Tinh th hc

GIO TRNH TINH TH HC

(DNH CHO SINH VIN NGNH CNG NGH HA HC )

Tinh th hc

MC LC
Chng 1: Kin trc tinh th ...................................................................................3 1.1 Cht rn v nh hnh , cht rn tinh th 4 1.1.1 Cht rn v nh hnh 4 1.1.2 Tinh th v cc tnh cht c bn ca tinh th 5 1.2 K hiu mng tinh th 6 1.3 S i xng ca tinh th 8 1.3.1 Cc yu t i xng nh hng 8 1.3.2 Cc yu t i xng trong hnh v hn 12 1.4 mng c s - Cc h tinh th 14 1.5 Mi bn kiu mng Bravais 15 1.6 Mt , khi lng th tch , cht st 16 1.7 Lin kt trong tinh th 18 1.7.1 Quan h gia hnh dng tinh th v thnh phn ha hc 18 1.7.2 Phn loi ha hc cc tinh th 19 Chng 2 : Cu trc tinh th 22 2.1 Phng php din t cu trc tinh th 22 2.1.1 Nguyn l xpcu 22 2.1.2 Cc hng trong 2 kiu xp cu 22 2.1.3 Kch thc cc hng 23 2.1.4 ngha ca nguyn l xp cu i vi ha hc tinh th 23 2.2 S phi tr v hnh phi tr 24 2.3 Cu trc cc n cht 26 2.3.1 Cu trc lp phng tm din 26 2.3.2 Cu trc lc phng 27 2.3.3 Cu trc lp phng tm khi 28 2.3.4 Cu trc lp phng n gin 29 2.3.5 Cu trc kiu kim cng 30 2.3.6 Cu trc grafit 31 2.3.7 Lin h gia loi lin kt ha hc v kiu cu trc 31 2.4 Cu trc cc hp cht ion hai nguyn t 32 2.4.1 Cu trc kiu cloua cesi (CsCl) 34 2.4.2 Cu trc kiu clorua natri (NaCl) 35 2.4.3 Cu trc kiu sfalerit (ZnS) 35 36 2.4.4 Cu trc kiu Fluorin (CaF2) 2.4.5 Cu trc kiu antifluorin 37 2.5 Cu trc ca mt s tinh th phc tp hn 38 38 2.5.1 Phc cht K2[PtCl6] 38 2.5.2 Cu trc kiu Peropskit (CaTiO3) Chng 3: Tnh a hnh v ng hnh 41 3.1 Tnh a hnh 41 3.2 ng hnh v dung dch rn 42 Chng 4: Nhng t/c vt l thng thng ca tinh th 45 4.1 Tnh ct khai hay tnh d tch ca tinh th 45 4.2 cng 46 4.3 Tnh dn nhit 47 4.4 Tnh p in , ha in , st in 48 4.5 Quang tnh 50 2

Tinh th hc

Chng 1 : Kin trc tinh th 1.1 Cht rn v nh hnh v cht rn tinh th

Vt cht tn ti di ba dng c bn : Rn , lng v kh . Ngi ta cng gi y l 3 trng thi ngng t ca cc ht vt cht . Ht y c th l nhng nguyn t , ion, phn t . trng thi kh , cc cht c nhng khong cch ln gia cc ht v cc lc tng tc gia chng vi nhau b . Chng c kh nng chim mt th tch bt k m ta dnh cho n , v tnh cht ch yu ca chng c xc nh bi tnh cht ca cc ht ring bit . Cn trng thi lng , cc ht ca cht nm cch nhau nhng khong bng kch thc ca chng , lc tng tc gia cc ht l ng k . Cc ht ca cht thng nht thnh nhng tp hp ln , trong phn b tng h theo mt trt t nht nh v chuyn ng c tnh cht dao ng ( th t gn ) . khong cch xa cc trung tm ca tp hp ( th t xa ) , trt t ny b ph v . bn ca cc lin kt gia cc tp hp ht trong cht lng khng ln , v vy trng thi lng cht chim mt th tch xc nh , nhng c kh nng thay i hnh dng di tc dng ca trng lc. Tnh cht ca cht trng thi ny c quyt nh bi tnh cht ca cc ht v cc tp hp ht , cng nh bi cc tng tc gia chng vi nhau . trng thi rn , cc cht chng nhng c kh nng bo ton mt th tch xc nh m cn gi nguyn hnh dng di tc dng ca trng lc.Tnh cht ca cht c xc nh bi thnh phn nguyn t cng nh cu trc ca n Cn phn bit cc cht rn gm cc vi tinh th ( cht rn tinh th ) v cc cht trng thi thu tinh ( cht rn v nh hnh ) .

1.1.1 Cht rn v nh hnh

V mt cu trc c th xp cht rn v nh hnh vo trng thi lng : Khi mt th lng b ng c ht sc t ngt , tnh linh ng ca cc ht b gim mnh , nht tng vt nhanh , cc mm kt tinh cha kp pht sinh v cu trc ca th lng nh b ng cng li . Th lng chuyn sang th v nh hnh . Trng thi v nh hnh khc trng thi lng mt im nh : Cc ht khng d dng di chuyn i vi nhau hay cng ( iu ny l im ging duy nht vi vt rn tinh th ). Tt c cc tnh cht khc n ging nh th lng v cu trc ca n l cu trc ca th lng , c trng bi s mt trt t ca cc ht . C th phn bit d dng vt th v nh hnh vi vt th kt tinh bng nhng c im d quan st ca trng thi lng m vt th v nh hnh mang theo : - Tnh ng hng : Cc tnh cht vt l ca n nh nhau theo cc phng khc nhau . - Phn bit bng ng nng chy - ng cong ch s thay i nhit ca vt th theo thi gian khi vt th c nung nng cho ti im nng chy : t0[C] t0C

q tc a) p m n

m b)

Tinh th hc a)Vt th v nh hnh . ng cong bin thin lin tc khng c im nng chy xc nh - lin kt gia cc ht khc nhau v lc . b) Vt th kt tinh . ng nng chy ca vt th kt tinh c nhng im gy m , n tng ng vi s bt u v kt thc ca qu trnh chuyn t cu trc tinh th sang cu trc lng ca vt cht ( qu trnh ngc li l qu trnh kt tinh ) . Trong giai on c nung , nhit ca tinh th tng dn (pm) . Ti nhit nng chy ca vt cht ( tC ) nhit ca vt ngng tng trong mt thi gian ( mn) . Thi gian ny di hay ngn cn ty thuc l nung nng t hay nhiu v khi lng tinh th ln hay nh . Sut thi gian ny ( t m n n ) nhit lng cung cp cho vt th khng dng tng nhit ca vt th m dng tng ni nng cho n bng nhng phn nng lng cn thit phi c ph v cc mi lin kt gia cc ht trong cu trc mng , a cc ht vo trng thi dao ng v di chuyn d dng i vi nhau hn - trng thi lng

1.1.2 Tinh th v cc tnh cht c bn ca tinh th

Tinh th l vt rn nu kt tinh tt c dng nhiu mt , cn i hnh hc . Bn trong , cc ht vt cht nh b ( nguyn t , ion , phn t ) phn b mt cch c trt t v tun hon trong mng khng gian . c khi nim v mng khng gian ta hnh dung c 1 h thng gm v hn nhng hnh hp ging ht nhau , sp xp cng chiu v kht vi nhau sao cho mi nh tr thnh nh chung ca 8 hp , mi cnh l cnh chung ca 4 hp .

Hp con ny c tn l mng c s . ( mng c s l n v tun hon nh b nht ca mng , th hin c y tnh i xng ca mng, tc n phi cng h vi h ca tinh th ) Tt c cc nh u l cc nt mng . Tp hp ca tt c cc nt l mng khng gian . Cc nt trn cng 1 ng thng lm thnh 1 hng mng ( 2 nt bt k ca mng xc nh 1 hng mng) . Khong cch gia 2 nt mng cnh nhau trn cng 1 hng c tr s c nh v c gi l thng s ca hng mng . Cc hng mng song song nhau c cng thng s hng, Ba nt khng cng trn 1 hng mng s xc nh mt mt mng . Tt c nhng mt mng song song nhau c cng mt nt v hp thnh 1 h mt mng . Khong cch gia 2 mt mng cnh nhau l 1 hng s i vi c h mt v c gi l thng s ca h mt mng hay gi tt l thng s mt mng .Cu trc ca 1 tinh th bao gi cng th hin nh 1 mng khng gian hay 1 s mng khng gian cng kch thc lng vo nhau . Cc ht vt cht ging nhau ca tinh th phn b trn nhng nt ca 1 mng khng gian . Bi tp : Mui n NaCl gm my mng khng gian cng kch thc lng vo nhau . Chng lng vo nhau nh th no ? i vi CsCl cng vy ?

Tinh th hc Khong cch gia cc ht cnh nhau trong a s cc tinh th rt nh , khong 1 vi A0 (1A0 = 10-8cm ) . Ngha l trn chiu di 1 cm ca khng gian tinh th c khong 108 ht tng n cc nt ng vi 108 nt . Do trong thc t ngi ta thng coi mng nh 1 h thng gm v h r r r hiu k hn v mng khng gian ta c th dng 3 vect tnh tin a , b , c khng ng phng tc dng ln 1 im - 1 nt gc ca mng , mt cch tun hon theo 3 chiu khng gian ta s nhn c mt h thng nt, chnh l nh ca mt h thng v hn nhng mng m ta gi l nhng mng c s trn vi 3 cnh l a, b , c . Z

c b a Y

Tt c mi ntr ca mang u suy c t nt mng gc bng nhng php tnh tin : r r r T = n1 a + n2 b + n3 c . khc , hai nt bt k Trong n1 , n2 , n3 l nhng s nguyn no . Ni mt cch r ca mng c th di chuyn ti ch ca nhau bng mt php tnh tin T . Khi chng ti ch ca nhau , cc nt cn li ca mng cng th ch cho nhau . V mi nt u hon ton tng ng nhau v v mng l mt hnh v hn nn sau khi cho mng tnh tin nh vy ta khng th phn bit c v tr cui cng v v tr u tin ca mng .Ngha l ton b mng tr li trng vi r chnh n . Cc php tnh tin T l cc php tnh tin bo ton mng . Tm li : Mng khng gian l v hn v c tnh tun hon 3 chiu . Chnh s sp xp ca cc ht vt cht theo qui lut mng khng gian to nn nhng tnh cht rt c trng cho tinh th , l tnh ng nht v d hng . Tinh th c tnh ng nht :Trn ton b th tch ti nhng im khc nhau c nhng tnh cht tng t nhau . Ni r hn , nu nghin cu tinh th theo nhng phng song song vi nhau qua cc im khc nhau trong tinh th ta thy chng c cng tnh cht . Tnh ng nht ny l kt qu tt nhin ca tnh tun hon ca mng : Nhng nt tng ng nhau lp li 1 cch tun hon trong khp khng gian ca mng . Tinh th c tnh d hng:Xt theo nhng phng khc nhau tinh th c tnh cht khc nhau . Tnh d hng l hu qu tt nhin ca vic phn b cc ht theo qui lut mng khng gian .Theo nhng phng khc nhau khong cch v lc lin kt gia cc ht thng thng khc nhau . 5

Tinh th hc Ngc vi tnh d hng trong tinh th , cht lng v rn v nh hnh c tnh ng hng , v trong chng s lng nguyn t ( phn t ) trung bnh trn mt n v chiu di v lc lin kt gia chng nh nhau theo mi hng .

1.2 K hiu mng tinh th

Nu ly mt nt mng lm gc , chn cc trc cha cc vect a , b , c lm cc trc ta X, Y , Z ; chn cc di a , b , c lm cc n v trc , ta c qui c v k hiu ca 1 nt , 1 hng mng , 1 mt mng nh sau : r r T = n1 a + Ta bi t m t nt b t k c a 1 m ng lin h v i g c b ng 1 vect t nh ti n r r n2 b + n3 c .N c ta trn 3 trc ln lt l n1a , n2b , n3c . Nu a , b , c l di n v ca 3 trc th ta ca nt tr thnh n1, n2 , n3 . K hiu ca nt s l {[ n1n2n3]} . Trng hp nt c ta ri vo phn m ca trc ta , ch s n tng ng phi mang du m trn u n . - Cch xc nh k hiu cho 1 hng mng , 1 mt mng tng t vi cch xc nh k hiu ca 1 cnh , 1 mt tnh th : + K hiu hng mng : Qua gc k 1 ng thng song song vi hng mng cn xc nh . Ngoi gc ra , nt gn vi nt gc nht nm trn ng thng ny c k hiu {[ n1n2n3]} , th k hiu ca hng mng s l [ n1n2 n3].Cc hng mng song song nhau c cng k hiu . + K hiu mt mng hoc 1 h mt mng ( dy mt mng song song nhau trong mng ) : Chn mt mng no ( nm trong h mt ny ) gn gc nht . V d : mt ny ct 3 trc ta theo 3 thng s n1a , n2b , n3c . Ta lp t s kp :
a a

:
1

b b

:
2

c c

=
3

:
1

:
2

= h :k :l
3

T s kp ny bao gi cng rt gn c thnh t s ca 3 s nguyn n gin nht l h:k:l . Vy k hiu ca mt mng cn xc nh s l ( h k l) . N cng l k hiu chung cho c h mt mng . Cc ch s hkl ca 1 mt mng ny cn gi l ch s Miller . V d : Z [001]

a c

[010] Y

X [100]

[210]

{[230]}

- Ch s Miller - Bravais trong h lc phng :

Ch s Miller trong h ta 3 trc khng thch hp i vi tinh th h lc phng , v cc phng hoc mt cng h c ch s khc nhau . biu din phng hoc cnh ( hng mng ) , mt ( mt mng ) tinh th trong h lc phng phi dng ch s Miller-Bravais, tng ng vi h ta gm 4 trc l 0X , 0Y , 0Z v 0U. Ba trc 0X , 0Y , 0U nm trn cng mt phng y ca c s , tng cp hp vi nhau 1
6

Tinh th hc gc 1200 v vung gc vi trc 0Z . Gc ta 0 l tm ca mt y . K hiu mt vi cc ch s ( hkil) . i= -(h+k) . Cch xc nh ch s Miller -Bravais hon ton ging nh trng hp ch s Miller . Z
(0001)

(1120) (01 1 0)

1.3 S i xng ca tinh th

T hn 150 nm trc , cc nh tinh th hc bit cch phn loi cc tinh th da vo s i xng v hnh dng bn ngoi ( quyt nh nhng tnh cht vt l ca vt liu ) cng nh nhng sp xp thc t gia cc nguyn t , ion , phn t to nn tinh th . Vy s i xng ca tinh th l g ? L s trng lp tinh th vi chnh n khi thc hin mt s thao tc thch hp ( dch chuyn trong khng gian ) l s trng lp theo qui lut cc tnh cht vt l ca tinh th cng nh cc phn t gii hn n nh mt cnh nh . m t chnh xc tnh i xng , mc i xng ca 1 hnh hay 1 tinh th no ngi ta dng nhng yu t i xng . Yu t i xng l thao tc thch hp hay php ton t bin 1hnh F thnh 1 hnh F khng phn bit vi F.

1.3.1 Cc yu t i xng nh hng hay cc yu t i xng trong hnh hu hn

Tm i xng [ C ]: Tm i xng C s lm trng kht hnh F vi nh F ca n bng php nghch o so vi im C .Hay :

L 1 im trong hnh c tnh cht : bt k ng thng no qua n u ct hnh ti 2 im cch u 2 bn n .

Nhn bit : Mt a din c tm C khi mi mt bt k ca a din c 1 mt tng ng nm pha xuyn tm i , song song, bng nhau v tri chiu i vi nhau . Lin h thy tinh th hnh lp phng , lng tr lc phng c tm C . Lng tr tam phng khng c tm C .

Mt i xng [P] Mt i xng l 1 mt phng chia hnh ra 2 phn bng nhau , phn ny i vi phn kia l nh ca nhau qua gng .
ng dng : Tm cc mt i xng trong hnh ch nht , hnh vung , hnh tam gic

Tinh th hc

Trc i xng xoay Ln ( n l 1 s nguyn ) l nhng ng thng qua tm im ca hnh m khi xoay hnh quanh n 1 vng 3600 bao gi hnh cng chim nhng v tr tng t v tr u tin 1 s nguyn n ln . n c gi l bc trc . Gc xoay b nht hnh tr li v tr tng t v tr u tin gi l gc xoay c s ca trc . Nu gi gc xoay c s l th bao gi ta cng c : = 3600/n. Ngha l 1 vng xoay 3600 bao gi cng cha 1 s nguyn ln gc .
Nh vy : Hnh thoi = 1800 = 3600/2 n = 2 L2

Tam gic u Lc gic u

= 1200 = 3600/3 n = 3 L3 = 600 = 3600/6 n = 6 L6

Hnh vung Hnh trn

= 900 = 3600/4 n = 4 L4

nh bao nhiu cng c . = 3600/ L Trc i xng bc 1 l trc c gc xoay c s = 3600/1 = 3600 . Mt vt c hnh dng mo m bt k khi xoay quanh 1 ng thng bt k bao gi cng tr li v tr u tin , nn trc i xng bc 1 khng mang ni dung i xng no . Bi tp : Tm cc yu t i xng c trong cc hnh : Lng tr tam , t , lc phng ; hnh bt din ; hnh lp phng ; hnh t din ...

nh l : Trong tinh th ch c cc trc i xng bc 1, 2, 3 ,4 v 6

Ni cch khc , trong tinh th khng c trc i xng bc 5 v bc cao hn 6 Ta bit mi tinh th u c xy dng t nhng ht vt cht phn b mt cch c trt t trong khng gian . Tt c nhng ht ging nhau phi phn b trn nhng nt ca cng 1 mng khng gian . Tnh cht c bn nht ca mng khng gian l tnh cht tnh tin tun hon . Chnh tnh cht ny gii hn s trc xoay cho php c c trong mng ( v cng l trong tinh th ) .Trc ht ta chng minh nh l : Trong mng lun c php tnh tin vung gc vi vi trc i xng xoay Ln

a1

r a

a2

Tinh th hc Cho trc Ln vung gc vi mt hnh v . Ly 1 nt mng a1 gn trc nht nhng khng nm trn trc . Xoay mng quanh trc 1 gc = 3600/n , a1 phi ti v tr nt a2 . Php tnh r r tin a1a2 hay a l php tnh tin bo ton mng . a vung gc vi Ln . l iu phi chng minh . Chng minh nh l : V mt phng vung gc vi trc Ln cho trc v cha 1 nt mng a1 . Vt xuyn ca trc qua mt phng l im A ( im A khng nht thit l nt mng ) . Xoay a1 quanh Ln 1 gc = 3600/n . a1 s n a2 tng ng ( theo nh ngha trc i xng v r tnh tin tun hon ca mng ) . Qua tc dng ca php tnh tin a , im A phi cho im B tng ng . Qua im B cng phi c trc Ln vung gc vi mt phng . Xoay im B quanh A 1 gc = 3600/n c im B . Xoay im A quanh B cng 1 gc = 3600/n c im A . B,B , A l nhng im tng ng vi im A. Theo tnh cht tnh tin tun hon ca mng ng thng AB song song vi ng AB phi c cng thng s a ( cc hng mng song song nhau th c cng thng hng ) Ngha l khong cch gia 2 im tng ng A gn nhau nht trn mi ng thng ny u bng a .Do khong cch gia Av B phi bng 1 s nguyn ln a . B A

a
a

AB = xa . Trong x l 1 s nguyn no . Trn hnh v ta s thy : AB = BA = AB = a 2cos =1- x = N cos = AB = a + 2a cos ( ) = a(1-2cos ) = xa hay 1-2cos = x N/2 iu kin x l 1 s nguyn dn n N cng phi l s nguyn nhng c th l dng hoc m .Ngoi ra cn iu kin cc gi tr ca cos na . Kt hp cc iu kin ta lp bng thng k sau : N -2 -1 0 1 2 Cos -1 -1/2 0 1/2 1 Gc xoay c s [] [1800 ] 1200 900 600 3600 Bc ca trc xoay [n] 2 3 4 6 1

Tm li trong tinh th ch c cc trc i xng bc 1 , 2 , 3 , 4 , 6 . chng minh khng c trc bc 5 v trc bc ln hn 6 trong tinh th cn c th dng cch khc . Gi thit trong mng tinh th c trc bc 5 [L5] . Ta ly 1 nt A1 gn trc nht nhng khng nm trn trc . V tnh cht ca trc i xng xoay mng phi lp li v tr u tin mi khhi ta xoay mng tng gc 3600/5 = 720 . iu ny i hi mt phng cha A1 vung gc vi L5 l 1 mt mng v trong mt ny ngoi A1 cn c A2 , A3 , A4 , A5 tng ng vi A1 , cng gn L5 nht , phn b u n 9

Tinh th hc

A5

A4

AX

A3

AX

A1

A2

xung quanh L5 . K 1 ng thng qua A1 v A2 ta c 1 hng mng thng s bng A1A2 .Qua A3 ta k ng song song vi A1A2 c 1 hng mng na c cng thng s vi hng A1A2 . . Trn chui mi , hai bn nt A3 phi c 2 nt Ax v Ax cch A3 nhng khong cch bng A1A2 = a . V thc t t hnh v ta thy nt Ax li gn L5 hn nt A1 , tri vi iu kin ban u ta nu , do gi thit v s tn ti trc L5 trong tinh th l khng ng . Bng cch tng t , ta chng minh c rng trong tinh th khng th c nhng trc bc 7,8 ...Tc l nhng trc bc cao hn 6 . Nu dng cch thit lp ny cho cc gi thit v trc bc 2 , 3 , 4 , 6 th kt qu li hon ton khc , khng i n nhng mu thun vi ga thit . Trc i xng nghch o : Lin (n l 1 s nguyn ) hay trc o chuyn . L 1 tp hp gm 1 trc i xng v 1 tm im tc dng khng ring l m ng thi . Ni cch khc , trc o chuyn c thit lp nn sau khi cho hnh quay 1 gc = 3600/n quanh trc i xng ri cho i xng qua tm im ca hnh th hnh tr li v tr tng t v tr u tin . V d : Cho hnh t din t phng ABCD ( Li42L22P) Mi mt ca hnh l 1 tam gic cn vi cnh y hoc AB hoc CD . ng thng qua im gia ca ca AB v CD chnh l trc i xng bc 2 ng thi l trc o chuyn bc 4 . Nu ta xoay hnh quanh trc 1 gc = 3600/4 hnh s sang v tr mi A1B1C1D1 . Cho hnh A1B1C1D1 i xng nghch o qua tm im O . Cc im A1 , B1, C1 ,D1 theo th t s ri n cc im D, C , A , B ( A1 D ; B1 C ; C1 A ; D1 B) . Ngha l hnh lp li v tr u tin trong khng gian . V d 2 : Cho lng tr tam phng c cc y l tam gic u . Trc L3 ng thi cng l trc o chuyn bc 6 (Li6) . Bi v sau khi cho hnh quay quanh trc L3 1 gc = 3600/6 = 600 v o xng qua tm O th hnh trng vi v tr ban u . V ta c cc trc i xng vi n = 1, 2 , 3 , 4 , 6 nn ta cng c cc trc nghch o Li1 ; Li2 , Li3 , Li4 , Li6 . Nhng trc i xng Li1 cng khng khc g 1 tm C ( Li1 = C ) , v vic xoay hnh quanh trc 1 gc 3600 tng ng vi vic khng cn xoay . Cho trc Li2 cng khng khc g cho 1 mt gng P t vung gc vi Li2 .Nhn hnh v di dy ta c th thy 2 im tng ng A1 v A2 c th suy ra ln nhau bng php i xng qua Li2 ( xoay quanh Li2 gc 1800 ri cho nghch o qua tm O ) hoc bng php i xng qua mt P ( vung gc vi Li2 v cha tm O )

10

Tinh th hc A1 A1

O P A2 Li2 = P

Li1 = C

Tc dng Li3 bng tng hp tc dng ca trc L3 v 1 tm i xng C . Cn tc dng ca trc Li6 li bng tng hp tc dng ca L3 v 1 mt P vung gc vi L3 . C th vit li nh sau : Li1 = C ; Li2 =P ; Li3 = L3C ; Li6 = L3P . Tm li , dng i xng bn ngoi c th thy c ca cc tinh th c din t ch yu bng cc yu t i xng : P , C , L2 , L3 , L4 , L6 , Li3 , Li4 , Li6

1.3.2 Nhng yu t i xng trong hnh v hn hay cc yu t i xng v tr

nghin cu cu trc bn trong ca tinh th c thun li , mng tinh th c coi l nhng hnh v hn v trong hnh ny i vi mi yu t i xng trn c v s yu t i xng cng loi song song nhau . V d : Trong mng tinh th NaCl : Ta c v s truc L4 v c P na song song vi nhau khi qua cc ion Na+ v Cl- . Tuy nhin hnh v hn c th c nhng yu t i xng m trong hnh hu hn khng th c c . l trc tnh tin , mt nh trt , trc xon c .

+ Trc tnh tin : Lt

L 1 phng trong hnh m khi ta tnh tin hnh 1 on thng nht nh song song vi phng th hnh s tr v v tr tng t v tr c trong khng gian v on thng gi l bc tnh tin hay chu k tnh tin . V d : Ta s dng mng NaCl LT Khi tnh tin ton b mng li NaCl t tri sang phi theo phng Lt mt on T bng khong cch gia 2 ion Na+ hoc Cl- lin nhau th mng s trng vi v tr c . L mt tp hp gm 1 mt i xng v 1 php tnh tin song song vi mt i xng , chng tc dng khng ring l m ng thi . y vic chuyn dch bng 1na on tnh tin c s . S dng mng NaCl trc sau cho i xng . L mt tp hp gm 1 trc i xng v 1 php tnh tin song song trc i xng ,chng tc dng khng ring l m ng thi . V d : Cho 1 hnh gm 1 h thng im A1 , A2 , A3 , A4 , A5 ... v tr nh hnh v

+ Mt nh trt : Pt

+ Trc xon c : LXn

11

Tinh th hc A4 A3 A3 L4 LX4 A2 A2

b) Ta c th thy hnh ny s c trc xo n c bc 4 (LX4 ) . Bi v : Khi lm theo nh 0 ngha , quay hnh quanh trc Lx4 mt gc 90 v tnh tin 1 bc T th hnh tr li v tr tng t v tr u tin . Hnh b/ khi xoay 900 th A1 , A2 , A3 , A4 , A5 ... s v tr ln lt A1 , A2 , A3 , A4 ... tip n tnh tin bc T th A1 n A2 ; A2 n A3 , ... Cc im A1 , A2 , A3 , A4 ... qua tc dng ca Lx4 s chuyn ng theo 1 ng xon c . Nu ng xon c theo chiu kim ng h th l trc xon c tri . Ngc li ta c trc xon c phi . Trc xon c c cc loi : Lx3 , Lx4 , Lx6 . Cn Lx1 tng ng vi trc tnh tin . Lx2 ng vi mt nh trt .

A1

A1

1.4 mng c s - cc h tinh th

tit trc ta thy 3 vect a , b , c hon ton xc nh 1 mng . l mt h thng v hn nhng nt . Chng chim v tr nh ca nhng hnh hp nh xc nh bi 3 cnh a , b , c xp kht nhau v ko di v tn trong khng gian . Mi hnh hp nh c tn l mng c s v ch cha 1 nt mng . mng c s l mng th hin y nht tnh i xng ca mng , ng thi l n v tun hon nh b nht ca mng .C tt c 7 dng mng c s tng ng vi 7 h tinh th : H 3 nghing : Mc i xng hng thp mng c s : hnh bnh hnh lch a b c ; 900 Yu t i xng trong mng : C

r r r

H mt nghing : Mc i xng hng thp (yu t i xng trong tinh th ch c th l L2 hoc P hoc L2PC ) mng c s : Lng tr y hnh bnh hnh hay hnh hp lch ab c ; = = 900 Yu t i xng ca mng : L2PC

12

Tinh th hc H trc thoi : Mc i xng hng thp ( yu t i xng trong tinh th ch c th l 3L2 hoc L22P hoc 3L23PC) mng c s : Hnh hp dim hay lng tr y ch nht ab c ; = = 900 = Yu t i xng ca mng : 3L23PC H tam phng : Mc i xng hng trung ( trong tinh th lun c 1 trc i xng bc 3 v ch c 1 trc bc 3 m thi ) mng c s : Hnh mt thoi hay a din y thoi a = b = c ; = = 900 Yu t i xng ca mng : L33L23PC H t phng : Mc i xng hng trung . Thuc h ny l nhng tinh th c trc i xng bc cao nht l L4 v ch c 1 L4 . mng c s : Lng tr y vung hay lng tr t phng a = b c ; = = = 900 Yu t i xng c trong mng : L44L25PC H lc phng : Mc i xng hng trung . Thuc h ny l nhng tinh th c trc i xng bc cao nht l L6 v ch c 1L6 . mng c s : Lng tr lc phng . ( lng tr y thoi trong lng tr lc phng ) a = b c ; = = 900 ; = 1200

1.5 Mi bn kiu mng Bravais

Yu t i xng ca mng : L66L27PC H lp phng : Mc i xng hng cao . Thuc h ny l nhng tinh th cha 4L3 mng c s : Lp phng a = b = c ; = = = 900 Yu t i xng ca mng : 3L44L36L29PC.

Tt c 7 c s trn cng l c s ca cc mng Bravair thuc 7 h tinh th khc nhau . Nu cc nt mng ch phn b nh ca mng , ta c nhng c s ca mng Bravair loi nguyn thy . Nu ngoi v tr nh , cc nt mng cn : - Phn b tm ca 2 y no ca mng ta c c s loi tm y - Phn b tm ca mng ta c mng c s loi tm khi . - Phn b tm ca cc mt ta c mng c s loi tm din

13

Tinh th hc

C 7 h v 4 loi mng khc nhau , nh vy theo tnh ton n gin s c tt c 7x4=28 mng Bravais khc nhau . Nhng Bravais chng minh ch c 14 ( xem hnh sau ) . Ta c th chng minh rng 1 s h khuyt i 1 s loi . V d : h t phng khng c c s Bravais tm y v tm mt : a) Gi s h t phng c mng tm y . Ta hy ly 2 mng cnh nhau v biu din chng trn mt phng vung gc vi trc i xng L4 .

a) b) Qua hnh a) ta nhn ra ngay : nguyn thy , c cnh bng na ng cho y ca tm y mi l mng s s , v th tch ca n cn nh hn Tng t nh vy qua hnh b) ta thy mng xy c t mng t phng tm din li nhn mng t phng tm khi lm c s . 14 mng Bravais ny l 14 b khung ca tt c cc tinh th

14

Tinh th hc H Ba nghing Nguyn thy ( P ) Tm y (C) Tm khi ( I) tm din (F)

Mt nghing Trc thoi

T phng

Tam phng

Lc phng

Lp phng

1.6 Mt , khi lng th tch , cht st

1.6.1 Mt (Z) Khi nim : Mt l thc th nh nht c th phn bit c v lp li 1 cch tun hon trong khng gian . i vi tinh th mc vi m , mt l 1 ht ( nguyn t , ion , phn t ) . 15

Tinh th hc V d : Trong kim loi ng , mt l 1 nguyn t ng . Trong CaCO3 : Mt l 1 kt hp ca 1 nguyn t Ca, 1 nguyn t C v 3 nguyn t xy . Cch xc nh s mt trong mng : Ht nm ngoi : khng tnh Ht nm nh : 1x1/8 =1/8 mt . Ht nm cnh : 1x1/4 = 1/4 mt . Ht nm mt : 1x1/2=1/2 mt Ht nm bn trong : 1 mt mng nguyn thy : Z = 8x1/8=1mt mng tm khi Z=8x1/8+1=2 mt mng tm y Z=8x1/8+2x1/2=2 mt mng tm din Z= 8x1/8+6x1/2=4 mt . 1.6.2 Khi lng th tch V Khi lng th tch V ca 1 cht l t s gia khi lng m ca vt v th tch V m n chim hay cng chnh l : V =
MZ V .N A

Trong : V l th tch ca mng . V=a.b.c hoc

V=a.b.c.sin . M l khi lng mol ca mt ; Z l s mt ; NA l s Avogadro bng 6,02 .1023. Mt cht rn x ch cha hir v xy . nhit t0=00C v di p sut p=1bar n kt tinh trong h lc phng . mng c s ca n c dng sau vi cc thng s : a=452pm , c=739pm . O H c O H 1/xc nh s nguyn t ca mi nguyn t cha trong mng X . 2/ T rt ra cng thc HXOY ca mt v s mt trong hp cht ny . Cho bit tn thng thng ca cht rn X. 3/ Xc nh khi lng th tch ca X 4/ nhit t0=00C , di p sut p=1bar cht rn ny khng phn ng ha hc vi nc lng khi lng th tch nc = 1,00.103kg/m3.

Bi tp ng dng

Xtatnh cht ca X khi nhng trong nc : a) t0=00C , di p sut p=1bar . b) Nu nhit tng , di p sut 1 bar c) Nu p sut tng , nhit t0=00 . Bi gii : 1/ Nguyn t xi : NO= 8x1/8 + 4x1/4 +2x1 = 4 Nguyn t hir NH= 4x1/4 + 7x1 =8 2/ Cng thc tinh th hc hay cng thc n v cu trc : N l tp hp tng s nguyn t trong mng : H8O4 . Vit di dng : HZXOZY. Suy ra Z=4 4 mt H2O . Vy hp cht X l nc .

16

Tinh th hc 3/ mng lc phng : y mng l 1 lng tr thng y thoi ( 1/3 mng lc phng ) . VNc = a.a.csin = a.a.c.sin1200 =a.a.c. v =
3 3 =(452.10-12)2.739.10-12. =1,31.10-28 m3 2 2

Khi lng mol: MN= 2MH+MO=18 g/mol = 18.10-3kg/m3.

Z .M 4.18.10 3 = = 9,15.10 2 kg/m3 28 23 V .Na 1,31.10 .6,02.10

4/ a) Nhng iu kin t ra l iu kin nng chy nc . Pha nc km c hn nc ( N < N) nn ni ln trn b mt pha lng . b) Khi nhit tng , nc nng chy v chuyn sang trng thi lng . d) Khi p sut tng m nhit khng i , th tch s gim i , do khi lng th tch tng ln . V vy nc chy thnh nc . /Dng ca mangan kt tinh theo h t phng vi cc thng s a=267pm, c=355pm, V= 7,19 .103kgm-3. Xc nh s mt ca mng v t suy ra cc kiu mng Bravais c th ca dng mangan v cht st ca kiu cu trc y . /Natri oleat C17H33COONa c khi lng th tch V= 840kgm-3, kt tinh kiu nguyn thy P ca h trc thoi . Ccthng s ca mng l : a=1,23nm ; b=664pm; c=756pm. Xc nh khi lng mol ca natri oleat xut pht t cc d kin cu trc .

1.6.3 cht st ( compac ) : P

L mt s khng th nguyn o t l khng gian b chim bi cc nguyn t hoc ion c coi l dng cu trong mng tinh th . Do P c gi tr trong khong 0 1. P =Th tch b chim /Th tch c sn = Th tch ca n nguyn t ca mng/th tchca mng P=
n 4 3 4 3 R j R j j =1 3 j =1 3 ( tit din y vung ); P= (tit din y thoi ) abc a b c sin
n

1.7 Lin kt trong tinh th

Ta bit rng cu trc tinh th thnh to do lc tc dng tng h ca cc nguyn t , cc ion khi th nng tng tc ca chng l nh nht . Trong cc cht khc nhau , lc gn kt cc nguyn t (ion) cng thng khc nhau , lm cho tnh cht ca chng khng ging nhau . Ngi ta phn bit cc dng lin kt chnh sau : - Lin kt ion - Lin kt ng ha tr - Lin kt kim loi - Lin kt tn d Van-dec-Van

1.7.1 Quan h gia hnh dng tinh th v thnh phn ha hc

Cu to ca mng li tinh th c th lin quan vi thnh phn ha hc ca cht . Quan h ny c th biu th nhiu hay t ngay c i vi hnh dng bn ngoi ca tinh th . Trong s nhng qui lut kinh nghim ta lu ti 2 qui lut : Ni chung thnh phn ha hc ca cht m cng n gin th tinh th ca n cng c tnh i xng cao V d : 50% nguyn t v gn 70% hp cht 2 nguyn t hnh thnh nhng tinh th dng lp phng ; 74-85% hp cht c 4-5 nguyn t trong phn t hnh thnh nhng tinh th dng tam phng v lc phng .Gn 80% hp cht hu c phc tp hnh thnh tinh th dng trc thoi v n t .Qui lut ny c th gii thch d dng : Nhng ht vt cht ( nhng hp phn ) ca mng tinh th m cng ging nhau th phn b cng c trt t trong khng gian . Tuy nhin khng th 17

Tinh th hc loi tr nhng trng hp ngoi l . Chng hn lu hunh kt tinh theo h trc thoi v 1 nghing . trong khi 1 s hp cht silicat c thnh phn phc tp li kt tinh theo h lp phng . Nhng cht c cu to ging nhau kt tinh thnh nhng dng tinh th tng t nhau . l qui lut ng hnh ca Mitscherlich . Ta s xt sau .

1.7. 2 Phn loi ha hc cc tinh th

Theo bn cht ca cc tiu phn ( ht cu trc ) v dng lin kt ha hc gia chng c th phn bit cc loi tinh th sau :

Tinh th nguyn t
Tiu phn cu to l nhng nguyn t phn b tht u n ti nhng nt ca mng khng gian v lin kt vi nhau bng lc lin kt cng ha tr . Lin kt ny to ra khi 2 hoc nhiu nguyn t gp chung nhau 1 s in t c 8 in t lp ngoi cng ( in t ha tr ). Lin kt cng ha tr c c im : + Lin kt c tnh nh hng , ngha l xc sut tn ti cc in t tham gia lin kt ln nht theo phng ni tm cc nguyn t . Hay ni cch khc l cc electron c nh v u tin theo hng n cc nguyn t gn nht nn lin kt l cng . H qu : Lin kt cng ha tr l mt lin kt mnh + Cng lin kt ph thuc rt mnh vo c tnh lin kt gia cc in t ha tr vi ht nhn . V d : Cc bon dng th hnh kim cng c lin kt cng ha tr rt mnh v 4 in t lin kt ( in t ha tr ) trong tng s 6 in t lin kt hu nh trc tip vi ht nhn ; trong khi Sn cng nhm vi cacbon th hin tnh lin kt cng ha tr rt yu v 4 in t ha tr ( trong tng s 50 in t ) nm xa ht nhn , do c lc lin kt yu vi ht nhn . V vy kim cng c nhit nng chy trn 35500C , trong khi Sn nng chy 2700C . + Lin kt cng ha tr c th xy ra gia cc nguyn t cng loi nh phn t Cl2 hoc cc tinh th kim cng , silic , gecmani - Lin kt cng ha tr c th xy ra gia cc nguyn t khc loi nhau gi l lin kt cng ha tr phn cc . Kiu ny c trng cho 1 s hp cht hp bi nhng nguyn t c m in gn nhau nh SiC, GaAs , GaP...( Tnh m in l kh nng ht in t ha tr ca ht nhn ca nguyn t ).Ta cn c th gp loi lin kt cng ha tr thc hin c nh i in t ca ring mt nguyn t - cn gil lin kt phi tr , n l dng c bit ca lin kt cng ha tr , mang tnh cht trung gian gia lin kt ng ha tr v lin kt ion . V d : Sfalerit ZnS , to thnh 4 mi lin kt , mt nguyn t S b ra 6 in t , m nguyn t km ch b ra 2 in t . y cng xy ra hin tng nhng in t , nhng khng phi nhng hn nh trong trng hp lin kt ion . Khi ng vai tr lin kt cc nguyn t thnh hp cht , cc in t dng lin kt phi tr lc th chuyn ng quanh nguyn t ny , lc li quay quanh nguyn t kia .. + Mi nguyn t ch to c mt s c hn cc mi lin kt quanh n .

Tinh th ion
Tiu phn cu to l nhng ion dng v m phn b lun phin u n ti nhng nt ca mng khng gian v lin kt vi nhau bng lc lin kt ion .Lin kt ion to ra do lc ht tnh in gia cc ion c in tch tri du v do lc y khong cch ngn . Ion c th n gin nh Cl- , Na+ , K+ ,Br- ... hoc phc tp nh NO3- , CO32- ... Lin kt ion c c im : Khng bo ha , khng nh hng trong khng gian v in trng ion hay s i xng ca my electron thng l dng cu . Tinh th ion c coi nh tp hp nhng qu cu khng bng nhau v mang in tch .Trong nhng tinh th ion CXAY , ion ca lin kt v l thuyt l 100% nhng him c nh vy . c tnh ion cng r khi hiu m in gia A v B cng ln ; lin kt ion i hi s kt hp ca 1 nguyn t c m in nh ( nm di v pha tri ca bng tun hon) vi cc nguyn t m in mnh ( trn v pha phi ) . Hai u kin ny gii thch ti sao cc halogenua kim l nhng tinh th ion bn .Cng ging nh lin kt cng ha tr , lin kt ion cng mnh (bn vng ) khi cc nguyn t cha t in t , tc l 18

Tinh th hc cc in t cho hoc nhn nm gn ht nhn .V d : Hydro (H) to vi F,Cl,Br , I cc hp cht HF, HCl, HBr , HI bng nng lng lin kt ion tng ng l 5,81, 4,44, 3,75, v 3,06 eV/mol Cc tnh cht : Cc ht tch in y l cc ion ( cation v anion ) . Khi lng v th tch ca chng ln hn cc electron rt nhiu ( ion 35Cl- c khi lng ln hn khi lng electron khong 65000 ln ) . V vy chng rt kh chuyn ng trong mng tinh th . trng thi rn , cc hp cht ny c dn in rt nh , nhng chng l nhng cht dn in tt trang thi nng chy hoc trong dung dch ( cht in ly) Kho st trng thi lin kt ha hc trong cc hp cht t nhin cho thy : -Tt c cc florua c lin kt gn nh n thun dng ion , lin kt ng cc ch mc t 2% KF n 20% AlF3 -Mt phn ln cc xyt c lin kt ch yu dng ion , tr thch anh (SiO2)v piroluzit (MnO2) c lin kt ng ha tr vt tri hn (54% v 65% ) -Cc sulfua ch yu l nhng hp cht nguyn t .Cc selenua , teluarua . acxenua , antimonua l nhng hp cht c lin kt ng ha tr mc cao hn Thng thng nhng nguyn t c gi tr m in mnh nht ng vai tr quyt nh trng thi lin kt trong hp cht . Theo Lbdev , nhng nguyn t nh F,O v Cl c kh nng to thnh nhng hp cht ion ; cn S , I , Te , As v Sb l nhng nguyn t to hp cht nguyn t . Trong t nhin , hp cht ion thng ph bin hn .

Tinh th kim loi

Tiu phn cu to chim v tr nhng nt ca mng khng gian l nhng ion dng kim loi , tc l nhng nguyn t kim loi mt bt 1 s electron lin kt yu ca chng . Nhng electron ny c kh nng di ng tng i t do trong mng li kim loi ( trong tinh th ) khng thuc hn nguyn t no , lc lin kt vi nguyn t ny , lc lin kt vi nguyn t khc v bng cch thc hin lin kt gia chng . Lin kt kim loi to ra do tng tc tnh in gia in tch m ca cc electron ca m my in t v in tch dng ca cc cation kim loi . Tnh cht : + Cc electron t do di chuyn trong ton b tinh th lm cho kim loi c dn in v dn nhit cao . + V mt nng lng , lin kt kim loi c coi l lin kt trung bnh + V mt quang hc , kim loi th hin kh nng phn chiu c trng do s dch chuyn electron trong min nng lng ca nh sng nhn thy .

Tinh th phn t
Tiu phn cu to chim v tr nhng nt ca mng li tinh th l nhng phn t nguyn vn c ha tr bo ha v lin kt vi nhau bng nhng lc yu thng thuc loi Van der Waals hoc lin kt hydro . Lin kt trong phn t ca chng thng l lin kt cng ha tr . -Lin kt Van der Waals l lin kt do hiu ng ht nhau gia cc nguyn t hoc phn t b phn cc trng thi rn . Lin kt ny thuc loi yu , rt d b ph v khi tng nhit .V vy nhng cht rn trn c s lin kt Van der Waals thng c nhit nng chy thp , cng nh v gin n nhit ng k - Lin kt hydro l dng trung gian gia lin kt Van der Waals v ion. N thc hin c nh nguyn t hydro ng gia v gy ra lc ht hai nguyn t mang in m .Thng c biu din l A - H...B . V d : HF : F- - H+ ... F- - H+ to thnh (HF)n ; n = 2 (dung dch ) ; n=4 ( th rn ) Nguyn nhn : V m in ca F rt ln nn trong mi lin kt H - F ny electron b ht lch mnh v pha F lm cho F tch in m ; nguyn t H ch cn li gn nh tr tri ht nhn mang in dng nn c th n kh gn nguyn t F v chui vo bn trong v electron ca nguyn t F ca phn t HF khc v hnh thnh mi lin kt mi vi nguyn t F ny . n=2-3 l nc ; n=5 l nc Tng t nh vy H2O : (H2O)n 19

Tinh th hc O ---H H----- H H ---O Nng lng lin kt hydro nh hn lin kt cng ha tr hay ion 10 ln nhng li 10 ln ln hn nng lng lin kt tn d .

Tinh th thc
Bn kiu tinh th vi cc kiu lin kt nu trn thc t l nhng trng hp gii hn v l nhng cu trc m hnh .Trong hu ht cc hp cht , ngi ta khng gp ch mt dng lin kt n thun nhng ta ch cn quan tm n nghing v dng no nhiu nht .. Cc tinh th thc thng cn gp cc dng lin kt c tnh cht trung gian , c nhng mc chuyn tip khc nhau . V d : Dng trung gian gia lin kt kim loi v lin kt nguyn t c gp 1 s n cht c tnh kim loi km in hnh nh As, Se . Hoc nhng dng trung gian gia lin kt ion v cng ha tr ( c gp nhng tinh th cu to t 2 nguyn t m s khc nhau v m in ca chng cha thc hin lin kt ion nhng hnh thnh lin kt cng ha tr phn cc ). Cho nn phn loi tinh th theo tnh cht ca lin kt cng khng c d dng . Hn na , trong 1 tinh th c th tn ti nhiu dng lin kt khc nhau . V d : Tinh th than ch c cu trc lp ; trong mi lp lin kt gia cc nguyn t cc bon l lin kt cng ha tr rt bn nhng lin kt gia cc lp l lin kt phn t .Hoc tinh th mui ngm nc c nhng dng lin kt sau : Lin kt ion gia cc cation v anion ca mui , lin kt cng ha tr phn cc trong phn t nc v lin kt ion lng cc gia cc ion v phn t nc .

20

Tinh th hc

Chng 2 : Cu trc tinh th

2.1 Phng php din t cu trc tinh th
2.1.1 Nguyn l xp cu :
din t cu trc tinh th c nhiu phng php nhng trong tinh th hc thng dng qui tc qu cu chng kht . Gi s ta c 1 s ln cc qu cu kch thc nh nhau , ta hy xp chng vo 1 khong khng gian gii hn cho cc qu cu u tip xc vi nhau sao cho cht st nht . C th c nhiu cch xp cu tha mn iu kin ny , trong c 2 cch n gin v c tnh cht c bn i vi tinh th hc . Ta xp tng lp mt . Trn mt mt phng khi cc qu cu xp khit nhau th c mi qu cu s tip gip vi tt c 6 qu cu khc xung quanh . Nu c 1 lp cu tng t , mun xp ln trn lp th nht cho kht , th phi t sao cho c mi qu cu ca lp th 2 lt vo ch trng gia 3 qu cu ca lp th nht v ngc li mi qu cu ca lp th nht cng lt vo ch trng ca 3 qu cu lp th 2 . l v tr cn bng bn vng , khin 2 lp cu khng th trt ln nhau m x dch c .

Nu ch c 2 lp cu th ta ch c mt cch xp duy nht . Nhng xp kht lp th 3 ln 2 lp ny th cng nh trn ta phi t sao cho mi qu cu ca lp th 3 vo gia 3 qu cu lp th 2 . Ta c 2 cch : Cch th nht: Di mi qu cu ca lp th 3 s c 1 qu cu ca lp th nht . l kiu xp cu lc phng ( t qu cu lp th 3 vo hng T). Cch th 2 : Di mi qu cu ca lp th 3 khng c qa cu no ca lp th nht . l kiu xp cu lp phng (t qu cu lp th 3 vo hng B ) . Hai kiu xp cu trn ging nhau t l khng gian b chim 74,05% , mi qu cu u c 12 qu cu tip gip .

2.1.2 Cc hng trong hai kiu xp cu

D xp cht nht , cc qu cu cng ch chon gn 3 / 4 khng gian . Gia chng l cc hng trng . C 2 loi hng hnh dng khc nhau . -Hng t din (T) to nn bi 4 qu cu . Ni tm 4 qu cu ny ta s c 1 hnh t din . -Hng bt din (B) to nn bi 6 qu cu . Ni tm 6 qu cu ny ta c mt hnh bt din . Hai kiu xp cu c s cng c 1 s lng hng nh nhau : ng vi n qu cu th c n hng bt din v 2n hng t din . Qua hnh trn cho thy mi qu cu c 6 hng bt din . Mc khc mi hng bt din li l chung cho 6 qu cu , do mi hng ch c 1/6 thuc qu cu cho . Nh th tnh trn mi qu cu ta c 1/6 x6 = 1 hng bt din . Tip tc , quanh mi qu cu c 8 hng t din . Mi hng t din li chung cho 4 qu cu nn mi hng t din ch c 1 / 4 thuc qu cu cho . Cho nn s hng t din tnh trn mi qu cu l 1/ 4 .8 = 2 . Cng c th tnh bng cch khc . c 2 kiu xp cu u nhn thy trn mt mt phng c 1 dy hng bt din xen k vi 2 hng t din . V vy s hng t din gp i s hng 21

Tinh th hc bt din . Ngoi ra , cc dy hng t din khc nhau v nh hng : C 1 dy hng nh t din ln trn li nm cnh 1 dy hng nh t din xung di . Hai kiu xp cu khng ging nhau v v tr tng i ca hng bt din v t din . Nu dc hng phn lp di mi hng bt din l 2 hng t din th l cch phn b hng trong h lp phng . Trng hp su phng c trng bng nhng dy hng cng loi dc theo hng phn lp . 2.1.3 Kch thc cc hng : Kch thc hng c nh gi bng bn knh qu cu ln nht c th t vo hng . Biu din hng t din :

K hiu bn knh nguyn t l R , bn knh hng l r qua r hnh v ta c :2R= a 2 (1) ; R+r = a 3 (2) Thay a c a (2) t (1) ta c R+r=
1 2R 3 3 3=R r = R( 1) = 0,225 R 2 2 2 2 1 2

Tng t nh vy ta tnh kch thc hng bt din v hng lp phng . Cc hng c vai tr quan trng trong nhiu trng hp . V d : trong qu trnh to thnh hp kim hoc chuyn pha , trong nhng iu kin xc nh, mt s nguyn t ca nguyn t hp kim chim ch trong cc loi l hng khc nhau ca mng kim loi nn , nu chng c kch thc ph hp , kt qu dn n thay i cu trc v tnh cht ca vt liu .

2.1.4 ngha ca nguyn l xp cu i vi ha hc tinh th

Nhiu nguyn t ha hc c kiu cu trc ca 1 trong 2 loi xp cu trn . V d : ng , vng, bc c cu trc tinh th chng kht kiu lp phng (hnh a) . Cn Mg , Zn , Be ... cc nguyn t chng kht kiu lc phng (hnh b). A A

z z z

z C B b)

a) Nguyn l xp cu cng hu hiu khi p dng m t cc hp cht ion . Trong cu trc ca chng nhng anion thng ln hn cation v kch thc v c xem l nhng qu cu xp kht nhau . Cc cation kch thc b hn nm cc hng . Trong tng trng hp c th , cc cation c th chim cc loi hng bng nhng phng thc ring .V d Trong cu trc NaCl , cc anion Cl- xp theo kiu lp phng , cc cation Na+ b hn chim ht s hng bt din . Trong nikelin (NiAs ) cc cation niken cng chim ht s hng bt din ca kiu xp cu lc phng do cc ion asen to nn . Trong cc v d trn t s s lng ion A :X trong n v cng thc u l 1:1 . Vic cc cation chim ht s hng bt din l ph hp vi s lng cc hng ny . Trong cc trng hp khc , t s Anion : Cation vn 1:1 nhng cc cation trong cu trc li khng phn b ti cc hng 22

Tinh th hc bt din m ti cc hng t din . ng nhin s hng t din ch b chim mt na . l trng hp ca sulfua km ( ZnS ) vi kiu xp cu lp phng (trong sfalerit) v kiu xp cu lc phng ( trong vuazit ) ca cc nguyn t lu hunh . Hng 4 mt y c 2 loi ( khc nhau v hng ) , cc cation km lp 1 trong 2 loi . Ngoi ra,trong hp cht loi AX cc cation cn c th chim 1 / 2 s hng t din bng nhng cch khc , l 1 trong nhng nguyn nhn lm cho cu trc thm a dng Cu trc ca cc hp cht loi AX2 cng c th ly 1 trong 2 kiu xp cu ca cc anion lm nn tng . S cation ( bng 1 / 2 ) c th chim 1 / 2 s hng 8 mt theo nhiu phng n khc nhau ( chng hn chng chim theo dy , c 1 dy hng cha cation li xen k 1 dy hng trng ; hoc theo lp , c 1 lp hng cha cation li chng ln 1 lp hng trng . V d : cc cation Cd2+ trong CdCl2 v CdI2 chon cc hng bt din thnh tng lp , khin cc hp cht loi ny cng phong ph v mt cu trc . Cc hp cht loi A2X3 , cc cation c th chim 2 / 3 s hng bt din do cc anion to thnh . V d : Al trong Al2O3 xp theo kiu sau:Dc bt c dy hng bt din no , c mt hng cha Al li xen k 2 hng trng . Cc hp cht cng thc A2X ( Li2O , Na2O ... ) c th c cu trc nh sau : Cc anion xp theo lut xp cu no , cc cation lp y cc hng t din . Php xp cu khng ch s dng m t nhng hp cht thuc 2 h tinh th c tnh i xng cao nht m nhng cu trc phc tp ca silicat cng c th m t c bng php xp cu (Pyroxen , amfibol ... ) Ngoi ra i vi nhng cu trc ca cc hp cht phn t php xp cu vn p dng c chng mc nht nh . Trng hp ny cc phn t c xem nh c dng cu . Phng php din t theo nguyn l xp cu ny u vit ch khng nhng cho ta khi nim v s phn b ca cc anion m cn cho bit qui lut phn b ca cation trong cu trc v mc cha y cation trong khng gian . Mt khc n c 1 ng dng quan trng l gp phn xc nh cu trc nhng hp cht mi . Nh nhng suy lun n thun hnh hc ngi ta c th gi nh nhiu s cu trc cho hp cht ang nghin cu . Nhng s s em ra th nghim chn ly s hp l . Tuy nhin y khng phi l phng php chnh xc v cc ht cu trc khng thc s l dng cu

2.2 S phi tr v hnh phi tr

Trong mt mng gi thit l v hn , mt nguyn t ( hay ion ) Ai s c bao bc bi mt s v hn cc nguyn t hay ion Aj khc, nhng khong cch ( gia cc nguyn t hay ion ) dj thay i . Gi tr nh nht d ca dj l khong cch gia Ai vi cc lng ging gn nht . Trong m hnh cu cng , n tng ng vi tng bn knh 2 qu cu tip xc nhau . S phi tr ca nguyn t hay ion Ai biu th s lng ging gn nht V , k hiu l x. A /V = [x] . Ni tm cc nguyn t (ion ) Aj vy quanh nguyn t (ion ) cho Ai bng nhng on thng s nhn c hnh phi tr ca nguyn t (ion) . S phi tr khng c th nguyn v khng ph thuc vo bn cht ha hc cc lng ging ca n . i vi mt hp cht c cng thc chung l AmBn , ta xc nh cc s phi tr ca mi cht A hoc B vi chnh n ( v d A/A, B/B ) v vi cht khc (A/B hay B/A) Ch mt trong ba khong cch dAA , dBB, hay dAB tng ng vi khong cch d cho nhng lng ging gn nht . Nh vy trong tinh th mui n (halit ) s phi tr Na+ /Na+ ; Cl-/Cl-; Na+/Cl-; Cl-/Na+ bng bao nhiu v hnh phi tr tng ng l hnh g ? Biu din s phn b ion trong mng li NaCl :

23

Tinh th hc

y mi ion Na+ hay ion Cl+ c bc quanh bi 4 ion khc du , cn 2 ion na nm bn trn v pha di ion trung tm . Vy trong tinh th mui n s phi tr Na+ /Cl-- , Cl/Na+ l 6 v hnh phi tr l bt din .Tng t nh vy Na+/Na+ = Cl-/Cl- = [12] Trong cc kiu cu trc tinh th ta hay gp 1 s s phi tr nh sau : Sft a din phi tr 3 Tam gic u 4 T din 6 Bt din 8 Lp phng Trng hp cc ion cng kch thc xp rt st c th s phi tr cc i l 12 . Cc kim loi d xp cu loi g cng c sft = 12 v c hnh phi tr l hnh 14 mt gm 6 mt vung v 8 tam gic u ( hnh a) Him hn c s phi tr 2 v hnh phi tr l hnh 2 qu t c trng cho 2 nguyn t xy trong CO2 kt tinh . Hnh phi tr c trng cho sft = 5 l hnh thp t phng ( hnh b). V d : Khong millerit ( NiS ) , cc nguyn t Ni nm gn st y vung ca thp . Vi sft = 6 nhng Mo trong molipdenit MoS2 c hnh phi tr l lng tr tam phng ( hnh c). Cn Sb trong antimonit Sb2S3 c sft = 7 v hnh phi tr do 1 lng tr tam phng v 1 thp t phng ghp li vi nhau qua mt gng ( hnh d).

hnh b hnh a hnh c

hnh d

y ta chp nhn gi thit n gin ha coi mi ion l 1 qa cu cng c bn knh xc nh . Cn trong thc t khng phi vy . Tr s bn knh ion khng nhng ph thuc vo bn cht thin nhin ca nguyn t b ion ha m cn ph thuc vo trng thi ion trong mng li tinh th nht nh , ch yu l ph thuc vo in tch ion . V d : rMn 2 + = 0 , 91 A ; rMn 3 + = 0 , 67 A ; rMn
0 0

= 0 . 52 A 0

24

Tinh th hc Tnh cht phn cc ca cc ion bn cnh trong tinh th c nh hng ln n bn knh ion cho .

2.3 Cu trc cc n cht

2.3.1 Cu trc lp phng tm din F
Cu trc ny in hnh ng , ngoi ra cn c nhiu kim loi khc : Kim th trung gian (Ca,Sr) ; Kim loi cui dy chuyn tip ndY ( vi y t 6 n 10 ) v d Fe...Cu, Rh ... Ag , Ir ...Au ; cc kim loi Al,Ce, Yb,Pb Th .v mt s phi kim c lin kt phn t ( mi kh qu trng thi rn ) . mng c s : Lp phng tm din Cc nguyn t t nh v tm cc mt hnh lp phng vi thng s aF (ch s F nh li kiu mng Bravais ) . Cc mt phng ca nhng hnh cu tip xc nhau c xp chng vung gc vi ng cho ca lp phng hay L3 . Thng s mng aF = ? Xt mt y lp phng , cc nguyn t hay qu cu tip xc nhau theo ng cho ca mt lp phng . Vy : aF 2 =4R aF= aF S m t Z : cht st P :
4R 2
= 2R 2

S phi tr [x]:
Z=8.1/8 + 6.1/2 =4

A/A = [12]

4 4 16 3 Z R 3 R 4 R 3 3 3 3 = = = 0,74 P= 3 3 3 aF (2 R 2 ) 16 R 2 3 2

y khng gian b chim ~74% nn tn ti cc hng tinh th hc ; l cc hng bt din (B) v t din (T). Hng B nm ti tm lp phng v trung im ca cc cnh S hng B s l : NB = 1 + 12/4 = 4 Hng t din T nm tm ca 8 lp phng con hay nm trn 4 ng cho ca lp phng (4L3) . S hng T s l : NT= 8.1= 8 Nhn xt : - S hng B bng s nguyn t hay s mt ca mng . - S hng T gp i s nguyn t thnh phn ca mng - Cc hng T m t mt tp hp lp phng n gin vi thng s a=1/2aF Kch thc hng T,B c nh gi bng bn knh qu cu ln nht c th t vo hng Cc hng c vai tr quan trng trong nhiu trng hp . V d : trong qu trnh to thnh hp kim hoc chuyn pha , trong nhng iu kin xc nh, mt s nguyn t ca nguyn t hp kim chim ch trong cc loi l hng khc nhau ca mng kim loi nn , nu chng c kch thc ph hp , kt qu dn n thay i cu trc v tnh cht ca vt liu .

2.3.2 Cu trc lc phng compac H

l cu trc ca rt nhiu kim loi : Cc nguyn t u tin ca ct 2 (Be,Mg) v ct 12 (Zn,Cd) , cc nguyn t chuyn tip ( ct 3,4,7 v 8) v phn cui ca dy lantan (Gd...Tm) mng c s :Trn c s xp cu lc phng biu din khng gian dng khng compac ca mng H (hnh a) Ta thy trong mi lp xp chng , mi nguyn t u c 6 lng ging r rt . Lng tr lc phng l a din c trng cho i xng lc phng . Tuy nhin kiu m t ny ch l biu din thun ty quy c v mng .V mng c s phi c th tch nh nht c lp li theo s tnh tin t 25

Tinh th hc gc khng cho php coi mt lng tr nh vy l mng c s . Lng tr lc phng compac l mt lng tr trc thoi (1/3 lng tr lc phng ) (hnh b) . y l hnh thoi IKJ. Cc thng s ca mng : A Gc IOK =1200 IJ = JK = OK= OI= ah Cc qu cu mt y tip xc nhau : ah=2R ; h=Ch/2=QG B G l tm ca tam gic u IOJ . Cc qu cu tip xc nhau nn OQIJ l t din . QI=QJ=QK=OI=OK=IJ=KJ =ah nn A Z a)

Ch Q O X
QG=h=
IQ
2

K P J b)

IG

IQ

2 IP ) 2 = 3

2 ah (

2 3 2 ah ) = 3 2

2 2 ah = ah 3

2 = 2R 3

2 3

Ch =2h = 2R

3 8

Hai thng s Ch v ah lin h nhau theo h thc :

Ch 8 = = 1,63 ah 3

T s Ch/ah ny l 1 c trng bit xem trong 1 tinh th lc phng thc , vic xp chng cc nguyn t c l l thng khng . Tht vy :
Ch = 1,63 S xp chng cc qu cu l cht st l tng ah C Vi Be : h = 1,57 S xp chng l cht st nhng b dt theo OZ . ah C Vi Zn : h = 1,86 S xp chng l cht st nhng b dn di theo OZ ah C Vi C : h = 2,73 S xp chng khng cht st grafit . ah

Vi Mg :

S mt Z :
Z= 8. 1/8 + 1 = 2 hay Z = 4.1/6 + 4.1/12 + 1 = 2

cht st P :

26

Tinh th hc

4 3 R P= 2 3 = a h C h sin 60 0 Z

4 3 R 3 = = 0,74 ( ging cht st ca mng lp 8 3 3 2 2 (2 R) 2 R 3 2 2

phng tm din ).

S tng t gia 2 tp hp F v H :
Hai tp hp ny thhc t khc nhau v tnh i xng v m ca chng , lp phng i vi F v lc phng i vi H do c 2 hay 3 lp chng nhau . Tuy nhin chng rt ging nhau v c 2 du c cht st P=0,74 v chung s phi tr 12. S ging nhau ny cho php xt ti s c mt cc hng xen k kiu bt din B v t din T trong mng H vi Z=2 cho 1 mng . NB=2 v NT = 4 mi mng . Cu trc dng lp phng tm din to thnh nhiu mt phng trt ( cc mt phng cha nhng nguyn t gn nhau nht ) . l cc mt phng vung gc vi 4 trc i xng bc 3 ( bn ng cho ca lp phng ) . Nh s trt ln nhau ca chng m c th dt mng hay ko di mt thanh kim loi . Cu trc dng lc phng ch c mt loi mt phng trt ( mt phng vung gc vi trc i xng bc 6 ) nn kh nng dt mng ko si ca chng km hn . Bi tp : 1/ Khi lng th tch ca nhm , kim loi kt tinh theo h lp phng kiu mng lp phng tm din l : V=2,7 103 kg/m3 . -Xc nh thng s ac ca mng nhm -T suy ra gi tr bn knh nguyn t . Gii : V= 2,7 103 kg/m3
ZM a = 405 pm a3Na

4R =a 2 R= a 2 /4 =143pm 2/ Coban , bn knh nguyn t 125pm . Kt tinh theo h lc phng cht st . - Xc nh thng s ah v Ch mng - Kim tra li nu khi lng th tch thc nghim V= 8,9 g/cm3 ph hp vi c s tnh ton khng . ( Thay gi tri R = 125pm vo cng thc phn trn )

2.3.3 Cu trc l p phng tm khi I

Cu trc ny l ca mi kim loi kim ( in hnh l Na) v ca nhiu kim loi chuyn tip nh -Fe , Eu , ca V , Mo , W...

mng c s :
Z A B A X aC Y Trong mng I , tp hp khng cn l cht st na , cc qu cu khng st nhau trong mt lp nhng st nhau gia cc lp . Vi chng kht kiu ABAB .. mng chp nhn mt mng lp phng tm khi , trong cc qu cu tip xc nhau dc trn ng cho ca hnh lp phng . a 3 =4R a =
4R 3 = 4R 3 3

S mt Z :
Z = 8.1/8 + 1 = 2 S phi tr : E/E =[8] ( nh hn so vi kiu F v H ) 27

Tinh th hc

cht st P : Nhn xt :

4 2 R 3 3 P= 3 = = 0,68 8 3 3 (4 R ) 3

Gim ng thi cht st v s phi tr khi chuyn t cc mng F v H sang I ; compac ca mng cng ln khi s phi tr cng ln v ngc li Dng lp phng tm khi c cu trc tng i rng nn gin d v ( V, Mo, W ) . Ring i vi kim loi kim , chng c bn knh ln nht so vi cc nguyn t khc ng sau n trong cng chu k nn lc ht gia cc nguyn t ln cn nhau yu . Trong tinh th cc nguyn t lin kt vi nhau bng lin kt kim loi yu , do vy m cc kIm loi kim c : - Khi lng 3 3 ring nh ( 0,53g/cm Li n 1,9 g/cm Cs . - Nhit nng chy , nhit si thp . Nhit nng chy nh hn 2000C - cng thp ( c th dng dao ct ) - dn in cao

Hng tinh th hc :
Cng nh trong mng F v mng H , tp hp mng tm khi c cc hng xen k . Tuy nhin , ngc vi cc tp hp F v H , nhng a din phi tr I khng cn u na . Cc hng B v T b bin dng , gi l B ( NB =6) v T (NT =12) . V tr C l hng B :C 4 lin kt di : A1 a 2 CA1 = CA2 = CA3 =CA4 = v 2 lin kt ngn
2

A2 E A5 D C A4 A6

A3 =6 NB = 6.1/2 + 12.1/4 V tr E chnh l hng T . NT = 4.6.1/2 = 12.

CA5 = CA6 =a/2 ( c 6 v tr nh vy tm ca 6 mt ) V tr D l hng B : C 4 lin kt di : DA5 = DA6 = ...=CA2 v 2 lin kt ngn l DA2=DA3 =a/2 ( c 12 v tr nh vy trung im ca 12 cnh ) Nh vy s hng B :

2.3.4 Cu trc lp phng n gin P

Thng s mng a=2R S phi tr E/E = 6

4 3 R 3 = = 0,52 cht st : P = 3 6 (2 R)

S hng lp phng Nc =1 S mt Z=1 Trong thc t khng c n cht no kt tinh dng mng lp phng n gin P .

2.3.5 Cu trc kiu kim cng D

ns np .
2 2

y l cu trc in hnh ca cc n cht : Si , Ge , Sn vi cu hnh lp ngoi

M t mng : Trong cu trc kim cng , cc nguyn t cacbon chim ng thi mi v tr ca

mng lp phng tm din F v mt na s hng t din ca n . 28

Tinh th hc

S phi tr : V mt s nguyn t t cc hng t din

T , s phi tr ca nguyn t cacbon E/E=4 S phi tr ny l s phi tr ca mi nguyn t ca mng v nhng nguyn t thuc mng F mt s phi tr thng thng [12] ca n tp hp ny . Nh vy : Cu trc ca kim cng gm cc t din ni vi nhau bi cc nh chung .

S mt : Z = 4 + 8.1/8 + 6.1/2 =8 Thng s mng : T hnh m t mng ta thy khong cch ngn nht gia cc nguyn t cacbon
(dc-c=2R) l trn ng cho chnh ca lp phng
3 3 3 a = 4.2 R = 8R 3 3 4 4 4 Z R 3 8. R 3 3 = = 0,34 ( Nh hn c mng P v I ) cht st P : P = 3 3 = 3 16 a 3 3 (8R ) 3

d=a

Kim cng kt tinh trong h lp phng kiu mng lp phng tm din nhng tp hp ca n l khng compac . Kt qu ny c gii thch nh sau : -Hng T c kch thc gii hn l vo y qu ln
r 0,225 ( coi r l bn knh qu cu ln nht lt R

vo hng T hay kch thc hng T , R l bn knh nguyn t cacbon ) , cc nguyn t cacbon xen
r = 1 s y cc nguyn t C chim cc v tr thng thng ca mng lp R

phng tm din ra xa , chng khng cn tip xc vi nhau na . H qu : Trong cu trc kiu kim cng mi nguyn t u c s phi tr bng 4 ( lin kt vi 4 nguyn t khc , l lin kt cc i on c t qui tc bt t : K=8-N cho cc nguyn t c 4 electron ha tr) . V cc nguyn t l nh nhau nn cng m in , lin kt trong kim cng thun ty cng ha tr vi gc C-C-C chnh xc l 109,470 , gi tr c trng ca cu trc t din , tinh th kim cung l mt i phn t cng ha tr 3 chiu . V mi electron u cp i nn kim cng l mt cht cch in v nghch t . Ch s khc x ca n l cao nht . Nng lng lin kt rt ln lm cho kim cng c nhit nng chy cao ( > 35500C ) , cng bng 10 theo thang Mohs Tnh trong ca n c gii thch nh sau : Nng lng tia kh kin khng mnh ph v lin kt C-C kch thch electron di chuyn trong tinh th . Cc nguyn t cng nhm nh Si , Ge , khng nh vy ; chng nhy hn vi nh sng nn m c v c th dn in ( c dng lm cht bn dn ) ; Sn c tnh cht kim loi r rt ( dn in , dn nhit ) . Nhit nng chy ca thic thp ( 2700C) .

2.3.6 Cu trc grafit G

Grafit l mt trong nhng dng lc phng ca cacbon , n l v d hon ho v vt liu 2 chiu vi bn cht cu trc lp . 29

Tinh th hc Ton b tinh th c th m t gm nhng lp cacbon xp chng ln nhau . Cc nguyn t cacbon trong mi lp gn nh nm trn mt mt phng gm nhng mt lc gic u . Hai lp nguyn t lin nhau khng tng ng v v tr . Cc mt li khng i din nhau . Cc lp phn b c qui lut, c th m t nh sau : Lp trn chu s tnh tin ngang 1 on bng v ln v phng 1 lin kt C- C ( d1=142pm ) . Lp th 3 tng ng vi lp ban u . - d1 = 142pm =2R; gc C-C-C l 1200 c trng cho cu trc tam gic u . d1 = d1 d2 Ch -Khong cch gia cc nguyn t cacbon 2 lp cnh nhau l rt ln d2=335pm, t s
ch = 2,73 ln hn 1,633 nhiu chng t cu ah

3d 2 2 3 3.2 R 3 a h sin 60 0 = ah ah = 1 = = .142 = 246 pm 3 3 2 3 3 3

trc khng cht st . - Lin kt gia cc lp l rt yu , c bn cht tng t nh lin kt Van-dec-van. Do than ch c tnh cht lp v mm . - Lin kt gia cc nguyn t cacbon trong mt lp kh bn , c bn cht ging nh lin kt trong benzen . y ta cng phn bit 2 dng lin kt . Nhng electron c cp i vi ah nhau v hnh thnh lin kt c cp c nh , cn nhng electron c th chuyn ng t do trong mt phng ca nhng vng 6 cacbon . V nh vy ngc vi kim cng , grafit dn in v dn in mnh theo phng song song vi mt phng XOY , ln hn 200 ln so vi phng vung gc . - Qui lut xp cu ch th hin trong phm vi tng lp

2.3.7 Lin h gia bn cht ca lin kt ha hc v kiu cu trc Cc n cht lin kt kim loi :
+ Kt tinh dng mng lp phng v lc phng . + S phi tr ln : 8 + cht st ln

Cc n cht kim c dng lin kt cng ha tr :

+ Cng kt tinh dng mng lp phng v lc phng

+ S phi tr nh + cht st nh Nguyn nhn : Mi nguyn t ca cht lin kt ng cc ch c th to thnh s mi lin kt ng cc ti a l K=8-N ( N l s hiu cc phn nhm ca bng tun hon , l nhng nguyn t thuc cc phn nhm ph na bn phi ca bng h thng tun hon ; nh vy N y bng 4, 5, 6, 7 ). Theo qui tc bt t ny ta d dng nhn c c im cu trc tinh th ca nhiu n cht . Chng hn , cu trc tinh th ca hydr v ca cc halogen gm nhng phn t ch cha 2 nguyn t : S mi lin kt K = 8-7=1 . Trong cu trc tinh th ca cc nguyn t thuc phn nhm ph 6 , nhng phn t ca chng thng c dng vng kn lu hunh v dng mch selen . Mi nguyn t lu hunh hay selen ch to thnh 2 mi lin kt ng ha tr . + Cu trc ca lu hunh : Phn t gm 8 nguyn t xp trn 2 mt phng song song to thnh phn t S8dng vng 2 tng : 30

Tinh th hc

Cc phn t ny ni vi nhau bng lc yu , lc Vandecvan . + Cu trc ca selen : Se Se Se Se Se Se

Tng t , mi nguyn t thuc phn nhm ph IV (C , Si , Ge , Sn ) u c kh nng xy dng 4 mi lin kt ng cc vi 4 nguyn t khc cng loi : C C

Do cc mi lin kt ng cc u c hng to vi nhau thnh nhng gc nht nh , v vy dng lin kt ny cc nguyn t thng c s phi tr thp . Khc vi dng lin kt ng ha tr , dng lin kt kim loi khng c nh hng . Lc lin kt ca mi nguyn t hng v mi pha vi ln nh nhau ( c i xng hnh cu ) . V th , trong mng tinh th ca n , nguyn t kim loi c xu hng tp hp quanh n mt s ln nht nhng nguyn t k cn . Xut pht t yu t hnh hc n thun l t s bn knh cc ht bng 1:1 c th thy cu trc kim loi vi dng lin kt ca n t n s phi tr cao nht ( thng l 12 ) V mt lin kt khng nh hng ca kim loi li tng t lin kt ion . Nhng tinh th ion khc tinh th kim loi ch : Lc lin kt ion l lc tng tc gia nhng ion tri du , s lng anion v cation trong n v cu trc ( cng thc ) xc nh do s cn bng ha tr , cn in tch dng v m trong tinh th kim loi vn cn bng . Cng v th , nguyn t ca cc nguyn t ny c th to thnh nhng hp cht thnh phn khng c nh - Cc hp kim .Nhng quan nim thng thng v cn bng ha tr ca cc nguyn t khng ct ngha c thnh phn ha hc ca phn ln cc hp kim . Thnh phn ca chng khng tun theo nh lut cn bng ha tr n gin v c th bin i trong nhng gii hn ln .

2.4 Cu trc cc hp cht ion 2 nguyn t

Cng thc tng qut : CXAY -Trong C l cation ; A l anion . -Trong tinh th ion : Tng nhng in tch dng phi ng bng tng nhng in tch m . Ngha l tinh th trung ha in tch . - cu trc bn vng cc ion tri du phi tip xc nhau . Cc anion c th tip xc nhau hoc cch nhau mt khong xc nh . Cc anion c bn knh ln hn cation nn cc anion s xp cu to mng ch , cc cation in vo cc hng trng . Kch thc cc hng trng y c hi khc vi kch thc trong cc n cht . Xt cu trc tinh th halit NaCl :

a 31

Tinh th hc

: y mi ion Na+ hay ion Cl+ c bc quanh bi 4 ion khc du , cn 2 ion na nm bn trn v pha di ion trung tm . Vy trong tinh th mui n s phi tr Na+ /Cl-- , Cl/Na+ l 6 v hnh phi tr l bt din .Tng t nh vy Na+/Na+ = Cl-/Cl- = [12] Nh vy c s phi tr 6 th quan h ca kch thc cc ion nh th no ? hay ni cch khc iu kin c s phi tr 6 ? Hay kch thc cc cation nh th no lt vo hng bt din . Xt tit din ca bt din c cha cc ng cho . di ca ng cho bng cnh a ca lp phng. Cnh ca tit din bng a cos450 = a Ta c : 2rA a
2 2

rA a rC rC

2 (1). iu kin cc cation C v anion A 2

2 (rA + rC) hay 1

tip xc nhau l : 2(rA + rC ) = a (2) T (1) v (2) : 2rA

rC 2 1 0,414 rA 2 2

(1 +

rC ) rA

Tr s 0,414 l gii hn di ca t

s bn knh ion i vi loi cu trc c 1 ion bc quanh bng 6 ion ngc du Vy gii hn trn l bao nhiu ? v khi rC / rA < 0,414 th sao ?. Ta thy rng khi gi nguyn bn knh ion vy quanh m bn knh ion trung tm gim xung th cu trc tinh th khng bn vng , v ta bit mng tinh th ch bn vng khi no cc ion khc du tip xc cht ch vi nhau . Do khi rC / rA < 0,414 th s ion khc du vy quanh phi gim xung v n s bn khi s phi tr bng 4 . Ngc li , khi tng bn knh ion trung tm ln n gi tr rC/rA = 0,73 th ion trung tm s c 8 ion vy quanh xp st cht , v ta ni s phi tr bn vng nht trong trng hp ny l 8 . C th : Dng hnh phi tr ca trng hp s phi tr 8 tnh rC/rA . Ta bit ion c s phi tr 8 th hnh phi tr l lp phng

rC

32

Tinh th hc

Ga thit anion A cc nh ca lp phng v c bn knh rA . a l cnh ca lp phng . Ta c : 2rA a (1) Gi rC l bn knh ca cation C. Cation ny tm ca lp phng .iu kin cho cc ion A v C tip xc nhau l : 2 ( rA + rC ) = a 3 (2) T (1) v (2) ta c : 2rA
2 ( rA + rC) ; chia 2 v cho 2rA ta c 1 3 1 r r (1 + C ) C 3 1 = 0,733 rA rA 3

Trong cc kiu cu trc tinh th ta hay gp 1 s s phi tr nh sau : Sft

rC rA

a din phi tr

3 0,15 < 0,22 Tam gic u 4 0,22 < 0,41 T din 6 0,41 < 0,73 Bt din 8 0,73 <1 Lp phng Trng hp cc ion cng kch thc xp rt st c th s phi tr cc i l 12 . Cc kim loi d xp cu loi g cng c sft = 12 v c hnh phi tr l hnh 14 mt gm 6 mt vung v 8 tam gic u . Nh vy : T t s
RC nhn bit loi hng m cation chim ch : RA R + 0,225 C <0,41 : Hng t din RA R + 0,41 C <0,73 : Hng bt din RA R + 0,73 C <1 : Hng lp phng RC

2.4.1Cu trc kiu Clorua cesi CsCl

Ta bit RCs =168pm ; RCl =181pm ; suy ra
+

nn Cs+ s nm trong hng lp phng to bi cc anion Cl- . C th biu din theo hnh v sau :

RC 169 R = = 0,934 0.73 < C < 1 R A 181 RA

Cl-

Nhn xt : -Khng theo qui lut xp cu c bn no . - Khng phi mng lp phng tm khi ; m do 2 mng lp phng n gin cng kch thc lng vo nhau v cch nhau 1 /2 ng cho khi ca mng . - S mt CsCl l 1 S tip xc ca cation Cs+ v anion Cl- dc theo ng cho ca lp phng cho ta gi tr l thuyt ca thng s33 mng

Cs+

- aCsCl :

aCsCl

Tinh th hc

a CsCl

3 = 2 ( rC + r A ) a CsCl =

2 3

( rC + r A ) =

2 3

(169 + 181 ) = 404 pm

- cht st P :
4 3 4 3 rC + rA 4 (169 3 + 1813 ) 3 3 P= = = 0,683 ( ln hn mng lp phng n gin) 3 3 aCsCl 404 3

S phi tr : Cs+/Cl- = Cl-/Cs+ =[8]; Cl-/Cl- = Cs+/Cs+ =[6] Cu trc kiu CsCl l cu trc ca cc halogenua MX : Trong M l ion kim c kch thc ln nh Cs ( tr CsF) , l NH4+ , l Ta( Tali ) tr TaF . Cc oxyt v hidrua khng c cu trc kiu ny . + R Na = 97 pm; RCl = 181 pm

2.4.2 Cu trc kiu Clorua natri NaCl

Na+ chim cc hng bt din to bi Cl- . Biu din nh sau : Cl Na RC R 97 = = 0,536 0,41 < C < 0,73 R A 181 RA

y l 1 trong cc kiu cu trc ph bin nht Cc anion phn b theo qui lut xp cu lp phng ABCABC...cc cation chim ht cc hng bt din . Hay t 2 mng lp phng tm din ( 1 ca Na+ , 1 ca Cl- ) cng kch thc lng vo nhau v lch nhau 1 /2 thng s mng a

- S mt NaCl : Z=4 - Thng s mng a : V cc ion Na+ v Cl- tip xc nhau dc theo cnh lp phng nn theo l thuyt : aNaCl = 2 ( RNa+ + RCl-) = 2( 97+181) = 556pm ( gi tr thc nghim 564,1pm) - cht st P :
4 3 4 3 4( R Na R ) + + 3 3 3 Cl = 16 (97 + 181 ) = 0,667 P= 3 3 3 a NaCl 556 3

( Gi tr ny gn vi ga tr ca cu trc CsCl nhng nh hn cu trc lp phng tm din ) - S phi tr : Na+/Cl- = Cl-/Na+ =[6] ; Na+/Na+ = Cl-/Cl- = [12] Kiu cu trc ca halit c trng cho cc halogenua ca kim loi kim ( tr halogenua Cesi ) , ca bc ( tr itua bc AgI) , cho cc oxyt , sulfua v selenua ca kim th cng nh cc sulfua , telurua ch , cng nhiu hp cht khc .

2.4.3 Cu trc kiu Sphalerit ( blende)

Sphalerit l 1 trong cc dng th hnh ca km sulfua ZnS . Mc d m in ca km v lu hunh chnh lch nhau khng ln nhng ta c dng cc ion Zn2+ v S2- m t cu trc ri s bn v chng sau :
RZn 2 + = 74 pm; RS 2 = 184 pm RC R 74 = = 0,401 0,225 < C < 0,41 R A 184 RA

Nn Zn2+ s chim hng t din ca mt trong hai kiu xp cu : Lc phng hoc lp phng ca S2- . S2- xp cu theo kiu lc phng ta c Vuazit ; S2- xp cu lp phng l sfalerit . 34

Tinh th hc - M t cu trc : S2S2-to mng lp phng tm din . S ht S2- trong c s l 4 . m bo trung ha in tch trong mng bt buc ch c 4 ht Zn2+ xp vo 1 /2 s hng T. Hai ht nm 1 /4 a ; hai ht nm 3 /4 a . Nhn xt : Ging cu trc kim cng . Ch khc : hng T l cc ht khc loi vi cc ht xp cu ; cn kim cng ton b u l mt loi C.

Zn2
+

a
- S mt : Z = 4 - S phi tr : Zn2+/S2- = S2-/Zn2+ = [4] ; S2-/S2- = Zn2+/Zn2+ = [12] - Thng s mng a: Xt ng cho ca lp phng : Ta thy 2 qu cu S2- v Zn2+ tip xc nhau trn ng cho lp phng (d) vi gi tr RZn + RS = d = a 3 a =
2+ 2

1 4

1 4

4( RZn 2 + + RS 2 ) 3

4 3

(74 + 184) = 596 pm

- Gi tr thc a= 541,1pm . Sai lch > 10% . iu ny dn n khng th coi Sfalerit l hp cht ion . Hiu m in gia km v lu hunh khng ln to lin kt ion . Lin kt Zn-S c c tnh cng ha tr r hn . L canxi florua . N cn c tn l hunh thch ch s pht hunh quang , nhng kh nng ny th hin yu . Khong vt ny mang tn la tinh l Fluorit c ngha l chy v n tan chy ngay nhit thp . Ngy nay, cng dng ca n l gip cho vic lm chy qung st khi luyn thp v l cht kh bt , cht kh mu ,cht lm tng nhanh qu trnh nu trong cng ngh sn xut thy tinh .
RCa 2 + = 99 pm; RF = 136 pm RC R 99 = = 0,723 0,73 0,73 C < 1 R A 136 RA

2.4.4 Cu trc kiu Fluorin( hunh thch ) : CaF2 (CA2)

Suy ra :S phi tr ca Ca2+/F- = [8]. Nh vy : - F- to mng lp phng nguyn thy v Ca2+ lt vo hng lp phng tng t CsCl . - S anion F- gp i s Ca2+ v in tch ca F- = -1 ; ca Ca2+ = +2 Dn n , cu trc ca CaF2 c th biu din bng 2 cch sau :

Ca2+ F(1) (2)

35

Tinh th hc S ht F- trong cu trc : 8 + 6 + 12 + 1 = 8 S ht F- trong cu trc : 8 S ht Ca2+ trong cu trc : 4

1 8 1 8 1 2 1 4

S ht Ca2+ trong cu trc : 8 + 6 = 4

1 2

Vy s mt trong c 2 kiu u nh nhau : Z = 4 - Thng s mng a : Xt trn ng cho lp phng : ( RC + R A ) = a 3 a =

1 4 4( RC + R A ) 3 = 543 pm

; F-/Ca2+ = [4] - S phi tr : Ca2+/F- = [8] Ca2+/Ca2+ = [12] ; F-/F- = [6] CaF2 bao gm 3 mng lp phng tm din cng kch thc lng vo nhau:Mng th nht vi ta nt u l {[000]} do cc ion Ca2+ chim ; mng th 2 vi ta {[ mng th 3 {[
311 ]} do F- chim . 444 111 ]}v 444

Cc Florua ca Sn , Ba , Ra , Pb , Cd , Hg u kt tinh theo kiu cu trc ny .

2.4.5 Cu trc ca AntiFluorin

Tin t anti c dng trong ha hc tinh th biu th kiu cu trc suy ra t mt kiu cu trc khc khi i v tr cc anion bng cc cation . l kiu ca hp cht C2A suy ra t CA2 . Trong C l cc cation kim ( Li, Na , K ,Rb ) cn A l xy . - M t cu trc : + oxy O2- xp cu kiu lp phng , tc to mng lp phng tm din . + Kim R+ s xp vo hng t din vi cc thng s tng ng O2a ' = 463 pm; a ' = 556 pm; a ' = 645 pm; a ' = 676 pm
Li Na K Rb

-Cho RLi = 68 pm; R Na = 97 pm; RK = 133 pm; RRb = 147 pm - Xc nh s phi tr : R+/O2- =[4] ; O2-/R+=[8] -Cc ion O2- c xp cht sit hay khng 4 xyt kim trn ? Ta thy : Nu xp cht st th cc O2- trong mi lp s st nhau . Ngha l : mt ca mng
+ + + +

R+

4 RO 2 = a 2 a =

4 RO 2 2

= 2R 2

Tnh RO :
2

Xt ng cho lp phng :
( RO 2 + RR + ) =

4( RO 2 + RR + ) a' 3 1 ' a 3 RO 2 = RR + ; a ' = 4 4 3

Lp bng Hp cht Li2O Na2O K2O

RO 2 (pm)

a =( 2 RO 373 404 412

2 ) a

mng st cht khng -

Ghi ch a < a -

132,24 143,47 146

483 556 645 36

Tinh th hc Rb2O

145

410

676

2.5 Cu trc ca tinh th phc tp hn

2.5.1 Phc cht K2[PtCl6]
Kt tinh trong h lp phng tng t Antifluorin . n v cu to l K+ v phc [PtCl]6- . Ion phc to mng lp phng tm din cn K+ chim 8 hng T ( hnh 1). Ion phc l 1 nhm trong Pt4+ c 6Cl- quy quanh chim 6 nh bt din ( hnh 2). K+

Pt4+ [PtCl6]2Clhnh 2

hnh 1

Cu trc ny c trng cho mt s hp cht c cng thc ABX3 . N hnh thnh trong trng hp cation B c kch thc va phn b trong cc hng bt din do anion X to nn . Cation A cng vi X xy dng mng lp phng tm din . Nh th ion A v X phi ging nhau v kch thc . Thng X l xy ; A l cc cation ha tr 2 nh Ca2+ , Ba2+ , Sr2+ , Cd2+ , Pb2+ . B l cc cation ha tr 4 nh Ti4+ , Sn4+ .Zr4+ . Biu din cu trc nh sau :

2.5.2 Cu trc ca Perpskit : CaTiO3

T cu trc ca phc ta khng cn vit di dng KCl.PtCl4 na .

B4+

O2O2B4+ A2+

A2+ (1) 37

(2)

Tinh th hc - S ht O2- : 6 . 1 /2 =3 theo (1) hay 12. 1 /4 = 3 theo (2) theo (1) hay 8 . 1 /8 = 1 theo (2) - S ht B4+ : 1 2+ - S ht A : 8 . 1 /8 = 1 theo (1) hay 1theo (2) S mt ABX3 : Z = 1 Xc nh s phi tr v hnh phi tr tng ng : 2+ 2A /O = [12] ; hnh phi tr l hnh 14 mt ( 6 mt vung v 8 tam gic u ) O2-/A2+ = [4] ; hnh phi tr l hnh vung B4+/O2- = [6] ; hnh phi tr l hnh bt din O2-/B4+ =[2] A2+/B4+ =B4+/A2+ = [8] ; hnh phi tr l hnh lp phng ABX3 l cu trc ca loi cht in mi tartrat . Danh t tartrat xut pht t tn gi cht u tin ngi ta pht hin c nhng tnh cht khc thng . l mui kali-natri tartrat (KNaC4H4O6.4H2O). Tnh cht khc thng l : Tnh st in : l tnh phn cc t pht , tc l phn cc khi vng mt in trung ca cht in mi . Tng t nh tnh st t vt liu c t tnh vnh cu . Trong vt liu st in phi tn ti nhng lng cc in vnh cu . Ta thy iu ny r rng nht BaTiO3 : nhit cao (> 1200C ) , BaTiO3 kt tinh trong h lp phng kiu CaTiO3 (hnh a). Nhng trong mng c s , mi ion titan c 6 ion xy quy quanh m khong cch gia tm ca ion xy v titan ln hn tng bn knh ca chng nn ion titan c th dch chuyn t do trong khong cch gia cc xy ( hnh b) . nhit cao cng chuyn ng nhit chuyn Ti4+ t ion xy ny n ion xy khc v nu v tr trung bnh ca tm ion titan trng vi tm i xng ca mng th tr s mmen in ca mi mng s bng khng do tnh i xng ca n . nhit < 1200C nng lng chuyn ng nhit thng thng khng 4+ chuyn Ti qua li gia cc ion xy bao quanh . Ti4+ thng thng gn 1 trong cc xy v v tr nh vy s lm mt tnh i xng ca cc ion tch in , ng thi trong mng c s s xut hin mmen in . Hnh dng ca mng c s vo lc ny b bin i , mng ko di theo hng ca trc i qua tm ca xy v titan gn nhau nht v c dng lng tr t phng (hnh C)

O2B4+ Hnh b) A2+ 38

Hnh a)

Hnh C)

Tinh th hc Nh vy khi Ti4+ trong mng c s gn 1 trong cc ion xy th ng thi bn thn n v cc ion cng du khc gn nhau nht cng c tc ng n cc ion titan trong nhng mng c s ln cn v lm cho s chuyn dch cc Ti4+ ni chung c tin hnh nhp nhng v cng phng . Chnh s chuyn dch ny dn n vic to cc min phn cc t pht . Trong mi mt min mmen in ca cc mng c s hng theo 1 chiu, nhng trong cc min khc nhau mmen in hng theo cc chiu khc nhau . Do vy nn tinh th khng to bn ngoi mnh mt in trng no . S phn cc ha ph thuc vo nhit v tnh cht phn cc ch th hin trong 1 khong nhit nht nh .Qu gii hn , cu trc tinh th s bin i v tnh cht phn cc s mt i ; nhit ny gi l nhit Curi ( hoc im Curi ) . Ti nhit Curi tr s t cc i . Cc cht st in c hng s in mi cc k cao cc tn s in trng tng i thp . V d : nhit phng hng s in mi ca BaTiO3 l 5000. Do vy cc t in ch to bng nhng vt liu ny c kch thc nh hn nhiu so vi cc t in lm bng vt liu in mi thng thng khc .

Chng 3 Tnh 3.1 Tnh a hnh :

a hnh v ng hnh

a hnh l hin tng trong cc cht c cng thnh phn ha hc li kt tinh theo nhng cu trc khc nhau . V d : cac bon kt tinh theo 2 kiu cu trc khc nhau dn n tnh cht khc bit nhau hon ton . l kim cng thuc h lp phng v grafit thuc h lc phng . Kim cng l 1 khong vt cng nht trong tt c cc khong vt . Tinh th ca n trong sut v khng dn in , t trng 3,51 . Grafit mm hn , tinh th mu en v dn in tt , t trng 2,22 . Ngi ta ni kim cng v grafit l 2 bin th a hnh ca cac bon . a hnh l hin tng rt ph bin . Hu nh tt c cc cht u c th tn ti nhng bin th a hnh ( dng th hnh ) khc nhau . Mi dng th hnh c 1 phm vi tn ti ( ty iu kin ) 39

Tinh th hc trn biu trng thi . Khi bin th ny chuyn thnh bin th khc th cc tnh cht ca n cng thay i theo ( ph thuc vo s phn b li ca cc nguyn t trong cu trc . S chuyn bin gia 2 bin th a hnh c th ch xy ra 1 chiu , ngha l bin th A c th chuyn thnh B nhng bin th B khng th chuyn thnh A c .Tuy nhin bn cnh nhng cht c kh nng chuyn bin 1 chiu li c nhng cht c th chuyn bin 2 chiu . V d : Thch anh tridimit cristobalit Kim cng c th bin thnh grafit . Trong 1 thi gian di , qu trnh ny vn c coi l 1 chiu , nhng ri ngi ta bin c grafit thnh kim cng di p sut v nhit cao - kim cng nhn to . S chuyn bin 2 chiu khng phi lc no cng thc hin c d dng . Thng vn c mt s ngng tr no .Trong mt s trng hp , trng thi n nh tm thi ca mt cht c th tn ti kh lu .Nh thy tinh c th tm thi hng trm nm cha chuyn v trng thi bn vng ca vt cht l trng thi kt tinh Trn quan im ha hc tinh th , ngi ta phn bit ra 4 loi bin i a hnh sau : Loi bin i a hnh c km theo s thay i s phi tr . V d : iu kin thng RbCl kt tinh theo kiu NaCl ( sft = 6 ) nhng khi nhit thp v p sut cao th tinh th RbCl c cu trc kiu CsCl vi sft 8 . Bn thn CsCl nhit 4450C th c cu trc kiu NaCl . Trong trng hp ny hin tng bin i a hnh c lin quan n mc phn cc ca cc ion c ln ( Cs , Rb ) khi iu kin ha l thay i . Buerger ( Bua-ge) a ra qui lut chung cho cc bin i a hnh ch lin quan n s phi tr : Nhng cu trc vi s phi tr ln thng bn vng nhit thp , p sut cao v ngc li . S phi tr nh thng c trng cho cc cu trc bn vng nhit cao hn v p sut thng .V d : Al2SiO5 c 3 bin th a hnh l silimanit , andaluzit v disten . Ba bin th ny khc nhau ch : silimanit : 1 / 2 s Al3+ c sft 6 v 1 / 2 s Al3+ c sft 4 ; to thnh nhit cao Andaluzit : 1 / 2 s Al3+ c sft 6 v 1 / 2 s Al3+ c sft 5 ; to thnh nhit thp hn Disten tt c Al3+ u c sft 6 ; to thnh nhit thp nht . Khi chuyn i a hnh s phi tr lun c bo ton nhng cch thc gn kt cc hnh phi tr ca cc cation thay i.V d : Trong 3 dng th hnh ca SiO2 l thch anh , tridimit . cristobalit th nguyn t Si u c s phi tr 4 nhng mi dng th hnh hnh phi tr t din ca Si gn kt vi nhau theo cch ring . Nu tch tng cp t din k nhau th trong Cristobalit hai hnh i xng nhau qua tm i xng . Trong tridimit chng i xng nhau qua mt i xng . Trong thch anh chng gn kt theo ng xon c . S bin i 2 chiu gia chng din bin chm theo s sau :

8700C

14700C

Thch anh

Triimit

Cristobalit

Bin i a hnh km theo s thay i trt t ca cc ht cu trc . Hin tng ny ph bin trong cc hp kim hay trong trng thch kali 40

Tinh th hc Loi bin i a hnh lin quan n s quay cc phn t ( hay radican ) trong tinh th . Hin tng ny ph bin trong cc hp cht hu c . ng dng ca bin i a hnh :To nn cc tnh cht k thut cn thit . V d : Ch to kim cng nhn to . Ch to 1 s vt liu c cng cao ngoi kim cong lm vt liu mi nh t -Al2O3 ( dng bt mm ) sang -Al2O3 ( ht mi cridn ) . 3.2 ng hnh v dung dch rn 3.2.1 Khi nim chung : Khi nim ng hnh do Mitscherlich a ra nm 1818 ch hin tng ca cc cht khc nhau v thnh phn ha hc nhng li cng hnh dng bn ngoi ca tinh th . ng nhn thy hai hp cht KH2PO4 v KH2AsO4 kt tinh c dng tinh th ging nhau (chng to thnh nhng tinh th dng hnh ghp ca 1 lng tr v 1 lng thp t phng ) . Hay cc mui cacbonat ca 1 lot kim loi ha tr 2 ( ZnCO3 , MgCO3 , FeCO3) , chng c chung lp i xng v cng dng tinh th . T 1913 p dng tia rngen xc nh cu trc tinh th , ngi ta nhn thy rng nhng cacbonat trn cn c chung 1 cu trc tinh th , thng s mng li ca chng xp x nhau . Vy nhng hp cht ng hnh phi ging nhau v hnh dng bn ngoi v v cu trc bn trong .Cho nn ng hnh l s tng hp ca 3 hin tng sau : - S tng t v cu trc tinh th -S tng t v ha hc , c hiu l 1 s nguyn t ca vt cht ny c th thay th c bng 1 s nguyn t ca vt cht kia . Nhng nguyn t ca ca cc nguyn t y c gi l nhng ht thay th ng hnh . -Hai vt cht gi l ng hnh th phi c kh nng to nn nhng tinh th hn hp , ngha l trong cu trc ca 1 tinh th c mt c 2 vt cht trn-gi l dung dch rn . V d :Hai hp cht AX v BX c chung cu trc mng v chung nguyn t X , A v B c kch thc gn nhau , lin kt ha l cng dng . Chng c th to nn dung dch rn nh s sau : AXAXAXAX BXBXBXBX AXBXAXAX XAXAXAXA XBXBXBXB XBXAXBXB AXAXAXAX BXBXBXBX AXBXAXAX y A , B l nhng ht thay th ng hnh .Dung dch rn loi ny gi l dung dch rn thay th .Ta cn c th gp dng dung dch rn gi l dung dch xen k ( xem s sau )

Thay th

xen k S sp xp nguyn t ha tan thay th v xen k vo dung mi c mng lp phng tm din -Mt (100)

41

Tinh th hc Nh vy , trong dung dch rn thay th , cc nguyn t hay ion chim ch hay thay th ng v tr nt mng ( nguyn t hay ion ng hnh vi n ) . Trng hp dung dch rn xen k, cc ht ( nguyn t hay ion ) xen k vo cc hng trng to bi cc nguyn t hay ion dung mi( nu trong dung dch lng cu t no nhiu hn c gi l dung mi v t hn l cht tan, th trong dung dch rn cng vy . Ngoi ra ngi ta phn bit chng theo cch : Cu t no gi li c kiu mng c gi l dung mi , cn cc nguyn t ha tan sp xp li trong mng ca cu t dung mi ) 3.2.2 Phn loi ng hnh :- Da vo tnh cht ca cc ht thay th ng hnh ta chia ra lm 2 loi ng hnh : ng hnh ng ha tr : trng hp ny dung dch rn to thnh nh cc ion cng in tch thay th nhau trong mng tinh th . V d : KCl - KBr ; MgCO3 - FeCO3 ; CaCO3 - MgCO3 ng hnh d ha tr : Trng hp cc ion khc ha tr thay th ln nhau V d : NaAlSi3O8 CaAl2Si2O8 ; FeCO3 ScBO3 y s thay th ng hnh l s thay th ca nhm : Fe2+C4+ Sc3+B3+ hoc Na+Si4+ Ca2+Al3+ . Da vo t l khi lng thay th nhau ca cc ht thay th ng hnh ta li phn lm 2 loi ng hnh : ng hnh hon ton v ng hnh b phn . ng hnh hon ton : xy ra nu nh cc ht thay th ng hnh c th thay th cho nhau trong mi phm vi ca t l , t 0 -100% . V d : Trng thch natri ( NaAlSi3O8 ) v trng thch canxi ( CaAl2Si2O8 ) to nn 1 dy ng hnh c tn l nhm ph Plagioclaz. ng hnh b phn : Xy ra khi cc ht thay th ng hnh ch c th thay th cho nhau trong 1 phm vi ca t l . V d : trong dy cacbonat CaCO3 - MgCO3 cho lmit__CaCO3.MgCO3.

3.2.3 iu kin c s thay th ng hnh

Quan st hin tng ng hnh mt cch k cng di nhiu gc khc nhau ta thy lin quan n nhiu vn . Kch thc ca cc ht thay th ng hnh khng c chnh lch nhau qu 15% . V d : Mg2+ v Fe2+ thuc nhng nhm khc nhau ca h thng nhng c 2 u c ha tr nh nhau v kch thc tng t . (Mg2+ 0,78 A0 , Fe2+ 0,83 A0 ) . KCl v LiCl hoc KF v KBr ging nhau v mt ha hc th li khng c hin tng ng hnh . l v Li+ v K+ hoc F- v Br- c kch thc khc nhau nhiu ( Li+ 0,78 , K+ 1,33 , F- 1,33 , Br- 1,96 ) . S xm nhp ca cc ht ha tan tuy khng lm thay i kiu mng tinh th dung mi song s lm x lch mng tinh th xung quanh cc v tr chng chim ch . Nh ta bit khng c hai nguyn t no c ng knh nguyn t ging ht nhau , nn i vi dung dch rn thay th , mt trong cc iu kin quan trng l s gn ging nhau v kch thc cc ht thay th ng hnh m bo cho mng tinh th dung mi khng b x lch qu mnh dn n mt n nh . S sai khc ny cng nh cng tt , ln nht cng khng th vt qu 15 % . Trong trng hp to thnh dung dch rn xen k th yu t kch thc y l ht ha tan c kh nng nm gn trong hng trng . M cc hng trng u rt nh , nn dung dch rn xen k ch hnh thnh khi cc ht ha tan c kch thc rt nh . iu kin bn ngoi , c bit l nhit c nh hng ln n kh nng ng hnh ca cc cht . v d : NaCl v KCl to nn hn hp ng hnh nhit cao nhng khi h nhit chng tch ri nhau ring bit . nh hng ca thnh phn anion : Ta thy rng Fe2+ v Mg2+ c th to dy ng hnh trong cacbonat v mt lot silicat nhng trong sulfua chng hon ton khng thay th cho nhau c . 42

Tinh th hc nh hng ca kch thc mng c s : Na+ v Li+ khng th thay th ng hnh cho nhau trong nhng hp cht n gin ( nh trong clorua ) v kch thc chng khc nhau xa

rNa + = 0,98 A0 ; rLi + = 0,68 A0 nhng cng chnh nhng ion ny li thay th cho nhau
trong nhng hp cht phc tp nh LiMnPO4 v NaMnPO4 . S chnh lch v ln ca cc ion Na+ v Li+ nh hng n kch thc mng NaCl v LiCl nhng khng lm cho thng s mng ca 2 pht pht khc nhau ng k Nh vy s ging nhau v kch thc ca cc ion l iu kin cn nhng cha Dng lc lin kt ca cc cht : Trong thay th ng hnh bn cht dng lin kt ca cc cht cng ng vai tr ng k v n xc nh kiu cu trc v do c dng ngoi ca tinh th . V d : trong hp cht MgO (periclaz ) v ZnO ( Zinkit ) Mg2+ v Zn2+ c bn knh kh gn nhau ( 0,78 v 0,83 ) , nhng MgO (periclaz ) v ZnO ( Zinkit ) khng c chung cu trc v Mg+ , Zn+ khng th thay th ng hnh cho nhau , v dng lin kt trong periclaz l ion , trong Zinkit l cng ha tr ng cc Trong mt s trng hp khng c hin tng thay th ng hnh ca cc cu t nhng vn c th to c dung dch rn . Nguyn nhn l trong cu trc c nhng nt mng b khuyt v nhng ht nguyn t ca nhng cu t khc c th chim nhng ch ny to nn dung dch rn . Vn ny c ngha rt quan trng trong thc t , v tinh th thc cc nguyn t ti cc nt mng thng hay phn b lch so vi i xng hnh hc ca tinh th v s phn b ca chng cng khng tun theo 1 qui lut no tht cht ch . Mt iu c trng na ca hin tng ng hnh l ht tinh th ca 1 cht ng hnh c th lm mm khi mo s kt tinh t dung dch chm ng ca 1 cht khc ng hnh vi n .

Chng 4 : Nhng tnh cht vt l thng thng ca tinh th v mi lin quan gia chng vi tnh cht i xng hoc cu trc ca tinh th 4 .1 Tnh ct khai hay tnh d tch ca tinh th :
Tinh ct khai ca tinh th l kh nng v ra hay tch ra theo cc mt ca n di tc dng ca 1 lc c hc . Ty theo mc d tch v nhn ca mt ct khai ngi ta phn ra lm 6 loi : -Ct khai rt hon ton ( slida ) -Ct khai hon ton ( amfibol) -Ct khai ( pyroxen ) - Ct khai khng hon ton ( livin [Mg,Fe]2SiO4 ) -Ct khai xu ( granat ) -Khng ct khai ( Thch anh ) ( Granat : A3B2[SiO4]3 ; A : Mg2+ , Fe2+ ,,Mn2+ , Ca2+ .... B : Al3+ , Fe3+ , Cr3+ Pyrxen : l nhm khong vt quan trng nht . N l thnh phn chnh ca nhiu loi c to thnh nhit cao . l cc silicat c thnh phn khc nhau ng k nh ipsit , enstatit . 43

Tinh th hc Amfibol : L nhm khong vt c quan h vi pyrxen v c vai tr to ln trong thnh phn . l nhng silicat phc tp .) Tinh th 1 cht c th ch b tch ra theo 1 mt nh mica , thch cao ; theo 2 mt nh amfibol , pyrxen ; theo 3 mt nh halit , canxit .Mc ct khai theo nhng mt khc nhau c th khc nhau . Kh nng ct khai c quan h cht ch vi c im ca cu trc tinh th . Bravais l ngi u tin ct ngha hin tng ny . Pht trin l thuyt v mng tinh th , ng gi thit rng mt ct khai thng song song vi cc mt mng c mt ht ln nht , v cc mt mng ny thng cch nhau nhng khong ln nht . Ta thy grafit c tnh ct khai theo lp .Tng t nh grafit , nhng n cht c kiu xp cu lc phng vi t s 2 thng s c/a 1,633 thng c tnh ct khai theo mt (0001). ct ngha tnh ct khai mt cch trn vn phi lu n cc lc lin kt ha hc trong nhng tinh th thc .Vulf l ngi u tin nhn thy iu ny . ng ly Sfalerit v kim cng lm v d Kim cng v sfalerit c cu trc mng lp phng tng t nhng chng ct khai theo nhng mt khc nhau . S S C
0 C 0,5A

ZnS

C C C C (110)

S 0,71A0 Zn S Zn S

C C C 0,29A0 C C (111)

ZnS
ZnS

S
S (100)

C
C ZnS

Sfalerit ct khai theo (110) ; kim cng theo (111) . sfalerit h mt {111} ch cha 1 loi ion hoc Zn2+ hoc S2- cho nn tuy nhng mt mng ny cch xa nhau nhng chng gn vi nhau bng lc ht nhng in tch tri du . Trong khi theo {110} mi mt mng u cha ng thi c 2 loi ion nn trung ha in tch . Cc mt ca h mt mng ny gn kt vi nhau bng lc yu hn nn ct khai tt hn . Tng t cho kim cng . Nh l thuyt ca Bravais v Vulf m i khi ch da vo tnh ct khai -mt hin tng c hc n thun - ngi ta c th rt ra nhng kt lun nht nh v cu trc bn trong ca mt tinh th

4.2 cng
cng ca tinh th l mc khng ca n i vi cc tc dng c hc C nhiu phng php xc nh cng ca mt tinh th . Trong thc t phng php thng dng nht l phng php xc nh gn ng theo thang Mohs . y l phng php so snh tng i kh nng co xt ln nhau ca mu nghin cu vi mu chun ca thang Mohs gm 10 khong sau : cng 1 (2,4) 2 (36) 3 (109) 4 (189) Mu chun Tan ( silicat manhe hydrxyt Mg3(OH)2[Si4O10) Halit NaCl Canxit CaCO3 Fluorit CaF2 44

Tinh th hc 5 (536) 6 (795) 7 (1120) 8 (1427) 9 (2060) 10(10060)

Apatit Ca5F(PO4)3 Octoclaz K[AlSi3O8] Thch anh SiO2 Tpa - Silicat nhm cha F Crion - Al2O3 Kim cng

- Al2SiO4(F,OH)2

Khi xc nh , ngi ta dng vt ny co ln vt kia . Nu trn b mt mu no c vt co , chng t vt ny mm hn vt kia v ngc li .Thang cng Mohs khng ch r cng tuyt i . V d : Khng phi cng 9 l cng gp 3 ln cng 3 . N ch c ngha l 1 khong no c th vch c tt c cc khang vt xp di n trong thang cng v ngc li , s b cc khong vt xp trn n vch c . Hai khong vt c cng cng s vch c ln nhau . V d : Thch anh vch c tinh th X nhng ortocla khng vch ni, th tinh th X c cng nh hn 7 v ln hn 6 theo thang Mohs .Kt qu thu c khng chnh xc nhng n gin . cho tin , mt s vt quen thuc dng gip ngi ta xc nh cng 1 cch nhanh chng nh sau : Mng tay c cng : 2,5 ng xu bng ng : 3 ; Li dao hoc knh : 5,5 . Dy thp : 6,5 xc nh cng chnh xc ngi ta dng cc phng php khc : : cng Brinen (HB): c xc nh khi p 1 vin bi tiu chun di ti trng P xc nh ln b mt vt liu , sau khi b ti trng bi s li 1 vt lm vi din tch mt lm F . HB =
P

D
2

2P

(D D2 d 2 )

D( D D 2 d 2 )

[kG/mm2]

- cng Vicke (HV): Dng mi nhn bng kim cng hnh thp t phng n xung b mt di lc p P . ln ca ng cho d ca du n xc nh bng knh hin vi . P ; = 1360 l gc gia cc mt thp . cng HV = 2 sin 2
2d

- cng Knoop (HK):Cch o ging nh o Vicke nhng mi m hnh thp c cu to sao cho vt o li c dng hnh thoi . b

L HK = P/F

45

Tinh th hc - cng ca tinh th c tnh d hng .Trong cng 1 tinh th nhng cng theo nhng hng khc nhau th khc nhau . V d : Tinh th disten Al2SiO5 . Dc theo chiu di tinh th c cng bng 4,5 nhng vung gc vi phng cho cng bng 7 . -Nhng mt c mt nguyn t ln nht s c cng ln nht ( nhng mt ny cng l nhng mt ct khai tt nht ca tinh th ) - cng ca vt cht cn c quan h vi t trng ( cht st nguyn t ) ca n . Kho st nhng bin th a hnh ca 1 cht ngi ta thy nhng bin th c t trng ln s c cng cao . v d : CaCO3 Can xit c t trng 2,72 , cng 3 Aragonit ... ... ... ... 2,94 ... ... 4 i vi cc tinh th khc loi nhau c 2 nguyn nhn ch yu dn n cng khc nhau : -Khi nhng iu kin khc nh nhau , cng ph thuc vo khong cch gia cc mt mng . Khong cch ny nh cng ln . - cng tng cng vi s ha tr : V d : dy NaF , MgO , ScN , TiC c cu trc kiu nh nhau ( NaCl ) . v khong cch gia cc mt mng tng t nhau , nhng cc hp cht t cc ion vi ha tr khc nhau dn n cng khc nhau : Hp cht ha hc Ha tr cc ion Khong cch mng ( 100) cng theo Mohs NaF 1 2,31 3,2 MgO 2 2,1 6,5 ScN 3 2,23 7,8 TiC 4 2,23 8,9

4.3 Tnh dn nhit minh ha tnh dn nhit ca tinh th ngi ta lm nhiu th nghim n gin . Ly 1 tinh th lp phng , ph sp ong ln mt mt ca n ri chm 1 u kim c nung nng ( to im nhit ) trn mt tinh th ., thy lp sp ong xung quanh u kim nng chy to thnh 1 vng trn . Cng lm th nghim tng t vi tinh th cc h khc , ngoi vng trn ra ta s nhn c nhng ng elip. Nhng ng ny cho ta khi nim v tc truyn nhit trn b mt tinh th . Tng t c 1 ngun nhit nm trong tinh th , t im , nhit s truyn ra xung quanh theo mi hng . Nu biu din tc dn nhit ca tinh th bng cc vecto , gc ca chng trng vi im nhit , th u ca chng lm thnh 1 mt ng nhit .Nh vy : -Tinh th h lp phng v cc cht v nh hnh c mt ng nhit dng hnh cu ( a) c ngha l tinh th h lp phng ng hng v tnh dn nhit : Nhit truyn trong tinh th mi hng u nh nhau . -Tinh th hng trung c mt ng nhit dng elipxoit trn xoay . Trc chnh C ( hay trc xoay ) trng trc i xng bc cao trong tinh th . Hnh elipxoit trn xoay c xc nh bng ln ca 2 bn trc : Bn trc C v bn trc ng vi bn knh ca tit din trn ln nht vung gc vi trc C . Nu tc dn nhit ca tinh th ln nht theo hng trc C th mt ng nhit elipxoit trn xoay c dng ko di theo hng C v ngc li hnh (b,c) . -Tinh th hng thp c mt ng nhit hnh elipxoit 3 trc khng bng nhau , c 3 bn trc vung gc vi nhau v c di khc nhau ( hnh d): + Tinh th h 3 nghing : v tr ca mt ng nhit khng xc nh . Mi tinh th c 1 cch nh hng ring ca mt elipxoit . +Tinh th h 1 nghing : c 1 bn trc trng vi L2 , cn 2 bn trc kia nm trong mt phng vung gc vi bn trc th nht . + Tinh th h trc thoi : Mt elipxoit ny hon ton c nh hng . 3 bn trc ca n trng vi 3 phng n( tc 3 trc i xng bc 2 ca tinh th ) ca tinh th . 46

Tinh th hc

a)

d) Nh vy dn nhit trong tinh th c lin quan n tnh i xng hay cu trc ca tinh th . Trong tinh th , nhng hng c dn nhit ln thng ng vi nhng hng mng c mt ht ln . Tnh dn nhit ca tinh th ph thuc nhiu vo mc sai hng trong cu trc ca chng . Cu trc cng nhiu sai hng tinh th cng km dn nhit .V d Mui n thin nhin c = 0,015 cal/cm .s.0C ; mui n tng hp c = 0,021 cal/cm .s.0C . Cc dung dch rn thng c dn nhit thp hn cc tinh th hp phn . Mt vt rn trng thi v nh hnh c dn nhit thp hn khi n trng thi tinh th . V d : Thy tinh thch anh ( SiO2) c = 0,0032 cal/cm .s.0C ;tinh th thch anh c = 0,0325 cal/cm .s.0C. iu ny gip ta d dng phn bit thy tinh thch anh v tinh th thch anh . Cm tay mt s nng ln , mt khng nng v n truyn nhit nhanh vo ton b th tch tinh th . 4.4 Tnh p in , ha in , st in Trong tinh th cc cht ch co tinh th dng lin kt kim loi c tnh dn in tt , v trong cu trc ca chng thng xuyn c mt cc in t t do . Nhng tinh th c trng bng dng lin kt ion v cng ha tr thng l nhng tinh th cch in . Tuy nhin bn cht cch in ca chng khng phi l vnh cu , m c th thay i di tc dng ca bc x hng ngoi, t ngoi , ca p lc hay ca nhit ... Tnh p in, ha in , st in l 3 tnh cht in tng i quan trng v mi 1 s vt liu in mi. Mt mt n gp phn xc nh tnh i xng ca tinh th, mt khc n cho php s dng tinh th vi nhng hiu ng c bit ch to nhng thit b c bit trong k thut ( in mi hay cht cch in khc vt dn c bn ch trong in mi khng c cc in tch t do . Khi t 1 thanh in mi BC trong in trng ca 1 vt mang in A , nu thanh in mi l ng nht th trn cc mt gii hn BC s xut hin nhng in tch tri du . Nu thanh in mi khng ng nht th ngay trong lng thanh in mi cng xut hin in tch . Hin tng trn in mi khi t trong in trng c xut hin nhng in tch c gi l hin tng phn cc in mi ). A C

b)

c)

1/ p in : l 1 tnh cht khc thng ca mt vi vt liu c cu trc tinh th phc tp v c tnh i xng thp nh bari titanat (BaTiO3) , bari v ch ziconat (PbZrO3) , amonidihydrophotphat (NH4H2PO4) v thch anh ... Tnh cht ny th hin :Khi nn hoc ko gin 1 s tinh th in mi theo nhng phng c bit trong tinh th th trn cc mt gii hn ca tinh th c xut hin nhng in tch tri du , tng t nh nhng in tch trong hin tng phn cc in mi . Hin tng ny c gi l 47

Tinh th hc hin tng p in thun .Nu i du ca lc tc dng , v d t nn sang ko hoc ngc li th in tch xut hin trn 2 mt gii hn cng i theo . Do c in tch tri du xut hin nn gia 2 mt gii hn ny c mt hiu in th .

Vt liu p in c ng dng trong cc linh kin chuyn i nng lng in thnh ng sut c hc v ngc li nh u ghi m , micrphon , my pht siu m , u o ng sut , u thu m . Trong 1 my ghi m , khi u kim dch chuyn theo cc rnh trn 1 a ht , bin thin ca p sut ln vt liu p in trong u m chuyn i thnh tn hiu in v c khuych i ln trc khi ra loa . tinh th nu trn cn gp hin tng gi l p in nghch nh sau :Nu ta t ln 2 mt ca tinh th mt hiu in th th n s b gin hoc nn . Nu hiu in th ny l 1 hiu in th xoay chiu th bn tinh th s b gin , nn lin tip v dao ng theo tn s ca in trng xoay chiu . Dao ng c hc ca bn tinh th to thnh nhng sng siu m truyn vo trong mi trng xung quanh . Tnh cht ny c ng dng ch to cc ngun pht siu m . Cc sng ny c th truyn i 1 khong ng k trong nc . Ngi ta s dng hiu ng ny vo phng tin thng tin gia cc tu ngm . Nghin cu cu trc nhng tinh th c tnh p in ngi ta thy rng nhng tinh th cha tm i xng khng th l vt liu p in c . Hiu ng p in cn ph thuc vo nhiu yu t khc : Nhng tinh th lin kt ion n gin nh cc halogenua khng ngm nc ca cc kim loi kim v kim th thng khng c tnh p in .Nhng nhng tinh th c cha c 2 dng lin kt ion v ng ha tr thng l nhng vt liu p in mnh nh Sfalerit ( ZnS) . Hiu ng p in thng thy trong mt s mui nh clorat , brmat , iodat . Ngy nay ngi ta ngghin cu c hn 500 cht p in khc nhau nhng mi ch c khong 1/10 s c em dng trong thc t . Trong thch anh l vt liu p in thng dng nht .

2/ Tnh ha in :
L kh nng dn in ca tinh th khng dn in khi b tc dng bi nhit . V d : Khi nung nng tinh th tuamalin hnh tr th 2 u ca n s tch in . Cc in cc s i du cho nhau nu ta lm lnh tinh th . Hiu ng ny ch pht sinh trong tinh th theo nhng hng hon ton xc nh . l nhng hng phn cc trng vi phng n ( l phng c bo ton qua bt k php bin i i x ng c trong tinh th ) ca tinh th v tinh th khng cha tm i xng . Do hiu ng ha in khi xut hin c km theo s gin n nhit ca tinh th nn n c th coi l trng hp c bit ca p in . ( Tuamalin l 1 loi silicat nhm c cng thc ha hc phc tp n ni Gin Ruskin phi ni rng cng thc ha hc ca n ging ci n thuc ca ng th thuc thi trung c hn l cng thc ca 1 loi khong vt thc s ).

48

Tinh th hc

3/ Tnh st in : l tnh phn cc t pht tc l phn cc khi vng mt in trng ca cht in mi . Tng t nh tnh st t vt liu c t tnh vnh cu . Trong cc vt liu st in phi tn ti nhng lng cc in vnh cu . V d : Trong tinh th BaTiO3 ( l cht st in ph thng nht ) , s phn cc t pht l h qu ca s sp xp v tr cc ion Ba2+ , Ti4+ , O2- trong mng c s . Cc ion Ba2+ nm cc nh ca c s mang tnh i xng t phng ( Hnh lp phng b gin nh theo 1 phng ).M men lng cc sinh ra do s x dch tng i ca cc ion O2- v Ti4+ ra khi v tr i xng ca chng . Cc ion O2- nm thp xung pha di 1 cht cn ion Ti4+ li dch ln trn so vi tm im ca mng c s . Nh vy mt m men lng cc ion vnh cu gn vi 1 mng c s . Tuy nhin khi nung nng BaTiO3 ln trn nhit Curie st in ca n (1200C) th c s s tr li khi lp phng v tt c cc ion u theo ng v tr i xng trong c s lp phng , vt liu by gi c cu trc tinh th kiu Perpskit v tnh cht st in bin mt .S x dch tng i ca cc ion O2- , Ti4+ u theo cng 1 hng cho tt c mi mng c s trong 1 min th tch nht nh ca hp cht. Cc cht st in c hng s in mi cc k cao cc tn s in trng tng i thp , v d , nhit phng hng s in mi ca BaTiO3 c th cao ti 5000.Do vy cc t in ch to bng nhng vt liu ny c kch thc nh hn rt nhiu so vi cc t in lm bng vt liu in mi khc .

4.5 Quang tnh

Tnh cht quang hc ca tinh th l do c im truyn nh sng trong mi trng ny quyt nh . iu li lin quan n tnh i xng ca cu trc tinh th . V tnh cht quang hc vt rn c phn lm 2 nhm ln : Cht ng hng quang hc v cht d hng quang hc . Tinh th thuc h lp phng v cht v nh hnh thuc nhm ng hng quang hc .Tinh th ca cc h lc phng , t phng , tam phng , trc thoi , mt nghing , ba nghing u l d hng quang hc . Trong mi trng ng hng , sng nh sng truyn i theo cc phng khc nhau vi vn tc nh nhau . Trong mi trng d hng quang hc, tc truyn sng nh sng s khc nhau theo cc phng khc nhau . Khi i qua mt phn cch 2 mi trung ng hng quang hc nh sng b khc x tun theo 2 nh lut : 1- Tia ti v tia khc x nm trong cng mt phng vi php tuyn ca mt phn cch 2 mi trung ti im ti ( im phn x ) 2- T s ca sin gc ti i1 v gc khc x i2 l mt i lng khng i , khng ph thuc vo ln ca gc ti i vi 2 mi trng cho :
sin i1 = n12 sin i2

Nhng vt th ng hng quang hc ( tinh th hng cao , cht v nh hnh ) ch c mt i lng chit sut . Vi tinh th hng trung v hng thp c khc . Mt tia sng chiu vo chng , ni chung thng tch thnh 2 tia khc x

tinh th hng trung 49

Tinh th hng thp

Tinh th hc Hai tia ny truyn trong tinh th vi 2 tc khc nhau , c 2 sng tng ng vi2 tia ny u phn cc v c phng dao ng vung gc vi nhau v vung gc vi phng truyn sng . Nh vy theo mi phng truyn cho trc tinh th s c 2 i lng chit sut ng vi 2 ta khc x . y l hin tng khc x kp hay hin tng lng chit .Hin tng ny th hin rt r tinh th canxit trong sut . Tc ca 2 sng khc x chnh nhau kh ln nn ng vi 2 gc khc x lch khi nhau nhiu . Khi nhn qua tinh th canxit ta s thy 1 nt ch thnh 2 . S khc nhau gia tinh th hng trung v hng thp : tinh th hng trung c1 trc quang hc , ngha l c mt phng m khi nh sng truyn theo phng y s khng b lng chit ,cn theo cc phng khc s b tch thnh 2 tia , mt tia thng (tun theo nh lut khc x v phn x ca cc ) v mt tia bt thng .Trc quang hc trng vi trc i xng bc cao nht ca tinh th tinh th hng thp c 2 trc quang hc , ngha l c 2 phng m khi nh sng truyn theo s khng b lng chit , cn theo cc phng khc s b tch thnh 2 tia u l tia bt thng

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