra t cc kim loi in hnh nh KNa2 u t
bn.
Khi c metalit to thnh thng km theo gim dn in v to ra vng
cm kh r rt. Th d magie v thic - to ra metalit Mg2Sn c tnh cht khc
nhau:
Mg (3-Sn Mg2Sn
Tnc C 650 271,8 795
dn 21 8 0,1
in (Hg=1)
Vng cm (khng c) 0,34
(eV)
cc metalit khng tan trong nc, nhng mt s metalit li tan trong amoniac
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lng, lc cng in ly thnh con v cng c phn ng trao i kp nh:
2Ca(NO3)2 + K4Pb = Ca2Pb + 4KNO3
Khi in phn dung dch hoc trng thi nng chy cc metalit, th cc
kim loi chuyn v cc cc khc nhau, kim loi no m in hn chuyn v
anot; cn kim loi dng in hn chuyn v catot, th d khi in phn dung
dch Na2Pb9 trong amoniac lng thu c natri catot v ch anot.
Mt s hp kim to ra t nhng kim loi vn khng c t tnh nh hp
kim Cu v Mn khi cho thm mt s kim loi khc nh Al, Su, As, Sb, Bi li c
t tnh rt mnh. iu c lin quan n s to thnh metalit.
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cng d, do vy nhng kim loi c tnh dng in b hn Zn th oxit kim loi
d b hiro v cacbon kh thnh kim loi, so vi cc kim loi c tnh dng
in cao hn km.Vi nhng kim loi ny cn phi nhit cao, chng hn:
2000 0 C
MgO + C = Mg + CO
0
1200 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
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
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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:
0
600 c
2NaClnc = 2Na + Cl2
in phn Al2O3 trong criolit (NaAlF6) nng chy h nhit nng
chy ca Al2O3 t 12000C n 9500C :
0
950 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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CHNG 2
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Bng 8. Mt s c im ca cc nguyn t kim loi kim
o o
(A) M+ (A) I1 (eV)
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K2O.Al2O3.6SiO2; mutcovit KHAl3(SiO4)3; cacnalit KCl.MgCl..6H2O; kainit
K2SO4.MgSO4.MgCl2.6H2O; xinvinit NaCl.KCl ; xinvin KCl....
Rubii v xezi l nhng nguyn t rt phn tn, thng gp dng tp
cht ln trong qung ca cc kim loi kim khc, do khong vt dng khai
thc rubii v xezi l mt s qung c cha liti v kali.
Trong qung ca actini v urani c ln cc du vt franxi. V d trong
mt tn qung uran c khong 1,34. 10-11 g franxi.
(3) Trong c th ng vt, natri ch yu tp trung trong cc dch m (bch
huyt v mu), cn kali c trong bn thn ca m. Kali c nhiu trong gan, l
lch. Natri c nhiu trong bo thai ca ng vt.
Kali rt cn cho cy trng nh la, ng, khoai ty... Rubii c trong c ci
, trong cc loi nho...
(4) Trong nc i dng, cc kim loi kim u dng ion M+ vi thnh
phn trung bnh nh sau :
Nguyn Hm lng Nguyn Hm lng
t % mg/l t % mg/l
Li 1,5. 10 5 0,150 Rb 2. 10"5
0,2
Na 1,0353 10,354 Cs 3,7. 10"8 3,7. 10-
5
K 0,0387 387,5
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(27,85%); ng v 87Rb cng c tnh phng x nhng chu k bn hy l 6,2.1010
nm.
Cs c n 24 ng v, nhng ch c 133Cs l ng v thin nhin (100%),
cn li l ng v phng x.
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(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.
Tnh cht Li Na K Rb Cs
Khi lng ring (g / 0,53 0,97 0,86 1,53 1,87
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cm3)
Nhit nng chy (Tnc, 180 98 64 39 29
C)
Nhit si (Tnc 0C) 1370 883 760 700 670
dn in (so vi Hg 11 21 14 8 5
=1)
cng (so vi kirn 0,6 0,4 0,5 0,3 0,2
cng = 10)
Th in cc (V) -3,01 -2,71 -2,92 -2,98 -2,92
m in(1) 1,0 0,9 0,8 0,8 0,8
(1)
Theo Pauling.
Cc kim loi kim u c dn in cao ph hp vi thuyt vng ca
kim loi v cc kim loi kim c vng s ch mi b chim bi mt na s
elcctron. dn in cao hay thp cn ph thuc vo s nguyn t kim loi
trong mng tinh th ngha l ph thuc vo s nguyn t trong 1 cm3 kim loi
trng thi rn.
(2) Nhit thng hoa ca cc kim loi kim c gi tr nh sau :
Li Na K Rb Cs
Nhit thng hoa (kj / 150,6 108,8 92,1 87,8 79,5
mol)
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di dng nhng bc x vng nhn thy. V d vch vng ca quang ph natri
xut hin khi electron nhy t mc 3p xung mc 3s.
(3) Cc kim loi kim c kh nng ha tan ln nhau.Hp kim Na v K
(24% Na v 76% K) l mt cht lng. ng c - 12,60C.
Cc kim loi kim u d tan trong thy ngn to ra "hn hng"(xem
chng 8 mc 8.4). V d 1, hn hng "ca liti c thnh phn LiHg2, LiHg, Li2
Hg, Li3 Hg...
Cc kim loi kim cng to ra hp kim vi nhiu kim loi khc. V d vi
liti to ra LiMg2, LiAl, Li3Al...; natri to ra hp kim vi Sn nh NaSn6, NaSn4,
NaSn2, NaSn, Na2 Sn, Na3 Sn2...
Cc kim loi kim tan c trong amoniac lng to ra dung dch, trong
cc kim loi c ion ha, v vy dung dch long ca natri dn in ging
nh cht in li, ngi ta cho rng trong dung dch c cc ion sonvat ha
[ Na(NH3)X ]+ v cc ion [(NH3)n]. Khi nng ca Na ln hn, dung dch c
mu xanh m, c nh kim v c tnh dn in kim loi, t ngi ta cho rng
ngoi cc electron kt hp vi cc phn t NH3 cn c th c cc "electron t
do" trong dung dch.
(4) Cc ion kim loi Li, Na, K khng c, nhng hiroxit ca chng c tc
dng n mn da nn thng gi cc cht LiOH, NaOH, KOH l kim n da.
(5) Cc kim loi kim u c nhiu ng dng trong thc t.
Liti c dng ch to mt s hp kim. C nhiu ng dng quan trng
l hp kim ca li vi Ag, Mg, Zn, Cd, Pb, Ca. V d hp kim ca Ai c 1% Li
lm tng bn c hc v khng b n mn ; hp kim ca Cu c 2% li lm
tng dn in; thm 0,4% liti vo ch, cng ca ch tng gp 3 ln
ng dng quan trng nht ca li l ngun iu ch triti:
6 1 3 4
Li + n = H + He
3 0 1 2
Ngoi ra liti cn c dng lm cht mang nhit trong l phn ng ht
nhn.
Natri c dng nhiu trong phn ng nhit kim. Phng php nhit natri
c dng iu ch titan, ziconi v mt s kim loi khc.
Hp kim ca Na v K c dng nhiu trong cc phn ng tng hp hu
c. Natri dng hn hng c dng lm cht kh mnh ; Na v hp kim Na -
K cn c dng lm cht truyn nhit trong l phn ng ht nhn v mt s
thit b khc.
Di tc dng ca tia t ngoi cc kim loi Na, K, Rb, Cs u c kh nng
phng electron ra khi b mt kim loi nguyn cht, cng ca dng electron
c phng ra t l vi cng ca tia sng c hp th. Li dng tnh cht
ny ngi ta dng Rb v Cs lm t bo quang in dng trong v tuyn
truyn hnh...
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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), K2Sx,
Rb2Sx,Cs2Sx (X = 2 6) bng phn ng gin tip.
Cng tng t, selen v telu cng phn ng trc tip vi kim loi kim to
ra monoselenua M2Se v monotelua M2Te.
(5) Vi nit phn t, ch c liti l c phn ng trc tip to ra Li3N :
6Li + N2 = 2Li3N
phn ng xy ra chm nhit thng, nhng 5000C phn ng xy ra
mnh hn.
Cc kim loi kim cn li cng to ra hp cht dng M3N khi cho hi kim
loi tc dng vi "nit hot ng" trong trng phng in m :
6M + N2 = 2M3N
Cc hp cht thng c iu ch bng phn ng gin tip khi nung
hirua trong lung kh nit:
6NaH + N2 = 2Na3N + 3H2
Nitrua ca cc kim loi kim u c mu ( nhit phng c mu ),
bn trong khng kh kh, nhng nhanh chng b phn hu khi tip xc vi H2O
to ra amoniac:
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Na3N + 3H2O = 3NaOH + NH3
(6) Cc kim loi kim cng phn ng trc tip vi photpho nhng rt kh
khn. Li3P to ra khi nung liti kim loi vi photpho , sn phm thu c c
mu nu. Na3P l cht rn mu hung, to ra khi nung natri vi photpho
5000C. Rubii to ra hp cht c thnh phn Rb2P5 khi nung hn hp gm Rb
v P trong chn khng 5000C ; cn xezi cng to ra Cs2P5 khi nung hn hp
photpho vi xezi kim loi trong ampun hn 400 5000C trong thi gian
373 - 423 gi.
Cc photphua u b phn hy trong khng kh m to ra PH3 :
Na3P + 3H2O = 3NaOH + PH3
(7) Cacbon ch ha hp trc tip vi liti to ra cacbua Li2C2. Cht ny
nhit cao b phn hy to ra n cht :
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) :
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2Na + 2NH3 = 2NaNH2 + H2
sn phm b nc nng phn hy thnh amoniac do ion amiua phn ng
vi H2O:
NH2 + HOH = OH + NH3
(11) Khng nhng ch phn ng vi cc axit mnh lo ra H2 m cn c
th thay th hir trong cc axit hu c to mui ln nh NaCH3COO,
C6H5COONa.
Khi un nng hir sunfua hoc nung trong hir clorua, cc kim loi kim
u to ra mui sunfua v clorua tng ng:
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
TiCl4 + 4Na = Ti + 4NaCl
t0
Becb + 2Na = Be + 2NaCl
C2H5I + 2Na + I C2H5 C2H5 C2H5 + 2NaI
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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:
(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 :
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Na2O2 KO2 RbO2 CsO2
Ni Chung, cc peoxit v supeoxit u bn vi nhit, khng b phn hy
khi nung chy.
Tt c u ht m mnh v b chy ra trong khng kh.
Cc supeoxit u l cht d bay hi. Chng u tc dng mnh vi H2O
hoc vi axit:
M2O2 + 2H2O = 2MOH + H2O2
M2O2 + H2SO4 = 2M2SO4 + H2O2
vi Supeoxit cn to ra O2:
2MO2 + 2H2O = 2MOH + H2O2 + O2
2MO2 + H2SO4 = M2SO4 + H2O2 + O2
cc peoxit v supeoxit u l cht oxi ha mnh.
(4) Na2O2 l Cht c nhiu ng dng trong thc t. Trong k thut c
iu ch bng cch nung natri kim loi trong chn bng nhm 1800C vi oxi
hay khng kh kh.
L cht rn mu hi vng (do c ln tp cht). Nng chy 4600C v phn
hy r rt gn 6000C.
Na2O2 tc dng mnh vi H2O v pht nhiu nhit do to ra hirat
Na2O2.8H2O v sau b thy phn to ra O2:
2Na2O2 + 2H2O = 4NaOH + O2
cn nhit thp hay trong dung dch long th b phn hy to ra H2O2 :
Na2O2 + 2H2O = 2NaOH + H2O2
Na2O2 l Cht oxi ha mnh. Cc cht d chy nh rm, bng, bt than, bt
nhm, lu hunh, b bc chy v gy n khi tip xc vi Na2O2. Cc Cht hu
c nh ete, axit axetic, nitro benzen, glixerin c ln nc trn vi Na2O2 cng
gy n mnh.
Trong ha hc phn tch,dng ph qung sunfua bng cch nu nng
chy qung vi hn hp gm Na2O2 v Na2CO3 trong chn bng bc :
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:
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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
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- 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
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
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tan (mol / l) d 5,4 29,8 22,6 16,9 20,2
30 C
Zn + OH + H2O = HZnO2 + H2
HZnO2 + OH = ZnO22- + H2O
2Al + 2OH- + 2H2O = 2AlO + 3H2
Sn + OH + H2O = HSnO2 + H2
Tng tc vi mt s phi kim nh Si, C, P,S, halogen :
Si + 2OH + H2O = SiO32- + 2H2
Cacbon kh NaOH nng chy to ra Na v mui cachonat:
6NaOH + 2C = 2Na + 2Na2CO3 + 3H2
Photpho trng (khng phi photpho ) phn ng vi dung dch kim c
to ra photphin v nam hirophotphin (cc nguyn t khc trong nhm VA
khng phn ng):
4P + 3OH + 3H2O = PH3 + 3H2PO2
Tc dng vi axit v oxit to thnh mui.
Hp th CO2, SO2 to ra mui cacbonat hoc sunft :
CO + 2OH = CO32 + H2O
SO + 2OH = SO3 + H2O
n mn s v thy tinh to ra silicat:
SiO2 + 2OH = SiO32 + H2O
Tc dng vi mt s mui to ra kt ta hiroxit ca cc kim loi nh
Mg(OH)2, Cu(OH)2... hoc to ra nhng baz yu nh :
NH4Cl + NaOH = NH3 + NaCl + H2O
CH3NH3Cl + NaOH = CH3NH2 + NaCl + H2O
(3) Khi cn mt lng nh hiroxit rt tinh khit ngi ta cho kim loi
kim tc dng vi H2O:
2Na + 2H2O = 2NaOH + H2
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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 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:
dp
2NaCl + 2H2O = 2 NaOH + Cl2 + H2
ngn khng cho kh ch tip xc vi dung dch NaOH, ngi ta dng
mng ngn bng li st ph aming bao quanh cc dng.
Dung dch thu c c cha 8% NaOH cn ln rt nhiu NaCl, v vy khi
c dung dch, NaCl c ha tan b hn nn kt tinh trc, c lp nhiu ln
thu c NaOH c hm lng cao.
KOH cng nh NaOH, d tan trong nc, trong metanol v etanol. Trong
k thut cng iu ch KOH bng cch cho K2CO3 tc dng vi nc vi hoc
in phn dung dch KCl c mng ngn. Khi lm bay hi dung dch cng c th
thu c KOH rn, nhng thng dng trc tip dung dch c khong 50%.
Kili hiroxit c dng ch yu trong cng nghip sn xut x phng
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mm, lm kh cc kh. hp th kh CO2...
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Tr LiF (T, = 3,8.10-3), cc halogenua khc u d tan trong nc
(bng 10).
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Bng 10. tan ca cc halogenua kim loi kim (mol/l 180 C)
F- CI- Br I
Li 0,1 18,6 20,3 12,2
Na+ 1,1 5,8 8,6 11,8
K+ 15,9 4,5 5,4 8,6
Rb+ 12,5 7,2 6,5 7,2
Cs- 24,2 10,9 5,6 2,8
Bng12 Nng lng hirat ha cc cation kim loi kim (kj / mol)
T trn, theo chiu tng t Li+ n Cs+ nng lng mng li gim v nng
lng hirat ha cng gim xung.
Trong cc ngha i t Li+ n Cs+, nng lng mng li gim xung
nhanh chng nn ha tan tng; tri li trong cc halogcnua khc, ha tan
cc mui li gim do nng lng hirat ha gim.
tan cc halogenua kim loi tng khi tng nhit (hnh 19). Ngi ta
li dng kh nng ny tch cc mui clorua khi hn hp. V d ha tan
ca Nacl v KCI c gi tr sau (gam/100gam H2O):
t 0C 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
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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 YZ ZZXZ AY +BX, cn bng s chuyn dch v pha
to ra hai mui trong c mt phn t gm cc ion nh hn v mt phn t
gm cc ion ln hn. V d:
ZZX
NaI + RbCl YZ Z NaCl + RbI
Bng 13. Nhit nng chy (Tnc) v nhit si (Ts) ca cc halogenua
kim loi kim (0C)
F- Cl- Br- I-
Li+ Tnc 842 606 549 453
Ts 1676 1382 1310 1170
Na+ Tnc 995 800 740 610
Ts 1702 1454 1393 1300
K+ Tnc 856 768 728 682
Ts 1505 1417 1376 1330
Rb+ Tnc 780 717 681 642
Ts 1410 1883 1350 1305
Cs+ Tnc 684 638 627 621
Ts 1251 1303 1300 1280
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(2) Nam clorua (NaCl) l mui quan trng nht trong cc halogenua ca
kim loi kim. NaCl l hp cht ion, tinh th c mng lp phng tm din.
Trong thin nhin, NaCl c trong nc bin khong 2,7% theo khi lng;
c trong mui m, nhng m mui ln c lp dy n 1000m hoc ln hn.
Cng nh KCl, NaCl tinh th c trong sut cao i vi tia trng thy v tia
hng ngoi nn c dng ch to mt s dng c quang hc .
Khi nng chy, mt phn NaCl bay hi nhng mc km hn so vi KCl.
Ngi ta xc nh c 8000C, p sut hi ca NaCl l 1 mmHg; cn KCl
8000C l 4,5 mmHg .
Ngi ta khai thc mui n t nc bin bng cch un nng hoc bng
cch phi nng; mui n cng c th khai thc t mui m bng phng php
ngm , bng cch ha tan ngm sau bm dung dch ln ri kt tinh li.
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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:
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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).
(2)' Cc mui cacbonat ca kim loi kim u tan , dung dch u c tnh
kim mnh do Phn ng thu Phn ;
Nhng khi nung nhit cao hn, cc mui b phn hy thnh oxit v
kh CO2:
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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:
Cn cc mui kim loi kim khc iu ch bng cch cho Coi tc dng
vi hiroxit:
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8520C . Cao hn 8520C, bt u b phn hy (hnh 22).
D tan trong nc , qu trnh tan pht nhiu nhit do s to thnh hirat. T
dung dch, nhit di 32,50C, nam cacbonat kt tinh dng
Na2CO3.10H2O.
Gia khong 32,5 37,50C, Na2CO3.10H2O mt nc kt tinh bin thnh
dng heptahirat Na2CO3.7H2O ; trn 37,50C bin thnh monohirat
Na2CO3.H2OV n l070C mt nc hon ton to thnh Na2CO3 khan (hnh
23).
T hnh 23 cho thy tan ca Na2CO3 .10H2O tng ln theo nhit cn
tan ca Na2CO3. H2O li gim xung.
Na2CO3.10H2O ln hoa nhanh ngoi khng kh to thnh bt trng
Na2CO3.5H2O.
Khi tan trong nc Na2CO3 b thy phn lm cho dung dch c tnh kim:
Thc cht phn ng trn l thun nghch , ha tan cc cht trn 200C
c gi tr nh sau:
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NaCl NH4HCO3 NaHCO3 NH4Cl
tan (g/100gH2O) 36 21 9,6 37,2
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
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sau Na3AlO3 b phn hy bi H2O v CO2:
tc 0 25 100
tan 105 113,5 156
(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 dung dch KCl bng phng php in phn:
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MgCO3.3H2O:
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.
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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
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H2SO4 c:
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:
t0C 0 20 40 100
tan(g/100gH2O) 36,3 51,4 67,3 121,6
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V H2SO4 c Cho n khi c mt khi trong sut , lm lnh cht lng, c
nhng tinh th KHSO4:
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ng trung ha KOH vi HNO3.
Ngi ta cng iu ch KNO3 bng phn ng trao i gia NaNO3 vi KCl:
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:
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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+ Cs+
MCIO4 0,76 g (140 C) 1,17g(140C)
M2[PtCl6] 0,028 g (200 C) 0,009 g (200 C)
MH[C4H4O6] 1,17g(250C) 8,9 g (250 C)
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CHNG 3
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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
0
(5) Be v Mg kt tinh theo mng lc phng (hnh1).Vi Be (a = 2,268 A ;
0
c = 3,594 A .
Mi nguyn t Be c bao quanh bi 12 nguyn t khc; 6 nguyn t nm
trong cng mt mt phng c khong cch l a.
0 0
Vi Mg c a = 3,22 A ; c = 5,56 A ; mi nguyn t Mg cng c bao
quanh bi 12 nguyn t khc .
0
Canxi kt tinh theo mng lp phng tm din (hnh li c cnh (a = 5,56 A
(dng - Ca). Mi nguyn t Ca c bao quanh bi 12 nguyn t khc c
0
khong cch gia hai nguyn t d: 0,5 a 3 = 3,94 A . 3000C , - Ca chuyn
thnh dng th hnh - Ca c tnh i xng km hn; 4500C chuyn thnh
dng th hnh - Ca c mng lc phng tng t Mg.
Stronti, tng t canxi, kt tinh theo mng lp phng tm din c
0 0
a = 6,05 A v d = 4,27 A .
0
Bari kt tinh theo mng lp phng tm khi c (a = 5,01 A . Mi nguyn
0
t bao quanh bi 8 nguyn t khc, c khong cch d = 0,5 a 3 = 4,34 A
(hnh 1).
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thin nhin dng hp cht. Trong v qu t Ca v Mg thuc loi nguyn t
ph bin nht v c phn b nh
Mg 2,0 2,1
Ca 2,0 3,6
Sr 1,0. 10-2 4. 10-2
Ba 5,7. 10-2 5. 10-2
Ra 9,0. 10-12 1. 10 -10
(2) Khong vt chnh ca berili l beryl BeAl2(SiO3)6 hay
3BeO.Al2O3.6SiO2. Mt s dng beryl trong sut c mu khc nhau do ln tp
cht c gi l ngc. V d ngc bch c mu lc (tp cht l hp cht ca
crom), lam ngc c mu xanh da tri ...
Hp cht thin nhin c cha magie c dng cacbonat nh qung manhezit
MgCO3; qung olomit MgCO3.CaCO3; dng clorua nh qung bisophit
MgCl2.6H2O; Cacnalit KCl.MgCl2.6H2O; dng sunfat nh kizerit MgSO4.H2O;
kainit KCl.MgSO4.3H2O; dng silicat hoc hirosilicat nh bt tale
Mg3H2(SiO3)4 hay Mg2[Si4O10].Mg(OH)2; qung atbet CaMg3(SiO3)4...
Khong vt c cha canxi dng cacbonat l dng canxit aragonit CaCO3
olomit CaCO3.MgCO3; dng sunfat nh thch cao (xelenit) CaSO4.H2O;
anhirit CaSO4; xighenit K2SO4.CaSO4.H2O; gloherit NaI2O4.CaSO4, dng
florua nh fluorit CaF2 apatit 3Ca3(PO4)2.CaF2 v.v....
Strontiv banric trong cc qung ch yu l strontianit SrCO3 ,viterit
BaCO3 xelestin SrSO4; barit BaSO4 .
Radi l nguyn t phng x, c trong cc qung ca gurn nh qung
cacnotit K2(UO2)2(VO4)2.3H2O) Trong nc i dng , thnh phn trung bnh
ca cc kim loi kim th nh sau (theo A.P. Vinogradov 1967):
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xng v l thnh phn khng th thiu ca mu.
(5) Hm lng ca cc kim loi kim th c trong cc mu do cc tu
Apollo 11 - 12 v Luna - 6 a t Mt Trng v ba vng khc nhau c gi tr
nh sau:
Hm lng trung bnh (s gam /1 g mu
Nguyn
)
t
Apollo-11 Apollo-12 Luna -6
Be 0,2. 10-5 - 0,25. 10-5
Mg 0,045 0,072 -
Ca 0,080 0,071 -
Sr 17. 10-5 17. 10-5
22. 10-5
Ba 20. 10-5 42. 10-5 18,5. 10-5
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
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kh BeFl.
(3) Trong cc kim loi kim th th magie c nhiu ng dng trong k thut.
Trong cng nghip ngi ta iu ch ma gie bng phng php in phn MgCl
tinh khit hoc cacnalit khan nng chy (MgCl2.KCl) hoc hn hp mui clorua
tng ng nhit khong
700 - 7500C trong thng in phn bng thp ng thi l cc m. Cc dng l
mt tr than ch t trong ng s xp c l nh cho kh clo thot ra ngoi
(hnh 26).
trnh khng cho magie lng tp trung phn trn cht in phn khng
b khng kh oxi ha, ngi ta thi chm mt lung
kh H2 trn b mt ca magie lng.
c MgCl2 thm vo, ngi ta iu ch t manhezit
MgCO3 hoc t olomit MgCO3.CaCO3 theo phn ng:
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:
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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:
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kim.
Nhit nng chy v nhit si cao hn v bin i khng u nh cc kim
loi kim, v cc kim loi kim th c cu trc mng tinh th khc nhau, trong
khi cc kim loi
kim li c cng mt loi mng tinh th; mt khc lin kt trong kim loi kim
th mnh hn nn nhit nng chy Tnc v nhit si Ts cao hn.
Mi nguyn t kim loi kim th u c hai electron s nn vng s c lp
y, v nu vy cc kim loi kim th phi l cht cch in hoc bn dn in;
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thc t chng li c dn in cao v gn tng ng cc kim loi kim ?
iu c th c gii thch rng vng nng lng s v p c mc nng lng
gn nhau nn d xen vo nhau, hai electron s c nng lng nm trong vng kh
rng cha electron to ra cht cch in, nn chng u c dn in
cao.
Cc kim loi kim th c cng khc nhau, cng nht l beng. iu kin
thng, Be gin, nhng khi un nng li do; magie do c th dt mng v c
th ko di thnh si. (2) Vic chuyn cc kim loi kim th t trng thi rn
sang trng thi hi cn tiu th nhng nng lng nh sau:
Be Mg Ca Sr Ba
Nhit thng hoa (kj / mol) - 153 180 205
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lng ion cao lm cho cc ion M2+ d to ra.
Cng do nng lng ion ha th nht thp hn nn cc kim loi kim th cng
d mt mt electron ha tr to ra mc oxi ha +l, v d trong hp cht CaCl
khi nung hn hp CaCl2 + Ca 10000C.
(4) Berili l nguyn t c nhiu ng dng trong nhiu ngnh k thut, chng hn
k thut hng khng v k thut nguyn t.
Loi thp c cha 1% Be c tnh bn cao, khng mt tnh n hi ngay khi
t nng .
Berili ln vo ng lm tng cng, bn c hc v bn ha hc m
khng lm gim dn in ca ng; hp kim ca ng c cha 2% berili c
sc chng gy gp bn ln ng nguyn cht.
Hp kim ca magie c nhiu ng dng trong cng nghip t, my bay v ch
to my; trong hai hp kim quan trng l hp kim "manhali" v hp kim "
electron"." Manhali" l hp kim ca nhm c cha 5 - 30 % Mg, rn v bn hn
nhm nguyn cht, v cng d ch ha v d bo nhn hn. " Electron" cng l
hp kim m thnh phn chnh l magie. ngoi ra cn c nhm, km, mangan;
i khi cn c Cu, Be, Ti... Hp kim ny c tnh c hc tt, nh. Trong ngnh
luyn kim ngi ta cn dng magie kh vanai, crom, titan...Phc cht c
cha Mg ca vng pofirin l c s cu to ca phn t clorofin.
Canxi, stronti, bari c s dng rt hn ch v hot tnh cao ca chng.
Canxi c dng trong luyn kim mu, lm cht kh lin kt cc tp cht c
hi nh S, P, C d.
Stronti c dng trong k thut n in chn khng hp th khng kh cn
st li v trong k ngh luyn ng thanh loi S, P, C khi kim loi.
Mt lng nh bari cng c ng dng tng t trong luyn ng v ch kh
oxi; lm sch kim loi khi lu hunh v cc kh. Cho thm bari vo ch tng
cng ca hp kim in.
Rai l nguyn t phng x u tin c dng vo cc mc ch thc t, ch
yu trong y hc cha cc khi u v mt s bnh khc.
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(3) Khi un nng trong khng kh, Be v Mg to ra oxit Mo, cn cc kim loi
kim th cn li th ngay nhit thng to ra oxit MO, v c mt phn
peoxit MO2 v nitrua M3N2.
Vi lu hunh, khi un nng to ra sunfua dng MS.
Cc kim loi kim th cng to ra vi selen v tu cc hp cht dng MSe v
MTe nhng bng phng php gin tip.
(4) Cc kim loi kim th phn ng trc tip vi nit to ra cc nitrua cc
nhit khc
nhau.
Be3N2 to ra khi cho bt berili tc dng vi nit nhit khong 527 - 9270C;
Mg3N2 780 - 8000C; Ca3N2 khong 500 - 6000C; Sr3N2 khong 400 -
5000C; Ba3N2 khong 260 - 6000C.
Vi photpho cng c phn ng trc tip to ra Be3P2; Mg3P2 to ra khong
330 - 5300C trong ampun hn; Ca3P2 nhit khong 5730C; cn Ba3P2
nhit 400 - 4500C
(5) Khi un nng vi cacbon trong chn khng hoc trong kh quyn hidro,
berili to ra Be2C v BeC2 khong 1700 - 21000C. Nc phn hy Be2C to ra
CH4, cn BeC2 - to ra C2H2.
Phn ng xy ra trong iu kin tng t vi magie to ra Mg2C3 740 - 7600C
v to ra MgC2 6000C. Nc phn hy Mg2C3 to ra C3H4, cn MgC2 to ra
C2H2.
Canxi, stronti v bari cng phn ng trc tip vi cacbon to ra CaC2, SrC2 v
BaC2; nhng nhng hp cht thng iu ch bng cch nung oxit kim loi
tng ng vi cacbon. Cc hp cht b thy phn cho axetilen.
silic cng c kh nng phn ng trc tip vi kim loi kim th; Mg to ra
Mg2Si - l hp cht t bn, b H2O phn hy chm, vi axit - b phn hy nhanh
hn; vi can xi to ra dng Ca2Si, cn stronti v bari to ra MSi v MSi2 (M l
Sr v Ba).
(6) Nhit to thnh cc hp cht trn, nu trong bng 16.
(7) Do c th in cc thp, cc kim loi kim th u c kh nng tc dng vi
H2O gii phng H2 V cng d dng y H2 ra khi dung dch axit.
Tuy nhin, trong thc t Be hu nh khng tc dng vi H2O, Mg khng tan
trong nc lnh v tan mt phn trong nc nng, do c hai kim loi u c lp
oxit bo v ngn cn tc
Bng 16 Nhit to thnh mt s hp cht ca cc kim loi kim th (kj / ng
lng gam)
Nguyn t oxit hirua florua clorua bromua iotua sunfua nitrua
Be 287 - 505 235 - - 117 93
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Mg 305 - 547 316 254 177 176 80
Ca 318 96 605 399 339 267 239 72
Sr 295 88,3 605 413 357 285 231 64
Ba 279 85 599 429 377 323 214 62
dng ca kim loi vi H2O; tri li, magie dng "hn hng" li phn ng rt
mnh vi H2O do khng cn lp oxit bo v:
Magie kim loi thc t khng tc dng vi kim, nhng vi Ca, Sr, Ba tan c
trong dung dch kim do phn ng vi H2O.
Tr Be, cc kim loi cn li c kh nng y hiro ra khi ru ngay nhit
thng, ring Mg th phi un nng:
(9) Cng nh kim loi kim, cc kim loi Ca, Sr, Ba tc dng vi amoniac lng
to ra dung dch mu xanh thm. Khi lm cho dung mi bay hi, cn li tinh th
mu vng ng l cc amoniacat c thnh phn khng i:
[Ca(NH3)6] [Sr(NH3)6] [Ba(NH3)6]
Hin nay ngi ta cha bit r lin kt gia kim loi vi cc phn t NH3 V
cng cha gii thch mt cch chu o v tnh dn in cao ca cc hp cht ;
ngi ta cho rng trong cc dung dch c cc cation [Ca(NH3)6]2+ hay
[Ca(NH3)6]+ v anion l cc electron t do.
Cng nh cc amoniacat ca cc kim loi kim, khi c mt ca cht xc tc,
chng hn plalin - cc amoniacat kim loi kim th b phn hy dn to ra cc
amiua:
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Cc amiua v imiua ca cc kim loi th ch bn dng tinh th, tng tc
mnh vi H2O to thnh hiroxit v amoniac, v d:
Khi tip tc un nng, cc amiua v imiua trong chn khng cao, s thu c
cc pcnitrua dng M3N4 v d penitrua ca stronti - l cht bt tinh th mu
nu. Cc penitrua b axit long phn hy thnh nit v mui amoni:
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3.6. Hirua ca cc kim loi kim th
(1) Tt c cc kim loi kim th u c kh nng to ra hp cht vi hiro ng
vi ha tr II ca kim loi (MH2). Tt c u l cht rn mu trng, bn tng
t BeH2 n MgH2 sau gim dn t CaH2 n BaH2.
(2) BeH2 khng iu ch c trc tip t cc nguyn t m bng phn ng trao
i gia BeCl2 vi LiH trong ru hoc bng cch cho Be(CH3)2 tc dng vi
AlLiH4:
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(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:
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:
Be Mg Ca Sr Ba
0
Bn knh ion M2+ ( A ) 0,34 0,74 1,06 1,26 1,33
Nhit hidrat ha ca oxit MO (kJ/mol) 14,2 40,6 66,5 81,6 102,5
(3) Beo c iu ch bng cch nung hiroxit hoc mui ca berili nh mui
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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:
Trong cng nghip, ngi ta iu ch MgO bng cch nung manhezit thin
nhin (MgCO3)
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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:
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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:
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:
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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:
(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:
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:
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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.
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:
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;
V vy, theo nguyn l chuyn dch cn bng, khi tng nhit th tan ca
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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:
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.
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dnh kt trong cng nghip xy dng.
Mg Ca Sr Ba
2+
Nng Ing hidrat ha ca ion M 1908 1577 1431 1289
Nng Ing mng li ca mui MF2 2908 2611 2460 2368
Nng lng mng Ii ca mui Ml2 2293 2058 - 1866
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SrCl2 c cu trc mng
florit; MgF2, CaCl2, CaBr2 c cu trc mng rutin; MgBr2, MgI2 , CaI2 , SrI2 c
cu trc mng bruxit.
Trong tinh th mng florit, cc con Ca2+ to ra mng lp phng tm din, c s
phi tr bng 8; cc ion F chim tm ca tm hnh lp phng nh (hnh 33).
Tr cc florua MF2 t tan, cc halogenua cn li u d tan, tan trong dung
dch bo ha c gi tr nh sau (bng 18).
Bng 1B. tan cc MX2 250C (mol / l).
Mui Mg Ca Sr Ba
MF2 1,3.10-3 2,2.10 -4 9,7.10-4 8,3.10 -3
MCI2 5,7 7,4 3,5 1,8
MBr2 5,6 7,5 4,2 3,4
Ml2 5,3 7,0 5,4 5,2
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:
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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:
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
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(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:
Trong dung dch nc, MgCl2 tn ti mt s dng hirat MgCl2. xH2O (x =2;
4; 6; 8; 12), bn hn c l dng hexahirat MgCl2. 6H2O, cht ny kt tinh c
t dung dch nc nhit thng.
Khi nung, nc kt tinh mt dn v cui cng to ra MgO:
MgCl2 l cht d tan trong nc, ht m mnh nn d chy ra trong khng kh;
kt hp vi mui clorua kim loi kim hoc amoni to ra cc mui kp. V d:
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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 20 40 60 100 260
tan CaCI2 (g / 100g H20) 42,5 60 65 74,5 115 137 159 347
S gam CaCI2 trong 100g H2O 6,0 11,5 16,5 21,0 25,0 41,5 69,0
Nhit si (C) 101 102 103 104 105 110 120
S gam CaCI2 trong 100g H2O 101 137,5 178 222 268 292 305
Nhit si (C) 130 140 150 160 170 175 178
Bng 20 Nhit ng c ca dung dch CaCl2
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
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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:
ngui chng b phn hy dn theo hng ngc li. B phn hy trong khng
kh m theo phng trnh:
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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:
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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:
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:
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kh tan trong nc. Tch s tan c gi tr nh sau (Tt):
Trong dung dch c cha d kh CO2, cc mui cacbonat ca Ca, Sr, Ba li tan
do to ra mui hirocacbonat M(HCO3)2:
Phn ng trn gii thch hin tng n mn vi trong thin nhin, v do phn
ng nn trong nc sng, nc ngm c cha mt lng ng k
Ca(HCO3)2.
Khi trong khng kh hoc khi un nng, cc mui u phn hy tch ra
CO2:
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
t0c 540 897 1290 >1360
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CaC03 0 0 0,1 - 0,4 1,8 6,9 22,2 63
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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:
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:
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.
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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
:
(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:
MgSO4. 12H2O bn trong khong t - 3,90C n 1,80C
MgSO4. 7H2O bn trong khong t l,80C n 48,30C
MgSO4. 6H2O bn trong khong t 48,30C n 680C
MgSO4. H2O bn trong khong cao hn 680C
MgSO4 Cng c iu ch bng cch cho MgO tan trong H2SO4 30%:
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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:
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Nung n gn 5000C, chuyn thnh dng khng tan trong nc, khng tng tc
vi nc, v vy khng th lm vt liu dnh kt, gi l thch cao cht.
Nung n khong 900 - 10000C l cht bt mu trng kh c kh nng ht m,
nn c dng lm kh. Khng kh m, sau khi qua ng ng CaSO4 ch cn li
khong 0,005 mg H2O trong mt lt khng kh.
Nung n 12000C bt u phn hy to ra CaO:
(5) SrSO4 thng gp trong thin nhin dng khong vt seletin, l nguyn
liu ch yu dng iu ch cc hp cht ca stronti.
SrSO4 rt t tan trong nc, 180C tan vo khong 11,4 m trong 100g H2O.
vi mui sunfat kim loi kim, chng hn K2SO4, (NH4)2SO4, Stronti sunfat to
ra nhng mui kp kh tan.
Cng tng t CaSO4, SrSO4 Cng b nhit phn tch ra SO3 nhng nhit cao
hn nhiu so vi CaSO4.
(6) BaSO4 l Cht bt mu trng, hu nh khng tan trong nc, 180C -100g
H2O ch ha tan c 0,22 mg BaSO4. Trong H2SO4 c ha tan ca BaSO4
tng ln do to ra phc cht.
BaSO4 nng chy 15800C v tip theo l bay hi hon ton. Bari sunfat
c iu ch bng cch kt ta t dung dch khi cho dung dch mui bari tc
dng vi dung dch H2SO4 hoc dung dch cha ion SO42- khc:
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CHNG 4
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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
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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
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B 6 .10-4 3. 10-4
Al 6,6 8,8
Ga 4. 10-4 1,5. 10-3
ln 1,5. 10-5 1. 10-5
Tl 3. 10-5 3. 10-4
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Nguyn Hm lng trung bnh (s gam /1g mu )
t Apollo - 11 Apollo -12 Luna - 6
-5
B 0,2.10 - 0,44.10-5
Al 0,056 0,074 -
-5 -5
Ga 0,45.10 0,4.10 0,45.10-5
Ln 3.10-9 9.10-9 0,17.10-5
Tl 0,6.10-9 2.10-9 2.10-9
4.3. iu ch nhm
(l) Ngi ta sn xut Al bng phng php in phn Al2O3 nng chy
trong criolit Na3AlF6 ( hay AlF3 . 3NaF).
Nguyn liu dng sn xut nhm l qung boxit v criolit cn nhiu tp
cht, mt khc tinh ch Al khi cc tp cht rt kh khn, v vy vic tinh ch
nguyn liu ban u li rt cn thit.
Boxit thin nhin cha khong 40 - 60% Al2O3 V tp Cht ch yu l
SiO2, Fe2O3...
Ty theo loi qung m thnh phn tp cht c thay i, chng hn boxit
trng cha SiO2 nhng hu nh khng c Fe2O3 ; boxit nu li c khong 27%
Fe2O3. c Al2O3 C tinh khit cao (khng cha qu 0,2% SiO2) v 0,04%
Fe2O3) ngi ta un nng bt boxit vi dung dch NaOH 40% 1500C di
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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
xi mng.
(2) V d tr criolit tri t l c hn nn ngi ta tng hp ly criolit
bng cch ha tan Al(OH)3 v Na2CO3 trong axit flohiric :
2Al(OH)3 + 3Na2CO3 + 12HF = 2Na3[AlF6] + 3CO2+ 9H2O
(3) Qu trnh in phn c thc hin 9500C, vi in p khong 5V v
cng dng khong 100000A. Thit b in phn l mt thng v st bn
trong lt gch chu nng. Trn lp ny c bc mt lp than dng lm cc m;
cc dng l nhng thi than cm vo thng in phn.
B mt cht lng trong l c ph mt lp rn cht in li cho khi
nng chy khi b ngui .
Trong qu trnh in phn c kh O2 bay ra ant tc dng vi C to ra
kh CO v CO2 ng thi c mt t flo cng bay ln, to ra mt t CF4, do vy
dng cc b n mn dn, nn trong qu trnh in phn phi h thp dn cc
dng xung.
Qu trnh in phn c tin hnh lin tc, sau mt thi gian , ngi ta
li cho thm
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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
0
(2050 C) nn khi Al2O3 tan trong criolit nng chy, h nhit xung khong
10000C. Nhm thu c c tinh khong 99,5%. Sau khi tinh ch li c th
t c tinh khit khong 99,998%.
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)
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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
0
2400 C. Phng php trn gi l phng pht nhit nhm, dng iu ch mt
s kim loi kh nng chy nh Cr, Mn, Fe, V, Tl ...
Vi nit, lu hunh , photpho, cacbon, Al cng ha hp trc tip cc
iu kin khc nhau to ra AlN, Al2S3, AlP, Al4C3, nhng hp cht ny u b
H2O thy phn to ra Al(OH)3 v hirua ca phi kim tng ng:
AlN + 3H2O = Al(OH)3 + NH3
Al2S3 + 6H2O = 2Al(OH)3 + 3H2S
AlP + 3H2O = Al(OH)3 + PH3
Al4C3 + 12H2O = 4Al(OH)3 + 3CH4
Nhm khng phn ng trc tip vi hir.
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(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.
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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..
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(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
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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)
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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:
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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 :
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HF, khi chng dung dch, cht rn thot ra dng hirat tinh th AlF3 .3H2O.
AlF3 khan l cht rn mu trng, khng tan trong nc, trong axit v
kim, kh tr v mt ha hc. Tuy nhin li c kh nng kt hp vi cc florua
kim loi kim to ra cc hp cht floanuminat ng vi cc cng thc M31 AlF6,
M21, AlF5, M1 AlF4; trong s quan trng nht l natri floaluminat (Na3AlF6)
c dng trong cng nghip sn xut nhm.
(3) Criolit (Na3AlF6) cn gi l bng thch l mt khong cht thin nhin,
ngoi phng php iu ch nu trn, ngi ta cn iu ch bng cch nung
hn hp gm canxi florua, kali
sunfat vi than to ra kali florua. Cho kali florua tc dng vi natri sunfat to ra
natri florua v hon nguyn li kali sunfat; sau nung natri florua vi nhm
sunfat thu c criolit :
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Na3AlF6 tinh khit l nhng tinh th mu trng dng lp phng, c khi
lng ring l 2,95g/cm3, nng chy 10000C. Rt kh tc dng vi axit nhng
li d b phn hy khi un nng vi kim hoc sa vi. Mt lng ln xoda v
Al2O3 c sn xut bng cch nung criolit vi CaCO3:
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thay i t 6 n 4. Nh vy, cu trc ime chim u th trong pha hi gn
nhit si, khi un nng n 8000C xy ra s phn ly thnh monome :
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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:
t0C 0 10 20 30 40 60 80 100
tan, S 43,8 44,9 45,9 46,6 47,3 48,1 48,6 49,0
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(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:
(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.
t0C 0 10 20 30 40 60 80 100
tan 31,2 33,5 3,.4 4,.4 45,7 59,2 73,1 89,0
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dung dch Al2(SO4)3 C phn ng axit mnh do b thy phn mt phn:
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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.
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...
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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.
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phn hy nhanh hn thnh NH3; khi cho hi H2O nu qu, Al2O3 li c ti
sinh :
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.
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Hp kim gm 18,1 % In vi 41 % Bi ; 22,1 % Pb; 10,6% Sn v 8,2% Cd
nng chy 470C dng trong y khoa b xng gy.
Hp kim gm 75% Ga v 25% In nng chy 16oC v hp kim gm
90% Ga vi 8% Sn; 2% Zn nng chy 19oC nn c dng ch to thit b
cha chy t ng.
Tali c dng ch hp kim vi Pb, Sn c kh nng chu axit. c
bit l hp kim c thnh phn 70% Pb, 20% Sn v 10% Tl Chu ng c hn
hp axit H2SO4, HNO3 v HCl. (3) C ba nguyn t u c kh nng tc dng
vi cc n cht v hp cht vi mc khc nhau.
Khi trong khng kh, Ga v In khng bin i do c bo v bi mt
lp oxit mu xm; cn tali th b oxi ha chm .
Khi nung nng, c ba u ha hp mnh vi oxi v lu hunh; vi clo,
brm phn ng xy ra ngay nhit thng, cn vi it th phi un nng.
Tng t nhm, gali hon ton bn i vi H2O, cn ini v nht l tali
b nc ph hy trn b mt khi c khng kh.
Axit sunfuric v nht l axit clohiric ha tan d Ga v In; cn Tl tc
dng vi HCl rt chm do to ra lp mui TlCl khng tan che ch b mt. Vi
axit nitric, Ga phn ng chm, cn tali phn ng rt mnh lit.
Tng t nhm, gali tan trong dung dch kim mnh.
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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.
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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)
TlF3 - 550 -
TlCl3 - 25 thng hoa
TlBr3 mu vng - -
TlI3 mu en - -
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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:
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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 :
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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 :
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CHNG 5
(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.
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Cng nh cacbon v silic, gecmani, thic, ch u c lp v ns2np2 vi s
electron ha tr bng s obitan ha tr, u to ra hp cht cng ha tr vi s oxi
ha -4, +2 v +4. Tuy nhin khi chuyn t Ge n Pb th bn ca bc oxi ha
+4 gim xung, cn bn ca bc oxi ha +2 tng ln. iu c gii
thch l do khi chuyn t Ge - Pb, s th t nguyn t tng ln, th cc obitan d
v f c nh hng n vic hnh thnh lin kt ha hc . Ngi ta cho rng khi
chuyn t Ge n Pb, tnh tr ca cc cp electron ns2 tng ln, vai tr tham gia
vo s hnh thnh lin kt ca cp electron ns2 gim xung, nn khuynh hng
to ra mc oxi ha +4 gim xung v khuynh hng to ra mc oxi ha +2 tng
ln. V d:
nh vy :
Nguyn t Ge Sn Pb
Electron ha tr 4s2 4p2 5s2 5p2 6s2 6p2
Bn kinh nguyn t 1,39 1,58 1,74
() Bn kinh ton 0,65 1,02 1,32
M2+ () Bn kinh 0,44 0,67 0,84
ion M4+ () Bn - 2,15 -
kinh ion M4- () 7,88 7,33 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
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a
t gecmani khc trong hnh chp bn mt vi di l 2.43
4 3
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(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 - - 1,25.10-6
Sn 0,6.10-6 - 3.10-6
Pb 1,2.10-5 4.10-6 4.10-6
(2) Trong cng nghip, thic c sn xut bng cch dng than kh
qung caxiterit 1300oC :
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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.
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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.
Phn ng in cc E0298
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Ge4+ + 4e = Ge + 0,124
GeO + 2H+ + 2e = Ge + H2O - 0,2
GeO2 + 4H+ + 4e = Ge + 2 H2O - 0,15
HGeO3- + 2 H2O + 4e = Ge +5OH- - 1,0
Sn2+ + 2e = Sn - 0,14
Sn4+ + 2e = Sn2+ + 0,15
Sn4+ + 4e = Sn +0,01
HSnO2 + H2O + 2e = Sn + 3OH- - 0,91
Pb2+ + 2e = Pb - 0,13
Pb4+ + 2e = Pb + 0,84
Pb4+ + 2e = Pb2+ +1,8
PbO+ H2O + 2e = Pb + 2OH- - 0,58
HPbO2- + H2O + 2e = PbO +3OH- - 0,54
PbO2 + H2O + 2e = PbO + 2OH- + 0,28
PbO2 + 4H+ + 2e = Pb2+ + 2H2O + 1,46
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thic to ra MX4, cn ch to ra PbX2 :
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] :
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thic to ra Sn(SO4)2 :
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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 :
GeO hu nh khng tan trong nc, nhng tan c trong axit v trong
kim mnh:
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(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 :
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Khi nung nng d dng b H2, C, CO kh n kim loi :
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 :
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PbO b kh thnh Pb:
PbO tan rt t trong nc, tan trong dung dch KOH , NaOH nng to ra
plombit; tan trong HNO3 long to ra mui Pb(II); tan trong HCI to ra PbCl2 :
(5) SnO2 c iu ch trong cng nghip bng cch nung chy thic
trong lung kh O2 hoc khng kh:
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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 :
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v sn phm cui cng l to ra litac .
Trong khi tnh o xi ha ca GeO2 v SnO2 l khng c trng th PbO2
li l cht oxi ha mnh.
PbO2 oxi ha axit HCI c to ra kh clo:
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Minium c iu ch bng nung PbCO3 hoc PbO trong lung khng
kh khong 4000C :
Trong mi trng axit, oxi ha Fe(II) thnh mui Fe(iil); oxi ha H2O2 to
ra O2:
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Hiroxit gecmani, thic, ch l nhng cht kt ta dng keo, kh tan
trong nc.
Ge(OH)2 Sn(OH)2 Pb(OH)2
Mu da cam trng trng
Tch s tan - 6,3.10-27 1,1.10-20
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(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:
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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 :
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hoc un nng dng hirat SnCl2.2H2O 130 - 1450C thu c SnCl2 khan.
Ngi ta cng iu ch bng cch gi SnCl2.2H2O trn H2SO4 c trong chn
khng nhit phng trong khong 10 ngy.
Thic (II) clorua ihirat SnCl2.2H2O c iu ch bng cch cho
thic ht tan trong dung dch HCI c ( D = 1 , 14g/cm3 ) nng. Thic tan chm
trong HCI nhng nu trong dng c platin th thic s ha tan nhanh hn ( do
to ra cp ganvanic Sn - Pt).
SnCl2 khan l cht rn tinh th trong sut , khng mu d tan trong nc
, trong ru v trong e. Kt tinh t dung dch nc dng ihirat
SnCl2.2H2O. Tinh th ihirat kt tinh dng hnh kim khng mu, nng chy
trong nc kt tinh 400C; khi un nng nc kt tinh b mt dn.
Sn(Il) clorua khan hoc hirat u b thy phn mnh to ra mui baz
t tan.
ngay c khi un nng dng ihirat cng to ra dng mui baz trn :
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SnCl2 c th chuyn dung dch mu vng nu ca mui Fe(ili) thnh xanh
nht ca mui Fe(II) :
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 :
Cng c iu ch bng cch cho PbO hoc mui cacbonat baz chm)
tc dng vi axit HCI:
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Mu sc khng mu khng mu khng mu vng
Tnc 0C ) 855 500 373 412
Ts 0C ) 1290 954 916 950
Tch S tan 2,7.10-8 1,6 .10-5 9,1.10-6 1,1.10-9
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- :
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Vi SnX4 c iu ch bng phn ng trao i :
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Nh vy trong tinh th PbF4 nguyn t Pb trng thi lai ha sp3d2 , do
PbF4 bn vng hn nhiu so vi cc halogenua cn li ca Pb(IV).
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C kh nng kt hp vi nhiu cht nh HCI:
Khng tan trong nc v trong dung dch axit long tr GeS, c tan mt
t v b thy phn:
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phn ng dng phc hi li cc bc tranh c v bng bt trng ch
[2PbCO3.Pb(OH)2 ] lu ngy ng mu en v mui ch b H2S trong kh
quyn phn ng to ra PbS.
SnS2 tan trong dung dch kim to ra thiostanat v stanat [Sn(OH)6] 2- :
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Dng tinh khit c iu ch bng cch cho SnO tan trong dung dch
HNO3 30% lm lnh nhit thp - 200C, tinh th thu c c thnh phn
Sn(NO3)2.2H2O.
D b phn hy, dng mui baz Sn2O(NO3)2 bn hn so vi dng khan,
un nng n 1000C mi b phn hy.
(2) Sn(NO3)4 c iu ch bng cch cho dng hirat SnO2 tan trong dung dch
HNO3 c :
(3) SnSO4 c iu ch bng cch cho Sn ht hoc SnO tan trong H2SO4 long:
SnSO4 l nhng tinh th hnh kim khng mu, tan trong nc, bn hn
so vi thic(II) nitrat. Dung dch thic(II) sunfat d tch ra kt ta dng mui
baz (SnOH)2SO4
SnSO4 c dng trong m in ( ph thic ln kim loi khc).
(4) Sn(SO4)2 c iu ch bng cch cho dng hirat SnO2 tan trong
dung dch axit sunfuric :
hoc cho tng lng nh dung dch H2SO4 50% Vo thic(IV) clorua, sau
lm bay hi hn hp .
Thic (IV) sunfat kt tinh dng Sn(SO4)2.2H2O l nhng tinh th nh ,
tan trong nc axit ha, c tc dng ht m.
(5) Cc mui tan ca chm) nh nitrat hoc axetat c iu ch bng
cch cho "litac", hiroxit hoc mui cacbonat ca ch (II) tc dng vi axit long
tng ng; cn cc mui khng tan ca ch (II) c iu ch bng phng
php trao i ion trong dung dch.
(6) Pb(NO3)2 dng tinh khit c th c iu ch bng cch cho ch ht
tan trong dung dch axit nc 65% :
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(7) Pb(CH3COO)2 ( tc ng ch ) c iu ch bng cch ha tan
ch(II) oxit trong axit axetic 50% :
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trong dung dch axit CH3COOH v c trong dung dch kim. 300oC phn hy
thnh PbO v CO2 :
Khi cho dung dch mui ch (II) tc dng vi Na2CO3 trong kim d
to ra cacbonat baz:
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CHNG 6
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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 4B 5B 6B 7B 8B 1B 2B
21 22 23 24 25 26 27 28 29 30
Sc Ti V Cr Mn Fe CO Ni Cu Zn
39 40 41 42 43 44 45 46 47 Ag 48
Y Zr Nb Mo Tc Ru Rh Pd Cd
57 72 73 74 75 76 77 78 79 80
La Hf Ta W Re Os Li Pt Au Hg
89 104 105 [106] [107] [108] [109]
Ac Rf Ha
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6.2. c im cu to nguyn t cc kim loi chuyn tip dy th nht
(1)
khng chuyn tip. Nguyn nhn l trong cc nguyn t chuyn tip, electron
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c thm dn vo cc obitan d, nhng obitan ny chn mnh in tch ht nhn
bi cc electron ns lm cho kch thc ca nguyn t khng bin i bao nhiu.
(3) V nng lng ion ha cng bin i t hn so vi cc nguyn t
khng chuyn tip, nguyn nhn cng nh trong trng hp trn, l khi s lp
electron ca nguyn t khng i, nh hng ca s tng in tch c b li
bi mc chn ca cc electron c in vo cc lp trong.
(4) Mc oxi ha ca cc nguyn t ny c trnh by hnh 47, trong
mc oxi ha thng gp nht v quan trng nht c ghi bng vng trn ln.
Nhn chung , ta thy mc oxi ha ca cc nguyn t ny thay i trong
khong t +l Cu v +7 Mn, trong ph bin nht i vi tt c cc nguyn
t l mc +2 v +3, ngoi l khng c mc +2 Sc v +3 Zn. Mi mc ox\i
ha ng vi mt cu hnh electron nht nh chng hn vi crom c cu hnh :
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Mc oxi ha +2 thng gp trong cc hp cht nh t v thng l hp
cht ion, chng hn cc oxit MO u c tnh baz. Cc ion hirat ha
[M(H2O)6]2+ u c bit trong dung dch cng nh trng thi tinh th ( tr
ion Ti2+ ). cc ion V2+ , Cr2+ , Fe2+ d b oxi ha bi khng kh trong dung dch
axit. Mu sc ca cc con hirat c a ra bng 31 .
C th thu c cc ion hirat ha ny khi ha tan kim loi, oxit, mui
cacbonat.v.v..ca cc kim loi tng ng trong axit cng nh khi in phn cc
mui M3+.
Nhng mui hirat ha m anion khng c kh nng to phc th thng
cha cc ion [M(H2O)6]2+ . Chng hn nh
Khi thm kim vo dung dch mui M2+ s to thnh hiroxit , c trng
hp c th to ra dng tinh th nh Fe(OH)2 Ni(OH)2 c cu trc tinh th dng
Mg(OH)2.
Khi thm HCO3- s to ra kt ta cacbonat ca mangan, st, coban, niken
v ng.
Vi mc oxi ha +3 cng l mc c trng cho cc nguyn t ang xt.
Ring vi Cu ch mi bit c mt t hp cht ca CU(III) v thng l khng
bn vi tc dng ca nc. Cc florua MF3 , cc oxit M2O3 thng l hp Cht
ion , cn cc hp cht khc nh cc clorua, bromua, sunfua... c c tnh cng
ho tr ng k.
Cc nguyn t t Ti n Co to thnh ion hirat ha tm mt [M(H2O)6]3+
, mu sc ca cc ion ny dn ra bng 31 .
Trong dung dch nc cc ion d b thy phn , th d:
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6.3. Tnh cht l - ha hc ca cc kim loi chuyn tip dy th nht
Tnh cht l - ha hc c th ca cc kim loi v cc hp cht ca chng
c trnh by c th trong cc chng sau, y ch nu mt s nhn xt
chung.
(l) Tt c u l nhng kim loi , ng nh, mt s c mu, nh coban c
mu lam nht, ng c mu nht.
u l nhng cht rn c cng cao (tr Cu); khi lng ring ln;
dn in dn nhit tt; kh nng chy v kh bay hi.
Mt s tnh cht nu trn c trnh by cc bng 2; 3; 4; 5; 6 chng
1.
(2) Tr S v Zn , cc nguyn t cn li u a ho tr, to ra cc hp cht
u c mu.
Tr mangan v st rt d tham gia phn ng, cc kim loi cn li
nhit phng t c kh nng phn ng , u bn vi s n mn. Khi t nng
u phn ng vi oxi, halngen, lu hunh v cc phi kim khc.
u phn ng mnh vi cc dung dch axit nh HF, HCl, HNO3, H2SO4
Cc nng v nhit khc nhau. Cc phn ng vi cc n cht v hp
cht c trnh by c th trong cc chng sau.
(3) Mt trong nhng tnh cht quan trng ca cc nguyn t chuyn tip l
tnh thun t.
Nh bit, da vo tc dng ca t trng, cc cht c chia ra lm
hai nhm l cc cht thun t v cc cht nghch t (hay phn t). Nhng ion,
nguyn t, hay phn t bt k c mt s electron cha ghp i ( c s l
electron) u gy nn tnh thun t, v t ra c mt electron trong s c t
trng cha khp kn , bt k vt liu no c cha cc tiu phn u b t
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trng ht. Ngc li, cc cht khng c electron c thn ( tc c s chn
electron ) - tr mt s ngoi l - u l cht nghch t.
Vic nghin cu t tnh ca cc cht l phng php hiu nghim
pht hin s electron khng ghp i trong cc nguyn t ha hc v trong cc
hp cht ca chng. n v dng nghin cu t tnh ca nguyn t, ton v
phn t l manheton Bom (8 ) v gi s mmen t hon ton gy ra bi n
electron khng ghp i ca nguyn t hay ion s c tnh theo phng trnh:
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Ni tm li, nguyn t v ion cc nguyn t h d u c tnh thun t
v c bit ba nguyn t Fe, Co, Ni v hp cht ca chng - ngay nhit
thng - li c tnh thun t c bit mnh, nn c gi l cc cht st t. Tnh
cht ny gy ra do cc nguyn t hay ton thun t rt gn nhau, xut hin tc
dng hp lc vi nhau lm cho tnh thun t tr nn rt mnh. Khng nhng b
nam chm ht , m cc cht st t di tc dng ca dng in - li tr thnh
nam chm.
Nhng cht c tnh st t khng nhiu lm m li cn ph thuc vo nhit
, chng hn Gd c tnh st t di 160C ; cn Fe (7600C) , Co (l0750C), Ni
(3620C) , trn nhit - tnh st t s mt.
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(1) Bn knh ca cc kim loi u ln hn so vi bn knh nguyn t ca
cc kim loi dy chuyn tip th nht. Tuy nhin, bn knh ca cc nguyn t
dy th ba khc nhau khng nhiu so vi bn knh ca cc nguyn t dy th hai
cng nhm, mc d s lp electron tng ln , iu c gii thch l do
hin tng co lantanit.
(2) Khc vi cc nguyn t dy mt khng to ra mc oxi ha +8; cn cc
nguyn t chuyn tip dy 2 v dy 3 c s oxi ha thay i t +l n +8 nh
nu trong hnh 49.
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Cc hp cht ng vi bc oxi ha cao li bn hn nhiu so vi dy chuyn
tip th nht.
Chng hn, W, Re, Ru, Pt c kh nng to ra cc hp cht nh WCl6 ,
ReF7, RuO4, PtF6; trong khi nhng hp cht tng t khng hnh thnh cc
nguyn t chuyn tip dy th nht.
(3) u l nhng cht rn c nhit nng chy cao, nht l W (Tnc =
3410 C ) v Re (Tnc = 31700C ) . Mt s tnh cht khc nh cng, khi lng
0
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Claste l hp cht m trong c tn ti lin kt ha hc gia cc
nguyn t ca cc nguyn t chuyn tip h d. V d hp cht cacbonyl hai nhn
dng claste ca mangan [Mn(CO)5]2:
Trong cacbonyl hai nhn trn c lin kt to ra trc tip gia 2 nguyn
t Mn do hai electron cha ghp i ca hai nguyn t mangan:
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Mt v d v claste tm mt l MoCl2 mu vng. Nhng d kin phn
tch Rnghen cho thy MoCl2 ng vi cng thc [Mo6Cl8]Cl4 . Trong ion phc
Mo4O84+ cc nguyn t clo nm gc ca hnh lp phng , cn cc nguyn t
molipen chim tm mt ca hnh lp phng ( hnh 52) .
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Nhng cacbonyl c dng iu ch kim loi tinh khit bng
phng php nhit phn; ngoi ra cn dng lm cht xc tc trong cc qu trnh
tng hp hu c ...
Ngoi nhng cacbonyl hai nhn nu trn, mt s kim loi chuyn tip
h d cn to ra nhng cacbonyl d nhn v a nhn khc, chng hn nh
MnRe(CO)10 :
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vng ( hnh 54). Nhng phn t c cu trc nh vy gi l cu trc bnh kp
hay l hp cht kiu xan uch.
Lin kt ha hc trong phn t ibenzocrom to ra theo c ch cho -
nhn do 18 electron (6 electron ca nguyn t Cr v 12 electron n ca hai phn
t C6H6) vi cc obitan t do ca nguyn t crom v hai phn t benzen; 18
electron ny trong trng ca mi ba tm ( mt nguyn t Cr v 12 nguyn t
C ca hai vng benzen).
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CHNG 7
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Nguyn Bn kinh Th i lc Nguyn Bn knh Th i lc
t nguyn t ion electro t nguyn ion electron
( ) ha I1 n (ev) t ( ) ha I1 (ev)
Cu 1,28 7,724 2,4 K 2,36 4,339 0 82
Ag 1,44 7,574 2,5 Rb 2,53 4,176 -
Au 1,44 9,224 2,1 Cs 2,74 3,893 -
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ha - kh ca cc hp cht ng vi cc trng thi oxi ha ca chng trong mi
trng axit:
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vi cc kim loi khc. Quan trng l qung cancopirit CuFeS, cancozin Cu2S ,
qung cuprit Cu2O, malachit Cu2(OH)2CO3 , tenorit cao.
Vi bc , thng gp dng khong cht acgentit Ag2S hn hp vi
qung sunfua ch. Ngoi ra cn c trong cc loi qung nh naumanit Ag2Se;
prustit Ag3AsS3
Vi vng, thng gp dng khong cht calaverit AuTe2 ; sinvanit
AgAuTe4 hoc petxit Ag3AuTe2.
(2) Tuy nhin, dng thng thng hn gp trong thin nhin l vng t
do, nm ri rc trong cc nham thch , trong ct. Cng ging nh vng, trong
thin nhin , ngi ta cng gp ng v bc trng thi t do.
(3) Trong nc ca i dng (tnh trong mt lt nc bin) c 3.10-3 mg
ng dng Cu2+ ; 3.10-4 mg bc dng AgCl21- , AgCl32- ; 4.10-6 mg vng
dng AuCl41-
(4) Trong cht sng gm ng vt v thc vt (tnh theo phn % khi
lng) th c 2.10-4 % ng . ng l mt trong nhng nguyn t rt c bit v
mt sinh vt hc . Nhiu loi cy nu c bn thm mt lng thch nghi cc
hp cht ca ng th nng sut thu hoch thng tng ln; trong s cc ng
vt th mt s loi nhuyn th nh hu , bch tuc c cha nhiu ng nht. C
th ngi v cc ng vt khc , ng ch yu tp trung gan. Mi ngy c th
ngi cn khong 5 mg ng, nu sinh vt b thiu ng, th qu trnh ti to
hemoglobin s gim, gy ra bnh thiu mu. Trong cc loi thc n th sa c
cha nhiu ng.
(5) Vic xc nh hm lng cc nguyn t him trong cc mu Mt
Trng ( do cc tu Apollo - 11 , - 12 v Luna - 6 a v Qu t ) trong ba vng
khc nhau , ngi ta thy Mt Trng cc nguyn t ng , bc , vng c
hm lng nh sau:
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bn hy l 2,2 1 ngy - m) v 64Cu (Chu k bn hy l 0 541 ngy - m ) ,
cn ng v km bn nht l 58Cu ( Chu k bn hy l 3 giy).
Ag c 19 ng v , trong c hai ng v thin nhin l 107Ag ( chim
5 1 ,35%) v l09Ag ( chim 48,65% ), cn li l cc ng v phng x t l02Ag
n 115Ag, trong ng v phng x bn nht 110Ag ( chu k bn hy l 270
ngy - m ).
Au c rt nhiu ng v t 183Au n 204
Au nhng trong ch c mt
ng v thin nhin l 197Au ( chim 100% ).
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php i (ra qung bng nc ) , ha tan vng trong thy ngn lng ( phng
php thy ngn ) to ra hn hng Au - Hg , sau cho hn hng thng hoa ,
thy ngn bay hi, cn li Au.
Phng php tt nht tch vng ra khi qung l phng php
xianua. Bn cht ca phng php ny l ha tan vng c trong bt qung bng
dung dch NaCN long (0,03 - O,2%), ng thi cho khng kh li qua, Au
chuyn vo phc cht :
Tinh cht Cu Ag Au
Khi lng ring ( g/ cm3 ) 8.93 10,49 19,30
Nhit nng chy ( Tnc , 0C ) 1083 961 1063
Nhit Si ( Ts, 0C) 2600 2210 2970
cng ( so vi cng ca 3 2,7 2,5
kim cng = 10)
dn in ( so vi Hg = 1 ) 57 59 40
dn nhit ( so vi Hg = 1 ) 46 49 35
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lng ca tp cht m dn in ca ng thay i. V d c khong 0,03%
mi tp cht sau y th dn in tng i so vi Cu nguyn cht l:
Tn hp kim Cu Sn Zn Mn Ni Al Fe
Bronz 80-90 5-10 2-10
ng thau 70-80 30-
ng en 90 20 10
Mayso 80 20
Thanh - ng
(hp kim 67 33
speculum) 1
Hp kim 50 5 40
Devarda 59 40
Constantan 55 41 4
Hp kim Denta
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dng lm trang sc (hp kim vi 7,5% Cu); mt s hp cht ca bc dng
trong cng nghip nh v trong y khoa , chng hn AgNO3 dng cha bnh co
tht , vim hng ... lm thuc tra mt ... Ion Ag+ c tnh tit trng rt mnh .
Nc trong cc bnh bng bc c th hng thng m khng thi, do c
mt lng rt nh ion Ag+ chuyn t thnh bnh vo dung dch tit trng.
(8) Vng c dng lm trang sc , dng m ln cc kim loi khc . L
kim loi ch yu m bo cho vic lu thng tin giy. Tin vng l hp kim
cha 90% Au v 10% Cu. H tin t Vit Nam trong cc th k trc l tin
ng, ch yu l hp kim ca Cu v Zn; c loi pha thm vng; c loi pha
thm st nh tin thi Vng triu Mc.
(9) Tt c cc hp cht tan ca Cu, Ag, Au u c !
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Phn ng cng tng t nh trn to ra Ag2S:
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nn u c tnh kh yu C ba kim loi u khng b H2OV hi H2O n mn.
Ring Cu ch phn ng vi hi nc nhit nung nng trng .
(9) Cu v Ag khng phn ng vi kim ngay c kim nng chy, v vy,
trong phng th nghim ngi ta dng chn bc nu nng chy cc cht kim
nhit cao; cn Au b kim nng chy n mn.
(10) C ba kim loi u khng phn ng vi cc axit khng c tnh oxit
ha, ngha l khng phn ng vi cc con hironi H3O+ trong dung dch axit.
Trong cc axit l cht oxi ha nh HNO3 , H2so4 c nng , Cu v Ag
u d tan cn Au ch tan trong axit c tnh oxi ha mnh lit, chng hn
H2SeO4 khan nng.
Cu v Ag khi tc dng vi HNO3 c to ra nh ioxit, cn HNO3 long
va phi ( khong 50% ) to ra nit oxit, sn phm to thnh cn c mui nitrat
v H2O:
hay
Ag khng tan trong nc cng thy v AgCl khng tan .
(12) Trong khng kh, H2SO4 n mn Cu to ra CuSO4 do s c mt ca
O2 trong mi trng
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Trong khng kh , Cu cng tan trong HCI c to ra dung dch mu
xanh ti ca phc cht :
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xut ha tr I v II, trong bn v c nhiu ng dng quan trng l cc hp
cht Cu(II). Bc cng to ra cc dn xut ha tr 1 , ha tr II, nhng quan trng
l hp cht Ag(I) . Vng to ra hp cht ha tr I v III trong quan trng l
cc hp cht Au(III).
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Vi dung dch H2SO4 long , to ra Cu v CuSO4:
Cu2O kh tan trong nc, nhng d tan trong dung dch amomac v
dung dch amoni sunfat do to ra phc cht :
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Ag2O bn di 1000C , nn c th lm kh 800C. Trn 1000C bt u
phn hy v n 3000C th phn hy hon ton thnh kim loi :
Hiroxit
(4) Ngi ta cha bit c CuOH! Khi cho dung dch mui Cu+ tc dng
vi dung dch kim mnh to ra kt ta mu vng, ngi ta cho rng kt ta
l dng hirat ha ca Cu2O .
(5) AgOH c hnh thnh khi cho dung dch KOH trong ru tc dng
vi AgNO3 -300C . Mt khc , khi cho Ag2O tc dng vi lng nc ln ,
dung dch thu c c tnh kim, c kh nng kt ta c hiroxit ca nhiu
kim loi , chng t trong dung dch c cha AgOH vo khong 2.10-4 mol/l. Qu
trnh phn ly trong dung dch :
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(7) CUF : Cho HF tc dng vi Cucl nhit cao hn 10000C to ra
CuF, sau lm ngui t t thu c tinh th mu thm .
(8) CuCl : c to ra khi nung Cu trong kh clo c hn ch hoc cho kh
hiro clorua kh qua Cu nung nng :
(9) CuBr iu ch bng cch nung nng mnh CuBr2 trong khng kh :
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Mu sc thm trng trng trng
Tnc( 0C ) 908 422 504 605
Ts (0C) 1100 (thng hoa) 1366 1345 1290
Tch s tan Khng tan 1.2.10-6 5,25.10-9 1.1.10-12
(T1 )
Cc dung dch khng mu trong amoniac hoc trong axit HCI , khi
ngoi khng kh s nhanh chng chuyn thnh mu xanh lc do ton Cui oxi
ha thnh Cu2+:
(13) AgCl c iu ch bng cch cho axit HCI hoc mui clorua tc
dng vi dung dch AgNO3 :
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v cc mui kim loi tng ng to ra cc axit phc hoc mui phc , chng
hn khi cho AgI tc dng vi Hi v KI to ra axit phc H[AgI2] V cc mui
phc khng mu nh K[AgI2] , K2[Agl3].
Cc halngenua bc cng c kh nng tan trong HNO3 c nng to ra
cc mui kp AgNO3.AgCI; AgNO3.AgBr; AgNO3.AgI .
Trong dung dch amoniac ha tan d dng AgCl; AgBr t tan hn, cn
AgI khng tan :
AgCl cng b kh khi nung nng trong lung kh H2 hoc bng dung
dch H2SO4long vi Zn ( to ra hiro mi sinh ) :
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Mu sc - vng vng xm vng nht
Tch s tan - 2.10-13 5.10-17 1,6.10-23
Nhit phn hy - 2900C 1150C 1200C
Hp cht xianua
(17) CuCN : thu c khi cho mui Cu(II) tc dng vi dung ch cha
ion CN- to ra kt ta Cu(CN)2, nhit thng kt ta ny nhanh chng phn
hy thnh CuCN v kh xianogen :
AgCN : thu c khi cho mui Ag+ tc dng vi dung dch cha CN- :
AuCN : ngi ta cho Au tan trong dung dch KCN khi c mt ca khng
kh to ra K[Au(CN)2] ( hoc thay th O2 bng H2O2 ) dng trong k thut m
vng :
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nhng li d tan trong dung dch KCN to ra phc cht bn:
Hp cht sunfua
(19) Cu2S trc iu ch bng cch nn mnh hn hp bt mn Cu v S
di p sut hng ngn atmotphe :
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hy thnh Cu v N2.
Ag3N cht bt mu en, to ra khi cho hi Ag tc dng vi NH3
12800C. Cng c to ra cho dung dch amoniac trong ru hoc axeton tc
dng vi Ag2O. Khng tan trong nc lnh , tan mt phn trong nc nng. Tan
trong HNO3 v cc axit v c khc .
(23) Cu2C2 mu hung ; Ag2C2 mu trng c to ra khi cho axetilen
CH - CH qua dung dch amoniac ca cc mui CuCl , AgNO3 :
Nhng cacbua ny khng tan trong nc v trong dung dch kim nhng
tan trong HCI to ra C2H2 . Trong khng kh , dng kh , d dng b phn hy
gy n !
Cc hp cht khc ca Ag(I)
(24) Trong cc hp cht cn li ca Cu(I), Ag(I), Au(I) th thc cht quan
trng l cc hp cht ca Ag(I). Hn na, Ag(I) li to ra c nhiu mui bn
hn so vi Cu(I) v Au(I) . Mt trong cc mui quan trng ca Ag(I) l AgNO3.
Mui ny c iu ch bng cch cho Ag tan trong HNO3 v sau kt tinh li
t dung dch :
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(26) Ag2CO3 c kt ta t dung dch AgNO3 v Na2CO3 hoc thi kh
CO2 vo dung dch mui nitrat amoniacat Ag(I) :
Anion Mu Tt Anion Mu Tt
CH3COO- trng 4.10-3 Fe(CN)63- da cam 1.10-22
C2O42- trng 1.10-11 Fe(CN)64- vng 1.5.10-41
CrO42- nu 1.1.10-12 MnO4- tm en 1,6.10-3
Cr2O72- 1.10-10 PO43- vng 1,3.10-20
7. 7 . Cc hp cht vi s oxi ha +2
Trong s cc hp cht ng vi bc oxi ha +2 th cc hp cht ca Cu(II)
c nhiu gi tr thc t nn di y ch nu cc hp cht ca Cu(II) .
Cc oxit
CuO c iu ch bng cch nhit phn Cu(NO3)2 , cacbonat baz
CuCO3.Cu(OH)2 hoc Cu(OH)2; trong cng nghip iu ch t malachit:
Khng tan trong H2O, d tan trong axit long to ra dung dch mui
Cu2+ :
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Ngi ta cng iu ch c Ag2O2 khi cho dung dch AgNO3 tc
dng vi hn hp gm Na2CO3 + K2S2O8 ; v cng iu ch c Au2O2 m
thc cht l mui AuI[AuIIIO2].
Hiroxit
Cu(OH)2 l cht kt ta keo mu xanh khi cho dung dch mui Cu2+ tc
dng vi dung dch NaOH hay KOH :
Cu(OH)2 tan trong axit to ra dung dch mui Cu2+ ; cng tan trong lng
d dung dch c kim mnh to ra mui cuprit mu xanh Na2CuO2 hay
Na2[Cu(OH)4]:
Tuy nhin Cu(OH)2 c tnh baz mnh hn hn tnh axit, th hin tnh
d thy phn ca Na2CuO2.
Cc halogenua
CUF2: c iu ch bng cch cho axit HF tc dng vi CuO un nng :
hoc cho CuO hay CuCO3, Cu(OH)2 tc dng vi axit HCI , sau cho bay hi
thu c tinh th .
CuBr2 : cho CuO tc dng vi HBr trong chn khng .
CuI2 : hin nay cha bit c CuI2 v khng bn, b phn hy thnh CuI
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v I2.
Di y l mt s tnh cht ca cc Cu(II) halogenua :
dng hirat ha CuF2.2H2O C mu lam , khi nung nng trong lung
kh HF to ra tinh th mu trng ( Tnc = 9500C ) ; t tan trong H2O lnh (4,7 g
/100g H2O 200C ).
CuBr2 l cht rn mu en , d b chy ra , trong dung dch nc c
mu nu ; khi kt tinh ph thuc vo nhit to ra CuBr2. 2H2O hoc CuBr2.
4H2O . D tan trong nc (126,8 g CuBr2. 4H2O / 100g H2O 200C ). Khi nung
nng, mt phn brom tch ra.
CuCl2 khan l cht rn c mu vng nu , Tnc = 4980C , khi nung n
9930C b phn tch to ra CuCl. D b chy ra trong khng kh . D tan trong
nc ( 72,8g CuCl2. 2H2O / 100g H2O 200C ). Khi tan trong nc mu sc
thay i dn. T dng hirat ha CuCl2 . 2H2O mu xanh l cy , khi c du vt
ca nc chuyn thnh mu xanh thm , khi thm t nc chuyn thnh hung
thm , nu pha long thm chuyn thnh mu lc v cui cng dung dch long
c mu lam.
Hin tng thay i mu sc nh trn c lin quan n s hnh thnh cc
ion phc ; mu xanh lam gy ra bi cc ion [Cu(H2O)6]2 + v mu thm gy ra
bi cc ion CuCl3- V CuCl42- , Chng hn theo phng trnh :
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Ngi ta cng iu ch c AgF2 bng cch cho flo tc dng vi
Ag . L cht bt mu en , b nc phn hy :
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Dng CuSO4 khan c mu trng, dng thng gp c mu xanh lam
CuSO4.5H2O, trng ny khi phi trong khng kh thnh dng CuSO4.3H2O; un
nng n 1000C to ra dng CuSO4.H2O ; 2500C th ha khan CuSO4. Khi
nung n 650 - 7000C to thnh CuO:
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hirat ha ca Cu2+ . cc mui u c th b kh thnh Cu bi cc kim loi ,
tr Ag, Au v kim loi h platin c dng in thp hn.
To ra kt ta Cu(II) hiroxit vi dung dch kim , cn vi dung dch
amoniac; th ban u cho kt ta hiroxit sau tan trong lng d amoniac
hnh thnh ion [ Cu(NH3)4]2+ .
Vi hiro sunfua to ra kt ta mu en CuS, cn tc dng vi kali
feroxianua K4[Fe(CN)6] to ra kt ta dng keo mu nu - socola ca Cu(II)
feroxianua Cu4[Fe(CN)6]trong mi trng axit yu hoc trung tnh.
Trong khi cc hp cht Cu(I), Ag(I) , Au(I) d dng b phn hy khi un
nng nh hoc khi chu tc dng ca nh sng, nn phi bo qun trong cc chai
mu ti, th cc hp cht ca Cu(II) li bn .
Tuy nhin niotuav xianua ca Cu(II) li km bn hn CuI v CuN v cc
ion I v CN- u c hot tnh kh cao.
-
Cu2O3 l Cht lng tnh , tan trong HCI v trong kim to ra cuprat mu
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:
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CHNG 8
CC NGUYN T NHM II B
Nguyn t Zn Cd Hg
Electron ha tr 3d104s2 4d10 5s2 5d106s2
Bn kinh nguyn t () 1,39 1,56 1,60
Bn knh ton M2+ ( ) 1,74 0,97 1,10
Th ln ha I1 ( ev ) 9,391 8,991 10,431
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cao hn c cc nguyn t d cn li , iu gy ra tnh cht khc bit gia
Hg vi Zn v Cd . Cc hp cht ca Zn v Cd bn hn , cn cc hp cht ca
Hg t bn hn . S khc bit cn thy ch Hg to ra cc hp cht cha
nhm Hg22+ , trong hai nguyn t Hg lin kt vi nhau bng lin kt cng
ha tr - Hg - Hg - cng do cu hnh 6s2 .
(5) Th in cc chun ca Hg rt cao, tri li Zn v Cd li c gi tr thp
. Hai kim loi ny xp trc Hg , th hin tnh kim loi mnh hn nhiu so vi
Hg.
Sau y l s th in cc chun ca chng trong mi trng axit :
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8.2 . Trng thi thin nhin v thnh phn cc ng v
(l) S phn b ca cc kim loi nhm II B trong v qu t ( ng vi
thnh phn thch quyn ) nh sau :
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245 ngy m; cn ng v 61Zn chu k bn hy ch c l 90 giy .
Cd c 19 ng v , trong tm ng v bn gp trong thin nhin 106Cd
(l,215% ); 108Cd ( 0,875 % ) ; 110Cd 12,39 % ) ; 111C( 12,7 % ) ; 112C( 24,07 % ) ;
113
Cd(12,26 % ) ; 114Cd (28,86% ) v 116Cd (7,58% ) . Trong cc ng v phng
x th ng v 100Cc chu k bn hy 470 ngy m l bn nht .
Hg c 24 ng v trong c by ng v thin nhin l 196Hg (0,04 %
); 198Hg (10,02%) ; 199Hg (16,84%) ; 200Hg (23,13%) ; 201Hg (13,22% );
202
Hg(29,80%) ; 204Hg(6,85% ). Trong cc ng v phng x c ng v 194Hg c
chu k bn hy l 130 ngy m .
8.3 . iu ch Zn, Cd , Hg
(1)Ni ta luyn Zn t cc qung blen km (ZnS ) hoc t qung calamin
(ZnCO3). Cc loi qung c lm giu bng cc phng php khc nhau,
chng hn phng php t hc tch oxit st ; phng php i ni ... T loi
qung c lm giu, qu trnh luyn km c tin hnh bng phng php
nhit luyn, qua hai giai on : giai on u l nung qung trong khng kh ,
cc loi qung u chuyn thnh oxit :
Di y nu tm tt qu trnh trn:
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mt phn Zn chuyn thnh bi t li thng (C) gn vi khoang ngng , c
lm ngui bng khng kh.
Lng km th thu c c cha khong 97 - 98 % Zn, tp cht l Pb ,
Fe; cn bi km c cha 80 - 90 % Zn , tp cht l Cd, Pb , Fe v c c Sb v As
...
(2) Trong cc qung blen v calamin c cha CdS . V vy trong qu trnh
luyn Zn cn thu c caimi . V Cd d bay hi hn Zn nn phn ln Cd cha
trong bi Zn.
tch Cd , ngi ta ha tan bi trong H2SO4 long , sau dng Zn
kh ion Cd2+ :
Tnh cht Zn Cd Hg
Khi lng ring ( g / cm3 ) 7,14 8,64 13,55
Nhit nng chy ( Tnc , 0C ) 419 321 -39
Nhit Si ( Ts , 0C ) 907 767 357
dn in ( so vi Hg = 1 ) 16 13 1
m in 1,6 1,7 1,9
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mmHg; vi Cd, c p sut hi l 3,13.10-2 mmHg 2910C ( gn vi Tnc = 3210C
). Ring i vi Hg th 200C c p sut hi l 1,33.10-3 mmHg.
V iu kin thng Zn kh gin , nn khng ko di c , nhng
khi un nng n 100 - 1500C li do v dai, khi un nng n 2000C li c th
tn c thnh bt . Tri li, Cd c th rn v ko di c .
(2) V c tnh, Zn trng thi rn khng c, nhng hi ca ZnO li rt
c , cn cc hp cht khc ca Zn li khng c. Vi Cd, dng kim loi
khng c , nhng cc hp cht ca Cd li rt c . c bit , thy ngn rt c
, cc mui ca thy ngn nh clorua , nitrat cc k c c tnh ca thy ngn
gy ra tc hi lm t lit h thn kinh , gim tr nh, vim lot li rng .... Lng
thy ngn cho php cc i trong khng kh cc nh my l 10-5 mg/lt. (3).
C ba kim loi u c kh nng to ra hp kim vi nhau v vi cc kim loi
khc , c bit l hp kim ca thy ngn gi l " hn hng " . Hn hng thng
l nhng hp cht ca thy ngn v kim loi ha tan trong thy ngn . Mt
s hn hng trng thi lng, mt s trng thi rn hoc nho. Hn hng ca
Na hoc K l cht rn tinh th ; hn hng ca Sn dng trng gng ...
Nhiu kim loi d to ra hn hng nh Au , Ag , Cu , Sn , Na, K ... mt
s khng to ra hn hng nh Mn, Fe , Ni ... bng phng php trc tip khi
ho tan cc kim loi trong thy ngn , v vy ngi ta dng bnh bng st
ct tr thy ngn .
Mc d qu trnh to ra hn hng l qu trnh pht nhit , nhng cc
kim loi trong hn hng khng thay i tnh cht ha hc ca n . V d hn
hng natri khi tip xc vi H2O vn to ra H2 v NaOH nhng m du hn :
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(4) Mt lng ln Zn c dng m ln st bo v cho st khi g, trn
b mt ca lp m c ph mt lp mng cacbonat baz ( ZnCO3.3Cu(OH)2 )
bo v cho kim loi .
Mt phn Zn dng iu ch hp kim nh hp kim vi Cu. Mt s hp
cht ca km dng trong y khoa nh ZnO dng lm thuc gim au dy thn
kinh, cha eczema, cha nga ...
ZnSO4 dng lm thuc gy nn, dng lm thuc st trng; dung dch
0,1 - 0,5 % lm thuc nh mt cha au kt mc .
Zn cn dng sn xut cc pin kh . Loi ph ny gm mt v ngoi
bng Zn ng thi l ant ; gia pin l mt tr bng than ch ng vai tr ca
catot. gia Zn v tr than cha hn hp h nho gm MnO2 , NH4Cl v bt
than . Phn ng xy ra trn b mt in cc khi phng in nh sau :
ant : Zn - 2e = Zn2+
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8.5. Tnh cht ha hc ca Zn , Cd , Hg
(1) Hot tnh ha hc ca cc nguyn t trong nhm II B gim dn khi
khi lng nguyn t tng . Trong dy th in cc Zn v Cd ng trc hiro ,
cn Hg sau hiro . Km l nguyn t kim loi trung bnh , cn Cd th km hn .
Mc d l kim loi ng sau hung , nhng li c hot tnh ha hc cao l do Hg
trng thi lng lm cho phn ng xy ra d dng hn .
(2) C ba kim loi u khng phn ng vi H2 , nhng H2 c kh nng tan
trong Zn nng chy to ra dung dch rn .
(3) Khi tip xc vi khng kh kh nhit thng , Zn , Cd v Hg u
khng b bin i , nhng khi nung nng th Zn v Cd b chy nhanh hn , cn
Hg th chm hn . Tt c u to ra oxit : ZnO , CdO , HgO .
C ba kim loi u phn ng trc tip vi lu hunh, vi Zn v Cd th
phi un nng, cn vi Hg xy ra ngay nhit thng khi nghin S bt vi
Hg ; phn ng to ra ZnS , CdS v HgS.
Vi Se v Te cng c phn ng trc tip to ra selenua v telurua tng
ng : MSe v MTe ( M l Zn , Cd , Hg ).
(4) Phn ng trc tip vi cc halogen to ra cc halogenua mu trng tr
HgI2 c mu .
(5) C ba kim loi u khng phn ng trc tip vi Ni , cc hp cht nh
Zn3N2 , Cd3N2 , Hg3N2 Ch iu ch c bng phng php gin tip .
Khi un nng c ba kim loi cng vi P trong ampun chn khng , th
Zn phn ng trc tip vi P 400 - 4500C to ra Zn3P2 ; Vi c 450 - 5000C
to ra Cd3P2 ; vi Hg nhit thp hn 275 - 3000C to ra Hg3P2.
(6) Zn , Cd v Hg khng phn ng vi C , Si , B v khng to ra hp cht
, tuy nhin cacbon ha tan mt t trong Zn v Cd nng chy , khi ngui
cacbon thot ra dng than ch .
(7) V mt nhit ng , Cd khng y c H2 ra khi H2O nguyn cht ,
nhng Zn li c kh nng khi so snh th in cc chun ca Cd, Zn vi.
E0 + = 0, 413V . Thc t, kh nng ca Zn li khng xy ra v trn
2H (pH=7)
H2
b mt bao ph mt mng oxit .
Khi nung Zn trong lung hi nc to ra oxit km :
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Cc zincat ch tn ti trong dung dch kim d v Na2ZnO2 b thy phn
mnh nh Na2SnO2 hay NaAlO2 , do trong dung dch nc khng phi l
Na2ZnO2 m l NalZn(OH)3], Na2[Zn(OH)4] , Ba2[Zn(OH)6] . Cc hp cht ny
tch c trng thi rn.
(9) Zn v Cd tan trong axit khng c tnh oxi ha nh HCI , H2SO4 long
to ra H2; cn Hg khng phn ng .
ion NO3- ng vai tr l cht oxi ha trong mi trng axit (H+) to ra ion
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NH4+
Cn trong mi trng kim , ion NO3- s b Zn kh thnh amoniac :
hay
Vi Hg , khi tc dng vi HNO3 long to ra Hot thut khi Hg d; cn
khi axit c d to ra Hg(II) nitrat :
hoc
Khng nhng th , Zn cn tan c trong dung dch mui amoni c do qu
trnh thy phn mui amoni to ra sn phm ph hy mng bo v !
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V d cc hp cht nh K2[ZN(OH)4]; [ZN(OH2)4]SO4; ZN(NH3)4]Cl2;
[ZN(NH3)2Cl2]; ZNO, ZNS, CdS, HgS u c cu hnh bn mt ng vi dng lai
ha sp3 (hnh 58).
Cn cc hp cht nh [Cd(NH3)6(NO3)2; [Cd(NH3)2Cl2]; CdO, CdBr2,
CdI2 u c cu hnh tm mt ng vi dng lai ha sp3d2 ( hnh 59).
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Sau y xt mt s hp cht quan trng ca Zn(II), Cd(II), Hg(II).
(2) Cc oxit MO
ZnO c iu ch bng cch nung mui cacbonat, nitrat, ferit km,
hoc nung bt km trong khng kh
Hoc bng cch trn dung dch nng HgCl2 vi K2CO3 hay Na2CO3:
Hg thu c t cc phn ng u c mu .
Khi cho dung dch kim d tc dng vi dung dch clorua hoc nitrat
Hg(II) to ra dng HgO mu vng :
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vi ZnO v CdO; khi tan, HgO to ra mi trng kim yu :
ZnO l cht lng tnh, trong dung dch axit to ra cc mui clorua,
sunfat km, cn trong dung dch kim d to ra zincat :
Hg(OH)2 rt khng bn, cn bng sau y chuyn dch mnh sang phi :
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Bn cht lng tnh ca Zn(OH)2 c th m t theo s :
Cd(OH)2 cng th hin tnh axit nhng rt yu; d tan trong dung dch
axit, cn trong kim c khi un si lu mi to ra caimat :
hay
Nhng amoniacat nh trn cng c to ra khi cho cc mui Zn2+ hay
Cd2+ tc dng vi dung dch amoniac, chng hn :
(4) Cc halogenua
Trong cc mui halogenua ca km, caimi, thy ngn th c ng dng
rng ri nht l ZnCl2 v HgCl2.
ZnCl2 khan c iu ch bng cch hay nht l un nng mui kp
ZnCl2.3NH4Cl trong lung kh hiro clorua kh :
hoc bng cch cho lung kh do hay HCl kh qua Zn nung nng, hoc bng
cch cho Zn ha tan trong axit HCl, sau lm bay hi dung dch trong lung
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HCl ( kh ) trnh hin tng thy phn :
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Cc halogenua ca Zn(II), Cd(II), Hg(II), nht l cc clorua, bromua,
iotua khi tc dng vi ion halogenua to ra phc halogenua tng ng. V d :
v vy ngi ta dng dung dch thu c sau khi cho Zn tc dng vi HCl (dung
dch ZnCl2 c) trong k thut hn thic ty lp oxit trn b mt ca kim loi.
Phn ng xy ra theo v d sau :
(5) Cc sunfua
ZnS l cht rn mu trng, c to ra khi cho H2S qua dung dch mui
km trong mi trng kim, hoc bng cch cho dung dch mui amonisunfua
tc dng vi dung dch mui km:
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Kt ta ZnS khng c hnh thnh khi cho H2S tc dng vi dung dch
mui km ca axit mnh ( v d HCl ), v ZnS tan trong axit mnh. ZnS khng
tan trong CH3COOH nn c th cho Zn(CH3COO)2 tc dng vi H2S :
CdS cng c iu ch bng cch cho H2S tc dng vi dung dch mui
caimi. CdS c mu vng chanh hoc vng ty theo iu kin kt ta.
HgS c bit di hai dng : en v . Dng mu en c to ra khi
nghin Hg vi S hoc khi cho H2S i qua dung dch mui Hg(II). Kt ta ny
mu trng sau chuyn thnh mu v cui cng chuyn thnh mu en.
Khi HgS en thng hoa chuyn thnh dng HgS l dng thng gp
trong thin nhin.
tan ca cc sunfua rt nh. Di y l gi tr tch s tan ca
chng :
- ZnS -ZnS CdS HgS HgS en
Tch s tan Tt 2.10-25 3.10 - 2 5 1.10 -27 5. 10-54 2.10-53
tan trong nc gim dn t ZnS n HgS. tan trong axit cng gim
tng t:
ZnS tan trong axit mnh, khng tan trong axit yu.
CdS khng tan trong HCl long, nhng tan trong trong HCl c, trong
HNO3 long, trong H2SO4 long nng.
HgS ch tan trong HCl c si. Tan trong nc cng thy to ra HgCl2;
tan trong dung dch kim ca natri hoc kali sunfua to ra mui thio :
HgS en tan trong HNO3 to ra mui nitrat. Khi un nng trong khng
kh to ra thy ngn v SO2 :
Khi nung ZnS v nh hnh trong lung kh H2S to thnh ZnS tinh th.
Dng ny khi c ln vi mt lng nh kim loi khc (nh Cu) th c tc dng
pht ln quang, ngha l sau khi chiu sng, n tip tc pht sng trong bng ti.
(6) Cc xianua
Cc xianua Zn(CN)2, Cd(CN)2, Hg(CN)2 c to ra khi cho dung dch
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cc mui M2+ tc dng vi dung dch xianua ca kim loi kim. V d :
Vi Hg(CN)2 ngoi phng php trn cn c th ha tan HgO trong dung dch
HCN:
(7) Cc nitrat
Zn(NO3)2 c iu ch bng cch cho Zn ht, hoc ZnO tan trong
HNO3 long:
sau khi lm bay hi dung ch, mui tch ra dng hirat Hg(NO3)2.H2O.
Hg(NO3)2 ch bn trong dung dch khi c mt ca HNO3 trnh hin
tng thy phn. Trong dung dch long, hon ton b phn hy :
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C ba mui u kt tinh mu trng, u d tan. ha tan trong 100 g
H2O 20oC vi Zn(NO3)2.6H2O l 118,4 g, cn vi Cd(NO3)2.4H2O l 153 g.
(8) Cc sunfat
ZnSO4 c iu ch bng cch cho v bo km tan trong dung dch
H2SO4 long, hoc nung ZnS trong khng kh :
HgSO4 tan t trong nc lnh, nhng khi un nng dung dch n 25oC,
to ra tinh th mui baz mu vng v H2SO4 t do:
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(9) Mui cacbonat
ZnCO3 c iu ch bng cch cho dung dch lnh KHCO3 hay
NaHCO3 bo ha CO2 tc dng vi dung dch mui km hoc cho lung kh
CO2 qua huyn ph Zn(OH)2 trong nc to ra kt ta trng :
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ZnH2 cng c iu ch bng cch cho ZnI2 tc dng vi LiH trong
ete :
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cht thy ngn (I). Khong cch Hg - Hg bin i trong khong t 2,5 - 2,7.
Km v caimi cng to ra cc ion Zn22+ v Cd22+ nhng hon ton khng
bn.
Ngi ta bit c nhiu hp cht Hg(I) nh Hg2O, cc halogenua
Hg2X2 v nhiu mui khc.
V ion Hg22+ khng mu nn a s cc hp cht Hg(I) u khng mu.
Hu ht u kh tan trong nc, ch c Hg2(NO3)2 l d tan nn thng dng
lm cht ban u iu ch cc hp cht Hg(I) khc.
Cc cht d tan th in li mnh v b thy phn to ra mui baz. V d
khi pha long Hg2(NO3)2 s c phn ng :
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Cng c th thu c bng cch cho thy ngn tc dng vi dung dch
Hg(NO3)2 trong nc :
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Khi un nng vi C hoc Na2CO3 th b kh n thy ngn kim loi :
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CHNG 9
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0,62); r = 0,67; r = 0,64).
Fe
3+
Cr3+
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(6) V mt cu to tinh th, c ba kim loi Cr - Mo - W u kt tinh theo kiu
lp phng tm khi( hnh 60 ) :
Vi Cr : : 2,8846
Mo : = 3,1464
W : = 3,1650
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Nguyn t Hm lng trung bnh ( s gam /1 g mu )
Apollo - 11 Apollo -12 Luna - 6
-3 -3
Cr 2,1. 10 2,8.10 5,3.10-6
Mo 0,5. 10-6 - -
W 0,3. 10 -6 - -
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oxit to thnh c kh n crom bng phng php nhit nhm; H2 khng kh
c Cr2O3 :
chuyn ha natri molipat thnh axit H2MoO4 khng tan, sau nung kt ta
H2MoO4 to thnh MoO3 :
sau khi nung kt ta, kh WO3 bng hiro hoc bng than :
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molipat, cc dung dch vonframat.
(2) C ba kim loi u c kh nng to thnh hp kim c bit vi st to
ra cc loi thp c bit.
Bng 39. Mt s hng s l hc quan trng ca Cr. Mo. W
Cr Mo W
3
Khi lng ring (g/cm ) 7,2 10,2 19,3
Nhit nng chy (Tnc,oC) 1875 2620 3380
o
Nhit Si ( Ts, C ) 2430 4800 6000
dn in (so vi Hg = 1) 4 20 18
m in 1,6 1,8 1,7
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ba kim loi :
Vi Cr to ra CrSe, Cr2Se3, CrSe4, CrTe.
Vi Mo to ra MoSe, MO2Se3, MoSe2, MoSe3, Mo2Te3, MoTe3.
Vi W to ra WSe2, WSe3, WTe2.
Tt c cc hp cht trn - tr hp cht ca crom - u bn trong dung dch
axit long v axit khng c tnh oxi ha nhit trong phng.
(3) Vi cc halogen, phn ng xy ra c mc khc nhau ph thuc vo
hot tnh ca cc kim loi v cc halogen; c ba kim loi u phn ng trc tip
vi flo ngay c khi ngui; vi clo phi un nng; molipen khng phn ng vi
iot; cn vonfram khng phn ng vi c brom v iot.
(4) Khi nung bt crom trong kh quyn nit to ra Cr2N 900oC v CrN
1200oC.
Vonfram tc dng vi ng khi nung 2800oC to ra WN3.
Photpho cng phn ng trc tip vi ba kim loi khi nung trong chn
khng, trong ampun bng thch anh to ra cc hp cht nh CrP, MoP, WP;
Cr3P, Mo3P; CrP2, MoP2, WP2...
(5) Phn ng trc tip vi cacbon to ra Cr2C3; Mo2C, W2C; MoC, WC
khi nung cc kim loi vi cacbon nhit cao; vi silic to ra CrSi, Cr3Si,
CrSi2; Mo3Si, MoSi2; W3Si, WSi3... cng nhit cao.
(6) V trn b mt c lp oxit c hot tnh ha hc km rt mng v bn
vng che ch cho kim loi, nn nhit thng, crom rt bn v mt ha hc.
Khi nung n nhit nng , crom kh c H2O to ra hiro :
Mo v W cng c kh nng .
Crom ha tan trong HCl v H2SO4 long nng to mui Cr(II) mu xanh
lam, sau mui Cr(II) b oxi ca khng kh oxi ha to ra mui crom(III) mu
xanh l cy :
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Nguyn nhn gy ra tnh bn ca crom trong cc loi axit trn l do to
ra lp oxit bo v b mt kim loi nn gy ra " tnh th ng " ca crom.
Tc dng vi dung dch mui ca nhng kim loi c th tiu chun cao
hn to thnh mui Cr(II) :
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(2) Crom(II) oxit (CrO) c iu ch bng cch phi hn hng
crom trong khng kh, nhng khng th thu c khi nung crom (II) hiroxit
Cr(OH)2. Hiroxit ny to ra khi cho mui Cr(II) tc dng vi dung dch kim
trong iu kin khng c khng kh :
CrO v Cr(OH)2 u tan trong axit khng c tnh oxi ha to thnh mui
Cr(II); khng tan trong kim, chng t ch c tnh baz.
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Ngi ta cng iu ch c CrF2 mu xanh ( Tnc = 1100oC); CrBr2
mu vng nht ( Tnc = 842oC); CrI2 mu ( Tnc = 195oC ), bng phng php
kh (t crom trong kh hiro halogenua ). Tr CrF2 t tan, cn li u d tan
trong nc.
hay
(5) Ngi ta bit c kh t cc hp cht ca Mo(II) v W(II).
cng c iu ch bng cch nhit phn WCl4 trong lung kh CO2 kh. WCl2
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l cht kh mnh, khi tc dng vi H2O gii phng kh H2 :
Cr2O3 khng tan trong nc, tan rt chm trong axit to thnh mui
Cr(III), v khi nung vi kim trong khng kh hoc vi cht oxi ha khc nh
KNO3 to ra cromat :
hay
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chy vi Na2CO3 v NaNO3 to ra natri cromat :
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(3) Crom(III) clorua (CrCl3) dng khan c iu ch bng cch
cho kh Cl2 qua crom nung nng :
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(4) Crom (III) sunfat (Cr2(SO4)3) c iu ch bng cch khuy bt
nho Cr(OH)3 trong H2SO4 c. Tinh th thu c c mu tm Cr2(SO4)3.18H2O
hoc Cr2(SO4)3.6H2O c mu lc.
Khi ng kt tinh vi mt mui sunfat ca kim loi ha tr 1 (Na+, K+,
NH4+, Rb+, Cs+, Tl+) tch ra tinh th phn crom mu tm thm c thnh phn
[M2SO4.Cr2(SO4)3.24H2O] trong phn kali d tan trong nc v c nhiu ng
dng thc t nh dng trong cng nghip dt, cng nghip thuc da.
Phn crom - kali l nhng tinh th hnh tm mt, mu tm thm, khi cho
nh sng truyn qua c mu ta.
Phn crom - kali c iu ch bng cch kh K2Cr2O7 trong dung dch
c axit ha bng H2SO4. Tc nhn kh tt nht l SO2 hoc C2H5OH; phn
ng xy ra theo phng trnh :
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phn :
(7) Crom (III) xianua (Cr(CN)3) to ra khi cho dung dch mui Cr(III)
tc dng vi dung dch xianua ca kim loi kim. Kt ta Cr(CN)3 tan trong axit
v tan trong dung dch xianua d to ra M3I[Cr(CN)6] :
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Anhirit cromic oxi ha c rt nhiu cht gy ra hin tng n, phn
ng mnh vi nhiu cht hu c, chng hn ru, giy u b bc chy khi tc
dng vi CrO3. Tuy nhin, CrO3 li tan trong axit axetic m khng gy ra hin
tng g.
(2) C ba oxit u l nhng cht kt tinh c mu khc nhau : MoO3 - mu
xanh (Tnc = 791oC); WO3 - mu vng (Tnc = 1473oC). Tinh th MoO3 v WO3 c
cu trc hnh tm mt; cn CrO3 c cu trc hnh bn mt :
Khi un nng, MoO3 v WO3 thng hoa khng b phn hy, chng t
bn t CrO3 - MoO3 - WO3 tng ln.
Khc vi CrO3, MoO3 v WO3 khng tan trong nc nn khng to thnh
axit nh CrO3. Tnh axit ca MoO3 v WO3 th hin khi tan trong kim to
thnh mui molipat v vonframat :
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Nh vy trong dung dch tn ti c hai dng ion CrO42- v Cr2O72- :
Nhng cromat tan quan trng l kali cromat K2CrO4 v natri cromat
Na2CrO4.10H2O. Nhng Cromat khng tan quan trng l ch(II) cromat PbCrO4;
bc cromat Ag2CrO4; v bari cromat BaCrO4.
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Dng tinh khit c iu ch bng cch cho dung dch AgNO3 tc dng
vi K2CrO4 :
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(5) Axit icromic (H2Cr2O7) v mui icromat ( Cr2O72-)
Axit icromic ch bit c trong dung dch c cu to tng t
H2SO7. Trong cc mui ca axit H2Cr2O7 th c bit l mui K2Cr2O7 v
Na2Cr2O7.2H2O l nhng mui quan trng, thng lm cht u iu ch cc
hp cht khc ca nguyn t .
Kali icromat (K2Cr2O7) c iu ch bng cch cho KCl tc dng vi
dung dch c Na2Cr2O7 :
cui cng l:
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Tnh oxi ha ca icromat th hin mnh trong mi trng axit. Trong
mi trng axit, cc mui icromat oxi ha c Fe2+ Fe3+; I- I2;
SO32SO42-..v.v...
Tnh oxi ha ca cc hp cht Mo(VI), W(VI)
ch th hin khi tc dng vi cht kh mnh.
(7) Ion icromat c cu to nh hnh 63.
n = 131o
CrOCr
dO-O(a) = 1,78 ; dCr-O(b) = 1,61.
hoc khi un nng icromat vi hn hp gm mui clorua kim loi kim trong
H2SO4 c:
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cc hp cht hu c. CrO2Cl2 b thy phn to ra CrO42-:
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CHNG 10
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crom v ca st. Mangan v crom to ra oxit thp (tnh baz) v trioxit (tnh
axit).
Mui cromat (CrO42- ) ng hnh vi mui manganat (MnO42-). Mangan
cng to nn phn tng t nh phn st K2SO4.Mn2(SO4)3.24H2O; hoc dng
mui kp nh (NH4)2SO4. MnSO4.6H2O tng t mui kp ca st (II). Ngoi ra
mangan cng to ra cc oxit MnO, Mn2O3.Mn3O4( MnO.Mn2O3) tng t cc
oxit ca st.
(4) Bng 40 l mt s c im ca ba nguyn t Mn, Tc, Re.
Bng 40. Mt s c im ca Mn, Tc, Re
Mn Tc Re
Electron ha tr 3d54s2 4d55s2 5d56s2
Bn knh nguyn t () 1,30 1,36 1,37
Bn knh ion M2+ () 0,91 0,95 -
Bn knh ion M3+ () 0,70 - -
Bn knh ion M4+ () 0,52 0,72 0,72
Bn knh ion M7+ () 0,46 0,57 0,57
Th ion ha l1 (eV) 7,43 7,23 7,87
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(6) V mt cu to, cc dng th hnh ca mangan u kt tinh theo kiu
lp phng; cn reni kt tinh theo kiu lc phng.
V d dng hnh th - Mn tn ti 1070 - 1130oC c dng cu trc
mng lp phng tm din c cnh = 3,862 , theo dng cu trc ca Cu. Cn
dng th hnh - Mn theo dng - Fe, ngha l kt tinh theo kiu lp phng
tm khi c cnh = 3,081.
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bn hy l 140 nm v km bn nht l 49Mn c chu k bn hy l 0,4 giy.
Tecnexi l nguyn t nhn to, cc ng v u c tnh phng x 1 trong
s ng v 99Tc bn nht c chu k bn hy l 2,12.105 nm.
Reni c 14 ng v.Cc ng v thin nhin l 185Re (37,07%); 187Re
(62,93%); cn li l cc ng v phng x.
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dng - Mn, bn trong khong 1070 - 1130oC; c khi lng ring l 7,21g/
cm3. Dng th hnh tn ti nhit cao hn 1130oC l dng - Mn:
- Mn - Mn - Mn - Mn
Tn ti: ( t thng ) ( 1070 C) ( 1130 C) (> 1130oC)
o o o
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Khi un nng bt reni trong kh quyn oxi 300oC to ra oxit Re2O7.
Mangan v reni u phn ng trc tip vi lu hunh, selen, telu to ra
cc hp cht nh MnS, MnSe, MnSe2, ReSe2, MnTe, MnTe2...
(3) Mangan ha hp trc tip vi nit to ra Mn3N2 nhit khong
600 - 1000oC khi cho bt mangan tc dng vi nit:
Mangan v reni phn ng trc tip vi photpho khi nung trong ampun
hn to ra cc cht Mn3P2, MnP, ReP...
(4) Mangan ha hp trc tip vi cacbon v silic to ra cc hp cht
Mn3C, Mn7C3; Mn3Si, MnSi...
(5) C mangan v reni u phn ng mnh vi cc halogen to thnh
mui dng MX2, v d:
Vi HNO3 to ra kh NO:
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10.6. Cc hp cht vi s oxi ha +2
(1) Mangan v reni to ra c cc hp cht ng vi cc s oxi ha th
n +7, ring tecnexi c cc s oxi ha +4; +6; +7. Trong , mangan c cc
hp cht quan trng ng vi s o xi ha+2; +4; +7; cn tecnexi v reni to ra
hp cht bn nht ng vi s oxi ha+7.
Di y ch nu cc hp cht Mn(II).
S phi tr c trng ca Mn(II) l bng 6 ng vi dng lai ha sp3d2 vi
s phn b lin kt tm mt.
Cc hp cht Mn(II) u c tnh thun t v u c nm electron c
thn. Cu to ca phc cht tm mt spin cao ca Mn(II) tng ng vi cu hnh
electron nh hnh 64.
S phi tr ca Mn(II) trong tinh th bng 6. Mt s hp cht lng t
u d kt tinh, c tnh ng hnh chng hn MnO v MnS c cu trc dng
NaCl...
Hnh 64. S phn b electron theo cc obitan trong phc cht Mn(II) tm mt spin cao
a s cc mui u d ha tan trong nc v u l mui bn nht ca
Mn(II). Khi tan trong nc, cc mui Mn(II) phn ly to ra phc - aquo
[Mn(OH2)6]2+ v dung dch c mu hng.
Mt s hp cht khng tan trong nc nh MnO, MnS, MnF2, Mn(OH)2,
MnCO3, Mn3(PO4)2.
(2) Mangan(II) oxit (MnO) c iu ch bng cch nhit phn Mn(II)
oxalat hoc cacbonat khi khng c khng kh (nung trong lung kh H2 hoc
N2):
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MnO l cht tinh th, mu xanh xm, Tnc = 1780oC. Khng tan trong
nc, khng phn ng vi nc. trng thi tinh th hon ton bn trong khng
kh, nhng dng bt d b oxi ha to thnh cc oxit cao:
Trong cng nghip, iu ch bng cch un nng MnO2 vi axit HCl cho
n khi khng cn kh clo thot ra:
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Trong tinh th hirat ha, mt s phn t H2O ng vai tr phi t.
trng thi khan to ra tinh th hnh phin mu hng. Nng chy 650oC, v
trong lung kh H2, MnCl2 bay hi 1190oC; H2 khng kh c MnCl2 nhng
khi un nng trong lung kh O2 hoc trong hi nc chuyn thnh Mn2O3.
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nhit thng, tinh th tch ra dng Mn(NO3)2.6H2O; nu cao hn
o
25 C - dng Mn(NO3)2.3H2O.
D tan trong nc, khi nung nng tch ra NO2 v MnO2:
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hipoclorit, KMnO4, v nhng tc nhn oxi ha khc u to ra MnO2 trong mi
trng kim:
Trong mi trng axit, MnO2 oxi ha mui Fe(II) thnh mui Fe(III), oxi
ha axit oxalic thnh CO2:
Oxi ha axit sunfur thnh Mn(II) ithionat; oxi ha H2O2 thnh O2:
Khi tc dng vi cht oxi ha mnh hn, MnO2 th hin tnh kh.
Khi cho MnO2 trn vi dung dch KOH 5% un nng 250oC ri cho
khng kh i qua s to ra K2MnO4 mu lc:
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trong cc mt n phng c trnh cacbon oxit. Dng lm cht oxi ha trong pin
kh hiro; dng trong cng ngh ch to dim.
Ngoi ra, MnO2 c dng lm cht oxi ha trong mi trng axit, lm
cht xc tc cho qu trnh nhit phn KCIl3... l
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(3) Ngi ta bit c mt s hp cht ca Re(VI) nh ReF6 c mu
vng nht; ReCl6 c mu xanh; ReOCl4, ReOF4; ReO3 c mu . Cc hp cht
u c tnh axit. Tr ReO3, cn li d dng b nc phn hy:
T dung dch bari pemanganat, cho thm mt lng H2SO4 cn thit, sau
khi tch kt ta BaSO4, dung dch cn li c cha HMnO4:
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Anhirit tng ng vi HMnO4 l Mn2O7.Mn2O7 l cht lng, mu xanh
thm thu c khi cho H2SO4 c 90% tc dng vi KMnO4:
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Trong mi trng kim:
(4) Ngi ta cng bit cc mui kim loi kim khc nh LiMnO4.3H2O
d tan; NaMnO4.3H2O d tan; RbMnO4 t tan (Tt = 2,9.10-3), CSMnO4 kh tan
(Tt = 9,1.10-5); mui pemanganat ca kim loi kim th, kim loi nng nh
Ca(MnO4)2.5H2O d tan; Ba(MnO4)2 tan; AgMnO4 t tan (Tt = 1,6.10-3);
(5) Cc hp cht Tc(II), Re(VII) tng t cc hp cht ca Mn(VII).
Cc oxit Tc2O7 v Re2O7 cng c iu ch bng cch un nng cc
axit HTcO4 v HReO4:
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axit mnh. Phng php iu ch ch yu l cho kim loi tng ng tc dng
vi HNO3 30%:
Tnh axit tng theo dy trn cng c th gii thch trong khun kh s
tng quan in tch v bn knh ca cc ion. Khi chuyn t Mn(II) - Mn(VII),
bn knh ca ion gim dn, in tch ca ion tng dn, nn kh nng tch ion H+
tng dn theo chiu t Mn(OH)2 n HMnO4.
bn ca ion MnO4- ln hn bn ca ion MnO42- cng c gii
thch trong phm vi ca thuyt obitan phn t nh sau:
Trong ion phc hnh 4 mt, chng hn nh MnO4-, CrO4-, MnO42-... th
cc obitan ca cht to phc tham gia hnh thnh lin kt gm 5 obitan (n-1)d;
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mt obitan ns v ba obitan np, vi cc obitan p ca bn phi t.
Trong ion MnO4- c 24 electron ha tr gm 7 electron ca nguyn t
Mn (3d54s2), 16 electron ca 4 nguyn t oxi O (2p4) v 1 electron do tch in
ca ion. Trong ion MnO42- c 25 electron ha tr tham gia hnh thnh lin
kt.
S phn b electron trong cc obitan phn t (MO) trong ion MnO4- v
ion MnO42- c cu hnh nh sau (hnh 65 ).
MnO4-: (lk )(lk )10 ()6
lk 8 lk 10 6 plk l
MnO42-: ( ) ( ) () ( )
Nh vy, trong ion MnO4- c mt electron ha tr chim MO phn lin
kt, do ion MnO4- km bn hn ion MnO4.
Tng t nh vy, trong cc ion MnO43-; MnO44- c 2 v 3 electron chim
MO phn lin kt nn cng km bn, v v vy chng ta hiu c tnh khng
bn ca s phi tr 4 trong hp cht Mn(IV) v cng hiu c v sao cc ion
MnO43-, MnO44- khng tn ti.
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CHNG 11
H PLATIN
43 44 45 46 47
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Re Osmi Iridi Platin Au
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0
c = 4,0795 A
Ru Rh Pd
Mng lc phng Mng lap phng tm din Mng lp phng tm din
0 0 0
a = 2,7085 A a = 3,8044 A a = 3,8907 A
0
c = 4,2816 A
Os Ir Pt
Mng lc phng Mng lp phng tm din Mng lp phng tm din
0 0 0
a = 2,7353 A a = 3,8938 A a = 3,9239 A
0
c = 4,3191 A
CC KIM LOI H ST
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(4) V cu to tinh th :
St c bn dng th hnh, c cu to nh hnh 66.
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11.3. Trng thi thin nhin v thnh phn cc ng v
(1) St thuc cc nguyn t ph bin nht cu to nn v qu t. Khong
vt ch yu ca st l manhetit (Fe3O4), hematit (Fe2O3), hematit nu
[Fe2O3.2Fe(OH)3]. Ngoi ra, mt lng st kh ln dng khong cht xierit
(FeCO3) v c trong qung vi lu hunh, asen nh pirt FeS2 ... tuy nhin pirit
khng phi l cht dng iu ch st m dng iu ch H2SO4. Hm lng
ca coban trong v qu t t hn nhiu so vi st. Khong vt quan trng ca
coban l cobantin ( CoAsS). Coban ln vi cc kim loi khc nh Cu, Ni, Ag,
Fe, Mn trong cc qung a kim.
Hm lng ca niken trong v qu t nhiu hn coban. Khong vt ch
yu ca niken l penlait l qung sunfua ca ni ken, ng v st. Ngoi ra cn
c cc loi qung khc nh gacnierit ( NiSiO3.MgSiO3 ), qung smantit l qung
arsenua ca Ni, Co, Fe.
(2) Trong cc thin thch c khong 5,15%Fe; 0,01%Co; 0,14%Ni(%
nguyn t), nhng trong cc thin thch st c n 90%Fe; 8,5Ni; 0,5%Co cng
vi mt t tp cht khc. Hng nm c n trn 1000 thin thch ri xung tri
t ch yu l thin thch st. Thin thch st ln nht nng 60 tn pht hin
nm 1920 Ty Nam chu Phi.
Trong c th ng vt , st c trong hemoglobin, chc nng chnh ca
phc cht ny l lin kt oxi phn t v chuyn oxi vo cc m. Ngoi ra, cn
c trong mioglobin l cht protein d tr oxi trong c bp; c trong phc cht
feritin cng l protein c chc nng to nn nhng hp cht khc cha st cn
cho c th ca sinh vt . Gan v l lch l b phn giu st nht trong c th.
Coban thuc s nguyn t quan trng i vi con ngi, vitamin B12 hay
cobanamin l phc cht ca coban c cha 4,5% Co v khi lng , dng
cha bnh thiu mu.
(3) Trong nc i dng, cc nguyn t h st, coban, niken dng
Fe(OH)3 ; Co2+ , CoSO4; Ni2+ , NiSO4 [ theo D. Golldberg ( 1963)] ng vi
thnh phn ha hc trung bnh nh sau ( theo A.P. Vinogradov -1967) :
Nguyn t Hm lng
% mg/l
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Fe 1. 10-6 0,01
-8
Co 5. 10 0, 0005
-7
Ni 2. 10 0, 002
(4) Hm lng ba nguyn t trong cc mu Mt Trng c cc hm
lng nh sau:
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Nu nung 5730C th to ra oxit FeO:
nu nung 270 - 280oC thu c niken t (hay, cn 350 - 400oC hoc cao hn
thu c niken bt, hon ton bn i vi khng kh.
Niken bt cng c iu ch bng phng php in phn dung dch
NiSO4 trong nc vi dng cc bng cc l ( Fe - Ni ), cn m cc bng Ni; pa
ca dung dch cht in phn khong t 4 - 4,5 .
(Niken tinh khit cng c th iu ch bng cch nhit phn niken
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tetracacbonyl Ni(CO)4 :
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Ni u l cht st t tc l cht b nam chm ht. Tuy nhin, trong bn dng th
hnh ca Fe, ch c - Fe mi c tnh st t, ngha l tnh st t ca st ch
nhit n 770oC, trn nhit tnh st t ca st bin mt, mc d mng
tinh th khng i, st ch cn li tnh thun t.
Coban c tnh st t nhit l0750C, cn niken - 3620C; trn nhit
tnh st t ca coban v niken s mt.
Mt s hp cht ca cc nguyn t trn cng c tnh st t, do ngi
ta lm giu qung st bng phng php t hc.
Ngoi tnh cht b nam chm ht , di tc dng ca dng in cc cht
st t s tr thnh nam chm . Tuy nhin, st nguyn cht ch tc dng nh mt
nam chm khi chu tc dng ca dng in, cn thanh thp khi nam chm ha
th sau vn tc dng nh mt nam chm vnh cu.
(3) St l kim loi quan trng nht i vi cc ngnh k thut v cng
nghip hin i. C ba kim loi c dng ch yu to ra cc hp kim c
bit l cc loi thp.
Nhiu hp cht ca st c ngha quan trng trong thc t nh FeCl3
dng lm cht ng t khi lm sch nc, lm cht cm mu, lm cht xc tc
trong ha hc hu c. Cc mui ferit ca kim loi ha tr hai dng trong k thut
my tnh.
Cc oxit ca st khng nhng l ngun iu ch nhiu hp cht ca st m
cn l ngun nguyn liu quan trng ca ngnh luyn kim en.
(4) Hn 3/4 lng coban c sn xut dng ch to thp v hp kim
c bit. Coban truyn cho thp tnh cng v tnh chu mn nn loi thp c
cha coban dng ch to cc dng c ct gt khc nhau.
Mt s hp kim ca coban dng trong k thut quc phng v k thut
tn la.
Coban l vt liu st t, nhiu hp kim ca co ban cng c tnh st t. Hp
cht gia cc kim loi ca coban v samari ( SmCo5 ) v mt s kim loi t
him khc c dng lm vt liu ch to nam chm vnh cu mnh.
ng v 2760 Co c iu ch theo phn ng:
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dng m ln b mt cc sn phm lm bng vt liu d b n mn.
Hp kim Monen ( A. Monel l gim c mt cng ty Canada ch to
ra loi hp kim ny) c bn cao vi mi trng n mn, c s dng nhiu
trong ngnh ch to my cho cng ngh ha hc , ng tu... Mt s hp kim
khc ca niken c dng sn xut cc loi tin thay cho bc.
Niken v hp kim ca n c dng trong k thut hng khng v v tr
, trong cng nghip ha cht dng lm cht xc tc.
(6) Mt iu cn ch l khi ni n tnh cht l hc ca st cn n
thnh phn tp cht c trong st vi hai loi :
St c tinh khit cao c cha di 0,001% tp cht, c t tnh tt v d
hn, nhng tnh cht c hc khng cao, bn km hn nhiu so vi gang v
cc loi thp; khng th dng trong vt liu ch to.
St tinh khit k thut cn gi l thp in k thut c cha 0,02 - 0,04%
cacbon, ngoi ra cn c cc tp cht khc nh oxi , nh, lu hunh, photpho
cng c t tnh tt v d hn, c tnh c hc cao, dng lm vt liu ch to.
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hay lng. 1600oC, 100g niken ha tan c 43cm3 hiro.
(3) iu kin thng st, coban v niken u bn vi khng kh v
nc.
Khi nung bt Fe trong khng kh hoc trong oxi to ra Fe3O4 :
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Co v Ni cng c phn ng tng t to ra COS v NIS.
Selen v tu phn ng trc tip vi Fe, Co, Ni:
Vi Fe to ra : Fese, FeSe2 ; FeTe, FeTe ; trong Fese v Fese2 l cht
bn dn.
Vi Co to ra : CoSe, CoSe2 ; CoTe, CoTe2.
Vi Ni to ra : Ni Se, Nise2 ; Nhe, NiTe2
(7) C ba kim loi u khng phn ng trc tip vi nit. Cc hp cht
nh Fe2N, Fe4N; Co2N, Co3N, Co3N2; Ni3N, Ni3N2 u c iu ch bng
phng php gin tip v u t bn. Tc dng vi photpho trong cc ampun hn
to ra dung dch rn ng vi cc hp cht c thnh phn Fe3P, Fe2P, FeP, FeP2 ;
Co2P, CoP, CoP3; Ni3P, Ni2P, NiP3.
(8) Fe, Co, Ni to ra hp cht vi cacbon ng vi thnh phn M3C v
M2C, trong quan trng nht l Fe3C:
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hp cht Co3B , Co2B , COB , COB2.
Cng tng t cch iu ch nh trn, niken to ra cc hp cht Ni3B,
Ni2B, NiB, Ni3B2, Ni4B3.
(10) Nc khng cha khng kh ha tan hu nh khng n mn st
nhit thng, v trn b mt d to ra lp mng Fe(OH)2 bo v cho kim loi
. Nhng khi cho hi nc qua Fe nung to ra Fe3O4 :
Hnh 67 cho thy st ha tan mnh nht trong dung dch H2SO4 khong
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50%.
Khi nhng thanh st vo HNO3 bc khi mt thi gian, sau nhng vo
dung dch cha ion Cu2+ hoc dung dch axit long nh HCI, H2SO4 st s mt
kh nng phn ng, ngha l st b th ng ha bi HNO3 bc khi, HNO3
long , lnh ho tan st to ra st(II)nitrat :
(13) Trong dung dch axit long nh HCl, H2SO4, coban kh tan hn so
vi st, to ra H2 :
Coban tan trong HNO3 long, v cng tng t nh st, coban cng b
th ng ha bi HNO3 c.
(14) Cc axit v c long tc dng vi niken chm hn st to ra H2:
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Khi t chy hi Fe(CO)5 trong khng kh to nn Fe2O3 :
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Co2(CO)8 l tinh th c mu da cam, bt u b phn hy 600C:
Cht ny c mu vng, Tnc = - 330C, tan trong dung dch kim to thnh
mui nh K[Co(CO)4] , NH4[Co(CO)4].
(3) bit c nikell tetracabonyl Ni(CO)4 l hp cht ca Ni(0) c cu
hnh bn mt ng vi dng lai ha sp3 ( hnh 69 ).
Ni(CO)4 khng tan trong nc, khng phn ng vi axit long, kim long,
d tan trong cc dung mi hu c.
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Khi un nng khong 180 - 2000C, Ni(CO)4 b phn hy to ra Ni nguyn
cht:
CC HP CHT VI S OXI HA +2
S phi tr ca Fe(II), Co(II) v Ni(II) l bng 6 v 4 ng vi cu hnh tm
mt v bn mt hoc mt phng vung .
(1) S phi tr 6 ca Fe(II) trong cc hp cht nh FeO (hnh 70); FeF2
(hnh 71); FeCl2 v a s cc ion phc nh [Fe(OH)2]62+ ; [Fe(OH)6]4- ;
[Fe(CN)6]4- .... Mt s phc bn mt ng vi s phi tr 4 ca Fe(II) nh
[FeCl4]2- , [Fe(NCS)4]2-...
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Hoc bng cch nhit phn Fe(II) oxalat ( cht rn mu vng) trong iu
kin khng c khng kh:
(2) Coban(II) oxit l oxit baz. CoO l cht rn mu xanh, to ra khi nung
Co(OH)2, CoCO3 hay Co(NO3)2 trong bu kh tr hay trong chn khng:
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Thc t khng tan trong nc, nhng d tan trong axit.
Hiro d dng kh NiO thnh kim loi:
Fe(OH)2 tan trong dung dch axit long khng c khng kh; tan trong dung
dch kim c to ra hipoferit :
khi lm lnh dung dch, tinh th hipoferit tch ra dng mu xanh - nu. Khi tan
trong nc b phn hy.
Khi cho Sr(OH)2 hay Ba(OH)2 tc dng ln Fe(OH)2 cng to ra cc
hipoferit tng t Sr2[Fe(OH)6] v Ba2[Fe(OH)6]
(2) Co(OH)2 tn ti hai dng th hnh : xanh v hng. Khi tc dng
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dung dch kim vi mui Co(II), lnh, to ra dng th hnh mu xanh; khi un
nng, kt ta Co(OH)2 chuyn thnh dng mu hng:
Co(OH)2 c tnh lng tnh, nhng nng v tnh baz. D tan trong axit,
tan trong dung dch kim c nng to thnh cobantit mu tm - xanh
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dng vi st nung nng:
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Khi cho H2O tc dng ln CoCl2 khan qu trnh li xy ra ngc li. S
thay i mu sc c dng trong cc m k xc nh m ca khng
kh.
Khi un nng dung dch CoCl2 hay mui coban khc cng c s thay i
mu sc. Mu hng ca dung dch CoCl2 long s chuyn thnh mu xanh khi
un nng hoc khi tng nng , hoc khi cho thm cc cht nh HCl c,
CaCl2, lm ph v s hirat ha ca Co2+, thay th cc phn t H2O trong cu
ni bng ion Cr-:
hay
(6) Niken(II) bromua v iotua c iu ch bng phn ng trc tip t
cc n cht :
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11.11 Cc sunfua ca Fe(II), Co(II), Ni(II)
(1) Cc sunfua FeS, CoS, NiS c iu ch bng cch nung cc kim
loi tng ng vi lu hunh, hoc bng cch cho (NH4)2S tc dng vi dung
dch mui ca cc kim loi , to ra kt ta mu en, thc t khng tan trong
nc. ( Tt(FeS) = 5. 10-18 ; Tt( -Co S) = 2,0. 10-25 ; Tt( - Ni S) = 1.10-24 ). Ngay sau khi
kt ta, c ba sunfua u d tan trong axit long k c axit yu nh axit axetic
. lu trong dung dch, CoS v NiS chuyn sang dng kh tan trong axit. V
cu trc tinh th, c ba sunfua u kt tinh theo kiu NiAs ( hnh 72 ; 73 ).
Do kin trc theo kiu NiAs nn c s gim khong cch trong mng li
0
so vi tng bn knh hiu dng ca cc con , v d vi FeS c d = 2,45 A trong
0 0
khi bn knh hiu dng ca ion Fe2+ = 0,83 A v ca S2- = 1,74 A , iu
c gii thch bng s bin dng tng h ca hai ion.
Mt iu cn ch l trong tinh th, v d FeS, mt phn nguyn t st c
th thay th bi cng mt s nguyn t lu hunh m cu trc v bn ca
tinh th khng thay i. Trong ba sunfua trn th FeS c nhiu ng dng thc t,
c dng lm nguyn liu iu ch H2S.
FeS thc t khng tan trong nc, nhng tan c trong axit long to ra
H2S.
Trong khng kh m, kt ta FeS dn dn b oxi ha thnh sunfat v cui
cng to thnh Fe2O3 :
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(2) St(II) isunfua FeS2 thng gp trong thin nhin dng qung git
st v qung maccasit.
FeS2 c th c iu ch bng cch nung nng FeS vi S:
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Ni chung, cc hp cht u bn vi khng kh, vi axit, vi kim, tuy
nhin khi nung nng b phn hy v khi tc dng vi H2SO4 c nng to ra CO:
(2) Khi cho KCN tc dng vi dung dch mui coban (II) hnh thnh kt
ta mu nu coban(II) xianua Co(CN)2 :
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dch t vng chuyn thnh mu , do s to thnh con [ Ni(CN)4 ]4- :
FeSO4 l cht kh tt, kh c mui Ag+ v mui Au3+ thnh kim loi:
http://hhud.tvu.edu.vn
Kh c HgCl2 ( hp cht cng ha tr ) thnh Hg2Cl2:
CoSO4 d tan trong nc nhng khng tan trong ru. Trong dung dch
nc 40 - 500C kt tinh dng CoSO4.6H2O.
CoSO4 cng to thnh mui kp vi kim loi kim v amoni, v d amoni
coban(II) sunfat mu :
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c dng lm cht m niken.
NiSO4 cng to ra mui kp vi cc kim loi kim, v d nh K2SO4 .
NiSO4.6H2O.
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Ni2O3 l Cht bt mu xm hoc en, do ngi ta dng Ni(NO3)2 to
mu xm trong cng nghip gm.
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CoCO3 thc t khng tan trong nc ( Tt = 8.10-13 250C ) , cn NiCO3 c
tch s tan Tt = 6,6. 10-9 nhng NiCO3. mNi(OH)2 li c tch s tan Tt = 1,7. 10-7
CC HP CHT VI OXI HA +3
Nh nu mc 11.2 hp cht ng vi s oxi ha +3 ca niken l khng
c trng, nn trong phn ny ch yu trnh by cc hp cht ca Fe(III) v
Co(III).
S phi tr ca Fe(III) l bng 6 v 4 ng vi s phn b tm mt v bn
mt. Chng hn FeCl3 trng thi hi ng vi cng thc Fe2Cl6 ( dng Al2Cl6 )
cn khi ha vo nc to ra phc cht tm mt [Fe(OH2)6]3+ .
S phi tr c trng ca Co(III) l bng 6, chng hn cc ion Co(OH2)6]3+,
[Co(NH3)6]3+.
Mu Sc Ca cc hp cht st (III) ph thuc vo bn cht ca anion. V d
FeCl3 - mu nu en; Fe(CNS)3 - mu mu; Fe2S3 - mu en; Fe(NO3)3.
6H2O - mu tm sng.
Cc hp cht ca Fe(III) u c tnh oxi ha; trong dung dch cc mui
Fe(III) b kh n mui Fe(II).
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Fe2O3 tan trong axit to thnh ion phc [Fe(OH2)6]3+ khng mu ; mu
nu ca dung dch mui st (III) l do mu ca sn phm phn ng thy phn,
tc l mu ca cc con phc hiroxo - aquo :
Khi nung vi C, hoc nung trong lung kh CO, H2 hoc kh than , Fe2O3
s b kh thnh Fe:
(3) Niken(III) oxit to ra khi nung trong khng kh mui cacbonat hoc
http://hhud.tvu.edu.vn
nitrat niken(II) 3000C :
(4) St(II, III) oxit ( Fe3O4) c thnh phn ng vi khong cht oxt st
t c iu ch bng cch nung nng Fe2O3 nhit trn 14500C :
Fe3O4 cng to ra khi cho lung hi H2O hoc CO2 qua st nung :
http://hhud.tvu.edu.vn
Fe3O4 b (Al, H2), CO kh thnh kim loi:
http://hhud.tvu.edu.vn
Kh nng ha tan trong axit ph thuc vo "tui" ca kt ta. Kt ta va
mi iu ch d tan trong axit v c v hu c, nhng lu mt thi gian th
li kh tan.
Khi un nng n 500 - 7000C s mt nc hon ton bin thnh Fe2O3:
http://hhud.tvu.edu.vn
cht in ly l KOH. S vn hnh ca loi cquy trn theo s :
Khi ha tan st trong axit HCl, sau cho kh clo qua dung dch, t dung
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dch ny tinh th hexahirat FeCl3. 6H2O s tch ra:
Trong khng kh, FeCl3 d b chy ra, nhng khi nung FeCl3 trong khng
kh hoc cho lung hi nc i qua s chuyn thnh Fe2O3 :
http://hhud.tvu.edu.vn
Phn ng trn dng iu ch Ki trong k thut t rt t do.
(4) Coban(III) florua bn nht trong halogenua ca Co(III) . CoF3 l
cht bt mu hung lc c th iu ch bng cch cho flo tc dng vi CoF2
3000C:
Khi un nng n 3000C trong lung CO2, CoF3 b phn hy thnh CoF2 v
F2.
(5) Coban(III) clorua rt khng bn. Khi cho Co(OH)3 tc dng vi HCl
khng thu c CoCl3 do phn ng:
http://hhud.tvu.edu.vn
chm. Tan trong ru , nhng khng tan trong H2SO4. Dung dch nc c mu
nu do b thy phn mnh, nhng nu cho thm H2SO4, phn ng thy phn
b hn ch v dung dch hu nh khng mu. Khi un si dung dch long, mui
baz s kt ta:
http://hhud.tvu.edu.vn
11.20. St (III) nitrat
c to ra khi ha tan v bo st trong HNO3 long gn 25% to ra
Fe(III) nitrat v hn hp cc oxit no khc nhau. nhit thng , ph thuc
vo nng , mui c th kt tinh dng khng mu hnh lp phng c
thnh phn Fe(NO3)3. 6H2O hoc dng n t mu tm c thnh phn Fe(NO3)3 .
9H2O.
St(III) thut tan trong nc to ra dung dch mu nu do thy phn, mu
s mt dn khi cho thm HNO3.
Trong cng nghip , st(III) thut c dng lm cht cn mu.
Fe2S3 thc t khng tan trong nc , tan trong dung dch HCl long:
http://hhud.tvu.edu.vn
K4[Fe(CN)6] , ngha l khng th cho mui Fe3+ tc dng vi dung dch KCN ,
v s to ra kt ta Fe(OH)3 do s thy phn KCN to ra mi trng kim.
K3[Fe(CN)6] l cht kt tinh mu - gch, khi nghin nh chuyn thnh
cht bt mu vng, tan trong nc cho dung dch mu vng.
Trong dung dch nc, khng c phn ng ca ion Fe3+ v ion CN- v ion
[Fe(CN)6]3- rt bn ( Kkb 10-44) :
http://hhud.tvu.edu.vn
c khi cho mui Co2+ tc dng vi KCN trong iu kin c cht oxi ha:
HP CHT CA ST VI S OXI HA +6
Hp cht gp dng ion FeO42- to ra khi oxi ha kim loi Fe hoc hp
cht ca Fe(III) bng cht oxi ha mnh trong mi trng kim mnh.
Khi nu chy Fe2O3 vi KNO3 v KOH to nn mui K2FeO4 theo phn
ng :
http://hhud.tvu.edu.vn
Cc ferat c mu sm, t bn trong dung dch nc, khi un nng nh
gii phng ra oxi
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TI LIU THAM KHO
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MC LC
Li ni u .............................................................................................................................. 2
CHNG 1
I CNG V KIM LOI
1. 1. S phn b kim loi trong thin nhin. V tr kim loi trong bng tun hon
3
CHNG 2
CC NGUYN T NHM IA (KIM LOI KIM)
http://hhud.tvu.edu.vn
2.10. Halogenua ca kim loi kim................................................................................. 41
CHNG 3
CC NGUYN T NHM IIA (KIM LOI KIM TH)
CHNG 4
CC NGUYN T NHM IIIA
( NHM - GALI - INI - TALI)
http://hhud.tvu.edu.vn
NHM V HP CHT CA NHM
CHNG 5
http://hhud.tvu.edu.vn
5.2. Trng thi thin nhin v thnh phn cc ng v............................................. 123
CHNG 6
I CNG V NGUYN T CHUYN TIP
6.1. V tr cc kim toi chuyn tip trong bng tun hon ...................................... 150
6.2. c im cu to nguyn t cc kim loi chuyn tip dy th nht (1) ...... 152
6.3. Tnh cht l - ha hc ca cc kim loi chuyn tip dy th nht ................ 155
CHNG 7
CC NGUYN T NHM IB
( NG - BC - VNG )
http://hhud.tvu.edu.vn
Oxit M2O ... ..175
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8.6. Cc hp cht vi s oxi ha + 2............................................................................. 200
CHNG 9
CC NGUYN T NHM VIB
(CROM - MOLIPEN - VONFRAM)
http://hhud.tvu.edu.vn
Crom(III) oxit ................................................................................... 226
Crom hiroxit (Cr(OH)3) .................................................................. 227
Crom(III) clorua (CrCl3).................................................................... 228
Crom (III) sunfat (Cr2(SO4)3)........................................................... 229
Crom(III) nitrat (Cr(NO3)3). ............................................................. 229
Crom(III) sunfua (Cr2S3) .................................................................. 229
Crom (III) xianua (Cr(CN)3)............................................................. 230
CHNG 10
CC NGUYN T NHM VII B
(MANGAN - TECNEXI - RENI)
CHNG 11
CC NGUYN T NHM VIII B
(ST - COBAN - NIKEN V H PLATIN)
http://hhud.tvu.edu.vn
11. 4. iu ch Fe, Co, Ni ............................................................................................... 259
CC HP CHT VI S OXI HA +2
CC HP CHT VI OXI HA +3
HP CHT CA ST VI S OXI HA +6
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PGS. NGUYN C VN
HA HC V C
Tp 2
(CC KIM LOI IN HNH)
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