You are on page 1of 298

6

NXB i hc quc gia H Ni 2007, 303 Tr.



T kho: Trng thi kt tinh, Tnh d hng, nh lut Veis, Yu t i xng, nh
lut Groth, Mt tinh th, Nguyn l Bravais, Bragg-Vulf, nh lut Goldschmidt.
Ti liu trong Th vin in t H Khoa hc T nhin c th c s dng cho mc
ch hc tp v nghin cu c nhn. Nghim cm mi hnh thc sao chp, in n phc
v cc mc ch khc nu khng c s chp thun ca nh xut bn v tc gi.

Mc lc


Li ni u ............................................................................................................................. 10
Chng 1 CHT KT TINH VI BN CHT D HNG, MT TINH TH......... 13
1.1 D hng..................................................................................................................... 13
1.1.1. Cc trng thi hnh hc ca vt rn................................................................... 13
1.1.2. nh ngha......................................................................................................... 13
1.1.3. Trng thi kt tinh............................................................................................. 15
1.1.4. Tnh d hng ca trng thi kt tinh................................................................ 16
1.1.5. Khi nim mng khng gian v d hng......................................................... 18
1.2 Mt tinh th ............................................................................................................... 18
1.2.1 Nguyn l Bravais v mt tinh th..................................................................... 18
1.2.2 K hiu mt (mt mng) ca tinh th ................................................................ 21
1.2.3 nh lut Hay.................................................................................................. 22
1.2.4 Ch s th t trong h su phng.................................................................... 23
1.2.5 nh lut cc i (nh lut Veis). Phng php pht trin i ....................... 25
1.2.6 Xc nh k hiu mt nh biu chun .......................................................... 26
Chng 2 HNH THI TINH TH .................................................................................... 28
2.1 Yu t i xng v s lin gia chng....................................................................... 28
2.1.1 Yu t i xng ................................................................................................ 28
2.1.2 S lin quan gia cc yu t i xng.............................................................. 32
2.2 Nhm im i xng v hnh n ca chng ............................................................ 34
2.2.1 Suy on nhm im i xng ......................................................................... 34
Gio trnh c s ha tinh th

Trinh Hn
Ngy Tuyt Nhung
7
2.2.2 Hng, h tinh th............................................................................................... 38
2.2.3 K hiu nhm im............................................................................................ 39
2.2.4 Khi lc v hnh thi tinh th.......................................................................... 42
Chng 3 HNH HC CU TRC TINH TH .............................................................. 47
3.1 i xng ca cu trc tinh th ................................................................................... 47
3.1.1 Yu t i xng trong mng tinh th................................................................ 47
3.1.2 Nhm i xng khng gian .............................................................................. 51
3.2 H im quy tc.......................................................................................................... 52
3.2.1 nh ngha......................................................................................................... 52
3.2.2 S bi ca h im quy tc ............................................................................... 53
3.3 c im dng quen ph thuc thnh phn v cu trc tinh th................................ 53
3.3.1 nh lut Groth ................................................................................................. 54
3.3.2 Cc loi dng quen............................................................................................ 54
3.3.3 Tc dng ca tp cht i vi dng quen.......................................................... 55
3.3.4 Dng quen ph thuc thng s chui................................................................ 56
3.3.5 Dng quen ph thuc mt ht ca mt mng............................................... 56
3.3.6 Dng quen v vect kt chui........................................................................... 59
3.4 C s phng php phn tch cu trc tinh th bng tia X........................................ 60
3.4.1 nh lut phn x Bragg-Vulf........................................................................... 60
3.4.2 Mt mng v cng ca tia giao thoa.......................................................... 63
3.4.3 Cc phng php thu nh nhiu x................................................................... 63
3.4.4 S b v cc bc phn tch cu trc tinh th .................................................. 67
Chng 4 KHI NIM C BN CA HO HC TINH TH .................................... 75
4.1 NHNG YU T XC NH CU TRC TINH TH......................................... 75
4.1.1. Cu hnh in t ca nguyn t ........................................................................ 75
4.1.2. Bn knh hiu dng ca nguyn t v ion......................................................... 76
4.1.3. S phi tr, a din phi tr v gii hn bn vng ca chng ........................... 78
4.1.4. Tnh phn cc ca ion....................................................................................... 81
4.1.5. nh lut Goldschmidt ...................................................................................... 83
4.2 CC DNG LIN KT TRONG CU TRC TINH TH..................................... 84
4.2.1 Lin kt ion ....................................................................................................... 84
4.2.2 Nng lng mng ca tinh th ion.................................................................... 88
4.2.3 Lin kt kim loi ............................................................................................... 90
4.2.4 Lin kt cng ho tr ......................................................................................... 92
4.2.5 Lin kt tn d .................................................................................................. 94
4.3 CC LOI CU TRC TINH TH TIU BIU.................................................... 96
4.3.1 Cch thc th hin loi cu trc........................................................................ 96
4.3.2 Phn loi cu trc tinh th................................................................................. 98
4.4 KHI QUT V CC LOI CHT KHC NHAU............................................. 105
4.4.1 Kim loi v hp kim....................................................................................... 105
4.4.2 Mt s hp cht hu c .................................................................................. 111
4.4.3 Sulfur v mui sulfur ...................................................................................... 113
4.4.4 Halogenur........................................................................................................ 121
4.4.5 Oxit v hydroxit .............................................................................................. 125
4.4.6 Carbonat, sulfat v phosphat........................................................................... 137
4.4.7 Silicat v alumosilicat ..................................................................................... 143

8


Chng 5 C IM CU TRC TINH TH THC................................................ 147
5.1 CC LOI SAI HNG TRONG TINH TH THC............................................. 147
5.1.1 Sai hng im................................................................................................. 147
5.1.2 Sai hng ng ............................................................................................... 148
5.1.3 Sai hng mt ................................................................................................... 148
5.2 NG HNH........................................................................................................... 150
5.2.1 Vect thay th ................................................................................................. 151
5.2.2 ng cu trc.................................................................................................. 154
5.2.3 Dung dch cng............................................................................................... 155
5.2.4 S phn r ca dung dch cng....................................................................... 158
5.3 A HNH................................................................................................................. 161
5.3.1 Mt s bin th a hnh................................................................................... 161
5.3.2 Trt t khng trt t..................................................................................... 164
5.3.3 a dng........................................................................................................... 164
5.3.4 Metamict ......................................................................................................... 165
5.3.5 Khong vt khng kt tinh.............................................................................. 166
5.3.6 Gi hnh........................................................................................................... 166
5.4 BIN DNG DO TRONG KHONG VT TO ........................................ 166
5.4.1 Olivin .............................................................................................................. 168
5.4.2 Disten (kyannit) .............................................................................................. 169
5.4.3 Enstatit ............................................................................................................ 169
5.4.4 Amphibol ........................................................................................................ 170
5.4.5 Mica ................................................................................................................ 170
5.4.6 Plagioclas ........................................................................................................ 170
5.4.7 Thch anh........................................................................................................ 171
5.4.8 Carbonat .......................................................................................................... 172
5.5 C TNH HO L CA TINH TH LIN QUAN VI CU TRC CA
CHNG.............................................................................................................................. 175
5.5.1 c tnh ho l lin quan vi dng lin kt ho hc trong tinh th ................. 175
5.5.2 Tnh cht in ................................................................................................. 178
5.5.3 Tnh cht quang............................................................................................... 179
5.5.4 Tnh rn c ca kim loi ............................................................................. 181
5.5.5 Tnh ct khai ................................................................................................... 182
5.5.6 Cc h s co c, gin nhit ............................................................................. 183
5.5.7 cng v nhit nng chy ...................................................................... 184
5.5.8 nh hng ca dng lin kt hydro n cc tnh cht ho l.......................... 186
5.5.9 Hiu ng chn ca ion .................................................................................... 188
5.5.10 ho tan....................................................................................................... 189
5.5.11 T trng............................................................................................................ 191
Chng 6 HA HC TINH TH CA MT S KHONG VT TO ............ 195
6.1. OLIVIN ............................................................................................................... 195
6.1.1 Cu trc tinh th.............................................................................................. 195
6.1.2 c im ho hc............................................................................................ 197
6.2. GRANAT............................................................................................................. 200
6.2.1. Cu trc tinh th.............................................................................................. 200
9
6.2.2. c im ho hc............................................................................................ 201
6.3. NHM SILICAT NHM Al2SiO5 .................................................................... 206
6.3.1. Silimanit AlIVAlVISiO4O............................................................................. 207
6.3.2. Andalusit Al
V
Al
VI
SiO
4
O................................................................................. 207
6.3.3. Disten Al
VI
Al
VI
SiO
4
O..................................................................................... 208
6.4. SILICAT O VNG........................................................................................ 209
6.4.1. Beryl Al
2
Be
3
Si
6
O
18
......................................................................................... 209
6.4.2. Cordierit (Mg,Fe)
2
Al
4
Si
5
O
18
.nH
2
O................................................................. 211
6.4.3.
Tourmalin(Na,Ca)(Mg,Fe,Mn,Li,Al)3(Al,Mg,Fe3+)6[Si6O18](BO3)(O,OH)3(
OH,F) ......................................................................................................................... 212
6.5. BIOPYRIBOL..................................................................................................... 214
6.5.1. Tng quan ha hc tinh th micapyroxenamphibol ................................. 214
6.5.2. Mt s khong vt biopyribol ......................................................................... 217
6.6. PYROXEN.......................................................................................................... 218
6.6.1. Cu trc tinh th.............................................................................................. 219
6.6.2. c im ho hc............................................................................................ 223
6.7. AMPHIBOL ........................................................................................................ 227
6.7.1. Cu trc tinh th.............................................................................................. 228
6.7.2. c im ho hc............................................................................................ 228
6.8. MICA X2Y46Z8O20(OH,F)4.......................................................................... 235
6.8.1. Cu trc tinh th.............................................................................................. 235
6.8.2. Muscovit ......................................................................................................... 241
6.8.3. Phlogopit - biotit ............................................................................................. 243
6.9. PYROPHYLLIT-TALC...................................................................................... 246
6.9.1. Pyrophyllit....................................................................................................... 247
6.9.2. Talc ................................................................................................................. 247
6.10. KHONG VT ST........................................................................................... 250
6.10.1. Kaolinit ........................................................................................................... 252
6.10.2. Illit................................................................................................................... 254
6.10.3. Smectit ............................................................................................................ 257
6.10.4. Vermiculit ....................................................................................................... 260
6.11. FELDSPAT ......................................................................................................... 265
6.11.1. c im cu trc ........................................................................................... 265
6.11.2. c im ho hc............................................................................................ 271
6.11.3. Song tinh ca feldspat ..................................................................................... 273
6.12. THCH ANH, TRIDYMIT V CRISTOBALIT (SiO2)................................... 276
6.12.1. Cu trc tinh th.............................................................................................. 277
6.12.2. c im ho hc............................................................................................ 279
6.13. MT S KHONG VT TO KHC ...................................................... 279
6.13.1. Calcit ............................................................................................................... 279
6.13.2. Aragonit .......................................................................................................... 280
6.13.3. Barit................................................................................................................. 282
6.13.4. Apatit............................................................................................................... 283
6.13.5. Corindon -Al2O3.......................................................................................... 284
6.13.6. Spinel .............................................................................................................. 287

10



LI NI U
Ngt mt th k qua, k t khi cu trc tinh th u tin c xc nh, xut hin nhng
thng tin ngy cng nhiu, ngy cng chnh xc v trt t bn trong ca cc cht kt tinh. Cng nh
, nn tng l thuyt ca cc mn hc lin quan n th kt tinh ngy cng thm cng c.
Ho hc tinh th c i tng nghin cu l mi quan h thnh phn cu trc tnh cht ca
vt kt tinh v l a ch ng dng ca nhng kt qu nghin cu cu trc tinh th. Cng vi s pht
trin ca ngnh gio dc v o to nc nh, trng i hc Tng hp nay l i hc Quc gia H
Ni tng a mn hc ny (vi 3 4 n v hc trnh) vo danh mc cc chuyn trong quy trnh
o to c nhn, thc s a cht hc, ho hc.
Phn u gm cc chng mt v hai, trnh by s lc nhng kin thc c s v cht kt tinh
v tinh th hc hnh thi. Chng ba l hnh hc cu trc tinh th, ch trng vo khi nim v cch suy
on 230 nhm i xng khng gian, h im quy tc, quan h dng quen cu trc v tm lc v
Roentgen tinh th hc. Chng bn gm nhng khi nim c bn ca ho hc tinh th, phn loi v
m t cc loi cu trc. Cui chng, c im ho hc tinh th ca mt s loi cht t nhin v nhn
to c trnh by khi lc.
Chng nm c ni dung v tinh th thc vi nhng sai khc ch yu trong cu trc v thnh
phn ho hc ca chng; k c cc hin tng a hnh, ng hnh, dung dch cng v s phn r, bin
dng do trong khong vt to v.v; tc l mt phn nhng g gii t nhin y bin c li
trn sn phm ca n. Chng nm l mt trong nhng ni dung chnh: tnh cht vt l, ho hc ca
tinh th trong mi lin quan ph thuc vi cu trc ca chng (do ng tc gi Ph Gio s Ngy
Tuyt Nhung son). Cui cng, chng su dnh cho nhng c im ho hc tinh th ca mt s
khong vt to chnh.
Cun sch hon thnh vi s gip , khuyn khch, chia s kinh nghim v ti liu v.v... ca
ng nghip. c bit, Ph Gio s Nguyn Tt Trm, Ph Gio s ng Mai c v cho nhiu
nhn xt qu bu, gip hon thin ni dung v hnh thc. Cc tc gi xin by t lng bit n.
Vi rt nhiu c gng mong t ti cht lng cao nht cho cun sch nhng bit rng, cun
sch ny cha th p ng c s mong i ca mi gii bn c, cc tc gi sn sng tip
nhn vi lng bit n v mi kin ng gp, mong sao cun sch ny s ngy cng b ch
hn.
Cc tc gi
11
M U
Ni dung mn hc
Cn c vo kt qu phn loi cc cht kt tinh theo cc tiu ch v c im thnh phn v cu
trc bn trong, vo kt qu nghin cu tnh cht ca chng, ho hc tinh th c nhim v gp phn x
l mi tng quan ca thnh phn ha hc v cu trc ca tinh th vi tnh cht ca chng, nhm gip
ngnh vt liu hc, ngc hc, v.v... rt ra nhng lun im mang tnh quy lut trong nghin cu ch
to, hoc x l ch tc nguyn liu khong vt, lm ra nhng vt liu mi vi tnh nng nh sn, hoc
nhng sn vt mi vi gi tr thng phm cao.
Vi t cch l sn phm ca t nhin, tinh th khong vt lun lu gi nhng du n ca cc
qu trnh xy ra su trong lng t. Kho st c im v thnh phn v cu trc tinh th ca khong
vt trong s ph thuc vo iu kin (nhit v p sut) thnh to l mt ni dung nghin cu ca
a cht.
S lc lch s pht trin mn hc
Mt trong nhng ngi t nn mng cho ho hc tinh th l Goldschmidt. Trong nhng cng
trnh v a ho hc, ng quan tm c bit n ngha ca mn hc ny. ng cng b nhiu
cng trnh Vin Hn lm Khoa hc Na Uy v nm 1954, sau khi ng qua i, nhiu cng trnh khc
ca ng c ng ti trong tp ch Ho hc tinh th.
Trc khi tr thnh mn hc c lp, ho hc tinh th tri qua nhiu giai on pht trin.
Hay R.Y. (1801) xut tng cho rng tt c cc hp cht tng ng v thnh phn
ho hc th s kt tinh theo mt a din tinh th nht nh. Quy lut ny c hiu chnh mt phn bi
mt vi pht kin sau .
Theo Wollaston W.H. (1808), mt s hp cht khc nhau v thnh phn ho hc li c dng
tinh th ging nhau. V d, calcit CaCO
3
, magnesit MgCO
3
v siderit FeCO
3
, chng kt tinh thnh
cng mt a din hnh mt thoi (gm 6 mt hnh thoi bng nhau).
Mitscherlich E. (1819) cng c pht hin tng t vi cp hp cht KH
2
PO
4
v KH
2
AsO
4
.
ng gi l hin tng ng hnh (isomorphism).
Hnh dng u n ca tinh th lm ny sinh khuynh hng tm nguyn nhn trong s sp xp
nguyn t bn trong a din. Ngay t nm 1675, Newton I. vit trong Quang hc rng khi tinh
th thnh to th khng nhng cc ht xp ngay hng thng li to a din u n, m nh kh
nng phn cc chng cn t xoay, hng cc u ging nhau v mt pha.
Hay R.Y. (1784) lm th nghim trn nhng tinh th c ct khai (tnh d tch gin thnh
tinh th a din di tc dng ca lc c hc) tt v i n gi nh rng tinh th ca mi cht hnh
thnh t nhng phn t xp song song v k nhau. Phn t ca mi cht kt tinh c dng a din
ring.
Nm 1813 Wollaston W.H. ngh thay phn t ca Hay bng nhng nt im ton hc
(chng hn, im trng tm ca phn t ). T , khi nim mng khng gian (tp hp nt im xp
theo mt trt t nht nh) ra i, nhm m t trt t sp xp bn trong tinh th. y l quan im tin
12
b, bi v cho n lc cha c phng php no gip nghin cu hnh dng ht (nguyn t, phn
t). ng thi, tng y cho php nghin cu kha cnh hnh hc ca s i xng trong mng tinh
th.
Chnh t , Bravais A. (1855) chng minh c 14 loi mng khng gian.
Nm 1890, Phedorov E.S. v Schoenflies A., mi ngi theo cch ring, i n cng mt kt
qu v cc t hp yu t i xng trong mng khng gian. Chnh s ra i ca 230 nhm i xng
khng gian y (xem ph lc 1) t nn mng l thuyt v cu trc tinh th cho ho hc tinh th hin
i.
T nm 1912, nhng thc nghim u tin ca Laue M., Bragg W.H. v Bragg W.L.
gip tm ra nng lc mi ca tia X l nhiu x trong mng tinh th. (Trc tia X ch c
coi l bc x dng xuyn thu v cng ph vt cht). Th k 20 chng kin s chn hng ca
ho hc tinh th, l thuyt hnh hc ca cu trc tinh th dn dn c cng c bng h
phng php phn tch cu trc tinh th vi chnh xc v t ng ha ngy cng cao. Cng
t , d liu thc t ca mn hc ngy mt tng cng; hng lot cht rn c phn tch
cu trc, bt u t n cht qua cc hp cht n gin, sang hp kim, silicat v hp cht hu
c.
Ngoi nhiu x Roentgen, cc phng php thc nghim khc nh nhiu x in t, quang
ph hng ngoi, cng hng t ht nhn v.v cng l nhng cng c b tr nghin cu
cu trc tinh th.

13
Chng 1
CHT KT TINH VI BN CHT D HNG,
MT TINH TH
Khc vi cht kh v cht lng, cht rn a dng hn. Nhng phn t cng thnh phn v
hnh dng c th sp t trong tinh th bng nhng cch khc nhau. c im ho l ca vt
cht thay i tu thuc cch thc sp t ny. Nh vy, nhng cht cng thnh phn ho hc
c th c nhng l tnh khc nhau. S a dng y khng c trng cho th lng v khng th
c trong th kh.
Trng thi rn a dng, cn ring tng cht kt tinh c th c nhng c th khng ging
nhau; nhng mt cht lng khng th cho nhng git khc nhau. Ly mui n lm th d: mi
tinh th NaCl c mt din mo ring, chng c th ln hoc b, dng lp phng hay khi
ch nht v.v. Di knh hin vi, mt lt mng kim loi c th cho thy tng tinh th vi
nhng nt hnh thi phn bit. Nu cn c th tch ring mt c th dng a din, c gi l
tinh th n. Di danh t tinh th nhiu khi c th hiu nh mt tinh th n, hoc khi
qut hn, nh mt vt kt tinh. Trong rt nhiu trng hp, vt rn bc l di dng tp hp
tinh th. Chng hn, hay kim loi bao gm cc ht khng c hnh dng nht nh, trong
iu kin cht nng chy ngui nhanh, s kt tinh bt u cng lc trn mi im ca n.
Nhiu tinh th cng pht trin trong mt khng gian hn hp ring, chng cn tr nhau, khng
ht no ch t th hin, to thnh a din ring.
Chng ny dnh cho d hng, mt thuc tnh ca vt rn.
1.1 D HNG
Khi ni v d hng hoc ng hng ca mt tinh th hy gn vi tnh cht c th ca
n. ng hng i vi tnh cht ny, n c th d hng trong tnh cht khc. Trc ht, hy
lm r bn cht ca tinh th vi t cch l mt trong ba dng tn ti ca vt rn.
1.1.1. Cc trng thi hnh hc ca vt rn
V mt hnh hc, vt rn c th tn ti mt trong ba trng thi sau: v nh hnh, tinh
th lng v kt tinh. i tng nghin cu ca tinh th hc hay ho hc tinh th ni ring
chnh l cht kt tinh. Trc ht hy lm r mt s khi nim.
1.1.2. nh ngha
Ngoi cc tnh cht gi l v hng m s biu hin khng ph thuc vo hng kho st
(v d: t trng), vt rn c nhiu tnh cht gi l c hng. Khi kho st tnh cht loi ny,
thng phi ch nh hng kho st: ng vi mi hng, tnh cht bc l mt cch ring, c
mt s o ring, khi i hng kho st th tnh cht thay i theo. T mt im tng tng
14
trong lng vt rn, hy o ln ca mt tnh cht theo mi hng. Chng hn, s bin
thin ca tc truyn nhit biu th bng tp hp v s vect vi gc chung t ti im
cho. Ngn ca cc vect to nn b mt lin tc di dng mt elipsoit (hnh 1.1). B mt lin
tc u n y c th hnh thnh do ngn ca mt vect, khi n xoay lin tc xung quanh
im gc theo ht thy mi chiu: va xoay va thay i ln (s o ca tnh cht).
Da vo hnh dng ca b mt ch th ny, c th phn bit hai trng hp sau: ng
hng v d hng.
- ng hng: vect ch th tnh cht xoay quanh gc m khng thay i ln d
theo hng no. B mt ch th s l mt hnh cu (hnh 1.1,a). Trong trng hp
ny, vt rn cho l ng hng i vi tnh cht ang kho st. V d: thu tinh
l vt ng hng i vi tnh cht truyn nhit ca n.
- D hng: khi vect ch th tnh cht thay i hng v ln bin thin theo, th
b mt ch th s khng cn l hnh cu na (hnh 1.1,b). Trong trng hp ny, vt
rn gi l d hng i vi tnh cht ang kho st. Nh vy, vt rn vn d hng
i vi mt tnh cht ny, c th tr nn ng hng i vi tnh cht khc.
C 2 trng hp d hng:
- D hng lin tc. B mt ch th s c dng mt elipsoit ba bn trc, hnh dng ca
n xc nh bng 3 gi tr bn knh khc nhau dc 3 hng trc giao. Elipsoit vi
b mt lin tc v u n y l biu hin ca d hng lin tc. Mi tnh cht c
trng bng mt elipsoit ring.
- D hng gin on. Tnh cht
ca vt biu th bng mt s c
hn cc vect chung gc thay
cho mt b mt lin tc. Dc
theo cc hng khc ngoi
hng ca cc vect y, tnh
cht khng bc l (vect c
ln bng khng). Mi tp hp
vect ny c trng cho mt
tnh cht nht nh ca tinh th
cho. i xng ca a din
tinh th cng l ca tp hp
vect th hin tnh cht ca vt
rn kt tinh (xem di).
Vt th v nh hnh khng c bn cht d hng gin on v lun ng hng i vi
phn ln tnh cht ca chng. Hu ht cc vt th v nh hnh l cht lng v cht kh. Mt
s vt rn cng c th tn ti th v nh hnh. ng cong ngng kt (th lng chuyn
sang th rn) ca vt th v nh hnh bin thin theo thi gian l mt th lin tc (hnh
1.2,a). Theo thi gian nhit gim, nht ca cht lng tng ( linh ng gim) tun t
ti mc khng th ghi nhn thi im cht lng chuyn sang th rn trong qu trnh chuyn
pha.
Tinh th lng l trng thi c th ca mt s hp cht hu c vi phn t phc tp.
Trong qu trnh ngng kt, vt cht loi ny tri qua trng thi trung gian. Trong giai on

Hnh 1.1
B mt ch th ca vt th ng hng (a) v d hng
15
ny, vt cht c c tnh va ca th lng, va ca cht kt tinh nh d hng quang hc. Vt
th tn ti trng thi trung gian ny mang tn tinh th lng (Lemann O., 1889). Chng c
hai loi tu trt t tng dn nh sau:
- Khi phn t u sp xp song song vi mt hng chnh, vi trt t theo mt
chiu khng gian, mc s khai. Th nematit ny thng d hng (khng phi d
hng gin on) v hu ht l cht lng.
- Khi phn t va xp song song va phn b thnh tng lp, tc l vi mt trt
t cao hn (theo hai chiu khng gian). Cht smectit ny c bn cht d hng gin
on v thng c dng nho v cng c th th rn. Chng gn vi cht kt tinh
hn.
1.1.3. Trng thi kt tinh
Tu iu kin ngng kt, chng hn nhit ca cht nng chy h nhanh hay chm, vt
cht c th ngng kt th v nh hnh hay th kt tinh. Ti iu kin kh quyn, i b
phn vt rn tn ti trng thi kt tinh. Tinh th hc l khoa hc v cht rn. Trng thi kt
tinh c nhiu thuc tnh, nhng nt c trng c bn nht ca chng l bn cht d hng
gin on.


Hnh 1.2
ng cong ngng t t trng thi lng sang rn v nh hnh (a) v rn kt tinh (b)

ng cong ngng kt trn th hnh 1.2,b cho thy sau giai on u h gim tun t,
nhit tr nn khng i (T
1
= const) ngay khi pha rn xut hin di dng nhng tinh th
mm u tin. Trong giai on t thi im t
1
n t
2
c pha rn v pha lng cng c mt.
Cc vi tinh t pht trin thnh a din ngy cng ln. Nhit li tip tc gim khi trong h
ch cn pha rn. Tinh th cng c th hnh thnh trong dung dch bo ho bng cch cho dung
mi bay hi hoc bng cch cho hi thng hoa v ngng t trong ngn lnh.
Tnh ng nht ca trng thi kt tinh. Mt vt gi l ng nht nu n c nhng tnh
cht ging nhau ti mi im trong ton th tch ca n. Bn cht ng nht ch c xc
minh, nu tnh cht c kho st theo nhng phng song song. Chng hn, nu hai chic
a cng kch thc, ct gt t mt tinh th theo cng mt phng, th chng phi bc l
bn c hc ging nhau; chng hn, chng u b gy di tc dng ca cng mt vt nng.
Khi tinh th c mt ct khai theo mt phng xc nh, n lun b tch v d dng dc
phng ca mt y di tc dng ca mt lc c hc; d cho lc y t vo im no ca tinh
16
th. R rng, vt kt tinh c cu trc nh nhau ti mi im ca n th n phi ng nht.
ng nhin, y cha tnh n nhng khuyt tt, sai hng sn c trong cu trc tinh th
thc (s ni chng V).
Tuy nhin, ng nht l khi nim mang tnh tng i: n tu thuc thang kho st.
Di knh hin vi, tinh th kim cng chng hn l mt vt th ng nht. Thc ra, n l mt
h gin on vi hn 177.10
9
ht/micromet khi; gia cc ht carbon l khong khng phi vt
cht. Nh vy, thang nguyn t khi nim tnh ng nht khng tn ti.
1.1.4. Tnh d hng ca trng thi kt tinh
Cht d hng (i vi tnh cht no ca n) l cht ng nht, m nu theo nhng
phng song song tnh cht y th hin nh nhau, th ni chung, theo nhng phng khng
song song tnh cht y th hin khc nhau. Cht kt tinh thng d hng. Nu t vt kt tinh
no ct gt hai thi kch thc nh nhau nhng theo nhng phng khc nhau th chng s
c nhng tnh cht khc nhau. Chng hn, cc thi ny s c sc bn c hc khng nh nhau.
Tnh d hng ca mt tinh th nht nh lin quan ti cu trc ca n, bi v theo nhng
phng song song th nguyn t (hay ion, phn t) ging nhau c sp t ging ht nhau,
cch nhau cng mt khong. Theo nhng phng khng song song, cc ht ni chung khng
sp xp u n nh nhau, do cc tnh cht dc cc phng ny phi khc nhau.
Mt tinh th d hng (hay ng hng) theo mt tnh cht, c th ng hng (d
hng) theo tnh cht khc. V d: tinh th thuc h lp phng lun ng hng i vi tnh
cht quang hc v d hng i vi cc tnh cht khc.
Nhng thc nghim sau y cho
thy tnh d hng ca vt kt tinh.
Hy chm u kim nung ln b
mt tm thch cao ph sn lp sp
ong mng (hnh 1.3). Lp sp b chy
ra t im chm ca u kim, trong
phm vi mt hnh elip u n; iu
ny chng t s d hng ca thch
cao i vi tnh dn nhit. Nu chm
u kim nng ln cc im khc
trn cng mt tinh th ny, s nhn
c nhng hnh elip ng dng v
cng mt nh hng (tnh ng
nht). Nh ln mt tinh th fluorit CaF
2
vi git acid sulfuric. Di tc dng ca n cc mt
tinh th b n mn thnh nhng h lm, hnh dng khc nhau trn nhng mt khc nhau. Hnh
n mn trn mt bt din c dng thp vi y tam gic u, trn mt lp phng thp c y
vung. Nhng hnh n mn c chung mt nh hng.

Hnh 1.3
Thc nghim v tc truyn nhit trn mt tinh th thch
cao ph sp ong
17


Cng nh tnh ng nht, d hng khng phi ch c ring cht kt tinh; tinh th lng
v i khi cht v nh hnh cng l nhng vt d hng. Ch d hng gin on l c hu
ca cht kt tinh. Sau y l mt s v d.
Tnh nhiu x ca tia X trong tinh th. Mt tinh th nm trn ng i ca chm tia X s
gy nhiu x i vi bc x ny. Mi mt tinh th cho t nht mt tia nhiu x vi mt hng
xc nh v mt cng xc nh. Nu nng lc nhiu x ca mi mt tinh th biu th bng
mt vect hng theo tia php ca mt, ln ca n ch cng (sc cng ph) ca tia, th
nng lc nhiu x ca tinh th i vi tia X biu th bng tp hp mt s vect chung gc (t
trng trng tm ca tinh th).
Tc mc ca mt tinh th. S pht trin ca tinh th trong dung dch bo ho xy ra
trong c ch xc nh; l s tnh tin ca mi mt tinh th, theo hng tia php (hnh 1.4).
Vect v
a
, v
b
, v
c
dc tia php ca mt tinh th cho thy ng vi mi mt l mt gi tr tc
tnh tin ca n trong qu trnh tinh th pht trin.
Tnh t to mt, bn nng ca cht kt tinh pht trin di dng mt a din, c th biu
din bng tp hp vect chung gc, mi vect th hin tc mc ca mt mt tinh th.
Mt lot tnh cht khc ca khong vt cng cho thy d hng gin on ca tinh th. V
d: tnh ct khai ca mt tinh th khng ging nhau theo nhng phng khc nhau. Nu vect
ch tnh ct khai t vung gc vi mt ct khai (theo tinh th b tch gin), cn ln ca
vect ch cht lng ca mt ct khai ( phn quang, chng hn), th tinh th c bao nhiu
phng ct khai s c by nhiu vect t chung gc ti trng tm tinh th.
Kh nng lin kt ca tinh th cng cht (song tinh) hay khc cht (epitaxy) theo mt mt
phng cng c th biu th bng vect dc tia php.
18
1.1.5. Khi nim mng khng gian v d hng
S sp xp trt t ca ht vt cht khin trng thi kt tinh khc hn vi trng thi khng
kt tinh. Nu trong mi cu trc tinh th, c th tch ring tng loi nguyn t, th cch phn
b ca nguyn t thuc mi nguyn t u ging ca nt thuc mt loi mng khng gian.
khi qut hnh nh ca mt mng khng gian c th cho ba vc t tnh tin

a,

b v

c
khng ng phng tc dng ln mt im (nt gc ca mng). Kt qu thu c l mt h
thng nt xp tun hon theo ba chiu khng gian, cc nt ny nm trn nh ca cc khi
bnh hnh bng nhau, xp song song v k nhau; vi ba cnh l a, b, c (hnh 1.5).
Mi nt ca mng khng gian u suy c t nt gc bng php tnh tin T

;
1 1 1
T n a n b n c = + +



y n
1
, n
2
, n
3
l nhng s nguyn
bt k. Ni cch khc, hai nt bt k ca
mng c th di chuyn ti ch ca nhau
bng php tnh tin T

. Khi , cc nt cn
li ca mng khng gian cng th ch cho
nhau. V cc nt ht thy u tng ng
v v mng khng gian l v hn, nn v tr
ca mng sau bc tnh tin hon ton
ging vi v tr ca n trc khi tnh tin.
T

l bc tnh tin bo ton mng.


Mng khng gian l v hn v c tnh tun
hon theo ba chiu.
ln ca vect tnh tin ch gi tr ca chu k tun hon ca mng. Gi tr y ni chung
khng bng nhau theo nhng hng khc nhau: chnh mng khng gian bc l tnh d
hng v mt hnh hc ca tinh th.
1.2 MT TINH TH
Theo L. Nray-Szab (1969), vic tm ra mng tinh th l minh chng u tin v s tn
ti ca cc ht (nguyn t). Ch khi nhng ngun nhiu x ri ny c t chc li theo trt
t ca mng khng gian, chng mi c nng lc giao thoa tia nhiu x ri phn x t
mt tinh th (xem 3.4.1), nu tinh th nm trn ng i ca chm tia X.
Trn y, cc thc nghim v d hng gin on c trng ca tinh th u lin quan ti
mt tinh th. Khi nim n thun hnh thi hc ny gn lin mng tinh th ra sao, di y
s cp k hn.
1.2.1 Nguyn l Bravais v mt tinh th
Mng khng gian (hnh 1.5) cho php ct ngha mt trong nhng khuynh hng ca cht
kt tinh l t gii hn bng nhng mt phng. l mt tinh th, mt khi nim c s ca
tinh th hc hnh thi, s c cp y.
Hnh 1.5
H thng cc nt im ca mng khng gian
19
Nu gn cho mi nt mng mt ion hay nguyn t, phn t, hay mt mu hnh (motif)
nguyn t (mt tp hp nguyn t xp theo mt trt t ring), th mng khng gian cha mt
ni dung vt cht s cho mt cu trc tinh th. Ni cch khc:
Mng khng gian + mu hnh nguyn t cu trc tinh th.
Hnh 1.6 gii thiu mu hnh nguyn t, mng lp phng ca cu trc tinh th cuprit
Cu
2
O (a) v pyrit FeS
2
(b)
cng mng khng gian ca
chng (c).
Trong thc t, khi lp
phng l dng thng gp
ca tinh th pyrit; iu ny
gi mi tng quan v
hnh dng gia a din tinh
th v mng ca cu trc
tinh th. Mt lp phng
ca cu trc cha ht tch in dng Fe
2+
v ht mng in m S
2
2
vi s lng ngang
nhau. Vi in tch trung ho, mt ny bc l mt lin kt yu gia cc lp nguyn t, mt
mt ct khai. a din tinh th gii hn bng mt s hu hn cc mt ca n. Song song vi
mi mt tinh th l mt h mt mng trong cu trc.
Mng khng gian ca cu trc tinh th c s h mt mng nhiu v hn; bi v ba nt
khng thng hng xc nh mt mt mng (hkl) v song song vi n l mt s v hn nhng
mt mng (ging nhau v cch u nhau) cng h. Tng ng vi mi h mt mng c th l
mt mt ca a din tinh th. H mt mng phn bit bng mt ht, tc l s nt trn mt
n v din tch v khong cch (gia cc) mt mng.
Hnh 1.7 l hnh chiu ca mng khng gian (hnh 1.6,c) trn mt ab; mi im tng
ng vi mt chui dc trc c, mi ng thng mt mt mng, tc l mt h mt mng k
hiu (hk0). Mi h mt mng c hai i lng c xem xt: D
hk0
l khong gia hai nt k
nhau trn hnh, t l nghch vi mt ht ca mt mng; d
hk0
l khong cch mt mng.


20


Hnh 1.7
Mng khng gian ca pyrit chiu trn mt (001) vi mt s h mt mng (hk0)

Trong trng hp pyrit FeS
2
(hay halit NaCl), mt mng (100) ng vi mt ca khi lp
phng c mt ht ln nht v khong cch mt mng tng ng c gi tr ln nht (hy
so snh vi cc h mt mng khc trn hnh 1.7). Trong v s mt mng (h mt mng) ca
mng khng gian thuc pyrit ch mt s nh c tiu ch ca mt tinh th, l nhng h
mt mng vi mt ht ln nht v vi khong cch mt mng ln nht. l tinh thn ca
nguyn l Bravais A. (1866) v mt tinh th.
Cng c th ni nh vy v cnh tinh th, ni mt tinh th ct nhau, mt trong nhng yu
t hnh hc ca a din tinh th. Trong v s chui mng ca mng khng gian thuc pyrit,
chnh nhng chui vi thng s chui nh nht (s ht tnh trn mt n v chiu di t gi
tr ln nht) s song song vi cnh tinh th.
a. (100); b. (110); c. (210); v d. (310)
(hk0): (100) (110) (210) (310)
D
hkl
a
a 2 a 5 a 10
d
hkl
a
/ 2 a 2 / 5 a 5 / 10 a 10
21

1.2.2 K hiu mt (mt mng) ca tinh th
V tr ca mi mt (mt mng) tinh th
hon ton c th xc nh bng cc on
(thng s) do mt mng ct trn ba (chui
mng) trc to OX, OY, OZ. Chui ng
vi trc to , nu c th, phi trng vi cc
phng c bit, tc l trc i xng hay
php tuyn ca mt i xng gng. Cc
on thng s ny ca mt tinh th o bng a,
b, c; tc l cc n v trn ba trc to .
cng l chu k tun hon ngn, mc du
khng nht thit ngn nht, nu chng thuc
phng c bit (xem thm php nh trc
tinh th hc).
Trn hnh 1.8 v tr ca mt mng 1, song
song vi Z, xc nh bng thng s 3a theo
trc X v 2b theo trc Y. Mt mng 2 bng
thng s 1a, 1b. Quy lut mng i hi cc
mt mng ca cng mt h phi bao qut (i
qua) tt c cc nt ca mng khng gian. T hnh 1.8 c th thy tt c nhng mt mng cng
h ny u ct cc trc to cng mt t l. Qu vy, cc mt mng 1, 1
'
, 1
''
, 1
'''
c cc
thng s sau:
Mt mng OX OY OZ
1 3 n v 2 n v
1
1
2
2
n v
2
1
3
n v
1 2 n v
1
1
3
n v
1 1 n v
2
3
n v
V tr ca c h mt mng, do ca mt tinh th quy nh bi h y, biu th bng t l
cc thng s ca chng o bng cc chu k tun hon tng ng:
5 5 4 2
3 : 2 : : : 2 : : 1: : p : q : r
2 3 3 3
= = = =






Hnh 1.8
Xc nh k hiu mt mng tinh th
1, 2, 3, 4 l giao tuyn ca chng vi mt hnh
22

y p, q, r l nhng s nguyn n gin (thng s Veis).
tin s dng (s khng thay cho v cc), hy dng gi tr nghch o ca thng s
Veis, tc l cc ch s Miller h, k, l k hiu cho mt tinh th: ba ch s vit lin trong ngoc
n (hkl). Nh vy, k hiu ca h mt mng 1 l (230) v
1 1 1
: : 2 : 3 : 0
2 3
=

.
Mt 2 c k hiu (110) mt 3 (210) v mt 4 (140) . Hnh 1.8 cng cho thy cc mt
mng thuc h (hkl) chia cc on a, b, c ln lt thnh h, k, l phn bng nhau.
K hiu chui mng (cnh) ca tinh th
Trong tinh th, chui mng i qua gc to c trng cho c h chui cho. Do ,
xc nh v tr mt chui mng (hay mt cnh tinh th) ch cn o to x, y v z ca mt nt
trn chui (i qua gc) bng cc n v a, b, c theo cc trc tng ng
c
z
b
y
a
x
, , v gin c.
Cc t s ny sau khi quy v t s ca cc s nguyn n gin r, s, t c vit trong mt ngoc
vung, gi l k hiu ca cnh [rst] (hnh 1.9).
1.2.3 nh lut Hay
Mi iu l gii trn l bn cht ca nh lut hu t
ca cc thng s, do y u Ha pht biu nm 1783 da trn
nhng kho st hnh thi tinh th; t s kp gia cc
thng s ca hai mt bt k thuc mt tinh th bng t s
gia cc s nguyn n gin.
Chng hn, mt tinh th cha hai mt: A
1
B
1
C
1
vi
cc thng s OA
1
, OB
1
, OC
1
v A
2
B
2
C
2
vi OA
2
, OB
2
,
OC
2
th
p n m
OC
OC
OB
OB
OA
OA
: : :
2
1
2
1
2
1
= =
vi m, n, p l nhng s nguyn v i vi tinh th
thc l nhng s nguyn tng i nh.

Hnh 1.9
Xc nh k hiu chui mng tinh th

Hnh 1.10
K hiu mt tinh th xc nh theo nh
lut Hauy
23
Mt trong nhng mt ct c ba trc to (v d A
0
B
0
C
0
) c th coi nh mt n v v
cc thng s ca n l n v o lng, dng cho cc mt v cnh khc ca tinh th cho.
tm k hiu ca mt mt no , hy dng nhng n v o lng trn o cc on
thng s ca mt, ly t s ca cc gi tr nghch o, loi b mu s sau khi quy ng, s thu
c ba ch s ca k hiu mt. Chng hn, k hiu ca mt A
1
B
1
C
1
(hnh 1.10) c xc nh
nh sau:
r q p
OC
OC
OB
OB
OA
OA
O O O
: : : :
1 1 1
=
l k h
r q p
: :
1
:
1
:
1
=
Tm li:
) ( : :
1 1 1
hkl l k h
OC
OC
OB
OB
OA
OA
O O O
= = =
Nh vy, k hiu ca mt n v l (111).
xc nh k hiu ca mt cnh no phi ly to ca mt im bt k ca n,
dng thng s mt n v o cc to y ri ly t s kp gia cc i lng thu c:
0
OA
x
:
0
OB
y
:
0
z
OC
= r : s : t [rst]
Kt hp vi nguyn l Bravais, nh lut Hay cho php khng nh: mt tinh th hay mt
ct khai song song vi h mt mng vi mt ht ln nht, khong cch mt mng ln nht
v k hiu (vi ch s Miller) n gin nht. y l nhng mt tinh th, hay hnh n, vi tn
sut gp ln nht (xem 3.3.5). Chng to nn dng quen ca tinh th; nhng mt khc ch gp
trong nhng iu kin t nhin nht nh v gi l mt gi nh.
1.2.4 Ch s th t trong h su phng
Trong h su phng c ba phng tng ng nm ngang v mc du ch ba trc OX,
OY v OZ cng xc nh v tr ca mt v cnh tinh th, i khi mt trc th t (nm
ngang) U vn c dng n, sinh ra php k hiu mt bng bn ch s (Bravais Miller). B
ba trc ngang (OX, OY v OU) gip thc hin d dng cc thao tc i xng bc ba, bc su
i vi mt v cnh, cho php nhn mnh s thng nht ca cc yu t hnh thi lin quan
nhau bng trc chnh. Tuy vy, ch s th t trong k hiu li bt tin trong tnh ton v n
cng thng b loi b bng nhng quy tc phn bit cho mt v cnh.

24

Hnh 1.11
Ch s i ca mt tinh th h su phng.
(a) AB l giao tuyn ca mt vi mt XYU, xoay quanh trc i xng bc ba,
(b) mt
Theo cch dng, BL//OU, tam gic ABL ng dng vi tam gic ANO, t
p q q p q q 1 1 1
; ;
p n pq nq q p n
+ +
= = + =
hay l:
1 1 1 1 1 1
;
p q n p q n
+ + + =


Nh vy, h k i + = .
Hnh 1.11 cho thy trong k hiu mt tng ch s theo ba trc tng ng bng khng, tc
l h + k = i v v th t k hiu bn ch s sang k hiu ba ch s v ngc li l bc chuyn
rt n gin. Trong trng hp u loi b ch s i , trong trng hp sau n c a vo
nh i = (h+k), tc l: (hkil) hkh kl + .
i vi k hiu cnh thuc h su phng cc bc chuyn khng n gin nh vy.
Mun loi b ch s th ba w th phi a n v gi tr O trc . Nh th, i lng c
th dn n v O (l W) phi c thm vo cho c 3 ch s u:
[rswt] = [rw sw ww t] = [rw sw o t] = [rw sw t] = [rst].
Bc chuyn ngc: [rst] = [rsot] = [r+f s+f f t].
Vi f l s bt k; nh vy ng vi mt k hiu ba ch s [rst] s c v s tp hp bn ch
s. c mt k hiu xc nh cn b sung mt iu kin. Chng hn, nu tng ba ch s u
trong k hiu [r+f s+f f t] bng khng (mc du trong trng hp cho iu khng chun
xc v hnh hc) ging nh k hiu mt, lc ny
r ' s'
f
3
+
= v
[ ]
( )
( ) [ ]
r ' s'
2r ' s' 2s' r '
r ' s' t ' t ' 2r ' s' 2s' s' r ' s' 3t ' rswt
3 3 3
+

= = + =



.
Nhn xt: Vic loi b mu s nh trn khng lm cho cnh i hng; k hiu ca n l
to ca nt bt k trn chui tng ng.
25
Vi ba trc ngang, vic chn mt n v cho h su phng s c hai cch: n ct nhng
on bng nhau trn XY, hoc trn U X . Mt n v s c k hiu ln lt l (1120) hoc
(1011) .
1.2.5 nh lut cc i (nh lut Veis). Phng php pht trin i
Xc nh k hiu cnh giao tuyn ca hai mt (h
1
k
1
l
1
) v (h
2
k
2
l
2
) bng cch nhn cho.

Bng cch ny cng c th tnh k hiu ca mt (hkl) song song vi hai cnh [r
1
,s
1
,t
1
] v
[r
2
s
2
t
2
].
Nh vy, hai mt xc nh mt cnh (i), hai cnh xc nh mt mt. Nu theo Hay,
mt gi nh v cnh gi nh ca tinh th c suy ra bng cch t trc mt phng v
ng thng vi k hiu hu t (phng php s hc) th theo Veis chng c suy ra bng
cch t trc mt phng song song vi hai cnh giao nhau v ng thng song song vi hai
mt giao nhau (phng php hnh hc). Bi v, mt gi nh ca mt tinh th c th nhn
c theo bn mt khng ct nhau thnh nhng cnh song song. l ni dung ca nh lut
Veis (1804) hay nh lut cc i. N cn c pht biu nh sau: Mt bt k ca mt tinh th
thuc v t nht hai i ca n.
Trong thc hnh mt gi nh v
cnh gi nh d dng suy ra bng vic
s dng hnh chiu ni. Tht vy, trn
li Vulf cung trn ln biu th mt i;
i gm cc mt song song vi mt
phng gi l trc ca i. im bt k
ca cung u c th biu th cho mt
thc/gi nh ca tinh th; n l hnh
chiu ni tia php ca mt. Trn li
Vulf, hai im hon ton xc nh mt
cung; tc l hai mt tinh th xc nh
mt i. Hai i dng t hai i mt bt
k l d kin xc nh mt mt gi
nh; ni cch khc, hai cung dng t
hai cp im ct nhau ti mt im, th
im ny chnh l hnh chiu ni tia
php ca mt cn tm. im va tm
c cng l hnh chiu ni ca mt
cnh gi nh, nu coi mt trong hai cung ni trn dng t cp im/cp cnh cho trc lm
d liu [13,14].Nu cn tm k hiu ca mt no ca mt tinh th, hy t im hnh chiu
ni ca bn mt cho trc k hiu v mt cn tm k hiu ln hnh chiu ni ri dng cc i
qua nhng mt c k hiu sao cho mt cha k hiu nm vo giao im ca cc cung i. Tuy

Hnh 1.12
Phng php pht trin i gip tm k hiu mt gi
nh
26
vy, i khi c th b qua bc trung gian xc nh k hiu i: c th s dng h thc hr +
ks + lt = 0.
Mt song song vi mt trc to th trong k hiu ca n ch s ng vi trc ny lun
bng 0. V d, mt song song vi OX th k hiu ca n c h = 0. Tht th, k hiu ca trc
OX l [100], do h.1 + k.0 +l.0 = 0, tc l h = 0.
Ngc li trong k hiu trc ca i song song vi mt to no : (100)/(010)/(001)
th tng ng k hiu th nht, th hai hay th ba s bng khng. Chng hn, i vi mt i
bt k cha mt (010) th 0.r + 1.s + 0.t = 0, do s = 0. Phng php pht trin i gip tm
mt gi nh c thc hin theo trnh t sau (hnh 1.12):
+ Qua cc mt to suy ra i ca cc trc to .
+ Qua mt n v v mt to suy ra cc mt (011), (101), (110).
+ T cc mt va nhn c suy ra cc mt (112), (121), (211).
+ T cc mt va c v cc mt to suy ra (012), (102), (120), (021), (201), (210),
(312), (231), (123), (321), v.v...
1.2.6 Xc nh k hiu mt nh biu chun
gii cc bi ton pht trin i nhm xc nh mt gi nh ca tinh th, c th s
dng cc biu chun. Hnh 1.13 l biu h lp phng, n dng xc nh k hiu mt
ca tinh th h lp phng; n cng p dng cho cc h bn phng, trc thoi, mt nghing
v ba nghing. K hiu mt ca tinh th h su phng vi h bn trc to c xc nh
nh biu hnh 1.14.

Hnh 1.14
Biu chun h su phng
Trn biu c dng cc cung (i), ti giao im ca chng l im hnh chiu ni tia
php ca cc mt thng gp, tc l mt vi cc ch s n gin. Hnh 1.15 cho thy hnh
chiu ni tia php ca mt s mt thuc tinh th h ba nghing. Cho trc hnh chiu v k
hiu mt (100), (010), (001) v (111). Hy tm k hiu mt , , v . Mt nm ti giao
27
im ca cc i (001) (111) v (100) (010). Theo biu hnh 1.13 c th thy, ti giao
im ca cc i (cung) tng t l mt (110). Vy k hiu mt l (110). Bng cch y k
hiu cc mt cn li tm c l: = (101) v = (011), trn cc i cung ln lt l: (001)
(100) v (010) (111), (010) (001) v (111) (100).




Hnh 1.15
Hnh chiu cc mt mt tinh th ca h ba nghing

28
Chng 2
HNH THI TINH TH
Nh ni, tinh th l vt rn d hng, ng nht. Cc ht to nn tinh th sp t thng
u trong khng gian. Bt ngun t bn cht , mt trong nhng thuc tnh ca tinh th l
kh nng t to hnh u n ring tu i xng bn trong ca mi pha rn. Trn a din tinh
th, cc nh, cnh v mt hay ni chung cc phn bng nhau ca n c th lp li nhau hoc
trng nhau nh nhng thao tc i xng. Nh vy, trong tinh th no vn d d hng i
vi mt tnh cht, tnh cht y c th bc l ging nhau theo nhng phng khc nhau (nu
chng l cc phng cn i [13]).
2.1 Yu t i xng v s lin gia chng.
Hai thao tc i xng l php phn chiu qua mt gng hay qua im v php quay
quanh trc; chng c th ho bng yu t i xng cc loi.
2.1.1 Yu t i xng
Tnh i xng bc l r trn b mt tinh th; s lp li c xc lp nh cc thao tc
chnh sau:
- Php phn chiu: cc phn bng nhau ca tinh
th c th lp li nhau, sau khi phn chiu trong
mt phng (mt gng) tng tng i qua trng
tm ca a din.
- Php quay: cc phn bng nhau ca a din
trng li nhau, sau khi quay quanh ng thng
tng tng i qua trng tm ca a din.
Tng ng vi hai thao tc y l hai yu t i xng
c trng cho hnh thi tinh th l mt i xng hay mt
gng v trc i xng hay trc xoay.
Ngoi hai yu t i xng ny cn c tm i xng hay
tm nghch o. y l php phn chiu qua im trng
tm. a din c tm nghch o th tng i mt i ca n
phi bng nhau v song song ngc nhau (hnh 2.1). Trong
trng hp ny, cc i mt i ny phi lp li nhau sau khi phn chiu qua mt im tng
tng nm trng vi trng tm ca a din.
Mt i xng hay mt gng: Hy b i tinh th mui n dng khi lp phng, n s
v ra thnh hai na bng nhau. a din lp phng bt k lun c ba mt gng trc giao,
song song vi cc mt vung ca a din (hnh 2.2,a). Ngoi ra, mt phng chia i khi a
din c th i qua i ng cho song song ca i mt i (hnh 2.2,b). Khi lp phng c
Hnh 2.1 a din cha yu t
i xng duy nht: tm i xng
29
6 mt gng loi ny v c thy n c 9 mt gng. Tinh th cc cht c mt, hai, ba, bn,
nm, by, chn mt gng. V d, tinh th thch cao CaSO
4
.4H
2
O ch c mt mt gng (hnh
2.3 v 2.4).

Hnh 2.2
Khi lp phng vi ba mt gng dc cc cnh (a) v su mt gng dc cc ng cho (b)
Trc i xng: Trong tinh th thch cao
c yu t i xng th hai l trc i xng.
y l ng thng i qua trng tm ca
hnh v vung gc vi mt gng (hnh 2.4).
Nu quay tinh th 360
o
quanh trc i
xng ny th a din tinh th s trng vi
chnh n hai ln. Mi ln ng vi gc
quay180
o
. l trc xoay (i xng) bc
hai hay trc hai. Trong tinh th khi lp
phng ca mui n, trc bc hai ni trung
im tng i cnh i; do n c 6 trc
hai. Ngoi ra, khi lp phng cn c ba
trc bc bn i qua trung im ca tng i
mt i v bn trc ba ni cc nh xuyn
tm i (hnh 2.5).
Trc bc bn c gc quay c s 90
o
, trc bc ba 120
o
. Vy, bc n ca trc
360
n

=


vi l gc quay c s, tc l gc quay nh nht cho php hnh trng vi n mt ln khi
xoay quanh trc.
Khi = 180
o
, n = 2, ta c trc xoay bc hai; khi = 120
o
, n = 3, trc xoay bc ba; khi
= 90
o
, n = 4, trc xoay bc bn; khi = 60
o
, n = 6, trc xoay bc su.

Hnh 2.3
Tinh th thch cao vi mt gng v trc bc
hai vung gc Trc bc hai song song mt hnh
(a) v vung gc mt hnh (b)
30




Hnh 2.4
Cc yu t i xng ca tinh th thch cao th
hin trn biu hnh chiu ni (cha k tm
nghch o ti giao im, xem sau)
Hnh 2.5
Cc trc bc hai, ba v bn ca khi lp phng
Trc i xng phc (trc phc).Trn y xt cc trc i xng n (trc n). Ngoi
php xoay (180
o
,120
o
, 90
o
, 60
o
), trc phc cha php nghch o gi l trc nghch o, cha
php phn chiu qua mt gng vung gc gi l trc gng.
Hnh 2.6,a gii thiu trc nghch o bc mt. im xoay mt vng quanh trc th tr v
im xut pht. Sau php nghch o im a ti v tr im a
1
. l tc dng ca trc nghch
o bc mt. Nu khng nghch o qua tm, m phn chiu qua mt gng vung gc vi
trc th im a s ti trng vi
'
1
a . l tc dng ca trc gng bc mt.

Hnh 2.6
Trc nghch o v trc gng bc mt (a) v bc hai (b)
S cho thy, trc nghch o bc mt tng ng tm i xng, cn trc gng bc
mt tng ng mt i xng gng.
Cc bc chuyn hnh hc ca trc nghch o bc hai th hin trn hnh 2.6.b. Trn s
, im a xoay 180
o
quanh trc th ti a, ri nghch o qua tm ca tinh th th ti a
1
. l
tc dng ca trc nghch o bc hai. By gi cho a

phn chiu qua mt gng vung gc th
n s v v tr
'
1
a . Nh vy, nh tc dng ca trc gng bc hai, im a ti trng vi
'
1
a
.

31
Trc nghch o bc hai tng ng trc gng bc mt hay mt gng (hnh b: t
im a sang a
1
), cn trc gng bc hai tng ng trc nghch o bc mt hay tm i
xng (hnh a: t im a sang a
1
).
Nhng thao tc thc hin bng trc nghch o bc ba th hin trn hnh 2.7,a. Mi im
a
1
, a
2
hay a
3
thuc phn trn ca tinh th c th ln lt trng vi mi im a
4
, a
5
hay a
6
ca
phn di bng php quay 120
o
quanh trc v phn chiu qua tm. im a
1
xoay 120
o
quanh
trc ti v tr a
2
ri nghch o qua tm ti trng vi a
4
; im a
2
xoay quanh trc ti a
3
,
ri phn chiu qua tm s trng vi a
5
; cng nh th, a
3
sang a
1
ri ti a
6.
y l tc dng ca
trc nghch o bc ba.

Hnh 2.7
Trc nghch o bc ba (a) v bc su (b)
Nu cc im phn trn tinh th sau khi xoay quanh trc, khng nghch o qua tm m
phn chiu qua mt gng vung gc, th chng s ln lt ti trng vi cc im phn di
(xem hnh 2.7,b). y l tc dng ca trc gng bc ba. Trong trng hp ny, mi im
phn trn nm ngay bn trn im phn di. By gi, nu cho mi im phn trn xoay 60
quanh trc (a
1
ti
'
1
a , a
2
ti
'
1
a v.v..) v ln lt nghch o qua tm tinh th th chng s ti
cc im phn di. y l trng hp ca trc nghch o bc su.
Quay li s hnh 2.7,a, c th a cc im phn trn ti trng cc im phn di
bng php xoay 60
o
v php phn chiu tip theo qua mt gng vung gc: thao tc ca trc
gng bc su.
Nh vy, trc nghch o bc ba tng ng trc gng bc su v trc nghch o
bc su tng ng trc gng bc ba.
Mt khc, trc nghch o bc ba l s kt hp ca trc xoay bc ba v tm i xng;
cn trc nghch o bc su (trc gng bc ba) l s kt hp ca trc xoay bc ba v mt
gng vung gc.
Hnh 2.8 gii thiu thao tc ca trc nghch o bc bn. dn cc im a
1
v a
2
pha
trn tinh th n cc v tr a
3
v a
4
pha di, hy cho chng xoay 90 quanh trc ri phn
chiu qua tm im. S cc im cho thy c th thay php nghch o qua tm bng php
phn chiu qua mt gng vung gc, m kt qu khng khc.

32

Hnh 2.8
Trc nghch o bc bn (a) th hin trn tinh th (b) v trn biu hnh chiu ni (c)
Nh vy, trc nghch o bc bn v trc gng bc bn l nhng yu t i xng tng
ng.
Nhn xt:
- Cc trc bc chn cha gc quay c s ca trc hai, ring trc bc su cn cha c
gc quay c s ca trc bc ba.
- Trc nghch o bc bn cha gc quay c s ca trc bc hai.
- Tinh th khng cha trc bc nm v trc bc cao hn su [13].
Tuy vy, trong thc t ch mt dng trc phc c s dng: trc nghch o. Hn na
trong i xng hnh thi chng hu ht c thay bng cc yu t i xng n: trc nghch
o bc mt thay bng tm i xng, trc nghch o bc hai thay bng mt gng, trc
nghch o bc ba thay bng trc xoay bc ba cng tm i xng v cui cng trc nghch
o bc su thay bng trc xoay bc ba cng mt gng vung gc.
Duy trc nghch o bc bn hay trc gng bc bn l khng th thay th bng bt k yu
t i xng no. V vy, tinh th hc hnh thi c by yu t i xng thng dng:
1) Tm i xng, hay tm nghch o, hay trc (i xng) nghch o bc mt, k
hiu 1 , hay C.
2) Trc xoay (i xng) bc hai hay trc hai, k hiu 2, hay L2.
3) Trc xoay (i xng) bc ba hay trc ba, k hiu 3, hay L3.
4) Trc xoay (i xng) bc bn hay trc bn, k hiu 4, hay L4.
5) Trc (i xng) nghch o bc bn, k hiu
4
, hay Li4.
6) Trc xoay (i xng) bc su hay trc su, k hiu 6, hay L6.
7) Mt i xng hay mt gng, k hiu m, hay P.
2.1.2 S lin quan gia cc yu t i xng
Mi a din tinh th ch c mt t hp yu t i xng biu th tnh i xng ca n.
Nhiu tinh th, tuy khc nhau v hnh dng, nhng li c chung nhng yu t i xng.
Chng hn, khi lp phng l a din tinh th ca mui n/halit NaCl v khi bt din u l
a din tinh th ca khong vt magnetit Fe
3
O
4
; cc a din ny c chung mt t hp yu t
33
i xng, mt nhm im: chng thuc mt lp tinh th. S lng a din tinh th th hng
vn v tng ln khng ngng theo thi gian. Chng tp hp li trong 32 lp tinh th vi mi
lp mt nhm im c trng cho i xng mi c th ca lp.
Nh k trn, trong tinh th hc hnh thi c 7 yu t i xng. Thot nhn, theo cch
t hp thng thng, t 7 yu t c th suy ra s nhm im nhiu hn 32. Thc ra, tinh th
hc c nhng quy tc nghim ngt p dng cho s t hp ny.
Quy tc mt
Hai trc bc hai giao nhau di gc 180 : n lm xut hin trc bc n vung gc vi
chng. Nu cc trc hai cng tn, trc n mi sinh s l trc xoay; nu chng khc tn th trc
bc n mi sinh s l trc nghch o. Nh s tng tc ca trc bc n, cc trc hai vung gc
vi n s tng s lng tng bng n, nu trc bc n l trc nghch o th vung gc s l cc
trc bc hai khc tn xen k nhau. Quy tc ny c th ho bng cc trng hp sau.
V d mt, vung gc vi hai trc xoay bc hai di gc 45
o
l trc xoay bc bn, ngoi
ra cc trc xoay bc hai vung gc s t s tng l 4. Trong v d hai, giao nhau di gc
45 l trc xoay bc hai v trc bc hai nghch o (hnh 2.9,a). Trc bc n mi sinh l trc
nghch o bc bn. Di tc dng ca trc bc hai trong n, s lng trc xoay bc hai
vung gc vi n s l 2, chng vung gc vi nhau. Xen gia chng l 2 trc bc hai nghch
o; trn hnh, chng thay bng 2
mt gng thng gc (yu t i
xng tng ng). Chng vung
gc nhau v nhn trc bc bn
nghch o lm giao tuyn. Trn
hnh 2.9,b l s ca v d th
ba, cc trc hai khc tn ct nhau
di gc 30. Trc i xng sinh
ra l trc nghch o bc su; n
biu th bng trc xoay bc ba cng
mt gng vung gc.
Quy tc hai
Mt i xng phn b trong a
din tinh th theo nhng cch sau :
- Vung gc vi trc i xng;
- i qua trc i xng, ct nhau di gc bng mt na gc quay c s ca trc xoay,
hay bng gc quay c s ca trc nghch o v nhn trc lm giao tuyn;
- Phn i gc gia 2 trc cng tn (xem hnh 2.9).
Quy tc ba
Trc cng tn c th ct nhau di nhng gc hon ton xc nh:
- Trc bc hai ct nhau di gc 60, 90, 120 v 180;
- Trc bc ba ct nhau di gc 703144 v 180;
- Trc bc bn ct nhau di gc 90 v 180;

Hnh 2.9
Cc trc hai khc tn (trc xoay v trc nghch o) ct nhau
sinh trc bc n nghch o vung gc a) di 45
o
cho trc
bn v b) di 30
o
cho trc su
34
- Trc bc su ct nhau di gc 180.
V d, trong a din lp phng, cc trc bc bn u ct nhau di gc vung, cn cc
trc bc ba th di gc 703144 (xem hnh 2.5) cc trc cng tn ny cng ct nhau di
gc 180.
Di nh sng ca quy tc ny, c th a ra khi nim trc phn cc; trc ni hai phn
khc nhau ca tinh th. Cc trc cn li ni hai u ging nhau ca tinh th; ni cch khc,
chng l hai trc ct nhau di gc 180, do tc ng ca t nht mt trong ba yu t i xng
m chng cha: tm i xng, mt gng/trc bc hai vung gc.
Quy tc bn
Nu tinh th c phng n (l phng khng chu tc dng ca yu t i xng), mi
yu t i xng c th trng vi n v khng th ct n di gc bt k. Ring trc bc hai c
th ct n di gc vung [13].
Cc trc nghch o bc bn (a) hay bc su (b) trn hnh 2.9 u trng vi phng n;
s trn hnh khng cho thy yu t i xng no ct chng, tr cc trc bc hai.
2.2 Nhm im i xng v hnh n ca chng
a din tinh th d phong ph, chng u quy v 47 hnh n. Tu tnh i xng ca
chng, s hnh n ny c suy on bng cc thao tc i xng ca 32 nhm im.
2.2.1 Suy on nhm im i xng
Nh trn ni, v mt hnh thi tinh th chia ra lm 32 lp; c trng cho i xng ca
mi lp l dng i xng, cn gi nhm im i xng hay nhm im (tt c cc yu t i
xng ca nhm im u nhn trng tm ca tinh th lm giao im, im bt bin).
Di y, s suy on 32 nhm im bng vic s dng 5 dng i xng n gin nht
(hnh 2.10). Tng ng vi chng l 5 hnh n (tp hp cc mt lin quan vi nhau nh cc
yu t i xng ca nhm im). Tham kho cc chng tng ng [13,14] bit thm cc
cch suy on nhm im v hnh n.
a) Tinh th dng ny khng c yu t i xng (ch c trc bc mt). Ht thy cc
mt trn a din tinh th u khc nhau, nn khng trng lp nhau. Mi mt cho
mt hnh n. l hnh n mt mt (hnh 2.10,a).
35

b) Tinh th cha tm i xng. Mi mt trn a din u c mt mt i bng n,
song song ngc chiu vi n. Hai mt i ny to hnh n gi l i mt (hnh
2.10,b).
c) i xng ca tinh th th hin bng trc bc hai (phn cc). Mi mt u c th
trng vi mt khc bng php xoay 180 quanh trc. Hai mt v tr tng qut
ny ko di s ct nhau nh hai mi nh (hnh 2.10,c) to nn hnh n hai mt
(trc).
d) Tng cp mt dng mi nh i xng nhau qua mt gng duy nht, cho hnh n
hai mt (hnh 2.10,d). Hnh n hai mt ny sinh ra do tc ng ca mt gng,
khc vi hai mt (trc) do trc hai sinh ra. Nhiu tc gi phn bit hai hnh n:
hai mt v hai mt trc, nn s hnh n s l 48 thay cho 47.
e) i xng ca a din biu th bng t hp 2 yu t i xng trc giao: trc xoay
bc hai v mt gng. Nh nhng thao tc i xng ny, mt v tr tng qut
ny (hnh 2.10,e) s sinh ra hnh n lng tr (trc thoi).
Di tc dng ca mi trc i xng bc cao, 5 dng i xng n gin km hnh n
ny s cho 5 dng i xng/hnh n cao hn.
Hnh 2.11 gii thiu 5 dng i xng/hnh n khc nhau, hnh thnh nh tc dng ca
trc bc ba i vi 5 dng i xng/hnh n chnh k trn. Chng hn, hnh n mt mt
xoay quanh trc bc ba phn cc cho hnh n thp ba phng (hnh 2.11,a). Sau ba ln quay
quanh trc bc ba ny, hnh n i mt to hnh n mt thoi vi cc yu t i xng l trc
bc ba, ba mt gng nhn n lm giao tuyn, ba trc bc hai vung gc vi n (mi trc hai
cn vung gc vi mt mt gng) v tm nghch o (hnh 2.11,b). Bng cch tng t,
hnh n hai mt (trc) cho hnh n mt thang ba phng vi trc i xng bc ba v ba
trc xoay bc hai phn cc vung gc (hnh 2.11,c).
36

Hnh 2.11
Nm dng i xng suy ra t s kt hp gia trc ba vi mi dng i xng n gin
Hnh n hai mt cho hnh n thp ba phng kp vi trc bc ba phn cc v ba mt
gng nhn n lm giao tuyn (hnh 2.11,d). Hnh lng tr trc thoi cho hnh n mt tam
gic lch ba phng vi trc bc ba, ba mt gng nhn n lm giao tuyn, ba trc bc hai v
tm i xng (hnh 2.11,e).
Ln lt thay trc i xng bc ba bng cc trc i xng cao hn v x l nh trn s
nhn c tt c cc t hp c trng ca 32 nhm im (mi nhm ly tn ca hnh n tng
qut ca n, xem thm bng 2.1) nh lit k di y [13,14].
Khng c yu t i xng:
1) Nhm im mt mt
Ch c trc i xng:
2) Nhm im hai mt (trc) vi trc xoay bc hai.
3) Nhm im thp ba phng vi trc bc ba.
4) Nhm im thp bn phng vi trc bc bn.
5) Nhm im thp su phng vi trc bc su.
6) Nhm im bn mt ba (ng gic) vi 4 trc bc ba nh hng nh 4 ng cho
ca khi lp phng v 3 trc xoay bc hai trc giao chy dc cc cnh ca n.
7) Nhm im bn mt trc thoi vi 3 trc xoay bc hai vung gc.
8) Nhm im mt thang ba phng vi trc xoay bc ba v 3 trc xoay bc hai vung
gc.
9) Nhm im mt thang bn phng vi trc xoay bc bn v 4 trc xoay bc hai
vung gc.
10) Nhm im mt thang su phng vi trc xoay bc su v 6 trc xoay bc hai vung
gc.
37
11) Nhm im tm mt ba (ng gic) vi bn trc bc ba nh hng dc 4 ng cho
ca khi lp phng, ba trc xoay bc bn dc cc cnh v 6 trc xoay bc hai ni
trung im cc cnh i ca n.
Ch c trc nghch o:
12) Nhm im i mt vi trc nghch o bc mt (tm i xng).
13) Nhm im hai mt vi trc nghch o bc hai (mt gng).
14) Nhm im mt thoi vi trc bc ba nghch o (trc xoay bc ba cng tm nghch
o).
15) Nhm im bn mt bn phng vi trc nghch o bc bn.
C trc v mt gng vung gc (trng hp trc chnh mang bc chn s c thm tm
i xng):
16) Nhm im lng tr (trc thoi) vi trc xoay bc hai, mt gng vung gc v tm
i xng.
17) Nhm im thp i ba phng vi trc xoay bc ba v mt gng vung gc. T
hp ny tng ng trc nghch o bc su.
18) Nhm im thp i bn phng vi trc xoay bc bn, mt gng vung gc.
19) Nhm im thp i su phng vi trc xoay bc su, mt gng vung gc.
20) Nhm im mi hai mt kp vi 3 trc bc hai song song vi cc cnh ca khi lp
phng, 3 mt gng vung gc vi chng, v 4 trc bc ba dc 4 cho ca khi lp
phng.
C trc v cc mt gng i qua (song song):
21) Nhm im thp trc thoi vi trc xoay i xng bc hai v hai mt i xng gng
trc giao nhn n lm giao tuyn.
22) Nhm im thp ba phng kp vi trc xoay i xng bc ba v ba mt gng giao
nhau di gc 120.
23) Nhm im thp bn phng kp vi trc xoay i xng bc bn v bn mt i
xng gng giao nhau di gc 45.
24) Nhm im thp su phng kp vi trc xoay i xng bc su v su mt gng
giao nhau di gc 30.
25) Nhm im bn mt su (tam gic) vi bn trc i xng bc ba nh hng dc 4
ng cho ca khi lp phng, ba trc bc bn nghch o chy dc cc cnh ca
n v su mt gng chy dc cc trc bc ba.
C trc nghch o v mt gng i qua (song song):
26) Nhm im mt tam gic lch bn phng vi trc bc bn nghch o, hai mt
gng nhn n lm giao tuyn v hai trc xoay bc hai vung gc vi trc nghch
o, phn i gc gia cc mt gng.
27) Nhm im mt tam gic lch ba phng vi trc bc ba nghch o, ba mt gng
nhn n lm giao tuyn v ba trc bc hai vung gc.
38
C trc v cc mt gng:
28) Nhm im thp i trc thoi vi ba trc bc hai trc giao, ba mt gng vung gc
vi chng v tm i xng.
29) Nhm im thp i ba phng kp vi trc bc ba, ba trc hai vung gc vi n v
bn mt gng (1 mt vung gc vi trc ba v i qua cc trc bc hai, cn li mi
mt cha mt trc bc ba v mt trc bc hai).
30) Nhm im thp i su phng kp vi trc xoay bc su, su trc xoay bc hai, by
mt gng (1 mt vung gc vi trc bc su + 6 mt i qua tt c cc trc) v tm
i xng.
31) Nhm im thp i bn phng kp vi trc xoay bc bn, bn trc xoay bc hai
vung gc vi n, nm mt gng (1 mt vung gc vi trc bc bn + 4 mt i qua
tt c cc trc) v tm i xng.
32) Nhm im tm mt su (tam gic) vi bn trc bc ba nghch o nh hng nh 4
cho ca khi lp phng, ba trc xoay bc bn chy dc cc cnh ca n, su trc
xoay bc hai phn i gc gia cc trc bc bn, chn mt gng vung gc vi cc
trc bc chn v tm i xng.
Trn y l tt c cc t hp c th c ca cc yu t i xng.
Thi gian u t khi c chng minh, khng phi ht thy 32 dng i xng u c v
d thc t nh hin ti. Cho ti nay, trong s hng vn cht bao gm cc tinh th t nhin
(khong vt) v nhn to cha c trng hp no nm ngoi 32 lp tinh th.
2.2.2 Hng, h tinh th
Cn c trn c im cc t hp yu t i xng c th chia 32 dng i xng thnh ba
hng:
- Hng thp; tinh th hng ny khng cha trc bc ba, bc bn, bc su.
- Hng trung; tinh th cha trc chnh thng ng; trc bc ba, trc bc bn v trc
bc su.
- Hng cao; tinh th cha 3 trc trc giao: bc bn (xoay hay nghch o) hoc bc
hai v lun cha bn trc bc ba.
Hng thp c 8 lp, hng trung 19 lp, hng cao 5 lp. Cc lp tinh th cn phn chia
thnh cc h sau:
a) H ba nghing khng c mt v trc i xng, c th c tm i xng.
b) H mt nghing ch cha mt trc hai v (hay) mt mt gng.
c) H trc thoi ch cha trc hai v mt gng; c th c n ba trc hai hay ba mt
gng trong h.
d) H bn phng nhn trc bc bc bn (trc xoay hoc trc nghch o) lm trc
chnh.
39
e) H su phng vi hai ph h u nhn cc trc i xng (trc xoay hay trc
nghch o) lm trc chnh: trc bc ba ca ph h ba phng v trc bc su ca
ph h su phng.
f) H lp phng thuc hng cao vi 4 trc bc ba.
2.2.3 K hiu nhm im
Nh ni trn, mi lp c trng bng mt t hp nht nh yu t i xng (mt nhm
im). Mi nhm im biu th bng mt cng thc tinh th hc tng ng. V d lp tm
mt su c cng thc: 3L
4
4L
3
6L
2
9PC (xem nhm im 32), lp thp i trc thoi: 3L
2
3PC
(nhm im 28), hay L
2
L
2
L
2
PPPC, vi cc trc hai (v cc mt gng) khng tng
ng. Lp thp i su phng kp L
6
6L
2
7PC, y cc trc bc hai (cng nh cc mt
gng) gm hai loi. tin li hn, thay vo cng thc kiu Bravais ny, mt s cch k
hiu khc ra i.
K hiu Schoenflies
Nhng nhm ch cha trc th k hiu ca chng u c ch C, bc ca trc biu din
bng ch s di. Chng hn, C
1
C
2
C
3
C
4
C
6
l nhng nhm vi mt trc duy nht cho mi
lp. Nhng nhm cha thm mt gng (nm ngang) vung gc c thm k hiu di h ngay
sau ch s ch bc ca trc. Do , k hiu C
2h
C
3h
C
4h
v C
6h
c trng ln lt cho cc nhm
lng tr (trc thoi), thp i ba phng, thp i bn phng v thp i su phng. Trc
cha thm mt gng (thng ng) th s c k hiu di v t ngay sau ch s, ch s ny
cng cho thy s mt gng thng ng tng ng: C
2v
C
3v
C
4v
v C
6v
.
Lp hai mt (s 13) c k hiu C
S
vi trc hai nghch o thay bng mt gng tng
ng.
Nhng nhm vi trc chnh v trc bc hai thng gc, m s lng ca chng cng ch
bc ca trc chnh, th biu th bng ch D. l cc lp bn mt trc thoi D
2
, mt thang ba
phng D
3
, mt thang bn phng D
4
v mt thang su phng D
6
.
Cc k hiu ny cha thm k hiu di h, nh D
2h
D
3h
D
4h
v D
6h
dng biu th ln lt
cc nhm im sau: thp i trc thoi, thp i ba phng kp, thp i bn phng kp v
thp i su phng kp.
Cc nhm mt tam gic lch bn phng v mt tam gic lch ba phng k hiu bng
D
2d
(hay V
d
) v D
3d
. Ch d cho thy mt gng nm cho, v tr phn i gc ca cc trc
bc hai. Nhng lp cha trc gng duy nht, bc bn v bc su, c k hiu S
4
v S
6.
Nh
bit, trc gng bc su tng ng trc nghch o bc ba, nn S
6
c th vit thnh C
3i
.
Cng v vy, lp i mt k hiu C
i
.
Cc lp ca h lp phng thng bt u bng T v O (tetrahedral: thuc t din v
octahedral: thuc bt din); T l nhm im bn mt ba (ng gic), O tm mt ba (ng gic),
in thm k hiu di h v d tu trng hp:
T
h
mi hai mt kp,
O
h
tm mt su (tam gic),
T
d
bn mt su (tam gic).
40
Bng 2.1
H thng tinh th theo h v lp
K hiu lp*
H/ph h Lp tinh th
1) 2) 3)
Ba nghing Mt mt
i mt
L
1
C
C
1

Ci = S
2
1
1
Mt nghing Hai mt trc
Hai mt
Lng tr (trc thoi)
L
2
P
L
2
PC
C
2
C
S

C
2h
2
m
2/m
Trc thoi Bn mt trc thoi
Thp trc thoi
Thp i trc thoi
3L
2
L
2
2P
3L
2
3PC
D
2

C
2v

D
2h

222
mm2
Mmm
Bn phng Thp bn phng
Thp i bn phng
Mt thang bn phng
Thp bn phng kp
Thp i bn phng kp
Bn mt bn phng
Mt tam gic lch bn phng
L
4

L
4
PC
L
4
4L2
L
4
4P
L
4
4L
2
5PC
Li
4
Li
4
2L
2
2P
C
4

C
4h

D
4

C
4v

D
4h

S
4

D
2d

4
4/m
422
4mm
4/mmm
4
4 2m
Ba phng Thp ba phng
Mt thoi
Mt thang ba phng
Thp ba phng kp
Mt tam gic lch ba phng
L
3
L
3
C
L
3
3L2
L
3
3P
L
3
3L
2
3PC
C
3
C
3i

D
3
C
3v

D
3d

3
3
32
3m
Su phng Thp su phng
Thp i su phng
Mt thang su phng
Thp su phng kp
Thp i su phng kp
Thp i ba phng
Thp i ba phng kp
L
6

L
6
PC
L
6
6L
2

P
6
6P
L
6
6L
2
7PC

L
3
P
L
3
3L
2
4P
C
6
C
6h

D
6

C
6v
D
6h

C
3h

D
3h

6
6/m
622
6mm
6/mmm
6
6
Lp phng Bn mt ba (ng gic)
Mi hai mt kp
Tm mt ba (ng gic)
Bn mt su (tam gic)
Tm mt su (tam gic)
4L
3
3L
2
3L
3
3L
2
3PC
3L
4
4L
3
6L
2
3Li
4
4L
3
6P
3L
4
4L
3
6L
2
9PC
T
T
h

O
T
d

O
h

23
m3
432
4 3m
m3m
Ch thch: * k hiu theo 1) Bravais, 2) Schoenflies, 3) Hermann-Mauguin
K hiu Hermann-Mauguin
Trc i xng k hiu bng s ch bc ca n, mt gng bng ch m. Trc xoay bc hai,
ba, bn v su k hiu ln lt 2, 3, 4 v 6. Vch ngang t pha trn ch s l trc nghch
o; 4 l trc nghch o bc bn (xem 2.1.1).
Cc nhm im khc k hiu bng nhng kt hp khc nhau ca cc ch s v ch m.
Mt gng vung gc vi trc i xng th gia n v trc c gch ngang hay cho dng
phn s. V d : 2/m l nhm vi trc bc hai vung gc vi mt gng (tm nghch o l
kt qu ng nhin). Nu 2 k t ny vit lin nhau th l v chng song song nhau (mt
cha trc). 222 l nhm im c 3 trc xoay bc hai trc giao;
2 2 2
m m m
l nhm thp i trc
thoi. K hiu ny rt gn thnh mmm: 3 mt gng trc giao sinh ra trn giao tuyn 3 trc
xoay i xng bc hai, tm i xng nm trn giao im. Nhng yu t i xng sinh ra l
41
kt qu ng nhin th khng ch ra trn php k hiu. Nh vy, nhm tm mt su (tam
gic) biu hin bng k hiu
4 2
3
m m
, hay vit tt thnh m3m.
Trc chnh s ng u trong k hiu nhm im tinh th cc h hng trung. Mt gng
thng gc nu c, s lm vi n mt v tr, di dng phn s. V tr th hai dnh cho yu t
i xng dc trc to OX (OU) v OY. V tr th ba (thng b trng trong ph h ba
phng) l cc yu t i xng dc hng phn gic ca cc gc gia cc trc ta ngang.
V d: nhm im 4/mmm.
H trc to tinh th hc
Tinh th h 3 nghing c h trc to tng qut nht. Cc on a, b, c trn 3 trc OX,
OY, OZ khng bng nhau, tc l cc trc khng tng ng. Cc gc gia OY v OZ,
gia OX v OZ, gia OX v OY cng khc nhau. Mi tinh th 3 nghing c nhng gi tr
xc nh ca cc gc v cnh y.
Trong tinh th 1 nghing c 2 gi tr gc bng gc vung, l gc gia OY v OX, gia
OY v OZ; gc gia OX v OZ l gc nghing, quy c ly gi tr ln hn gc vung. Cc
gi tr a, b, c khc nhau. Trong h, trc bc 2 v tia php ca mt gng c chn t trc
OY. Cn 2 trc kia, cng nh c 3 trc ca tinh th 3 nghing, u t theo cc cnh thng
gp nht (theo trc ca i pht trin nht), u tin OZ hn.
Tinh th trc thoi c h trc to trc giao, chy dc cc trc bc hai hay/v php tuyn
ca mt gng v khng tng ng, ging 2 h trn: a, b, c khc nhau.
Tinh th 4 phng cng c h trc vung gc v a v b bng nhau. Trc th 3 l c thng
ng lun trng vi trc i xng bc 4 (trc xoay hay trc nghch o). Cc trc ngang t
dc trc bc 2, hoc dc tia php mt gng, hoc dc theo cc i pht trin nht. c s
ca h 4 phng l t s a : c.
Tinh th h su phng c gc gia OX v OY bng 120 v hai gc vung, a =
b. Trc OZ ng trng vi trc bc ba v trc bc su. Ring ph h ba phng c mng mt
thoi vi a = b = c v gc gia cc trc tinh th hc bng (khi gc ny 90 mng chuyn
sang h lp phng). Thc ra, mng ny ch l trng hp c bit ca h su phng [14].
Tinh th h lp phng c cc trc to vung gc v tng ng do tc ng ca 4
trc bc 3. Chng song song vi 3 trc bc 4 (trc xoay hoc trc nghch o) hoc 3 trc
xoay bc 2. Nh vy thng s a l c s duy nht ca tinh th h ny.
i xng ton mt, phn na mt, phn t mt.
Mi h tinh th u c mt lp i xng cao nht v vi hnh n nhiu mt nht; l
s mt ca hnh n tng qut ca nhm im v l c s ca i xng cao nht y. l
lp i xng ton mt:
H ba nghing c lp i mt.
H mt nghing c lp lng tr (trc thoi).
H trc thoi c lp thp i trc thoi.
H bn phng c lp thp i bn phng kp.
Ph h ba phng c lp mt tam gic lch ba phng.
42
Ph h su phng c lp thp i su phng kp.
H lp phng c lp tm mt su (tam gic).
T lp i xng ton mt c th suy ra nhng lp cn li ca h bng cch h cp i
xng c hnh n tng qut (htq) tng ng: phn na mt v hnh n phn t mt. S
trin khai c th din t i vi h lp phng lm v d nh sau.
Bng 2.2
Cc cp i xng ca h lp phng
Dng i xng Cp i xng i lng i xng*
O
h
Dng i xng ton mt 48
T
d
O T
h
Dng i xng phn na mt 24
T Dng i xng phn t mt 12
* i lng i xng ca dng i xng tnh bng s mt ca hnh n tng qut ca
n.
2.2.4 Khi lc v hnh thi tinh th
a din tinh th biu hin di dng hnh ghp ca cc hnh n. Hnh n ca tinh th
hon thin c cc mt vi mi tnh cht ging nhau. Hnh n l tp hp cc mt lin quan
vi nhau bng cc yu t ca mt nhm im. N c suy ra t cc thao tc i xng ca
mt nhm im; hy t mt mt cho trc ti v tr no so vi cc yu t i xng, di
tc dng ca cc thao tc ny mt cho trc s cho mt tp hp cc mt, y l mt hnh n
hon chnh.
Vy, hnh n gn lin vi a din tinh th thng qua nhm im ca n. V mt l
thuyt, mi nhm im c th c mt s hu hn cc hnh n. Trong s c cc hnh n
c bit v mt hnh n tng qut duy nht vi s mt ln nht. Mt ca hnh n c bit
th hoc vung gc vi yu t i xng hoc song song vi chng, hoc ct xin cc yu t
i xng tng ng di cng mt gc (cc yu t i xng cng tn ca nhm im c
th khng tng ng nu chng khng trng nhau nh cc yu t i xng khc trong
nhm im). Hnh n gi l tng qut nu mt ca n nm ti v tr bt k so vi cc yu t
i xng ca a din tinh th. N ng vai tr tinh th hc rt quan trng; tn ca n c ly
t cho nhm im (tham kho bng 2.1), cn s mt ln nht ca n l i lng i
xng ca nhm im, nh lng cho mc i xng ca tinh th (bng 2.2).
Tt c c 47 hnh n [13,14] v chng phn b trn cc h nh trn bng 2.3. Ngoi
hnh n hai mt, nhiu tc gi cn k thm hai mt trc, nng s hnh n ln 48; tn ca
chng cng l tn ca cc nhm im m (P) v 2 (L
2
).
Bng 2.3
S phn b hnh n ti cc hng, h
Hng tinh th H S hnh n
Thp 7 (hoc 8)
Trung Bn phng
Su phng
9
16
Cao Lp phng 15
Mt s hnh n ca hng thp cng c mt hng trung. Hnh n c bit ca mt lp
c th l tng qut ca lp khc; chng hn, lng tr trc thoi l hnh n c bit thuc h
trc thoi, li l hnh n tng qut ca lp ton mt thuc h mt nghing. Nhiu hnh n
43
ca ph h ba phng cng c mt trong ph h su phng. l cc lng tr nh lng tr
ba phng, lng tr ba phng kp v cc thp i nh thp i ba phng, thp i ba
phng kp. Mt lot hnh n ca ph h su phng nh thp, thp i v cc lng tr cng
c mt trn tinh th cc lp ba phng.
Bng thng k cho thy mi tng quan ph thuc gia s hnh n v i xng ca h.
C th, i xng ca h cng cao th s hnh n ca n cng ln. Mi hnh n u c th
suy ra t 5 hnh n chnh (hnh 2.10) bng cch t chng vo tc dng ca cc trc i
xng vi bc khc nhau (hnh 2.11).
Hy quan st trn hnh 2.12, cc hnh n thay i ln lt trn cc h trc khc nhau t
tri sang phi; t hnh n i xng thp nht sang hnh n i xng cao nht. Hng gia l
hnh chiu ca chng trn mt nm ngang.
Trong h ba nghing, trc to khng tng ng v ct nhau thnh nhng gc bt k.
Hnh n tng qut vi i xng cao nht l hnh i mt vi k hiu {hkl}. Sang h mt
nghing vi = = 90, t mt mt v tr tng qut xut hin mt hnh n khc hn v i
xng cao hn: 2/m. l hnh lng tr trc thoi {hkl}. Trong h trc thoi, c gc cng
vung, nhng 3 thng s trn 3 trc to vn khc nhau, th mt cho trc ti v tr tng
qut s cho hnh n pht trin cao hn na vi i xng mmm. l hnh n tng qut
thp i trc thoi {hkl}. Trong h 4 phng vi cc thng s trc ngang bng nhau (a = b);
trc thng ng l trc bc bn thay cho trc bc hai ca h trc thoi. Hai hnh n s xut
hin vi cc mt u ct c 3 trc v vi i xng 4/mmm:
Hnh n c bit thp i bn phng {hhl}.
Hnh n tng qut thp i bn phng kp {hkl}vi mt ct ngang t gic kp u
n (ng t, hng gia, hnh 2.12).


Hnh 2.12
Hnh n i mt v thp i pht trin trong tinh th thuc cc h vi ba trc to
44
Trong h lp phng 4 trc bc ba lm xut hin hnh tm mt su {hkl}, tng qut
vi 48 mt, mt ct ngang ca n (ng t) ging hnh trn. Cng lp i xng cn c hnh
n c bit {111} tm mt, vi i xng cao hn thp i bn phng. Ngoi ra, c th cn
2 hnh trung gian gm 24 mt {hhl}: tm mt ba t gic vi h < l v tm mt ba tam gic vi
h > l (xem thm cui mc).
Hnh 2.12 (hng di) gii thiu lot hnh n sinh ra t mt cho trc, ch ct mt trong
ba trc to . Tinh th hng thp c ba hnh i mt {100}, {010} v {001}. Hnh n {100}
ca h bn phng l lng tr, trong h lp phng l hnh lp phng (su mt).
Nhng hnh n h lp phng v nhng thp i va k u l nhng hnh n kn v
c th mt mnh lm nn a din tinh th. Hnh i mt, lng tr trc thoi l nhng hnh n
m, ch bt gp chng trong hnh ghp.
By gi, thay vo cc mt v tr tng qut l cc mt ch ct 2 trc tinh th hc v song
song vi trc th ba, thc hin cch nh trn cng c th thu c hng lot hnh n t i
xng thp, t mt n hnh n i xng cao vi s mt nhiu hn (hnh 2.13).

Chng hn, mt song song vi trc c trong lp ton mt h ba nghing cng s cho hnh
n i mt, nhng vi k hiu { hk0 } v {hk0}. Hnh n {hk0} l lng tr trc thoi, tng
qut trong h mt nghing v c bit trong h trc thoi. Cng c bn mt, nhng lng tr
bn phng c k hiu {110}, cn k hiu {hk0} trong h bn phng li l hnh n lng tr
bn phng kp vi tm mt v mt ct ngang ging nh ca thp i bn phng kp (hnh
2.12). Trong h lp phng, k hiu {110} l ca hnh c bit mi hai mt thoi; ging nh
mi hnh n h lp phng, n cng l hnh n kn. Cc hnh lng tr trn hnh 2.13 u l
hnh n m: chng u phi kt hp vi hnh n khc trong a din, v d vi hnh i mt
y {001}, song song vi hai trc ngang.
Bng cch lun gii tng t, c th dn ra hng lot hnh n song song vi trc a. H
ba nghing, lp ton mt c cc hnh i mt {0kl} v { 0kl }. Hnh n {0kl} l lng tr trc
thoi ca cc h mt nghing (ton mt) v h trc thoi, l thp i bn phng trong i xng
phn na mt v ton mt h bn phng. H lp phng vi ba trc to tng ng c
mi hai mt ng gic, su mt bn tam gic (phn na mt v ton mt) ng vi trng hp
ny. Mi hai mt thoi l hnh n c bit vi k = l.
Mt song song vi trc b vi k hiu {h0l} hay {101} cho lot hnh n tng t, tr h
mt nghing s l i mt thay cho lng tr. Hnh 2.14 dn ra mt lot hnh n phn na mt
45
v ct c ba trc ta . l hnh mt mt trong h ba nghing, hai mt trong h mt
nghing, bn mt trc thoi trong h trc thoi, bn mt bn phng trong h bn phng v
bn mt (t din u) ca h lp phng.

Hnh n ca h lp phng v s lin quan gia chng (hnh 2.15)
Trn y, trong khi suy on hnh n hng thp v hng trung, thy xut hin nhng
hnh c s ca h lp phng (xem cc hnh 2.12 v 2.14): hnh lp phng vung gc vi
trc ta , hnh bt din vi trc ba lng cc, t din {111} v {11 1 } vi trc ba n cc.
Da vo i xng ring ca mt cc hnh ny, ta cho xut hin cnh nc nh hoc nh
mi thp ti trung im ca chng [14].

a) Hnh n hk0 dn
xut t hnh lp phng/su
mt:
Hnh mi hai mt ng
gic c th gi l su mt
hai ng gic nu cho xut
hin cnh trn mt hnh su
mt.
Hnh su mt bn (tam
gic) nu cho xut hin
nh trn mt hnh lp
phng.
Hnh mi hai mt thoi
{110} suy t hnh lp
phng qua hnh trung gian
su mt bn tam gic.
b) Hnh n {hhl} vi
h > l. Trong cc nhm im
m3m, 432, m3 mt tam gic
u ca bt din thay bng
Hnh 2.14. Mt s hnh n phn na mt pht trin t hnh 2.12 (hng trn)

Hnh 2.15
Lp phng, tm mt v nhng hnh dn xut
46
thp ba mi: hnh n nhn c l tm mt ba tam gic. Trong trng hp t din (43m v
23) s l bn mt ba t gic. Khi dc cc mt ny tng ti hn, tc l h0 th (hhl)
(011), cc hnh dn xut ny cng thnh mi hai mt thoi.
c) Hnh n {hhl} vi h<l dn xut ca hnh tm mt v bn mt. Hnh tm mt cho
tm mt ba t gic, hnh bn mt cho bn mt ba tam gic.
d) Hnh n tng qut
* Nhm im m3m: khi mt (111) chuyn vo v tr tng qut th mt tam gic u ca
hnh tm mt bin thnh 6 tam gic thng. Hnh n nhn c l tm mt su (tam gic).
* Nhm im 43m: mt (111) ca t din u chuyn vo v tr tng qut s nhn ln 6
ln: bn mt su (tam gic).
* Nhm im m3: Hnh n tng qut ca nhm c th suy t hnh lp phng; mt ca
mi hai mt ng gic vn dn xut t s nhn i bng 3 mt gng ca nhm im.
Hnh n l mi hai mt kp hay hnh hai mi bn mt.
* Nhm im 432 v 23: Cc hnh n ca chng suy t bt din hay t din c tm
mt ba ng gic v bn mt ba ng gic. Vi t cch l dn xut ca hnh lp phng, chng
c th gi l su mt bn ng gic v su mt hai ng gic.



47
Chng 3
HNH HC CU TRC TINH TH
Nhng ni dung v 32 nhm im v v 47 hnh n l nhng vn thun tu hnh thi,
thuc v tinh th hc v m. Sau khi xut hin phng tin phn tch cu trc tinh th (chng
hn, tia X v nng lc nhiu x ca n trong mng tinh th, u th k XX), kh nng i su
vo cu trc bn trong tinh th, vo tinh th hc vi m mi c rng m.
3.1 I XNG CA CU TRC TINH TH
Ni dung c bn s xem xt di y l 230 nhm i xng khng gian. Trong khun
kh ca chng ny, nhm im (t hp yu t i xng ca hnh hu hn) l ch xut pht
suy on nhm khng gian, tp hp yu t i xng ca hnh v hn.
3.1.1 Yu t i xng trong mng tinh th
Nhng yu t i xng ca a din tinh th, cng c mt ht thy trong cu trc tinh th.
l:
Trc xoay cc bc hai, ba, bn, su;
Mt gng;
Trong s cc trc nghch o, ngoi tm i xng v trc bc bn nghch o,
mng tinh th cng c cc trc nghch o bc ba v bc su (chng c mt
y khng phi di dng tp hp kiu Bravais L3C v L3P).
Nhng c trng ca mng, ngoi mi bn loi mng Bravais (hay php tnh tin), cc
yu t i xng phc l trc v mt i xng, m ngoi php xoay v php phn chiu cn
cha thm php trt. l:
Trc xon;
Mt nh trt.
Mi bn loi mng Bravais
Mng khng gian c m t nh h thng trt t cc nt im. Trong h thng y, 8 nt
bt k k nhau cho mt khi bnh hnh c s. Cho nn, mng khng gian c th xem nh h
thng cc khi bnh hnh c s xp song song v k nhau. Mt mng khng gian n gin
(nguyn thu), s khi bnh hnh c s bng nhau y bng s nt ca mng.
Mng khng gian c 14 loi xc nh. Mi loi c mt mng c s; n tiu biu cho
tinh th v mt i xng v tun theo nhng quy phm quc t v php nh trc. Cn nhc
li rng mi loi mng c th thay th bng chm cc vect (bc) tnh tin chung gc ti
nh. nguyn thu P hay R vi 8 nt ti nh th thay bng 3 vect tnh tin trng vi cc
cnh ca c s. Ngoi nguyn thu vi nt ti nh tc l 3 bc tnh tin trng cc cnh,
phi k thm:
48
mng tm khi I c thm nt ti tm , tc l bc tnh tin th t
xyz
T

dc
cho khi v vi ln bng mt na cho.
mng tm y C (hay A/B trong h trc thoi) c thm nt ti tm hai y, tc
l bc tinh tin th t
xy
T

(hay
yz
T

/
xz
T

) theo hng cho y v vi ln


bng mt na cho.
mng tm mt F c thm cc nt ti tm cc mt, tc l 3 bc tnh tin dc
ng cho cc y
xy
T

,
yz
T

v
xz
T

vi ln bng mt na cho.
Vy, mi loi mng l mt nhm bc tnh tin: mng nguyn thu P l 3 bc, mng
tm khi I 4 bc, mng tm y C 4 bc, mng tm mt F 6 bc. Tht ra, ch cn 3 bc
tnh tin l c trng cho mi loi mng [13].

Trc xon
Trong s cc trc phc bit c trc nghch o (gm php xoay v php nghch o)
v trc gng (gm php xoay v php phn chiu qua mt gng vung gc). Trc xon
(hnh 3.1) cng l trc phc: n bao gm php xoay bng 360 : n v bc trt. Mng khng
gian c th c trc xon bc hai, bc ba, bc bn v bc su.
Chng phn bit khng nhng bng gc quay c s, m cn bng ln ca bc trt.
V d: Trc xon bc hai 2
1
c gc quay c s 180 v bc trt t

bng 1/2 ca bc tnh


tin T

tng ng (bc tnh tin ca mng dc theo trc). Trc xon bc ba 3


1
c gc quay
c s bng 120 v bc trt
z
t

bng 1/3 ca
z
T

. Trong mng c nhng trc xon sau y:


T
4
T
4

49


2
1
3
1
3
2
4
1
4
2
4
3
6
1
6
2
6
3
6
4
6
5
.
Trong , mt s ghp vi nhau thnh nhng cp trc phi-tri: 3
1
3
2
, 4
1
4
3
, 6
2
6
4
v
6
1


6
5
. Di tc dng ca cc trc xon, nt mng phn b thnh cc chui song song vi
trc, cc chui li so le lm thnh ng xon xung quanh trc (hnh 3.1).
Mt nh trt (mt trt)
Mt nh trt (hnh 3.2) bao gm php phn chiu qua gng v bc trt song song
vi mt. Nt mng phn chiu qua mt v ng thi dch chuyn theo bc trt. Tu hng
v ln ca bc trt, mt nh trt chia ra nh sau:
Mt a c bc trt
x
t

dc theo chiu OX vi ln
x
T

: 2.
Mt b c bc trt
y
t

dc theo chiu OY vi ln
y
T

: 2.
Mt c c bc trt
z
t

dc theo chiu OZ vi ln
z
T

: 2.
Mt n v d c bc trt
xz
t

,
yz
t

v
xy
t

dc theo ng cho, ln ln lt bng 1 : 2


v 1 : 4 ln ca bc tnh tin tng ng, tc l bng:
yz xy
xz
T T
T
2 2 2
v
yz xy
xz
T T
T
4 4 4
[13]
Tng tc ca yu t i xng
Trc khi ni s suy on nhm khng gian hy ni n s tng tc ca cc yu t i
xng. Nhng quy tc cp trong mc 2.1.2 p dng cho hnh hu hn vn gi nguyn
hiu lc trong mng. Ln ny c s tham gia ca php tnh tin (bao gm bc tnh tin v
bc trt) [13,14].
Tng tc gia php tnh tin v yu t i xng
Trong trng hp tng qut, php tnh tin th t (dc ng cho khi ca mng tm
khi, bc tnh tin dc ng cho mt ca mng tm y hay tm mt) c th tc dng xin
gc ln yu t i xng dc cc trc to . Ht thy, chng u c ln bng mt na
ng cho cc loi. N s phn tch thnh 2 hay 3 thnh phn t


song song vi cc trc to
50
v c ln bng ln ca bc trt ph bin, tc l bng T
X
: 2, T
Y
: 2, T
Z
: 2 v song
song hoc vung gc so vi yu t i xng.
Thnh phn song song
//
t


hay hnh chiu ca php tnh tin xin trn yu t i
xng s tr thnh bc trt ca trc xoay, bin n thnh trc xon v ngc li,
c th trit tiu bc trt ca trc xon, khin n tr thnh trc xoay hay trc
xon khc. Mt gng thnh mt nh trt v ngc li, hoc mt nh trt c
th i tn cng nh n. Chng hn, vect
//
t


vi ln t
//
=
X
1
T
2
bin
m
XZ
/m
XY
(mt gng thng ng vung gc OY hay nm ngang) thnh a
XZ
/a
XY
,
bin a
XZ
/a
XY
thnh m
XZ
/m
XY
, bin b
XY
thnh n
XY
, bin n
XZ
thnh c
XZ
, bin c
XZ

thnh n
XZ
, v.v
Thnh phn vung gc t


hay l hnh chiu ca php tnh tin xin trn php
tuyn ca yu t i xng s lm xut hin yu t i xng cng tn v song
song, trong :
+ Mt gng cng tn (hay tm nghch o) cch mt (tm) c mt khong bng
1
2
t

v
pha tnh tin.
+ Trc xoay v trc xon bc n nm cch trc c mt khong bng
1
2
t

sin
2

, dc theo
hng to vi t


mt gc bng 90
2

, trong l gc quay c s ca trc. Trn hnh


3.3,a trc xoay bc bn chu tc dng ca t


= T

th sinh thm trc mi cng tn ti c li


sin45
2

theo hng (90 45 =) 45 so vi hng ca vect T

. Trc xoay bc bn mi
sinh s nm ti tm im ca hnh vung vi cnh T. Tng t, di tc dng ca bc tnh
tin vung gc T

, trc xoay bc ba (hnh 3.3,b) s c thm trc mi cng tn trn hng lm


thnh vi T

mt gc bng (90 60 =) 30, cch trc c mt khong bng T 3 : 3; trc mi


sinh s nm tm im ca tam gic vi cnh T.
Bng cch ,
t

lm cho trc bc hai ti hin pha tnh tin ging nh cch ca mt


gng hay tm nghch o.
+ Trc xoay bc cao v nghch o c th l tp hp yu t i xng n; v d, trc
xoay bc su = trc xoay bc ba + trc xoay bc hai, trc nghch o bc ba = trc xoay bc
ba + php nghch o, trc nghch o bc su = trc xoay bc ba + mt gng vung gc,
v.v) th mi yu t i xng n chu tc dng ca bc trt theo nhng quy tc ring ca
n. Chng hn, chu tc dng ca t


= T

trc xoay bc su s sinh ra nhng trc mi, cng


tn vi cc trc vn l thnh phn ca n. Trc xoay bc hai nm pha T

v cch trc su mt
on bng mt na di ca tnh tin. Trc xoay bc ba s nm ti tm ca tam gic u vi
cnh T, nh trn ni.
51


Hnh 3.3
Tng tc ca php xoay quanh trc bc n (a- trc bc bn; b- trc bc ba) vi
vct tnh tin

T vung gc, sinh ra trc mi cng bc ti tm ca a gic


(vung hay tam gic) vi cnh T
Trong trng hp trc nghch o bc bn th n vn bao gm hai thao tc i xng:
php xoay 90 v php nghch o qua im c bit; ngoi ra, n cn cha php xoay 180,
tc l trc xoay bc hai. Di tc dng ca vect vung gc t

cc trc xoay thnh phn u


xut hin theo cch ring, nh trn ni. im c bit (c tc dng nh tm nghch o,
nhng khng c l yu t i xng c lp) khng tch khi trc nghch o bc bn. Vy,
vect vung gc khng c tc dng y im c bit ra khi trc i xng ca n; nhng
nu vect song song c th bin trc xoay bc hai thnh trc xon, th n cng dch chuyn
im c bit i mt on bng mt na di ca n.
Cc mt i xng ct nhau th trn giao tuyn s sinh ra trc i xng (quy tc mt, xem
2.1.2). Trc mi sinh ny c th l trc xon; tu s bc trt song song (vi giao tuyn)
tng hp t cc mt nh trt giao nhau. Nu tng ca chng bng di T ca bc tnh tin
tng ng, chng trit tiu nhau, trc mi sinh s l trc xoay. Tng y bng T/2 chng hn,
trc y s l 2
1
/4
2
hay 6
3
.
Ring mt nh trt d vi bc trt bng cho mt (mt nh trt n c bc trt
bng 1/2 di ca cho), th n c c im ring:
Mt d ch c hng trt dc theo mt trong 2 cho mt.
Mt d ch c mt trong loi mng tm mt F; nh vy, chng khng tn ti n
c trong mng v phi i km cc mt vung gc cng tn.
Trc bc hai giao tuyn s xen k nhau v thuc hai loi tu chiu ca bc
trt t cc mt ct nhau: l trc xoay nu cc bc trt khc chiu v l trc
xon nu chng cng chiu [14].
3.1.2 Nhm i xng khng gian
Nh ch trn, tt c mi t hp c th c ca cc yu t i xng ca hnh hu hn (a
din tinh th) cho kt qu di dng 32 nhm im (dng i xng hay lp i xng).
Tng t, s kt hp ca cc yu t i xng trong mng s lm ny sinh 230 nhm (i
xng) khng gian. Hnh 3.4 gii thiu hai nhm thuc h tinh th mt nghing.
52

Nh ch trn, tt c mi t hp c th c ca cc yu t i xng ca hnh hu hn
(a din tinh th) cho kt qu di dng 32 nhm im (dng i xng hay lp i xng).
Tng t, s kt hp ca cc yu t i xng trong mng s lm ny sinh 230 nhm (i
xng) khng gian. Hnh 3.4 gii thiu hai nhm thuc h tinh th mt nghing.
3.2 H IM QUY TC (TNG NG)
3.2.1 nh ngha
Mt im bt k, v d khuyn trn trn hnh 3.4, c lp li v s ln di tc dng ca
cc php i xng thuc nhm khng gian dn n mt h im quy tc. Mi nhm i xng
khng gian c mt s nht nh cc h im quy tc. im ca h xc nh v tr ca mt loi
ht vt cht (nguyn t hay ion thuc mt nguyn t ho hc) trong khng gian ca cu trc.
Xc nh cu trc tinh th ca mt cht suy cho cng l nh v cho ht vt cht, tc l tm to
xyz cho im ny.
H im quy tc hay tng ng mt nhm khng gian l tp hp im lin quan vi
nhau bng cc thao tc i xng ca nhm. Mi h im hnh thnh nh cc thao tc i
xng tc ng ln im t trc ti mt v tr. V tr ng vi h im ny c i xng ring
v s bi ring (xem di y), ty vic n nm u so vi yu t i xng. H im quy
tc gi l c bit, v im t ti tm nghch o (hay ti im c bit ca trc nghch o),
mt gng v cc trc xoay. Khi im cho trc nm ti cc v tr khc, k c v tr trn trc
xon, hay mt trt s cho h im quy tc tng qut. ng vi im ny v tr c i xng
ring thp nht.
Mi nhm khng gian c s lng hu hn cc v tr khc nhau v i xng. (ng
nhin, c th c v s v tr c chung mt i xng). Ht vt cht c i xng ring khng th
nm ti v tr vi i xng bt k. Nhm chc
2
3
CO

chng hn, cc nguyn t phn b trn
tam gic u: oxy ti nh, carbon ti tm. Vi i xng 3m (vng tm nghch o), n khng
th nm ti tm nghch o ca nhm khng gian. N c th vung gc vi trc xoay bc ba
hoc vi mt gng, v.v... Mu hnh, phn t hoc ion phc vi i xng ring c th nm ti
v tr c bit no , bi v v cp i xng n khng thp hn so vi v tr ny. Vy,
ring n v cu trc vi i xng cao nht (ca ht cu chng hn) c th thch hp vi v tr
bt k.
53
i xng v tr cn c c s khc ca n: s bc t do. V tr (bt bin) ca tm nghch
o chng hn c s bc t do bng khng. Bt k s thay i no ca to cng lm bin
i h im quy tc. H im quy tc vi mt bc t do (n bin) ng vi v tr trn mt
hng c bit, v d: trc xoay. Dch chuyn dc theo hng y khng lm tng s im ca
h. im nm trn mt gng l thuc h im tng ng vi s bc t do bng hai. V tr
tng qut c s bc t do ln nht bng ba tng ng ta vi dng xyz ca n.
3.2.2 S bi ca h im quy tc
Theo nh ngha, cc im ca h phi phn b u khp khng gian v c s lng ln
v hn. Mc d vy, vn c th nh lng cho n bng s bi. c s ny quy nh s im
ca h tnh cho mt mng c s. H im tng qut c s bi ln nht; im ca n chu tc
dng ca nhiu yu t i xng nht. N l sn phm ca tt c cc thao tc i xng ca
nhm khng gian. V vy, s bi ca h im quy tc tng qut l i lng i xng ca
nhm khng gian, c s ny p dng trn i vi nhm im.
H im c bit lun c s bi nh hn s bi ca h im tng qut. N nh hn bao
nhiu ln l tu thuc i lng i xng ca v tr im c bit. V d, h im vi i
lng i xng ca v tr bng 2 (v tr trn mt gng hoc trn trc xoay bc hai chng hn)
s c s bi bng mt na s bi ca h im tng qut. V tr vi i lng i xng bng 4
(trc xoay bc bn, 2/m hay mm2, chng hn) l thuc h im vi s bi nh hn 4 ln so
vi h tng qut.
lm r hn khi nim h im quy tc, hy quay li vi hnh 3.4. Nhm khng gian
Cm (vi s th t 8 ca bng 230 nhm khng gian, ph lc 1) gm 2 h im quy tc sau
y:
H (a) c s bi 2 v to ca im ban u xOz, trn hnh l khuyn trn.
H (b) c s bi 4 v to ca im ban u xyz, trn hnh l ch thp.
Gi d, mt hp cht dng A
2
X c nhm khng gian xc nh l Cm. i chiu t s
hm lng nguyn t A v X vi cc s bi, c th gn gi nh nguyn t A vo h im (b)
v X vo h (a).
3.3 C IM DNG QUEN PH THUC THNH PHN V CU
TRC TINH TH
Tu iu kin nhit v p sut thnh to, tinh th ca mt khong vt thng c cu
trc ni ti vi trt t n nh v c trng. Chnh bn cht y l nguyn nhn ca nhiu thuc
tnh ca tinh th khong vt, trong c hnh thi a din ca chng. Hnh thi u n ni
ln nng lc ca tinh th l t gii hn bng cc mt phng. Cc mt ny li giao nhau cho
cnh v nh. Nh bit, a din tinh th l hnh ghp ca mt (trong 47) hay nhiu hnh
n. Tu mc i xng, mi a din tinh th c lit vo mt trong cc lp/h/hng tinh
th. V d tinh th ca khong vt pyrit FeS
2
(xem hnh 1.6,b v 4.3.2) thng c dng khi
lp phng (vi ba h kha trc giao) hoc mi hai mt ng gic, hoc hnh ghp ca hai
hnh n trn, hoc hnh ghp ca hnh mi hai mt ng gic vi hnh tm mt (bt din
u). Lp tinh th mi hai mt kp m3, h lp phng.
Ni dung s ni n di y l dng quen trong mi lin quan vi ha hc tinh th ca
vt kt tinh. Dng quen hoc dng thng gp ca khong vt hay ca cht rn ni chung
hnh thnh trong khong nhit , p sut v mt trng ha hc nht nh. a din tinh th
54
ca dng quen c trng bng t hp nhng hnh n xut hin nhiu nht, tc l vi tn sut
gp ln nht (xem thm 3.3.5). Nhng hnh n khc khng gp thng xuyn trn b mt
ca a din s cho nhng mt gi nh.
3.3.1 nh lut Groth
Cn c s liu thng k v i xng hnh thi ca khong 20 000 c th kt tinh, trong
c hn 2000 khong vt, t u th k XX, Groth P. v nhiu ngi khc v sau cho thy:
Cht kt tinh vi thnh phn ho hc cng n gin s c i xng hnh thi cng cao
v, ngc li, thnh phn ca n cng phc tp, i xng ca n cng thp.
Tht vy, n cht kim loi v cc hp cht vi thnh phn ha hc n gin nh oxit,
sulfur, halogenur thng kt tinh theo i xng ca h lp phng v h su phng. Silicat
thng c thnh phn phc tp, tinh th ca chng phn ln thuc cc h mt nghing, trc
thoi v ba nghing. Trong cc hp cht hu c khng th c nhiu tinh th vi i xng cao,
bi v chng thng c thnh phn ho hc rt phc tp.
Bng 3.1 khng nh iu va ni bng s liu thng k v s phn b ca tinh th t
nhin v nhn to theo cc h khc nhau.
Bng 3.
S lng tinh th thng k theo cc h v hng
H tinh th Thng k theo h Thng k theo hng
Lp phng 516 (7,63%) Hng cao v hng trung
Su phng 493 (7,28%) 1336 (19,74%)
Bn phng 327 (4,83%)
Trc thoi 1922 (28,40%) Hng thp
Mt nghing 2844 (42,03%) 5431 (80,26%)
Ba nghing 665 (9,83%)
6767 (100,00%) 6767 (100,00%)
Tuy vy, khng th khng ch ra nhng trng hp c bit ca nh lut Groth.
Lu hunh t sinh chng hn, tinh th ca n cht ny thng thuc h trc thoi hay h
mt nghing. Granat A
3
B
2
(SiO
4
)
3
vi A l mt s cation ha tr hai v B cation ha tr ba, l
nhm cc khong vt silicat kh phc tp v thnh phn ho hc, m tinh th ca chng li c
i xng ca h lp phng. Mt s zeolit silicat khung c ngha ln i vi cng ngh ho
hc, nh:
chabazi
t
Ca
2
Al
2
(Si
4
O
12
).6H
2
O,
faujasi
t
(Na
2
,Ca)(Al
2
Si
4
O
12
).6H
2
O,
v..v

vi thnh phn rt phc tp th c i xng ca h su phng v lp phng.
3.3.2 Cc loi dng quen
Tu iu kin thnh to, tinh th mt cht c th c cc mt pht trin khc nhau. Thm
ch, ngay c khi cc a din ca hp cht do cng mt lot hnh n to nn, mc pht
trin khc nhau ca cc mt cng dn n nhiu dng quen khc nhau: dng tm, dng thi,
dng kim, dng thp v.v
Dng quen ca tinh th c th chia lm 4 loi:
55
Lng tr tiu biu cho hnh thi tinh th vi trc chnh (trc i xng bc ba, bc bn,
bc su). Trng vi n cng l trc ca i rt pht trin. Trong s tinh th cc h hng thp
cng gp dng quen ny.
Thp v thp i cng c trng cho cc h thuc hng trung. Nhiu khi, dng quen gm
c thp v thp i ghp vi lng tr. Dng thp v thp i cng ph bin trong tinh th ca
cc h thuc hng thp.
ng thc l dng quen ca cc tinh th pht trin ng u hay gn nh ng u theo
c ba hng khng gian. Thuc dng ny l tinh th h lp phng. Trc ht, trong s dng
quen ny phi k n cc a din tinh th dng khi lp phng, mi hai mt thoi, bt din,
t din, mi hai mt ng gic v.v Mc du vy, dng quen ny cng c mt trong s tinh
th cc hng khc.
i mt thng gp tinh th thuc cc h ca hng trung. a din ca dng quen ny
thng pht trin mnh theo hai chiu khng gian, to nn dng tm, dng bn. Chng thng
c hnh n i mt c trng pht trin thng gc vi trc chnh.
3.3.3 Tc dng ca tp cht i vi dng quen
Hot tnh ho hc ca cc tp cht lin quan ti nng lc hp ph ca mt tinh th i vi
chng cng nh hng phn bit ti cc hng khc nhau ca tinh th, trong qu trnh pht
trin ca n. Th d kinh in v nh hng ca tp cht i vi dng quen ca tinh th l
trng hp mui n. Tp cht CO(NH
2
)
2
bin dng quen lp phng ca n thnh bt din
u (theo Rom de lIsle, 1783).
V d: tinh th chlorat natri NaClO
3
ln ln trong dung dch sch th c dng khi lp
phng (khi kt tinh nhanh) hay hnh ghp ca hnh lp phng v hnh t din (khi kt tinh
chm). Tp cht sulfat natri Na
2
SO
4
lm cho tc tnh tin ca mt t din gim

. Khi hm
lng ca tp cht y vt 0,5% dng quen ca tinh th chlorat natri chuyn sang dng t
din u.
Khong vt epsomit MgSO
4
.7H
2
O vn c dng quen ko di vi cc mt pht trin ca
i [001] thuc 3 hnh n: 2 hnh n i mt {100} v {010} v hnh n lng tr trc thoi
{hk0}. Di tc dng ca tp cht Na
2
B
4
O
7
, tinh th epsomit c xu hng co rt chiu di.
Hm lng ca tp cht 0,01% lm cho di ca n gim ng k. Khi hm lng ny t
0,1% tinh th tr nn ng thc vi cc mt pht trin tng i ng u ca 2 hnh i
mt k trn v 2 hnh n hai mt {h0l} v {0kl}, ngoi hnh lng tr trc thoi. Dng tinh th
epsomit tr nn p dt li, do tp cht c hm lng 0,4%. Cc mt pht trin khng cn l
lng tr v i mt na, thay cho chng l 2 hnh hai mt.
Trong nhng iu kin ho l khc nhau v vi s c mt ca tp cht cc loi, khong
vt c th bin ho thnh nhiu dng quen, trong khi cu trc ca n vn khng thay i.
Chng hn a din tinh th ca khong vt calcit c hn ba trm dng rt khc nhau. Trong
khi , tinh th calcit nhn to khng c dng no khc, ngoi a din mt thoi quen thuc.
Nhng bin i tng t c th gii thch bng quy tc Gibbs Curie Vulf. Theo ,
tc mc ca tng mt tinh th ph thuc vo nng lng b mt ca n. Nng lng ny

S pht trin ca mt tinh th, hay ni cch khc b rng ca n, t l nghch vi tc tnh tin ny
v lin quan vi khi nim thp pht trin (xem tc ln ca mt v hnh dng bn ngoi ca tinh th
[13], trang 322).
56
cng cao tc mc cng ln. Nh vy, cc mt thng gp nht ca tinh th li l ni c
nng lng b mt nh nht. S thm nhp ca cc tp cht vo tinh th ang ln s lm gim
nng lng b mt ca n. Nhng mt khc nhau c kh nng hp ph khng ging nhau i
vi mt tp cht, mi mt tinh th c kh nng hp ph chn lc i vi tp cht cc loi.
3.3.4 Dng quen ph thuc thng s chui
Mt iu ng ch l trong s dng quen ca tinh th thng bt gp mi tng quan t
l nghch gia phng ko di (hay bp dt) v ln ca thng s mng theo phng y.
Bng 3.2
Tng quan gia c im hnh thi v t s cnh mng qua mt s khong vt tiu biu
Tn hp cht Nhm khng gian Cnh mng () c im dng quen
Milerit -NiS Lp thp ba
phng kp, R3m
a = 9,62;
c = 3,16.
c/a = 0,328
Tinh th hnh kim
ko di theo trc [001]
Molybdenit MoS
2
Lp thp i
su phng kp,
P6
3
/mmc
a = 3,16;
c = 12,32.
c/a = 3,899
Tinh th dng tm
theo mt {001}
Anthophyllit
(Mg,Fe)
7
Si
8
)
22
(OH)
2
Lp thp i
trc thoi,
Pnma
a = 18,56;
b = 18,08;
c = 5,28.
2c/(a+b) = 0,288
Tinh th hnh kim
ko di theo theo
trc [001]
Talc
Mg
3
Si
4
O
10
(OH)
2
Lp lng tr
trc thoi, C2/c
a = 5,29;
b = 9,17;
c = 18,85;
2c/(a+b) = 2,607
Tinh th vy theo mt {001}
Tinh th thng pht trin ch yu theo phng ca chui vi di thng s nh nht.
Ngc li, dc theo chiu thng s mng ln tinh th li thng bp dt. iu ny s tr nn
sng t, cn c vo nguyn l Bravais v mt tinh th (xem 1.2.1). Theo , mt tinh th pht
trin nht thng song song vi (h) mt mng vi mt ht ln nht. Cc mt mng ny
cch nhau mt khong ln nht, hay l chui mng vung gc vi chng c thng s ln nht.
Nu tinh th bp dt dc chui y l bi v theo cc hng khng gian vung gc vi n tinh
th c tc mc nh. y cng l ni c nng lng b mt thp, tc mc cng thp,
theo quy tc Gibbs Curie Vulf. Ngc li, nu chui mng c ln thng s nh nht th
song song vi n s l trc ca i pht trin nht. Dc hng ny, tinh th c nng lng b
mt ln, tc mc cao. l phng ko di ca tinh th (bng 3.2).
3.3.5 Dng quen ph thuc mt ht ca mt mng
Trong mng tinh th, song song vi (h) mt mng vi mt ht v khong cch mt
mng ln nht l mt tinh th pht trin nht. T , mt ht ca mt mng (hkl) t l thun
vi khong cch mt mng d
hkl
v t l nghch vi din tch S
hkl
ca hnh bnh hnh c s ca
n.
Trong mng nguyn thu ca h lp phng, S
hkl
ca h mt mng (hkl) tnh bng cng
thc sau (xem thm 1.2):
S
2
hkl
= h
2
+ k
2
+ l
2

tnh S
hkl
i vi cc h tinh th khc, c th s dng cng thc sau:
2 2 2 2 2 2 2
hkl 100 010 001 100 010 010 001 001 100
S h S k S l S 2(hkS S cos klS S cos hlS S cos ); = + + + + +
57
trong : S
100
=

bc sin, S
010
= ca sin, S
001
=

ab sin ; = 100:010, = 010:001,
= 001:100
*
; h, k, l k hiu mt.
Kt qu tnh ton cho php sp t cc mt mng theo trnh t gim dn ca mt ht
(hay tng dn ca S
2
hkl
)

i vi mng nguyn thu lp phng nh sau.
hkl 100 110 111 210 211 221 310 311
S
2
hkl
1 2 3 5 6 9 10 11
Tng t, i vi mng tm mt
hkl 200 220 111 311 420 422 442 620
S
2
hkl
4 8 3 11 20 24 36 40
V i vi tm khi
hkl 110 200 211 310 222 420 442 622
S
2
hkl
2 4 6 10 12 20 36 44
Kt qu tnh ton cho thy, tinh th vi mng lp phng nguyn thu thng c dng
quen l khi lp phng, v d: CsCl vi nhm khng gian Pm3m. Tinh th thuc mng lp
phng tm mt c dng quen c trng l khi bt din u; chng hn, cc kim loi vng,
bc, ng vi nhm khng gian Fm3m. Khi mi hai mt thoi l dng quen ca tinh th vi
mng lp phng tm khi, v d: cc khong vt thuc h granat vi nhm khng gian Ia3d.
Kt qu tnh ton l thuyt d bo s hin din ca hnh i mt {001} trn a din
tinh th cc khong vt ny. Trn thc t, cho n nay thch anh cha chng kin cc mt ca
hnh n ny; cn trn b mt tinh th lu hunh th n ch hng th yu v tn sut gp. S
c mt ca trc xon bc hai lm cho h mt mng vung gc gim 2 ln khong cch v
mt ht (hnh 3.5). Trc xon bc ba vung gc lm gim 3 ln cc c s ny ca h mt
mng (hnh 3.6). Nh vy, trong trng hp thch anh, k hiu {0001} phi thay bng {0003}
v mt mng ca hnh i mt ny s ng cui dy thay v ng u (theo kt qu tnh ton
l thuyt): tn sut gp ca n phi thp nht.

*
C th thy y l din tch hnh bnh hnh c s ca cc mt mng (100), (010) v (001). Din
tch S
hkl
t l nghch vi khong cch mt mng d
hkl
: th tch mng c s V (=S
hkl
d
hkl
) = const trong mt
mng tinh th.
58


Hnh 3.5
S c mt ca trc xon bc hai
lm gim hai ln khong cch gia
cc mt mng vung gc
Hnh 3.6
S c mt ca trc xon i xng
bc ba lm gim ba ln khong cch
gia cc mt mng vung gc
Cui th k XIX u th k XX, cng vi cc nh tinh th hc ngi Php, Phedorov E.S.
khng nh nguyn l Bravais bng cc quan st dng quen ca hng lot tinh th khong
vt. Trong , cc tc gi nhn thy mt s sai khc cn chnh l. Donnay I.D.H. v Harker
D. (1937) ch ra tm quan trng ca yu t i xng vung gc i vi tn sut gp ca
mt tinh th. V d: dng quen ca thch anh v lu hunh.
Tng t, nhng k hiu (nh nk nl) gii thch s c mt ca mng tm mt v tm khi
(gn vi trc xon v mt nh trt) thay cho mng nguyn thu, nh thy trn dy trnh t
cc mt mng. Bng 3.3 cho thy vai tr ca trc xon cc bc i vi mt mng vung gc.
Bng 3.3
S gim mt ht ca mt mng do nh
hng ca trc xon vung gc
Trc xon Mt mng gim mt ht
2
1
4
2
6
3
Gim hai ln
3
1
3
2
6
2
6
4
Gim ba ln
4
1
4
3
Gim bn ln
6
1
6
5
Gim su ln
Trc xon Mt mng gim mt ht
2
1
4
2
6
3
Gim hai ln
3
1
3
2
6
2
6
4
Gim ba ln
4
1
4
3
Gim bn ln
6
1
6
5
Gim su ln


59
Mt mng vung gc vi mt i xng nh trt, m khng trng vi hng ca bc
trt trn mt i xng, s c mt ht v khong cch mt mng gim i. So vi mt
gng, mt nh trt a,b,c v n lm cho cc c s ny gim 2 ln; mt nh trt d lm chng
gim 4 ln.
Hnh 3.7,a l s phn b cc mt nh trt d trong nhm khng gian thp i trc thoi
Fddd ca tinh th lu hunh trc thoi. Cc mt i xng ny lm gim hn mt nguyn t
lu hunh trn mt mng (001). Hnh 3.7,b cng chng t hnh n i mt y c kch thc
rt hn ch.

Hnh 3.7
Bin th a hnh trc thoi ca lu hunh
a) S mng ca cu trc tinh th, vi mt i
xng nh trt d;
b) a din tinh th ca lu hunh trc thoi.
Hnh 3.8
S cc vect kt chui dc hng
[100], [010] v [001]
Mt F: (100), (010) v (001); mt S:
(110), (101) v (011); mt K: (111).
3.3.6 Dng quen v vect kt chui
Mt s tc gi (Niggli,1926; Kleber,1954; Hartman, Perdok, 1955) coi ba hng khng
gian [100], [010] v [001] ca cc trc tinh th hc l nhng hng c lc lin kt mnh nht
v c gi l cc vect kt chui tun hon
1
hay vect PBC. y cng thng l cc trc
i.
Tu s lng vect song song, cc mt tinh th chia lm 3 loi (hnh 3.8)
2
:
1) Mt bng phng (mt F) song song vi t nht 2 vect kt chui tun hon. Trn
hnh 3.8 l (100), (010) v (001). Cc mt ca n vi cht lng b mt tt, ta
mt ct khai hon ton. Chng c th xut hin trn b mt dng quen iu
kin sinh thnh bt k, tc l c tn sut gp ln nht.
2) Mt bc thang (mt S) ch song song vi mt vect kt chui tun hon l cc
mt cht lng b mt trung bnh. l (110), (101) v (011) trn hnh 3.8.
3) Mt g gh (mt K) khng song song vi vect kt chui tun hon no. Hnh
3.8 mt (111) c th coi l mt gi nh, c tn s gp thp nht.

1
Vect PBC, periodic bond chain vector.
2
Mt bng phng hay mt F, mt bc thang hay mt S v mt g gh hay mt K (flat face, stepped face
v kinked face).
60
V d: tinh th ca khong vt halit c dng quen l khi lp phng {100}, hon ton
p ng vi mt F. Cn mt {110} v {111} ca n ln lt l mt S v K.
Cui cng, hnh thi ca tinh th khng ch xc nh bng cu trc ca n, m cn bng
iu kin mi trng, ni n sinh ra v pht trin. Tng quan gia dng quen v cu trc
tinh th ch nn xem nh c s hc thuyt v hnh thi tinh th ni chung. Mc du nhng
quan st thc t, i km cc s liu thng k v hnh thi tinh th thc ph hp gn nh hon
ton vi kt qu tnh ton v trnh t tn sut gp ca cc hnh n, s bin i dng quen
tinh th phn ln ph thuc vo c im ho l va ca bn thn tinh th, va ca hon cnh
sinh thnh ca n. Dng quen l tng ca tinh th, xc lp bng l thuyt cho php phng
on nhng iu kin sinh thnh thun li nht. Nghin cu nhng sai khc ca vt th kt
tinh so vi dng quen l thuyt ny gip ti lp iu kin thc t ca mi trng ni sinh ra
n.
Vy, d dng nhn thy ngha ln lao ca vic nghin cu hnh thi ca cc tinh th
khong vt, nht l khi nh gi iu kin ho l ti ch.
3.4 C S PHNG PHP PHN TCH CU TRC TINH TH
BNG TIA X
Tia X l bc x in t nh nh sng thng, nhng c bc sng ngn hn nhiu (tia X
dng trong tinh th hc c bc sng t 0,5 2,5). Ngoi bc x in t hoc bc x hunh
quang gn lin vi hiu ng quang in, vt cht c tia X chiu ti s pht ra bc x th
cp vi bc sng bng hoc rt gn vi bc sng ca bc x s cp; l nhng tia X
khuch tn. Hin tng ny c tm quan trng bc nht, bi v trong trng khuch tn khng
thay i bc sng, cc nguyn t nh nhng ngun tp hp thnh mng tinh th, cc bc x
khuch tn t chng s c th giao thoa. V khong cch nguyn t trong mng cng c ln
vi bc sng tia X, nn c th quan st c hin tng giao thoa: thay v mt nng lng
rt thp phn tn trong khng gian, by gi bc x tp trung theo nhng hng xc nh v
vi cng ln gp nhiu ln. Khai thc cc nh nhiu x ny gip phn tch nh tnh v
nh lng cc pha tinh th trong hn hp cng nh xc inh v tr ca nguyn t trong tinh
th.
3.4.1 nh lut phn x Bragg-Vulf
Khi chm tia X chiu vo tinh th, trn ng i n s lm cho cc in t dao ng vi
cng tn s. in t b kch thch ny hp ph mt phn nng lng v tr thnh ngun pht
sng mi ca bc x Roentgen cng tn s, cng bc sng. Ni chung, cc sng pht sinh
ny trit tiu nhau, nhng trong vi hng nht nh chng tng cng ln nhau, to mt hiu
ng giao thoa.

61



Hnh 3.9
iu kin ca nhiu x tia X t chui nguyn t
Hnh 3.10
Nn nhiu x t chui nguyn t
Khi mt chui nguyn t b tia X bn ph th mi ht c coi nh tm pht sng. Nu
cc sng ny cng pha, chng giao thoa v nhiu x xy ra. Hnh 3.9 cho thy cc tia 1 v 2 s
cng pha nu khong AB cha mt s nguyn ln bc sng, ni cch khc AB = n = c cos
( y n l nhng s nguyn).
Khi n t mt gi tr ring, khng i, hng ca mi tia nhiu x s biu th bng
mt hnh nn vi trc l chui tm pht sng. Gc ca hnh nn ph thuc vo i lng n (s
ln bc sng cha trong hiu ng i, trn hnh i lng n = 1). Bi v iu kin nhiu x
c thc hin vi nhng gi tr khc nhau ca n, s c mt h nn chung nhau mt nh v
mt trc (hnh 3.10).
Mng ba chiu c ba hng trc ng vi ba chui; mi chui ring mt chu k tun hon
v u c kh nng to mt h nn vi gc ring. Cc nn nhiu x t ba h-ng trc khng
ng phng c th ct nhau hoc khng. Ch khi chng ct nhau th theo phng ca giao
tuyn mi xut hin mt tia giao thoa, trn
hnh 3.11 hng ca n biu th bng mi
tn v c ghi nhn bng nhng cch
khc nhau (trn phim hay trn biu ).
iu kin quy nh cho ba nn ct
nhau nh trn hnh th hin di dng ba
ng thc c lp (ng thc Laue), trong
cc gc
1
,
2
,
3
ca ba nn xc nh
hng chung (dc theo mi tn). sn
sinh mt hiu ng nhiu x th c ba ng
thc u c tho mn.
t lu sau khi cng b nhng ng
thc ny th W.L. Bragg v J.V. Vulf
chng minh rng tia nhiu x bi tinh th
ny li c xem nh phn x t mt h
mt mng. Khng ging s phn x thng

Hnh 3.11
Ct nhau theo mt giao tuyn chung l ba nn nhiu
x t ba chui khng ng phng
62
thng, n khng phn x di nhng gc ti bt k. Vi di sng nht nh, tia X s
phn x t mt mng di nhng iu kin nht nh.
Chng c th hin bng h thc:
n = 2dsin
vi n l nhng s nguyn, - di sng, d - khong cch mt mng, - gc to bi mt
mng vi tia ti hay tia phn x. ng thc cn gi l nh lut Bragg-Vulf, n th hin mt
cch n gin s tho mn ng thi c ba iu kin Laue.
Hiu ng nhiu x tng hp khng phi t mt mt mng ring l m t hu ht mt
mng cng h, mi mt mng gp mt phn nh trong tia nhiu x tng hp ca c h.
hiu ng nhiu x (phn x) c cng ln c ghi nhn, tia "phn x" t mi mt
mng ca h ht thy phi cng mt pha vi nhau.


Hnh 3.12
Hin tng giao thoa ca tia Roentgen trong
mng tinh th

Hnh 3.13
nh Laue ca vesuvianit (nhm im 4/m2/m2/m) Tinh th
hng trc chnh dc tia X ti: s phn b nt nhiu x
cho thy trc bc bn v bn mt i xng gng i qua
n (Hng trc a
1
v a
2
c in thm v sau)
Trn hnh 3.12 chm tia ti L vi di sng , di gc trt phn x t cc mt
mng N
1
, N
2
, N
3
, , N
n
cng h, vi khong cch d.
ng thc Bragg-Vulf vit vi nhng bc phn x khc nhau:
bc mt = 2dsin
1

bc hai 2 = 2dsin
2

bc ba 3 = 2dsin
3

v.v....
Chia cc ng thc ny cho nhau theo tng v, s c sin
1
: sin
2
: sin
3
... = 1 : 2 : 3...
Vy, tia Roentgen n sc ch phn x t mt mt tinh th (mt h mt mng tng ng)
di nhng gc m t s sin ca chng bng t s gia cc s nguyn.
63
ng i ca hai tia qua O v B hn km nhau mt on = ABC; chng giao thoa nu
AB + BC = 2AB = n = 2dsin; trong l di bc sng ca tia, d khong cch mt
mng, n = 1, 2, 3,...
l nh lut Bragg Vulf, c s ca phng php.
3.4.2 Mt mng v cng ca tia giao thoa
Cng ca tia giao thoa ph thuc vo mt nguyn t ca mt mng tng ng.
Mt mng c mt ht cng cao th cng phn x ca n cng ln. Mt mng vi mt
ln nht thng c ch s Miller n gin nht v nhng mt mng cng h thng cch
nhau nhng khong d ln nht.
Khi s dng tia X n sc ( = const) t mt h mt mng xc nh s xut hin mt s
phn x vi cc bc khc nhau. Chng hn, nu phng trnh Bragg-Vulf c tho mn, ng
vi n = 1 s xut hin phn x bc mt, vi n = 2 l phn x bc hai, vi n = 3 l phn x bc
ba, v.v... Ph giao thoa thuc lot tia ny s c cng gim dn u theo trnh t ca t s
sau: 100 : 20 : 7 : 3 : 1 (nu quy c coi cng ca phn x bc mt bng 100).
Hnh 3.9 cho thy s bc phn x n t mt h mt mng xc nh l mt s hu hn: tng
cc on AB v BC bng n khng th ln hn 2d. Do:
n
sin 1
2d

=
cho nn s lng phn x n t mt h mt mng khng th ln hn 2d : , tc l
2d
n

.
Mun tng s phn x t mt h mt mng, c th chn bc x vi bc sng nh hn.
Mt khc, trong mt mng ba chiu nht nh c th c v s cch dng h mt mng.
Dng nh s tia nhiu x cng s nhiu v hn. Thc ra, mt h mt mng c th cho t
nht mt phn x bc mt: n = 1 th 2d/ nht thit khng th nh hn 1, tc l d
2

.
Vy, trong v s h mt mng ca mng tinh th ch mt s hu hn cc h c nng lc
phn x: H mt mng vi d
2

< khng th cho tia phn x. Tia phn x vi k hiu pqr l tia
bc n phn x t h mt mng (hkl). D dng nhn thy gia cc ch s pqr ca phn x v
cc ch s hkl ca h mt mng tng ng c mi tng quan n gin:
p = nh q = nk r = nl
3.4.3 Cc phng php thu nh nhiu x
mng tinh th c th cho tia giao thoa th theo nh lut Bragg-Vulf cn phi bin i
lin tc, trong thi gian thu nh, mt trong hai i lng: di sng hay gc ti gia mt
mng v hng ca tia X nguyn sinh.
a) Trong trng hp u, tia X c s dng l bc x trng (tinh th t c nh so vi
hng ca tia ti). S thu nh ca tinh th c nh cho thy sau khi xuyn qua mu, tia ti
khng i hng v li trn phim phng hay knh nh mt nt ti tm ca tm nh. Lm
vi tia ti nhng gc khc nhau l cc tia nhiu x cng thay i. Chng to nh giao
64
thoa gm nhng nt cng m nu cng ca tia cng ln. Mi nt ng vi mt tia phn
x t mt h mt mng ca tinh th. Nhng h thuc mt i th cc nt ng vi chng tp
hp trn cc ng cong. Tu theo gc gia trc ca i v tia ti thay i t (0 n 90)
ng cong i c dng elip, parabol, hay ng thng (hnh 3.13). Nu tia ti song song vi
mt trc i xng hay mt mt i xng no ca tinh th, s phn b nt trn nh Laue
phn nh trung thc i xng ca yu t y. Do nh cung cp nhng thng tin s b (i
xng ca nh ny lun cha tm nghch o, d tinh th khng c tm) v nhm im v nh
hng ca ht, nht l khi ht khng cn nguyn dng a din.
Khi bc vo nghin cu cu trc mt tinh th, phng php Laue c s dng tm
nhm im i xng cho tinh th v nh hng (dng v sau, cho phng php tinh th
xoay chng hn) cho n, nht l khi mu tinh th khng c dng a din. Nhc im ca
phng php (mang tn Laue) l ch mi tia nhiu x (mt nt trn phim nh nhiu x) c
th l tp hp ca nhiu tia vi di sng khc nhau, bt tin cho x l kt qu thc nghim,
chng hn, cng ca hiu ng nhiu x.
b) Bng cch xoay tinh th trong chm tia n sc,
c th thc hin kh nng th hai, tc l thay i gi tr
gc . Trong qu trnh xoay lin tc, tinh th s ln lt
tri qua nhng nh hng khc nhau. Khi gc trt
tho mn cng thc Bragg-Vulf n s cho tia giao thoa.
y l phng php tinh th xoay. Tinh th n t
trong bung chp hnh ng, mt hng tinh th hc ca
n (trc c chng hn) c chn lm trc xoay, trng
vi trc ca hnh ng. Chm tia X n sc hng ti
tinh th. Cc tia nhiu x to nn b mt ca cc nn
giao thoa v tho mn iu kin ccos = n, trong c
l thng s (cn xc nh) thuc chui mng song song
vi trc xoay ca tinh th. nh ca cc nn trng vi
tinh th, trc c l trc chung ca chng (hnh 3.14).
Mt nn ct phim hnh ng thnh cc ng lp
(hnh 3.15). Gc xc nh bng khong cch gia ng lp 0 v ng lp 1, hay ng
lp 2, v.v... ng lp trn phim khng phi ng lin, m gm nhng nt m nht khc
nhau. S dng cng thc trn ca Laue d dng xc nh thng s dc cc hng trc xoay.
Ch sau khi c nh hng bng phng php trn, mu mi a vo chp theo phng
php tinh th xoay. Theo s chp n gin nht ca phng php tinh th xoay, thng tin
nhiu nht c th khai thc t nh ny l thng s mng v do v loi mng ca tinh th.


Hnh 3.14
S chp tinh th xoay
65

Hnh 3.15
ng lp trn phim hnh ng do cc tia (mt nn) ct mt phim (hnh bn tri). Trn phim tri phng
(bn phi) cc nt/tia cng khc nhau
Tuy nhin, bit loi mng ca tinh th, c th s dng quy lut xut hin ca cc tia
giao thoa, thng qua k hiu ca chng. Mi tia giao thoa c k hiu ng vi mt mng lin
quan, n cn c cng . y u l nhng s liu khng th thiu nu mun i su vo cu
trc tinh th. Cc tia phn x phn b trn nh di dng cc nt dy c trn hng lot ng
lp. S chp vi phn gii thp ny khng cho php khai thc nhng thng tin chun
xc v cc tia ny.
Phng php Weissenberg gip tng phn gii ca phng php. Theo s bung
chp, phng php ny cho php tm phim hnh ng (vi trc trng vi trc xoay ca tinh
th) dao ng thng u dc trc v ng b vi chu k xoay ca mu. Nh vy, cc nt nhiu
x c phn b ri rc khp mt phim, dc cc ng hnh sin thay cho cc ng lp song
song. C th nh gi cng tia giao thoa thng qua vic so snh m tng i ca
cc nt trn phim. Cch lm ny rt dy cng, m khng cho kt qu tin cy.
c) Phng php bt (Debye-Scherre). Kh nng th hai ny cn c th thc hin bng
cch khc. Thay cho vic lm thay i nh hng ca tinh th n, c th khai thc n di
dng bt. Gm v s ht n tinh hn n, mi ht mt nh hng ring, mu bt trong
bung chp khng khc mt tinh th n xoay lin tc quanh tm im ca n theo mi
hng. iu kin giao thoa ca nh lut Bragg Vulf c tho mn hiu qu hn na, v
mu bt khng bt ng, m cn chuyn ng xoay trong chm tia ti.
Mi tia nhiu x xut pht t mu bt to nn mt h nn nhn tm mu lm nh
chung, nhn tia ti lm trc chung, vi cc gc ti nh bng 4
1
, 4
2
, 4
3
, v.v... B mt ca
mi nn l tp hp ca nhng tia nhiu x sinh ra t nhng mt mng nh nhau, cng nm
di mt gc vi tia ti. Tm phim di t vng quanh trc mu, p st mt trong ca
bung chp hnh trng, ct h hnh nn thnh cc ng vch lin cong khc nhau trn
tm phim gi l biu Debye (hnh 3.16b).

66






Hnh 3.16
Phng php bt vi nhiu x k.
a. Nhiu x k XDS - 2000 vi ng Roentgen (1), gi (2), ng m (3), gic k
(4).
b. Biu ca thch anh bt ghi trn nhiu x k i chiu vi nh Debye ca
n.Hiu ng nhiu x bc mt vi ch s Miller ca h mt mng tng ng.
c. S chp mu bt trn nhiu x k
K hiu tm c cho tng vch trn biu gip xc nh thng s mng ca tinh th.
u im ca phng php l ch mu a vo chp khng nht thit l tinh th n. Nu
vic xc nh k hiu cc vch nhiu x c th thc hin d dng i vi tinh th hng cao,
kh hn i vi hng trung, th i vi tinh th hng thp iu ny khng lm c trong
nhiu trng hp. l mt bt tin ca phng php Debye.
Phng php bt tr nn tin li, chnh xc v thng dng hn do s ra i ca nhiu x
k (hnh 3.16a).
Ti v tr xut pht, tia X n sc song song vi mt phng ca mu bt (nn vo a
phng) v chiu thng vo ng m. Khi vn hnh, ng m quay ng b vi mu (hnh
3.16c)tc l vi tc gc gp I, ng m tip nhn c tia nhiu x t mu. Sau khi
phn x t mt mng, tia i thng vo ng m (hay bung ion ho, theo s chp ca
Bragg, tng c s dng trong nhng nm 19191922) ri c khuch i. Gc nghing v
67
cng tia s n tay ngi dng di dng biu hoc bng s (hnh 3.16b). Trong s
chp bng phim khin mi tia phn x bn ph hng trm, hng ngn ln vo ng mt im
trn mt phim trong sut thi gian chp nhiu gi.
Trong gic k tinh th bt xoay ng b vi chuyn ng ca ng m, s cho cc tia
phn x xut hin ln lt, mi tia mt ln duy nht. Mi ln ng m nhn tn hiu th cng
lc trn bng giy (chuyn dch ng b) xut hin mt vch (di dng im cc i ca
ng cong, hnh 3.16b). V tr ca tia (gc 2), cng (chiu cao ca im cc i) v
xut x ca n (d ca h mt mng tng ng) c th c ngay trn biu . Nhiu x k cn
lm cho phng php bt nhanh chng v chnh xc gp bi.
3.4.4 S b v cc bc phn tch cu trc tinh th
Phn tch cu trc tinh th ca mt cht l phn nh v tr khng gian ca tng nguyn t
thnh phn. D s dng phng php no cng trnh to ln ny lun i hi mt s lng ln
nht cc tia phn x. Chng c coi l n tr nu hi nhng c trng sau:
Gc nghing 2 (gc ca tia giao thoa so vi tia nguyn sinh).
Cng .
Mt mng pht sinh phn x.
Hai c trng u c khai thc ngay trn nh hay biu , trong cng cc tia
xc nh bng m tng i ca cc nt do tia tc dng ln phim nh hay bng nng lc
ion ho ca tia. Cn gc nghing biu th bng v tr ca ng m, bung ion ho so vi tia
nguyn sinh.
K hiu mt mng ca phn x c xc nh trc tip trn nh tinh th xoay v bng tnh
ton trong phng php Debye-Scherrer v Laue. Nu xc nh k hiu ca phn x i vi
tinh th h bn phng, h su phng v h lp phng l vic lm tng i d dng th
i vi tinh th hng thp li cc k kh khn.
Vic phn tch cu trc mt tinh th thng c cc nhim v sau:
a) Xc nh kch thc mng c s.
b) Xc nh nhm im i xng.
c) Xc nh s n v cng thc trong mng.
d) Xc nh loi mng tinh th.
e) Xc nh nhm khng gian.
f) Xc nh s phn b nguyn t trong mng.
Xc nh kch thc mng c s: Cn tm cc hng s mng: a, b, c, , , . Nu i
tng kho st l tinh th n, hng s mng tm trc tip theo khong cch gia cc ng
lp trn nh tinh th xoay quanh cc trc tinh th hc. Cn trn mu bt th hng s mng xc
nh bng phng php tm k hiu cho cc h mt mng sinh ra hiu ng phn x. Hy
xem xt h lp phng lm v d.
Mi lin quan gia khong cch mt mng v ch s Miller ca mt mng th hin bng
cng thc bnh phng. i vi h lp phng:
68
2 2 2
2 2
1 + +
=
h k l
d a

Nu kt hp vi cng thc ny, phng trnh Bragg-Vulf c dng sau:
( )
2
2 2 2 2
2
sin
4

= + + h k l
a

trong l gc trt, di bc sng, a thng s mng c th tnh c sau khi
phn nh c k hiu cho cc tia giao thoa. Bi v h, k, l l nhng s nguyn, nn
h
2
+ k
2
+ l
2
= m
c th nhn nhng gi tr sau: 1, 2, 3, 4, 5, 6, 8, 9, 10, 11, 12, 14, 16, v.v... Mi gi tr
sin
2
th hin bng s nguyn m ln tha s chung
2
/(4a
2
) cho mi gi tr ca sin
2
. em s
nguyn m phn tch thnh bnh phng ca ba s nguyn s tnh c ch s h, k, l ca mt
mng cn tm. Khi gi tr di bc sng bit th t tha s chung
2
/(4a
2
) s xc nh
ngay gi tr cnh ca lp phng c s.
Xc nh nhm im i xng l bc k tip sau khi tm c kch thc ca c
s. nh Laue khng cho php phn bit lp i xng cha tm nghch o v lp khng cha
tm. Khai thc n phi kt hp vi biu gic k v nhng s liu khc l gii php tin cy
tm nhm im cho tinh th.
Xc nh s n v cng thc trong mng. ng vi c s l s nguyn ln Z n v
cng thc. y l nhm nguyn t ng vi cng thc ho hc ca cht kt tinh. Th tch V
ca c s c th tnh c v bit ln cc hng s mng. Nu bit t trng (c nhiu
phng php vt l o t trng ca tinh th) th khi lng ca c s c tnh theo cng
thc M = V.. Nu hp cht c nghin cu c cng thc dng A
m
B
n
C
p
; cn a, b, c l
nguyn t lng ln lt ca A, B, C, th khi lng n v cng thc (tnh bng n v oxy)
biu th bng:
h
2
+ k
2
+ l
2
= m
f = ma + nb + pc
v tnh bng gam th gi l mol. Nu gi L (s Avogadro) l s n v cng thc trong
mt mol, th khi lng mt n v cng thc l f / L. T :
h
2
+ k
2
+ l
2
= m
23
. . . .6,023.10
. . ; ;

= = =
+ +
f V L V
V Z z z
L f ma nb pc

Nu Z = 2, c s cha 2m nguyn t A, 2n nguyn t B v 2p nguyn t C.
Xc nh loi mng. Trong trng hp h lp phng, sau khi tm c ln cnh
mng, th vic tip theo cn lm l tm thng s chui dc cho khi v cho mt. Nu s o
bng na di cc ng cho tng ng, th mng tm c s l tm khi hay tm mt,
tm y. Mng lp phng nguyn thu, tm khi v tm mt c t l cc chu k tun hon ln
lt l:

69
d
100
: d
110
: d
111
= 1:
1 1
2 : 3
2 3
= 1: 0,707 : 0,577
d
100
: d
110
: d
111
= 1:
1
2 : 3
3
= 1: 1,414 : 0,577
d
100
: d
110
: d
111
= 1:
1 2
2 : 3
2 3
= 1: 0,707 : 1,155.
Trn nh Debye Scherrer c th tm nhm tnh tin bng cch i chiu cc vch ca
n vi mi phn x thuc mt loi mng xc nh. Nu loi mng l tm khi th phn x
quan st c c ch s h + k + l = 2n, cn cc phn x vi ch s h + k + l = 2n + 1 lun thiu
vng. Trong mng nguyn thu s c cc phn x (100), (010), (001), (110), (101), (011),
(111), (200), (020), (002) v.v...; trong mng tm khi mt na phn x b tt, phn x quan st
c l (110), (101), (011), (200), (020), (002), v.v...


Hnh 3.17
S cc phn x ca mng nguyn thu lp
hng
Hnh 3.18
S cc phn x ca mng tm mt lp
phng
Kinh nghim cho thy trong tinh th h lp phng, t l cng ca phn x cc bc 1,
2, 3, 4, 5 bng 100 : 20 : 7 : 3 : 1. Hnh 3.17 dn ra s phn b ca phn x pht sinh t cc
mt (100), (110), (111) ca tinh th vi mng lp phng nguyn thu. Hnh 3.18 l s
tng t ca tinh th vi mng lp phng tm mt. Bng 3.4 thng k mt vi bc phn x
c trng t cc mt (100), (110) v (111) ca kim loi ng, cng nh nhng bc phn x
thiu vng so vi mng nguyn thy lp phng.
Trong mng tm mt lp phng gia hai mt mng nguyn thu l mt mt mng trung
gian ging chng c v trt t v mt ht. iu ny cng quan st c trn cc mt mng
(110). Bi vy gi tr sin ca cc phn x thuc mng tm mt phi ln gp i so vi gi tr
y mng nguyn thu. Do , c th thy tinh th ng l thuc mng lp phng tm mt.
Thng thng mng nguyn thu ca mi h tinh th u c nhiu nht cc phn x cng
ln. Cc loi mng khc thiu hn mt lot cc phn x, nu c th cng ca chng rt
yu.
Bng 3.4
Lut tt trong mng tinh th kim loi ng
Mt mng Phn x xut hin Phn x khng c
(100) Bc hai v bc bn Bc mt v bc ba
(110) Bc hai v bc bn Bc mt v bc ba
(111) Bc mt, bc hai v bc ba
70
Xc nh nhm i xng khng gian. Nhm khng gian c xc nh bng cch sau:
Trc ht lit k nhng nhm khng gian thuc nhm im (coi nh xc nh theo phng
php trn) ca tinh th. Trong s nhng nhm ny hy chn ly nhng nhm ph hp v
loi mng (coi nh xc nh). T nhng nhm va chn hy loi b nhm no khng ph
hp v h im quy tc, i chiu vi thnh phn ho hc ca tinh th. Cui cng da vo
lut tt (tham kho International Tables for X-ray Crystallography) chn ra nhm khng
gian duy nht, trc khi lit k tng lot phn x thiu vng theo lut c trng cho mi nhm
i chiu.
Nu so snh cc nhm i xng khng gian thuc cng mt lp i xng d dng nhn
thy s khc nhau gia chng l chng loi mt nh trt v trc xon ca chng.
Yu t i xng loi ny li trn biu Roentgen nhng lut tt c trng. Lut
tt bao gm nhng tia/nt ng b thiu vng trn biu . H thng tia tt c ni n
khi xc nh loi mng. Chng hn nu mng nguyn thy cho tia nhiu x k hiu bt k, th
mng tm khi ch li trn biu nhng nt/nh im vi k hiu h + k + l = 2n.
Trc xon to ra nhng lut tt trong s nhng tia phn x t h mt mng vung gc.
V d, trc xon bc hai song song vi trc Z ca tinh th cho tia tt trong s cc tia k hiu
00l vi l l s l. iu ny c ct ngha l trc xon to ra trong mng nhng mt mng
mi c nng lc phn x. Hnh 3.19 cho thy vung gc vi trc xon l cc mt mng mi
(ng t).

Hnh 3.19
Trc xon bc hai v bc bn c tc dng lm xut hin lut tt ring
Tng t, mt i xng nh trt li lut tt ring trong s mt mng (hk0), (h0l) hay
(0kl). Hin nay hnh thnh mt s hon chnh cho php xc nh nhm i xng khng
gian bng s c mt nhng lut tt c trng trn biu Roentgen.
Nhng v d va nu ch ra iu c ngha nht l nhng hiu ng nhiu x pht sinh
t h mt mng song song vi mt phng to . Trn biu Roentgen tinh th xoay (hnh
3.15) mt mng ny ng vi ng lp s 0 (xch o). V l do y trong phn tch cu trc
tinh th nhng hiu ng nhiu x ca ng lp s khng thng c chp ring cho mi
trc to . Trong bung chp loi ny, tinh th va xoay xung quanh mt trc va chuyn
ng (qua li) dc trc y. l phng php trin khai ng lp; n cho php xc nh
nhanh chng k hiu ca tia nhiu x v c xem l mt phng php thng dng trong kho
st tinh th vi cu trc phc tp, i xng thp.
Xc nh v tr nguyn t trong mng
71
Cu trc tinh th c hiu nh s sp xp trt t ca nguyn t trong tinh th. N bao
gm nhng thng tin v to ca tt c cc nguyn t, v khong cch nguyn t, nhm i
xng khng gian v v s n v cng thc (ca mng c s).
Nhm mc ch xc nh v tr cho nguyn t, trc ht cn xem xt s pht sinh tia
nhiu x t mt mng cha mt vi loi nguyn t v do nhng nguyn t ny khng phn
b ti nt mng. Hnh 3.20a gii thiu 4 mng, hnh 3.20b vn cc y cha cc phn t
mt cht thnh phn AB. Hy xem xt mt "phn x" no pht sinh t h mt mng cho
vi cng khong cch d (cc mt mng vung gc mt hnh) di cng mt gc (c hai
trng hp u cho tia "phn x" cng hng). Trn hnh b, mi loi nguyn t cho mt h
mt mng: hai h A v B tng ng v u ging h mt mng a. i vi mi h mt
mng ring l, d A hay B, cc tia "phn x" u cng pha.

Hnh 3.20
Mng nguyn t (a) thay bng mng phn t (b) ch lm thay i cng
nhiu x
Mc du vy, khi A v B nm trong mt tng th (mng A v mng B lng vo nhau),
cc phn x xut pht t hai h A v B s khng cng pha; bin tng ca cc sng phn
x t hai h mt mng s gim, so vi trng hp gi nh rng nu A v B cng nm chung
trong mt h, tc l nu x = 0. Nu i lng x = d/2 th cc phn x bc chn (n = 0, 2,
4...) t cc mt mng A v B s cng pha; trong khi , cc phn x bc l s ngc pha
nhau. Nh vy, nu A v B l nhng nguyn t ca cng mt nguyn t ho hc th nhng tia
ngc pha ny s loi b nhau, khng cho hiu ng nhiu x.
Bi v cc nguyn t A v B thuc cc nguyn t khc nhau, hiu ng nhiu x xut pht
t c hai h ny khng hon ton trit tiu nhau, chng ch hn ch cng ca nhau.
iu ny cho thy cng ca tia nhiu x t nguyn t ph thuc vo s lng in t
ca n, tc l vo s hiu nguyn t (vo bn cht ca nguyn t).
V vy, trong phn tch cu trc cn tnh n mt i lng gi l tha s nguyn t f,
nu A v B thuc cc nguyn t khc nhau th f
A
f
B
. Tha s nguyn t f c trng cho nng
lc nhiu x ca nguyn t, ln ca n ph thuc vo s lng in t v s phn b (cu
hnh) in t trong nguyn t.
Trong trng hp tng qut x 1/2d. Hiu s pha gia cc tia "phn x" t mt mng A
v mt mng B s bng 2x/d i vi nhiu x bc mt, bng 2nx/d i vi nhiu x bc n.
T th d va xt trn d dng nhn xt: s lng cc tia nhiu x v s phn b ca chng
trong khng gian (th hin bng s lng cc nt v s phn b ca chng trn nh nhiu x)
ph thuc vo kch thc ca mng c s, loi mng v nhm i xng khng gian. Cng
72
ca tia nhiu x li xc nh bi s lng nguyn t, loi nguyn t v v tr tng i ca
chng trong mng tinh th.
Trong th d trn sng nhiu x xut pht t mi loi nguyn t c gi nh l cng c
mt pha ban u nh nhau. Trn thc t, pha ban u i vi cc mng nguyn t khc nhau
ni chung c s chnh lch tu thuc to nguyn t hay ni cch khc, tu thuc v tr ca
gc to chn trong mng.
Bi vy, pha ban u ca tia nhiu x (tng) vn l mt n s.
Trong tinh th cha tm i xng, nu ti t gc to th lch pha s mt, pha
ban u lc ny s c gi tr bng 0 hay . iu ny lm cho tin trnh phn tch cu trc tr
nn n gin: ch cn phi xc nh du ca i lng gi l tha s cu trc.
Nu bit trc to nguyn t trong mng th hon ton c th tnh c cng cc
hiu ng nhiu x.
Tng quan gia cng I ca tia nhiu x lin quan vi h mt mng hkl tng ng
v to x
j
y
j
z
j
ca nguyn t j trong mng l:
I = k [
j
f
j

i2 (hxj + kj + lzj)
]
2
=kF
2
hkl

y tha s k biu th mt s hng s vt l v yu t thc nghim; f
j
l tha s nguyn
t; tng ny bao qut tt c cc nguyn t trong mng, v c gi l tha s cu trc F
hkl
,
ln ca n xc nh bng s hiu nguyn t (loi nguyn t) v v tr nguyn t trong
mng.
V vy, nu trn c s nhng phn on no m gi nh mt m hnh cu trc cho
tinh th ang nghin cu, th hon ton c th thm nh iu .
Mun th, hy tnh cng ca mi hiu ng nhiu x, da vo to gi nh ca cc
nguyn t, ri i chiu vi cng nhiu x o c trn nh nhiu x hay trn biu . Nu
c s trng khp gia s liu tnh ton vi s liu thc nghim th m hnh cu trc gi nh
c coi l xc ng. Nu khng trng khp th m hnh xut khng ng. Hy gi nh
mt phng n khc v hy thm nh li bng tnh ton. Trong khi xut mt cu trc cho
tinh th cn tham kho nhm khng gian ca n v cc h im quy tc c th c. y l
phng php duy nht c dng trong mt thi gian di nhm phn tch cu trc tinh th,
gi l phng php th v sai.
Phn tch cu trc bng phng php iu ho
Nu bit to nguyn t trong mng, c th tnh tha s cu trc F
hkl
theo cng thc
tng cc dao ng iu ho nguyn thu cng tn s:
F = (f
A
cos
A
+ f
B
cos
B
+)
2
+ (f
A
sin
A
+ f
B
sin
B
+)
2

vi
A
l pha ca cc nguyn t A,
B
l pha ca cc nguyn t B. Nu tinh th c tm
i xng v gc to t th cng thc tr nn n gin hn:
F = 2f
A
cos
A
+ 2f
B
cos
B
+
Tng t iu ni trong mc trn, bng cch so snh gi tr tha s cu trc tnh ton
(l thuyt) vi gi tr thc nghim (vi cng o trn biu Roentgen v F I ) c th
thm nh m hnh phng on ca cu trc tinh th.
73
ng nhin, vn cn c nhng php gii khc; chng hn xut hin kh nng tnh
mt in t trong tinh th. Do mt in t trong tinh th l mt hm lin tc v tun
hon nn c th phn thnh chui Fourier. Tnh ton l thuyt cho thy tha s cu trc l h
s trong chui ny. Do , nu bit tha s cu trc c th tnh mt in t cho mi im
ca mng. Gi tr ln nht ca mt ny ng vi v tr ca nguyn t.

Hnh.21
Bn phn b mt in t (a) ca diopsit, CaMgSi
2
O
6
, chiu trn mt
(010). Cu trc tinh th ca iopsit (nhm khng gian C2/c) l kt qu rt
ra t (a) (theo Bragg W. L, 1929)
Thng thng mt in t c tnh trn mt chiu ca hai mt to . T kt qu tnh
ton ti hai mt chiu s thu c ba to ca mi nguyn t, tc l xc nh v tr ca n
trong khng gian.
Biu thc tnh mt in t chiu trn mt XOY ca c s tinh th c tm i xng
c dng sau:
( ) ( )
1
cos2
+


= +


hko
k
x y
xy F h k
S a b

y S l din tch mt chiu ca mng; x v y l to ca im cn tnh mt . Du
cng ca tha s cu trc c ngha l pha ban u ca cc tia nhiu x bng khng, tc l
trng vi pha ca tia xut pht t gc to . Du tr ca tha s cu trc cho thy hai pha
ngc nhau. Kt qu tnh ton cho php dng cc ng ng tr trn bn phn b mt
in t (hnh 3.21).
Tuy nhin, y vn cha phi l phng php trc tip. T thc nghim ch c th thu
c gi tr tuyt i ca tha s cu trc F
hk0
m vn cha bit trc c pha ban u
(du ca F). Nh th ch c th gii bi ton ngc, chui Fourier c s dng thm nh
v chnh l phng n ra (xem di). Cho nn phng php Fourier dng nh khng c
g u vit so vi phng php th v sai.
Phng php Patterson cho php dng chui F
2
chiu trn mt XOY bng cng thc sau:
74
P
(xy)
=
2
0
+


hk
k
F cos2(h
a
x
+k
b
y
).
Trong nhng trng hp ny khng cn d kin bt k no khc ngoi nhng s liu thc
nghim. Nhng im cc i trn hnh Patterson khng phi l v tr nguyn t. Cc nh ny
ph thuc vo tha s nguyn t ca cc cp nguyn t AA, AC, BC, v.v... v vo ln
vect gia chng. Hng ca cc nh v khong cch ca chng vi gc to tng ng
mi vect gia cc nguyn t trong cu trc.
Hnh 3.22a l hnh chiu mt c s ca mt cu trc gi nh vi 4 nguyn t. Tng
ng, cc nh phn b trn hnh chiu Patterson th hin trn hnh 3.22b. S nh tng vt:
nu s nguyn t l N th s nh l N(N 1). S chuyn di t Hnh b sang hnh a l bn
cht ca vic x l hnh chiu ca chui Patterson. Phng php ny t ra hu hiu nu trong
thnh phn ca hp cht nghin cu c mt nguyn t nng, bn cnh n cc nguyn t
khc u nh (s hiu nguyn t trong h thng tun hon u thp). Bi v, cao ca
nh trn hnh chiu Patterson t l thun vi s hiu nguyn t. V d hp cht Pt(NH
3
)
2
Cl
4
.
Bn cnh nhiu nh ng vi vect ni nguyn t nng vi nhng nguyn t nh, d dng
nhn ra mt nh cao hn ng vi vect ni hai nguyn t nng, chng hn, vect PtPt
v d va nu.

Hnh 3.22
S xut hin cc nh im trn hnh chiu Patterson
a- Hnh chiu ca cu trc; b- Hnh chiu Patterson tng ng

75
Chng 4
KHI NIM C BN CA HO HC TINH TH
Thnh tu thc nghim ngt mt th k qua chng t tnh ng n ca khi nim v
nhm khng gian. Cho n nay cha tng gp tinh th no m khng thuc mt nhm im
hay mt nhm khng gian no . Chnh mng khng gian vi nguyn t gp mt ni nt
mng sinh ra mng tinh th. Chng ny s ni ti tp tnh ca nguyn t trong mng.
4.1 NHNG YU T XC NH CU TRC TINH TH.
NH LUT GOLDSCHMIDT
Khi sp xp theo s ca mt loi mng, nguyn t mang theo cc bn sc ha hc
ring. Khi l mt ion, n c th c ha tr no ; tng ng, n c mt bn knh xc nh, v
thng mang dng cu. Hn na, n cn chu s chi phi ca nhiu yu t khc nhau khi nm
trong trt t ca t chc mng.
4.1.1. Cu hnh in t ca nguyn t
Nh vt l hc an Mch N. Bohr (1913) pht trin nhng m hnh ph bin t trc
bng vic a ra nhng m hnh h mt tri da trn hiu ng quang in. Trong m hnh ny
Bohr gi nh rng in t chuyn ng quanh ht nhn trn nhng qu o (hay mc nng
lng) trn vi bn knh tu thuc nng lng in t. Ht nhn nguyn t gm proton v
neutron (ring hydro ch c 1 proton duy nht trong ht nhn). in t phn b trn cc v
(lp) k hiu n, gi l s lng t chnh hay l K, L, M, N Chng hn, n = 1 (K), n = 2 (L),
v.v
Mc du vy, nguyn l bt nh tn ti trong th gii vi m (W.L. Heisenberg, 1927) cho
thy i vi ht c bn nh in t khng th ni v qu o ch xc ca in t khi n
chuyn ng quanh ht nhn.
Nm 1926, E. Shrodinger tp hp nhng thnh tu c trc trong m hnh mi ca mnh
v biu din n thnh mt phng trnh sng vi m hnh l thuyt xy dng trn c s c hc
lng t. Bn phn b mt tn sut in t quanh ht nhn, tc l m my in t, c
th xem nh bc nh mt in t tp hp t hng triu ln chp ti mt v tr xyz trong khng
gian nguyn t. Vy, l thuyt sng ca Shrodinger miu t chuyn ng ca in t thng
qua khi nim tn sut gp ca mt in t xc nh trong mt n v th tch (khng gian)
nh b.
v tr ca in t c xc nh trong khng gian ba chiu cn k n cc s lng t.
S lng t chnh n l phng trnh ca khong r t in t ti ht nhn.
S lng t l quy nh hnh dng vng khng gian (orbital) thng gp in t. Trng
thi khc nhau ca l (0, 1, 2, n1) c k hiu ch tng ng; trong thng gp nht l
cc ph lp.
76
0 1 2 3
s p d f
Dng cu l orbital s, p l dng qu t v nh hng theo trc, cn d l dng orbital thay
i.
S lng t m hn ch hng ca in t c dng nhng s nguyn t 1 n +1. Khi l =
0 th m ch c mt gi tr m = 0, c ngha ph lp s ch c mt orbital.
S lng t s quy nh hng xoay ca in t, bi v n ch c th xoay theo mt trong
hai hng, nn s ch c hai gi tr
1
2
v +
1
2
. in t xoay c xem nh thanh nam chm
thu nh, n sinh ra t trng khi va chuyn ng trong orbital va xoay quanh trc ca n.
Thng thng, do in t xoay theo hng trong nguyn t, n c biu th bng mi tn;
mi orbital c hai in t ng vi hai mi tn trong mi : hng ln trn (bn tri) v hng
xung di (bn phi). Chng hn, in t duy nht ca orbital 1s ca nguyn t hydro biu
th bng mt mi tn hng ln trn; 1s ca nguyn t hli c hai in t biu th bng mi
tn hng ln trn v mi tn xung di.
4.1.2. Bn knh hiu dng ca nguyn t v ion
Khi nguyn t thiu hoc tha in t th tr thnh ion mang in tch. Ion tch in m
(anion) c s d in t, tc l in t vt s cn thit trung ho in tch ht nhn. Ion
tch in dng (cation) do khng s in t cn thit trung ho in tch ht nhn.
Nguyn t v ion c cu to khc nhau. Khi tp hp li thnh tinh th, chng c lc tng tc
thay i. S sp xp ca chng trong khng gian tinh th cng ht sc a dng. V vy, cc
cht vi thnh phn ho hc khc nhau thng c cu trc tinh th khng ging nhau.
Mt trong nhng c s quan trng nht ca cu trc tinh th l khong cch gia cc
nguyn t hay ion tri du k nhau. T , mi nguyn t hay ion trong tinh th lun c mt
lc tc dng i vi mi nguyn t hay ion vy quanh. Mi ht c mt vng nh hng, mt
cu tc dng quanh n. Bn knh ca cu tc dng y gi l bn knh (hiu dng) ca nguyn
t hay ion.
Xc nh bn knh nguyn t v ion. Ngay sau khi c nhng kt qu thc nghim v
khong cch nguyn t ca nhiu cu trc tinh th, nhng c gng u tin c thc hin
nhm xc nh bn knh nguyn t v ion. Phng php phn tch cu trc bng tia X cho
nhiu s liu khong cch anioncation vi chnh xc cao, nhng khng th cho thng tin
v bn knh ion. Chng hn, khng th gii trc tip n phng trnh vi n n s dng a) v b)
di y. Trong khi ch cn bit bn knh ca mt ion, cng tm tt c cc gi tr cn
li. Mi u, nhng gi tr tnh c cho bn knh ca ion chlor khng c cng nhn; l
do khng lu s ph thuc ca bn knh vo trng thi in tch ca nguyn t (gi tr bn
knh hu hiu ca nguyn t ghi trong ph lc 4). Chng hn, bn knh ca nguyn t natri
ln hn bn knh ca ion natri Na
+
.
Nm 1920, gi tr bn knh ca mt s ion c xc nh nh vic s dng cc hp
cht vi cu trc cng loi NaCl. Trong s ny c hai cp hp cht vi khong cch nguyn
t bng nhau:

77
Mg S 2,60 Mn S 2,59 a)
Mg Se 2,73 Mn Se 2,73 b)
Mt khc, cn nh rng anion l ion d in t, nn thng c kch thc ln hn cation
l ion thiu in t. i chiu cc gi tr trn c th thy khong cch ion khng i trong
mi cp hp cht, d thnh phn cation thay i; chng t i lng ny hon ton ph thuc
vo cc anion kch thc ln. Ch cn thay cc anion selen hay lu hunh bng anion oxy, s
thy khong cch cation anion tng ln, nu magnesi thay bng mangan:
Mg O 2,10 Mn O 2,24
Vic khong cch nguyn t bng nhau hay xp
x bng nhau trong cc cu trc sulfur hay selenur
ca magnesi v mangan cho php gi nh rng
anion trong cc hp cht ny ging cc qu cu tip
xc nhau. Bit rng khong OA trn hnh 4.1 bng
hai ln bn knh ca anion, khong KA (tnh c
khi bit ta xyz ion) bng mt na cnh hnh
vung, d dng tm c bn knh ion:
(OA)
2
=(OK)
2
+(KA)
2
=2(OK)
2
T , bn knh ca anion lu hunh
(2R
S
)
2
= 2(2,60)
2
; tc l
2,60
2
= 1,83. Tng t, bn knh ca anion selen bng
2,73
2
=
1,93.
T nhng gi tr bn knh anion va xc nh v khong cch nguyn t trong cc cu
trc ca nhng hp cht tng ng c th ln lt tnh c bn knh cation:
Mg S 2,60 Mg
2+
0,77
Mg O 2,10 O
2
1,33
Mn O 2,24 Mn
2+
0,91
Ca O 2,38 Ca
2+
1,05
Ph lc 3 lit k gi tr bn knh hu hiu ca cc ion (xp theo h thng tun hon cc
nguyn t ho hc) ph bin trong th gii khong vt. Xt c im cc nguyn t v nhng
bin thin ca bn knh ion lin quan vi nhng c im y, c th khng nh cc quy lut
sau:
- Theo chu k (hng ngang) ca h thng tun hon bn knh cc ion gim, trong khi
ho tr ca chng tng, chng hn:
Na
+
Mg
2+
Al
3+
Si
4+

R
A
() 0,98 0,74 0,57 0,41
- Theo nhm (ct dc) s hiu cc nguyn t tng th bn knh ion tng theo, v d:

Hnh 4.1
Xc nh bn knh ion theo phng
php Lande (1920)
78
Li
+
Na
+
K
+
Rb
+
Cs
+

R
A
() 0,68 0,98 1,33 1,49 1,65
Trong h lantan (cc nguyn t t him ho tr ba) vi s th t tng t 57 (lantan) n
71 (luteci) c hin tng gim bn knh ion: La
3+
1,04; Lu
3+
0,80. Hin tng ny nh
hng ti gi tr bn knh ca hng lot kim loi khc. V d, n lm xut hin cc i nguyn
t c gi tr bn knh ion bng nhau, mc du chng thuc hai chu k khc nhau: zirconi
hafni, niobi tantal v.v... Hin tng gim bn knh cng bt gp nhm cc nguyn t cui
ca h thng tun hon bt u t actini (s hiu 89).
Nhng c im mang tnh quy lut va k lm xut hin kh nng: nguyn t ca mt
s nguyn t c mt cng nhau trong mt v tr tinh th hc ca cu trc vt rn. y l cc
nguyn t phn b dc ng cho t pha trn bn tri xung pha di bn phi ca bng
tun hon (ph lc 3). Ni cch khc, chng c th c th thay th ng hnh cho nhau trong
tng khong vt, khi hi nhng iu kin cn thit, trc ht l do chng c bn knh ion
xp x bng nhau (xem chng 5).
- Kch thc ion thuc cng mt nguyn t ho hc c th bin i tu thuc in tch
ca n: cation vi in tch ln hn th c bn knh nh hn v ngc li, cation in tch
cng nh thng c bn knh cng ln. V d:

Ha tr Mn
o+
Mn
2+
Mn
3+
Mn
4+
S
2
S
o
S
6+

Bn knh, 1,29

0,91

0,70

0,52

1,82

1,04

0,29

4.1.3. S phi tr, a din phi tr v gii hn bn vng ca chng
S phi tr ca mt nguyn t trong cu trc tinh th n cht l s nguyn t gn nht
vy quanh n. Trong tinh th ion, s phi tr ca ion l s ion tri du, gn nht vy quanh n.
V d: trong cu trc tinh th halit mi ion natri c su ion chlor gn nht vy quanh. Ngc
li, mi ion chlor nm gia su ion natri gn nht. Nh vy, trong khong vt ny c hai loi
ion u cng c s phi tr su.
Ion vi bn knh cng nh th c s phi tr cng thp: bn knh ion natri bng 0,98 th
s phi tr ca n trong cu trc NaCl bng su; vi bn knh 0,79, ion km c s phi tr
bng bn. C hai hp cht u c cng thc thuc dng AX, tc l mng ca chng cha
hai loi nguyn t s lng nh nhau.
Trong cc hp cht dng khc, mi loi nguyn t c s phi tr ring. Chng hn, trong
cu trc tinh th fluorit CaF
2
s phi tr cation calci bng tm, ca anion fluor bng bn. l
hp cht dng AX
2
; cn hp cht dng A
2
X, chng hn argentit Ag
2
S c s phi tr bn ca
cation bc, tm ca anion lu hunh.
iu kin cn cu trc bn vng l cc qu cu ion ngc du phi tip xc nhau. Nu
cu anion tip xc nhau, cn cu cation qu nh s dch chuyn t do trong khong trng gia
cc anion, cu trc tr nn km bn vng (hnh 4.2). Trong trng hp ny, iu phi xy n
l cc ion t phn b li, dn n cu trc vi s phi tr nh hn nhng bn vng.
79


Hnh 4.2
S bin i t cu trc bn vng vi s phi tr cao sang cu trc vi s phi tr thp hn
Nm 1922, gii hn bn vng cho cc s phi tr khc nhau c xc lp, cn c trn
t s bn knh gia cation v anion. Di y, trn v d NaCl s din gii php tnh v gii
hn bn vng cho mt s phi tr. Trong cu trc ny, ion natri c s phi tr su, ngha l su
anion chlor nm trn nh ca hnh bt din, cation natri nm ti tm hnh. Hnh 4.1 l mt ct
qua tm cc cation v anion. Nu gi R
X
l bn knh ca cation v R
A
l ca anion, th: 4R
X
=
(2R
X
+ 2R
A
) 2 hay l R
A
: R
X
= 2 1 = 0,41.
Gi tr ny l gii hn di ca bn vng thuc s phi tr su. Trong trng hp
anion c bn knh nh hn so vi cation, t l R
A
: R
X
= 1 : 0,41 = 2,41. y l gii hn trn
ca s phi tr su. Nhng trong khong R
A
: R
X
t 0,41 n 2,41 cng c cc gii hn trn
1,37 v di 0,73 ca s phi tr 8.
T l bn knh ion tng ng cc s phi tr v hnh phi tr khc nhau nh sau.
R
A
: R
X
S phi tr Hnh phi tr
0 0,15 6,45 2 Gnh cn
0,15 0,22 4,45 6,45 3 Tam gic u
0,22 0,41 2,41 4,45 4 T din u
0,41 0,73 1,37 2,41 6 Bt din u
0,73 1,37 8 Lp phng
Tuy vy, R
A
: R
X
ln hn 1 ch hin thc i vi s phi tr 8, v cation ln nht l Cs
+
th
bn knh ch t 1,65, cn anion vi kch thc nh nht l F

th bn knh bng1,33.Trong
trng hp ny, R
A
: R
X
= 1,24 v lot gi tr gii hn trn ca R
A
: R
X
khng tn ti i vi
ion n (gm mt nguyn t). Chng c th c ngha no khi p dng cho ion phc nh
[Co(NH
3
)
6
]
3+
v.v (xem thm 4.1.5). Hy tham kho cc halogenur di y, s thy nhng
gii hn hnh hc ghi bng trn xc thc n u.
Hp cht LiI LiBr LiCl NaI NaBr LiF NaCl KI KBr RbI
R
A
: R
X
0,31 0,35 0,38 0,45 0,50 0,51 0,54 0,60 0,68 0,68
Hp cht KCl NaF (CsI) RbBr RbCl (CsBr) (CsCl) KF RbF CsF
R
A
: R
X
0,73 0,74 0,75 0,76 0,82 0,84 0,91 1,00 1,12 1,24
Phn ln cc hp cht trn u c cu trc loi halit vi s phi tr 6, tr ba hp cht
trong ngoc c s phi tr 8. i vi chng, c ba u c R
A
: R
X
> 0,73, quy tc gii hn hnh
hc c khng nh. T chui hp cht NaFCsF c th nhn thy khng nht thit cht
kt tinh lun c c phi tr cao nht, ngay c khi chng c R
A
: R
X
ph hp. ng ra, i
vi mi cht cc gii hn di v trn c bn cht khng nh nhau. Mt khi gii hn di
(0,41 ca s phi tr 6) b vt qua, cu trc s km bn vng do anion tip xc nhau. Nu
80
R
A
: R
X
> 0,73, s tip xc ion cha xy ra cho n khi R
A
: R
X
= 2,41, m trong khong 0,41
2,41 cn c cc gii hn bn vng ca s phi tr 8.
Chc chn, ch ring lun gii hnh hc s khng cn c cho phi tr mi, khi gi tr
R
A
: R
X
t 0,73. Vn cn c soi xt di gic ni nng ca cu trc. Tuy vy, vic
su hp cht bng trn vi loi cu trc halit u c R
A
: R
X
> 0,73 khng chng t s thiu
cn c ca gii php hnh hc trong vic s phi tr ph thuc t s bn knh ion. Nh trn
ni, cc trng hp ny khng ging cc ng cu trc khc ca NaCl l ba halogenur liti vi
R
A
: R
X
< 0,41. C th tm hiu cc bit l ny khi kho st hin tng phn cc ca ion.
a din phi tr

ca mt cation l a din nhn (tm im) cation y lm tm v ly


(tm im) cc anion vy quanh lm nh. Nh vy, y l a din tng tng, hnh thnh
do ni tm im cc anion gn cation trung tm nht v vy quanh . Trong cu trc tinh th
ca mui n (halit), a din phi tr c dng bt din u (hay hnh tm mt). C th ni,
trong trng hp ny ion natri c phi tr bt din. Nu ni tm im ca bn nguyn t lu
hunh phi tr quanh nguyn t km trong cu trc tinh th ca sulfur km, th a din phi tr
c dng mt t din u (hnh bn mt). Khi lp phng ng vi s phi tr tm, hnh tm
mt lp phng (hnh 4.3) ng vi s phi tr mi hai.

Cn lu , mt s phi tr c th ng vi nhng a din phi tr khc nhau. Cu trc
tinh th ca khong vt molybdenit MoS
2
chng hn, vi s phi tr su nguyn t molybden
ging natri trong mui n, n c hnh phi tr khng phi bt din, m lng tr ba phng
(xem hnh 4.12). Khi lp phng dng Tomson cng c s phi tr 8 nh khi lp phng;
hnh phi tr ny ch c mt cp mt vung song song.
Sphi tr adin phi tr R
A
: R
X


Khng th nhm ln a din phi tr vi a din tinh th. Hn na, khng phi mi a din phi tr
u c i xng tng ng vi 32 nhm im.
81
Hnh 4.3
a din phi tr v cc s phi tr tng ng
T tng ca Pauling v a din phi tr khng ch c ngha phng php lun: n
c xem nh phng tin ph tr trong Roentgen tinh th hc. Lch s pht trin tinh th
hc chng kin nhiu i thay trong nhn thc v tinh th. Nu lc u, tinh th c m
t nh s xp cht ca nhng phn t dng a din (Hay R.Y., 1784), th v sau, n c
xem nh h thng cc phn t xp theo trt t ca mng ba chiu gm cc nt im (Bravais
A., nm 1866). By gi, tm im phn t a din phi tr l ni ca cation; ng vi chng
l cc nt im ton hc thuc mng khng gian, cn cu anion th chia x v nhng a din
(phi tr) khc nhau. iu ny gip m t v ti lp cu trc tinh th vi s h tr ca cc m
hnh a din thng thng.
4.1.4. Tnh phn cc ca ion
Khi tham gia thnh to tinh th ion thng c xem nh c dng cu. Nhng khi nm
trong in trng ca cu trc tinh th, cu ion c th s bin dng. Di tc dng ca in
trng y, cc in t ca ion, nht l in t vng ngoi gn kt yu, d dng b cun ht v
mt pha. Ht nhn ca ion mang in dng th b cun ht v pha khc. Kt qu, trng tm
ca in tch dng v ca in tch m, vn trng nhau trong cu ion, gi y tch ri nhau
mt khong nht nh: ion tr nn mt lng cc. Hin tng ny gi l s phn cc ca ion.
Nu gi l l khong cch gia hai in tch e m v dng ca ion, th el l momen lng
cc: i lng biu th tnh phn cc ca ion. Momen lng cc t l thun vi hiu th ca
trng in E:
el = E
vi l i lng khng i, th hin tnh b phn cc ca ion. Tnh cht ny mnh hn
nhng nguyn t vi kch thc ln v vi lin kt yu trong v in t. Thng thng,
bn ca lin kt in t xc nh ch yu trong cch gn kt nguyn t ca hp cht. Cho nn,
nguyn t ca cng mt nguyn t ho hc s bc l tnh b phn cc khng ging nhau, khi
chng tham gia to nn nhng hp cht khc nhau. V d: ion chlor trong NaCl b phn cc
mnh hn so vi ion ny trong HCl. hiu r hn bn cht ca hin tng, hy a thm
khi nim v nng lc gy phn cc ca ion ny i vi ion khc.
S ph thuc ca tnh b phn cc v nng lc gy phn cc ca ion i vi bn knh
ion R
i
ca chng din bin r rt trong dy nguyn t kim loi kim:
Li Na K Rb Cs
R
i
() 0,69 0,98 1,33 1,49 1.65
0,06 0,19 0,91 1,90 2,85
1,7 1,0 0,6 0,5 0,4
S liu dn cho thy, tnh b phn cc ca ion t l thun vi bn knh ca n, cn
nng lc gy phn cc th t l nghch. Cation vi bn knh nh v in tch ln thng c kh
nng gy phn cc mnh. Bn thn chng hu nh khng b phn cc. Cation vi 18 in t
lp ngoi nh ng, bc, vng, km, cadimi, thu ngn cng c nhng c tnh y. Anion ho
tr thp c tnh b phn cc mnh nht. i vi ion ca nhiu nhm khc, thng k di y
cng cho thy quy lut y.
82
Theo chiu dc t di ln v chiu ngang t tri sang phi: gi tr bn knh ion v tnh b
phn cc gim, nng lc gy phn cc tng. Trong phn t, tc dng phn cc n phng
lm hnh thnh lng cc v co rt khong cch gia cc ion. Trong cu trc tinh th cn tnh
n tc dng ng thi t cc ion phi tr i xng; chng gy phn cc t nhiu pha ln ion
trung tm. Trong trng hp ny khng nht thit c lng cc hnh thnh, nhng nht nh
khong cch ion phi co rt v do s phi tr thng gim theo.
He Li
+
Be
2+
B
3+
O
2
F

Ne Na
+
Mg
2+
Al
3+
S
2
Cl

Ar

K
+
Ca
2+
Sc
3+
Se
2
Br

Kr Rb
+
Sr
2+
Y
+
Te
2
I

Xe Cs
+
Ba
2+
La
3+

Nhn y, hy ni v s ph thuc ca khong cch AX i vi s phi tr. Hin tng
phn cc lun c ch trong mi tinh th mc khc nhau. N xut hin mnh m nht
trong phn t ring l, chng hn dng AX vi s phi tr 1. Khi s ny tng th c th thy
trc s tng theo ca khong AX. Trong v d v hai bin th a hnh ca NH
4
Cl; khong
cch (NH
4
)
+
Cl

tng t 3,27 ln 3,35,v s phi tr t 6 tng thnh 8 (cu trc t loi


NaCl i thnh loi CsCl). Cp hp cht sau cng cho thy s ph thuc y. Vi cu trc loi
NaCl, SrO c s phi 6 ca Sr, th khong SrO bng 2,57. Cn SrZrO
3
vi loi cu trc
perovskit (CaTiO
3
vi Ti nh lp phng, Ca tm, O trung im ca cnh) c phi tr
12 ca Sr, th khong SrO bng 2,89.
Nh vy, nh hng co rt khong cch ca phn cc i vi tng ion cn ph thuc vo
s phi tr ca n. iu ny gy kh khn cho vic nh gi nh hng ny i vi khong
cch nguyn t. Bng sau y do Goldschmidt khi qut v s ph thuc ca khong cch ion
vo s phi tr c th l mt gii php. S phi tr 6 ph bin nht trong s hp cht ion, cho
nn khong AX i vi s phi tr 6 ly lm 100%; nhng phn ln kim loi li c s phi
tr 12, v th khong AA i vi s phi tr 12 ly lm 100%.
i vi tinh th ion i vi tinh th kim loi
S phi tr AX () S phi tr AA ()
12 112 12 100
8 103 8 98
6 100 6 96
4 94 4 88
Ion kh b phn cc thng to thnh cu trc cc tinh th i xng cao; trong quanh
cation/anion l cc anion/cation phi tr u n, nh vn thng thy trong loi cu trc
NaCl. Nu thay ion natri bng ion bc gy phn cc mnh v chlor bng cc halogenur, d
dng nhn thy s bin thin khong cch AgX do bc gy phn cc i vi halogenur:
Hp cht AgX, R
Ag
+ R
X
,

Khong cch co rt, % Loi cu trc
AgF 2,46 2,46 0 Halit
AgCl 2,77 2,94 5,8 Halit
AgBr 2,88 3,09 6,8 Halit
83
AgI 2,99 3,33 10,3 Sphalerit
Khong cch AgX co rt mc tng dn cho ti khi cu trc chuyn i ti AgI (vi
R
Ag
: R
X
= 0,51) t s phi tr 6 sang s phi tr 4. Khong cch khc thng ca cu trc cho
php kt lun v s bin dng (do hin tng phn cc) ca v in t.
Vai tr ca phn cc s tr nn rt ng k khi cc ht tng tc l ion gy phn cc
mnh v ion d b phn cc. Kt qu nhn c l nhng nhm chc (radical) bn vng
(CO
3
)
2
, (NO
3
)

, (SO
4
)
2
, (PO
4
)
3
, v.v

. Trong cc hp cht carbonat v nitrat, khong cch


nguyn t gia carbon/nit v oxygen ln lt bng 1,26 v 1,22, tc l nh hn c bn
knh ion oxy (1,36). Lin kt ho hc trong cc nhm chc ny mnh ti mc chng khng
b phn hu trong dung dch. Cu trc tinh th cho thy cc nhm chc c th sp xp xen k
vi cc ion khc nh mt ht vt cht c lp. V d trong cu trc tinh th calcit CaCO
3

(hnh 4.18).
iu tng t c th ni v cc cu trc lp nh CdCl
2
, CdI
2
v MoS
2
(xem 4.3.2). Lp
Cd/Mo nm xen gia hai lp I/Cl/S v gy phn cc mnh i vi chng. Lc lin kt bn
trong tp ba lp ny mnh hn hn so vi lc gn cc tp ny vi nhau, ko theo tnh ct khai
dc theo (0001) ca cc pha rn ny.
4.1.5. nh lut Goldschmidt
Nhng iu lun gii t u chng l nhm gii thch nhng yu t nh hng n cu
trc tinh th. Theo Goldschmidt, cu trc tinh th xc nh bi s n v cu trc trong
mng, tng quan kch thc gia cationanion v c tnh phn cc ca ion. Nn xem n
v cu trc l nguyn t hay ion, i khi l nhm nguyn t, tc l phn t hay ion phc.
Ion n trong cu trc tinh th l n v cu trc dng cu. Trong tinh th nhiu cht ion
phc khng c dng cu. Trong s anion thng gp nhiu hn, nhng cation phc cng
khng him. T gc ho hc tinh th ch nhng ion c i xng khc i xng ca hnh
cu mi gi l ion phc. Ion n c th cha mt hay nhiu proton th hnh dng khng thay
i so vi hnh cu; bi v proton c kch thc khng ng k. Chng hn ion OH

v ion
O
2
khng khc nhau my. Cc ion nh SH

, SeH

, TeH

v NH
2
cng nh cc ion
4
NH
+
v
4
PH
+
u mang dng cu. Mc du chng c hnh vi hi khc trong mng tinh th v i
xng ca chng suy gim trong vng nhit thp.
Trong anion phc (cng gi l radical) lin kt gia nguyn t trung tm (nhn radical)
v cc nguyn t bin c bn cht trung gian gia lin kt ion v lin kt cng ho tr. Gi d
gia cc nguyn t ny ch c lc ht tnh in tc ng th kh c th ni v s hnh thnh
radical. V d trong mng tinh th spinel Al
2
MgO
4
, nhm t din MgO
4
khng phi l radical
theo quan im ha hc: bn cht cng ho tr khng ng k trong lin kt gia Mg
2+
v O
2
.
Khng ging nh c tnh ca nhm
2
4
SO

, nhm MgO
4
khng th di chuyn trn vn t
hp cht ny sang hp cht khc m khng bin i. Cc kt qu phn tch Fourier cho
thy gia cc nguyn t lun duy tr mt in t kh ln khi chng lin kt nhau bng lc
cng ho tr. iu ny ph hp vi lun thuyt Lewis, theo in t chung gia cc nguyn
t to nn dng lin kt cng ho tr.

Xem thm quy tc Pauling cui 4.2.1 v 5.5.9. Hiu ng chn ca ion.
84
ng quan tm trong s cc ion phc l radical n nhn. Trc ht l ion vi thnh phn
AX
3
, trong X thng l oxy cng c th l lu hunh. Radical c dng tam gic u vi
nhn l nguyn t A. V d
3
BO

,
2
3
CO

v
3
NO

. Trong hng lot trng hp nguyn t


nhn nh ln khi mt phng ca cc nguyn t oxy. Lc , ion c dng thp ba phng;
l trng hp cc radical halogenat
3
ClO

,
3
BrO

v
3
IO

.
Radical AX
4
thng to ion vung hay t din. Nhng radical t din nh
4
4
SiO

,
3
4
PO

,
2
4
SO

,
4
ClO

v.v c vai tr ln trong t nhin. Nhiu t din ghp li thnh radical a nhn.
Chng hn hai t din to nn radical nh pyrophosphat, pyrosulfat, v.v Gc ho tr
SOS, POP, SiOSi thng c gi tr dao ng trong khong 110140 (Linton H.,
Truter M.R., 1961).
Nu v s cc radical n nhn ghp li (trng hp) theo mt chiu khng gian, anion s
c dng chui. Radical hnh tam gic ca borat ghp li thnh chui metaborat
n
2 n
(BO )

.
Tng t, cc ion metasilicat, metaphosphat, v.v vi cc t din ghp li thnh chui vi
cc chu k tun hon thay i, gm 2, 3, 4, t din. V d (Si
2
O
6
)

, (Si
3
O
9
)

, (Si
4
O
12
)

. Cc
chui ny c th khp hai u li cho ion dng vng kn. V d vng ba
6
3 9
Si O

, vng bn
4
4 12
P O

. Tinh th lng tr su phng ca khong vt beryl Be
3
Al
2
Si
6
O
18
l silicat o vng
(gm 6 t din vi nhn silic). Diopsit CaMg(SiO
3
)
2
cha radical chui t din silicoxy.
S trng hp c th din bin theo hai chiu khng gian to nn cc radical dng l nh
4
4 10
Si O

(mica, chlorit), hay ba chiu nh trong cc dioxit silic t nhin hay trong cc feldspat.
4.2 CC DNG LIN KT TRONG CU TRC TINH TH
Tinh th l nhng thc th bn vng do cc ht vt cht tng tc vi nhau m to dng
nn. Trong tinh th ca cc cht khc nhau, lc gn kt cc nguyn t (phn t hay ion) vi
nhau c th mang bn cht khng ging nhau. Lin kt trong cu trc tinh th c 4 dng
chnh:
lin kt ion l dng thnh hnh trong cc hp cht v c v khong vt (cn gi l
hp cht ion),
lin kt kim loi thng c trong tinh th kim loi v hp kim,
lin kt cng ho tr gn cc nguyn t thnh phn t v thnh hp cht nguyn t,
lin kt tn d gp ch yu trong hp cht hu c khi gn cc phn t vi nhau.
4.2.1 Lin kt ion
Lc tng tc tnh in gia cc ion mang in tri du lm nn lin kt ion. Chng hn,
trong cu trc tinh th halit, lin kt ca anion chlor v cation natri c dng ion. Bi v v
in t ca anion v cation u tch in m, nn c th gi nh rng trong hp cht loi ny,
cc ht phi duy tr mt khong cch hp l, va nhm trnh mt lc y cho v in t
ca hai ion.
Nu coi ion nm trong trng thi tng tc, c phm vi nh hng vi bn knh hiu dng
xc nh, th cu trc tinh th c xem nh khi cu xp cht. Tuy vy, lun gii v s
phn b ion trong tinh th, cn lu khng ch yu t hnh hc thun tu, m c iu kin
85
trung ho in tch tng th ca ton cu trc (xem li 4.1.4). Bn trong tinh th halit, vy
quanh mi ion chlor ch c 6 ion natri, mc du tng quan kch thc ht cho php sp t
ti 12 cation xung quanh mi anion. Quanh mi cation natri cng c 6 anion chlor. S lng
ion ho tr mt (Cl

v Na
+
) bng nhau m bo trung ho in tch: trong iu kin hai ion
tri du u cng mt s phi tr. Nu trong NaCl ion cc loi u c phi tr 6, th CsCl vi
cng t lng 1 : 1 li c s phi tr chung l 8. T l bn knh gia cation v anion i
khc. l nguyn nhn khin hai hp cht tng t nhau v bn cht ho hc ny kt tinh
thnh hai loi cu trc khc nhau. Nu tng quan kch thc v nng lc ca ion l nhng
yu t xc nh s phi tr trong cc hp cht n gin, th i vi loi hp cht phc tp phi
p dng thm nhng quy tc khc (Pauling L., nm 1929).
Quy tc Pauling
a) a din phi tr ca cation do cc anion vy quanh n to nn. Khong cch cation
anion o bng tng bn knh ca chng. S phi tr ca cation xc nh ch yu bng t l bn
knh ca n vi anion

. Cu trc tinh th c th xem nh s gn kt a din phi tr cc loi


ca cation; trong , mi anion tr nn mt ht trung gian, ni cc a din y vi nhau.
b) Quy tc ho tr tnh in. Trong cu trc tinh th bn vng, tng nng lng ca cc
mi lin kt ni mt cation vi cc anion gn k ng bng in tch ca cation y. Lc lin
kt tnh in (o bng gi tr tuyt i) l in tch ho tr ca ion (z) chia cho s phi tr (n)
ca n, tc l z : n. Gi tr nhn c gi l ho tr tnh in, l s o lc lin kt m cc ion
lin k nhn c t n. Trong NaCl chng hn, ion natri c 6 ion chlor vy quanh trong a
din phi tr bt din v lc lin kt mi ion chlor nhn t n, ho tr tnh in, l 1/6. Nh
vy, 6 mi lin kt ni ion Na
+
trung tm vi 6 ion Cl

gn nht quanh n hon ton trung ho


in tch ca cation natri trung tm. Anion chlor cng c 6 cation natri gn k, cho nn ho tr
tnh in ca mi mi lin kt cng bng 1/6. Nh th, in tch ca anion chlor c trung
ho bi 6 mi lin kt ni ion trung tm vi 6 cation natri (phi tr bt din).
Quy tc ho tr tnh in cho php nh gi bn cht lin kt a din phi tr trong cu
trc tinh th. Trong cu trc bn vng, tng gi tr cc ho tr tnh in t cc cation trung
tm ca a din phi tr ng bng in tch ca anion gia cc a din phi tr. Chng hn,
trong cu trc tinh th grosular Ca
3
Al
2
(SiO
4
)
3
, cation Ca
2+
phi tr lp phng (s phi tr
bng tm), Al
3+
phi tr bt din (s phi tr bng su) v Si
4+
phi tr t din (s phi tr bng
bn). Nh th, cc lc lin kt m ion oxy nhn t cation Ca
2+
, Al
3+
v Si
4+
ln lt bng 2/8
= 1/4, 3/6 = 1/2 v 4/4 =1. trung ho in tch 2 ca n th ion oxy phi thuc v hai a
din lp phng ca Ca
2+
, mt bt din ca Al
3+
v mt t din ca Si
4+
(2 1/4 + 1/2 +1 = 2).
y l lin kt c s ca cc a din phi tr trong grosular.
Tinh th c gi l ng cc, nu tt c cc mi lin kt ca n u c bn nh nhau.
Khong vt thuc nhm spinel chng hn, c cng thc tng qut AB
2
O
4
, trong , A l
cation ho tr hai nh Fe
2+
hay Mg
2+
v B l cation ho tr ba nh Al
3+
hay Fe
3+
. Nhng hp
cht loi ny tng c gi l aluminat v ferat. Danh php ny cho thy mt nhm chc
tn ti trong cu trc, v d
2
3
CO

. Trong thc t, cc d liu ca phng php nhiu x tia X
chng t ion A phi tr bn v B phi tr su. T , lc lin kt oxy nhn t A (ho tr tnh
in) bng 2/4 = 1/2 v t B l 3/6 = 1/2. Nh vy mi mi lin kt u cng mt bn
vng (ho tr tnh in ca A v B u c chung mt gi tr l 1/2) v tinh th nhm ny l cc
oxit ng cc.

Tham kho 4.1.5. nh lut Goldschmidt


86
Khi cation c nh, in tch cao, phi tr vi anion c ln, in tch thp, th nhm chc
bn chc s hnh thnh

. V d: carbonat v nitrat. Gi tr tnh c v bn ca cc lin kt


bn trong cc nhm chc ny cho thy, ho tr tnh in tng lun ln hn mt na in tch
ca anion. iu ny c ngha l trong nhm chc anion lin kt vi cation bng mt lc ln
hn so vi lc lin kt m n c th c i vi cc cation khc. Chng hn, trong nhm
carbonat, C
4+
phi tr ba vi O
2
, do ho tr tnh in 4/3 ln hn mt na in tch ca
anion oxy. l nhm chc hnh tam gic, n v cu trc c s ca khong vt carbonat.
Mt v d khc l nhm chc sulfat, S
6+
phi tr bn vi O
2
, ho tr tnh in 6/4 = 3/2 > 1.
V gi tr ny ln hn mt na in tch ca anion oxy, sulfat to nn mt anion phc lin kt
bn vng, trong oxy gn vi lu hunh mnh hn so vi mi lin kt gia n vi cc
cation khc trong cu trc. y l n v cu trc hnh t din, nn tng ca mi hp cht
sulfat. Nhng hp cht loi ny c cu trc khng ng cc/d cc.
ng nhin, nu nhm chc c coi nh n v cu trc, trong cc hp cht loi ny
tt c cc mi lin kt ca nhm chc vi cc cation u c chung bn vng, ging nh
mi lin kt ca mt tinh th ng cc. Tng t, trong barit, mi mi lin kt ca Ba vi
nhm chc
2
4
SO

u nh nhau v bn. Tinh th vn c gi l ng cc, mc d bn
cnh lin kt yu hn ca Ca v Ba vi cc nhm chc, cn c mt cc lin kt mnh CO v
SO.
Hy xt mt trng hp khc, trong lc lin kt gia cation trung tm vi cc anion
phi tr ng bng mt na in tch ca anion. Ti y, mi anion c th lin kt vi mt
cation khc bt k, cng vng chc nh lin kt vi cation trung tm. Cation khc ny c
th l cng mt nguyn t. y l trng hp nhm chc ca silicat vi oxy nh t din v
silic nm ti tm im. Lin kt gia silic v oxy c ho tr tnh in bng 4/4 = 1, ng mt
na ho tr ca anion oxy. Nh th, t din SiO
4
c th lin kt vi ion silic khc v nh th
s c hai t din gn vi nhau, thng qua mt oxy chung, to nn nhm chc (Si
2
O
7
)
6
. Cng
bng cch y, cc t din SiO
4
c th gn kt (trng hp) vi nhau to thnh chui, lp hay
khung, tu s lng anion oxy m mi t din gp vo trng hp l 2, 3 hay c 4. Chnh mc
trng hp y lm nn s a dng ca silicat (xem hnh 4.36).

Tham kho 4.1.4.Tnh phn cc ca ion v 5.5.9.Hiu ng chn.


87


Hnh 4.4
T din (hng trn) v bt din (hng di) gn kt qua nh (a), qua cnh (b) v qua mt (c)
c) a din phi tr thng gn vi nhau qua nh chung. Nu cc a din gn kt qua
cnh, qua mt chung, cu trc tr nn km bn vng. Bi v, lc ny khong cch cation
cation co rt lm cho lc y gia chng tng. Bng sau cho thy, trn v d t din v bt
din, khi chng gn nhau qua cnh hay qua mt chung, khong cch gia cc cation gim so
vi khi a din gn nhau qua nh (xem thm hnh 4.4).

Lc y cation cation pht sinh cng tr nn mnh m, nu cation c ho tr cao v bn
knh nh. Chng hn, khi t din vi Si
4+
ti tm; c bit nu t din gn kt qua cnh hay
mt chung, khong cch gim ln lt cn 58% hay 33%.
Khong cch cationcation
a din phi tr a din chung nh a din chung cnh a din chung mt
T din 1 0,58 0,33
Bt din 1 0,71 0,58
d) Khi tinh th cha trong cu trc nhiu loi cation, nhng cation ho tr cao v s phi
tr nh thng c xu hng khng gn cc a din phi tr vi nhau. Trong nhng trng hp
khc, khi cc a din gn kt nhau qua cnh chung, cnh y d dng thu nh, in tch m dn
ti ni y v cc cation th gin ra mt khong cch ln hn. Kt qu, lc y cationcation
c khc phc mt phn.

88

Hnh 4.5
Cu trc tinh th amphibol mt nghing (C2/m) th hin bng a din phi tr
t din T, bt din M
1
, M
2
, M
4
v lp phng bin dng M
4
(theo Papike J.J. v
nnk, 1969)

e) Mt hp cht c th cha trong thnh phn nhiu cation a dng v ha hc, th mi
nhm ca chng c th gm nhng cation ging nhau v mt tinh th hc. Bi vy, trong cu
trc ca hp cht, cc v tr tinh th hc dnh cho chng ch l mt s hn ch. iu ny th
hin trong cu trc amphibol (hnh 4.5). y, tuy thnh phn gm nguyn t nhiu nguyn
t, cc v tr khc bit nhau v mt tinh th hc th hn ch v s lng. Mi v tr c th cha
ion thuc cc nguyn t khc nhau. Hnh cho thy v tr t din T (T
1
v T
2
), bt din M (M
1
,
M
2
v M
3
c kch thc v hnh dng khc nhau cht t), v tr M
4
(hnh phi tr khng u
n ca s.p.t. 8), v tr A vi kch thc ln, m hnh phi tr khng u n v v tr ca
nhm OH

.
V tr t din l ca Si
4+
v Al
3+
. V tr M
1
, M
2
v M
3
dnh cho Mg
2+
, Fe
2+
, Mn
2+
, Al
3+
,
Fe
3+
v Ti
4+
. V tr M
4
c th do Ca
2+
v Na
+
chim. V tr A c th l ch ca Na
+
hay K
+
.
Cn nhm OH

cng chung mt v tr vi Cl

hay F

. Nh vy, 13 ion thuc nhiu nguyn t


phn b trong 5 v tr tinh th hc khc nhau [gm t din, bt din, lp phng bin dng, v
tr A rng ln v v tr OH

].
Tnh trng hn ch v v tr tinh th hc cn biu hin s loi anion tham gia phi tr
cation. Su anion thuc phi tr bt din thng ch c hai loi (4 anion oxy v 2 anion
hydroxil).
4.2.2 Nng lng mng ca tinh th ion
Khi nim nng lng mng ng vai tr ng k trong vic gii thch nhiu c tnh ca
tinh th ion. Nng lng ny l hm ca in tch cc ion tham gia vo cu trc, ca gi tr
bn knh ca chng v o bng cng cn thit phn hu 1 gam mol ca cht, tc l bin
n thnh nhng ion ring l.
C th xc nh nng lng mng bng phng php thc nghim. Nng lng tnh c
chnh l nng lng c gii phng trong mt lot qu trnh ni tip nhm hnh thnh tinh
th: bin nguyn t t do thnh ion ri tp hp chng thnh cu trc tinh th. V nguyn l kt
tinh l qu trnh to nhit; cc ion t do vn c nng lng d tr; khi kt tinh th nng lng
89
y c gii phng. Chng hn, khi cho kh chlor tc dng ln kim loi natri hnh thnh
tinh th NaCl, nng lng gii phng l 97,7kcal/gam mol.
Lng nhit ny khng ph thuc cch thc hnh thnh tinh th. Qu trnh ny c th tri
qua my giai on: to kh natri, bin natri nguyn t thnh ion Na
+
, bin chlor phn t thnh
chlor nguyn t, ri chlor nguyn t thnh Cl

. Hai ion tri du ny tng tc cho NaCl s


gii phng lng nhit tng ng. Theo Born M. v Haber F. (1919), lot phn ng trn c
vit di dng sau:
D
U J E Q
2
= + + +
vi l nhit thng hoa kim loi, J th nng ion ho kim loi, D nhit phn li phn t phi
kim, E nng lng do phi kim thu in t, Q nhit gii phng do phn ng. Phng php thc
nghim ny cho php xc nh nng lng mng ca hp cht n gin vi chnh xc t
5%.
Nng lng mng cng c xc nh bng phng php ca Born M. v Lande
A.(1918), cn c vo lc tng tc ca cc ion tch in tri du. Lc ny tnh bng in tch
ion v bng khong cch r gia chng
1 2
2
z ez e
K
r
=
vi z
1
e v z
2
e l in tch ca cc ion tri du to ra tinh th (e l in tch in t, z
1
v z
2

l ho tr nguyn t cng o bng gi tr tuyt i). Nu khong r ln v hn th lc K bng
khng. khong cch gii hn lc tng tc gia cc ion tri du mang du m, ng vi lc
ht; ion tip cn nhau n mt khong cho php ng vi trng thi lin kt bn vng. Lc
mang du dng l lc y gia hai ion tch in cng du v khng mt hp cht bn vng
no hnh thnh khong r bt k no. Nh vy, hp cht bn vng ng vi tng nng lng
mang du m, y chnh l iu kin hnh thnh tinh th ion.
Nng lng mng l nng lng tng tc ca mi ion trong mng v c gii thch
nh sau. N bng cng sn sinh khi cc ion t v cc tip cn nhau sp xp thnh cu trc
tinh th. Cng tnh bng lc K khng i nhn cho on ng. Khi lc bin i cng vi
khong cch th h thc tnh cng c dng tch phn. Nh vy, cng sinh ra khi hai ion tip
cn nhau n khong R bng:
2
1 2
z z e
U
R
=
hay i vi ng lng phn t gam N ca hp cht:
2
1 2
z z e
U N
R
=
Bi v ion sp xp khng ging nhau trong nhng cht khc nhau v trong tinh th khng
ch c lc ht m cn c lc y gia cc ion, nn nng lng mng tnh theo cng thc sau:
2 2
az e n 1
U N
R n

=



vi a l hng s Madelung ph thuc loi cu trc; cn n l i lng lin quan n tnh
n hi ca tinh th.
90
Capustinsky ch ra rng, tnh ton nng lng mng gn ng cho mt cht, c th
khng cn xc nh hng s Madelung a; v hng s ny t l thun vi s ion trong n v
cng thc n. i vi hp cht n gin, ng a ra mt cng thc gn ng:
1 2
A X
m.z z
U 256,1
r r

=
+

trong , r
A
+ r
X
l tng bn knh cc ion. Nm 1943, cng thc ny c ng sa li v
c dng sau:
1 2
A X A X
m.z z 0,345
U 256,1 1
r r r r

=

+ +


4.2.3 Lin kt kim loi
Kim loi c nhng c tnh nh khng thu quang, nh kim, dn nhit, dn in v.v...
iu ny l do nguyn t to nn chng bng dng lin kt c bit, gi l lin kt kim loi.
Ngay t nm 1900, Drude P. gi nh rng nhng c tnh ny lin quan ti cc in t t
do c mt trong tinh th. Chng bt khi cc nguyn t kim loi v chuyn ng trong
khng gian gia cc ht mang in t dng. Lc lin kt phn b u n theo mi hng
(c i xng ca hnh cu). Khc vi tinh th ion vi s lng xc nh ca cation v anion
do nhu cu trung ho in
tch, trong cu trc kim loi
vn c s trung ho gia
in tch dng ca nguyn
t v in tch m ca in t
chuyn ng xung quanh. V
vy, hp cht to nn t
nhng kim loi khc nhau
thng khng tun theo quy
tc ho tr m ch ph thuc
nhng yu t hnh hc. Trong
tng nguyn t kim loi in
t chim nhng mc nng
lng xc nh, nhng trong
tinh th kim loi c s
chuyn ng t do ca in
t t nguyn t ny sang
nguyn t kia.
Tc dng ca lc lin kt
kim loi vi i xng dng
cu to cho nguyn t kim
loi mt xu hng c trng:
chng sp xp thnh tinh th
theo nguyn l xp cu cht
nht, tc l vi phi tr ti a
l 12. Kim loi c ba loi cu
trc c trng:
91
Xp cu theo lut lp phng vi phi tr 12.
Xp cu theo lut su phng vi phi tr 12.
Xp cu theo s mng tm khi lp phng vi s phi tr 8.
* Hai lut xp cu c bn
Nu xp cc qu cu cng bn knh trn mt phng, sao cho chng u tip xc nhau
(cht nht), th mi qu cu s c 6 qu khc vy quanh (hnh 4.6,a). Hy xp kht hai lp cu
ny ln nhau c hnh 4.6,b. Lp th ba c th xp chng kht ln hai lp kia theo hai cch
khc nhau. Tm ca qu cu lp th ba nm ngay trn tm cu lp mt (xem li hnh va
dn). Chng cng c th nm ti v tr trung gian: di mi qu cu ca lp trn khng c cc
qu cu ca lp di (hnh 4.6,c). Trong trng hp u, tun t cc lp c th biu din di
dng cng thc sau:
ABABAB
y l lut xp cu su phng, vi A l lp 1, B l lp 2. Lp th 3, th 5, th 7 v.v...
u lp li lp th nht. Lp th t, th su, th tm v.v... u lp li lp th hai. Trng hp
hai s c cng thc vi dng:
ABCABCABC
Trong tun t ny, tm cu lp bn nm i lp vi tm cu lp mt, lp nm i lp vi
lp hai, v.v... y l lut xp cu lp phng. Hai lut chnh ny u c cht cao nht:
74,05%. Loi cu trc th ba ca kim loi tng ng vi mng lp phng tm khi c
cht ch t 68,1%

.
c tnh ca tinh th kim loi nh nh kim, dn nhit, dn in v.v..., u do khi in t
t do phn b gia cc ht nhn nguyn t, chng duy tr trng thi chuyn ng c trong th
nng chy. i vi nhng tinh th c cu trc cng loi v c cng s in t ho tr, khong
cch nguyn t cng ln th im nng chy v im si cng thp, h s n nhit v h s
n hi cng cao.
Trong s nhng kim loi
cng cu trc v khong cch
nguyn t xp x bng nhau,
kim loi no c s in t ho
tr ln th lc lin kt ca n
cng mnh; im nng chy,
im si v cng cao; h s
n nhit v h s n hi thp.
V d: cu trc ca kim loi
Mg v Zr l lut xp cu su
phng vi khong cch
nguyn t 3,2; nhng s in
t ho tr ln lt bng 2 v 4,
cho nn chng khc xa nhau v
nhit nng chy (657
o
C v

Nguyn l xp cu cn p dng m t cu trc vi cc n v cu trc khng c dng cu. Tham kho


4.4.2. Mt s hp cht hu c.
92
1860
o
C). H s n nhit v h s n hi ca Zr nh bng mt na ca Mg, cng ca Zr
ln gp 3 ln cng ca Mg.
Kim loi lun c tnh do, tc l kh nng dch chuyn ca mt phn tinh th so vi phn
kia. D dng v thun li l dch chuyn song song vi phng ca mt cc lp cu. Trong
lut xp cu su phng, cc lp song song vi mt (0001), tc l vung gc vi trc chnh
ca tinh th. Trong lut xp cu lp phng c ti bn hng phn lp. S dch chuyn xy ra
theo hng vung gc vi mt trong bn trc bc ba (hay vi mt trong bn ng cho ca
khi lp phng). Kim loi thuc lut xp cu su phng ch vi mt hng phn lp c
do thp hn so vi kim loi thuc lut xp cu lp phng (tham kho 5.5.4).
c im ca dng lin kt kim loi dn n s a dng ca hp kim. Chng hn, vng
v bc c cng loi cu trc theo lut xp cu lp phng v cng gi tr bn knh nguyn t.
Bi vy, chng c th thay th lin tc cho nhau trong cu trc tinh th. iu ny cng l nt
c trng cho cc cp kim loi sau y: molybden wolfram v paladi platin. Vi bn knh
chnh lch 12,5%, cc nguyn t ng v vng thng khng th thay th nhau mi t l.
Trong nhng iu kin nht nh, chng c th to thnh cc hp kim vi nhng t lng khc
nhau. Hnh 4.7 l nhng v d ca cu trc hp kim loi ny vi t l Cu : Au l 3 : 1 v 1 : 1.
4.2.4 Lin kt cng ho tr
Trong nhng hp cht ion, nguyn t ca cc nguyn t khc xa nhau v bn cht ho
hc. Khi to thnh hp cht, mt s d dng mt mt hay nhiu in t ho tr ca chng. S
khc li d dng thu nhn nhng in t . Trong hp cht nguyn t (hp cht vi dng lin
kt cng ho tr) xu hng nhng v xu hng thu in t ca mi nguyn t th hin gn
nh nhau. Khi nm ti nhng v tr n nh trong mng tinh th, cc nguyn t phi c lp v
ngoi cng bo ho in t.
H
C
H
C
H
H
H H

Mt lot nguyn t c kh nng t ti lp v n nh trn bng cch dng chung mt
hay nhiu i in t. l nhng nguyn t thuc nguyn t ging nhau hoc gn nhau v
tnh in m (ph lc 4), tc l khng khc bit nhau v bn cht ho hc. Trong cng thc
phn t ca cc cht loi ny, mi mi lin kt cng ho tr tng ng mt i in t dng
chung. V d: H
2,
CCl
4,
NH
3,
CH
4,
C
2
H
4
. Mi cp in t dng chung cng thng biu hin
bng mt nt gch.

93
Mt trong nhng iu ng k, lm cho lin kt cng ho tr khc hn lin kt ion, l
ch mi nguyn t trong cu trc ch to mt s hn ch cc mi lin kt quanh n. V d,
trong trng hp hydro, mi nguyn t ch lin kt vi nguyn t th hai cng loi; n khng
thu nhn thm nguyn t th ba no khc. Trong cc cht loi ny, mi nguyn t ch to
thnh s mi lin kt k ti a l:
k = 8 N
(N l s hiu nhm ca bng tun hon cc nguyn t ho hc). Chng thuc nhng
nguyn t ca cc phn nhm ph vi N bng 4, 5, 6, 7 (xem thm ph lc 2). Theo quy tc
ny, d dng nhn bit c im cu trc tinh th ca nhiu n cht. Chng hn cu trc tinh
th hydro v cc halogen (nhm 7) gm nhng phn t ch cha hai nguyn t: s mi lin
kt bng 8 7 = 1.
Trong cu trc tinh th ca cc nguyn t thuc nhm ph su, nhng phn t ca chng
thng c dng vng kn hay dng mch (hnh 4.8). V d: mi nguyn t lu hunh hay
selen ch to thnh hai mi lin kt cng ho tr. Tng t, mi nguyn t thuc phn nhm
ph bn (C, Si, Ge, Sn) u c kh nng xy dng bn mi lin kt cng ho tr vi bn
nguyn t cng loi.
Do lin kt cng ho tr u c hng v to vi nhau nhng gc vi gi tr nht nh,
nguyn t lin kt vi nhau bng lc cng ho tr thng c s phi tr thp.
Ring carbon trong kim cng (hnh 4.9), cng nh lu hunh hay km trong sphalerit, 4
mi lin kt ca mi nguyn t u c hng xc nh: y l lin kt nh hng; gc gia
chng bng 109
o
28. Nhng nu trong trng hp nh lu hunh (hnh 4.8) lin kt cng ho
tr thc hin bng s giao ho ca cc in t ho tr (c thn trong orbital) thuc phn lp
3p
4
vi nhau, th trong nhiu trng hp khc in t giao ho li thuc cc phn lp khc
nhau (sp, dp, sp
2
, dp
2
). Trong trng hp ny, ngay trc khi xy ra lin kt thng c hin
tng phn b li in t gia cc phn lp. Tr li vi carbon, cu hnh in t ca n:

1s
2
2s
2

2p
2


Bnh thng, vi 2 in t c thn phn lp
2p
2
, nguyn t ch to 2 mi lin kt cng ho tr
vi ho tr 2, v d trong CO. Nhng, ho tr 4 vn
thng gp carbon: trc khi ho hp, nguyn t
phn b li in t, chuyn chng vo trng thi
kch thch. Mt trong 2 in t ca phn lp 2s
2

phi chuyn vo orbital trng ca phn lp 2p
2
.
Cu hnh in t ca carbon l 1s
2
2s
2
2p
2
v sau
khi lai ghp tr thnh:
1s
2
2(sp
3
) 2(sp
3
) 2(sp
3
) 2(sp
3
)










Nhng orbital lai ghp 2(sp
3
) ny ca nguyn t to vi nhau mt gc xc nh v
hng v pha cc nh ca t din u vi tm l nguyn t carbon. Chng xen ph cc
Hnh 4.9 Cu trc tinh th kim cng
94
orbital tng ng ca nguyn t C khc to nn tinh th kim cng. Khong cch CC rt
ngn, gi tr ca n (1,444) thng nh hn khong cch tng ng ca lin kt ion.
Chng hn, i vi sphalerit, to thnh bn mi lin kt, nguyn t lu hunh b ra
su in t, nguyn t km ch b ra hai in t. Cho nn hai trong bn mi lin kt s th
hin bng mi tn thay cho nt gch.
Cu trc kim cng (hnh 4.9, 4.14), cng nh cu trc sphalerit (gn nh cng loi cu
trc) u c nt chung l mi nguyn t c bn nguyn t khc vy quanh; trong trng hp
kim cng, mi nguyn t b ra bn in t v thu v bn: cp in t ca mi mi lin kt l
thuc hai nguyn t khc nhau. Tuy nhin, to thnh mi lin kt cng ho tr, hai in t
ca n khng nht thit phi xut pht t cc nguyn t khc nhau.
\ \
C C Zn S
\ \ \ \
Tu ln ca hiu gi tr
in m (ph lc 4) ca chng,
hai nguyn t A v X c th cho
mt hp cht A
m
X
n
bng dng
lin kt vi bn cht tri ca
mt trong hai dng l ion hay
cng ho tr. Nhiu tc gi nh
Pauling, Povarennykh v.v...,
m t tng quan trn bng
th (hnh 4.10).
Kho st trng thi lin kt
ho hc trong s ln hp cht t
nhin cho thy:
Tt c cc fluorur
u c lin kt gn nh thun tu ion. Lin kt cng ho tr ch mc t 2%
trong KF n 20% trong AlF3. Cc chlorur kim loi kim c t 27% n 33% bn
cht cng ho tr trong lin kt.
Phn ln cc oxit c lin kt ch yu dng ion, tr thch anh SiO2 v pyrolusit
MnO2. Hai cht khong vt ny c lin kt cng ho tr tri hn: ln lt bng
54% v 65%.
Sulfur ch yu l nhng hp cht nguyn t: lin kt cng ho tr mc t 68%
(trong argentit Ag2S) n 88% (trong molybdenit MoS2). Selenur, tellurur,
arsenur, antimonur c lin kt vi bn cht cng ho tr cn cao hn.
4.2.5 Lin kt tn d
Trong s n cht, ch c cc nguyn t nhm 8 ca h thng tun hon (He, Ne, Ar, Kr,
Xe) mi kt tinh bng lc lin kt tn d. Lc tn d hay van der Waals rt yu ny lin kt
cc nguyn t bo ho in t lp ngoi cng. N cng l lc gn kt cc phn t vi
nhau (ch : lc lin kt cc nguyn t bn trong phn t li c bn cht khc, lin kt ion

Hnh 4.10.
ng cong ph thuc ca t l (%) lin kt ion vo hiu gi tr
in m ca anion vad cation trong cu trc
95
hoc cng ho tr). Mt s kh ln cht kt tinh hnh thnh nh lin kt tn d: l hu ht
cc cht hu c, hydro, oxy
Vi lc lin kt van der Waals, ht (nguyn t kh tr, phn t, v.v...) c khuynh hng
tp hp quanh n s lng ln nht nhng ht cng loi to thnh tinh th. V vy, y l
dng lin kt khng c hng v khng bo ho.
So vi lc bn trong (gn kt cc nguyn t) tng phn t, lc van der Waals nh hn
nhiu ln. Nhng chnh dng lin kt ny l nguyn nhn ca nhiu tnh cht vt l quan trng
ca vt rn loi ny: im nng chy, cng, h s gin n nhit, v.v... Chng thng c
im nng chy thp, cng nh v gin n nhit ng k. Bng cch so snh nhit nng
thng hoa ca mt hp cht phn t vi nng lng phn li ca phn t cht , d dng nhn
thy lc tn d khng ng k so vi lc lin kt khc. Chng hn, hydro rn c nng lng
thng hoa bng 0,5kcal/mol, trong khi nng lng phn li ca phn t hydro khong
100kcal/mol. Nu em nng lng mng ca mt s cht loi ny so snh vi nng lng
mng ca cc hp cht ion, th s thy s khc nhau cng ln.
Sau y gii thiu vi nt s lc v mt dng lin kt, trung gian gia cc lin kt tn d
v ion. l lin kt hydro.
Nhng bc x cc mnh thng dng xc nh cu trc tinh th cng khng gip pht
hin nguyn t hydro, do nng lc nhiu x nh yu ca n. Ch c th on bit lin kt
hydro bng cc du hiu sau:
Nu hai nguyn t mang in m ni vi nhau bng mi lin kt hydro (tc l c
nguyn t hydro ng gia) th khong cch gia chng thng nh i mt cch
khc thng.
Gc HOH ca lin kt hydro bng 109o.
Nng lng ca lin kt hydro dao ng trong khong kh ln: 5 10kcal/mol; khong
cch nguyn t (OO chng hn) thay i t 2,54 (trong KH
2
PO
4
) n 2,76 (trong nc
). Khong cch cng nh lin kt cng mnh. Nng lng lin kt hydro nh hn nng
lng lin kt cng ho tr hay ion 10 ln nhng li 10 ln ln hn nng lng lin kt tn d.
Khi gc lin kt bng 109
o
, dng lin kt hydro c v ging lin kt cng ho tr. Nhng
lin kt hydro y li ging lin kt ion. Nguyn t H mt in t duy nht bin thnh
proton, c xu hng thu ht mt lng ti a cc ion tri du, nhng ch cn hai nguyn t
mang in m (oxy chng hn), H
+
qu nh b b ph hon ton. Trong thc t, khong H
O thng c coi l c nh (khong bng bn knh ca O
2
).
Tuy nhin, kt qu nghin cu bng ph hng ngoi cho thy khong cch HO trong
mt phn t nc bit lp bng 0,8 (ngn hn 0,4 so vi khong cch bnh thng). Khi
kt tinh thnh mng nc , proton (cc dng) ca phn t nc ny ht oxy (cc m)
ca phn t nc kia. Lc ht nh hn lc ht tnh in gia cc ion trong phn t
nc . V vy, khong cch gia hai nguyn t oxy trong nc kh ln. Cho nn khng
th ni proton nm cch u hai nguyn t oxy; mi lin kt hydro khng i xng. Trong
trng hp nc , proton c th khng dnh lu hn vi mt nguyn t oxy no, m lun
chuyn t nguyn t ny sang nguyn t kia. Xung quanh mi phn t nc c bn mi
lin kt hydro, tc l mi phn t b vy quanh bi bn phn t nc khc.
Sau khi xt nhng dng lin kt ho l ch yu c th nhn thy rng mt hp cht bt k
khng ch c mt dng lin kt n thun. Lin kt ha l trong tinh th thc thng c tnh
cht trung gian gia hai, ba dng v ch t nhiu c bn cht ca mt trong nhng dng lin
96
kt k trn. Hin nay ngi ta cha c mt phng php hu hiu no biu din chnh xc
mt dng lin kt thc. Nh th, chng hn mt hp cht c gi l ion nu dng lin kt
ca n c tnh cht nghing v dng ion.
Cng v l do mi s phn loi cc cht da trn c s lin kt ho l u khng ng
vng c. Tuy nhin, iu khng lm gim ngha to ln ca lun thuyt v lin kt ho
l i vi ho hc tinh th.
4.3 CC LOI CU TRC TINH TH TIU BIU
i tng xem xt di y khng phi cu trc tinh th ca tng cht c th. Trong h
thng kho st y, loi cu trc tp hp cc cht khc nhau v ho hc, v dng lin kt
trong mng, nhng cng chung mt trt t phn b ht vt cht. Mt trong nhng cht ng
cu trc c bit n sm nht s dng gi tn cho c loi cu trc. ng nhin, loi cu
trc khng bao hm chi tit c th; nh kch thc mng chng hn, v iu ch trng l
cch sp xp ca ht trong phm vi mng c s. i khi, loi cu trc cn bao hm nhng
cu trc gn ging, sai khc t nhiu v i xng.
4.3.1 Cch thc th hin loi cu trc
Mi cch th hin cu trc c u im ring, c hiu qu truyn t ring ty trng hp.
C 4 cch th hin cu trc (u l s ca c s) sau y:
a) H thng nt im, ng hn l chm m hay khuyn trn vi tm im ch th nhn
ca ht vt cht. M hnh cu trc kim cng nh trn hnh 4.9 l v d. Nu cch n gin
ny cn hiu qu i vi cu trc ca n cht, th i vi hp cht tng i phc tp, n
khng gip phn bit cc loi ht vt cht vi bn knh khc nhau chng hn.
b) H thng cc qu cu kch thc thay i (hnh 4.22), tu thuc bn knh ht vt cht
cc loi. Nu cn, s dng cc mu sc phn bit loi ht. Thng thng, mu dng cho
oxy, vng m cho silic v.v... Cch ny cng c nhc im ring, nht l khi hp cht c
nhiu loi kch thc ht; ht nh
b thng b khut sau ht ln.
Trong hai cch trn, cc ht
thng ni nhau bng ng lin
hay ng t, m nht khc
nhau, nhm tng hiu qu th hin
hnh khi v biu din mi lin kt
ha l.
c) H thng cc a din phi
tr: cu trc tinh th phc tp
thng biu din di dng a
din phi tr cc loi, thng gp
l cc hnh bt din u v t din
u. Trong khi cu anion xp
cht, ng vi n qu cu anion l n
khoang bt din v 2n khoang t
din; chng c th cha cu cation
bn knh ln lt l 0,41 v 0,22
97
(coi bn knh anion l n v). Hnh 4.11 cho
thy cc khoang t din v bt din sp xp
thnh chui (song song trc chnh) theo quy lut
ca 2 lut xp cu. Nu trong xp cu su
phng (hnh 4.11,a) tng cp chui khoang t
din nm xen k gia cc chui khoang bt
din, th xp cu lp phng (hnh b) s xen
k 2 : 1 ny cho thy ngay trong tng chui.
Theo quy tc ha tr tnh in, cc cation c
khc nhau s khng chim ht s khoang trng
y, chng chim tng phn theo t lng quy
nh trong thnh phn ho hc v theo nhng s
ring. Nhng a din phi tr cha cation ny
s gn vi nhau to thnh s cu trc cho
mi cht. Ngoi nhng a din thng thng,
cu trc c th c nhng a din khc. V d
hnh lp phng, hnh tm mt lp phng v.v...
Hnh 4.12 gii thiu m hnh cu trc ca
khong vt molybdenit MoS
2
xy dng bng
cc khi lng tr ba phng, chng l a din
phi tr ca nguyn t molybden (xen gia cc
lp ny l ny l lp bt din trng).
i vi nhiu trng hp n gin, din t hiu qu mt loi cu trc, ch cn s
dng vi ba cu n gin (xem 4.3.2), m khng nht thit nh n hnh v.
d) Cch y khng lu, nhu cu th hin cu trc tinh th trn mt phng lm xut hin
hnh chiu c s ca n. Mt chiu ny (l mt hnh v) i qua tm ca c s. Trn , cc
vng trn c tm ng vi v tr nguyn t. ng knh vng trn thay i, t l thun vi
khong cch t tm nguyn t n mt chiu. Nguyn t nm pha trn mt chiu th hin
bng vng m, nguyn t pha di bng vng thanh nt. Nhng ht nm ti mt chiu th
biu din bng vng trn nh hay bng mt nt im.

Hnh 4.13
Nguyn t A, B, C, D th hin bng khuyn trn trn mt chiu nm ngang
Hnh 4.13 cho bit cch th hin nguyn t A, B, C, D bng vng trn (hnh bn phi)
mt chiu dng song song vi cc cnh y ca t din u ABCD v i qua tm ca n (hnh
bn tri). Nguyn t cch u mt chiu AA = BB = CC = DD, cho nn cc vng trn ng
vi bn nguyn t cng bng nhau, i vng AB m hn CD, v chng pha trn mt
chiu, v d: cu trc kim cng (hnh 4.14). Nguyn t carbon nh lp phng v tm
hai y th hin bng tm ca 8 vng trn ln (hnh bn phi). Bn nguyn t ti tm cc mt
bn ng vi 4 vng trn nh; tm ca chng nm trn mt chiu. Bn nguyn t cn li nm
trn trong lng ; 2 pha trn, 2 pha di mt chiu v cng cch u mt chiu mt

Hnh 4.12
Cu trc tinh th ca khong vt molybdenit
MoS
2
th hin bng lng tra din phi tr
ca nguyn t Mo (theo Belov N.V., nm 1947)
98
khong bng 1/4 cnh . Ti hnh bn phi chng l bn vng trn vi ng knh bng 1/2
ca vng ln



Hnh 4.14
Cu trc tinh th kim cng Bn tri: m hnh mng, bn phi: th hin bng
khuyn trn trn mt chiu nm ngang
4.3.2 Phn loi cu trc tinh th
Cu trc tinh th c th phn loi theo hp cht ho hc. n cht kim loi v phi kim
hp thnh nhm A. Nhm B bao gm cc hp cht gm hai thnh phn hoc phc tp hn,
cng c th cha nhm chc. Chng hn, cu trc ca hp cht dng AX thuc nhm B, ca
hp cht AX
2
thuc nhm C, cu trc hp cht dng A
n
X
m
thuc nhm D. Nhng hp cht c
hn hai loi nguyn t m khng cha nhm chc th thuc nhm E. Cha nhm chc khc
nhau l cu trc thuc cc nhm F, G, H, K; cu trc silicat thuc nhm S. H thng phn loi
ny c nhc im ring; nhng hp cht khc nhau v loi cu trc v v tnh cht th tp
hp trong mt nhm.
Mt nguyn tc phn loi khc da vo dng lin kt ho hc: cu trc vi lin kt kim
loi, cu trc vi lin kt cng ho tr, v.v... Nhc im ca h thng ny rt r: phn ln
hp cht c trng bng lin kt trung gian.
By gi, nu lu mi tng quan ngc gia kch thc ca c s v dng quen ca
tinh th (xem li mc 3.3.4), th c th xp cc cu trc tinh th vo ba nhm chnh:
Cu trc ng thc;
Cu trc lp v dng lp;
Cu trc chui v dng chui.
Nhm mt tp hp nhng cu trc h lp phng v nhng cu trc cc hng khc vi t
l
c
a
hay
2 2
c
a b
+


hay
2 2
b
a c
+


hay
2 2
a
b c
+


xp x bng 1 (tc l c cc thng s cnh gn
bng nhau). Nhm hai gm cc cu trc vi t l c/a ln hn mt, nh hn mt l c/a ca cc
cu trc nhm ba (xem hnh 4.6 v 4.4.1).
a) Cu trc ng thc
99
Loi cu trc ng Cu hay l lut xp cu lp phng vi nhm khng gian Fm3m l nn
tng ca s ng loi cu trc ng thc. Nguyn t ca nhiu kim loi (ng, vng, bc,
ch, niken, cobalt, bch kim, st, nhm, scandi, calci, stronti, nguyn t t him, v.v..., xem
ph lc 2), cng nh mt lot hp kim, u xp theo lut ny.
Loi cu trc halit NaCl. C s ca cu trc l lut xp cu lp phng ca anion Cl

.
Cation Na
+
chim ht s khoang bt din. Ion dng ny cng xp theo s ca ion m. S
phi tr ca hai loi ion u bng 6. Tt c khoang t din u b trng.
Cu trc ca cht khong vt pyrit FeS
2
(xem hnh 1.8,b); nguyn t st chim v tr ca
natri, cp nguyn t lu hunh S
2
(dng gnh cn, ho tr 2) nm ti ch ca chlor. Nhm
dng trc S
2
nh hng ln lt theo hng bn trc bc ba ca lp phng. Nhm khng
gian ca pyrit Pa3 khc hn ca halit Fm3m. Mng lp phng tm mt tr thnh nguyn
thu, mt nh trt thay cho mt gng. Cu trc calcit CaCO
3
(xem hnh 4.18) cng c th
xem nh cng loi, bi v cation Ca
2+
sp t ging nh Fe
2+
trong pyrit v Na
+
trong halit.
Anion
2
3
CO

hay
2
2
S

tuy khng c dng cu nh Cl

nhng li ging n v trt t sp xp.


Loi cu trc halit c trng cho halogenur ca kim loi kim (tr cesi), ca bc (tr
AgI); cc oxit, sulfur v selenur ca kim loi kim t; cc sulfur, selenur v tellurur ca km,
mangan, cobalt, nickel, st, bch kim, v.v (xem cc bng 4.2, 4.9, 4.10 v 4.17).
Loi cu trc sphalerit ZnS. Cng nh trong cu trc halit, c s ca cu trc sphalerit l
xp cu lut lp phng ca nguyn t lu hunh. Khc vi halit, trong sphalerit nguyn t
km chim khoang t din; ch mt na s khoang ny b chim. Chnh v th, tm nghch
o v trc xoay bc bn bin mt: nhm khng gian ca sphalerit l F 3m. Khoang t din
cha km nh hng song song nhau, ngc vi hng ca khoang trng. Nu c hai loi
nguyn t thay bng nguyn t carbon th cu trc thu c s l ca tinh th kim cng
(xem hnh 4.14).
Loi cu trc sphalerit ZnS cng ph bin trong cc hp cht AX, thuc loi ny c
halogenur ng, sulfur, selenur, tellurur ca beryli, km, cadimi, thu ngn cng nh mt s
arsenur v antimonur (ca Ca v Al). L bin th a hnh h su phng ca sphalerit, vurtzit
c cng thnh phn ha hc v cng phi tr t din ca km, nhng nguyn t lu hunh ca
n li xp theo lut xp cu su phng (xem cc bng 4.7 v
4.8).
Loi cu trc fluorit CaF
2
. Tng t sphalerit, cu trc
fluorit cng c nn mng l lut xp cu lp phng, nhng do
nguyn t calci to nn. Cc nguyn t ny gin rng ti mc
khoang t din c th cha nguyn t c ln nh fluor, v chng
b chim ht, khng ging trng hp sphalerit, s phi tr ca
calci bng 8, ca fluor 4. Nhm khng gian gi nguyn Fm3m
(hnh 4.15). Loi cu trc fluorit v fluorit ngc (A
2
X) thng
gp trong sulfur, halogenur v oxit (xem cc bng 4.1, 4.12, 4.16
v 4.20).
Loi cu trc st (-Fe) hay l mng lp phng tm khi vi nhm khng gian Im3m
l s cu trc ca nhiu kim loi ngoi st: crom, vanadi, molybden, wonfram, niobi, titan,
ziriconi, bari, kim loi kim v s ln hp kim (xem ph lc 2). Nu coi 2 loi nguyn t l
ng nht, tc l thuc cng mt nguyn t ho hc, th cu trc ny theo s mng lp
phng tm khi. Ni cch khc, trong loi cu trc clorur cesi CsCl, nguyn t ca mi
nguyn t sp xp theo s mng lp phng nguyn thu; hai loi nguyn t ny lng vo
100
nhau v cch nhau 1/2 ng cho khi ca mng. S phi tr ca c hai loi nguyn t u
bng 8, a din phi tr l khi lp phng. Nhm khng gian Pm3m.
Loi cu trc ny bao gm cc halogenur cn li ca cesi (tr fluorur cesi thuc loi cu
trc halit), halogenur ca tali (tr fluorur tali), ca amoni (nh NH
4
Cl, NH
4
Br v NH
4
I) v
hng lot hp kim (AgCd, AgLi, AgMg, AlCo, AlFe, BeCo, BeCu, v.v...) (xem bng 4.11).
Loi cu trc spinel MgAl
2
O
4
. Nguyn t oxy xp theo lut xp cu lp phng, magnesi
nm ti khoang t din, nhm ti khoang bt din. c s cha 8 n v cng thc. Nguyn
t Mg ch chim 8 trong s 64 khoang t din, nguyn t Al chim 16 trong 32 khoang bt
din. Cng thc ng vi mng c s l Mg
8
Al
16
O
32
. Phn ln khoang cc loi b b trng,
do nhm i xng khng gian ca loi cu trc l Fd3m (mt nh trt d nm thay mt
gng v tr to ), i xng thp hn so vi i xng ca lut xp cu. Dc trc bc ba
cation kim loi phn b trn cc lp gm hai loi.
Xen gia cc lp nhm phi tr bt din l lp nhm v magnesi vi t l Al : Mg = 1 : 2.
Loi cu trc ny bao gm khong 60 hp cht (nhm spinel) vi cng thc tng qut AB
2
X
4
.
V d: hercynit Fe
2+
Al
2
O
4
, gahnit ZnAl
2
O
4,
galaxit MnAl
2
O
4
, chromit Fe
2+
Cr
2
O
4
, v.v Trong
nhm spinel mt s hp cht c cu trc hon i gia A v B. Cng chim v tr A vi cation
ha tr hai c c 50% cation ha tr ba. S cation cn li nm ti v tr B. Chng hn, magnetit
Fe
3+
(Fe
2+
Fe
3+
)O
4
v magnesioferrit Fe
3+
(Mg Fe
3+
)O
4
(xem hnh 6.36 v bng 4.22).
Vi cng thc ha hc ng dng ca spinel, cu trc forsterit Mg
2
SiO
4
gn ging cu
trc ca n. Nguyn t oxy xp theo lut (khng phi lp phng) gi su phng. Nhng,
vi s gp mt ca cation cc loi, olivin khng c cu trc lp; 1/8 khoang t din do
nguyn t silic chim. Nguyn t magnesi chim mt na s khoang bt din (xem 6.1).
Mt phn ln silicat khung c th lit vo
nhm cu trc ng thc, in hnh l cristobalit,
bin th SiO
2
nhit cao. Cu trc ny c th suy
ra t cu trc kim cng (hnh 4.14); nm ti ch
ca carbon l nhm t din SiO
4
(silic nm ti tm
t din, oxy ti nh, xem 6.11 v hnh 4.16). Ni
cch khc, nguyn t silic xp theo hai s ca
mng lp phng tm mt (a v c, xem cui mc
4.4.1); hai F
LP
ny cch nhau 1/4 ng cho khi.
Nguyn t oxy nm trung im khong SiSi,
nhn s phi tr 2. Silic c phi tr t din vi 4 oxy
(xem thm hnh 4.36). Ging kim cng, cristobalit
cng kt tinh thnh bt din (xem chi tit 6.12).
Nu b qua nhng tnh cht vt l ph thuc
vo i xng, v d: tnh ct khai, hiu ng ho
in, p in; th c im ca cu trc ng thc
l thng ng hng i vi hng lot tnh cht. Chng hn, tc truyn sng sng, truyn
nhit, dn in, gin n nhit.
b) Cu trc lp v dng lp



101

















Khc vi cu trc ng thc,
cc cu trc lp c c im d
hng r nt. Trong lut xp cu su
phng t l thng s gia trc ng
v trc ngang c : a = 1,633; mt
mng (0001) lun l mt c mt
ht ln nht. Bi v mt ht ca
cc mt vung gc vi trc c v song
song vi n l khc nhau, nn t l
c/a cng ln hn 1,633 th c im
d hng ca lut xp cu su
phng cng r nt. Chng hn, cu
trc cc kim loi km v cadimi c t
s c/a ln lt bng 1,86 v 1,89; s
bin dng ca xp cu su phng
lm cho cu trc phn lp cng mnh
(hnh 4.27).
Loi cu trc magnesi Mg hay
lut xp cu ...ABABAB... l s
cu trc chung cho hng lot nguyn
t kim loi nh Be, Os, Rh, Sc, Gd,
Y, -Cr, Cd, Ti, Zr, v.v... v nhiu
hp kim (xem thm 4.4.1). C s ca
Hnh 4.18
Cu trc tinh th ca calcit
102
nhiu loi cu trc tinh th ca cc hp cht. Trong , khoang t din v khoang bt din do
cc nguyn t kch thc nh v trung bnh chim mt phn theo nhng s ring.
Chng hn, cu trc corindon -Al
2
O
3
l lut xp cu hai lp bin dng i cht ca
nguyn t oxy. Nguyn t nhm chim 2/3 s khoang bt din, khoang t din b trng hon
ton. Cc khoang bt din trng nm xen gia cc cp khoang cha nhm, nu kho st dc
theo cc trc tinh th hc (hnh 4.17). Hematit Fe
2
O
3
, ilmenit FeTiO
3
, geikielit MgTiO
3
,
pyrophannit MnTiO
3
u thuc loi cu trc corindon.
Cu trc calcit CaCO
3
rt ging cu trc loi halit. V tr do calci chim gi trong calcit
tng t v tr ca natri trong halit. Thay th ch cho chlor l nhm chc
2
3
CO

. Bi v nhm
chc ny khng c dng cu, cu trc calcit khc vi cu trc halit ch c s lp phng
ca halit b bin dng. N bp dt dc mt trc ba v bin thnh mt thoi R, nh t vi gc
102
o
(thay cho 90
o
). Nu ion hnh cu l ch giao nhau ca bn trc xoay i xng bc ba th
calcit ch gi li mt trc . Trc chnh ny xuyn tm nhm chc v vung gc vi mt
phng ca chng. Dc trc bc ba ny, cc tam gic ca nhm chc xen k ngc chiu nhau
(hnh 4.18).
Cc nhm hnh phng ny song song vi nhau, gy nn c im d hng r rt ca cu
trc v ca cc tnh cht (xem thm 6.13.1). Thuc loi cu trc ny l mt lot carbonat (Mg,
Zn, Co, Fe, Mn, Cd, v.v...), nitrat (Na, Li), mt s borat ca t him v.v...
Cu trc lp ca iodur cadimi CdI
2
xy dng trn c s lut xp cu hai lp ca iod.
Nguyn t cadimi chim mt na s khoang bt din, lp bt din ny nm xen gia cc lp
khoang bt din rng. Lc gn kt cc tp bt din vi nhau l lc lin kt tn d. Loi cu
trc ny c trng cho hng lot iodur (Mg, Ca, Mn, Fe, Co, Pb),
bromur (Mg, Mn, Fe, Cs), sulfur, selenur, tellurur (Ti, Zr, Sn, Ta,
Pt), hydroxit nh brucit Mg(OH)
2
(xem hnh 4.19 v cc bng
4.3, 4.14 v 4.23).
Tng t, cu trc lp ca chlorur cadimi CdCl
2
cng c
cc tp bt din ca Cd, xen gia chng l tp bt din rng;
nhng cc nguyn t Cl xp theo lut lp phng. Loi cu trc
ny bt gp trong mt s halogenur khc (xem bng 4.15). Gibcit
Al(OH)
3
vi nhm ho tr ba chim 2/3 s khoang bt din c
coi l mu hnh l O hai bt din. Cn brucit vi cation chim ht
hnh phi tr bt din th to thnh l O hai bt din ca silicat
lp. Sau y l mt s v d.
Nhm SiO
4
trong cu trc cc khong vt ny gn kt vi nhau theo cch ring, to nn
nhm chc dng l (hnh 4.20) vi cng thc [Si
4
O
10
]
4
. Cc l t din u c hai mt khc
nhau; nu pha y t din trung ho in tch, th pha nh (vi ion oxy cn d in tch
1) ca chng tp trung tt c in m ca nhm chc. L ba bt din (Al+OH)
2+
ca kaolinit
trung ho in tch 4

ca n, bng cch gn ngay vi n t pha nh t din v cng vi n
to ra tp hai l TO.

Hnh 4.19
Cu trc tinh th ca CdI
2
103

Hnh 4.20
Cu trc tinh th kaolinit
Hnh 4. 21
Cu trc tinh th ca pyrophyllit

Kaolinit Al
2
[Si
2
O
5
](OH)
4
Pyrophyllit Al
2
[Si
4
O
10
](OH)
2

Muscovit KAl
2
[AlSi
3
O
10
](OH)
2
Phlogopit KMg
3
[AlSi
3
O
10
](OH)
2

Cc tp ny gn vi nhau bng lin kt yu. Trong pyrophyllit, cu trc bao gm cc tp
ba l TOT lin kt trc tip vi nhau (hnh 4.21). L Al+OH kp gia hai l nhm chc;
chng u hng mt l tch in m v pha l Al+OH d in tch dng. Trong ba l ca
cu trc muscovit v phlogopit, 1/4 nguyn t silic b nhm thay th; in tch m d s do
cation K
+
trung ho. Bng cch , n gn cc tp ba l vi nhau (xem thm 6.8, 6.9, 6.10 v
cc hnh 6.24, 6.25 v 6.26).
Tinh th vi cu trc lp hay dng lp thng c biu hin d hng r nt. Song song
vi mt lp, thng l hng ct khai hon ton v ch s khc x t gi tr cao nht, cn
theo hng vung gc th thp nht. Theo hng ny h s gin n nhit v co c cng cho
gi tr cao nht. Thng thng, vi cu trc lp in hnh, tinh th c cng thp v dng
quen hnh tm.

c) Cu trc chui v dng chui
Loi cu trc rutil TiO
2
(mt trong nhng bin th a hnh ca dioxit titan). Nguyn t
titan phi tr bt din, c 6 nguyn t oxy vy quanh. Mi oxy li nm gia 3 nguyn t titan,
ng vi phi tr tam gic u. Cc khi bt din titanoxy gn vi nhau bng cnh chung, to
nn chui song song vi trc bc bn i xng. Cc chui ny gn vi nhau qua nh ca bt
din. Nhm khng gian P4
2
/mnm (hnh 4.22). Cng loi vi cu trc ny l stishovit, khong
vt vi s phi tr 6 khc thng ca Si
4+
v do trng lng ring cao nht so vi cc bin
th a hnh khc ca silica. Kiu ghp song tinh ph bin ca rutil ph hp vi c im cu
trc ca n: chui bt din c th ghp vi nhau bng cnh bt k ca a din phi tr, to
song tinh dng khuu in hnh (hnh 4.23). Thuc loi cu trc rutil c cc khong vt nh
cassiterit SnO
2
, platnerit PbO
2
, pyrolusit MnO
2
, cc fluorur ca Mg, Zn, Mn, Fe, Co, Ni, Pd
(xem bng 4.13) v nhng hp cht vi cng thc AX
2
khc.
104














Loi cu trc nickelin NiAs. C s ca cu trc l lut xp cu hai lp do nguyn t arsen
to ra. Nguyn t nickel chim ht s khoang bt din gia 6 qu cu arsen, cc khi bt din
cha nickel gn vi nhau qua mt
chung to nn chui ko di theo
hng trc i xng bc su. Dng
chui ca cu trc th hin s khc
nhau v khong cch gia cc nguyn
t nickel NiNi: 2,52 dc hng c so
vi 3,61 dc hng a. Cng loi vi
cu trc ny c pyrrhotin Fe
1 x
S

(x
khng vt qu 0,2). Cu trc thuc
loi sai hng Frenkel; st ho tr hai
khng th chim ht s khoang bt
din do nhu cu trung ha in tch
ca h. Hin tng ny gy ra s thiu
ht in tch dng; v vy, mt lng
tng ng Fe
3+
vo thay cho Fe
2+
.
iu ny s ni r hn chng V.
Nhiu ng cu trc khc ca nickelin
lit k trong bng 4.4.
Loi cu trc chui in hnh
thuc v pyroxen v amphibol (hnh
4.24). Trong pyroxen cc t din SiO
4

kt ni nhau qua nh chung, to nhm
chc [Si
2
O
6
]
4
dng chui dch dc ko
di v hn dc trc tinh th hc chnh.
Trong amphibol, nhm chc [Si
4
O
11
]
6



Hnh 4.22
Cu trc tinh th ca rutil
Hnh 4.23
S gn kt song tinh dng khuu ca rutil
105
l chui kp gm 2 chui n pyroxen (xem cc hnh 4.5, 4.36, 6.10 v 6.11).
Cc cation ho tr hai nh Ca
2+
, Mg
2+
, Fe
2+
hay cp cation ho tr mt v ba nh
Na
+
+Al
3+
, Li
+
+Al
3+
, Na
+
+Fe
3+
lm nn phn cation trung ho in tch m ca hai nhm chc.
i vi cu trc chui, nt c trng l dng quen ca tinh th hnh lng tr gi bn phng
trong pyroxen v gi su phng trong amphibol; gc gia cc mt thuc hnh n {110} ln
lt gn bng 90
o
v 120
o
. Theo hng thng gc vi chui, h s n hi v gin n nhit
thng ln hn theo hng song song vi chui. Ch s khc x theo hng dc theo chui
thng ln hn, tc l truyn sng sng thng nh hn so vi hng vung gc.
4.4 KHI QUT V CC LOI CHT KHC NHAU
4.4.1 Kim loi v hp kim
phn bn phi bng h thng tun hon cc nguyn t ho hc l cc nguyn t phi
kim. Phn ln cc nguyn t ha hc l kim loi (khong 75), m in hnh l cc nguyn t
nm phn tri ca bng. Ch yu, chng c cu trc n gin vi i xng lp phng v
su phng. Theo nhng quan nim hin i, kim loi v ion c hnh dng gn vi ht cu.
Li do tnh v hng ca dng lin kt ca chng, kim loi c xu hng kt tinh theo s
xp cht ca cc lut xp cu. Vic nguyn t ca mng kim loi c i xng dng cu
c chng minh bng php phn tch bn (mt in t) Fourier.
thng hiu cu trc cc pha kim loi cn lm r vai tr ca bn knh nguyn t. T
nm 1926, Goldschmidt nhn thy gi tr bn knh ca cng mt nguyn t ph thuc vo
phi tr; bn knh ca ht vi phi tr 12 c gi tr cao nht, phi tr 8 bn knh gim 3% gi
tr; trong trng hp phi tr 6 v 4 bn knh cn gim na (xem 4.1.4). Khong cch nguyn
t trong cu trc kim loi v hp kim c th coi bng tng bn knh ca hai ht lin k. Trong
nhiu trng hp i khi khong cch nguyn t nh hn tng bn knh ca chng. Cc pha
ny xy ra hin tng co rt khong cch nguyn t, m nguyn nhn c th nm s thay
i trng thi ion ha. Ngay c nhng pha hp kim thuc cng mt loi cu trc vn c s
chnh lch ng k v khong cch nguyn t gia gi tr o c trong cc pha tng ng v
gi tr tnh ton tng bn knh.
Tr mt s bit l, cu trc ca tt c cc kim loi c xc nh (xem ph lc 2); bn
knh nguyn t ca chng lit k trong ph lc 4.
Cu trc tinh th kim loi
Nhng loi cu trc ph bin nht ca kim loi bao gm:
Xp cu su phng (ABABAB), l loi cu trc magnesi.
Xp cu lp phng (ABCABC ), l loi cu trc ng.
Mng lp phng tm khi (Ilp), l loi cu trc -st.
cht (t l phn trm khng gian do cu nguyn t chim) v s phi tr cao chng t
nguyn t kim loi vi lin kt v hng v khng bo ho c xu hng thu ht s lng ln
nht cc nguyn t cng loi (xem thm 4.2.3).
Trong trng hp kim loi vi lut xp cu lp phng (mng lp phng tm mt) s
vic r; mi nguyn t nm cch nhng khong nh nhau ti 12 ht phi tr. Cng c th
ni nh vy i vi phi tr 8 ca kim loi vi mng lp phng tm khi. Xp cu su
phng c coi l cht nht, khi t s c/a = 1,633. Nu tng quan thng s mng c gi tr
106
khc, nh vn thy trong thc t, th khong cch nguyn t ca phi tr 12 s c 2 gi tr.
Nhng ngoi hai trng hp ca Zn v Cd, chnh lch ny khng ln (xem sau).
i vi nhiu kim loi, hin tng a hnh kh c trng. Chng hn, ceri c th c 2 loi
cu trc xp cu lp phng v su phng ty nhit thay i, st c cu trc lp phng
tm mt v tm khi, v.v Kim loi thuc cc phn nhm t IA, IIA, IB n nhm VIIIB ca
h thng tun hon u kt tinh theo mt trong ba loi cu trc k trn. Ring trong s cc
kim loi ca cc phn nhm khc v mangan, ngoi cc loi cu trc y, cng bt gp mt s
ln loi cu trc khc.
-Mn c loi cu trc xp cu lp phng bin dng. Nguyn t u c s phi tr 12,
nhng chng phn ho thnh hai loi ng vi cc khong cch nguyn t 2,36 v 2,67.
-Mn c cu trc tng t vi lut xp cu lp phng, nhng bin dng dc trc xoay
bc bn khin cho c s c cnh thng ng a co rt: a/a = 0,93 (hnh 4.25).
Kim loi indi c cu trc cng loi nhng t l a/a = 1,08.

Hnh 4.25
Cu trc -Mn thuc loi ABCABC bin dng dc trc trc xoay
L
4
. mng tm mt ABCDEFGH chuyn i thnh mng tm khi
MBNCHQGP vi th tch gim 50%


Hnh 4.26
Cu trc kim loi thy ngn. Hg xp theo lut xp cu ABCABC bin dng dc
trc L
3
ng: mt thoi c thng s gc 7242 (b), bnh thng l 60 (a)
Theo nguyn l Bravais th hai cu trc ny chuyn t h lp phng sang h bn
phng. mng c s chuyn t tm mt sang tm khi vi th tch gim mt na.
107
Cu trc ca thu
ngn: V nguyn tc,
mng lp phng tm
mt c th biu din di
dng mt thoi (nguyn
thu), vi gc gia cc
cnh l 60
o
. mng tm
mt ca thu ngn l
mt thoi c gc gia cc
cnh l 72
o
32

(hnh
4.26).
Cu trc loi xp cu
su phng thng bin
i theo trc chnh lm
thay i t l thng s
mng c/a, m khng ko
theo s bin ng v i xng. Hnh 4.27 l mng ca cu trc tun theo lut xp cu su
phng l tng: c/a = 1,633, tc l khng c chnh lch v khong cch gia cc nguyn t
k nhau, d chng cng lp hay khc lp, c li y lun bng tng bn knh ca cp nguyn t
k nhau. i chiu vi trng hp ny l hai cu trc sai khc nhiu nht. l beryli, km
v cadimi vi c/a ln lt bng 1,57; 1,86 v 1,89.
Mt lot nguyn t ho hc ng cu trc, khc nhau v tng quan thng s mng vi
cc gi tr c/a thay i so vi 1,633. Ngoi km, cadimi v beryli, phn ln trong s 28
nguyn t c c/a xp x nh hn gi tr l tng. Nhng sai lch ny gi v s bin dng ca
ht cu nguyn t sang elipsoit trn xoay.
Cu trc tinh th hp kim
Nguyn t kim loi thuc cc nguyn t khc nhau c th khng tng tc vi nhau, c
th rn ln th lng. Trong thi cc khc,
hai kim loi c th phn ng vi nhau
to thnh hp cht ho hc xc nh. Gia
hai gii hn , nhng h trung gian c th
tn ti:
Kim loi tan vo nhau trng
thi lng, khi chuyn sang
trng thi rn chng to eutecti;
Gia hai kim loi c th hnh
thnh dung dch cng mi t
l thnh phn.
V mt hnh hc, hnh 4.28 l s
kt hp theo nhng cch khc nhau ca
hai loi ht. S lng tng i ca hai
loi trong c 4 trng hp l nh nhau,
nhng s phn b ca chng li khc
nhau. Trong trng hp A, nguyn t hai
loi phn b hon ton ngu nhin; tn
108
sut gp ca nguyn t trng v en l nh nhau ti im bt k. Trng hp ny tng
ng vi trng thi hon ton khng trt t. N khc hn trng hp hon ton trt t D; l
cu trc tinh th ca nhiu hp cht v c. Gia hai trng thi ny c th c hai trng hp
trung gian.
Trng hp B c th c nguyn t phn b theo trt t tm gn; nguyn t en v
trng ch duy tr c phi tr trt t trong tng phm vi nh hp. Trn B ny khng tm
thy i nguyn t en no nm cch nhau c li nh nht. Nhng thng tin hin c v cu
trc vi m ca pha dung dch cng cho thy chnh s phn b y c trng cho phn ln pha
kt tinh ny.
Trng hp C khng ch c trt t tm gn, trong cn c trt t tm xa. Tinh th pha
hp kim phn ln c cu trc c trng ny. iu cho thy gia dung dch cng v hp
cht khng c ranh gii r rt; trong t nhin v trong phng th nghim vn c th bt gp
dung dch cng vi trt t cao v vn c hp cht khng duy tr c trt t hon ho.

Hp kim vi loi cu trc ng (Cu).
Kim loi c n vi chc nguyn t ng cu trc vi Cu (xp cu lp phng), cha k mt
s ch khc rt t so vi loi cu trc ny. Chng hn mangan v thu ngn.
Hp kim c th cng kt tinh theo s ny, y t lng gia cc nguyn t kim loi
c th thay i trong gii hn ln. Da vo cu trc ca kim loi ng (hnh 4.29,a) c th
nhn din cu trc ca hng lot hp kim. Trc ht, hy lu cch tnh s nguyn t ng
trong mng lp phng tm mt ca n. Cu ti nh l chung cho 8 , nn n ch c 1/8 v 8
Cu cc nh ch c (1/8) 8 = 1 nguyn t Cu () thuc mng cho. Cu tm cc mt
ch tnh 1/2 v 6 mt tnh (1/2) 6 = 3 Cu (). Lng nguyn t Cu tnh trn mng c tng
l:
() + () = 1 + 3 = 4.
Trong cu trc hp kim Cu
3
Au (hnh 4.29,b), nguyn t ca hai kim loi phn b ti v
tr ca mng lp phng tm mt. Nh vy, cu trc khng cn thuc mng tm mt: bc
tnh tin ph dc ng cho ca cc mt bin mt; n thuc mng lp phng nguyn
thu. Kim loi vng nm ti nh , vi to im u 000 v s bi l 1.
109
Nguyn t ng, vi s bi l 3, chim v tr ti tm ca cc mt; tc l chng chim ti
3/4 v tr ca mng tm mt lp phng.
Cu trc ca hp kim Pt
7
Cu (hnh
4.29,c) c nguyn t platin (vi s bi bng
7) chim ti 175% s v tr ca 2 h im
quy tc thuc mng lp phng tm mt.
25% v tr cn li l ca nguyn t ng:
chng nm ti nh ca mng vi s bi l
1.
Gi d hai loi nguyn t trong hp
kim CuAu (hnh 4.29,d) thuc mt nguyn
t ho hc, th cu trc s thuc mng lp
phng tm mt. Nhng d dng nhn thy
hai loi nguyn t xp thnh lp xen k
nhau; trt t cc lp hon ton ging nhau.
Nu xt trn mng, nguyn t ng nm
nh v tm cc mt y ca ; cn
nguyn t platin chim v tr tm cc mt
bn. Mi loi nguyn t chim 50% s im
lut xp cu ABCABC lm cho i
xng chuyn sang h bn phng; khng
phi do mng bin dng, m do chnh s
phn b ca cc loi nguyn t trong hp
kim.
Cu trc PtCu (hnh 4.29,e) c th suy
ra t cu trc kim loi thu ngn. Cc cnh
mng ca PtCu u tng gp i. Tng t
cu trc ca thu ngn, mng ca cu trc
hp kim ny l kt qu bin dng ca lp
phng tm mt (n b bp dt theo hng
ca mt trong 4 trc bc ba; 3 trong 4 trc
do bin mt; cn i xng th tr
thnh ba phng). Gi d, c th ng nht
hai loi nguyn t ca hp kim, th c th
thy rng cc ht cng loi xp theo lut
ABCABC bin dng. Khong cch
nguyn t cng lp th ln hn khong cch
cc ht khc lp.
Vy, ngoi s bin dng ca mng, i
xng ca cu trc tr thnh ba phng cn
do chnh s sp xp cc ht. Nguyn t
thuc hai nguyn t phn b xen k nhau
theo tng lp vung gc vi trc bc ba.
Hp kim vi loi cu trc st (-Fe)



Hnh 4.30
Loi cu trc -Fe (a) ca cc hp kim Cr
2
Al (b); NaTl
(c) v Fe
3
Al (d)
110
Fe c cu trc thuc mng lp phng tm khi; nguyn t st u c s phi tr 8,
hnh phi tr lp phng, s bi bng 2 (hnh 4.30,a).
Cu trc tinh th hp kim Cr
2
Al. Thot nhn, c th thy hnh 4.30,b gm 3 tm khi
ging Fe nu coi hai loi nguyn t l thuc mt nguyn t. Thc ra, nguyn t mi loi
phn b trn cc lp ring vi cng mt trt t sp xp. Cc lp song song, cch u nhau,
u vung gc vi trc chnh v trch nhau 1/2 ng cho mt y mng. Hai lp crom
lin k nm xen k vi tng lp nhm n l. S bi ca 2 h im ln lt l 4 v 2, trong
khun kh ca nhm khng gian P4/mmm.
Cu trc tinh th hp kim TlNa v AlFe
3
. Hy tng tng ct lp phng ca mi cu
trc bng 3 mt trc giao ti tm ca . Nh th, c th ni mi hnh l tp hp ca 8 tm
khi lp phng nh, gi d hai loi nguyn t ca mi hp kim l thuc mt nguyn t ho
hc. Trn thc t, cc ht ca mi cu trc u nm trn cc im ca 4 v tr c bit thuc
mng tm mt lp phng (F
LP
).
Trong cu trc TlNa v AlFe
3
, nguyn t mi loi chim 2 h im nh sau (hnh 4.30,c
v d).
Tl : 000 v
1 1 1
4 4 4
; Na :
1
00
2
v
1 1 3
4 4 4

Al :
1 1 3
4 4 4
; Fe : 000;
1
2
00 v
3 1 3
4 4 4

Nhn chung, trong cu trc n gin ca hp kim loi ny, nguyn t ca mi nguyn t
c th chim mt phn, hay chim ht cc im ca mng F
LP
theo bn v tr c bit nh sau:
a) V tr 000 bao gm nh v tm cc mt ca .
b) V tr
1
2
00 bao gm im gia ca cc cnh lp phng.
Hai v tr sau nm trn cho khi, mi v tr 4 im chia u cho 4 ng cho, c th l:
c) V tr
1 1 1
4 4 4
v
d) V tr
1 1 3
4 4 4
.
Hy im li cu trc cc hp kim va m t.
Cu
3
Au: Tt c cc nguyn t ca hp cht Cu
3
Au ch chim ht mt h im ca mng
F
LP
; trn hnh 4.29,b cc nh lp phng ng vi 1/4 s im trong v tr a) l ca Au, 3/4
s im cn li l dnh cho Cu.
Pt
7
Cu: Ton b nguyn t Cu trong Pt
7
Cu (hnh 4.29,c) ch chim 1/4 s im ca a), 7/4
s im cn li ca hai h im F
LP
, tc l 3/4 s im ca v tr a) v tt c cc im ca v
tr c), u l ch ca Pt.
CuAu: Mi loi nguyn t trong CuAu nm ti 1/2 s im ca v tr a), sao cho cc lp
ca mi loi nguyn t u xen k nhau, nh trn hnh 4.29,d.
TlNa: mt na s nguyn t Tl chim ht v tr c), na kia chim ton b h im ca v
tr a); Na chia u cho 2 v tr: b) v d) cn li (hnh 4.30,c).
111
AlFe
3
: Trong AlFe
3
, nguyn t ca n phn b trn c 4 v tr c bit ca F
LP
. Nhm
chim d), st chia u cho 3 v tr a), b) v c) (hnh 4.30,d).
Qu trnh trt t n nh trong pha hp kim
Nhng nghin cu chi tit cc pha rn trong h CuZn cho thy trong vng nhit cao
pha -CuZn c cu trc hon ton khng trt t. Nhit h thp, trt t t gi tr rt cao
v hon ton c th lit n vo loi cu trc CsCl. Qu trnh bin i trng thi y t
khng trt t sang trt t v ngc li din bin trong mt khong nhit xc nh, m
khng phi t bin mt gi tr nhit nh trong bin i a hnh.
trt t cng thp, bn thn n cng d b ph b. Trt t cao c tc dng gy cn tr
i vi s xut hin ca tnh trng khng trt t. Nu tng nhit mt cch tun t th lc
u c th thy trt t gim chm v khng ng k. Nhit tng tip tc th tnh trng
mt trt t tng nhanh dn v cui cng, trt t bin mt hu nh t bin. Chng hn, trt
t bt u gim mnh trong pha CuZn khi nhit t khong 390C v kt thc sau gn
20C. Bradley A.J. v Jay A.H. (1932) nghin cu chi tit kha cnh cu trc ca qu trnh
trt t ho trong h FeAl.
Tr li mng lp phng, nu c 4 v tr a, b, c v d u cha nguyn t Fe th y l
hnh nh 8 tm khi ca cu trc -Fe ghp li. Khi thnh phn gm 50% nguyn t Fe v
50% nguyn t Al v Al chim cc im ca v tr a) v b); Fe chim cc im ca v tr c) v
d), th y l 8 mng ca hp cht FeAl kt tinh theo loi cu trc CsCl.
Nu nguyn t Al thm nhp dn vo pha -Fe tinh khit th pha hp kim trng thi
nhit cao vi thnh phn nguyn t Al t 0 25% l mt dung dch cng in hnh,
Al phn b ngu nhin trong cu trc Fe. Tn sut gp Al trong cc v tr a), b), c) v d) t l
thun vi lng Al ho tan. Bt u t 25% Al tr i, Al cng nhiu, dung dch cng cng tr
nn trt t trong cu trc. Nguyn t Al bt u chim c) v d), y Fe sang a) v b). Qu
trnh ny kt thc khi thnh phn nguyn t nhm t 50%, trt t t gn 100% ng vi
cu trc FeAl.
Nu s nung t t ch thch hp, trt t c th n sm hn. Bt u t 18%
thnh phn nguyn t, nhm bt u y st chim v tr c). Vi 25% thnh phn
nguyn t nhm, loi cu trc mi ra i vi cng thc Fe
3
Al. Tuy vy, trt t cha ti
100%: mt phn v tr c) vn cn c st. Hm lng nhm c tng cng tip th cc
nguyn t ny s y ht st khi v tr c), lc ny Al vt qu 25% thnh phn nguyn t.
Chng xm ln v tr d), b dn v tr c). Tn sut gp Al c) v d) nh nhau khi hm lng
Al t 38%. Cu trc trt t FeAl c c khi thnh phn Al ln hn 38%.
4.4.2 Mt s hp cht hu c
Cc hp cht hu c thuc loi cu trc phn t. Dng lin kt gn nguyn t thnh phn
t thng mang bn cht cng ho tr. Phn t tp hp nhau to nn tinh th bng lin kt van
der Waals. y l lin kt v hng; c th thy trc rng phn t trong tinh th c xu
hng tp hp quanh n s lng ln nht cc phn t k cn. Mc du phn t khng c
dng cu, chng vn c th xp cht trong cu trc. Phn ln hp cht hu c c phn t vi
s phi tr 12. Cn c cc s liu v hnh dng v kch thc phn t, cng nh v th tch
mng c s, cht ca nhiu cu trc c xc nh. i lng ny dao ng trong
khong t 60 n 80%. R rng, nguyn l xp cu ni chung c th p dng cho cc cu trc
hu c. Phn t thng c dng bt k, khng u n; khi xp cht, ch li ca ht ny lp
112
vo ch lm ca ht kia. Trong iu kin nht nh, vi bn nng t xoay quanh trc ring
hay quanh tm im, phn t tr nn c dng ng, dng cu v i xng cao hn.
Cu trc tinh th metan CH
4
. Nu nguyn t carbon nm ti tm ca phn t t din u,
th 4 nguyn t hydro ti nh; iu ny m bo cho s o n nh (khong 109) ca gc
ha tr HCH. i
xng cao v kh nng
t xoay, phn t
metan lm nn nhm
khng gian Fm3m ca
cu trc tinh th, s
bi n=4, thng s
mng a = 5,89 (
nhit 180C).
Tm im ca phn t
phn b ti cc nt
ca mng lp phng
tm mt.
Cu trc tinh th
adamantan C
10
H
16
c xc nh rt sm, cng do phn t ca n c i xng cao vi nhm im 4 3m (hnh
4.31). Trong khun kh lp phng (ng t) mi cp CH
2
chia nhau nm trng trn hai
mt gng vung gc nhn trc 4 lm giao tuyn; cc ht carbon ca chng phn b ti v tr
a) ca L
LP
. Cn 4 cm CH chia u cho 4 trc xoay bc ba v dng trc ca chng trng vi
4L
3
, nguyn t carbon nm v tr c) ca F
LP
. Mi nguyn t carbon ca cm CH
2
, vn c
2 mi lin kt vi 2 hydro, li c 2 lin kt vi 2 carbon ca 2 cm CH. Mi carbon ca cm
CH ( c 1 mi lin kt vi hydro) lin kt vi 3 nguyn t carbon ca 3 cm CH
2.
Vy, mi
nguyn t carbon ca phn t c 4 mi lin kt c trng, nh hng u n v to nn
nhng gc ho tr HCH n nh. Phn t adamantan sp xp song song vi nhau, tm im
ca chng phn b theo s ca mng lp phng tm mt. Kch thc mng a = 9,426;
s bi im n = 4.
Cu trc tinh th benzen C
6
H
6
.
Cu trc cc cht thm c nghin
cu k hn so vi cc lp hu c
khc. Tt c cc nguyn t carbon
ca phn t C
6
H
6
u nm trn mt
mt phng (hnh 4.32,a). Vic phn
t ca n nm ti tm i xng
chng t s cn bng ca cc lin kt
gia carbon vi nhau. Khong CC
thay i t 1,374 n 1,382. Gc
ho tr CCC t 11928

n
12042. Cc thng s hnh hc ca
cu trc nh sau: a = 7,460; b
= 9,666; c = 7,034. Nhm khng
gian Pbca (hnh 4.32,b).
Hnh 4.31. Cu trc phn t adamantan

Hnh 4.32. Cu trc phn t benzen (a)
v hnh chiu mng tinh th trn (010) (b)
113

Cu trc ca parafin C
29
H
60
. Cng nh trong tt c cc hp cht bo, nguyn t carbon
xp thnh chui dch dc, vi khong CC chng 1,54, vi gc CCC c trng 109,5
(hnh 4.33,a,b). Trong tinh th, cc chui ny xp kht, song song vi trc c (hnh
4.33,c). Mng trc thoi ca parafin c kch thc nh sau: a = 7,45; b = 4,95; c =
77,2. Nhm khng gian Pnma. Phn t parafin trong tinh th thng dao ng nhit xung
quanh trc c. Tip cn im si, chng xoay quanh trc v c dng ng; do i xng tinh
th t trc thoi bin thnh su phng.
4.4.3 Sulfur v mui sulfur
y l hp cht ca kim loi vi lu hunh, selen, tellur v bn kim (arsen, antimon v
bismut). Cc bn kim ny kt hp vi lu hunh to anion phc ca mui sulfur. So vi Se,
Te v bn kim, S l anion quan trng nht v ph bin hn c trong t nhin. cha (g/t)
ca cc nguyn t ny trong ca Tri t (theo Goldschmidt) nh sau:
S Se Te As Sb Bi
520 0,09 0,0018 5 1 0,2
Trong iu kin t nhin, S thng gp trong hai trng thi ho tr: 2 trong anion S
2
v
+6 trong [SO
4
]
2
ca sulfat. Do vy, linh ng ca S trong v Tri t xc nh bng
oxy ho ca n; trong mi trng kh S cho sulfur, iu kin oxy ho n cho sulfat. Qu
trnh oxy ho ca lu hunh din bin theo trnh t sau:
S
2
S
2
2
S
o
S
4+
S
6+
Bn knh ca S
6+
(0,34) rt gn vi ca P
5+
(0,35) v Si
4+
(0,39); t c th thy
kh nng thay th ng hnh gia [SO
4
]
2
, [PO
4
]
3
v [SiO
4
]
4
. Do S ho hp to thnh hp
cht vi Fe, Ni, Cu, v.v, S tch khi dung th silicat ngay giai on u ca qu trnh
phn d magma. Lu hunh gp trong m khong kh thnh v nhit dch vi khi lng ln
nht. y l ngun S chnh cung cp cho sulfur ca hng lot kim loi (Cu, Zn, Pb, Ni, Co,
Mo, Hg, Ag, v.v). S cng tn ti trong sn phm hu magma vi hm lng ln, chng t
n l thnh phn ca kh ni la. Dung nham ni la qun o Hawai cha ti 5,5% SO
3
.
Kh H
2
S ng vai tr quan trng trong thnh to sulfur. Khi nhit tng, n khng bn vng
v phn hu thnh hydro v lu hunh; trong nc phn li ging phn t nc theo s :
H
2
S H
+
+ (SH)

; (SH)

H
+
+ S
2

cha trung bnh ca S trong magma 520g/t; trong trm tch 1300 g/t; trm tch
st cha t hn v ct kt cha nhiu hn gi tr ny. Nc lc a cha S nhiu hn hai ln so
114
vi nc bin. Ngun lu hunh cung cp cho nc l nh khong vt sulfur b oxy ho.
Theo hm lng trong nc bin th lu hunh ng hng th t, sau Cl, Na v Mg; n tn
ti dng sulfat, nhng nhng bin kn thiu oxy nh Bin en th H
2
S l dng tn ti ca
S.

Ngun gc ca S c th phn bit bng thnh phn ng v. Lu hunh c 4 ng v
bn vng l S
32
, S
33
, S
34
v S
36
vi ph bin ln lt l 91,1%, 0,74%, 0,4% v 0,0016%.
T l S
32
/S
34
c gi tr khng i trong thin thch 22,2; bin ng cc ngun khc. Trong
trng hp t l ny c gi tr ln hn 22,2 th S c ngun gc sinh hc, S c l l ny nh hn
22,2 l S hnh thnh t ngun gc v c. Tp tnh ca lu hunh di su kh ging ca
selen v tellur. Sulfur st y rt giu Se do c thay th ng hnh Se S. Cng nh Se v
Te, S to khong vt c lp v tp trung trong m khong nhit dch. Selen v lu hunh u
b thc vt hp th, mt s cha Se n 15000g/t. Khc vi S, Se khng tp trung trong nc
bin.
c im ho hc tinh th
Sulfur v mui sulfur thuc hng cc hp cht n gin, cha S, Se, Te, As, Sb v bn
cnh chng 20 nguyn t di dng cation. Quan trng nht l 6 nguyn t Ni, Co, Fe, Cu, Ag
v Pb. Chng u c i lc vi S, phn no vi As (Ni, Co v Fe) hoc vi Te (Cu, Ag, Au v
Hg). Theo c im a ho cc cation ny thuc loi siderophil v chalcophil. Kim loi ca
sulfur v mui sulfur c phi tr bt din v t din; ngoi ra l phi tr tam gic, lng tr,
v.v V d, galen PbS, nickelin NiAs c phi tr bt din; sphalerit ZnS, argentit Ag
2
S c
phi tr t din ca kim loi (tham kho 4.3.2). Ngoi ra, molybdenit MoS
2
v covelin Ag
2
S
c cu trc lp. Mui sulfur c cu trc phc tp hn, cu trc mt s trong chng c th suy
ra t cc cu trc n gin ca sulfur (Hellner, 1958).
Sulfur thnh phn n gin th c cu trc vi i xng cao, cn mui sulfur vi thnh
phn tng i phc tp th tinh th c i xng thp. Phn ln sulfur kt tinh h lp phng,
s khc su phng, s cn li trc thoi, t nht l sulfur mt nghing. Tri li, cc mui
sulfur phn ln kt tinh h mt nghing hay trc thoi. Ch 10 mui sulfur ca Cu, Ag v
kim loi him nh Ge, Sn v V thuc h lp phng. Thng thng, khong vt sulfur c tinh
th hon thin, nht l sulfur cha cation Fe, Ni, Co, Zn v Pb. Mui sulfur thng gp
dng tp hp, thng kt khi hay kt ht, i khi dng tp hp si.
Sulfur, selenur v tellurur
H thng tun hon cc nguyn t ha hc cho thy S, Se, Te v Po nm cng nhm ph
VIb vi O; chng u c lp v in t ngoi cng ging nhau. Mc du vy, xt ring hnh
vi ha hc tinh th, chng c nhiu im khc xa oxy. C th tm li gii cho iu ny cu
to cc lp v in t bn trong v s chnh lch ln v kch thc ht. So vi oxy, cc
nguyn t ny c gi tr in m thp hn nhiu, nn chng khng to nhiu hp cht ion vi
kim loi. Nhng hp cht n gin m anion S
2
, Se
2
, Te
2
, Po
2
to vi kim loi kim v
kim th cha hn l nhng hp cht ion. Vi bn cht chalcophil ca lu hunh v cc
nguyn t cng phn nhm, cc hp cht y gn nh nhng cht ng cc vi cc mi lin
kt dng trung gian gia cng ha tr v kim loi. V d, mt s sulfur kim loi vi loi cu
trc halit v fluorit. Khong vt galenit PbS mang thuc tnh ca kim loi; nh c mu xm
c trng, nh kim mnh v dn in tt; nhng n li gin, khng rn c. Tp tnh ny
rt c trng cho nhiu sulfur, selenur, tellurur.
Kim loi phn nhm IA thng cho cc sulfur, selenur, v.v... vi loi cu trc fluorit
ngc khng mu, tan trong nc v tan trong nc, S

d

thy phn cho SH

v

H
2
S (xem
115
bng 4.1). Khong cch ht khng cho thy s chnh lch gia cc gi tr thc nghim v l
thuyt, nht l i vi cc ht kch thc khng ln.
Nhm khng gian O
h
5
= Fm3m, Z = 4, phi tr 8 4
Bng 4.1
Sulfur, selenur, tellurur v polonur kt tinh loi cu trc fluorit ngc
Hp cht a, A B,
thc nghim
A B,
l thuyt
Hp cht a, A B,
thc nghim
A B,
l thuyt
Li
2
S 5,708 2,47 2,55 Na
2
Po 7,473 3,24
Li
2
Se 6,005 2,00 2,66 K
2
S 7,391 3,20 3,13
Li
2
Te 6,504 2,82 2,87 K
2
Se 7,676 3,32 3,24
Na
2
S 6,526 2,83 2,80 K
2
Te 8,152 3,53 3,45
Na
2
Te 7,314 3,17 3,12 Rb
2
S 7,65 3,35 3,26
Kim loi phn nhm IIA, tr Be, u to vi lu hunh v nguyn t cng phn nhm
nhng pha rn thuc loi cu trc halit (xem bng 4.2). Khong cch ion khng c s chnh
lch nhiu gia gi tr l thuyt v thc nghim. Cc hp cht tng t ca beryli thuc loi
cu trc sphalerit vi phi tr t din v lin kt ch yu l cng ha tr. Khng nghi ng rng
Be khc hn cc kim loi IIB kia.
Trong s sulfur ca kim loi phn nhm IIIB c LaS kt tinh theo loi cu trc halit.
mng lp phng cha khng La, chng phn b ngu nhin trong khoang bt din do S
to ra; dung lng ca n ng vi cng thc La
2
S
3
.
Nhm khng gian O
h
5
= Fm3m, Z = 1, phi tr 6 6
Bng 4.2
Sulfur, selenur, tellurur v polonur kim loi kim kt tinh loi cu trc halit
Hp cht a, A B,
thc nghim
AB,
l thuyt
Hp cht a, A B,
thc nghim
AB,
l thuyt
MgS 5,1913 2,59 2,55 SrS 6,0079 3,00 3,01
MgSe 5,463 2,73 2,66 SrSe 6,2320 3,12 3,12
CaS 5,6836 2,84 2,86 SrTe 6,660 3,33 3,33
CaSe 5,924 2,96 2,96 BaS 6,381 3,19 3,19
CaTe 6,357 3,18 3,17 BaTe 7,000 3,50 3,51
CaPo 6,51 3,26 BaSe 6,589 3,29 3,30
Tng t Sn, Ta v Pt, kim loi ca phn nhm IVB cng cho cc disulfur ging nh
TiTe
2
, tc l kt tinh theo loi cu trc lp CdI
2
(xem bng 4.3). Dng lin kt ca chng u
mang tnh trung gian gia ion v cng ha tr. S bin ng v t lng thng xy ra trong
mt s pha, nh TiS
2
, TiSe
2
v TiTe
2
; hm lng Ti tng tun t chuyn dn sang loi cu
trc nickelin NiAs vi cng thc ln lt TiS, TiSe v TiTe.
Nhm khng gian D
3h
2
= R m, Z = 1, phi tr 6 3
Bng 4.3
Sulfur, selenur v tellurur kt tinh loi cu trc iodur cadimi CdI
2

Hp cht a, c, Hp cht a, c,
TiS
2
3,412 5,695 CoTe
2
3,8921 5,3744
TiSe
2
3,548 5,998 NiTe
2
3,869 5,307
116


Nhm khng gian D
6h
4
= P6
3
/mmc, Z = 2, phi tr 6 6
Bng 4.4
Sulfur, selenur, tellurur kim loi kt tinh loi cu trc nickelin
Hp cht a, c, Hp cht a, c,
VS 3,367 5,825 FeS 3,450 5,882
VSe 3,587 6,009 FeSe 3,643 5,970
Vte 3,813 6,132 FeTe 3,816 5,673
TiS 3,30 6,44 CoS 3,374 5,187
TiSe 3,548 5,998 CoSe 3,6294 5,3006
TiTe 3,842 6,403 CoTe 3,8921 5,3744
CrS 3,462 5,765 NiS 3,428 5,340
CrSe 3,691 6,031 NiSe (20) 3,6613 5,3562
CrTe 3,963 6,17 NiTe 3,965 5,365
MnTe 4,146 6,709 PdTe 4,1521 5,6719
MnTe (20) 4,1429 6,7031 RhTe 3,99 5,66
Phn nhm VB c vanadi v phn nhm VIIIB c phn ln kim loi tham gia thnh phn
ca monosulfur, monoselenur v monotellurur. Chng u kt tinh theo loi cu trc nickelin
(bng 4.4). Thuc loi cu trc ny cn c CrS, CrSe v CrTe. Khi S tng trong cu trc th
CrS cho pha mi mt nghing phc tp hn. Cr
2
S
3
kt tinh theo loi cu trc nickelin vi
nhiu v tr b trng.
Cng phn nhm vi Cr phi k thm Mo v W; chng ch c trong disulfur v diselenur.
V cu trc molybdenit MoS
2
vi phi tr lng tr ba phng do 6S to nn th trn y ni
n (xem hnh 4.12). ng cu trc vi molybdenit cn c tungstenit WS
2
v WSe
2
; chng
cho cc vi tinh mm, mu xm en dng graphit.
Phn nhm VIIB c Mn tham gia vo cc pha MnS v MnS
2
vi cc selenur v tellurur
ng cu trc tr MnTe. Khong vt alamandit mu lc thuc loi cu trc halit l mt trong
ba bin th a hnh ca MnS. Hai bin th khc mu tht ng cu trc vi sphalerit v
vurtzit. MnS
2
c cng cu trc vi pyrit cng tn ti trong t nhin. Khc vi n, MnS
2
c nh
TiTe
2
3,764 6,526 RhTe
2
3,92 5,41
ZrS
2
3,66 5,85 PdTe
2
4,0365 5,1262
ZrSe
2
3,80 6,19 PtS
2
3,544 5,029
VS
2
3,355 6,134 PtSe
2
3,731 5,072
SnS
2
3,646 5,880 PtTe
2
4,018 5,211
-TaS
2
3,319 6,275
117
kim cng, mu nu v ct khai hon ton; nguyn nhn ca s khc bit ny cn cha bit
r. Reni to mt vi sulfur, trong ReS
2
kt tinh dng vy mng lc gic, c l thuc loi
cu trc molybdenit.
Sulfur, selenur v tellurur ca nguyn t h st v platin l nhng hp cht quan trng, s
ln c trong t nhin. Ht thy, chng c tnh bn kim v kt tinh theo nhng loi cu trc
tng ng vi c im y. Tr NiTe, monosulfur, monoselenur v monotellurur ca kim loi
h st u thuc loi cu trc nickelin (bng 4.4), chng u c s thiu ht kim loi gn
ging pyrrhotin. V nhiu phng din, tt c chng u tng t cc pha hp kim.
Nhm khng gian T
h
6
= Pa3, Z = 4, phi tr 6 4 (1+3)
Bng 4.5
Sulfur, selenur, tellurur kim loi kt tinh loi cu trc pyrit
Hp cht a, Hp cht a,
MnS
2
6,107 RhS
2
5,585
MnSe
2
6,430 RhSe
2
6,002
MnTe
2
6,951 RhTe
2
6,441
FeS
2
5,417 RuS
2
5,58
NiS
2
5,676 RuSe
2
5,933
NiSe
2
5,9604 RuTe
2
6,372
CoS
2
5,535 OsSe
2
5,6075
CoSe
2
5,8611 OsSe
2
5,933
OsTe
2
5,369
Loi cu trc rt quan trng, thng c mt trong hp kim l pyrit FeS
2
ni trn. Fe
c 6S gn nht vy quanh, S c 3Fe v 1S to phi tr t din, khong S S = 2,05 (xem
bng 4.5). ng cu trc cn c nhiu hp cht khc cha nguyn t phi kim phosphor, arsen,
antimon v bismut. Thnh phn pyrit rt n nh, trong khi diselenur nickel c s bin thin
gii hn ca kim: NiSe
1,952,05
. Cobaltin CoAsS cng cu trc nh gersdorfit NiAsS; mng
tinh th ca chng rt gn vi ca pyrit (1/2 S
2
thay bng As) vi s phn b ngu nhin ca
lu hunh v arsen.
St c sulfur khc ni trn l pyrrhotin. Fe
1x
S vi x = 0 0,2 l pyrrhotin dng dung
dch cng khuyt tt (xem 5.2.3), nhit nng chy gia 1190C v 400C l dung dch
cng hon ton, vi thnh phn t Fe
1x
S n FeS. 0 254C l trng bn vng ca
pyrrhotin mt nghing vi thnh phn Fe
7
S
8
. Bin th a hnh khc ca FeS
2
l marcasit
(bng 4.6) vi khong S S trong S
2
bng 2,21 v vi phi tr ging nh trong pyrit.
Arsenopyrit FeAsS vi loi cu trc marcasit, As y thay chn ca S. Monosulfur cobalt
kt tinh theo nickelin, disulfur cobalt theo pyrit, Co
9
S
8
theo pentlandit (Fe,Ni)S
2
(hnh 4.34),
Co
3
S
4
theo spinel. Tt c, chng u mang tnh bn kim, u dn in tt. Ring CoSe v
CoTe u c cu trc ca nickelin, cn CoSe
2
v CoTe
2
mang cu trc ln lt ca pyrit v
marcasit.
118
Monosulfur nickel
nhit cao c loi cu
trc loi nickelin, khi
thiu ht Ni n cho bin
th mt nghing. Cn pha
ba phng (mt thoi) l
khong vt milerit; pha
nhit thp ny c phi
tr 5 cho c hai loi
nguyn t. NiSe cng
thuc loi cu trc
nickelin. NiS
2
v NiSe
2
thuc loi cu trc pyrit.
Pentlandit (Fe,Ni)S
2

l khong vt rt quan
trng. mng lp
phng ln thit lp trong lut xp cu lp phng ca kim S. Kim loi chim gi c hai
loi khoang t din v bt din (b), ring khoang t din tp hp li thnh cm tm ci vi i
xng ring m3m (a); tm ca cm ny v ca bt din u phn b theo lut xp lp phng
tm mt (c), ging loi cu trc halit (hnh 4.34). Theo Milovsky v Kononov (1985), hnh bt
din ca Fe v Ni c th nm trong nhn ca cm tm (?). Cng thc cu trc ca pentlandit
vit thnh (Fe
4
Ni
4
)
IV
(Fe,Ni)
VI
S
8
.
Nhm khng gian D
2h
1
= Pnnm, Z = 2, phi tr 6 4 (1+3)
Bng 4.6
Sulfur, selenur, tellurur kim loi vi loi cu trc marcasit
Hp cht a, b, c, Hp cht a, b, c,
CoTe
2
5,3189 6,3185 3,8970 FeSe
2
4,800 5,726 3,582
FeS
2
4,445 5,425 3,388 FeTe
2
5,351 6,272 3,857
Sulfur ca kim loi phn nhm IB c chalcosin Cu
2
S. Nguyn t S phn b theo lut xp
cu su phng; nhng nhit trn 105C cu trc mi gi i xng y, di nhit ny
n tr thnh mt nghing. Covelin CuS l th d v mt khong vt vi thnh phn rt n
gin m cu trc lp kh phc tp. Trong Cu
+
c phi tr t din, Cu
2+
nm ti tm tam
gic u vi nh l S
2
. Anion dng trc S
2
2
nh hng thng ng v nm ti y t din.
Cu trc c th xem nh dng nn t lp tam gic xen gia lp kp i t din. Lin kt cng
ha tr S S ni cc lp ny vi nhau. Kim loi Ag to hai sulfur Ag
2
S vi cu trc n gin.
Thuc i xng mt nghing l khong vt acantit, pha bn vng nhit thng; nguyn
t S xp theo mng lp phng tm khi, Cu phi tr vi 3S thnh hnh phi tr thp ba
phng. Trn 179C l acantit lp phng.
Nhm khng gian T
d
2
= F 3m, Z = 4, phi tr 4 4
Trong s sulfur ca kim loi phn nhm IIB c ZnS vi hai bin th hai loi cu trc
(xem 4.3.2) quan trng: sphalerit v vurtzit. Hai bng 4.7 v 4.8 lit k cc hp cht ng cu
trc. HgS ng cu trc ca sphalerit l metacinnabar; cinnabar , khong vt ph bin nht
thuc lp mt thang ba phng, c chui xon Hg S Hg chy dc trc c. CdS ca loi cu
trc vurtzit gp trong t nhin l khong vt greenockit. CrAl
2
S
4
v ZnAl
2
S
4
c cu trc loi
spinel v kim loi cng phn b khng trt t. Khi cation ha tr hai i khc, cu trc chuyn
119
sang mng mt thoi, v d MgAl
2
S
4
v FeAl
2
S
4
. Di tn tillit, khong vt PbSnS
2
ng cu
trc vi SnS tc l th bin dng ca loi cu trc halit.
Bng 4.7
Sulfur, selenur, tellurur v polonur kim loi kt tinh loi cu trc sphalerit
Hp cht

a, A B,
thc nghim
AB,
l thuyt
Hp cht a, A B,
thc
nghim
AB,
l thuyt
BeS 4,865 2,11 2,10 CdS 5,832 2,52 2,53
BeSe 5,13 2,18 2,20 CdSe 6,05 2,62 2,63
BeTe 5,626 2,44 2,38 CdTe 6,477 2,80 2,80
BePo 5,826 2,52 2,48 HgS 5,854 2,53 2,52
-MnS 5,61 2,43 HgSe 6,074 2,60 2,63
-MnSe 5,83 2,53 HgTe 6,429 2,80 2,79
ZnS 5,406 2,35 2,35 -Ga
2
S
3
5,182 2,25 2,31
ZnSe 5,66 2,45 2,45 Ga
2
Se
3
5,42 2,35 2,41
ZnTe 6,09 2,64 2,63 Ga
2
Te
3
5,886 2,55 2,59
ZnPo 6,28 2,72 2,72 -In
2
S
3
5,371 2,33 2,48
Nhm khng gian C
6v
4
= P6
3
mc, Z = 2, phi tr 4 4
Bng 4.8
Sulfur, selenur v tellurur kim loi vi loi cu trc vurtzit
Hp cht a, c, Hp cht a, c,
MgTe 4,54 7,39 ZnS 3,811 6,234
Al
2
Se
3
3,890 6,30 CdS 4,132 6,734
-MnS 3,996 6,446 CdSe 4,300 7,007
-MnSe 4,13 6,73 -Ga
2
S
3
3,685 6,028
Phn nhm IVA c cu trc lp SnS
2
kt tinh theo CdI
2
. Sulfur ch duy nht galenit PbS
c cu trc loi halit. Sulfur thori c nhiu tnh cht c bit: chng chu nhit cao (im si
ca ThS l 2200C) v tt c chng u nghch t. dn in ca chng kh cao; lin kt
trong chng v bn cht thuc dng kim loi. Cng c th ni nh vy v uran; cc sulfur n
gin nht ca n cng l vt liu chu nhit. im si ca US v U
2
S
3
l 2000C, ca US
2
l
1850C.
Trong phn nhm khong vt stanin Cu
2
FeSnS
4
v qung ng ph bin nht l
chalcopyrit CuFeS
2
u thuc h bn phng c cu trc tng t cu trc sphalerit. Mi
nguyn t u c phi tr t din; ring lu hunh th trong stanin n phi tr vi 2Cu + 1Fe +
1Sn, trong chalcopyrit vi 2Cu + 2Fe; khong cch S S = 3,6 3,8; t l thng s mng
c hai cu trc c/a = 1,96. Cu trc lp SnS
2
kt tinh theo CdI
2.
Sulfur ch duy nht galenit
120
PbS c cu trc loi halit. Cc ng cu trc ca spinel cha kim loi nhm VIII l mt s
khong vt nh (Co,Ni)
3
S
4
, Co
2
CuS
4
, Ni
2
FeSe
4
v FeCr
2
S
4
, cha k nhiu dung dch cng
sinh ra t nhng pha y.
Nhm khng gian O
h
5
= Fm3m, Z = 1, phi tr 6 6
Bng 4.9
Sulfur, selenur, tellurur v polonur kim loi nng vi loi cu trc halit
Hp cht a, Hp cht a, Hp cht a, Hp cht a,
SnTe 6,32 LaSe 6,063 NdSe 5,909 YbTe 6,53
PbS 5,935 LaTe 6,423 NdTe 6,261 ThS 5,682
PbSe 6,122 CeS 5,776 SmS 5,970 ThSe 5,875
PbTe 6,452 CeSe 5,992 SmSe 6,200 US 5,484
PbPo 6,599 CeTe 6,360 SmTe 6,594 Use 5,750
ZnSe 6,138 PrS 5,738 EuS 5,968 UTe 6,163
MnS 5,221 PrSe 5,947 EuSe 6,185 PuS 5,536
MnSe 5,45 PrTe 6,322 EuTe 6,584 PuTe 6,183
LaS 5, 854 NdS 5,6892 YbSe 5,879
Cu trc cc sulfur ca lantanit (thng c ha tr ba) v actinit kh ging nhau. CeS c
dng lin kt na kim loi na cng ha tr v c cu trc loi halit, ging nhiu sulfur,
selenur v tellurur khc ca lantanit; CeS c thnh phn n nh, nhng Ce
2
S
3
c th cha
lng d lu hunh, kt qu l thnh phn ca n c th bin thin lin tc cho n Ce
3
S
4
.
ThS v ThSe vi cu trc loi halit thng c nhiu thuc tnh bn kim. Monosulfur ca U,
Th v Pu u c cu trc loi halit (bng 4.9); U
4
S
3
khc US ch nguyn t S trong tm
mng lp phng b khuyt. Do , cnh mng co rt i cht, a = 5,494.
Mui sulfur
Phn ln khong vt ca mui sulfur cha nhm anion do cc bn kim As, Sb v Bi kt
hp vi S to nn. Cc nhm ny ch yu ha hp vi ba kim loi l Cu, Ag v Pb. Thut
ng mui sulfur c xut ln u ch rng hp cht ny l mui ca mt trong lot
acid m nguyn t oxy thay bng lu hunh. Vic a ra cc acid gi nh vi mui ca
chng l mt c gng nhm gii thch c s ha hc ca nhm khong vt gm gn 100 dng
ny. Xt v bn cht ha hc tinh th th cc hp cht ny khc vi sulfur, sulfarsenur v
arsenur. As, Sb v c Bi ng vai kim loi trong cu trc ca cc mui ny; cn trong
sulfarsenur v arsenur cc bn kim ny chim gi v tr ca lu hunh. V d, arsenopyrit
FeAsS vi loi cu trc marcasit, As y thay chn ca S. Nhng arsen i vo enargit
Cu
3
AsS
4
nh mt kim loi phi tr t din ca loi cu trc vurtzit. Mui sulfur c th gi l
mt sulfur kp. Chng hn, enargit c th c cng thc l 3Cu
2
S.As
2
S
5
.
Lin kt trong mng mui sulfur i khi mang tnh ion, nht l khi kim loi mang tnh
in m r nt. Khi cha kim loi kim chng c lin kt dng ion v loi cu trc halit; v d
NaBiS
2
v NaBiS
2
vi cc kim loi sp xp ngu nhin. AgSbS
2
c mng tinh th ca halit
121
bin dng thnh mt nghing. Nhng phn ln chng mang dng lin kt ng cc. Lin kt
ny thng tr thnh dng lin kt kim loi khi chuyn t pha ny sang pha khc. Khi , tinh
th c nh kim, dn v tnh gin.
Mui ny thng c loi cu trc sulfur hoc rt gn vi chng; nht l loi cu trc
sphalerit v vurtzit vi phi tr t din. Enargit Cu
3
AsS
4
, mt qung ng quan trng, c
mng trc thoi suy ra t mng vurtzit. ng cu trc ca n l stibioenargit Cu
3
SbS
4
.
Cng thng gp nhng cu trc vi phi tr va t din, va bt din. Phi tr su cn
cho thy hnh phi tr c hu l lng tr ba phng kiu nickelin, v d 6S quanh Bi trong
PbBi
2
S
4
. Nguyn t S hay ion ca mui sulfur rt thch hp vi cch phn b ca cc lut xp
cu. Cu trc lp cng khng him y.
4.4.4 Halogenur
Mui ca cc acid HF, HCl, HBr v HI to lp khong vt vi gn 80 c th; ph bin
nht l cc chlorur ca Na, K, Mg, Pb, ri n fluorur ca Ca, Na v Al. Ngoi nhng cation
quan trng k trn, trong thnh phn ca halogenur cn c cc kim loi nh Cu, Ag, Hg,
Fe, Mn, v.v Cc nguyn t halogen c i lc ln vi in t; cho nn chng thuc hng cc
cht c nng lc oxy ho mnh nht:
F Cl Br I
i lc vi in t, kcal/mol: 95 86 84 74
Th nng oxy ho kh: +2,85 +1,36 +1,07 +0,53
Bn knh ion phi tr 6, : 1,33 1,81 1,96 2,20
V tn sut gp trong v Tri t cc halogen xp theo th t thp dn nh sau: Cl, F,
Br, I v u l nhng nguyn t a in hnh. Chng thng xuyn c mt trong kh ni
la, t chng ngng t v i vo thu quyn. Xem lit k sau th thy fluor l halogen ph
bin nht trong magma:
Nguyn t halogen F Cl Br I
cha, g/t 600 314 1,62 0,3
Do rt gn vi oxy v hydroxil v kch thc, fluor c th trao i ng hnh vi chng
trong thnh phn cc khong vt tng ng nh hornblend, mica, tourmalin, apatit, v.v F
tp trung trong pha mun ca qu trnh phn d magma; cha ca n rt cao trong khong
vt kh thnh pegmatit v nhit dch. V d, topas Al
2
[SiO
4
](F,OH)
2
, ambligonit LiAl[PO
4
]F.
Fluor cn gp trong cc fluorur phc tp, a dng nh Si-fluorur, B-fluorur v Al-fluorur,
cng nh cc fluorur t him; nhng quan trng nht l fluorit. Mt s sn phm ca hot
ng phun kh cha ti 7% F.
Chlor tham gia vo cu trc khong vt khng ph thuc vo fluor, v n c bn knh ion
ln hn hn. N ng vai tr ng k di dng anion ph; v d, nhm scapolit v sodalit.
Vi ho tan cao, chlorur vi thnh phn n gin khng gp trong magma; nhng
chlorur Fe, Mn, Mg, Al, v.v tn ti di dng sn phm ca hot ng phun kh. Chlor l
nguyn t quan trng trong qu trnh kh thnh v nhit dch: n tham gia thnh phn khong
vt (thch anh, sphalerit, v.v) di dng bao th lng.
Thng thng, F km linh ng mi trng ngoi sinh, bi v chng hn khi ho hp
vi Ca n cho fluorit bn vng. Trong khi , chlor li l nguyn t linh ng do ho tan
122
tt ca cc chlorur kim loi kim, cc hp cht ph bin ca Cl trong iu kin ngoi sinh. Cl
c nh mt phn lc a, v n to ra cc chlorur kh ho tan vi cc kim loi nng nh
thu ngn, bc, ng v ch. Nc bin cha khi lng ng k nguyn t chlor v 3
halogen kia vi lng nh hn nhiu. Kh nhiu Cl i vo nc bin di dng kh, trong
thi gian ni la phun tro.
So vi F v Cl, hai halogen cn li l nhng nguyn t phn tn in hnh, hm lng cao
nht ca chng c th c trong qu trnh nhit dch; y, mt s kim loi nng nh ng,
bc, ch, thu ngn c th lm kt ta Br v I. Phong ho lm cho Br (cng nh I) i vo dung
dch, hay c nh di dng bromur ca kim loi nng, ri i vo t. cha trung bnh ca
Br trong t l 6,5g/t, so vi 140g/t ca F. Nc bin cha nhiu Br hn so vi F hay I: 65g/t
so vi 1,3g/t ca F.
Kh quyn cha I dng hi, t bng con ng hp ph trc tip hoc do ma n i
vo t ( cha khong 2g/t). N ho hp vi kim loi kim trong t ri b cun ra bin
(bin cha 1/4 lng I ca v Tri t). Dong ru bin l ni tp trung I v chnh l ngun I
cng nghip quan trng. Cc cha bitum v m khong nitrat cng cha nhiu I.
Ngoi mt s ng v khng bn, fluor v iot cn c F
19
v I
127
. Hai halogen kia, mi
nguyn t c hai ng v bn vng Cl
35
+ Cl
37
v Br
79
+ Br
81
, cng mt s ng v nhn to
khng bn.
c im ho hc tinh th
Halogenur l nhng hp cht ion vi cu trc va ng cc va d cc. Cu trc d cc
cha nhm t din [BF
4
] nh ferucit Na[BF
4
] v avogadrit K[BF
4
], hoc nhm bt din [SiF
6
]
hay [AlF
6
] nh hieratit K
2
[SiF
6
] v cryolit Na
3
[AlF
6
]. Theo Babst (1950), bt din
alumofluorur c th trng hp qua nh F chung thnh chui, hay thnh lp, thnh khung (lin
tc hoc gin on), tng t s trng hp t din silic oxy trong silicat. Ti bt din ny Al
c th nhng ch cho Mg.
Trong hp cht ng cc cc anion khc nhau b phn cc, tng ln t F n I, lm cho
lin kt trong cu trc c tnh cng ho tr, cng tng ln t F sang I ( ho tan gim theo)
xem v d sau :
T l ca lin kt cng ho tr, % ho tan, mol/l
AgF 10 Cao
AgCl 24 9,0.10
6

AgBr 26 4,5.10
7
AgI 46 1,0.10
8
Thnh phn nguyn t ca halogenur t nhin c cc cation in hnh nht l: Al, Pb, Cu,
Na, Ca, K v Mg; sau l Ag, Hg, Fe, Mn, Si, NH
4
, Bi, B, TR, v.v Trong s khong vt
c 50 chlorur, 25 fluorur; cc hp cht khc t hn v ch yu l bromur, iodur ca Ag v Cu.
Halogenur cha O v OH c th xem nh khong vt chuyn tip sang oxit, mt s khc cha
H
2
O.
Phn ln halogenur l hp cht mt cation, hp cht hai cation khng nhiu v thng l
tng cp ln b: K Na, K Mg, K Ca v Pb Cu. Ph hp vi nh lut Groth, phn ln
halogenur c tinh th i xng cao, ch yu loi AX (halit, sphalerit, v.v) v AX
2
(fluorit
CaF
2
, CdI
2
, v.v). Trong s 80 halogenur nghin cu k, 20 hp cht thuc h lp phng
(tm mt su v bn mt su), 15 ca h su phng (k c ph h ba phng), 15 ca h bn
123
phng, s cn li kt tinh theo cc h trc thoi v mt nghing. Halogenur kim loi nng cha
OH v H
2
O thng c i xng thp.
Halogenur kim loi ca phn nhm IA v IIA c dng lin kt ion, ca nhm VIIIB c
lin kt ion v lin kt dng trung gian gia cng ha tr v phn t. Halogenur ca kim
thng l nhng hp cht phn t. Bt u t fluor, s hiu nguyn t cng tng th bn knh
ion cng tng tnh in m cng gim. Yu t ny c ngha quyt nh trong vic xc nh
dng lin kt ca hp cht. T , fluorur c dng lin kt mang tnh ion mnh nht trong s
nhm hp cht ny. Mt khc, trng thi ha tr cng c vai tr nht nh; ion vi ha tr thp
thng c tnh in m nh, lin kt vi halogen bng lc ion thun li hn ion vi ha tr
cao. V d, PbCl
2
l hp cht ion, PbCl
4
l hp cht phn t.
Fluor rt gn vi oxy v kch thc ion tng ng v tnh in m mnh nh nhau; cho
nn fluorur ging oxit nhiu biu hin. C th i chiu tng t gia chlorur v sulfur,
gia bromur v selenur, gia iodur v tellurur. Trong halogenur, ranh gii gia bn cht ion
v ng cc nm cc gi tr in m 1,8 v 1,9 ca cation. Hn 100 halogenur kim loi
c bit ti; trong nhiu loi cu trc thng gp nht l halit, chlorur cesi, fluorit, rutil,
iodur cadimi v chlorur cadimi (xem 4.3.2). Chlorur thic SnCl
2
l loi cu trc thuc hp
cht ion, cn sphalerit v vurtzit thuc halogenur cng ha tr.
Trc ht, cation ha tr mt c ln kt tinh loi cu trc CsCl. Bng 4.10 v 4.11 gii
thiu cc ng cu trc ca halit v CsCl, trong c halogenur amoni. Ion NH
4
+
c i xng
ca t din; nh kh nng t xoay, n tr nn dng cu. Tuy vy, fluorur amoni c phi tr t
din v loi cu trc vurtzit. Khong cch nguyn t o c trong AgCl, AgBr v AgI kh
chnh lch so vi gi tr l thuyt. iu ny cho thy lin kt trong cc hp cht ny ngy
cng thin v cng ha tr nu chuyn t chlorur sang iodur.
Nhm khng gian O
h
5
= Fm3m, Z = 1, phi tr 6 6
Bng 4.10
Halogenur vi loi cu trc halit NaCl
Hp cht
(C)
a, A B,
th.nghim
AB,
l thuyt
Hp cht
(C)
a, A B,
th.nghim
AB,
l thuyt
LiF (25) 4,02620 2,01 2,01 LiBr(26) 5,5013 2,75 2,66
NaF 4,6344 2,32 2,34 NaBr (26) 5,9772 2,99 2,98
KF 5,347 2,67 2,65 KBr (25) 6,5966 3,30 3,29
RbF 5,63 2,81 2,81 RbBr 6,854 3,43 3,45
CsF 6,008 3,00 2,97 NH
4
Br (138) 6,90 3,45 3,39
AgF 4,92 2,46 2,46 AgBr (26) 5,7745 2,89 3,10
NaCl (25) 5,64029 2,82 2,83 LiI 6,000 3,00 2,89
LiCl 5,1398 2,57 2,50 NaI 6,4728 3,24 3,22
KCl 6,2931 3,15 3,14 KI 7,0655 3,53 3,53
NH
4
Cl (250) 6,52 3,26 3,24 NH
4
I 7,2613 3,63 3,63
-RbCl(27) 6,5810 3,29 3,30 RbI (27) 7,342 3,67 3,69
-CsCl (450) 7,02 3,56 3,46 AgI (25,
AgCl (260) 5,5491 2,78 2,94 3700 atm) 6,07 3,03 3,34
Nhm khng gian O
h
1
= Pm3m, Z= 1, phi tr 8

124
Bng 4.11
Halogenur vi loi cu trc chlorur cesi
Hp
cht
Nhit
, C
a, AB,
th.nghim
AB,
l thuyt
Hp
cht
Nhit
, C
a, A B,
th. nghim
AB,
l thuyt
RbCl 190 3,74 3,24 3,40 CsBr 25 4,2953 3,71 3,72
NH
4
Cl 3,8684 3,34 3,34 CsI 26 4,5679 3,95 3,96
NH
4
Br 26 4,0594 3,51 3,49 TlCl 26 3,8421 3,33 3,30
NH
4
I 16 4,37 3,78 3,74 TlBr 3,976 3,44 3,45
CsCl 20 4,1180 3,56 3,57
Bi v ion c dng cu v lin kt ion c dng v hng, thun li cho phi tr bo ha
ti a, loi cu trc xc nh trc ht theo tng quan kch thc ion. Nhng bn vng
ca cu trc loi ny ph thuc vo nhit v p sut; cc yu t ny i khc s ph b loi
cu trc, lm xut hin bin th a hnh khc. Chng hn, NH
4
Br nhit bnh thng
thuc loi cu trc CsCl, khi T > 138C s chuyn sang loi cu trc halit.
Halogenur phn nhm IIA kt tinh theo hai loi cu trc chnh l fluorit v rutil. Thuc
hai loi cu trc ny ch yu l hp cht ion, ri hng lot hp kim. C th thy trn bng
4.12 cc difluorur kim loi phn nhm IIb v europi, ngoi fluorur ca kim loi kim t v
SrCl
2
.
Nhm khng gian O
h
1
= Fm3m, Z = 4, phi tr 8 4
Bng 4.12
Halogenur kim loi vi loi cu trc fluorit
Hp cht,
(C)
a, A B,
th.nghim
AB,
l thuyt
Hp cht,
(C)
a, A B,
th.nghim
AB,
l thuyt
CaF
2
(28) 5,46295 2,36 2,36 CdF
2
5,3880 2,34 2,36
SrF
2
5,7996 2,51 2,55 HgF
2
5,54 2,40 2,45
BaF
2
6,169 2,68 2,76 EuF
2
5,796 2,51 2,49
RaF
2
6,368 2,76 2,76
PbF
2
(20) 5,93629 2,57 2,57 SrCl
2
(26) 6,9767 3,02 3,03
Nhm khng gian D
4h
14
= P4/mnm, Z = 2, phi tr 3 6
Hp
cht
a, c, AB,
th.ngh.
AB,
l.th.
MgF
2
4,625 3,052 1,992 2,11
MnF
2
4,8734 3,3099 2,11 2,21
FeF
2
4,6966 3,3091 2,10 2,16
CoF
2
4,6951 3,1769
NiF
2
4,6506 3,0836 2,00 2,11
PdF
2
4,956 3,389 2,16 2,13
ZnF
2
4,7034 3,1335 2,04 2,16
Trong s difluorur cng ph bin loi cu trc rutil; thnh phn kim loi nhm II c Mg,
Zn v mt s khc (bng 4.13). Phn nhm IIA cn c BeCl
2
trc thoi, cu trc dng chui
(BeCl = 2,02) vi phi tr 4 ca Be v 2 ca Cl. BeF
2
ng cu trc vi cristobalit.
Dihalogenenur kim loi ca phn nhm ny v nhiu kim loi ha tr hai khc cn cho thy
loi cu trc lp ca CdI
2
v CdCl
2
(xem 4.3.2). Mng tinh th dng ln t nhng lp (I/Cl)
Cd(I/Cl) vi dng lin kt ion bn trong; gia cc lp vi nhau l lc tc dng van der
Waals. Loi cu trc CdI
2
l ca cc bromur v cc iodur v TiCl
2
(bng 4.14).
125
Nhm khng gian D
3h
2
= P3m, Z = 1, phi tr 6 3
Bng 4.14
Halogenur kim loi vi loi cu trc iodur cadimi CdI
2
Hp cht a, c, Hp cht a, c,
TiCl
2
3,561 5,87 VI
2
4,00 6,670
MgBr
2
3,81 6,26 MnI
2
4,16 6,82
TiBr
2
3,629 6,492 FeI
2
4,04 6,75
VBr
2
3,768 6,180 CoI
2
3,96 6,65
MnBr
2
3,82 6,19 ZnI
2
4,25 6,54
FeBr
2
3,74 6,17 CdI
2
4,240 6,855
CoBr
2
3,68 6,17 GeI
2
4,13 6,79
MgI
2
4,14 6,88 PbI
2
4,59 6,86
CaI
2
4,48 6,96 IbI
2
4,48 6,96
TiI
2
4,110 6,820 ThI
2
4,13 7,02
Ring Ag
2
I

c cu trc ngc ca CdI
2
. Fluor vi tnh in m thp khng c hp cht
vi loi cu trc ny. Mt s hp cht thiu ht cation trong v tr bt din s cho cng thc
tng qut l BX
3
. Nh ch trn, CdCl
2
cng l loi cu trc lp tng t; ch khc l Cl xp
theo lut xp cu lp phng. Ngoi dihalogenur nhm II, bng 4.15 cn c chlorur, bromur
v iodur ca kim loi nhm VIIIB v Mn.
Rt gn nhau v th t cc lp trong mng tinh th, hai loi cu trc CdI
2
v CdCl
2
c th
trao i cc lp vi nhau. Khi kt tinh t dung th, CaI
2
s c cu trc trung gian gia hai loi
cu trc trn: (ABACABAC); th t cc lp lp li sau mi lp th t. Loi cu trc mi
ny thuc h su phng.
Nhm khng gian D
3d
5
= R3m, Z = 1, phi tr 6 3
Bng 4.15
Halogenur kim loi vi loi cu trc chlorur cadimi CdCl
2

Hp cht a, Hp cht a,
MgCl
2
6,35 3640 ZnBr
2
6,64 3418
MnCl
2
6,20 3430 ZnI
2
7,567 3237
FeCl
2
6,19 3336 NiI
2
6,92 3242
CoCl
2
6,17 3326 CdBr
2
6,63 3442
NiBr
2
6,47 3330
4.4.5 Oxit v hydroxit
Lp ny c gn 150 oxit v hydroxit kim loi v kim, chim gn 5% trng lng chung
ca cc loi . Dioxit silic t do, di dng thch anh v cc bin th, khng lit vo lp ny
(xem 6.12); theo c im ho hc tinh th v cng sinh, chng l silicat khung thuc lp
silicat v alumosilicat. Oxit ng vai tr cc k quan trng trong v Tri t. L nguyn t
ph bin nht, oxy chim 91,83% th tch v 49,13% trng lng ca n (Kostov I., 1971).
Tnh a tiu biu ca n th hin cha tng dn t di su ln b mt Tri t.
Thu quyn cha cha 86%, kh quyn 23,15%. cha trung bnh trong magma 46,42%,
trong gabro 45,11% v grannit 48,53%. Qu trnh kt tinh magma cho thy khong vt
ngho oxy hnh thnh sm, mun hn l khong vt giu oxy. Vic magnetit tr thnh khong
vt ph thng xuyn ca magma chng t giai on u ca kt tinh magma lng oxy
khng ln. iu ny cn th hin ch khi m khong ngoi sinh ca mangan b bin cht th
126
oxit mangan ho tr cao ca n l pyrolusit MnO
2
ho thnh oxit mangan ho tr thp nh
braunit 3Mn
2
O
3
.MnSiO
3
, mangannit MnO(OH) v hausmannit Mn
3
O
4
. S bin ng hm
lng oxy c th thy mt ln na trong t hp cng sinh khong vt c ngun gc su.
Chng xut hin khi phn ng ho hc xy ra gia dng dung dch t di su v vy
quanh hay tn ti t trc. V d, hin tng tng t khin hematit Fe
2
O
3
ho thnh
magnetit Fe
3
O
4
.
Lin kt tri trong oxit thng l dng ion, tng phn vi cu trc sulfur vi lin kt
dng ion, cng ha tr v kim loi. Trong khun kh ca lp ny, mt s khong vt l ngun
qung chnh ca st (hematit v magnetit), chrom (chromit), mangan (pyrolusit, cng vi cc
hydroxit, manganit v romanechit), thic (casiterit) v uran (uraninit).
Oxy c ba ng v bn vng l
16
O,
17
O v
18
O cng tham gia vo qu trnh to khong;
s ph bin ca chng ln lt bng 99,76%, 0,042% v 0,198%. i lng
16
O/
18
O th hin
mc phn d ca hai ng v trong cc qu trnh a cht khc nhau. Khong vt giu ng
v nh
16
O thng thnh to cch ngun pht sinh mt khong xa hn so vi khong vt
giu ng v nng
18
O. T l ng v ny ca bin cht thng thp hn ca magma v
c th dng lm tiu ch phn bit cc ny. iu kin ngoi sinh nh phong ho v trm
tch gip cho ng v nng
18
O tch t; m n thng tp trung trong carbonat.
Ty t lng ca kim loi vi oxy, oxit n gin c X
2
O, XO v X
2
O
3
. Oxit phc hp,
XY
2
O
3
, c kim loi thuc hai nguyn t khng ging nhau.
Phn t nc c nhng tnh cht c bit gip n tip cn oxy, lm cho n tr thnh tc
nhn cho cc oxit hnh thnh. Phn t nc gm nguyn t oxy v ion hydro, cc ht proton
ny phn b khng i xng trong cc lp v in t ca oxy. T hnh thnh lng cc.
Hydro thc ra khng phi l ion, nhng n cng vi phn t nc cho ra i ion phc bn
vng l oxoni:
H
+
+ H
2
O H
2
O
+
+ 200 kcal
Oxoni ng vai tr quan trng trong s thnh to khong vt v i vo thnh phn ca
chng. S bin i hm lng H
+
(pH) c ngha to ln cho vic thu phn cc hp cht t
nhin. Chng hn, vic sulfat st ho tr ba thng bn vng pH < 3 thu phn thnh
hydroxit theo phn ng sau:
Fe
2
(SO
4
)
3
+ 6H
2
O 2Fe(OH)
3
+ 3H
2
SO
4

Ngoi pH, mt nhn t quan trng khc gp phn hnh thnh oxit v hydroxit l th nng
oxy ho kh Eh; n c trng cho nng lng oxy ho theo phn ng thun nghch sau:
Fe
2+
Fe
3+
+ e
Khi cc gi tr nhit v pH tng th th nng oxy ho kh gim, y nhanh qu trnh
oxy ho ca h.
c im ho hc tinh th
Khong 30 nguyn t tham gia thnh phn ca oxit v hydroxit, ch gn 50% s c vai
tr ng k trong khong vt ca lp ny. Oxit cha st chim s lng ln nht (gn 50 c
th). Sau n lt oxit niobi v tantal, titan, mangan, calci, nguyn t t him, v.v
Thnh phn ca cc khong vt lp ny rt n gin; thng ch mt hoc hai nguyn t kim
loi ho hp vi oxy, nhm hydroxil hay vi cc phn t nc.
127
Kh nng thay th ng hnh v ng cu trc khin cho s ln khong vt lp ny c th
ho tan vo nhau. in hnh v mt ny l cp tantalit FeTa
2
O
6
FeNb
2
O
6
columbit, dung
dch cng bn vng mi nhit ; Fe
2+
trong thnh phn ca chng li c th trao i vi
Mn
2+
. Mt v d khc l b ba l hematit Fe
2
O
3
, ilmenit FeTiO
3
v rutil TiO
2
. Hematit ilmenit
l dy ng hnh lin tc nhit trn 600C, cn cc cp ilmenit rutil v hematit rutil li
c quan h eutecti. Thay th ng hnh cng ho tr thng c trong magnetit FeFe
2
O
4
v
chromit FeCr
2
O
4
. Trong Fe
2+
nhng ch cho Mg
2+

v Mn
2+
, trong khi Fe
3+
v Cr
3+
nhng ch cho Al
3+
, Mn
3+
v Ti
4+
.
Cc loi cu trc chnh ca cc thnh vin thuc lp ny xc nh ch yu do cc anion
O
2
v OH

kch thc xp x, ri sau l do cc cation i vo nhm trung ho in tch ca
khung anion. Khung ny l cc lut xp cu lp phng v su phng ca anion hai loi.
Cc cation nm ti cc khoang t din v bt din. S phi tr 6 (bt din) l ph bin i vi
chng. Oxit phc tp v thnh phn v cu trc thng thay i s phi tr. V d, calci ca
CaO c s phi tr 6, nhng trong perovskit n li c phi tr 12. Magnesi phi tr 6 periclas
MgO, trong spinel li l 4. Ging nh nguyn t t sinh v sulfur, oxit v hydroxil thuc cc
lp i xng cao: ch yu l lp phng, su phng v bn phng.
Kim loi vi in m nh, thuc phn nhm IA IIIA v to ion vi lp v in t
dng kh tr thng to oxit n gin v vi dng lin kt ion. Kim loi thuc phn nhm
IVB VIB c in m ln; lin kt trong cc oxit ca chng thng mang tnh trung gian
gia cc dng ion v cng ha tr. Oxit ca Pd v Pt hay ca nguyn t phn nhm IB IVB
phn nhiu mang dng lin kt cng ha tr, oxit ca nhiu kim vi s hiu khng ln (B,
Si, Ge) c lin kt chuyn tip c trng. Tnh trung gian cn r rt hn na trong cc oxit
ca kim loi nhm VII v nhm VIII; c bit, nguyn t vi ha tr cao nht d dng cho
hp cht phn t, nh Mn
2
O
7
, RuO
4
, OsO
4
, v.v...
Oxit vi lin kt ion khng c cc loi cu trc a dng nh cc halogenur. Tng t
halogenur, cu trc ca oxit bin i c quy lut theo h thng tun hon cc nguyn t. Hy
bt u t oxit nguyn t ho tr mt. Cu trc mt s oxit cha c nghin cu, chng hn,
oxit kim loi ha tr mt. Tr Cs
2
O, cc A
2
O cn li (bng 4.16) u thuc loi cu trc
fluorit; nhng v tr cation li do anion O
2
chim, tc l chng thuc loi fluorit ngc.
Cs
2
O c cu trc ngc ca CdCl
2
v khong Cs O = 2,86; Cs Cs = 4,19.
Nhm khng gian O
h
1
=Fm3m, Z = 4, phi tr 8 4
Bng 4.16
Oxit kim loi vi loi cu trc fluorit ngc
Hp cht a, A B,
th.nghim
AB,
l thuyt
Hp cht a, A B,
th.nghim
AB,
l thuyt
Li
2
O 4,628 2,00 2,10 K
2
O 6,449 2,79 2,76
Na
2
O 5,561 2,41 2,44 Rb
2
O 6,755 2,93 2,93
Oxit kim loi phn nhm IIA c loi cu trc c trng l halit, tr BeO; Be kch c qu
b c s phi tr 6, gn nh lun c phi tr 4 v BeO (bromelit) kt tinh loi cu trc
vurtzit. Bng 4.17 lit k cc oxit thuc loi cu trc halit, chng c dng lin kt t nhiu
hoc ch yu mang tnh cng ha tr. Khong cch nguyn t rt khp vi tng bn knh.
Nhm khng gian O
h
5
= Fm3m, Z = 1, phi tr 6 6
128



Bng 4.17
Oxit kim loi vi loi cu trc halit NaCl
Hp cht
(nhit )
a, AB,
th.nghim
AB,
l thuyt
Hp cht
(nhit )
a, AB,
th.nghim
AB,
l thuyt
MgO, 20C 4,2112 2,11 2,08 CdO 4,6918 2,35 2,35
CaO 4,8105 2,40 2,40 TaO 4,439 2,22 2,22
SrO 5,1396 2,57 2,56 PaO 4,961 2,48 2,48
BaO, 25C 5,5391 2,77 2,74 UO 4,93 2,47 2,47
VO, (800) 4,062 2,03 PuO 4,958 2,48 2,48
NbO 4,2097 2,10 AmO 5,01 2,50 2,50
MnO 4,4444 2,22 2,20 TiO 4,180 2,09 2,212
FeO 4,3088 2,15 2,14 NpO 5,01 2,50 2,50
CoO 4,2603 2,13 2,15 EuO 2,1439 2,57 2,53
NiO, 275C 4,1946 2,10 2,14 YbO 4,86 2,43
Phn nhm III c oxit scandi, itri, indi v tali, cha k oxit cc oxit kim loi nhm lantan
(bng 4.18). Loi cu trc ca chng l Mn
2
O
3
lp phng vi mng c ln, phi tr 6 vi 6
oxy khng phi nh bt din, m ti 6/8 nh khi lp phng; hai nh khuyt i nhau
dc cho mt hoc cho khi. Cu trc ny c th suy ra t cu trc fluorit, bng cch loi b
1/4 anion. Phi tr ny c th xem nh trung gian gia 6 v 8 (bt din v lp phng) vi
tng quan kch thc cation: anion l 0,53 0,76. Khong cch nguyn t hiu chnh,
nh lm i vi oxit loi fluorit.
Nhm khng gian T
h
7
= I3a, Z = 16, phi tr 6 2
Bng 4.18
Oxit kim loi vi loi cu trc Mn
2
O
3
Hp cht

a, A B,
th.nghim
AB,
l thuyt
Hp cht a, A B ,
th.nghim
AB,
l thuyt
Mn
2
O
3
9,41 2,01 2,01 Tb
2
O
3
10,70 2,29 2,29
Sc
2
O
3
9,79 2,09 2,07 Dy
2
O
3
10,63 2,27 2,27
Y
2
O
3
10,60 2,27 2,27 Ho
2
O
3
10,58 2,26 2,26
In
2
O
3
10,12 2,16 2,17 Er
2
O
3
10,54 2,25 2,25
Tl
2
O
3
10,57 2,26 2,27 Tm
2
O
3
10,52 2,25 2,25
Sm
2
O
3
10,85 2,32 2,32 Yb
2
O
3
10,39 2,22 2,22
Eu
2
O
3
10,84 2,32 2,32 Lu
2
O
3
10,37 2,22 2,22
Gd
2
O
3
10,79 2,30 2,30
Trong phn nhm IVB titan to nhiu oxit khc nhau; TiO vi loi cu trc halit l pha
nhit cao v c th thay i thnh phn phm vi rng. Ti
2
O
3
thuc loi cu trc
corindon, cn TiO
2
vn l rutil, quan trng nht trong s cc bin th a hnh ca TiO
2
. Phn
ln oxit k trn bng 4.19 thuc phn nhm VB VIIB v nhm VIII, ch yu thuc loi hp
cht ion. Anatas cng l TiO
2
h bn phng c c s l lut xp cu lp phng ca O
2
.
Bin th trc thoi ca TiO
2
l brookit c O
2
xp theo lut xp cu nm lp trung gian gia
cc lut hai v ba lp vi phi tr bt din bin dng. Dioxit thori thuc loi cu trc fluorit.
Oxit kim loi ca phn nhm VB rt khc nhau; VO thuc loi cu trc halit vi lin kt
trung gian gia ion v kim loi. V
2
O
3
c cu trc ca corindon, VO
2
ng cu trc ca rutil.
NbO gn ging halit, nhng thiu Nb cc v tr (000) (1/2 1/2 1/2).
129
Kim loi phn nhm VIB c ha tr thay i, oxit c cu trc khc nhau. Cr
2
O
3
kt tinh
theo loi cu trc corindon. CrO
2
theo rutil. MoO
2
v WO
2
thuc loi gi rutil, chng u
thuc h mt nghing.
Trong s oxit kim loi ca phn nhm VIIa MnO c cu trc ca halit vi lng oxy i
khi d tha, dn n cng thc MnO
1,13
; mng t din ca Mn
3
O
4
sp xp nh trong cu trc
spinel. MnO
2
ph bin nht, thnh phn oxy thng thiu ht, khng bao gi tng ng vi
cng thc. Trong khong vt pyrolusit -MnO
2
vi t nhiu khuyt tt tng t, mt phn
mangan c ha tr ba, m bo trung ha in tch cho h.
Kim loi ha tr hai trong phn nhm VIII thng tham gia thnh phn ca oxit vi loi
cu trc halit, thnh phn khng bao gi khp vi cng thc l thuyt; iu ny ph thuc p
sut ca oxy khi kim loi b oxy ha. NiO nhit thng c cu trc ca halit vi mng
bin dng sang trc thoi, nhit 270 n mi tr li i xng lp phng. Cc ion ny d
oxy ha cho ha tr ba. Hematit Fe
2
O
3
l pha bn vng vi loi cu trc corindon v c tnh
bn dn, trong khi chnh corindon cch in ngay c nhit cao. Magnetit Mn
3
O
4
c cng
cu trc vi spinel, Co
3
O
4
ng

cu trc nhng bin dng sang trc thoi.
Kim loi nhm platin t i lc vi oxy, nhng chng cho mt vi oxit vi cu trc c
o, v d PdO v PtO. Nguyn t oxy xp theo trt t ca mng tm y bn phng dt,
nhng mng c s ca ton cu trc th gm hai C
BP
ny; trong lng c s c 4 Pt xp
ti v tr c nh (x = 1/4, y = 1/4, z = 1/4) ca mng F
BP
. iu ny chng t phi tr hnh
vung ca kim loi vi 4 oxy. Cc hnh vung ny gn vi nhau qua cnh thnh chui song
song vi cho y; cc chui ny li kt vung gc tng i vi nhau qua mt oxy chung. V
tr ca oxy c xc nh bng phng php nhiu x neutron. RuO
2
, OsO
2
v IrO
2
c
mng tinh th kiu gi rutil.
Oxit kim loi phn nhm IB l nhng hp cht ng cc in hnh. Oxit ng v bc u
c cu trc lp phng loi cuprit Cu
2
O (hnh 1.6,a). Oxit km v cadimi ca phn nhm IIB
c lin kt trung gian gia ion v cng ha tr; chng u khng c tnh cht kim loi. ZnO
thuc loi cu trc vurtzit, cn CdO loi halit (bng 4.17).
Ngoi oxit nhm, kim loi phn nhm IIIA to oxit vi nhiu ha tr khc nhau. Cho n
nay ch oxit kim loi ha tr ba mi c cu trc tinh th c nghin cu. ng k nht l -
corindon, mt trong nhng pha ng vai tr ln (xem 6.13.5). Trong s ng cu trc nhiu
oxit kim loi l ca phn nhm ny (bng 4.18). Mng tinh th c cha tng i bt din
AlO
6
ghp chung y song song (0001); iu ny gi v s tn ti ca phn t c lp
trong loi cu trc nh oxit nhm.
Cn ni thm, corindon c cng ch sau kim cng (theo thang Mohs); n to lp v
rn chc bo v cho cc dng c bng nhm. V kim loi chrom cng c th ni nh vy.
corindon, trc nay vn ng nhn l trioxit nhm, thc ra y ch l dioxit nhm cha thm
tp ph Na
2
O. Trong khi tng hp ruby, nguyn liu c dng l -corindon, hp cht c
cu trc ca spinel vi cation sp xp khng trt t v thiu vng nhiu v tr. Thnh phn
ca n Al
2,67
O
4
vit thay cho Al
3
O
4
(a = 7,861). Thuc v loi cu trc ny cn -Ga
2
O
3
. Trong
bin th -Ga
2
O
3
mt phn kim loi c phi tr t din, phn khc phi tr bt din (vi khong
GaO ln lt bng 1,83 v 2,00).
Phn nhm IVA kim loi thic v ch khc hn hai bn kim silic v germani. H Pb O
c nhiu nhiu pha vi cu trc phc tp l Pb
2
O
3,
PbO
2,
Pb
3
O
4
, Pb
5
O
8
. Ring PbO
2
v SnO
2
c cu trc loi rutil. Mt trong hai bin th ca GeO
2
cng ng cu trc vi rutil, bin th
130
th hai c cu trc ca thch anh , nhng ha tan trong nc. Ring v dioxit silic s ni
trong 6.12.
Phn nhm VA ch c Bi
2
O
3
c

th gi l oxit kim loi. Trong cc bin th ca n c pha
kt tinh h lp phng vi loi cu trc Mn
2
O
3
. N ch c th n nh khi cha tp cht. Khi
nhit 710 tr ln n cho bin th bn phng. Phn nhm VIA c PoO
2
vi loi cu trc
fluorit, nhit thng c mu xanh da tri v thnh phn thay i. Khi nhit tng cao
n cho bin th bn phng mu .
Nhm khng gian D
3d
6
= R3c , Z = 2, phi tr 6 4
Hp
cht
a, AB,
(th.ngh.)
AB,
(l th.)
-Al
2
O
3
5,1272 5517 1,91 1,89
V
2
O
3
5,467 5545 2,00 1,97
Cr
2
O
3
5,3613 5506 1,96 1,94
-Fe
2
O
3
5,4271 5515,8 1,97 1,95
Ti
2
O
3
5,454 5906 2,05 2,01
-Ga
2
O
3
5,32 5550 1,95 1,94
Rh
2
O
3
5,47 5543 2,02 2,00
Nhm khng gian O
h
1
= Fm3m, Z = 4, phi tr 8 4
Hp cht a, AB,
(th.nghim)
AB,
(l thuyt)
PoO
2
5,65 2,43 2,43
CeO
2
5,40 2,34 2,34
PrO
2
5,36 2,32 2,32
Pr
6
O
2
5,468 2,365 2,32
TbO
2
5,213 2,26 2,26
ThO
2
5,57 2,41 2,42
PaO
2,2
5,505 2,38 2,38
UO
2
5,47 2,37 2,37
NpO
2
5,436 2,35 2,35
PuO
2
5,397 2,34 2,34
AmO
2
5,388 2,33 2,33
CmO
2
5,372 2,32 2,32
Nhm lantan khng c monooxit. Thng ch c Ac
2
O
3
cng vi oxit ca cc nguyn t
bn knh ln nh La, Ce, Pr v Nd vi cu trc da trn lut xp cu su phng bin dng;
cation c phi tr bt din mo m, oxy th by nm pha trn mt mt ca bt din to thp
ba phng. Khong cch nguyn t kh khp vi tng bn knh. S hiu nguyn t tng, bn
knh cng thu nh (< 1), cu trc tinh th cng thay i. Bt u t Sm
2
O
3
chng u c cu
trc loi Mn
2
O
3
(xem bng 4.18). Khong cch A B c gi tr tnh ton lun ln hn 0,10
0,13 so vi gi tr o c. Mt s lantanit c th to oxit trng thi ha tr +4 vi loi cu
trc fluorit (bng 4.20). Oxy c th b trng nhiu v tr, khuyt tt phn b ngu nhin, v d
Pr
6
O
11
. Di cng thc PrO
2
, oxit lun thiu ht t nhiu lng oxy v lun cha ng thi
cc ha tr khc nhau ca cation (Pr
3+
v Pr
4+
).
131
Oxit ca cc actinit rt a dng. Loi cu trc halit c mng tinh th b nguyn t kim
loi xen k bng mng tm mt lp phng ring. Nguyn t oxy nm ti khoang trng gia
cc kim loi. V dn cc oxit ny c th so snh vi kim loi. Thnh phn ca chng
khng n nh; bi v mt phn v tr b b trng. Nhn thy ch ThO c cu trc ca chnh Th
l mng tm mt lp phng; cc oxit khc nh PaO, UO, NpO, PuO v AmO u c mng
tinh th ca halit, mc du bn thn cc kim loi ca chng li kt tinh theo loi cu trc
khng lp phng. Th, Pa, U, Np v Am cng cho dioxit vi loi cu trc fluorit.
Oxit kp l nhng hp cht ca oxy vi hai hay nhiu kim loi khc nhau. Cc cht rn
ny ngy cng tng v s lng v v ngha thc t (lm vt liu chu la, st t, bn dn,
v.v...). Mng tinh th ca chng xy dng t cu nguyn t xp cht. Loi cu trc ph bin
l halit, fluorit, rutil, perovskit v spinel.
Kim loi ca cc phn nhm IA v IIA khng to oxit kp.
Kim loi phn nhm IIIB to vi nhau cc oxit nh LaScO
3
, YScO
3
v LaYO
3
. Cc hp
cht ny kt tinh theo loi cu trc perovskit bin dng thnh trc thoi (xem di). Aluminat
itri Y
3
Al
2
(AlO
4
)
3
c cu trc ca granat vi radical t din ging silicat o n (xem 6.2.1).
Hnh thnh di p sut rt ln, InGaO
3
c cu trc vi s xen k nhau ca cc lp bt din
InO
6
v thp i ba phng GaO
5
. GaInO
3
, EuInO
3
v NyInO
3
l hp cht cng loi.
Phn nhm IVB c mt vi oxit kp. Trong cc oxit ca n Ti thng phi tr bt din;
hnh phi tr ny kt vi nhau bng tt c cc nh oxy, to nn mng ba chiu vi thnh phn
th hin bng cng thc TiO
3.
Phn b trong nhng khoang ln ca khung bt din ny l
cation bn knh ln hn, nh Sr
2+
, Ba
2+
, Pb
2+
, v.v Nu cation th hai c kch thc khng
ln (< 1), th metatitanat ny kt tinh theo kiu halit. V d, Li
2
TiO
3
c 32 ion oxy trong
mng lp phng tm mt. Cc ion Ti v Li phn b ngu nhin trong khoang bt din. Bin
th a hnh mt nghing ca n c cation sp xp trt t trong khoang bt din. Ilmenit
MgTiO
3
c cu trc loi corindon vi s sp xp trt t ca hai loi cation. Orthotitanat
magnesi Mg
2
TiO
4
c loi cu trc spinel vi cation hon i v tr, ion Ti v mt phn Mg
nm trong khoang bt din, khoang t din l v tr ca Mg cn li.
Loi cu trc c nghin cu nhiu c dng tng qut ABX
3
(X: O, OH hay halogen).
mng lp phng vi s n v cng thc 1 l l tng; B nm ti nh, A ti tm, X ti
trung im ca cnh. Ring v hp cht CaTiO
3
m trong t nhin c tn perovskit, th ngay
t u r l vi lng chit sut mnh n khng th thuc h lp phng vi ng hng
quang hc.
Khong vt CaTiO
3
vi mng tinh th c xc nh l thuc h trc thoi, Z = 4,
mng khng gian D
2h
16
= Pcmn. SrTiO
3
kt tinh theo mng lp phng nh cha 1 n v
cng thc. Sr
2
TiO
4
, Sr
3
Ti
2
O
7
v Sr
4
Ti
3
O
10
c mng phng theo perovskit. Trong cu trc
ca chng, lp SrTiO
3
xen gia cc lp SrO. Cng c mng nh ca perovskit nhng bin
dng thnh bn phng l BaTiO
3
. Hp cht ny c tnh in mi, c bit c hng s in
mi ln v thay i di tc ng ca in trng. Hng s ny cn ph thuc rt r vo nhit
, bi v BaTiO
3
c mt vi bin th tn ti nhng khong nhit khc nhau. Khi nung n
120C n tr thnh lp phng, khi ngui n chuyn sang i xng trc thoi, ri sau thnh ba
phng (mt thoi).
Bng 4.21
Oxit kp vi loi cu trc perovskit CaTiO
3
Hp cht a() c() T trng Hp cht a() c() T trng
132
a) Perovskit vi mng lp phng nh v Z =1Nhm khng gian O
h
1
= Pm3m, phi tr
12 6
SrTiO
3
3,9080 5,12 BaZrO
3
4,1898 6,24
SrFeO
3
3,869 BaSnO
3
4,1167 7,24
KTaO
3
3,9885 BaCeO
3
4,397
EuTiO
3
3,905
b) Perovskit vi mng lp phng ln v Z = 8
CaMnO
3
7,465 BaThO
3
8,985
SrCoO
3
7,725 LaVO
3
7,842
SrZrO
3
8,218 5,43 LaFeO
3
7,852
SrSnO
3
8,070 6,42
c) Perovskit vi bn phng nh v Z = 1
BaTiO
3
3,992 4,036 PbZrO
3
4,1585 4,108 8,10
PbTiO
3
3,9044 4,1522 7,97 PbHfO
3
4,136 4,099 10,21
d) Perovskit vi mng mt thoi v Z = 1
Nhm khng gian D
3d
5
= R3m
Hp cht a() T trng Hp cht a() T trng
NdAlO
3
5,286 6025 6,91 LaAlO
3
5,357 6006
PrAlO
3
5,307 6020
) Perovskit vi trc thoi v Z = 4
Nhm khng gian D
2h
16
= Pbnm
Hp cht a() b() c() T trng Hp cht a() b() c() T trng
YAlO
3
5,179 5,329 7,370 5,35 SmFeO
3
5,394 5,592 7,711 7,26
YCrO
3
5,247 5,518 7,540 5,75 EuFeO
3
5,371 5,611 7,686 7,34
YScO
3
5,431 5,712 7,894 4,94 GdFeO
3
5,346 5,616 7,668 7,52
YFeO
3
5,302 5,589 7,622 5,67 GdAlO
3
5,247 5,304 7,447 7,43
LaFeO
3
5,556 5,565 7,862 6,63 EuAlO
3
5,271 5,292 7458 7,25
PrFeO
3
5,495 5,578 7,810 6,79 SmAlO
3
5,285 5,290 7,473 7,16
NdFeO
3
5,441 5,573 7,753 7,01
H perovskit c th bao gm cc hp cht ion vi cng thc B
2
X
3
hay ABX
3,
trong A l
cation ln, B cation c va, cn X c th l O
2
, OH

, F

, Cl

, Br

, I

(bng 4.21).
Phn nhm VB. Tt c niobat u c th l oxit kp; chng khng c anion phc niobat
dng o. Trong cc niobat kim loi kim c NaNbO
3
v KNbO
3
thuc loi cu trc
perovskit trc thoi. Cc oxit kp thuc loi cu trc perovskit cn c NaTaO
3
h trc thoi,
KTaO
3
h lp phng vi mng nh. Vanadi mang tnh chuyn tip; n va to vanadat vi
cc radical n gin v phc tp, va cho cc oxit kp. Nguyn t ny c nhiu ha tr khc
nhau (3, 4 v 5). Vanadi ha tr 5 khng th c mt trong tinh th perovskit; bi v d c bn
knh thch hp, phi tr bnh thng ca V
5+
khng phi l 6 (bt din) m 5. Oxit kp
MgV
2
O
4
vi vanadi ha tr ba thuc loi cu trc spinel. Cn VMg
2
O
4
cha vanadi ha tr
bn, c cu trc spinel hon v cation gia cc v tr t din v bt din.
Phn nhm VIB. Chrom tuy c nhng anion phc rt c trng nh CrO
4
, Cr
2
O
7
, v. v,
nhng cc oxit kp ca n vn thng gp hn. l LiCrO
3
, NaVO
3
, CuFeO
3
v nhiu na.
133
Cr
2
O
3
to dung dch cng vi oxit cng loi ca nhm; mu sc ca cc pha ny ph thuc
vo cha Cr. Khi bt din CrO
6
trong cu trc khng lin kt vi nhau th tinh th c mu
; cn nu hm lng Cr tng, tc l khi cc bt din ny gn vi nhau bng oxy chung th
n c mu lc. Cc chromit nh YCrO
3
v LaCrO
3
u c mng trc thoi ca loi cu trc
perovskit.
Phn nhm VIIB. Mangan va c manganat va c oxit kp. BaMnO
2
su phng c cu
trc gn vi thch anh nhit cao. Bn cnh manganat Ca v Ba cha c nghin cu cu
trc, MnCr
2
O
4
, MnAl
2
O
4
v mt s oxit khc (bng 4.22) u ng cu trc vi spinel.
MnTiO
3
c mng tinh th loi ilmenit v LaMnO
3
c cu trc gi lp phng loi perovskit.
Mn
3
O
4
(ging nh Fe
3
O
4
) l s kt hp ca hai oxit thuc Mn
2+
v Mn
3+
, gp di dng
khong vt hausmanit Mn
2
MnO
4
; cu trc thuc h bn phng phng theo spinel.
Nhm VIII. Mt trong nhng oxit st vi cng cng thc nh hausmanit l magnetit
FeO.Fe
2
O
3
c nh kim, tnh st t v dn in kh tt nh s trao i in t gia Fe
2+
v
Fe
3+
. Mt bin th khc, -Fe
2
O
3
cng c cu trc loi spinel nh magnetit Fe
3
O
4
, nhng
trong mng khng st cho cc v tr. Ti v tr ca 24 Fe trong mng -Fe
2
O
3
ch c 21 +
1/3 nguyn t Fe. LiFeO
2
l mt trong nhng ferit cha kim loi kim, n c cu trc phng
theo loi halit. Nguyn t Li v Fe phn b ngu nhin trong mng. Chng s sp xp c
trt t khi ferit ny c x l nhit tr thnh bin th bn phng.
Ferit nhit cao vi cu trc gn nh cristobalit l KFeO
2
. Mng tinh th ca ilmenit
FeTiO
3
rt ging vi ca hematit; kim loi phn b trong chng theo trt t ca loi cu trc
corindon. Hp cht Fe
2
TiO
4
kt tinh theo mng spinel v bt gp trong t nhin di dng
khong vt ulvit (ulvospinel). Titanomagnetit l s pha trn ca ulvit v magnetit. St cng
vi chrom to khong vt quan trng l chromit FeCr
2
O
4
thuc nhm spinel. Jacobsit
MnFe
2
O
4
v Magnesioferrit MgFe
2
O
4
cng thuc nhm ny (xem 6.13.6). ng cu trc vi
chromit cn c NiCr
2
O
4
, mt sn phm tng hp.
Hp cht tng t ca Co khng c nhiu nh ca st. Cc oxit kp nh Co
3
O
4
,
MgCo
2
O
4
, TiCo
2
O
4
, CoCr
2
O
4
v CoAl
2
O
4
thuc loi cu trc spinel (bng 4.23). CoTiO
3
lit
vo loi ilmenit. Oxit kp ca cobalt v lantan LaCoO
3
c mng trc thoi bin dng t loi
cu trc perovskit. Oxit ca Fe
3+
to vi stronti v bari hp cht vi cc cng thc
SrO.6Fe
2
O
3
v BaO.6Fe
2
O
3
u thuc v cu trc -corindon. Trong hp cht ca st ha tr
su BaFeO
4
c t din FeO
4
gn vi CrO
4

v kch thc.
Nhm khng gian O
h
7
= Fd3m, Z = 8, phi tr 4 6
Bng 4.22
Oxit kp kt tinh theo loi cu trc spinel
Hp cht Khong vt a, T trng Hp cht Khong vt a, T trng

MgAl
2
O
4
spinel 8,0808 3,581 CoAl
2
O
4
8,09 4,44

MgV
2
O
4
8,421 4,23 CoCr
2
O
4
8,34 5,20

MgCr
2
O
4
Mg-chromit 8,320 4,42 CoFe
2
O
4
8,41 5,24

MgFe
2
O
4
Mg-ferit 8,37 4,53 CoCo
2
O
4
8,09 6,04

MgCo
2
O
4
8,123 4,96 NiAl
2
O
4
8,046 4,50

MgRh
2
O
4
8,53 6,29 NiCr
2
O
4
8,316 5,24

MgGa
2
O
4
8,296 5,298 NiFe
2
O
4
trevorit 8,36 5,33
MgIn
2
O
4
8,83 ZnAl
2
O
4
8,087 4,61
TiMg
2
O
4
8,456 3,53 ZnV
2
O
4
8,400 5,18
TiMn
2
O
4
8,691 4,49 ZnCr
2
O
4
8,337
134
TiCo
2
O
4
8,448 5,07 ZnFe
2
O
4
franklinit 8,437 5,33
TiZn
2
O
4
8,456 5,33 ZnCo
2
O
4
8,124 5,94
VMg
2
O
4
8,403 3,55 CdCr
2
O
4
8,584 5,89
MnAl
2
O
4
Galaxit 8,285 4,03 CdFe
2
O
4
8,696 5,82
MnCr
2
O
4
8,44 4,931 CdGa
2
O
4
8,59 6,62
MnFe
2
O
4
8,59 4,83 CuAl
2
O
4
8,09 4,55
FeAl
2
O
4
Hercinit 8,10 4,34 CuCr
2
O
4
8,37 6,69
FeCr
2
O
4
Chromit 8,42 4,98 CuFe
2
O
4
8,39 5,38
FeFe
2
O
4
Magnetit 8,3940 5,198 CuCo
2
O
4
8,055 6,28
Hercinit FeAl
2
O
4
thuc nhm spinel. Oxit st ha tr ba c th to vi oxit nhm pha
dung dch cng hn ch ( cha ca Fe
2
O
3
c th t gn 1%). Vi oxit itri n cho YFeO
3
,
vi oxit lantan cho LaFeO
3
u thuc mng trc thoi ca loi cu trc perovskit. Bng 4.22
k cc oxit kp ca nickel, kim loi ny cn c NiTiO
3
cng mng tinh th vi ilmenit. Oxit
kp ca nickel v niobi ng cu trc vi columbit (Fe,Mn)Nb
2
O
6,
tc l c NiNb
2
O
6
cng c
cu trc rt gn vi loi rutil (trirutil).
Kim loi ca phn nhm IB khng c nhiu oxit kp. ng k nht l loi cu trc spinel
ca cc hp cht gia ng vi nhm, chrom, st v cobalt; nh thy trn bng 4.22. Phn
nhm IIB cho thy cc oxit ca km kh a dng; oxit ca n vi cc kim loi kim cha c
cu trc tinh th no c xc nh. Phn ng ca km vi oxit bari 1000C cho BaZnO
2
,

mng su phng ca n gn vi cu trc thch anh nhit cao. ng cu trc vi n l
BaMnO
2
v BaCoO
2
. Cu trc ca SrZnO
2
ging vi cristobalit. Oxit km cng vi oxit
ca mt s kim loi khc sinh ra c lot ng cu trc ca spinel. Ngoi ra, n cng cho cc
oxit kp kt tinh theo loi rutil (columbit). Mng tinh th bn phng ca ZnMn
2
O
4
ging vi
mng ca hausmanit. Tr nhng ng cu trc ca spinel lit k, cadimi kt hp vi titan
cho CdTiO
3
, n c cu trc mt nghing bin dng t mng lp phng perovskit.
Trong s cc kim loi ca phn nhm IIIA nhm c mt trong s rt ln oxit kp. Cng
vi liti, nhm to pha dung dch cng dng spinel; t l gia hai oxit l 1 : 1. Pha spinel khc
c thnh phn LiAl
5
O
8
; v tr ca hai Mg do Li+Al chim gi. Cu trc ca NaAlO
2
v KAlO
2
(a = 7,69) rt ging vi cu trc ca cristobalit nhit cao. Chrysoberyl BeAl
2
O
4
( qu)
thuc loi cu trc olivin vi radical (BeO
4
)
4
v phi tr bt din ca nhm. Vi cng thc
tng t, nhng MgAl
2
O
4
li

l spinel thc th (xem chi tit 6.13.6). Nhng oxit ghi trn
bng 4.22 l nhng v d trong s hng trm thnh vin ca nhm spinel. Calci tham gia vo
nhiu spinel, vi cc tnh cht c bit chng l nhng thnh phn chnh ca cc loi ximng.
Trong CaAl
2
O
4
mt nghing cc t din AlO
4
kt ni nhau bng 4/4 oxy nh, to nn
mng ba chiu ging tridymit vi cc vng su t din. Trong mng mt phn calci phi tr
bt din, phn khc phi tr 9. Tinh th lp phng Ca
3
Al
2
O
6
l mt trong nhng thnh t
thng gp nht ca xi mng v l ng cu trc ca perovskit. Mt trong nhng oxit kp ca
calci vi thnh phn phc tp Ca
12
Al
14
O
35
c cu trc ca s mng lp phng tm khi
v ging cu trc granat; Ca c phi tr bt din, t din AlO
4
ghp vi nhau bng tt c oxy
chung to ra khung ba chiu. Sr
3
Al
2
O
6
v Cr
3
Al
2
O
6
u c cu trc loi perovskit. Spinel
bari c cu trc su phng; t din ca nguyn t nhm to nn mng ba chiu ging ca
tridymit, trong mng y bari c phi tr 9 ti cc l hng ln. Gali cng vi magnesi to nn
oxit kp MgGa
2
O
4
; trong mng 16 Mg phn b trong t din, s cn li trong bt din vi
khong Mg O ln lt l 1,9 v 2,012. Cng vi km, gali to nn cu trc spinel tng
t. Oxit kp ca gali v calci CaGa
2
O
4
c hai bin th a hnh: trc thoi v mt nghing. Hai
oxit khc ca gali LaGaO
3
v NaGaO
3
cng c cu trc trc thoi thuc loi perovskit. Indi kt
135
hp vi magnesi v calci cho cc spinel MgIn
2
O
4
v CaIn
2
O
4
; vi lantan n to cu trc loi
perovskit vi cng thc LaInO
3
.
Trong s kim loi phn nhm IVA thic to nhiu oxit kp. Thuc loi cu trc perovskit
CaSnO
3
c mng trc thoi, SrSnO
3
mng lp phng ln, BaSnO
3
mng lp phng nh.
Thic to vi cobalt SnCo
2
O
4
v SnZn
2
O
4
u thuc loi cu trc spinel. Thic ha tr bn cho
CdSnO
3
vi cu trc perovskit.
Phn nhm VA c Sb v As to hng lot oxit kp. Trong mng LiSbO
3
nguyn t oxy
sp xp theo lut xp cu su phng. Liti v antimon u phn b trong khoang bt din do
oxy dng nn. Cc bt din SbO
6
to chui bng cch ni vi nhau qua cnh chung. Cu trc
ca oxit kp do arsen to vi nhiu cation ha tr hai cng dng trn c s lut xp cu hai lp
ca oxy v c hai loi cation u phi tr bt din. l trng hp ca cc oxit sau
CaAs
2
O
6
, SrAs
2
O
6
, CoAs
2
O
6
, HgAs
2
O
6
v PbAs
2
O
6
. Antimon cng cho cc pha tinh th
tng t khi ha hp vi cc kim loi kim th cng nh Cd v Hg. Thuc loi cu trc rutil
l hai lot oxit kp vi Sb ng vai cation th hai. CrSbO
4
v MnSbO
4
c mng nh;
CuSb
2
O
6
, MgSb
2
O
6
, FeSb
2
O
6
, CoSb
2
O
6
v NiSb
2
O
6
u c mng ln (trirutil) v bin dng
thnh mt nghing. Cu trc tinh th ca KSbO
3
mng ba chiu (vi cng thc Sb
2
O
6
) dng
ln t cc hnh phi tr bt din ca Sb gn kt qua cnh v nh. Bin th a hnh khc ca n
c cu trc loi ilmenit.
Nhm lantan cho nhiu oxit kp vi nhng c tnh st in v st t. Phn ln, chng
thuc loi cu trc perovskit (xem bng 4.21), cng thc tng qut ABO
3
vi A l nguyn t
phi tr 12 v B phi tr 6. BaCeO
3
v BaPrO
3
l oxit c mng tinh th vi mng lp phng
ln, CeAlO
3
v PrAlO
3
vi mng mt thoi nh. CdAlO
3
, EuAlO
3
, PrScO
3
, NdVO
3
,
SmCrO
3
,

v.v vi mng trc thoi. Cc actinit c hai oxit kp thuc loi cu trc perovskit:
CaUO
3
v SrUO
3
.
Hydroxit ca kim loi thng c nhng loi cu trc khc hn so vi nhng loi ca oxit;
mc du v hnh dng v kch thc ion OH

rt ging ion O
2
. Nhm hydroxil cng rt gn
so vi ion F

. Hydroxit ca kim loi cc phn nhm I v II tt c u d mt nc v bin


thnh oxit. Chng hn, CuOH, AgOH, AuOH thm ch khng th tn ti trng thi rn.
Trong hydroxit thng c lin kt hydroxil, y gia hai ion OH c lc ht tng h,
m khng c s phn b li proton sn c trong ion ny. Ion OH

d dng nhn bit nh gii
hp ph hng ngoi c trng 2,9; ion hydroxil trc ht l dipol, trong tm l in tch
m, khong 1 cch n l in tch dng. Do t xoay quanh trc O H n c i xng
hnh tr. Chnh s phn cc trong mng lm cho in tch m ri khi tm ion oxy, ht
nguyn t hydro ca ion OH

khc, v nh vy lin kt hydroxil xut hin. Trong trng hp
phn cc mnh hn, nguyn t hydro c th di chuyn sang ion OH

khc; nhng trong
trng hp hydroxit iu ny khng xy ra.
Cu trc hydroxit cha c kho cu y nh cu trc oxit; vy m lnh vc ny
t nhng thnh tu nht nh. Hydroxit thng xut hin di dng kt ta v nh hnh, b
ri. V d, Fe(OH)
3
, Cr(OH)
3
; trong iu kin tnh lng, chng thng chuyn sang trng thi
kt tinh (nhng iu ny khng phi lc no cng xy ra). Nhiu hydroxit nhanh chng mt
nc.
Hydroxit kim loi phn nhm IA thng to cu trc lp cc dng khc nhau ty phi tr
ca cation. Trong cu trc LiOH ion Li
+
phi tr t din vi 4OH

. Cc t din ny cng lin


kt li thnh lp; trong cation liti cng nm trong mt lp, cn anion OH

phn b v hai
pha. Cu trc lp h trc thoi l ca NaOH nhit cao, cation Na
+
c phi tr 5 ng vi bn
136
knh ln hn ca n. Khong Na
+
OH

bng 2,40 so vi gi tr tnh ton 2,35. Khong
OH

OH

gia cc lp l 3,02, nh hn nhiu so vi gi tr tng ng trong LiOH


(3,60). Khi nhit tng cao, mng tinh th NaOH tr nn i xng hn v chuyn sang
loi cu trc halit. Cc bin th cu trc tng t cng c KOH v RbOH; khong K OH
= 2,84. Ion Na vi phi tr 5 cng c trng i vi cc hydroxit khc; khong Na OH =
2,36 (so vi gi tr l thuyt 2,37). Mi hydroxit kim loi kim rt d ha tan trong nc,
ring LiOH b nung nh mt nc v bin thnh oxit.
Trong s hydroxit kim loi phn nhm IIA Mg(OH)
2
v Ca(OH)
2
bt gp dng khong
vt brucit v portlandit, c hai chung mt loi cu trc CdI
2
(bng 4.23). K thut nhiu x
neutron v cng hng t ht nhn cho php xc nh v tr ca proton.
Phn nhm IIIB c mng Sc(OH)
3
thuc loi cu trc perovskit. ScOOH ng cu trc
vi boehmit (xem di y).
Nhm khng gian D
3d
3
= P3m, phi tr 6 3
Bng 4.23
Hydroxit vi loi cu trc iodur cadimi CdI
2
Hp cht a, c, AOH, Hp cht a, c, AOH,
Mg(OH)
2
3,148 4,768 2,09 Co(OH)
2
3,173 4,640 2,18
Ca(OH)
2
3,5853 4,895 2,33 Ni(OH)
2
3,117 4,595 2,11
Mn(OH)
2
3,35 4,69 2,30 Cd(OH)
2
3,495 4,698 2,33
Fe(OH)
2
3,258 4,605 2,23
Hydroxit kim loi nhm IVB c mc nghin cu cu trc cn thp hn. Hydroxit titan
vi ha tr thp d dng b oxy ha. Ti(OH)
4
khi cn ti l cht v nh hnh; theo thi gian
n chuyn thnh anatas, ri thnh rutil (c hai u l TiO
2
), do hydroxit titan phi c
xem l oxit ngm nc. Tnh trng ca hydroxit kim loi nhm VB cng khng khc my.
Trong s kim loi phn nhm VIB chrom to mt s hydroxit, nhng ch CrOOH mi
c bit ti vi loi cu trc CdI
2
. Cc hydroxit ca molybden khng mt hp cht no c
cu trc c xc nh. Trong mng mt nghing ca acid H
2
MoO
4
.H
2
O cc bt din MoO
6
lin kt vi nhau qua nh oxy chung to thnh lp, ri cc lp ny li xp chng nhau nh
H
2
O
+
hay H
2
O
2+
.
Hydroxit kim loi phn nhm VIIB Mn(OH)
2
thuc loi cu trc lp CdI
2
; MnOOH c
cu trc gi marcasit. Kt qu phn tch nhiu x neutron cho thy ion hydro ch lin kt vi
nhng ion oxy xc nh. Bin th trc thoi ca n ng cu trc vi diaspor (xem sau y).
Nhm VIII ch c hydroxit h st. C ba hp cht Fe(OH)
2
, Co(OH)
2
v Ni(OH)
2
u c
cu trc loi CdI
2
. Goetit v limonit FeOOH u kt tinh theo diaspor. Bin th khc,
lepidochrosit, lit vo loi cu trc boehmit.
Kim loi phn nhm IB ch c mt hydroxit cho pha tinh th di dng ht nh; l
Cu(OH)
2
h trc thoi ging cu trc ca lepidochrosit, khong Cu O bng 1,94. Trong
nhng hydroxit kim loi phn nhm IIB Zn(OH)
2
vi mt bin th c cu trc lp loi CdI
2
,
gn ging n l bin th th hai; mng trc thoi xy dng trn c s cc t din [Zn(OH)
4
]
2
gn kt vi nhau, m mi nhm OH u l chung cho hai t din; nh vy, mng ba chiu
nhn c ging nh cc bin th ca SiO
2
. Khong Zn O = 1,95, OH OH =
2,83.
Khong vt hydrargillit hay gibbsit (xem 4.3.2) Al(OH)
3
ng vai tr ln v l mt trong
nhng thnh phn ca qung nhm bauxit. Lp bt din trong cu trc ch 2/3 khoang bt
137
din cha Al
3+
, bt din bin dng mnh do cnh chung co rt nhm trnh lc y tng h
gia cc cation nhm. Khng nhng th cc lp ny khng lin k nhau, m cch nhau bng
mt lp bt din rng. Lc gn chng vi nhau l lin kt hydroxil, di ca n 2,75
2,82, nh hn nhiu so vi khong OH OH trong mi lp 2,94 3,46.
AlOOH c hai bin th a hnh; diaspor v boehmit. C s ca mng trc thoi goethit
diaspor -AlOOH l O
2
v OH

xp theo
lut xp cu su phng, ion nhm chim
ht mt na s khoang bt din. Cc bt
din ny ni nhau qua cnh O OH
lm nn chui n, cc chui n li kt
i vi nhau bng cnh chung OH OH
ca bt din, to chui kp i chy dc
trc c. Xen gia cc chui kp i ny l
cc chui kp i khng cha nhm.
Trong mng chui kp ni vi nhau qua
nh oxy (hnh 4.35). Nhm khng gian
Pbnm.
Khong cch nguyn t trong mng khc nhau t nhiu. iu ny chng t s tn ti ca
lin kt hydroxil gia cc nguyn t xc nh; vai tr tch cc ca ion OH c khng nh
nh ph hp ph hng ngoi khu vc 3. Nhiu x neutron cho php n nh v tr ca
proton.
Goethit -FeOOH ng cu trc vi diaspor; bin th ca chng bt gp trong t nhin l
lepidochrosit -FeOOH v boehmit -AlOOH u c nhm khng gian Amam. Chng cho
thy nhng khc bit trong cu trc so vi pha ; O v OH tun theo lut xp cu lp phng,
bt din lin kt nhau bng nh to chui, chui gn vi nhau qua cnh cho lp un
np song song {010}. Cc lp gn vi nhau thnh mng qua dng lin kt hydro gia hai oxy,
mi lin kt ny th hin bng OH

.
4.4.6 Carbonat, sulfat v phosphat
Trong t nhin, hp cht vi oxy chim s p o. Ngoi silicat s ni sau, y
ch cp mt s trong cc lp vi trn 1000 khong vt:
a) Carbonat, nitrat, borat.
b) Sulfat, chromat, tungstat, molybdat.
c) Phosphat, arsenat, vanadat.
Bng 4.24
Ho tr tnh in trong cu trc vi anion phc
Anion phc Ho tr tnh in
trong anion phc
Ho tr tnh in
ngoi anion phc
CO
3
2
4 : 3 2 : 3
SO
4
2
3 : 2 1 : 2
PO
4
3
5 : 4 3 : 4
SiO
4
4
1 1

Hnh 4.35
S cu trc diaspor gm cc cp chui bt
din cha nhm, xen gia chng l cc cp
chui rng
138
Nhng khong vt khc nhau v ho hc ny c chung nhng anion phc XO
3
v XO
4

bn vng vi mi lin kt XO kh mnh. Mi anion oxy tip nhn t cation trung tm mt
lc lin kt ln hn mt na nng lng tng ca n (bng 4.24). Ni cch khc, n ch cn
non mt na nng lng dnh cho cation ngoi nhm chc. Lc lin kt bn trong nhm chc
lun ln hn nng lng gn cc anion phc ny vi cc cation khc ngoi nhm chc; to
nn cc hp cht khng ng cc hay d cc

.
V d, CO
3
2
; tng quan bn knh ion R
C
: R
O
cho php cation carbon phi tr 3 vi
anion oxy, to nn n v cu trc phng hnh tam gic u vi carbon ti tm. Ho tr tnh
in ca lin kt C O bng 4 : 3. iu ny c ngha l mi oxy dnh hn 50% in tch
(2) ca n to nhm chc; in tch cn li (2 : 3), cha n 50% dnh lin kt vi cc
cation Ca
2+
.
Vai tr ca phn cc s tr nn rt ng k khi cc ht tng tc l ion gy phn cc
mnh v ion rt d b phn cc. y l trng hp gia cation ho tr cao ho hp vi anion
oxy, to nn nhng nhm chc (radical) bn vng nh CO
3
2
, NO
3

, SO
4
2
, PO
4
3
, v.v
Trong cc hp cht carbonat v nitrat khong cch nguyn t gia carbon/nit v oxy ln lt
bng 1,26 v 1,22, tc l nh hn c bn knh ion oxy (1,36).
Lin kt ho hc trong cc nhm chc ny mnh ti mc chng khng b phn hu trong
dung dch v dung th. Trong cu trc tinh th cc nhm chc c th ng vai mt ht vt
cht c lp ging nh cc ion khc. V d trong cu trc tinh th calcit CaCO
3
(xem hnh
4.18); nhm CO
3
2
c th ng vo v tr ca Cl

, cn Ca
2+
chim ch ca Na
+
trong loi cu
trc halit.
Trong anion phc lin kt gia nguyn t trung tm (nhn radical) v cc nguyn t phi
tr c bn cht trung gian gia lin kt ion v lin kt cng ho tr. Grimm, Brill, Hermann v
Peters (1938) chng minh iu vi s h tr ca php phn tch chi tit bn (mt
in t) Fourier ca thch anh. Gi d gia cc nguyn t ny ch c lc ht tnh in tc
ng th kh c th ni v s hnh thnh radical. V d trong mng tinh th spinel Al
2
MgO
4

nhm t din MgO
4
khng phi l radical, v bn cht cng ho tr khng ng k trong lin
kt gia Mg
2+
v O
2
.
Khng ging nh c tnh ca nhm SO
4
2
, nhm MgO
4
khng th di chuyn trn vn
t hp cht ny sang hp cht khc m khng bin i. Cc kt qu phn tch Fourier cho
thy gia cc nguyn t lun duy tr mt in t kh ln, khi chng lin kt nhau bng lc
cng ho tr. y l lc do cc in t dng chung to nn.
Carbonat
Trong cc hp cht v c ca carbon c n khong 80 khong vt; l mui ca acid
carbonic thuc lot nguyn t oxyphil v chalcophil. Him c carbonat cha uran. Ngoi ra,
carbon c xu hng siderophil r rt, n c mt trong thin thch vi hm lng ng k
(0,16%) v trong magma (0,03%). Nh oxy ho, n to anion CO
3
2
v i vo khong vt
ngun gc magma dng y.
Thng thng, CO
2
tch t giai on mun ca qu trnh kt tinh magma v nhiu
trng hp n ng vai quan trng trong phn d magma, nht l trong hnh thnh kim.
l carbonatit, loi gm ton carbonat calci trong thnh phn. iu cho thy dioxit

Xem 4.1.4. Tnh phn cc ca ion; quy tc Pauling (cui 4.2.1) v 5.5.9. Hiu ng chn ca ion.
139
carbon tp trung ln di su. Trong cc thnh to pegmatit v nhit dch n c nh trong
carbonat hoc di dng bao th kh hay lng ca khong vt thch anh, sulfur, v.v
Dioxit carbon vi nhit ti hn 31C ho tan nhiu trong nc. ho tan t l thun
vi p sut cho n gii hn xc nh, qu ngng y kh b nn khng ho tan na m tch
thnh pha ring. ho tan ca CO
2
t l nghch vi nhit , do c th gi nh rng CO
2
tp

trung trong dung dch nhit dch nhit thp. S hot ng ca cc dung dch ny to ra
nhiu m khong magnesit quan trng v kinh t.
Khi ni la hot ng, CO
2
v CO phun ra vi khi lng ln cng vi cc kh cha
carbon khc. Chng i vo khng trung, t i vo c th sinh vt v vo trong nc b
mt. Trong iu kin ngoi sinh, CO
2
phn ln tn ti di dng CaCO
3
, phn cn li nm
trong cy xanh qua quang hp bin thnh hp cht hu c. Nc bin cha CO
2
nhiu hn
khng kh gn 50 ln. Bin v i dng ng vai iu ho lng CO
2
ca khng kh. Carbon
ca nc bin tn ti di dng CO
2,
ion carbonat, bicarbonat v phn t H
2
CO
3
khng phn
li. Trong hnh vi ca nguyn t ny vi sinh vt ng vai quan trng; mt s lm tng, s khc
lm gim pH ca nc. Bng cch chng iu ho s kt ta ca CaCO
3
. Bn thn chng
cng sinh ra CaCO
3
trong hot ng sng.
Carbon c hai ng v bn vng l C
12
v C
13,
hm lng ca chng trong carbonat ln
lt bng 98,89% v 1,11%. T l C
12
/C
13
dao ng: thp trong vi, cao trong thc vt.
Carbonat cng c s khc nhau v gi tr t l ny. V d, dolomit: 88,1%, carbonat i oxy
ho: 90,7%. T l ny cng c s dao ng no trong calcit ngun gc khc nhau v c
s dng lun gii iu kin thnh to khong vt.
c im ho hc tinh th
Carbonat c anion phc kh bn vng CO
3
2
, trong bicarbonat cc ion ny gn vi nhau
bng lin kt hydro. Kch thc ca n trong calcit c xc nh; tm im ca cc
nguyn t u nm trn cng mt phng; khong cch OC bng 1,294. Khong OO trong
CO
3
2
l 2,21, nh hn hn so vi ng knh ca ion O

(2,64 2,70); iu ny chng t


tc ng phn cc mnh ca ion trung tm C
4+
v dng lin kt ny c mt phn bn cht
cng ha tr.
(a) Ba phng
Mg
2+
Zn
2+
Fe
2+
Mn
2+
Ca
2+

0,72 0,74 0,78 0,83 1,00
magnesit smithsonit siderit rhodochrosit calcit
(b) Trc thoi
Ca
2+
Sr
2+
Pb
2+
Ba
2+

1,00 1,18 1,19 1,35
aragonit strontionit cerusit witherit
Khc vi silicat hay borat, carbonat khng c nhng nhm chc a dng, bi v khng c
s trng hp ca CO
3
2
vi nhau qua oxy chung. Nhm CO
3
2
c nng lc ho hp vi hng
lot cation ho tr hai, cho cc hp cht t nhin vi bn vng mc khc nhau. Di
y, cc khong vt thuc hai lot (a) ba phng v (b) trc thoi xp theo th t gim dn ca
bn knh cation.
V Ca
2+
c gi tr bn knh trung gian, CaCO
3
c mt c hai lot bin th a hnh: calcit
ba phng v aragonit trc thoi. Trong phm vi mi lot, cation c th thay th ng hnh
cng ho tr; gia Mg, Zn, Fe, Mn v Ca lot (a) v lot (b) gia Ca, Sr v Pb. Trong
c nhng dy ng hnh lin tc l CaCO
3
MnCO
3
, FeCO
3
MnCO
3
, FeCO
3
ZnCO
3
.
Nhng kh nng cn li u hn ch t nhiu. Chng hn, calcit c th cha MgO nhiu nht
l 8%, cn magnesit tip nhn ch ti 6% CaO (theo Baronnet A., 1988).
140
Gia hai lot cn khong vt trung gian khc l dolomit MgCa(CO
3
)
2
v ankerit
FeCa(CO
3
)
2
. Ngoi ra, carbonat cha nhm OH u thuc h mt nghing, l malachit
Cu
2
CO
3
(OH)
2
v azurit Cu
3
CO
3
(OH)
2
. Trong cu trc phc tp ca chng c s trao i gia
cc cation ho tr mt: OH

v F

, OH

v Cl

.
V mt cu trc, tt c cc carbonat u c nt ring l cha cc radical tam gic phng
CO
3
2
(tham kho hnh 4.18 v ch gii i km), m hu ht chng xp song song ngc (xp
kiu xuyn tm i). Cn c theo cch cation v anion phn b c th chia carbonat thnh cc
nhm cu trc sau (theo Milovsky A.V. v Kononov O. V., 1985).
Cu trc phi tr nh calcit, siderit, v.v
Cu trc chui nh aragonit, malachit, v.v
Cu trc lp rt him.
Mt vi tnh cht lin quan vi c im ho tinh th
Hnh thi tinh th carbonat lin quan vi c im cu trc v iu kin thnh to. Vi
cu trc phi tr, hp cht thng c tinh th t hnh v dng quen thay i. Chng hn, calcit
c tinh th hnh mt thoi hay mt tam gic lch ba phng v thay i theo iu kin thnh
to. Carbonat vi cu trc chui thng cho dng quen lng tr di hoc tp hp dng cu to
tia.
Phn ln carbonat thng khng mu hoc trng. Ngoi ra, mu sc ca chng thng
ph thuc vo thnh phn nguyn t gy mu ca lot nguyn t chuyn tip, phi tr cng O,
OH v Cl. Chng hn Cu
+
gy mu lc, lam sng hay lam; Co
2+
cho mu thm, Mn to
mu hng. Mu nu ca siderit FeCO
3
do mt phn Fe b oxy ho. Ring calcit v vi
carbonat khc th khi nguyn cht thng khng mu. Hiu ng phng x c th cho tm mu
sinh ra cc mu lam, hng, nu pht vng, v.v Bn cht ngoi sc cng c ch trong calcit.
V d, calcit xanh m v en l do tp cht bitum, mu lc do bao th chlorit hay actinolit.
Cc gam mu c l do hematit. Carbonat kim loi kim t c xu hng pht quang trong
nh sng cc tm.
Vic cc radical tam gic phng xp t song song l c im cu trc to nguyn nhn
ca bn cht d hng s ln carbonat: lng chit sut cao trong calcit, aragonit, v.v, a
sc trong malachit, azurit, v.v...
Sulfat
Trong ph nhm VIb, lu hunh v selen c c im ging nhau v tp tnh ha hc tinh
th. Mc du vy, nu selen ch c diselenat Se
2
O
7
2
th lu hunh to nhiu radical va n
nhn va a nhn. Trong s cc anion n nhn ca n, lu hunh c SO
3
2
di dng thp
ba phng dt v SO
4
2
gn nh mt t din u c th gn kt thnh anion hai nhn: cho
S
2
O
7
2
qua mt oxy chung. Tellur thng cho tellurat nh Na
2
H
4
TeO
6
, tc l cc mui ca
acid Te(OH)
6
; i khi n cng to ion dng t din TeO
4
. Poloni l nguyn t mang tnh bn
kim r rt v khng cho acid oxit.
Khong vt ca lp ny l mui ca acid sulfuric. Thnh phn ca chng bao gm cc
kim loi nh Fe, K, Na, Cu, Mg, Al, Ca, Sr, Ba, v.v Mt s sulfat t nhin cha thm cc
anion ph nh SeO
4
, PO
4
, SiO
4
, MnO
4
, AsO
4
, v.v... Trong anion t din SO
4
2
lu hunh c
ho tr cao nht (+6). Lin kt ion l dng ch yu trong cc khong vt thuc lp ny. Thay
th ng hnh cng ho tr v khc ho tr khng ph bin. c bit gia barit BaSO
4
v
141
celestin SrSO
4
l dy thay th ng hnh lin tc. Ngoi ra, trong barit cn c s trao i gia
bari v ch.
Sulfat l nhng hp cht khng ng cc in hnh. n v cu trc c s ca chng l
nhm SO
4
2
. Nhm lin

kt gin tip vi nhau thng qua cc cation v cc anion ph, k c
phn t nc. Tu kch thc ca chng, cc cation c th c s phi tr 6, 8, 12. Gia anion
phc SO
4
v cc cation l s phn b khng d cc. iu ny ct ngha xu hng ca khong
vt lp ny l to nn dng quen tng i ng thc.
Tuy nhin, sulfat c thnh phn kh phc tp; cn c vo nh lut Groth, chng c i
xng tng i thp, thng thuc h mt nghing, trc thoi. Dng quen ca tinh th chu nh
hng ca phn t nc tham gia vo thnh phn sulfat. Anhydrit CaSO
4
c dng quen ng
thc, trong khi gypsit CaSO
4
.2H
2
O c tinh th lng tr v dng tm. Thuc ph h ba
phng cng c khng t sulfat. S t l tinh th lp phng v su phng.
Hu ht cc sulfat ca phn nhm IIA ng vai tr nht nh trong khong vt hc v l
nguyn liu quan trng cho cng nghip. Kt tinh h trc thoi, BeSO
4
khan c cu trc
ging cristobalit; bi v c Be
2+
v S
6+
u phi tr t din vi O
2
, cc a din phi tr ny
cng gn vi nhau qua cc ion oxy chung v d dng p ng quy tc Pauling v ha tr tnh
in. Khong cch Be O = 1,56, S O = 1,53; khong cch trung bnh O O = 2,50
trong SO
4
, l 2,50 v 2,65 trong BeO
4
. Mng tinh th ca tetrahydrat BeSO
4
.4H
2
O cng
cha Be phi tr t din, nhng vi 4 phn t nc. Hai loi t din, Be(OH
2
)
4
v SO
4
, cng
phi hp to nn mng bin dng ca loi cu trc sphalerit. Khong cch Be H
2
O = 1,62.
Sulfat ca cation c ln hn Mg
2+
c cu trc khc loi vi i xng trc thoi v phi tr
bt din ca cation; khong cch Mg O thay i; 2,01 vi 2 oxy v 2,09 vi 4 oxy, do
hnh phi tr ca Mg l bt din bin dng nhiu. MgSO
4
hp ph nc rt mnh, v d
epsomit MgSO
4
.7H
2
O. Khong vt ny c mng trc thoi ln hn. Cc bt din
Mg(OH
2
)
6
2+
lin kt vi nhau bng lc hydro.
Anhydrit CaSO
4
l khong vt rt ph bin. Ca c s phi tr 8 v hnh phi tr l mi
hai mt tam gic. N gn qua cnh chung vi t din SO
4
to nn chui dc trc z. Nguyn
t lu hunh v calci cng nm trn mt i xng gng {100} v {010} (nhm khng gian
Amma). Do vy, dc hai hng ny c ct khai tt hn {001}. Thch cao CaSO
4
.7H
2
O cng
l khong vt rt phong ph. Cu trc gm cc lp song song {010} cha nhm SO
4
gn cht
vi Ca. Xen k l cc lp phn t nc dc mt i xng nh trt; lin kt gia chng l lc
hydro yu, iu ny ct ngha ct khai hon ton dc hng ny. Ct khai ny s bin mt
cng vi s gim t trng do thch cao mt nc khi nung.
Phosphat
L nguyyn t a oxy r rt trong iu kin ca Tri t, phosphor thng tp trung
trong cc thnh to magma sm. So vi magma acid, magma mafic thng giu
phosphor hn, tuy pegmatit ca acid i khi cng cha nhiu phosphat (ch yu apatit hay
phosphat ca cc nguyn t t him v ca Li, Mn, Al, Be, v.v...). M khong nhit dch
thng ngho phosphor.
Nh c bn knh gn bng nhau, phosphor v silic (0,35 v 0,39)c th thay th ng
hnh cho nhau, cho nn d dng gii thch s c mt ca phosphor trong thnh phn ca mt
s silicat v ca silic trong mt s phosphat. Apatit v cc phosphat khc l ngun chnh cung
cp phosphor cho phosphat ngoi sinh hnh thnh. Khi cc b phong ho thng cho
142
phosphat d ho tan ca kim loi kim: t , phosphat calci v cc kim loi khc c th kt
ta.
Mc d vy, phosphor di chuyn rt nhiu vo cc bn nc ln, chng kt ta di
dng cc phosphat ho tan km hay i vo c th sng. Cc sinh vt tip nhn phosphor t
nc bin v nh vy chng lm tng tc kt ta phosphor y. Bi v phosphor trong
nc bin c trng thi ho tr cao nht, th nng oxy ho kh ca mi trng khng phi l
yu t quyt nh; m chnh gi tr pH c ngha ln cho phosphat thnh to. i lng pH
tng thc y s kt ta phosphat calci, ging nh tp tnh ca carbonat calci trong iu kin
tng t.
Cc vng nc su bin v i dng l ni hi cc yu t chnh, cng l ni thun
li cho chng tc ng phi hp nhm tng cng lng phosphor; l cc yu t sinh hc
v ho l. Chng hn, nhit thp hn, m p sut ring phn ca CO
2
th cao hn. cha
phosphor cao nht (> 300mg/m
3
) ghi nhn c l su khong 500m, cng l ni CO
2
c
p sut ring phn cao nht (1210
4
atm). Phosphat calci s kt ta tng nc mt, ni
phosphor theo dng nc bin dng ln gp cc yu t thun li: pH tng v p sut ring
CO
2
gim.
Sinh vt hp ph khi lng ln phosphor t nc bin. Phn v cng v phn xng
ca chng c thnh phn chnh l phosphat calci. Chng cn cha phosphor trong cc c quan
di dng hp phn ct yu ca cht nguyn sinh.
c im ho hc tinh th
Phosphor v arsen c th to anion phc bng phi tr bt din vi 6 nguyn t fluor hoc
hydroxil, lin kt ha hc trong mang tnh cng ha tr. Ring antimon c phi tr t din
vi fluor trong anion phc dng (Sb
2
F
7
), tc l hai t din ghp i. i vi oxy phosphor v
arsen thng c phi tr t din, thm ch c th c phi tr thp ba phng vi nh l P/As.
Hai nguyn t ny cn to vi oxy nhiu loi radical a nhn. Anion phc ca phosphat c
hai loi chnh:
T din gn kt vi nhau bng ion oxy chung v mi oxy ny thuc v c hai t din.
Bng cch y radical c th bao gm hai, ba n t din; hn na, radical hnh thnh c th
c dng chui vi cng thc (PO
3
)
n
nh tng gp trong mt s metaphosphat. i khi
chui khp li thnh vng, v d tetrametaphosphat nhm h lp phng AlPO
3
c anion vng
bn P
4
O
12
.
Arsenat, vanadat v phosphat ch yu u l sn phm ca cc qu trnh ngoi sinh. Tuy
s lng ln (250 dng khong vt), nhng chng ng vai tr khng ln trong thnh phn v
Tri t. Khong vt c tm quan trng trong thc tin s xem xt chng 6 l apatit
Ca
5
(PO
4
)
3
(F,Cl,OH).
Trong thnh phn ca phosphat, phosphor tham gia trng thi ho tr cao nht (5+) lin
kt vi oxy to thnh anion phc [PO
4
]
3
. Thnh phn cation ca phosphat (ch yu thuc
v cc nguyn t a ) gm Al, Fe, Mn, Ca, Zn, Cu v Pb. Ngoi cc khong vt khan, mt
lot phosphat cha kh nhiu nc; lng nc thay i mnh, mi n v cng thc c t 1,
2 ti 8 phn t.
Phosphat l nhng hp cht ng cc, chng c n v cu trc dng t din bn vng
(lc lin kt PO ln hn so vi lc gn nhm chc ny v cation khc). Cation cc loi ng
vai cu ni gia chng vi nhau. [PO
4
] v [AsO
4
] thay th ng hnh mc hn ch, nhng
gia cc nhm [VO
4
] v [PO
4
] hon ton khng c kh nng y. Vanadi ho tr bn c mt
143
trong phosphat CaV
2
O
2
[PO
4
]
2
.5H
2
O, ng vai cation, m khng i vo thnh phn anion
phc. Kh nng thay th ng hnh gia [PO
4
] v [SiO
4
] c th hin thc do c tn ti nhng
cp ng cu trc silicat phosphat:
Thch anh Si
2
O
4 Al[PO
4
] Berlinit
Olivin (Mg,Fe)
2
[SiO
4
] LiFe[PO
4
] Triphylit
Zircon Zr[SiO
4
] Y[PO
4
] Xenotim
Datolit CaB[SiO
4
]OH CaBe[PO
4
]OH Herderit
Gia Al
3+
(0,57) v Fe
3+
(0,67), cng nh gia Fe
2+
(0,83) v Mn
2+
(0,91) lun c
thay th ng hnh do cc cp ion c bn knh xp x. Thnh phn phosphat tng i phc
tp, nn chng kt tinh ch yu theo cc h hng thp. Dng quen ca phosphat ni chung
thuc loi ng thc, bi v cu trc ca chng c tnh cht phi tr.
4.4.7 Silicat v alumosilicat
Silicat (bao gm c alumosilicat) l lp khong vt ln nht. Gn 25% s khong vt
bit v khong 40% s khong vt ph bin l thuc lp ny. Tr mt s ngoi l, hu ht cc
khong vt to magma u l silicat v alumosilicat

. V th, chng chim ti hn 90%


trng lng ca v Tri t. Ti y, t trng ca tng nhm khong vt rt khc nhau, xem
bng 4.25. Hn na, trong tng 92 nguyn t ho hc pht hin ti v Tri t, ch 8 nguyn
t chim gn 99% trng lng ca n (xem bng 4.26).
Bng 4.25
T trng (%) ca cc nhm khong vt trong v Tri t
Plagioclas 39 Pyroxen 11 St 5
Feldspat 12 Amphibol 5 Silicat khc 3
Thch anh 12 Mica 5 Cc lp khc 8
n v c s ca cu trc silicat l t din SiO
4
, n nhn cation Si
4+
lm tm im v cc
anion O
2
lm nh. Mi lin kt mnh vi bn cht na ion na cng ho tr l nhn t m
bo cho n bn vng. Theo Pauling L. (nm 1960) mi lin kt ny mang bn cht ca lc ht
ca cc ion tri du v s giao ho ca cc in t dng chung. Tng nng lng lin kt ca
Si
4+
chia u cho bn O
2
k bn. Mi lin kt c nng lng ng bng mt na ho tr ca
oxy.
Mi anion ny phn b nng lng ng u vo mi mi lin kt vi silic, d dng cho
vic gn kt cc nhm t din vi nhau. S gn kt t din y gi l s trng hp (thut ng
thng dng trong ho hc hu c). Chnh nng lc trng hp ny lm nn tnh a dng ca
cu trc silicat. Trong , tng i t din chia nhau mt nguyn t oxy (lin kt qua nh l
ch yu). Nu t din khng bao gi gn vi nhau qua cnh chung v nht l qua mt chung,
l bi v cc ion silic in tch cao s nm qu gn nhau, pht sinh lc y: cu trc tr nn
km bn vng (xem quy tc Pauling, cui 4.2.1).

Xem chi tit chng 6. Ho hc tinh th ca mt s khong vt to .


144

Bng 4.26
T trng (%) ca 8 nguyn t ho hc trong v Tri t
(theo Mason B. v Moore C. B., 1982)
Nguyn t ha hc Phn trm trng lng Phn trm nguyn t Bn knh ion,
O 46,60 62,55 1,36
Si 27,72 21,22 0,26 (4)*
Al 8,13 6,47 0,39 (4)
Fe 5,00 1,92 0,78 (6)
Ca 3,63 1,94 1,00 (6)
Na 2,83 2,64 1,02 (6)
K 2,59 1,42 1,51 (8)
Mg 2,09 1,84 0,72 (6)
Tng 98,59 100,00
* Trong ngoc l s phi tr thng gp ca ion
Tu thuc s lng (mt, hai, ba, hay c bn) anion oxy t din gp vo s trng hp,
silicat s cho nhng ph lp khc nhau. Hnh 4.36 th hin nhng s trng hp khc nhau
ny. Silicat vi nhm SiO
4
4
c lp, tc l cc t din khng gn vi nhau, gi l silicat o
n. C hai t din ghp i l silicat o kp. Nu s t din trng hp nhiu hn, cu trc
vng kn hnh thnh c cng thc tng qut Si
X
O
3X
vi X = 3, 4, 6. y l silicat o vng,
chng hn vng bn vi n v cu trc l [Si
4
O
12
]
8
hay vng su [Si
6
O
18
]
12

Hnh 4.36.
Silicat phn loi theo mc trng hp ca t din SiO
4
145
T din lin kt c th to silicat chui [Si
2
O
6
]
4
ko di theo mt phng. Hai chui
ghp song song cho silicat chui kp vi t lng silic : oxy = 4 : 11. to nn silicat vng
hay chui mi t din gp vo hai anion oxy, ghp thnh silicat lp vi thnh phn anion
phc [Si
2
O
5
]
2
mi t din gp vo ba anion oxy. Khi c bn oxy ca t din u trng dng
vo s trng hp th xut hin silicat khung vi thnh phn SiO
2
. Dioxit silic t nhin ny c
hng lot bin th a hnh: -thch anh, -thch anh, tridymit, cristobalit, coesit v stishovit.
Cu trc tinh th ca cc silicat ny (tr stishovit c cu trc loi rutil v phi tr bt din ca
nguyn t silic) khc nhau gi tr gc ho tr OSiO bin i trong khong t 160 180.
ng nhin, cc khong vt silica ny ch l nhng silicat khung n gin. Nh vai tr ca
nhm, ph lp ny phong ph v a dng hn.
Nguyn t nhm l thnh phn quan trng ca v Tri t sau silic v oxy. Cation Al
3+
c hai s phi tr: 6 v 4 (xem bng 4.27). Chnh nh vai tr kp ca n, cation nhm kh ni
bt trong ho hc tinh th ca silicat. Khi nhm phi tr vi 4 nguyn t oxy to t din u
AlO
4
, a din phi tr y cng chim mt khng gian nh t din SiO
4
v cng gn kt vi n
trong s trng hp. l do kh nng thay th ng hnh ca nhm i vi silic v chim v
tr tinh th hc nh n.
Bng 4.27.
S phi tr ca cc cation ph bin trong silicat
xp theo trnh t gi tr bn knh gim (theo Dana, J. D., 1993)
Cation Phi tr Bn knh,
K
+
8-12 lp phng - tm mt lp phng 1,51 (8) 1,64 (12)
Na
+
8-6 lp phng - bt din 1,18 (8) 1,02 (6)
Ca
2+
8-6 lp phng - bt din 1,12 (8) 1,00 (6)
Mn
2+
6 bt din 0,83 (6)
Fe
2+
6 bt din 0,78 (6)
Mg
2+
6 bt din 0,72 (6)
Fe
3+
6 bt din 0,65 (6)
Ti
4+
6 bt din 0,61 (6)
Al
3+
6 bt din 0,54 (6)
Al
3+
4 t din 0,39 (4)
Si
4+
4 t din 0,26 (4)
S thay th khc ha tr ny xut hin him hoi t silicat o n, pht trin tun t
cng vi s trng hp. Nhng n silicat khung th c ch thay th ng hnh ny tr nn
nht thit, nu khng ph lp ny tr nn gii hn cc thnh t n gin [SiO
2
]
o
. Nh c
1/3 n 1/2 Si
4+
thay bng Al
3+
, silicat khung c thm feldspat [AlSi
3
O
8
] v feldspathoid
[(Al,Si)O
2
]. Mi cation Al
3+
thay th cho mt cation Si
4+
lm di d mt in tch m, ko
theo s thay th khc. in tch ny s do cc cation kch thc ln nh kali, natri hay calci
trung ho. D kch thc ca chng gn nhau, nhng in tch li khc nhau, s thay th kp
ca cp Na
+
+ Si
4+
bng cp Ca
2+
+ Al
3+
bo m trung ho in tch trong ton cu trc.
Trong silicat khung c nhng khng gian rng ln, rt ph hp vi cc kim loi kim c ln.
Vi vai tr th hai, nhm phi tr su ging nh nhiu cation khc, c chc nng gn cc
nhm t din vi nhau bng lin kt tri ion, khng mnh bng lin kt bn trong t din.
Nh vy trong cu trc silicat, nhm va thay th silic trong phi tr t din, va thay th
146
magnesi, st, v.v trong phi tr bt din, gp phn to nn tnh a dng cho lp khong vt
ny.
Cc cation ho tr khc nhau nh Mg
2+
, Fe
2+
, Mn
2+
, Fe
3+
, Al
3+
, Ti
4+
, Zr
4+
v.v, u
chim nhng v tr tinh th hc gn nh nhau trong cu trc (xem bng 4.27). Cp cation ln
v ho tr thp l Ca
2+
v Na
+
nm trong v tr vi phi tr tm/su. Nhng ion ln nht, ph
bin trong silicat l ca nguyn t kali, rubidi, bari, kim him v kim th. Chng khng
thay th cho natri v calci. Chng thng bt gp trong silicat vi s phi tr cao. Gia chng
v cc ion ph bin khc t khi to thnh dung dch cng.
Cn c vo vai tr ca nhng nguyn t thng gp nht c th vit cng thc tng
qut cho cc silicat nh sau:
X
m
Y
n
[ Z
p
O
q
] W
r

trong , X l cation in tch thng nh v kch thc ln s phi tr tm v cao hn; Y l
cation c va, ho tr hai n bn v phi tr su; Z l cation c nh, phi tr t din, in tch
ln; O l oxy, in tch m kch thc ln; W l cc anion ph nh OH

, Cl

, F

, v.vt s
p/q ph thuc vo mc trng hp ca b khung silicat, cn m, n, r th bin i theo nhu
cu trung ho in tch.
V tr tinh th hc l ni dnh cho nguyn t trong cu trc tinh th v ring i vi
cation th v tr ca chng l tm a din phi tr. Khong vt c th c mt s cation ging
nhau v v tr tinh th hc. Trong trng hp cu trc phc tp, nhng v tr ny c kch thc
khng ging nhau; cation vi kch thc phn bit c th ph hp vi tng loi a din phi
tr. Chng hn, 2 v tr cation vi phi tr bt din, k hiu l M1 v M2. Bt din M1 bin
dng nhiu th b nh hn so vi bt din M2 bin dng t. Nh vy, M1 ph hp vi cation
nh hn nh Al
3+
, Fe
3+
, Mg
2+
, cn M2 l ch ca cation Fe
2+
, Mn
2+
, Ca
2+
.
147
Chng 5
C IM CU TRC TINH TH THC
Theo lun thuyt hnh hc ca cu trc tinh th, cht kt tinh l mt kin trc khng
gian ba chiu, u n, tun hon ca ht vt cht (nguyn t, ion, phn t). iu ng
vi trng hp l tng, rt qu v rt cn bn ca cht kt tinh; nhng y ch l mt
trong nhng kh nng ca trt t. So vi tinh th l tng, mng tinh th thc thng
cha nhiu loi sai hng khc nhau.
5.1 CC LOI SAI HNG TRONG TINH TH THC
Nghin cu c im vt l ca tinh th thc, t nhin hay nhn to, cho thy nhng
vt th y lun c nhng sai hng cp nguyn t trong cu trc ca chng. Sai hng
loi ny tc ng ln nhiu c im ca cht kt tinh nh bn, dn, bin dng c
hc v mu sc. Sai hng trong cu trc bao gm sai hng im, sai hng ng v sai
hng mt [13].
5.1.1 Sai hng im
Trong mng c nhng v tr b trng vn dnh cho ht vt cht no (sai hng im
kiu Schottky). Pyrrhotin vn l mt khong vt vi thnh phn ho hc khng c mt t
lng xc nh: Fe
1X
S; st lun thiu ht mt lng no ; Fe
2+
lun b trng mt s v
tr ca n trong khoang bt din do lu hunh (S
2
xp theo lut ABABAB) to nn.
Phn thiu ht in tch dng to thun li cho mt s Fe
3+
vo thay Fe
2+
(xem loi cu
trc nickelin, 4.3.2,d v dung dch cng khuyt tt, 5.2.3).
Mt khi nt trng xut hin, in t c th lp vo lm ny sinh tm mu. y l
trng hp ca khong vt fluorit, khi anion fluor ri b v tr khin in tch m ti ch b
thiu ht. in t d dng b ht vo (hnh 5.16 v li gii thch).
Khi ion ri b v tr ca n, n nm xen gia cc nt dnh cho ion khc s lm nn
sai hng kiu Frenkel. Sai hng loi ny xy n vi cation thng xuyn hn so vi
anion; vi kch thc thng nh, cation dch chuyn c phn d dng hn. Sai hng
Frenkel lm cho tinh th tr nn dn in tt; ion t rng buc vn ng trong mng di
nh hng ca in trng. V d, trong AgCl cation bc bt u di chuyn khi nhit
t 146C.
Sai hng tp cht cng l sai hng im, khi ion ngoi lai xen vo gia cc nt mng
hay nm vo ch ca mt hay vi ion. Sai hng loi ny gy bin ng thnh phn ho hc
ca cht ch, mc du nhng thay i ny rt nh (tnh bng phn triu hoc nh hn)
nhng mt s tnh cht nh mu sc c th b tc ng mnh bi tp cht ny.
Sai hng im bao gm cc nguyn t xen (gia cc nt mng) v cc nt trng
nguyn t. Nt trng ny ng vai chnh trong s khuch tn; v mi khi nguyn t b thu
148
ht, ti lp vo , n s b li ng sau mt nt trng mi. Nguyn t xen c th khng
ging nguyn t ca nt mng; vi nhng tc ng v ho hc tinh th (khc v kch thc
ht, khc v ho tr), chng c th nh hng ti tnh do ca tinh th. S c mt ca nc
trong thch anh c chiu hng lm tng tnh do bng tc dng thu phn i vi lin kt
SiO.
5.1.2 Sai hng ng
y l s tp trung sai hng dc theo chui mng; n to ra mt s gin on trong
cu trc, gi l lch mng. Khi mt mt mng trong cu trc b gin on thay v ko di
lin tc song song vi cc mt mng khc, l lch mng bin hay lch bin (hnh 5.1,a).
Lch bin th hin bng du ; vch ng ch hng mt mng b gin on, vch ngang
biu th mt trt. Giao im ca 2 vch l ni ng lch mng l ra; l cnh bin, ni
gin on ca mt mng d, ni cu trc mng b bin ng mnh nht.
Nh lch bin m mt trong hai na ca mng d dng dch chuyn song song vi mt
trt di tc ng ca mt lc (theo hng ca vch ngang). Cng vi s trt y, lch
bin s dch chuyn (theo kiu su o) dn tng on thng s chui, cng chiu vi lc
tc ng, cho n khi thot hn ra ngoi.
Hnh 5.1,b cho thy hnh nh ca mt lch mng xon/lch xon; cc nguyn t xung
quanh ng D phn b trn mt ng xon. Di tc dng ca ng sut, lch xon dch
chuyn dn theo hng vung gc vi vect ca lc, ri cng thot ra ngoi.
5.1.3 Sai hng mt
Bin dng n hi ca mng xung quanh mt lch mng to nn trng ng sut ti
ch vi ni nng tng cao. Bng kh nng dch chuyn ca chng, cc lch mng ri rc
trong mng thng tp hp, sp xp li theo hnh th u n. Khi ni nng tr nn thp
nht, hnh th ny mang tn vch lch mng. y l mt trong nhng biu hin ca sai
hng mt, ni tp trung cc lch mng cng loi (lch bin hoc lch xon). Cc vch ny
chia ct ht thnh nhng min nh (hnh 5.1,c). Cc min nm hai bn vch lch mng vi
nhau, c th ny xoay mt gc nh quanh mt trc so vi c th kia. y chnh l cu trc
bn vng ca tinh th thc: vic xoay mng hai bn vch khin cho lch mng cc loi c
th cng tn ti trong mt trt t khng hon ho (gi l kin trc khm/mosaic) ca tinh
th.
Song tinh
Theo nh ngha, song tinh l lin kt i c quy lut ca tinh th cng bin th a
hnh

. Trong mt song tinh, mng khng gian ca hai c th thng lin quan vi nhau v
nh hng tinh th hc, c th ho bng cc lut song tinh, tc l bng yu t i xng
ca song tinh, nh mt gng hay trc xoay bc hai. Cc yu t i xng ny phi song
song vi mt mng hay chui mng. Trong trng hp n gin, cu trc ca mt trong
hai c th trng vi cu trc ca c th kia khi cho phn chiu qua mt ghp hay mt phn
cch. Mt mng ca mt ghp cng k hiu ca n, chng hn (310) trn hnh 5.1,d, u c
ngha i vi mng ca c hai c th. Ni cch khc, cc nt trn mt ny u c s chnh

Song tinh a hp v thc cht vn l lin kt tng i


149
hp vi mng khng gian ca c hai pha; chng u thuc v cc chui mng v mt
mng ca chng. Tuy nhin, v cu trc vi m, mt song tinh v vng ln cn th hin mt
dng sai hng mt.


Hnh 5.1.
S mt s sai hng trong cu trc tinh th
a) Lch bin vi mt mng gin on (d). b) Lch xon.
c) Sai hng mt chia ct tinh th thnh cc min lch nhau.
) Song tinh vi mt ranh gii (130) v siu mng do mt phn
nguyn t (mu en) ca hai c th to nn
Mng song tinh l mng bao qut chung cho hai c th. Trn hnh 5.1, mng song tinh
th hin bng cc nt en, tnh lin tc ca n biu th bng = 0 ( l nghing song
tinh, gc gia tia php ca mt song tinh v mng song tinh, gc ny bin thin trong
khong t 0 n khong 6): tia php ca mt song tinh (310) cng l chui [310] ca c
hai c th v trng vi mt trong cc chui ca mng song tinh. Tnh lin tc ca mng
song tinh l iu kin cn bn ca tnh n nh song tinh; nghing ca n cng nh,
tn sut gp cng ln.
V ngun gc, s hnh thnh song tinh c ba trng hp (Buerger, 1945).
Song tinh pht sinh trong qu trnh pht trin ca tinh th khong vt. S pht
trin hon thin ca mt tinh th l tng thng tun th mt trnh t u n.
Nm trong dung dch bo ho hay trong dung th, a din tinh th tng trng
l nh cc ht vt cht (ion, nguyn t, phn t v.v) tun t tip cn b mt
ca n. Ht xp vo hng, ht hng ny sang hng khc, ph y mt tinh th,
150
lm thnh lp. Lp (hng) n cha hon thnh th lp (hng) kia cha th pht
sinh (tham kho [13]). Ch cn ht vt cht nm khng ng ch, trt t vn u
n s b gin on.
V d, trn hnh 5.1,d, mt (310) c th xem nh du vt ca mt trong nhng mt ca
tinh th bn tri (nguyn thu). Trong khi n ang tng trng, mt ht c th tip cn v
tr ng vi trt t ca mng tinh th ny. y l trng hp tinh th pht trin bnh
thng, cu trc nguyn thu khng b gin on. Trong trng hp ht tip cn mng tinh
th bn phi th tinh th tri ngng pht trin; bin c ny cho cu trc song tinh. y l
song tinh nguyn sinh, ngun pht sinh phn ln cc song tinh tip xc v song tinh mc
xen.
Song tinh hnh thnh sau chuyn pha. Thch anh nhit cao (hnh 5.5,b) vi
nhm khng gian P6
2
22 chng hn, sau khi chuyn sang pha nhit thp
P3
2
21 (hnh 5.5,c) th cu trc phn li thnh hai phn lin quan vi nhau bng
php quay 180 quanh trc chnh 3
2
. l song tinh lut Dauphin. B t nng
th song tinh bin mt v thch anh nhit cao khng song tinh c phc hi.
Mt v d khc, Kfeldspat gm sanidin (C2/m) pha nhit cao, orthoclas
(C2/m) pha nhit trung bnh v microclin pha nhit thp ( C1 ). Trong
bc chuyn t pha mt nghing sang ba nghing, cc yu t i xng ca mt
nghing bin mt. Nhng vng microclin (ba nghing) xut hin, lin kt vi
nhau bng cc lut song tinh albit v periclin; y l song tinh mng li quen
thuc trong microclin (xem thm 6.11.3).
Song tinh bin dng sinh ra do lc c hc. Nu lc tc dng khng ln
ph v cu trc th n c th lm cho cc mt mng trt song song vi nhau v
theo hng ca lc c hc. Song tinh bin dng ny thng gp trong kim loi
v trong vi; chng hn song tinh lin phin rt thng gp trong calcit (hnh
5.8 v mc 5.4.8).
Sai hng mc khc nhau bt gp trong cu trc tinh th hu nh thng xuyn.
Kin trc khm c Laue M. ni n (nm 1913), sau khi pht hin trong fluorit. Kin
trc ny lm gim bn c hc ca vt kt tinh; theo Stranski I., ht tinh th cng ln
cng km bn vng. Chng hn, tinh th halit vi mt ct ngang 10
5
cm
2
b ph v di
lc nn

gn bng gi tr l thuyt tnh cho NaCl hon thin. Vi mt ct ngang 1000 ln ln
hn tinh th d dng b ph v ch vi mt lc 100 ln nh hn.
Nh vy, khi nh gi tinh th mt cht khng ch lu c im tinh th hc v ho
hc ca n, m c cht lng, tc l mc hon thin ca cu trc.
5.2 NG HNH
Nhng cu trc sai hng cn c th xut hin khi hnh thnh tinh th hp cht phc
tp, m c im ca chng lin quan ti khi nim ng hnh, do Mitscherlich E. (nm
1819) a ra ln u. Theo , cht ng hnh l nhng cht khc nhau v ho hc, kt
tinh thnh a din ging nhau hay gn ging nhau, khi ng nhn thy cp hp cht
KH
2
PO
4
v KH
2
AsO
4
kt tinh thnh cng mt dng a din. Chng u l hnh ghp ca
hai hnh n: lng tr v thp i bn phng; gc gia (101) v (011) ca hai a din u
151
bng 58 (gi tr hiu chnh v sau ln lt bng 5758 v 5752, vi t s cnh mng 1
: 0,939 v 1 : 0,938).
T lu, vic nghin cu cc trng hp khc nhau v ng hnh dn n kt lun v
thnh phn ho hc ca cht ng hnh; chng ch khc nhau s thay th ( t l 1:1) ca
nguyn t ny bng nguyn t khc, thng gn ging nhau, nhng i khi khc nhau v
bn cht. Mt v d khc, trong khi cp hp cht CaSO
4
v SrSO
4
, tng t v ho hc,
khng bc l nng lc ng hnh, th hai cp CaSO
4
NaClO
4
v SrSO
4
KClO
4
li c nng
lc y. Trong nhng trng hp ny kch thc ca cc n v cu trc tng ng ng
mt vai tr nht nh. Tinh th ca hai mui xy dng t cation v anion phc, nh cc cp
trn, c th l nhng cht ng cu trc v ng hnh vi iu kin anion ca chng gn
nhau v kch thc v v t l bn knh gia cation vi anion, khng ph thuc ho tr v
c im nguyn t. Bn knh ca Sr
2+
1,27 ln hn hn ca Ca
2+
1,04 ; Sr thay cho Ca
s ph v s bn vng ca cu trc sulfat v dn n s hnh thnh cu trc mi. Anion
ClO
4

c cng dng t din v cng kch thc nh SO
4
2
, ion Na
+
(0,98) gn vi Ca
2+
v
ln; mc du ho tr khc nhau, CaSO
4
v NaClO
4
l cp ng hnh. Ion K
+
(1,33) ln
hn hn ion Na
+
lm cho n khng th i vo cu trc NaClO
4
; nhng ng hnh ca
SrSO
4
v KClO
4
l c tht.
Trong thay th ng hnh bn cht ca lin kt ho hc cng c ngha ln v n xc
nh loi cu trc v do c dng tinh th. V d, periclas MgO v zincit ZnO thot nhn
c th coi l ng cu trc; bn knh hu hiu ca Mg v Zn kh gn nhau (0,78 v 0,83).
Nhng lin kt ion chim u th trong periclas cn trong zincit l lin kt cng ho tr. V
vy, cu trc ca chng ln lt thuc loi halit v vurzit.
5.2.1 Vect thay th
Phng thc hiu qu m t s thay th ng hnh l vic s dng khi nim vect
thay th (theo F.S. Spear, 1993) hay vect trao i. Ging nh vect trong khng gian
x,y,z, vect thay th cng c hng v ln: hng ch s thay th nguyn t ny bng
nguyn t khc, ln xc nh s lng nguyn t (b) thay th. nhn vect gia 2
im trong khng gian x, y, z, hy ly ta im u tr i to im cui. Cng vy,
mun c vect thay th gia 2 thnh phn khong vt, cng ly thnh phn ca 2 khong
vt tr cho nhau. Chng hn, vect thay th gia orthoclas v albit l:
KAlSi
3
O
8
(orthoclas)
NaAlSi
3
O
8
(albit)
= K Na = KNa
1
S chnh lch gia orthoclas v albit l KNa, m theo php k hiu ca vect thay
th, hiu ny vit thnh: KNa
1
. Du tr sau Na c ngha l khi mt nguyn t kali i vo
thay th, th mt nguyn t natri s b y ra.
Vect thay th NaK
1
cp s trao i tng t, nhng theo chiu ngc li. Vect
thay th trnh by mt thc th ho hc; n cho thy s khc nhau gia 2 cng thc khong
vt hu quan.
Thut ng c ch thay th hay c ch trao i cng ph bin trong vn liu. S thay
th ca nguyn t ny cho nguyn t khc l mt qu trnh vt l, khng cp n chiu
hng ca n. Vect thay th c 2 loi: vect thay th n cho thy s thay th ca mt
152
nguyn t bng mt nguyn t, nh KNa
1
ni trn. Vect thay th kp th hin s thay
th ca cc cp nguyn t vi nhau. V d: plagioclas;
NaAlSi
3
O
8
(albit)
CaAl
2
Si
2
O
8
(anorthit)
= NaSi CaAl = NaSiCa
1
Al
1
Trong s thay th kp trn, Na
+
v Ca
2+
c trng thi ho tr khc nhau; chng khng
th thay th trc tip cho nhau (nh trong thay th n), v cn duy tr tnh trung ho in
ca tinh th. Vy, Na
+
v Si
4+
cp i vi nhau v thay th cho cp Ca
2+
v Al
3+
; in tch
tng ca mi cp u bng +5.
Bng 5.1 gii thiu nhng vect thay th hay nhng c ch thay th ph bin, bt gp
trong khong vt to . C l, ph bin nht l vect trao i FeMg
1
, li thng gp
trong mi khong vt cha st v magnesi. S thay th ny gn nh l tng v thng
dng trong a nhit k. Thng thng, nhng khong vt giu magnesi c bn nhit
cao hn so vi nhng dng giu st. FeMn
1
cng ph bin, nhng ch c trong s t mi
trng to khong; bi v cc loi giu mangan cng him. Granat l bit l ng ch ,
n cha khi lng kh ln thnh phn mangan (spesartin) trong cc bin cht bc thp.
Nhng vect thay th bao hm calci (CaMg
1
, CaFe
1
, CaMn
1
) thng ph bin trong
pyroxen, amphibol, granat v carbonat. Ni chung, chng khng hon ho v trong nhiu
trng hp thng c min gin on. V d: Trong hai cp khong vt:
- diopsitclinoenstatit (CaMgSi
2
O
6
Mg
2
Si
2
O
6
) v
- tremolitMg-cummingtonit (Ca
2
Mg
5
Si
8
O
22
(OH)
2
Mg
2
Mg
5
Si
8
O
22
(OH)
2
),
u bc l min gin on. Mt solvus tng t cng tng gp trong granat:
gia grosular (Ca
3
Al
2
Si
3
O
12
) v pyrop (Mg
3
Al
2
Si
3
O
12
).
C hai trng hp CaMg
1
v CaFe
1
u c min gin on, nhng trong dung dch
cng th nht min gin on rng hn so vi trng hp th hai: v kch thc th calci
v st gn nhau hn so vi calci v magnesi.
Mt vect trao i khc cng bc l solvus l Fe
3+
Al
1
. C ch thay th ny thc hin
trong cp granat grosularandradit; granat vi thnh phn ny thng c lp lnh ng sc
v/hay d hng v tnh cht quang hc. Nguyn nhn l s phn r (xem di) dung
dch cng (Hira v Nakazawa, 1986). Epidot cng thuc vect thay th ny v cng cha
min gin on vng nhit thp. Min gin on cn ph bin trong nhiu cp thay
th khc. Thng gp nht l trao i kiu plagioclas NaSiCa
1
Al
1
vi vi ba min gin
on.
Bng 5.1.
Bng lit k nhng vect trao i ph bin trong khong vt to
Vect trao i Khong vt tiu biu V d Ghi ch
KNa
1
Feldspat, feldspathoid,
mica, amphibol
KAlSi
3
O
8

NaAlSi
3
O
8
Orthoclasalbit
Mi nhm khong u
c min gin on.
FeMg
1
Olivin, pyroxen,
amphibol, mica, talc,
granat, chlorit, serpentin,
Fe
2
SiO
4
Mg
2
SiO
4
Fayalitforsterit
Rt ph bin. Gp trong
mi silicat Fe-Mg
chnh. Dung dch cng
153
Bng 5.1.
Bng lit k nhng vect trao i ph bin trong khong vt to
Vect trao i Khong vt tiu biu V d Ghi ch
staurolit, chloritoit,
cordierit, carbonat, v.v
gn nh lin tc.
FeMn
1
Ging nh ca FeMg
1
.
c bit trong granat.
Fe
3
Al
2
(SiO
4
)
3


Mn
3
Al
2
(SiO
4
)
3

AlmandinSpesartin
Rt ph bin trong
giu Mn.
Dung dch cng gn
nh lin tc.
CaMg
1

Olivin (th yu), pyroxen,
amphibol, granat,
carbonat.
Ca
3
Al
2
(SiO
4
)
3

Mg
3
Al
2
(SiO
4
)
3

GrosularPyrop
Ph bin trong hu ht
cc nhm khong. Min
gin on rng gp
trong a s nhm.
CaFe
1
Olivin (th yu),
pyroxen, amphibol,
granat, carbonat.

CaFeSi
2
O
6

Fe
2
Si
2
O
6
Hedenbergit
Ferosillit
Min gin on khng
ln nh CaMg
1
Fe
3+
Al
1
Zoisit, epidot, granat,
pyroxen, amphibol,
spinel.
Ca
2
Al
3
Si
3
O
12
OH


Ca
2
AlFe
2
Si
3
O
12
OH
Clinozoisitpistacid
Rt c th c min gin
on trong epidot,
granat, v.v
Cr
3+
Al
1
Granat, spinel
MgCr
2
O
4
MgAl
2
O
4
Cromitspinel

F(OH)
1
Cl(OH)
1
Mica, amphibol, talc,
topaz,v.v
Mg
3
Si
4
O
10
F
2

Mg
3
Si
4
O
10
F
2
(OH)
2

Fluorotalctalc
Gp trong mi trng
giu Cl, F.
Al
VI
Al
IV
Mg
1
Si
1

Thay th kiu
tschermak
Pyroxen, amphibol, mica,
talc, chlorit,
serpentin,v.v
CaAlAlSiO
6

CaMgSi
2
O
6

Al-diopsitdiopsit
Al thay th l ch yu
trong hu ht silicat. C
l khng lin tc.
NaAl
IV

1
Si
1

Thay th kiu
edenit
Amphibol, mica.
NaCa
2
Mg
5
AlSi
7
O
22
Ca
2
Mg
5
AlSi
8
O
22
Edenittremolit.
Kim loi kim thay th
trong amphibol hay
mica.
NaSiCa
1
Al
1
IV

Thay th kiu
plagioclas
Plagioclas, pyroxen,
amphibol, jadeit.
NaAlSi
3
O
8

CaAl
2
Si
2
O
8

Albitanorthit
Nhiu min gin on;
p sut cao
NaSi bn vng hn
CaAl.
NaAl
VI
Ca
1
Mg
1
Thay th kiu
jadeit hay
glaucophan
Pyroxen, amphibol.
NaAlSi
2
O
6

CaMgSi
2
O
6
Jadeitdiopsit
Khng lin tc. NaAl bn
vng p sut cao.
TiAl
2
Mg
1
Si
2

Thay th kiu
titan-tschermak
Pyroxen, mica,
amphibol, v.v
CaTiAl
2
O
6

CaMgSi
2
O
6

Ti-tschermakdiopsit
Thay th titan trong
silicat.
TiFe
2+
Fe
3+
2
Oxit, amphibol, mica,
v.v
FeTiO
3
Fe
2
O
3

Ilmenithematit
S thay th titan trong
oxit
Ghi ch : S La M ch s phi tr ca ion ng trc n.
trng ti v tr tinh th hc, s ni thm di.
154
y cng l s thay th gia jadeit v Ca-tschermak trong pyroxen, glaucophan v
tschermakit trong amphibol, cng nh paragonit v margarit trong mica. Mi nhm khong
vt ny u cho thy nhng min gin on dc vect ny. y l kiu trao i c ngha,
bi v ni chung, NaSi thng thay th CaAl khi p sut tng. Mt cp thay th quan trng
khc l ca kiu tschermak (Al
VI
Al
IV
Mg
1
Si
1
) v phin bn ca n (Al
VI
Al
IV
Fe
1
Si
1
).
Qu trnh thay th ny xy ra trong nhiu silicat, nh pyroxen, amphibol, mica, chlorit,
serpentin v cordierit.
Thay th kiu edenit NaAl
IV

1
Si
1
c mt trng. Amphibol v mica u c th c
trng ti v tr ca nguyn t kim loi kim; vy khong vt ca c hai nhm u c kiu
thay th ny. Mc du vy, s thay th vi trng c th cho thy mt khong vt bt k.
Trong amphibol v mica, min gin on thng thy dc vect thay th kiu edenit.
Chng hn, gia actinolit v edenit, muscovit (hay paragonit) v pyrophyllit, cng nh
gia biotit (hay Na-phlogopit) v talc. Trong Caamphibol, thay th kiu edenit thng kt
hp vi thay th kiu tschermak t s khong 1 : 1 (mc du t s ny thay i tu thuc
loi v mi trng PT) cho vect thay th kiu pargasit
NaAl
IV

1
Si
1
+ Al
VI
Al
IV
Mg
1
Si
1
= NaAl
VI
Al
IV
2

1
Mg
1
Si
2

Bnh thng, amphibolit p sut trung bnh (80 90% tnh a dng ho hc ca Ca-
amphibol) l nm gia actinolit v hornblend dc vect thay th kiu pargasit (hay phin
bn Fe ca n l NaAl
VI
Al
IV

1
Fe
1
Si
2
).
Bng 5.1 c hai vect thay th: kiu titantschermak
TiAl
IV
2
Mg
1
Si
2
v TiFe
2+
Fe
3+
2
. Titan him khi c nhiu trong silicat (mc du, n l
nguyn t ch yu trong cc oxit nh rutil v ilmenit); tuy vy, n l nguyn t quan trng:
lng titan thay th d dng bin i theo nhit . Nhiu cng trnh nghin cu thc a
v trong phng th nghim u chng t mi tng quan trong amphibol, mica v
pyroxen. Hiu ng ny s c p dng lm a nhit k. TiFe
2+
Fe
3+
2
l vect gia
ilmenit v hematit v xy ra trong oxit. Nhng kh nng khc cho s thay th titan c th
l c ch Ti trng bt din: TiMg
2
quan st c trong mica, v TiAl
1
(OH/F)
1

trong titannit (sphen).
Mt vect quan trng khc l thay th kiu glaucophan hay jadeit: NaAl
VI
Ca
1
Mg
1
.
S thay th ny xy ra gia diopsit v jadeit trong pyroxen v gia tremolit v glaucophan
trong amphibol. y l s thay th rt quan trng, n din bin cng vi s gia tng ca p
sut, bi v glaucophan v jadeit u l nhng khong vt p sut cao. Vect thay th ny
cha mt hay hai min gin on trong c hai nhm pyroxen v amphibol. N c th suy ra
t 2 vect thay th kiu plagioclas v kiu tschermak:
NaAl
VI
Ca
1
Mg
1
= NaSiCa
1
Al
1
Al
VI
Al
IV
Mg
1
Si
1

Khi nim ng hnh khng tch khi hai khi nim khc: ng cu trc v dung dch
cng.
5.2.2 ng cu trc
155
Nhng tinh th gi l ng cu trc hay cng loi cu trc, khi cc nguyn t thnh
phn chim nhng v tr tinh th hc tng t trong mng ca chng, bt k bn knh
nguyn t hay dng lin kt trong mng khc nhau nh th no. Kch thc tng i ca
nguyn t cc loi trong hp cht l yu t quan trng hng u i vi phi tr ca chng
v do loi cu trc. Chng hn, tt c cc tinh th thuc nhm khng gian Fm3m, trong
nguyn t cc loi vi cng phi tr 6 v u c cng s lng trong cng thc, th u
thuc loi cu trc halit NaCl. Mt lot khong vt thnh phn khc nhau nh sylvin KCl,
periclas MgO, bunsenit NiO, galen PbS, alabandit MnS, chlorargyrit AgCl v osbornit TiN
u chung loi cu trc ny.
Hai khong vt stishovit SiO
2
(bin th a hnh p sut cao ca silica)

v rutil TiO
2
cng ng cu trc, c cng nhm khng gian P4
2
/mnm v cation trong c 2 khong vt
(Si
4+
hay Ti
4+
) u c phi tr bt din. Trong mi bin th bit ca silica (k c thch
anh), cng nh tt c cc silicat trong v Tri t, silic u c phi tr t din.
5.2.3 Dung dch cng
Dung dch cng l mt cu trc khong vt trong mt v tr (h im quy tc) b
chim bi hai hay nhiu nguyn t (hay nhm nguyn t) ho hc khc nhau nhng t
lng thay i. S thay th ng hnh trong cu trc tinh th ph thuc nhng yu t sau:
Kch thc so snh ca cc ion, nguyn t thay th nhau. Ni chung, s chnh
lch v kch thc gia cc ion hay nguyn t nh hn 15% m bo kh nng
thay th rng ln. Nu bn knh ca hai nguyn t khc nhau t 15 n 30%, th
s thay th s hn ch v him c; nu s chnh lch vt 30% th s thay th
ng hnh gn nh khng xy ra.
in tch cc ion thay th nhau. Nu in tch nh nhau, Mg
2+
v Fe
2+
chng
hn, th khi xy ra thay th cu trc vn trung ho in tch. Nu cc ion khng
cng ho tr, nh trng hp Al
3+
thay th Si
4+
, mt s thay th b sung s phi
xy ra trong cu trc nhm duy tr trung ho cho in tch tng.
Nhit khi xy ra thay th ng hnh. Nhit tng cao lm cho dao ng
nhit ca cu trc tr nn mnh m hn, v tr nguyn t cng tr nn rng m
hn, dung sai s ln hn i vi s thay th ng hnh. Vy, nhit cao c
th mong i mt thnh phn ho hc a dng hn cho cu trc so vi khi
nhit thp.
Di y, hy cp n cc loi dung dch cng.
a) Dung dch cng thay th
S thay th cation cation hoc anion anion l thay th n gin nht. Trong mt
hp cht ion dng A
+
X

, A
+
c th b thay th tng phn hay ton b bi B
+
m ho tr
khng thay i. Chng hn, Rb
+
nm ti v tr ca K
+
trong KCl hoc biotit. Anion Y

c
th th chn mt phn hay tt c X

trong AX. Chng hn, Br



c mt trong cu trc KCl,
ti ch ca Cl

. Trong dy lin tc ca cc dung dch cng olivin (Mg,Fe)


2
[SiO
4
],

Mg
2+
c
th b thay th tng phn hay ton b bi Fe
2+
. Cc thnh phn u v cui ca dy ny l
forsterit Mg
2
[SiO
4
] v fayalit Fe
2
[SiO
4
]. Mt th d khc l dung dch cng (Mn,Fe)[CO
3
]
nm gia hai khong vt rhodochlrosit Mn[CO
3
] v siderit Fe[CO
3
]. Chui thay th lin
156
tc ca anion nm gia hai hp cht KCl v KBr l th d khc v dung dch cng. Kch
thc ca chng thay i trong khong 10% cho php hai anion thay th lin tc t Cl

sang Br

v ngc li.
Nu trong cng thc tng A
2+
X
2
cation B
3+
thay th cho A
2+
th mt trong nhng gii
php nhm duy tr in tch tng l cation C
+
cng i vi B
3+
: 2A
2+
= 1B
3+
+1C
+
. S thay
th kp loi ny th hin trong cu trc ca saphir; Fe
2+
v Ti
4+
th chn 2Al
3+
trong
corindon -Al
2
O
3
. Dy dung dch cng plagioclas nm gia hai thnh phn u cui l
albit Na[AlSi
3
O
8
] v anorthit Ca[Al
2
Si
2
O
8
] th hin bng thay th kp sau: Na
1+
Si
4+
=
Ca
2+
Al
3+
.
Ca
2+
thay th Na
+
trong cu trc plagioclas, Si
4+
s b Al
3+
th chn trong khung Si
O. ng thc cho thy in tch tng ca c hai v u nh nhau; chng t cu trc vn
trung ho. Mt th d v thay th kp hu hn l dung dch cng ca hai pyroxen, diopsit
CaMgSi
2
O
6
v jadeit NaAlSi
2
O
6
. ng thc thay th kp vit nh sau: Ca
2+
Mg
2+
=Na
+
Al
3+
.
b) Dung dch cng xen k
Khc vi dung dch cng thay th, trong cu trc ca dung dch cng xen k nguyn t
ca nguyn t ny khng thay th nguyn t thuc nguyn t kia, m phn b khong
khng gian gia chng. Tiu biu ca dung dch cng loi ny l tinh th thp dung dch
ca carbon trong st. Khi C ho tan trong -Fe vi cu trc xp cu lp phng, th dung
dch nhn c l thp austenit. Trong qu trnh ti, nhit h chm ti 700C n chuyn
thnh pha pelit l hn hp ca ferit v cementit. Ferit l dung dch cng xen k ca C trong
-Fe v -Fe vi hm lng carbon ti a 0,06%. Cn cementit l hp cht ho hc ca
st v carbon, Fe
3
C. Nu tr hon qu trnh chuyn pha ca austenit n 150C th nhit
ny qu trnh din bin theo hng khc. Loi thp cng hnh thnh y l martensit.
Pha ny l dung dch qu bo ho ca C trong -Fe vi 1,6% C; tinh th thuc h bn
phng vi t s c/a = 1,07.
Trong v d trn, dung dch khng cha nhiu phi kim trong cu trc kim loi. Nhiu
trng hp, nguyn t ho tan nm ti khoang trng loi no ca lut xp cu (thng
cht nht) ca nguyn t kim loi. Lc ny, tng quan gia cc nguyn t thnh phn th
hin bng t lng n gin; theo c im cu trc, pha tinh th ny khng khc hp cht
ho hc thng thng. Chng c gi l cu trc xen k. Trong ScN chng hn, nguyn
t kim loi phn b theo lut xp cu lp phng, nguyn t phi kim nm ti khoang bt
din ging loi cu trc halit. Do nh hng ca nguyn t phi kim khch trong cu trc
xen k, kim loi ch i khi phi thay i cu trc c th. Kim loi tantal chng hn, n
vn kt tinh theo mng lp phng tm khi; nhng trong cu trc xen k TaC, s c mt
ca nguyn t carbon lm cho nguyn t tantal thay i cch phn b; chuyn sang lut
xp cu lp phng tm mt. Phi chng y l trng hp c o ca a hnh.
i khi, khoang trng gia cc nguyn t kim loi li do nhm nguyn t phi kim
chim. Cu trc xen k ca trng hp ny tng ng vi thnh phn MeX
2
, v d: LaC
2
,
ThC
2
, ZrH
2
, v.v ng nhin, trong nhng cu trc cng thnh phn, nu ht thy
khoang t din u b chim th loi cu trc s i khc; l CaF
2
m khng phi NaCl.
Dung dch cng xen k khng ch gp kim loi. Trong s hp cht v c c th ly
dung dch ca Na trong oxit volfram. WO
3
gn ging perovskit CaTiO
3
v cu trc.
Nguyn t oxy ca hai cht u phn b nh nhau, volfram phn b nh Ti. Ring v tr
157
ca Ca trong CaTiO
3
b trng trng hp oxit volfram. Nguyn t Na kim loi thm
nhp vo ch trng ny; nu chng chim ht cc v tr y, dung dch c thnh phn
NaWO
3
v tr thnh mt hp cht ho hc ging CaTiO
3
. Trong nhng trng hp trung
gian, khi Na chim tng phn cc v tr y, dung dch nhn c s l nhng pha vi thnh
phn bin i; theo , ho tr ca volfram bin i theo, tng phn tng ng ca nguyn
t volfram ho tr su s chuyn sang ho tr nm.
Nh vy, cng vi s hnh thnh cc dung dch cng xen k ny, c th xut hin s
chuyn di lin tc ( trng dn dn b lp cho n ht) ca cu trc t loi ny (WO
3
)
sang loi khc (CaTiO
3
). cng l s chuyn di lin tc v thnh phn gia hai hp
cht ho hc. y l hin tng mi trong ho hc, m bn cht ca n ch tr nn sng t
nh s pht trin ca ho hc tinh th. K h gia cc nguyn t, ion thc s l nhng ch
trng trong cu trc. Khi chng b lp bng nhng ion v nguyn t khc th pha kt tinh
mi s ra i; l dung dch cng xen k.
Trong mt s cu trc, nh beryl Be
3
Al
2
[Si
6
O
18
], ch trng ny rng m thnh dng
ng, do cc nhm chc vng su [Si
6
O
18
] chng ln nhau to nn. Cc kt qu nghin cu
beryl chng t mt lng ng k ca K
+
, Rb
+
, Cs
+,
H
2
O v CO
2
trong knh dng ng lc
gic y. Phn t H
2
O v CO
2
gn vi cc nguyn t oxy bn trong vng su bng lin kt
yu. Cc ion c ln, ho tr mt ca kim loi kim R
+
, nh kali, rubidi, cesi cng nm
trong , nhng chng c gn kt vng chc hn nhiu. l do c ch thay th kp
sau y: Si
4+
= Be
2+
+ 2R
+
v Si
4+
= Al
3+
+ R
+
. Theo ng thc u, hai cation kim loi
kim ho tr mt vo trong vng su; cn trong ng thc sau, ch mt cation R
+
ti .
Dung dch cng loi ny cn bt gp trong nhm zeolit. Nhm khong vt ny thuc
ph lp silicat khung, trong cc t din (SiO
4
) v (AlO
4
) kt thnh khung. Trong khung
y, nhng hang rng v nhng knh di c ng knh t 2 n 7. Chng m ng cho
s thm nhp d dng vo trong tinh th, v chng cng cha c phn t nc. Nh lin
kt hydro, cc phn t ny gn vi khung AlSi. Nhit tng nh cng y chng
khi v tr xen k m khng gy bin dng khung silicat. Khi c sn nc v nhit cho
php, zeolit li nhim cc phn t nc vo khe h m t chng ra i.
Sau cht, hy ni i iu v s khc nhau gia dung dch cng thay th v dung dch
cng xen k. Nu dung dch loi mt khng th phn bit dung mi v cht ho tan (nu
c th ni nh vy), th trong loi hai hai khi nim ny gi nguyn gi tr. Ti th d v
zeolit nhim nc nhng lng thay i th, mt iu tng nh nghch l, nc khng
ng vai dung mi, m tr thnh cht ho tan. S khc nhau th hai l ch cht ch v
cht thay th phi cng chung dng lin kt trong dung dch cng thay th; cn trong dung
dch cng xen k dng lin kt ca hai thnh t c th hon ton khc nhau.
c) Dung dch cng khuyt tt
Dung dch cng khuyt tt hnh thnh khi mt cation ho tr cao vo thay cho nhiu
cation ho tr thp hn nhm gi cn bng in tch. S thay th ny ch xy ra trong mt
v tr nguyn t, cc v tr khc b b trng. V d, khi Pb
2+
vo thay cho K
+
trong
amazonit, bin th xanh tri pht lc ca microclin K[AlSi
3
O
8
] ny phi y hai cation kali
i do nhu cu cn bng ho tr: K
+
+ K
+
= Pb
2+
+ , to nn mt nt trng, c th l mt
tm mu, trong mng tinh th.
Trong thc t, nhiu hp cht khng tun theo mt t lng thnh phn xc nh. t
lu, pyrrhotin c gi nh l cha d mt lng nguyn t lu hunh so vi t lng 1 :
158
1. Gii ho hc tng a ra nhiu cng thc nh Fe
6
S
7
hay Fe
n
O
n +1
nhm nhn mnh iu
d thng ny. Phng php Roentgen tinh th hc cho thy trong khong vt pyrrhotin,
nguyn t lu hunh phn b theo lut xp cu su phng, nguyn t st c phi tr su
vi lu hunh. Nu mi khoang bt din u b chim, th cng thc ca pyrrhotin l
FeS (loi cu trc NiAs). Nhng v tr trong khoang bt din b khuyt mt phn, thnh ra
cng thc ca khong vt vit thnh Fe
1X
S,vi x bin thin t 0 n 0,2.
Khong vt nh pyrrhotin l dung dch khuyt tt, bi v trong cu trc ca n mt h
im quy tc khng c chim ht. Khi Fe
2+
thiu vng trong mt s khoang bt din, m
mng lu hunh vn nguyn vn, cu trc s khng trung ho in. Rt c th, trong s ion
st c mt s c ho tr ba b p s thiu ht in tch. Nu qu vy, cng thc ca
pyrrhotin trung ho in tch vit thnh: Fe
2+
13X
Fe
3+
2X

X
S; trong l v tr ca
cation b b trng. Nu x bng 0,1 th ng vi 0,1 ch trng s c 0,7 Fe
2+
v 0,2 Fe
3+
trong
cu trc ca pyrrhotin. Ni cch khc, st ba thm nhp cu trc bng s thay th nh sau:
Fe
2+
+ Fe
2+
+ Fe
2+
=

Fe
3+
+ Fe
3+
+ .
Mt th d khc ca dung dch cng khuyt tt l maghemit -Fe
2
O
3
, mt sn phm
oxy ho ca magnetit Fe
3
O
4
(Fe
2+
Fe
3+
2
O
4
). Maghemit cng l spinel thiu st, trong v
tr t din v bt din ca cation b thiu ht ng k. Thnh phn ca khong vt th hin
bng cng thc sau: Fe
3+
Fe
3+
1,67

0,33
O
4
, trong cho thy s thiu ht st ho tr ba.
T thay th ng hnh
Khuyt tt v cu trc khuyt tt khng ch bc l nhng khong trng vng nguyn
t ngay ti v tr dnh cho chng. Hy xem xt cu trc cc hp cht spinel MgAl
2
O
4
lm
th d. Mt nghch l trong cu trc ca chng l ch bt din l khoang trng ln th
cha ion c nh (bn knh ca Al
3+
0,57 so vi ca Mg
2+
0,74); khoang trng t din
nh li cha Mg ln. Trong Ga-spinel MgGa
2
O
4
(r
Ga
= 0,62), mt s (c th ti 50%)
nguyn t gali ri v tr bt din, ti nm trong khoang t din cng vi magnesi. Ti y,
ion thuc hai nguyn t chim khoang t din theo quy lut ngu nhin, hon ton ging
nh cc nguyn t th chn nhau trong cu trc ca dung dch cng thay th. Theo thnh
phn ho hc th nhng pha ny thc s l nhng hp cht ho hc, cn v cu trc chng
li ging nh dung dch cng thay th. C th gi chng l dung dch cng t thay th hay
cht t ng hnh (xem thm 6.13.6).
5.2.4 S phn r ca dung dch cng
Trong s hnh thnh dung dch cng nu c s thay th gia hai nguyn t (hay ion)
vi kch thc chnh lch nhau nhiu, th iu ny ch xy ra mc hn ch. Tuy nhin,
nhit cao lm cho cu trc gin n, nguyn t dao ng vi bin ln hn; cc v tr
ca nguyn t vn khng ging nhau, nay tr nn bt phn bit hn. Kt qu, s thay th
gia cc ion ny tr nn bt kh khn, trong nguyn t khc loi hon v nhau theo
cch ngu nhin.
Dung lng bnh qun ca mi v tr tr nn ng u (hnh 5.2,a). Mt minh chng
ca s thay th ny l gia Na
+
v K
+
trong feldspat (bn knh ion ln lt bng 1,18 v
1,51, cng c s phi tr 8). iu kin nhit thp khng thun li cho chng thay th
ng hnh; ch cho dung dch cng hn ch K-Na-feldspat nm gia hai cc albit v
orthoclas (hnh 5.3). Nhng nhit khong 1000C, chnh lot silicat ny l pha dung
159
dch cng gia hai pha u v cui: Na[AlSi
3
O
8
] v K[AlSi
3
O
8
]. Khong vt nhit cao
ny vn ng nht, nhng v cha cc cation khc bit nhau v kch thc, nn khi lm
vo iu kin nhit thp n s tr nn khng bn vng v b phn r (hnh 5.2,b).

y l qu trnh xy n vi mt dung dch cng; khin n b tch ra thnh hai (hoc
c th nhiu hn) pha rn khc nhau; mc du khng c vt liu mang n hoc mang i.
Ni cch khc, khng c s bin ng v thnh phn trong h.
Di knh hin vi in t phn gii cao c th quan st cc phin dy c 1m ca
amphibol, cc phin tch t khong vt ch u c cng mt hng tinh th hc. Phin
hornblend u song song vi (001) trn nn khong vt ch grunerit, phin grunerit tch ra
t pha ch hornblend th theo hng (100). Trong feldspat kim c th quan st hin tng
phn r dung dch cng bng mt thng: phin feldspat giu natri gn song song vi
(100) trong khong vt ch feldspat kali. S mc xen mang tn perthit ny cn bt gp
thang nh hn, phi dng n knh hin vi thm ch k thut nhiu x Roentgen mi
pht hin c.
Loi mc xen c quy lut sinh ra do phn r dung dch cng ny bt gp trong nhiu
h khong vt: felspat kim, amphibol, pyroxen v oxit st.
Xut x ca kin trc (mc xen) phn r thy r trn gin TX hnh 5.4,a). Trc
honh l s bin thin thnh phn (phn trm phn t) gia hai silicat ng cu trc.
A[Si
X
O
Y
]

v B[Si
X
O
Y
] thuc nhm pyroxen/amphibol mt nghing. Kch thc ion ca A
v B chnh lch khong 25%. S liu phn tch ho hc i vi 2 pha nhit thp ny
cho thy tn ti gia chng l dung dch cng hn ch. iu ny ch th trc thnh phn
ng vi nhit thp T
4
.
160
Dung dch cng gia hai khong vt thnh to nhit T
1
. Ti vng nhit thp
hn c mt min solvus, cc mi tn dc ng bin cho thy s thay i v thnh phn
ca khong vt ng sinh khi nhit h thp. Hnh 5.4,b l s lt mng cc pha kt
tinh (vi thnh phn X
i
) vi mt trnh t xut hin. Ln lt t trn xung, trc ht l pha
ng nht, dung dch cng hnh thnh nhit T
1
. Sau l ht cha cc phin li khai
song song vi (001) sinh ra nhit T
2
. Di cng, ngoi cc phin th hn dc (001),
trn ht khong vt mt lot phin song song vi (100) xut hin nhit T
4
.

Hai silicat gi nh ny c th bt gp trong basalt. Lot dung dch cng lin tc c
th thy trong vi thnh phn tng t v bn vng nhit T
1
. Vng nm gia T
1
v
T
4
ca gin trng thi cho thy min solvus. l trng TX trong s ho tan gia
hai cu t gim u t nhit cao xung nhit thp. Mi thnh phn nm trong min
ng vi hai pha cng tn ti, thay cho mt pha ng nht pha trn min.
Hy ly thnh phn X
1
lm v d. Ti vng pha trn min solvus, nhit T
1
, cu
trc silicat cn trng thi nng lng cao cho php ion A v B (d kch thc chnh lch
ti 25%) phn b trong cng h im quy tc mt cch ngu nhin. Thnh phn ny c
lm ngui rt chm, khi t nhit T
2
th cu trc khng cn d dng cho php cation A
v B phn b hon ton ngu nhin c na. Nhng ng sut xut hin trong cu trc, do
chnh lch kch thc ca cation, gy nn s khuch tn ca ion A

sn sinh ra nhng
min silicat giu A

. S khuch tn ng thi ca ion B



cng lm xut hin nhng min
giu B

trong cu trc (xem li hnh 5.2,b).


Ti y bt u qu trnh phn r dung dch cng: mt khong vt vn ng nht phn li
thnh hai khong vt khc nhau v ho hc. T T
2
nhit tip tc h gim th min gin
on m rng ra. Di iu kin cn bng, cc tm mc xen do phn li s c thnh phn
ng vi im dc ng bin ca min gin on. Cp im ny ni vi nhau bng ng
ngang cho thy chng cng tn ti. Ti nhit thp nht T
4
, c th thy cc tm
(A,B)[Si
X
O
Y
]

vi thnh phn X
2,
nh hng ng lut tinh th hc (hnh 5.4,b), mc xen
161
trong khong vt ch (B,A)[Si
X
O
Y
] vi thnh phn X
3
. Mc du s phn li ion bn trong
cu trc silicat bt u T
2
l qu trnh phc tp thang nguyn t, n pht sinh ch
yu do cu trc khng nng lc vt qua s khc bit v kch thc ion. Nhit h
lm cho nng lng ca cu trc gim theo.

Hnh 5.4.
Gin T X ca pyroxen/amphibol
Qu trnh phn r dung dch cng l s khuch tn nguyn t xy ra trng thi rn.
Nhit tng (ng nng cng tng theo) lm cho nguyn t dao ng nhiu hn v tng
thm c hi cho chng bt khi nguyn t vy quanh, di chuyn ti v tr mi. Nh vy,
tc khuch tn ph thuc nhiu vo nhit . Khi nhit h xung, s lu ng ca
nguyn t tr nn hn ch; thnh ra qu trnh khng th t n pha cui vi thnh phn
tinh khit. Kch thc cc tm mc xen c th bin ng theo nhiu thang , nh ni
trn, v ph thuc vo tc h nhit ca h thng. Nhit h chm th thi gian dnh
cho nguyn t khuch tn cng c nhiu; kin trc mc xen phn r s c ht th hn.
Nhng ngui nhanh c th bo tn c kin trc ng nht nhit cao ca chng,
mc d l trng thi gi bn. Nu nhit h vi tc trung bnh, kin trc phn r
dung dch cng pht trin c th l cc tm mc xen vi tinh.
5.3 A HNH
a hnh l nng lc ca mt hp cht ho hc kt tinh theo nhiu loi cu trc (tu
thuc s thay i nhit v p sut). Nhng cu trc khc nhau ca mt nguyn t ho
hc hay mt hp cht ho hc gi l cc bin th a hnh.
5.3.1 Mt s bin th a hnh
Bng 5.2 lit k cc bin th a hnh ca khong vt. Hnh 5.5 gii thiu cu trc tinh
th ca ba trong s cc bin th a hnh thuc silica (SiO
2
), hnh 5.6 biu trng thi PT
162
vi cc trng bn vng ca khong vt a hnh SiO
2
. Nu mt cht ho hc c th c
nhng cu trc tinh th khc nhau, th l v cc cu trc y khc nhau v ni nng E.
Ph bin nht trong bin cht l thch anh. Trong iu kin bnh thng ca v Tri
t, thch anh thng tri qua s bin i pha: gia -thch anh (nhit thp) v -thch
anh (nhit cao). Tt c thch anh tn ti iu kin nhit v p sut ca kh quyn
u l -thch anh, sn phm bin i a hnh ca -thch anh do s h gim nhit
(xung thp hn 537C, p sut kh quyn), phn ng xy ra cng vi s thay i gc ho
tr SiOSi, nhanh chng v c th o ngc. Phn ng loi ny khng i hi ph b cu
trc cng cc mi lin kt, khng cn n s thay i ln v ni nng.




Hnh 5.5.
Cu trc tinh th ca cc bin th a hnh SiO
2
chiu trn mt (0001)
a) Tridymit; b) Thch anh nhit cao; c) Thch anh nhit thp
Bng 5.2.
Mt s khong vt a hnh tiu biu
Thnh phn Tn khong vt
H v nhm khng
gian
cng T trng
Kim cng Lp phng Fd3m 10 3,52
C
Graphit Su phng P6
3
/mmc 1 2,23
Pyrit Lp phng Pa3 6 5,02
FeS
2
Marcasit Trc thoi Pnnm 6 4,89
Calcit
Su phng R c
3 2,71
CaCO
3
Aragonit Trc thoi Pnam 3,5 2,94
-thch anh Su phng P3
1
21 7 2,65 SiO
2
-thch anh Su phng P6
2
22 2,53
163
Tridymit Su phng P6
3
/mmc 7 2,20
Cristobalit Lp phng Pd3m 6,5 2,20
Coesit Mt nghing C2/c 7,5 3,01
Stishovit Bn phng P4
2
/mnm 4,3


Hnh 5.6.
Biu trng thi P-T ca cc bin th a hnh SiO
2
p sut o bng kilobar = 1000 bar; 1 bar = 0.987 at (Theo Cornelis K.v
nnk,1993)
Cristobalit v tridymit hnh thnh trong iu kin nhit cao v p sut tng i
thp, nh trong dng dung nham giu SiO
2
. Theo bng 5.2, t trng ca chng u t gi
tr thp nht (2,20) trong s cc bin th ca SiO
2
. Mt khc, cristobalit v tridymit u l
nhng bin th gi bn trong iu kin kh quyn. C hai khong vt u phong ph trong
dung nham lc nguyn c. Nhng chng c y cho thy rng, phi cn n mt nng lng
phn ng cao c th bin i mng tinh th ca cristobalit (hay tridymit) sang trt t ni
ti kiu thch anh nhit thp.
Coesit v stishovit bn vng p sut cao n rt cao (xem biu PT, hnh 5.6),
thng bt gp ti cc h thin thch. Coesit tn ti di dng bao th trong granat v cc
khong vt eclogit vng Alp (Chopin v nnk, 1991). Chng cng c t trng cao v rt cao,
nu so snh vi cc bin th SiO
2
khc. Vi phi tr cao d thng ca silic, stishovit c
coi nh sn phm ca phn ng nng lng cao ca s bin i t cu trc vi phi tr t
din v vi dng lin kt cng ho tr l chnh sang cu trc vi phi tr bt din ca silic
v vi dng lin kt mang bn cht ion. Nhng khc nhau gia cc bin th ca FeS
2
, ca
C v ca CaCO
3
(bng 5.2) cng chng t rng s chuyn i a hnh y l nhng bin
164
ng ln lao vi s ph b cu trc c, hnh thnh mng tinh th mi. y l phn ng
nng lng cao, xy ra chm v khng th o ngc.


5.3.2 Trt t khng trt t
a hnh lin quan vi bin i trt t khng trt t thng quan st thy trong hp
kim v trong khong vt. Trt t hon ho ch gp im khng tuyt i (0K tng
ng 273,15C). trng thi ny cc nguyn t trong cu trc sp t trn v tr tinh th
hc ring, tc l ti h im quy tc xc nh. Nhit tng ko theo dao ng nhit ca
ht trong cu trc, trt t hon ho b ri lon; cho n khi t n mt nhit cao no
, th s thu c trng thi hon ton ri lon, khng trt t hon ton. Gia hai thi cc
ny l cc trng thi khng xc nh, v d: feldspat kali (KAlSi
3
O
8
). Khung ca nhm
chc (AlSi
3
O
8
)

c

cu trc gm nhng vng bn t din trong Al chim (1/4) v tr
trong khoang t din ging nh ca Si; v n th chn silic trong khong vt.
Sanidin l bin th nhit cao vi nhm khng gian C2/m. Nguyn t nhm ca n
phn b ngu nhin (hon ton khng trt t) trong cu trc khung ca alumo-silicat ny.
Nh vy, Al
3+
c tn sut gp bng nhau cho c 4 t din (ca vng bn); ni cch khc,
n chia u cho 4 t din (cc hnh 6.29 v 6.30): tnh bnh qun mi t din cha 1/4 ion
nhm. Vng bn s c i xng ring l 2/m. Vi trt t thp nht, cng thc ho tinh
th ca sanidin vit thnh:
K[(Al,Si)
4
O
8
]
Microclin l bin th nhit thp ca K-feldspat. Vi nhm khng gian C1 bin th
ny c trt t cao nht. Mi ion nhm phn b (mt Al
3+
/vng bn) ti mt t din xc
nh ca vng bn, 3 t din cn li l ca silic. Vng ny khng cn gi c i xng
c v cng thc ho tinh th vit nh sau:
K[AlSi
3
O
8
]
Orthoclas l bin th trung gian. N cng chim v tr trung gian c v trt t. Ion
nhm ch phn b ti 2/4 t din ca vng bn, mi ion nhm chia u cho 2 t din ny.
i xng ca vng bn ch cn l trc xoay bc hai. Bin th ny c cng thc ho tinh
th:
K[(Al,Si)
2
Si
2
O
8
]
5.3.3 a dng
a dng

(politypism) l trng hp ring ca a hnh, p dng i vi tng bin th


a hnh (vn ch mt thnh phn ho hc); trt t nguyn t ca bin th ch duy tr theo
hai chiu khng gian, tc l theo tng lp. Cc cu trc ca bin th y ch khc nhau cch
phn b cc lp, tc l gi tr thng s ca chui thng gc vi mt lp.

Tham kho v d hnh 6.27 v ch gii i km.


165
Carbur silic SiC, vurtzit ZnS, mica v cc silicat lp u c hin tng a dng. Ring
v vurtzit, mt trong hai bin th a hnh ca sulfur km, c nguyn t lu hunh xp theo
lut xp cu su phng ABABAB (trong khi , bin th a hnh th hai sphalerit c
nguyn t lu hunh xp theo lut lp phng, tc l ABCABC). Loi cu trc vi
kch thc c ca c s ca cc dng vurtzit lit k nh sau:
Loi cu trc Thng s c, Loi cu trc Thng s c,
4H 12,46 6H 18,73
8H 24,96 10H 31,20
(H : H su phng)
B dy ca cc lp c s ny l 3,12 . Bng lit k cho thy ln ca cc thng s
c u l bi ca gi tr ny.
Cu trc ca mica v silicat lp khc u bao gm cc lp c s TO hoc TOT vi i
xng ring thuc h mt nghing (T l l t din silicoxy, O l l bt din kiu brucit
Mg(OH)
2
hay gibbsit Al(OH)
3
). Cc lp ny xp song song trong silicat theo cc trt t
khc nhau. i xng ca vng su quanh nhm OH l su phng; nhng khi cc lp c
s xp chng ln nhau, cc vng su ny khng i din nhau, m lch nhau, trt tng
i mt vect vi ln n nh l a/3 (a l thng s mng) theo ba phng cch nhau
120. Mi phng c cp vect ngc nhau.
Mt s loi cu trc ca mica c gii trnh di y.
a) Nu cc lp lch nhau lun theo mt chiu, tc l trt theo 1 vect [1], cu trc
nhn c s gi nguyn cu trc mt nghing vi nhm khng gian C2/m : loi cu trc
1M.
b) Nu cc lp lch nhau theo 2 vect ngc nhau [1,I] th loi cu trc l 2O thuc h
trc thoi vi nhm khng gian Ccm2
1
.
c) Nu cc lp lch nhau theo hai vect cch nhau 120, chng hn [1,2] th l cu
trc vi i xng mt nghing C2/c, l loi cu trc 2M
1.

d) Khi lp c s trch nhau theo c ba vect, nh [1,2,3], s c loi cu trc 3T, vi
nhm khng gian P3
1
12 hay P3
2
12.
Cc loi cu trc mica ph bin nht l 1M (2/m), 2M
1
(C2/c) v 3T (P3
1
12) (hnh 6.27).
5.3.4 Metamict
Khong vt gi l metamict khi cu trc tinh th b phn hu mc khc nhau,
mc du nhiu khi n vn cn gi c hnh dng a din ca n. Tt c cc khong vt
metamict u cha trong cu trc nguyn thu ca n nhng nguyn t phng x, nh uran
v thori, ngun pht sinh bc x alpha gy phn hu i vi khong vt ch. Nguyn t
phng x c th loi b hon ton trt t tun hon quanh n. Tuy vy, hin tng ny c
phn kh hiu bi v mt s khong vt cha nguyn t phng x cha ti 0,5% vn b
metamict ho. Trong khi nhiu c th khc cha nguyn t phng x nhiu hn li duy tr
c trng thi kt tinh.
Qu trnh metamict ho din ra theo giai on. Mc phn hu cu trc khong vt
c th ghi nhn, khi p dng phi hp cc phng php nhiu x tia X v hin vi in t
166
phn gii cao. Cu trc trt t cao th hin trn cc biu bng cc hiu ng r nt. Cc
giai on phn hu khc nhau phn nh qua s suy gim hiu ng nhiu x.
Khong vt cha b metamict ho c th c ct khai tt, sn phm metamict ho s
khng bc l tnh cht y, thay vo l vt v v s. Nhiu khong vt metamict c dng
a din tinh th v nh th chng cho thy dng gi hnh (xem di y). Khi nung,
khong vt metamict c th hi phc trng thi kt tinh v tng t trng ca n.
5.3.5 Khong vt khng kt tinh
Theo nh ngha, khong vt thng c trng thi trt t cao trong s phn b nguyn
t. Mc du vy, vn thng gp cc dng khong vt vi trt t thay i, mt s nh
khong vt keo v thu tinh, xp loi v nh hnh. Khong vt keo hnh thnh trong iu
kin nhit thp, p sut thp v thng trong qu trnh phong ho. V d mng , ct
trong cc hang ng. Limonit FeO.OH.nH
2
O v alophan (silicat nhm ngm nc) l
nhng khong vt v nh hnh thng gp.
Thu tinh giu silica thng c trong vt liu phun tro, chng c trt t tm gn c
trng. Mc du Si
4+
v Al
3+
trong cu trc vn duy tr phi tr t din, ging trong silicat
kt tinh.
Opal c mc v nh hnh thp hn. Thnh phn ho hc ca n c th l
SiO
2
.nH
2
O vi cha nc trung bnh khong 4 n 9% trng lng. Trn nh hin vi
in t qut opal mu trng phn cho thy n cu to t nhng ht silica ng knh xp x
3000; chng xp kht theo lut su phng ABABAB bng lin kt yu. Trong
phm vi cc ht cu y, opal duy tr c trt t sp xp cc t din SiO
2
.
5.3.6 Gi hnh
Khong vt gi l gi hnh khi n tn ti di hnh thi a din ca mt khong vt
khc. Mt bin th gi hnh c th vn bo tn hnh thi a din nguyn thu ca n, tuy
cu trc tinh th v thnh phn ho hc bn trong bin i. Bn trong a din tinh th
ca pha ny c th l thnh phn ho hc v cu trc tinh th ca pha khc. V d, pyrit
FeS
2
c th bin i n limonit FeO.OH.nH
2
O, nhng vn gi nguyn c mi nt hnh
thi ca pyrit. Khong vt ny c m t l bin th gi hnh ca limonit theo pyrit.
Gi hnh c th hnh thnh bng cc cch sau y:
a) Thay th. Trong qu trnh ny ng thi vi s chuyn i tun t ca vt liu
nguyn thu l s thay th tng ng ca vt liu mi; mc du gia chng khng xy ra
phn ng ho hc. V d, silica thay th si g cho g ho hay mc thch. Thch anh c
th thay th fluorit to v bc quanh khi lp phng fluorit.
b) Bin i. Trong s hnh thnh ca gi hnh loi ny vic vt liu c chuyn i hoc
vic vt liu mi chuyn n ch ng vai tr th yu. l do cc vt liu ny c th
khng khc nhau lm v thnh phn ho hc; ngoi ra, y c s can thip ca cc qu
trnh sn c trong iu kin kh quyn nh hydrat ho, oxy ho, v.v... Chng hn, anhydrit
CaSO
4
c th i thnh thch cao CaSO
4
.2H
2
O v galen PbS bin thnh anglesit PbSO
4
.
5.4 BIN DNG DO TRONG KHONG VT TO
167
Mng tinh th vi nguyn t sp xp u n v tun hon thc ra khng bao gi hon
ho. iu ny cng r hn i vi cc tinh th khong vt; vi t cch l sn vt ca mi
trng si ng, y bin c ca lng t. Ngay t trong qu trnh sinh thnh v pht trin,
chng lun hm cha nhng tim n; sai hng v khuyt tt thng xuyn c nguy c xut
hin. Trn y, u chng ni n cc sai hng cc loi.
Hy bt u t nhng sai hng im, phn nhiu lin quan n cu trc. Bn cnh ,
cu trc tinh th cn c sai hng im do tp cht, do nguyn t xen k. Khc vi nguyn
t ca mng, cc nguyn t xen k ny nh hng khng tt ti tnh do ca tinh th, bi
nhng hiu ng mang tnh cu trc (kch thc khc nhau) v hiu ng in (in tch
khc nhau). Ngc li, s c mt ca phn t nc trong mng tinh th thch anh chng
hn, c xu hng lm tng tnh do, bi tc dng thu phn i vi lin kt Si O.

Do hot ng trt do, trong lng tinh th c th tn ti min lch mng; ti , mng
tinh th thiu s lin tc vn c ca n vi vng xung quanh. Min ny gii hn bng vnh
ng bin khp kn (hnh 5.7) gi l ng lch mng hn hp (vung gc vi ng
lch mng hn hp ny l vect ca lch bin v cn vect song song vi n l lch xon).
Di tc dng ca ng lc trt ct n (cn gi l vect Burgers biu th bng mi tn)
mng dch chuyn v min ny m rng. Ti tt c cc im , ng lch mng hn hp
c vect lun xin gc vi n v c th phn tch thnh hai thnh phn: thnh phn lch
bin vung gc v thnh phn lch xon song song vi ng.
ln ca vect Burgers th hin mc bin dng ca mng, tng ng vi thng
s chui trong hng trt, tc l hng ca lch xon. Dc theo ng lch mng hn
hp, vect lm vi n mt gc thay i t im ny sang im khc. Nhng ln v
phng (n khng c ngha v chiu) ca n th lun khng i. Do , vect Burgers l
mt hng s ca lch mng, th hin nng lng ti thiu vn dng cho mt bc dch
chuyn (bc trt) c s ([9], Tr.283293).
Trong mi cu trc xc nh ch c mt s khng nhiu vect Burgers bn vng, n
tng ng vi thng s nh nht, hay vi lin kt ho hc mnh nht ca mng tinh th.
Cn mt trt th song song vi mt mng vi mt ht ln nht (do , n trnh ct qua
cc lin kt ho hc mnh).
Song tinh bin dng hay song tinh c hc l mt trong nhng kiu bin dng do. N
s tr nn ng quan tm khi song tinh c mt s h trt, chng hn trng hp ca
feldspat hay calcit.
Song tinh loi ny thnh to trong lng tinh th, bao gm mt khi lch mng so vi
phn cn li ca mng tinh th (mng ch); thng do khi lch mng xoay mt gc nht
nh quanh mt trc so vi mng ch. Trong hu ht trng hp, khi lch mng c th
168
sinh ra t mng ch nh mt bc (trt ct) trt ct n S song song vi mt K
1
(mt
song tinh) v dc theo hng trt
1
. Bc trt ct n S l mt hng s ca song tinh
v tnh bng biu thc S = 2tg(/2) (hnh 5.8).

Do bc trt n S, hnh cu bin thnh elipsoit v mi mt u xoay tr hai tit din
trn ca elipsoit (cng l tit din chung ca hai hnh): l mt K
1
v mt K
2.
Song tinh
cng c th hnh thnh nh bc trt n S song song vi mt trt K
2
v dc theo
hng trt
2
.

Mt s tc gi chuyn x l kha cnh tinh th hc ca song tinh xc nh
h song tinh bng 4 yu t K
1
K
2

2
. Di y, trong khi ni n cc trng hp c th,
h song tinh c s dng s gm mt song tinh K
1
, hng song tinh
1
v bc trt n
S (Klassen-Nekliudova, 1964).
Di y l s lc v bin dng trt trong mt s khong vt.
5.4.1 Olivin
mng c s : a [100] = 4,76
b [010] = 10,21
c [001] = 5,99
Vect trt ct n dc b[010] ng vi nng lng ng lc 4 ln ln hn so vi
hng a [100] hay c [001], bi v nng lng ny t l thun vi bnh phng ln ca
vect.
Cu trc tinh th ca olivin ly lut xp cu hai lp ca anion oxy lm c s. Mt
(0001) ca n ng vi (100) ca mng trc thoi (theo Poirier, 1975). Ngoi (100), mt
mng dy c nht (c th l mt trt) l (011) v (010), ng vi cc mt lng tr ca lut
xp cu su phng (hnh 6.2).
Tuy nhin, cu trc ca olivin gm cc t din SiO
4
c lp vi lin kt Si-O m mt
trt khng th ct qua. Nh vy, tr (010) tt c cc mt mng dy c ca xp cu su
phng u khng phi l mt trt. T gc ho hc tinh th c th ni (010) l mt
trt ca olivin.
Mt khc, Blacic (1971) cho rng s thu phn i vi lin kt Si-O c th to
thun li cho bin dng trt. Kt qu thc nghim i vi olivin cho thy hu ht h bc
trt d bo cho khong vt ny (bng 5.3) u tn ti trong khong gi tr no ca
nhit , p sut, v.v...
169
Bng 5.3.
Cc h trt chnh trong olivin
(+ ph bin; khng ph bin)
Nhit thp Nhit cao
(100) [001]
+
{110} [001]
{110} [001]
+
(010) [100]
+
(100) [010]

{0kl} [100]
+
(001) [100]
{101} [010]

5.4.2 Disten (kyannit)
Disten l bin th ba nghing ca Al
2
SiO
4
O. Cu trc tinh th c t din SiO
4
c lp
v nhng nguyn t oxy khng lin kt vi Si. Hnh 6.8,a l s cu trc tinh th ca
disten. Cc nguyn t nhm u phi tr bt din, mt na s a din ny gn vi nhau qua
cnh chung to nn chui song song vi [001]. Cc chui ny li kt vi nhau nh cc bt
din cn li v cc t din SiO
4
. Nhng quan st ho hc tinh th cho php d bo mt
trt thun li c th l (100) v n song song vi chui dy c nguyn t oxy dc [001]
v vect Burgers ngn nht ng vi b = 4,57 . Trn thc t, Mugge (1883) v Friedel
(1964) tm ra mt trt (100) ny cho disten. Ngoi vic khng inh iu ny bng thc
nghim, Raleigh (1965) i n kt lun rng [001] l hng trt thun li ca disten.

Hnh 5.9.
(a) Song tinh (lut) albit: Hng song tinh
1
v chiu dng ca n,
mi mi t nng vi mt thnh phn plagioclas (hm lng anorthit). (010) l
mt song tinh K
1
.
(b) Song tinh periclin: Hng song tinh
1
= [010] v chiu dng ca
n, v tr ca mt song tinh K
1
ng vi mi thnh phn plagioclas (hm lng
anorthit). K
1
l mt ct trc thoi.
5.4.3 Enstatit
170
Enstatit l Mg-pyroxen trc thoi thuc dy dung dch cng (Mg,Fe)
2
Si
2
O
6
. Cu trc
tinh th (hnh 6.11) gm t din ni nhau qua nh thnh chui dc hng [001]. y l
hng thun li cn bi v n song song vi chui ca thng s c = 5,2 ngn nht. Ngoi
ra, hng [010] vi b = 8,9 l mt gi v mt mng (100) thun li v mt nng lng,
bi v n song song vi hai hng trn.
Mugge (1898) quan st mt (100) un cong quanh trc [010] trong tinh th pyroxen
trc thoi t nhin v i n kt lun v s tn ti ca h trt (100) [001]. Nhng quan
st y c khng nh v sau bng cc thc nghim tin hnh c lp ca Turner et al
(1960), Griggs et al (1960), Raleigh (1965), Green v Radcliffe (1972), Coe v Muller
(1973) v sau cng l Kohlstedt v van der Sande (1973). c bit, hai tc gi ny cng
nm quan st bin dng vi vect Burgers song song vi [010].
5.4.4 Amphibol
Cu trc tinh th ca tt c cc amphibol vi thnh phn ho hc thay i thng c
chui kp c trng do t din SiO
4
ghp li (hnh 6.17). Nh th, amphibol lin quan cht
ch vi pyroxen m nhm chc chui cng l nt c trng. Hornblend Ca
2
(Mg,Fe
2+
)
3
(Al,Fe
3+
,Ti)
2
(Si
3
AlO
11
)
2
(OH)
2
l amphibol duy nht c nghin cu tnh do.
Cng nh i vi pyroxen, c th d bo h trt ca cu trc s l (100)[001] khng
ct qua bt c lin kt SiO no. Bng thc nghim tin hnh trn hornblend v s dng
thm kt qu thc nghim ca Turner, Rooney v Riecker (1969, 1973) khng nh h
trt d bo trn.
5.4.5 Mica
Hai khong vt to chnh ca mica l biotit K
2
(Mg,Fe)
6
(Si
6
Al
2
O
20
)(OH)
4
v
muscovit K
2
Al
4
(Si
6
Al
2
O
20
)(OH)
4.

Chng thuc h mt nghing v c cu trc lp vi nhm chc dng l do t din
SiO
4
kt li (hnh 6.24, 6.25 v 6.26). Cu trc gi su phng ca hai l t din to nn
cc lp TOT, ri cc lp cation kali kt ni chng vi nhau. C th suy on rng trt do
s d dng xy ra dc theo mt mng (001), v lin kt ion ti y c th b ph b. Hng
trt c th c l dc theo mt mng dy c kali, tc l [100] vi khong K-K ngn nht
v [110] ng vi hng [1120 ] ca li t din gi su phng.
Mgge (1898) sau nhng thc nghim trn mica kt lun v h trt l (001) [100]
v (001) [110]. Nhng nghin cu v sau chng t ngoi (001) mica khng cn mt trt
no khc (Brg v Handin, 1966; Horz v Arhens, 1969; Horz, 1970; Schneider, 1972;
Etheridge et al, 1973). Cc hng trt cng c khng nh l [100] (Brg v
Handin, 1966) hay l [100] v [110] (Etheridge et al, 1973).

5.4.6 Plagioclas
Feldspat bao gm nhng khong vt to ph bin. Nhng tnh do ca chng cha
c nghin cu nhiu. Ring tnh cht ny ca feldspat kim th hon ton cha c bit
171
ti. Plagioclas c thnh phn thay i t NaAlSi
3
O
8
v CaAl
2
Si
2
O
8
v cu trc khung t
din (Al,Si)O
4
.
Theo Borg v Heard (1969, 1970), nhit trong khong t 50 n 800
o
C v p sut
t 5 n 10kB, mi thnh vin ca dy plagioclas u bc l tnh do mt cch tng t.
Seifert (1965) quan st mt trt trong albit t nhin. n tinh th albit nhit thp
nhit 800
o
C v 10kB cho thy mt trt (010) v hng trt [001].
Plagioclas bc l song tinh vnh cu trong thc nghim v bin dng trt (Brg v
Handin, 1966, Brg v Heard, 1969, 1970). Trong khi tin hnh thc nghim v bin dng
Starkey (1964) nhn thy nhng h song tinh c hc ng vi lut albit v periclin (bng
5.4, hnh 5.9). Tt c cc plagioclas trong dy t An
30
n An
95
tr An
44
u cho thy song
tinh albit v periclin.
Bng 5.4.
Song tinh albit v periclin trong plagioclas
Lut song tinh Mt song tinh Hng song
tinh
ng sut (An
55
)
Albit
(lut vung gc)
K
1
= (010)
1
= v t
(xem hnh 5.9)
S = 750

Periclin
(lut song song)
K
1
= v t,
gn vi (001)

1
= [010] S = 750

5.4.7 Thch anh
Thch anh SiO
2
l silicat c cu trc khung gm cc t din SiO
4
kt ni nhau qua
nh. Chng c hai bin th a hnh bn vng nhng trng P-T khc nhau (hnh 5.6).
Thch anh (nhit thp) kt tinh h ba phng (hnh 5.5,c) c i xng
phi tri tu thuc s phn b ca t din silicoxy quanh cc trc xon i xng
bc ba.
Thch anh (nhit cao) l bin th bn vng nhit trn 573C v p
sut kh quyn (hnh 5.5,b). Thch anh c i xng su phng; s chuyn
ho t sang khi nung l qu trnh xy ra cng vi s dch chuyn hn ch
ca nguyn t, khng gy ra s gin on lin kt ho hc. i xng phi tri
vn bo tn trong thch anh .
Trt do trong thch anh i hi ph b lin kt cng ho tr mnh SiO v hnh nh
rt kh thc hin.



Bng 5.5.
Cc h trt chnh trong thch anh v
(+ ph bin; khng ph bin)
Mt trt H trt
iu kin nhit

172
Mt y
{0001}[1120 ]
+ Nhit thp
Lng tr bc mt
{1010 }[0001]
+ Nhit cao
Lng tr bc mt
{1010 }[1210 ]
+ Nhit cao
Lng tr bc mt
{1010 }[1213 ]
Nhit cao
Lng tr bc hai
{1120 }[0001]
Nhit cao
Thp bc hai
{1212 }[1123 ]
Nhit cao
Thc ra, thch anh lun cha mt lng nc nht nh. Vi cha H
2
O ti
0,0015% trng lng (10
4
H/Si) thch anh gi l kh (Griggs, 1967). Tinh th thch anh
nhn to vi hm lng nc ti 8,8.10
3
H/Si c th bin dng trn nhit ti hn
380C, di ng sut 10 n 20 ln thp hn so vi thch anh t nhin kh (theo Griggs
v Blacic, 1965). Cc tc gi ny cn cho rng khi lin kt SiO b thu phn th tnh lu
ng ca bin dng s c tng cng. Nh th, khng th tin hnh thc nghim v bin
dng ca thch anh nu khng bit cha nc ca mu (xc nh bng ph hp ph tia
hng ngoi).
Di p sut kh quyn v nhit trn 600C, bin dng trt do xut hin trong
thach anh vi h trt y {0001}[1120 ]. Nhit t 700C l lc c trt do vi h
trt lng tr (bng 5.5), v d: {1010}[0001].
Thch anh kh ch c trt do theo h {0001}[1120 ] nhit gn 750C v theo
h {1010}[0001] trn 750C. Trt do theo mt lng tr c th km theo trt do dc
mt thp (vi ch s Miller thp). Thch anh cng c chung nhng h trt ca thch anh
.
5.4.8 Carbonat
Calcit CaCO
3
v dolomit CaMg(CO
3
)
2
l hai carbonat to chnh. Ngoi chng ra,
khng mt carbonat no c xem xt y. Cn aragonit, vn cha c s liu no v
bin dng do ca n; mc du bin th a hnh ca carbonat calci ny c th c mt trong
qu trnh bin cht p sut rt cao (trn 8 10kB 400C).
Cu trc tinh th
Calcit v dolomit u thuc h ba phng (xem thm hnh 4.18). Cu trc c 4 n v
cng thc trong mng mt thoi vi cnh [100], [010] v [001] trng vi cc cnh ct khai
hon ton. Hnh 5.10 cng cho thy mng th hai ca calcit/dolomit di gp i vi dung
lng ch bng mt na. C hai mng u ly [111] lm hng chung.
Cu trc c th kho st theo php nh trc su phng, vi cc quy c sau: c
[0001] ng vi [111] (trc chnh i xng bc ba), {1011} NG VI {100} (MT CT
KHAI). MI MT C TH K HIU BNG 4 CH S BRAVAIS-MILLER ( hkil ) vi i
= (h + k) hay ba ch s Miller (HKL) (hnh 5.11).
Dolomit c cu trc t-ng t calcit, ngoi vic Ca v Mg xen nhau dc [0001].
173


Hnh 5.10.
Cu trc tinh th calcit. Quan h gia ct
khai mt thoi v mng c s mt thoi
Hnh 5.11.
Cc mt mng trong calcit. Mi mt c hai k hiu: ba
ch s Miller (HKL) v bn ch s Bravais Miller ( hk il )
H trt
Calcit. H trt trong n tinh th calcit v trong hoa c nghin cu rt chi tit
(Turner, Griggs v cng s, 1951, 1953, 1954, 1956, 1960, 1970, 1972; Mugnier, 1973,
Braillon et al, 1974 v nhiu ngi khc). Bng 5.6 lit k nhng h trt bit, trong
c hai h chnh l r = (100)[011] v f = (111) [101] xc lp trn n tinh th (Turner et al,
1954) bin dng bng thc nghim di p sut thu tnh v nhit thay i.
Bng 5.6.
Cc h trt trong calcit
Mt trt k hiu bng ch (Hnh 5.11), bng 4 ch s Bravais-Miller v 3 ch s Miller
theo mng ct khai. Hng trt k hiu bng giao tuyn ca cc mt trt.
Mt trt Hng trt
S h
tng ng
Ghi ch
r
1
(1011) (100)
[r
1
: f
2
]
[(1011) : (2021)]
[011]
3 Ph bin
f
1
( 2021)
(111)
[r
2
: f
3
], [r
3
: f
1
]
[(1011) : (0221)]
[(0111):( 2021)]
[101], [011]
6
a
2
(1210 )
(011)
[r
1
: f
2
]
[(1011) : (2201)]
[011]
6 Rt him

174

Hnh 5.12.
Song tinh trong calcit
Mi tn ch chiu ca trt ct n
Hnh 5.13.
Song tinh trong dolomit
Mi tn ch chiu ca trt ct n
Dolomit. H trt duy nht c bit trong dolomit l h trt y (0001) [1120]. Kt
qu ny do Johnsen l ngi u tin t c, Higgs v Handin (1959) nghin cu y
hn trn tinh th n, nhit 25 500C v 5kB. Trong cc mu nh hng thun li
(i vi hng trt song song [f
1
: f
3
] hay vung gc vi r), duy nht h trt y ny
xut hin nhit di 400C. 400C song tinh f xut hin v khong 500C th
hon ton nhng ch cho h trt y.
Song tinh bin dng
Calcit. Song tinh trn mt e = { 012} ph bin nht trong calcit. Ngay nhit
trong phng, c th nhn c song tinh ny di lc nn vung gc [0001] (Turner et al,
1954). Gi tr cao ca ng lc S = 2tg1915
/
= 0,694 tng ng vi kh nng ti a trong
thc nghim, t c bng lc ko song song trc C (hnh 5.12, bng 5.7).
Mt song tinh k hiu bng ch (hnh 5.11), bng 4 ch s Bravais-Miller v 3 ch s
Miller theo mng ct khai. Hng song tinh k hiu bng giao tuyn ca cc mt.
Bng 5.7.
H song tinh trong calcit
Mt song tinh
Hng song
tinh
S h
tng ng
e
1
( 012)
(011)
[e
1
: a
2
]
[( 012):( 2 0)]
[100]
3
r
1
(10 1)
(100)
[r
1
: f
2
]
[(10 1):(2 01)]
[011]
3
f
1
( 021)
(111)
[f
1
: a
2
]
[( 021):( 2 1 0)]
[211]
3
175
Dolomit. Song tinh c hc pht hin ln u tin trn mu t nhin (Fairbairn v Hawks,
1941). l song tinh f (hnh 5.13, bng 5.7) v ng lc S = 2tg1622

= 0,587.
5.5 C TNH HO L CA TINH TH LIN QUAN VI CU
TRC CA CHNG
Gia cu trc ca tinh th v cc tnh cht ho l ca chng c mi lin quan cht ch.
Mt s tnh cht nhy cm vi cu trc, lin quan nhiu n loi n v cu trc, cch sp
xp cc nguyn t; bao gm cc tnh cht c hc nh tnh ct khai, cng, hoc nh hnh
thi tinh th, song tinh. Mt s tnh cht vt l khc li chu nh hng ch yu ca cu
hnh in t ca nguyn t v dng lin kt ho hc, nh tnh dn in, tnh dn nhit,
gin nhit. V d, dn in cao ca kim loi sinh ra nh s tn ti ca cc in t t do,
tnh cht ny th hin khng ch khi kim loi trng thi rn m c khi nng chy.
Tuy nhin, a s cc tnh cht lin quan ng thi vi c im phn b cc n v
cu trc ln dng lin kt gia chng. Cc bin th a hnh (kim cng v graphit, calcit v
aragonit, disten v silimanit) cho thy nhng bng chng r nht v vai tr quyt nh
ca loi cu trc v dng lin kt ti tnh cht ho l ca cht kt tinh. V d sau v cc
bin th a hnh ca carbon th hin r rng mi lin quan (bng 5.8, hnh 5.14).
Bng 5.8.
Tnh cht ca ba bin th carbon
Bin th
S phi
tr
Dng lin kt
v loi cu trc
Tnh cht Vng dn, eV
Kim cng 4 ng cc, ba chiu Rt cng, trong sut, cch in 6
Graphit 3 ng cc/van der Waals,
lp
Mm, khng thu quang, mu
en, tnh kim loi
0
C
60
3 van der Waals, phn t Mm, mu en, bn dn ~1


Hnh 5.14.
Ba loi cu trc ca carbon
a) phn t - C
60
, b) lp - graphit, c) ba chiu - kim cng

5.5.1 c tnh ho l lin quan vi dng lin kt ho hc trong tinh th
176
Hng lot cc tnh cht vt l, trong c tnh cht nhit, tnh cht c, tnh cht in
(v d, dn in, dn nhit ca kim loi) ph thuc ch yu vo dng lin kt ho
hc.
bn vng ca cc tinh th thng c nh gi theo cch n gin nht qua tnh
cht nhit v tnh cht c ca chng. Tinh th cng cng, nhit nng chy cng cao c
ngha l tinh th cng bn vng. Khi nghin cu cc cht c cng loi cu trc, ngi ta
nhn thy c s bin i song song ca cng v nhit nng chy cng vi s thay
i thnh phn ho hc. V th, mt s tnh cht c v nhit thng c xem xt ng
thi. Cc tinh th c mi lin kt ion thng c trng bi t trng v cng trung bnh,
nhit nng chy cao, dn nhit v dn in thp. dn in ca cc tinh th ion
km, v cc ion rt bn vng, chng khng d dng thu np electron hoc y chng i.
Cc tinh th c mi lin kt ng cc thng c cng cao, chu nhit, cch in.
cng cao lin quan vi lc rt mnh ca mi lin kt ng cc. Tri li, cc cht vi
mi lin kt kim loi c dn in cao, nhng cng thng thp n trung bnh. Lin
kt tn d (van der Waals) c lc lin kt yu, v th cc tinh th vi mi lin kt ny
thng mm, i khi do, nhit nng chy thp. nh hng ca dng lin kt ti mt s
tnh cht ho l ca tinh th c th hin trong bng 5.9.
Cc hp cht t nhin thng chu s chi phi ht sc phc tp ca qu trnh v mi
trng thnh to; v th, rt him khi chng cha mt dng lin kt, a phn l hai hoc
nhiu dng lin kt cng tn ti. Trong cc hp cht d lin kt ny, cc tnh cht chu nh
hng ca mi dng lin kt bn trong. Thng thng tnh cht c hng rt r. V d,
trong khong vt graphit, mi lin kt ng cc rt mnh gn cc nguyn t carbon thnh
tng lp mng; cc lp gn vi nhau bng mi lin kt van der Waals yu, v th mt ct
khai c hng song song vi mt lp (hnh 5.15).
Bng 5.9.
Mt s tnh cht c trng cho cc dng lin kt (L.K.)
Tnh cht L.K. ion L.K. cng ho tr L.K. kim loi
L.K.
van der Waals
Lc Mnh Rt mnh
Dao ng,
thng trung bnh
Yu
C
cng trung bnh
n cao tu thuc
khong cch ion
v in tch, rn
cng cao
cng thp n
trung bnh, rn
c, un c, d
dt mng
Mm, i khi do
in
Dn in km khi
th rn, dn in tt
khi th lng
Cch in khi
th rn v nng
chy
Dn in tt
Cch in khi
th rn v lng
Nhit*

Tnc trung bnh n
cao tu thuc
khong cch ion v
in tch, Dn thp
Tnc cao, Dn thp.
dng nguyn t,
phn t khi nng
chy
Tnc v Dn dao
ng. dng
nguyn t khi nng
chy
Tnc thp, Dn cao.
dng phn t
khi nng chy
ho tan
Ho tan trong dung
mi phn cc thnh
dung dch cha ion
Kh ho tan
Khng ho tan, tr
trong acid hoc
trong dung dch
kim nh phn ng
ho hc
Ho tan trong
dung mi hu c
thnh dung dch
Cu trc
Khng hng, cu
trc c i xng v
s phi tr cao
C hng, cu
trc c tnh i
xng v s phi tr
Khng hng, cu
trc c i xng v
s phi tr cao
Khng hng,
i xng thp lin
quan vi hnh
177
thp dng phn t
V d
Halit NaCl, fluorit
CaF
2
, phn ln
khong vt
Kim cng C,
sphalerit ZnS,
phn t O
2
, phn
t cht hu c,
graphit (mi lin
kt mnh)
ng Cu, bc Ag,
electrum (Au, Ag),
phn ln kim loi
Sulfur (mi lin
kt yu), hp
cht hu c,
graphit (mi lin
kt yu)
Tnh cht L.K. ion L.K. cng ho tr L.K. kim loi
L.K.
van der Waals
Lc Mnh Rt mnh
Dao ng,
thng trung bnh
Yu
C
cng trung bnh
n cao tu thuc
khong cch ion
v in tch, rn
cng cao
cng thp n
trung bnh, rn
c, un c, d
dt mng
Mm, i khi do
in
Dn in km khi
th rn, dn in tt
khi th lng
Cch in khi
th rn v nng
chy
Dn in tt
Cch in khi
th rn v lng
Nhit*

Tnc trung bnh n
cao tu thuc
khong cch ion v
in tch, Dn thp
Tnc cao, Dn thp.
dng nguyn t,
phn t khi nng
chy
Tnc v Dn dao
ng. dng
nguyn t khi nng
chy
Tnc thp, Dn cao.
dng phn t
khi nng chy
ho tan
Ho tan trong dung
mi phn cc thnh
dung dch cha ion
Kh ho tan
Khng ho tan, tr
trong acid hoc
trong dung dch
kim nh phn ng
ho hc
Ho tan trong
dung mi hu c
thnh dung dch
Cu trc
Khng hng, cu
trc c i xng v
s phi tr cao
C hng, cu
trc c tnh i
xng v s phi tr
thp
Khng hng, cu
trc c i xng v
s phi tr cao
Khng hng,
i xng thp lin
quan vi hnh
dng phn t
V d
Halit NaCl, fluorit
CaF
2
, phn ln
khong vt
Kim cng C,
sphalerit ZnS,
phn t O
2
, phn
t cht hu c,
graphit (mi lin
kt mnh)
ng Cu, bc Ag,
electrum (Au, Ag),
phn ln kim loi
Sulfur (mi lin
kt yu), hp
cht hu c,
graphit (mi lin
kt yu)
Ch thch: * Tnc l nhit nng chy, Dn l h s gin nhit
Trong nhiu trng hp, mt cht cng tn ti nhiu dng lin kt, c th mt vi
tnh cht ch ph thuc vo mt dng lin kt. V d, tnh cht c ca cht hu c ch ph
thuc vo mi lin kt yu nht, khng chu nh hng ca mi lin kt th hai l ng
cc. Ngc li, tnh cht quang hc ca chng li ph thuc vo cc lc lin kt bn trong
phn t, cn lc van der Waals hon ton khng gy nh hng.
178

Hnh 5.15.
Mt ct khai song song vi mt lp trong
khong vt graphit lin quan vi mi lin kt van
der Waals yu gia cc lp
Hnh 5.16.
M hnh cu trc khuyt tt ca fluorit
CaF
2
Mt electron
lp vo l trng do ion fluor li, to ra mt
tm mu
c im lin kt ion c th quan st c nhiu mui, trong c cc halogenur
ca kim loi kim, chng b phn li thnh ion khi ho tan trong dung mi phn cc. Tuy
nhin, nu mt cht khng ho tan khng c ngha l lin kt ca n khng phi lin kt
phn cc lin kt ion. Tht vy, chng hn i vi cc oxit, nng lng lin kt gia cc
ion trong oxit ln hn trong cc halogenur kim v ln n mc hng s in mi ca n-
c khng bt cc ion ra khi tinh th.
Ngoi ra, mt s hp cht, thng c mi lin kt ng cc, di nh hng ca hng
s in mi ln ca dung mi phn cc, c th phn li thnh cc ion trong dung dch, mc
d trng thi kt tinh chng khng phi l hp cht ion (v d HCl, HBr).
5.5.2 Tnh cht in
S tn ti ca nhng in t t do trong mng tinh th to cho kim loi nhng tnh
cht vt l c bit: dn in, dn nhit, khng thu quang, nh kim (nng lc phn quang
cao). Cc in t di chuyn t do trong kim loi, nhng khng th bt ra ngoi mng do b
ngng th nng chn li. vt qua ngng th nng ny, in t cn tiu th mt
cng. Nu khi dng nng lng ca tia sng th hiu ng bt in t gi l hiu ng
quang in. Hiu ng tng t c th quan st thy cc hp cht vi lin kt ng cc.
in t, sau khi bt khi qu o, vn li bn trong tinh th to nn dn in cho
cc cht ny (hiu ng quang in bn trong). Trong iu kin bnh thng (khng c
chiu x) cc cht nh vy khng phi l cht dn in, k c khi trng thi kt tinh ln
khi nng chy.
Trong cc tinh th ion cng quan st thy hiu ng quang in bn trong, nng lng
bt in t bng ng th nng ion ho. Khng c chiu x, tinh th ion cng nh hp cht
lin kt ng cc khng dn in. Nhng khc vi hp cht ng cc, cc cht ion dn
in khi nng chy, lc tnh dn in xut hin bi s dch chuyn ca chnh cc ion.
179
Cc cht vi cu trc khuyt tt thng c nhng tnh cht rt c bit. V d, trng
hp v tnh dn in ca AgI. Cht ny c bit ba bin th. Hai bin th nhit thp
thuc cu trc loi sphalerit v vurtzit. Bin th nhit cao vi cu trc khuyt tt bn
vng nhit t 145,6C n nhit nng chy 552C. Cc nguyn t (anion) iod phn
b theo cc nt mng lp phng tm khi, cn cc nguyn t (cation) bc nm trong cc
l trng. Do s l trng nhiu hn s ht bc, cc cation c th dch chuyn khp trong
mng ging nh cht lng hoc cht kh.
c im ny ca cu trc dn n nhng tnh cht c bit ca cht. dn in ca
bin th AgI loi ZnS gn nhit nng chy (142,4C) bng 0,00033cm
2
/mol. Vic chuyn
i AgI t bin th nhit thp sang bin th nhit cao dn n s nhy vt dn
in ln vi nghn ln (1,31 146,5C). S tng nhit tip tc km theo s tng dn
in, khi n gn nhit nng chy, dn in t gi tr l 2,64. iu th v l i l-
ng ny cn vt ln trn dn in ca cht trng thi nng chy (2,36 552C).
5.5.3 Tnh cht quang
Tnh cht quang hc rt nhy cm vi i xng. Ph thuc vo h i xng, mt
quang sut c hnh dng v tnh cht khc nhau; da vo c th d dng d on nhng
biu hin ca tinh th di nh sng phn cc. Mc d phn ln cc tnh cht quang hc
chu nh hng mnh ca thnh phn ho hc, mt s trong chng nh ch s chit sut,
lng chit sut, quang du li ph thuc nhiu vo c im cu trc. Ch s chit sut
ph thuc vo mt ht ca cu trc, n thng c gi tr thp cu trc khung. Lng
chit sut cao hoc rt cao c coi l du hiu pht hin cc khong vt c cu trc
mch hoc lp. Cc cu trc cha khuyt tt l nguyn nhn gy mu mt s khong vt
nh fluorit, thch anh. Trong cu trc cc khong vt ny, cc tm mu c th hnh thnh
do s thiu ht ion hoc nguyn t mt nt mng hoc s xut hin ion hay electron d
tha khong gia cc nt mng (hnh 5.16 v 5.17).
Di tc dng ca bc x, mt trong cp in t ca oxy b bt ra; lm xut hin m
tm mu dng l trng. Tnh cht quang hc cng ph thuc rt nhiu vo dng lin kt
ho hc. Cc hp cht ion c tnh cht quang hc khng thay i, d trng thi kt tinh
hay dung dch. Hp phn in ca tia ti lm bin dng lp v in t ca ion. khc x
ca tng ion l thc o bin dng ( phn cc) ca chng, tng t l thun vi kch
thc ion v t l nghch vi bn vng ca lp v in t. Trong cc hp cht ion, anion
ng vai tr quyt nh ti khc x v gi tr ny tng t l thun vi in tch (xem
bng 5.10).

180
Hnh 5.17.
M hnh cu trc thch anh bnh thng(a)v thch anh m khi khuyt tt (b): Al
3+
+ H
+

thay th Si
4+


Bng 5.10.
S ph thuc ca khc x vo kch thc v in tch ca ion
Ion F

O
2
Cl

Br

Ne Na
+
Mg
2+

Bn knh,
khc x, cm
3

1,33
2,5
1,36
7,0
1,81
9,0
1,96
12,6
2,20
19,0
1,60
1,00
0,98
0,5
0,74
0,3
Trong cu trc i xng (phi tr) cng nh trong dung dch, khc x ion l kt qu
tng hp ca tt c cc ion b phn cc. i vi cu trc khng i xng, khc x cng
c quyt nh bi s bin dng ca ion; nhng hin tng ny gy ra khng ch do hp
phn in ca tia sng m cn do in trng ca cc ion k bn to ra s phn cc mt
chiu. Hin tng ny c dng trong ho tinh th xt on cu trc tinh th. Cc tinh
th ion, tr mui ca cc kim loi chuyn tip v nguyn t t him, thng trong sut v
khng mu.
Cht ng cc (vi lin kt cng ho tr) khc hn cc cht ion v tnh cht quang hc
do chng c nhng in t ng thi thuc hai nguyn t. Tuy nhin, bn vng ca mi
lin kt li dao ng rt ln: cc bn kim cng, yu hn silic hoc ZnS, thic yu
n mc cht ny c nhiu tnh kim loi. S gim bn vng ca mi lin kt ko theo
s hp th ph nh sng bc sng di. nhng cht ny, tnh quang dn xut hin khi
chng c chiu bi nhng nhng tia c bc sng tng ng vi di ph hp th ca
chng. Kim cng c tnh quang in trong vng ph cc tm, silic - nh sng nhn thy,
ring thic c c trng bi dn kim loi.
Hp cht ng cc c gi tr chit sut cao, tng ng vi nh kim cng (theo phn
loi trong khong vt hc). Chng thng c mu v khng trong sut. Trong dung dch,
c im phn b in t khc hn trong tinh th, v vy tnh cht quang hc cng khc
hn. y chnh l c im c bn m hp cht ng cc khc vi hp cht ion.
i vi cc cht c mi lin kt trung gian ion - ng cc th mc chuyn tip nh
hng n gi tr chit sut (bng 5.11).
Hp cht phn t c tnh cht quang hc gn nh khng i khi cc trng thi khc
nhau: rn, lng, kh. Cc hp cht vi mi lin kt van der Waals thng trong sut, khng
mu. Nu cu trc gm cc phn t dng si (phn ln parafin) hoc dng tm (n-
dichlorobenzen) th tinh th c tnh d hng quang hc r rng vi quang tnh dng
trong trng hp th nht v quang tnh m trong trng hp th hai.
Tnh cht quang hc ca tinh th c s dng rng ri xc nh v tr cc phn t
khng ng thc trong cu trc.

Bng 5.11.
S ph thuc chit sut tinh th vo mc lin kt ion - ng cc
Hp cht % mi lin kt ng cc Gi tr chit sut
181
KBr

RbCl
36
} = 8
28
1,559
} = 0,065
1,494
KI

CsCl
48
} = 22
26
1,667
} = 0,133
1,534
LiBr

RbF
43
} = 40
3
1,784
} = 0,388
1,396
LiI

CsF
54
} = 52
2
1,955
} = 0,507
1,448
MgS

CaO
65
} = 46
19
2,271
} = 0,433
1,838
CaTe

BaS
75
} = 54
21
2,510
} = 0,355
2,155
Hp cht % mi lin kt ng cc Gi tr chit sut
KBr

RbCl
36
} = 8
28
1,559
} = 0,065
1,494
KI

CsCl
48
} = 22
26
1,667
} = 0,133
1,534
LiBr

RbF
43
} = 40
3
1,784
} = 0,388
1,396
LiI

CsF
54
} = 52
2
1,955
} = 0,507
1,448
MgS

CaO
65
} = 46
19
2,271
} = 0,433
1,838
CaTe

BaS
75
} = 54
21
2,510
} = 0,355
2,155
5.5.4 Tnh rn c ca kim loi
Kim loi c tnh rn c nu n chu c bin dng do. Bin dng do l kh nng
tng phn ring l ca tinh th c th trt tng i so vi nhau khi c lc tc dng t
bn ngoi. R rng s trt nh vy s c thc hin d dng nu lp cu xp kht ny
trt trn lp cu xp kht kia. S trt ngu nhin gia hai lp cu khng xp kht khng
thun li cho bin dng do. Trong trng hp ny, cc qu cu ca lp th nht s chn
su hn vo nhng khong trng gia cc qu cu ca lp th hai, gy cn tr c hc cho
182
s trt. V vy, khi cc iu kin khc l nh nhau th kim loi c cu trc lp phng
tm khi s c tnh rn km hn kim loi c cu trc lp phng tm mt.
Cc sn phm kim loi thng l tp hp tinh th nh phn b khng trt t. Khi
cn c mt yu t cu trc th hai rt quan trng, quyt nh n kh nng bin dng do
ca kim loi, l s lng cc hng vung gc vi mt xp kht cc qu cu (hng
phn lp). Nu mi ht tinh th c s hng phn lp cng ln th hai ht tinh th k nhau
cng c nhiu hng trt song song hoc gn song song vi nhau. Nh vy, xc sut xy
ra bin dng do cng ln. Bi v s trt phi i qua mt s lng ln cc tinh th.
Trong trng hp ny c th thy r s khc nhau gia cu trc chng kht su
phng v chng kht lp phng. Trong cu trc chng kht hai lp ch c mt hng
phn lp, cn trong cu trc chng kht ba lp c n bn hng phn lp trng vi bn
trc bc ba. Nh vy, bin dng do bt u t mt ht tinh th kim loi c kiu xp cu
su phng, c th b chn li ti ranh gii vi ht tinh th khc; v t c kh nng cc
ht k nhau c mt xp cu trng hoc gn trng nhau. Tri li, s tn ti ca bn hng
phn lp trong tinh th kim loi c cu trc chng kht lp phng lm tng ln rt nhiu
xc sut trng hoc gn trng ca cc mt xp cu trong hai tinh th k nhau. Nh vy, c
th thy, cc kim loi c cu trc chng kht lp phng l kim loi c tnh rn c cao
nht.
5.5.5 Tnh ct khai
Ngi u tin th gii thch hin tng ct khai trong tinh th l O. Bravais. Xut
pht t hc thuyt mng tinh th ng xut gi thuyt l mt ct khai {hkl} s song song
vi mt c mt mng ln nht, hay nhng mt mng nm cch xa nhau nht, tc l c
d
hkl
ln nht. tng l chnh xc nu nh cc n v cu trc trong tinh th l cc
phn t ng thc nh Bravais gi thit. Trong trng hp , r rng l khong cch cc
i s tng ng vi lc lin kt yu nht v to iu kin cho mt ct khai i qua. Tuy
nhin cch gii thch gin n nh vy cho hin tng ct khai ch ng vi nhng trng
hp khng phc tp, v d i vi graphit.
Nhng th nghim nhm kim tra hc thuyt cu trc tinh th xc minh rng trong
tinh th ca a s cc cht v c thiu vng cc phn t. Cc tinh th ny c cu to t
cc nguyn t ring l khng gn vi nhau theo nhm thnh phn t v v th khng th
xem chng nh cc nt mng. Cc nguyn t lin quan vi nt mng bng nhng quy lut
phc tp hn nhng nh lut ca h im quy tc.
V d, cc hng s mng su phng ca magnesi kim loi l: a = 3,20, c = 5,20, c/a =
1,62. Nu cc nguyn t magnesi phn b theo cc nt ca mng, th theo nh gi thuyt
ca Bravais ta s c ct khai theo mt y. Tuy nhin, magnesi kim loi khng c ct khai.
Nguyn t ca n xp xp theo cch chng kht cc qu cu kiu su phng vi t l rt
gn vi t s l tng c/a bng 1,633. iu c ngha l khng c bt k mt d thng
no v khong cch gia cc nguyn t trong cu trc magnesi kim loi v do khng c
kh nng ct khai theo mt y. Trong cu trc ca km v cadmi, t s c/a vt tri t s l
tng (1,86 v 1,89), v v th, lc lin kt gia cc nguyn t theo trc chnh yu hn rt
nhiu theo hng vung gc, do , ta c th ch i ct khai theo mt y. Thc t cho
thy, chng c ct khai rt tt theo hng trn (tham kho hnh 4.27).
183
Vulf W.V. xy dng l thuyt v tnh ct khai trn c s thng k s liu thc
nghim v cu trc tinh th. tng rt d hiu nu so snh tnh ct khai ca sphalerit
vi kim cng, hai cht ny c cng mt loi cu trc nhng li ct khai theo nhng hng
khc nhau. ZnS c ct khai theo mi hai mt thoi {110}, kim cng theo tm mt
{111} (hnh 5.18). Trn hnh 5.19 l s cc mt mng trong cu trc ZnS theo cc mt
lp phng, mi hai mt thoi v tm mt. Khong cch mt mng d
hkl
ln nht ng vi
hnh tm mt (d
111
= 0,866 so vi d
100
= 1).
i vi kim cng, theo hng ny s c ct khai. Trong cu trc ZnS, tng ng vi
khong cch l hai lp cha cc nguyn t cng loi (Zn hoc S). Lc lin kt ln gia
chng khin cho sphalerit khng c ct khai theo hng ny. Trong khi , cc mt mng
gm nguyn t ca c hai loi nguyn t bo ho in tch nn lin kt vi nhau yu
hn mc d nm gn nhau hn. l trng hp vi mt mi hai mt thoi trong ZnS. V
th, sphalerit xut hin ct khai song song vi mt {110}.



Hnh 5.18.
Ct khai theo mt {111} trong kim cng v mt
{111} trong sphalerit
Hnh 5.19.
Lt ct cu trc ca sphalerit (ZnS) vung gc
vi mt lp phng, mi hai mt thoi v tm
mt
Trong cu trc silicat lp, cc t din oxy v silic trong lp gn vi nhau bi mi
lin kt ion ng cc rt mnh, cn cc lp ch gn vi nhau bng lin kt ion hoc hydro
yu qua cc cation ho tr thp, iu ny gii thch tnh ct khai rt hon ton theo mt y
ca cc khong vt silicat lp. Tng t, ct khai theo lng tr cc khong vt nhm
pyroxen v amphibol phn nh mi lin kt yu gia cc chui n, chui kp t din silic
(xem hnh 6.12, 6.18).
5.5.6 Cc h s co c, gin nhit
Cc cht c lc lin kt mnh v loi cu trc chng kht theo cc lut xp cu c
co cc tiu c trng. i vi cc kim loi, gi tr co theo s liu ca Reis dao ng
trong khong t 0,3.10
6
n 4,5.10
6
cm
2
/kg. Cc oxit kh nng chy cng c gi tr co
cng bc [(0,5 1).10
6
cm
2
/kg].
Cc mui v c thng c trng bi cu trc chng kht, tuy nhin nu trong thnh
phn ca chng c cc kim loi kim ho tr 1 vi lc lin kt ion yu, th chng c co
ln hn ng k so vi cc trng hp ni trn. V d, vi cc mui kim loi kim, co
dao ng t 1 n 6. co ca cc kim loi kim c cu trc chng kht lp phng tm
khi dao ng t 9 n 61. Cc hp cht hu c phn t c co nm trong khong (20
184
50).10
6
cm
2
/kg. Bng 5.12 cho thy r nh hng ca loi cu trc ti co ca cc mui
kim loi kim.
Bng 5.12.
nh hng ca loi cu trc ti co (cm
2
/kg) ca cc mui kim loi kim
Hp cht LiCl NaCl KCl RbCl CsCl*
A X, 2,57 2,81 3,14 3,27 3,57
H s co ( .10
5
) 3,50 4,18 5,65 7,40 5,90
xp cht ca ion, % 78,66 65,66 65,01 50,16 68,44
* V loi cu trc, CsCl khc hn vi cc hp cht cn li trong bng (xem thm
4.3.2,a).
Cc mui c cu trc loi NaCl c co tng cng vi s tng khong cch gia
nguyn t.
Cu trc loi CsCl c h s co nh hn rt nhiu so vi d on theo kiu din bin
u n ca cc cht khc trong bng 5.12. Nguyn nhn chnh l cht xt rt thp cu
trc chng kht ca cc hp cht vi cation bn knh ln so vi cu trc loi CsCl. iu
ny th hin rt r qua hin tng gim th tch n 15% ca cc halogenur rubidi khi
chuyn i cu trc t loi NaCl sang loi CsCl di p sut cao.
Cc hp cht vi cation phn cc mnh c h s co nh, v khng k khong cch gia
nguyn t l nh nhau th cc anion trong cu trc ny cng co li bt thng do b phn
cc. C th ly v d cc mui halogenur bc (bng 5.13)
Bng 5.13.
H s co (cm
2
/kg) ca cc mui halogenur bc v natri
Hp cht AgCl NaCl AgBr NaBr (AgI) NaI
A X, 2,77 2,81 2,88 2,98 2,99 3,23
H s co ( .10
6
) 2,40 4,18 2,74 5,09 4,14 7,01
H s gin nhit ca cc nhm cu trc trn thay i tng t h s co. Cc kim loi
kt tinh trong loi cu trc chng kht, cc oxit kh nng chy, cc sulfur c h s gin th
tch c 0,0001 0,001, cc mui v c cng c h s gin khong (0,0004 0,001).
H s gin th tch ca cc kim loi kim dao ng t 0,0018 n 0,0025. Cc hp cht
hu c phn t c h s gin t gi tr cao nht n 0,003. C th quan st s bin i h
s gin th tch theo s bin i khong cch nguyn t qua dy mui halogen ca natri
(bng 5.14)
Bng 5.14.
Mi quan h gia khong cch nguyn t v h s gin
Hp cht NaF NaCl NaBr NaI
A X, 2,31 2,81 2,94 3,18
.10
4
39 40 43 48
5.5.7 cng v nhit nng chy
Hai tnh cht cng v nhit nng chy c trng cho bn vng c hc v
nhit hc ca hp cht. cng ca mt cht lin quan vi kh nng b mt ca n chng
185
li tc ng mi; cht b mi mn khi lc lin kt b ph hu. bn vng ca lc lin kt
trc tc ng c hc bn ngoi li lin quan vi c im i xng ca qu o electron
tham gia to mi lin kt. V d, trong kim cng, tinh th c xy dng t cc nguyn t
gn vi nhau bi mi lin kt ng cc (qu o sp
3
, xem thm 4.2.4) mnh c tnh nh
hng cao. S dch chuyn nguyn t hoc s bt ph n ra khi lin kt i hi mt lc
rt ln. Chnh v vy m kim cng c cng rt cao.
Trong cu trc tinh th, s xp xp nguyn t theo cc hng khc nhau thng khng
ging nhau; v th, cng cng thay i theo hng (d hng), nhng thng khng
nhiu. Tuy nhin cng c nhng trng hp c bit; v d, khong vt disten Al
2
SiO
5
c
cng trn mt (100) thay i t 4 n 7 tu thuc vo hng. Cc kim loi v cc mui
c cng v nhit nng chy dao ng trong mt gii hn rng. Nhn chung, c th
ni, cc hp cht ny cng hn v c nhit nng chy cao hn cc hp cht hu c. Cc
hp cht hu c mm v c nhit nng chy thp do chng c mi lin kt van der
Waals yu. Di y s xem xt cc yu t nh hng n cng v nhit nng chy
ca cc hp cht v c.


Hnh 5.20.
Mi tng quan nghch gia nhit nng chy v khong
cch ion trong hp cht ion
Hnh 5.21.
Mi tng quan nghch gia cng v khong cch
ion trong hp cht ion

Bng 5.15.
S thay i cng v nhit nng chy ph thuc vo khong cch nguyn t ca cc hp
cht ion
Hp cht (BeO) MgO CaO SrO BaO
A X, 1,65 2,10 2,40 2,57 2,77
cng (theo thang Mohs) 9,0 6,5 4,5 3,5 3,0
Nhit nng chy, C 2570 2800 2585 2430 1923
Nhit nng chy v cng ca cc tinh th ion ph thuc vo khong cch gia
cc ion, khong cch ion cng nh th nhit nng chy H cng cao (hnh 5.20), cng
cng ln (hnh 5.21). Khi cu trc cng loi, cc cht vi cc ion cng ho tr s c
cng v nhit nng chy gim nu khong cch nguyn t tng (bng 5.15).
186
Tt c cc cht trong bng 5.15 u kt tinh trong cu trc loi NaCl, tr BeO c cu
trc loi vurtzit. Lin kt ho hc trong cc hp cht gn vi dng ion. Cc hp cht ng
cc cng ging cc hp cht ion v c im thay i cng v nhit nng chy khi
c s thay i khong cch nguyn t (bng 5.16). Tt c cc cht trong bng u kt tinh
trong cu trc loi kim cng sphalerit.
Bng 5.16.
S thay i cng v nhit nng chy ph thuc vo khong cch nguyn t ca cc
cht ng cc
Nguyn t C C C Si Si Si Ge Ge
A A, 1,54 1,89 2,35 2,43
cng (thang Mohs) 10,0 9,5 7,0 6,0
Nhit nng chy,C 3500 2700 1420 958
Vi cc hp cht c khong cch nguyn t xp x c th thy r nh hng ca ho
tr n cng v nhit nng chy (bng 5.17).
Bng 5.17.
nh hng ca ho tr n cng v nhit nng chy
Hp cht NaF MgO ScN TiC
A X, 2,31 2,10 2,23 2,23
cng (thang Mohs) 3,5 6,5 7,5 8,5
Nhit nng chy,C 988 2800 3180
Tuy nhin, trong cc cht trn, c im lin kt ho hc thay i ng k khi ho
tr thay i; iu ny cn c xem xt khi nh gi mc nh hng ca ho tr n gi
tr cng v nhit nng chy.
Bng 5.18
nh hng ca lin kt Ion n cng v nhit nng chy
Loi cu trc CaF
2
CdCl
2
* NaCl NaCl NaCl NaCl NaCl
Hp cht SrF
2
MgCl
2
NaCl AgCl AgBr LiCl AgF
A X, 2,58 2,63 2,81 2,77 2,87 2,57 2,48
Nhit nng chy, C 1280 712 840 455 422 614 435
Loi cu trc NaCl ZnS NaCl ZnS NaCl ZnS NaCl
Hp cht NaF CuCl SrO CdS BaO CdTe PbS
A X, 2,31 2,34 2,57 2,52 2,77 2,80 2,97
Nhit nng chy, C 992 422 2430 1750 1923 1041 1120
cng (theo thang Mohs) 3,0 2,5 3,5 3,0 3,5 3,0 3,0
* Hp cht CdCl2 c cu trc lp gn ging ca CdI2 (hnh 4.19), nhng khc vi I
ca n Cl xp theo lut xp cu lp phng.
S bin i cu trc phi tr t loi ny sang loi khc (v d, t loi NaCl sang ZnS)
nh hng khng nhiu n cng v nhit nng chy, nhng s khc bit gia cu
trc phi tr v cu trc lp dn n s bin i r rt cc tnh cht vt l. S thay i cc
ion c cu trc 8 - in t sang ion 18 - in t (hay ni chung l cc ion khng c cu
hnh in t ca kh tr) dn n thay i nh v cng nhng thay i kh ln v gi tr
nhit nng chy (bng 5.18)
5.5.8 nh hng ca dng lin kt hydro n cc tnh cht ho l
187
Lin kt hydro l dng lin kt yu, nng lng ca n ch khong 5 10 kcal/mol, nu so
snh vi lin kt ion hoc lin kt ng cc th nng lng lin kt hydro ch bng phn
chc ca cc lin kt trn. iu ny dn n mt nhn thc sai lm l dng lin kt hydro t
nh hng n cc tnh cht ho l. Tuy nhin, nu so snh vi lin kt tn d th thy nh
hng ca lin kt hydro li l ng k v nng lng lin kt ca n mnh gp mi ln.
Ly cc hp cht phn t lm v d, trong bng 5.19 l mt vi thng s ca cc hydrur
khc nhau.

Nhng d thng v nhit nng chy v nhit si ca cc hp cht ca fluor, oxy
v nit lin quan vi lin kt hydro tn ti trong cc hp cht trn c th rn, lng v kh.
Theo cc s liu trong bng 5.19, bng cch ngoi suy ng cong ni cc nhit nng
chy ca H
2
TeH
2
SeH
2
S (hnh 5.22), c th d bo nhit nng chy ca H
2
O l
100C, tuy nhin thc t li l 0C.
C th hiu c s chnh lch ln gia cc gi tr nhit tan ca bng trong thc t
vi gi tr nhn c bng phng php ngoi suy, nu so snh ng nng phn t vi
nng lng lin kt hydro. ng nng phn t bng phn chc kcal/mol, l qu nh, ch
thng lc lin kt van der Waals ch hon ton khng th ph v lin kt hydro.
Bng 5.19.
Nhit nng chy (nng chy, C) v nhit si (si, C) ca mt s hydrur phn t
Hp cht Nng chy, C Si, C Hp cht Nng chy, C Si, C
HF 83 +20 NH
3
78 33
HCl 112 84 PH
3
134 88
HBr 88 67 AsH
3
116 62
HI 51 35 SbH
3
88 17
H
2
O 0 +100 CH
4
184 162
H
2
S 86 60 SiH
4
185 112
H
2
Se 66 41 GeH
4
166 88
H
2
Te 51 2 SnH
4
150 22
188
5.5.9 Hiu ng chn ca ion
Cc phn t vi mi lin kt ion, trung ho v in tch, c th l nhng lng cc
mnh. u m ca cc phn t c th ht u dng ca phn t th hai, v cc phn t
khc c th tin li gn v c th b gi li kh cht. Cc cht vi cu trc nh vy c p
sut hi nh, d kt tinh v nhit nng chy thp.
Ta hy xt phn t kiu CF
4
, nguyn t cacbon nm tm, c kch thc nh c
bao quanh bi cc nguyn t fluor c kch thc ln hn hn v tnh in m mnh hn.
Trong trng hp ny, cc nguyn t F chn nguyn t C trung tm. Carbon b chn,
khng th ht cc u m ca cc phn t khc, bi vy phn t CF
4
khng c bt k
khuynh hng lin kt no vi cc phn t tng t. Hp cht loi ny d bay hi v c
nhit nng chy thp. Chng thng gi l hp cht ng, ngc vi hp cht m
loi NaCl. Nu nguyn t (ion) nm tm c kch thc nh, cc ion chn ca n li ln,
th cht s c mi tnh cht ca hp cht ng. Mt cht vi ng dng cng thc trn nh-
ng nguyn t (ion) tm c kch thc ln v nhng ion chn khng ln s mang cc tnh
cht ca mt hp cht m. V d 4 ion chlor chn hon ton ion thic v bn knh ca Sn
4+

= 0,67, ca Cl

= 1,81, r
a
: r
x
= 0,37. Nhit si ca SnCl
4
l 114C. Bn ion fluor c
bn knh 1,33 khng th chn hon ton ion thic, hp cht SnF
4
si 705C.
So snh cc hp cht halogenur ca nhm v bo cng c th cho kt lun tng t.
Trong hp cht AlCl
3
, ion nhm kch thc nh b chn bi 3 ion chlor, bi vy nhit
si ca AlCl
3
thp

(81C). AlF
3
si nhit cao hn 1000C v nhm khng b chn hon
ton. Ion bo c kch thc nh (B
3+
= 0,20) nn n b chn hon ton bi 3 ion fluor, v
th n tn ti dng kh khi nhit bnh thng, nhit nng chy bng 127C.
S chn khng ch xy ra vi phn t m cn vi cc ion phc. Tuy nhin cc hin
tng i km c khc m t trn, trong c th k n p sut hi, nhit si. Cc
tnh cht khc c lin quan n s chn ion, ion phc (v d SO
4
2
) c th gi cht cc
cation trong tinh th bng lc tnh in.
Kch thc ca ion chn s quyt nh thnh phn v in tch ion phc. Ta hy xt
cc anion phc ca cc oxyacid. T s bn knh gia cation S
6+
(0,29), Si
4+
(0,39) v
P
5+
(0,35) v oxy ln lt l 0,21; 0,29; 0,26 (rt gn vi gii hn di ca s phi tr 4).
Nh vy s c 4 ion oxy bao quanh cc cation trn v s phi tr 4 tng ng vi t s r
a
: r
x

nm trong gii hn 0,22 n 0,41. Cc ion phc l: [SiO
4
]
4
, [PO
4
]
3
, [SO
4
]
2
.
Ion [SO
6
]
6
v cu hnh [SO
6
]
6
t c kh nng tn ti. Trong thc t cha gp acid
orthosulfuric v cc mui ca n, nhng tn ti cc mui ca acid orthotelluric Te(OH)
6

nh Ag
6
TeO
6
(Te
6+
= 0,56, r
a
: r
x
= 0,41) v orthoiodic H
5
JO
6
, v d Ag
5
JO
6
(bn knh
J
7+
Te
6+
). T s bn knh C
4+
(0,2) trn bn knh oxy bng 0,15 tho mn s phi tr 3.
T c th thy, ion CO
3
2
c kh nng tn ti, cn ion CO
4
4
th khng.
T cc v d trn c th thy, xem xt hin tng chn thm ch vi quan im hon
ton tnh in (nh Kossel, Goldshmidt, Van-Arkel lm) cng cho php suy lun nhng
quy lut c gi tr nht nh.

Tham kho 4.1.4, Tnh phn cc ca ion v quy tc Pauling cui 4.2.1.
189
5.5.10 ho tan
Trong cc mc trn chng ta xem xt mt s tnh cht lin quan n bn vng
ca vt cht kt tinh nh cng, nhit nng chy ho tan cng l mt tnh cht
c trng cho bn vng. Mt mui s ho tan trong nc nu nh lc ht ca cc phn
t nc ln hn nng lng mng. ho tan ca cc mui halogen ca kim loi kim
c trnh by trong bng 5.20.

Bng 5.20.
ho tan ca cc halogenur kim loi kim
(mi tn ch chiu tng ca bn knh ion)
Cation Anion
F Cl Br I
Li
Na
K
Rb
Cs
0,1(18C) 16 11
1,0(15C) 6,1 11 10
16 (18C) 3,7 4,5 7,6
12 (18C) 6,4 5,8 6,5 (7C)
24 (18C) 9,6 6,0 (25C) 1,7
Cation Anion
F Cl Br I
Li
Na
K
Rb
Cs
0,1(18C) 16 11
1,0(15C) 6,1 11 10
16 (18C) 3,7 4,5 7,6
12 (18C) 6,4 5,8 6,5 (7C)
24 (18C) 9,6 6,0 (25C) 1,7
Trong bng trn, ho tan c tnh 0C (nhit khc t trong ngoc). Cc s
liu cho thy khng c mi lin h tuyn tnh gia ho tan v bn knh ion. R rng l
ho tan khng nhng ph thuc vo nng lng mng m cn ph thuc vo gi tr
nhit hydrat ho, m gi tr ny ph thuc vo kch thc ion khc vi nng lng mng.
S liu gn ng v nhit hydrat ho H c th thu c bng cch o nng lng ho tan
L:
H = U L
U nng lng mng.
Nguyn nhn s tng vt ho tan ca LiCl, LiI, NaBr, NaI lin quan vi loi cu
trc ca chng. Lc lin kt gia cc ion trong mng yu i do t s bn knh ca chng
gn vi t s tinh th hc ca cu trc loi NaCl (0,41). Trong cc cu trc loi ny, lc
y gia cc ion tip xc nhau hoc gn tip xc nhau tng ln rt mnh. S tng cao
ho tan ca KF, RbF v CsF c gii thch bi cht xt thp (xp) ca cu trc. Tt c
cc cht ny nu xt theo t s r
a
: r
x
phi c cu trc loi CsCl nhng thc t chng li kt
tinh trong cu trc loi NaCl.
S tng ho tr ko theo s gim mnh ho tan bi v ng thi vi s tng ho tr,
nng lng mng tng nhanh hn rt nhiu so vi nng lng hydrat ho. Bi vy, oxit v
sulfur ca cc kim loi ho tr 2 khc hn halogenur kim loi kim v ho tan. Chng
hu nh khng ho tan trong nc, mc d chng c loi cu trc tng t.
190
Bt u t cc ion ho tr 3 c th ni n hiu ng chn, nh n mi lin kt gia cc
phn t yu i, dn n ho tan tng ln. nh hng ca ho tr ion v hiu ng chn
n ho tan c thy r qua cc s liu trong bng 5.21.
nh hng ca cu hnh in t ca ion ti ho tan cng rt th v. Stivel K. Y. cho
rng cation ng vai tr quyt nh gy nn bin dng ca anion trong mng hoc phn t
nc trong dung dch. C th phn bit 4 trng hp khc nhau:
anion d b phn cc hn phn t nc;
anion kh b phn cc hn phn t nc;
cation gy phn cc yu do kch thc ln, in tch nh, v 8 - in t;
cation gy phn cc mnh do kch thc nh, in tch ln, v khng phi loi 8 - in
t.
Bng 5.21.
Mi lin quan gia ho tan vi ho tr cation v hiu ng chn
Hp cht NaF NaCl CaF
2
BaF
2
AlCl
3
PrCl
3
ThCl
4
SnI
4

ho tan 1,0 6,1 0,0002 0,009 6,0 4,2 tt tt
r
a
+ r
x
2,31 2,79 2,37 2,71 2,38 2,81 2,76 2,87
Bn trng hp trn c biu din phn gia s ca hnh 5.23. Phn cc d hn
nc l cc ion Cl

, Br

, I

, OH

; kh hn l F

v cc ion phc kiu (SO


4
)
2
, (ClO
4
)

,
(PtCl
6
)
2
. Cation gy phn cc yu l Ba, Na; gy phn cc mnh l Mg, Ag.
Khi mt anion b phn cc d hn nc ho hp vi mt cation gy phn cc mnh,
nng lng mng s tng nhanh hn nng lng hydrat ho. Bi vy, nhng cht cha
nhng anion d b phn cc v cation kch thc nh, in tch ln hoc c lp v ngoi
18 in t, s c ho tan nh hn nhiu so vi cc mui tng t nhng c cation kch
thc ln, v 8 in t (trng hp A C, hnh 5.24, mi tn ch hng tng ho tan).
Nu so snh ho tan ca cc mui A v B, tc hai hp cht vi cng mt cation gy
phn cc mnh (v d, Ag
+
) nhng hp cht th nht, anion d b bin dng hn nc (v
d, Cl

), hp cht th hai - kh hn nc (v d, F

), th ho tan ca cc hp cht th
hai mui fluor, s ln hn so vi cc hp cht u tin mui chlor. Trong cc mui ca
chlor, nng lng ph tr (do bin dng anion) l nng lng mng, cn trong cc mui
fluor l nng lng hydrat ho.


191
Hnh 5.23.
S minh ho nh hng ca cc yu t khc nhau ti ho tan
Ion natri gy phn cc yu, bi vy nng lng ph tr do phn cc s khng xut
hin trong cu trc NaF cng nh trong nc. Ion bc, ngc li, gy phn cc mnh. Do
phn t nc b phn cc mnh hn F

, nn Ag
+
c xu hng chuyn vo dung mi. Kt
qu, ho tan ca AgF s ln hn ho tan ca NaF (D B).
Hng tng ho tan D C c xc nh bi gi tr nng lng mng. Hp cht
NaCl c khong cch Na Cl ln hn, nng lng mng tng ng nh hn v nh vy,
ho tan ln hn so vi NaF. Nng lng ph tr khng gy nh hng ti qu trnh ho
tan do mc b phn cc ca anion bi ion natri trong tinh th v ca phn t nc trong
dung dch l rt nh.
Bng 5.22 trnh by gi tr ho tan ca mt s mui (mol/l nc) s minh ho
nhng iu ni trn. Do O
2
v S
2
b phn cc yu hn nc, cc hp cht ca chng vi
b-kim loi (v d Zn, Cd) ho tan yu hn cc oxit v sulfur ca a-kim loi (Mg, Ca).
ho tan, nh ni trn, ph thuc rt nhiu vo loi cu trc. Cc hp cht c
cu trc phn t v phc tp, ho tan tt hn cc hp cht c cu trc phi tr. Da trn c
s , trong phn tch nh tnh c th dng ion chlor (b sung HCl) tch cc cation b
ho tr mt (Ag
+)
v cation ho tr hai vi kch thc ln (Pb
2+
) ra khi cc cation b ho tr
hai (Zn, Cd) v cc cation ho tr ln hn. Nhm cc cation th nht to vi chlor cc cu
trc phi tr khng ho tan (AgCl, PbCl
2
), nhm th hai cu trc phn t v lp d ho
tan (ZnCl
2
, CdCl
2
). Cc nguyn t sau cng c th lm kt ta bng S
2
nh b sung
dihydro sulfur (v d ZnS).
Bng 5.22.
ho tan ca mt s mui
Ion F

Cl

Br

SO
4
2
2OH


Na
+
1,0 6,1 11,3 10,6
Ag
+
14,0 6.10
6
4,5.10
7
1,3.10
6

Tl
+
3,6 9.10
3
8,5.10
4
6.10
4

Mg
2+
2,19 1,5.10
4

Ca
2+
1,3.10
2
2,5.10
2

Sr
2+
6.10
4
3,3.10
2

Ba
2+
6,3.10
6
2,5.10
1

5.5.11 T trng
T trng ca cht kt tinh ph thuc vo thnh phn ho hc v cu trc tinh th, trong
c bit quan trng l trng lng nguyn t, sau l ho tr v kch thc ion ca
nguyn t ho hc tham gia vo thnh phn. V vn v d trong th gii khong vt th
hin mi quan h trn: cc khong vt to sm mu (khong vt femic) cha nhiu st,
magnesi thng c t trng ln hn cc khong vt sng mu (khong vt salic) giu nhm,
silic, kim loi kim. S dao ng thnh phn ho hc ca mt khong vt (sphalerit,
wolframit, v.v) hay mt nhm (vi cng chung loi cu trc) khong vt (olivin, granat,
v.v..) dn n s bin i t trng (xem bng 5.23) cng nh hng lot cc tnh cht vt l
khc.
192
Bng 5.23.
S ph thuc t trng vo thnh phn ho hc ca cht kt tinh
Nhm khong vt Khong vt Cng thc ho
hc
T trng
Olivin Forsterit Mg
2
SiO
4
3, 22
Fayalit Fe
2
SiO
4
4, 40
Granat Pyrop Mg
3
Al
2
Si
3
O
12
3, 58
Almandin Fe
3
Al
2
Si
3
O
12
4,32
Plagiocla Albit NaAlSi
3
O
8
2,62
Anorthit Ca Al
2
Si
2
O
8
2,76
Spinel Spinel MgAl
2
O
4
3,55
Magnetit FeFe
2
O
4
5.20
Chromit FeCr
2
O
4
5,09

T trng cht rn cng ph thuc vo mc xp cht cc nguyn t, tc l ph thuc
vo loi cu trc, nhn chung t trng gim t cu trc phi tr n cu trc khung. C rt
nhiu v d v s ph thuc ca t trng vo s xp xp nguyn t, ion; tuy nhin, nhng v
d in hnh v r nt nht vn l cc bin th a hnh (xem bng 5.2). Trong c cc
bin th ca carbon nh kim cng v graphit. Cc nguyn t carbon c cch xp xp khc
nhau trong mng tinh th ca hai khong vt trn (xem hnh 5.14,b v c). Kim cng c
cu trc phi tr cht xt, mi nguyn t carbon c 4 nguyn t khc bao quanh, khong
cch gia cc nguyn t l nh nhau v u bng 1,54. Trong khi , graphit li c cu
trc lp vi cc nguyn t carbon xp kht nhau trong tng lp, mi nguyn t tip xc vi
3 nguyn t khc, khong cch gia hai nguyn t lin k l 1,42. Tuy nhin, gia cc
lp li c mt khong rng l 3,40. iu ny dn n s chnh lch ln gia t trng ca
kim cng (3,52) v graphit (2,23).
Tng t, cc bin th a hnh ca oxit silic cng c t trng khc nhau do s xp xp
cc nguyn t oxy v silic khc nhau, c bit, oxit silic v nh hnh c t trng nh nht
v dao ng nhiu nht do s phn b ln xn, khng cht ca cc nguyn t oxy v silic.
c bit, vi s phi tr su ca silic i vi oxy, stishovit c t trng ni tri so vi cc
bin th a hnh khc u c s phi tr bn: 4,3 so vi 2,20 ca tridymit v cristobalit,
2,53 v 2,65 ca thch anh.
193
Mt v d khc cng cho kt qu tng t, l hai bin th ca carbonat calci: calcit
v aragonit ln lt thuc cc h ba phng v trc thoi (xem mc 6.12 v hnh 4.18). C
th nhn thy rng trong c hai cu trc calcit v aragonit mi nhm CO
3
u c bao
quanh bi 6 nguyn t Ca, tuy nhin mi quan h phn b gia Ca v O th khc nhau.
Trong calcit (hnh 5.24,a), mi nguyn t oxy ca nhm CO
3
rng buc vi 2 nguyn t
Ca, v nhm CO
3
ny nm chnh gia b ba nguyn t Ca trn v di trong mng c
s mt thoi.
Trong mng c s ca aragonit (hnh.5.24,b) mi nguyn t oxy nm gia 3 nguyn
t calci, hai nhm CO
3
lin h vi nhau qua tm i xng s ln lt nm gn vi b ba
nguyn t Ca trn v di. Vi s xp xp cc nguyn t nh trn, cu trc ca aragonit
xp cht hn calcit. mng c s su phng cha 6 n v cng thc CaCO
3
ca calcit
c cc thng s a = 4,9908; c = 17,05951; tng ng, th tch mng c s bng
367,8743
3
; 2 mng c s cha 12 n v cng thc CaCO
3
tng ng vi th tch
735,7486
3
. Trong khi mng c s trc thoi cha 4 vct CaCO
3
ca aragonit c cc
thng s a = 7,968; b = 5,741; c = 4,959. Tng ng, th tch mng c s bng
226,8459
3
; 3 mng c s cha 12 phn t CaCO
3
tng ng vi th tch 680,5378
3
.
iu ny dn n kt qu trng lng ring ca aragonit (2,93) ln hn ca calcit
(2,71) (xem bng 5.24). Trng lng ring ca cc bin th a hnh CaCO
3
c th tnh theo
cng thc: = M/V, vi V l th tch ca mng c s v khi lng ca n M = Z(f/L),
trong Z l s n v cng thc trong mng, f mol ca CaCO
3
bng 100,09 g (nguyn
t lng ca Ca l 40,08, C 12,01, O 16,00), L s Avogadro (s n v cng thc
cha trong 1 mol).
Bng 5.24.
Trng lng ring ca cc bin th a hnh CaCO
3
Bin th Z M, g V, cm
3

Calcit 6 600,54 367,8743 10
24
2,710
Aragonit 4 400,36 226,8459 10
24
2,930
Trong s khong vt silicat, c th thy mt xu hng r rng l cu trc o c t
trng ln hn silicat c cu trc mch, silicat mch li c t trng ln hn silicat lp, silicat
v alumosilicat khung. T trng thp nht l ca khong vt zeolit; cu trc khung rng ca
chng c cc khoang rng ln ni vi nhau bng cc knh di.
Trong cc khong vt alumosilicat, cu trc khung ph bin nht l cc khong vt
nhm feldspat, feldspathoid v zeolit. Chng c chung c im cu trc c bn l khung
alumosilicat c cu thnh t cc t din (Si,Al)O
4
, mi nh oxy chung cho hai t din.
in tch m ca mng c cn bng bi cc cation, ch yu l Ca, Na, K, nm trong cc
khoang trng ca mng. Cu trc ca feldspat cht nht, trong cc cation (Na, Ca, K)
nm trong cc khoang tng i nh, c bao kn bi cc oxy to khung (xem cc hnh
6.29 v 6.30). Cc cation gn cht vi khung n mc chng khng th di chuyn d dng
nu nh cc mi lin kt ca khung khng b gin on. S thay th Na hoc K bng Ca
bt buc ko theo s thay i t s Si/Al.
Cu trc ca feldspathoid tng i m hn, cc ion (Na, Ca, K, trong mt s trng
hp l cc anion xc nh) thng khng chim ht cc khoang trng ln thng nhau. V
th, feldspathoid c cc knh, theo cc ion c th ra vo, i khi cc phn t nh c th
i qua m khng ph v khung. Cu trc khung ca zeolit ging vi cu trc ca
194
feldspathoid, nhng a s cn m hn v cha cc khoang, knh kch thc ln. Cc vng
ca khung thng cu to t 4 n 6, 8, 10, 12 t din (hnh 5.25 v 5.26). Cc knh c
chiu rng t 2,8 n 9 ( feldspathoid khong 2,2). Do , t trng ca feldspat,
feldspathoid, zeolit gim dn t 2,6 2,7 (feldspat) sang 2,3 2,5 (feldspathoid) n 2
2,3 (zeolit).



Hnh 5.25.
Vng 12 t din SiO
4
trong cu trc khung ca mordenit

Hnh 5.26.
S cu trc ca chabasit vi cc khoang
trng ln thng nhau
Cc nt en biu din nguyn t silic, cc
nguyn t oxy khng c th hin



195
Chng 6
HA HC TINH TH CA MT S KHONG
VT TO
6.1. OLIVIN
H trc thoi (+) () (Mg,Fe)SiO
4
forsterit Mg
2
SiO
4
fayalit Fe
2
SiO
4

mng a = 4,75; b = 10,20
c = 5,98
a = 4,82; b = 10,48; c = 6,09
Z = 4 Z = 4
Nhm kh. gian Pbnm Pbnm
nh hng Np = y; Nm = z; Ng = x Np = y; Nm = z; Ng = x
Mt trc quang (001) (001)
d
hkl
chnh, 4,29 (10); 2,41 (8); 1,498 (7) 2,24 (7); 1,734 (8);
Olivin (Mg,Fe)
2
SiO
4
l nhm
nesosilicat ph bin, nht l trong magma
nhit cao. Nguyn t oxy trong
nesosilicat xp cht theo lut su phng
ABABAB theo hng [100]; khin cho
olivin c t trng v cng tng i cao,
v c ct khai (010) v (100). Mc du trong
silicat ni chung, vic ion nhm thay th ion
silic xy ra ph bin v d dng, lng thay
th ny trong nesosilicat l thp.
(Mg,Fe)olivin c dung dch cng
hon ton gia Mg
2
SiO
4
(forsterit) v
Fe
2
SiO
4
(fayalit). i lng d
130
c th dng
xc nh thnh phn trong lot ng hnh
ny (hnh 6.4). Mt dy ng hnh lin tc
tng t cng quan st c trong (Fe,Mn)
olivin. Thnh phn ca hu ht cc olivin
(hnh 6.1) biu din trn h CaOMgOFeOH
2
O. Lot dung dch cng ph bin nht ca h
ny l FoFa. Tng i him l olivin thuc cc lot monticelitkirschteinit v fayalit
tephroit Mn
2
SiO
4
.
6.1.1 Cu trc tinh th
C s ca cu trc l lut xp cu su phng ca anion oxy thnh lp theo (100). Cc t
din SiO
4
khng trng hp nhau, cu trc cho thy chng hng nh v hai pha i nhau dc


196
theo [010] v ni vi nhau bng cation trung gian phi tr bt din. Cu trc ca olivin ch yu
ph thuc vo kch thc v ho tr ca cation trung gian ny (hnh 6.2). so snh c th
xem cu trc spinel (trang 104 v 105).
(Mg,Fe)olivin c dung dch cng hon ton gia Mg
2
SiO
4
(forsterit) v Fe
2
SiO
4

(fayalit). Mt dy ng hnh lin tc tng t cng quan st c trong (Fe,Mn) olivin. Thnh
phn ca hu ht cc olivin biu din (hnh 6.1) trn h CaOMgOFeOH
2
O. Lot dung
dch cng ph bin nht ca h ny l FoFa. Tng i him l olivin thuc cc lot
monticelitkirschteinit v fayalittephroit Mn
2
SiO
4
.
S phn b ca Fe
2+
v Mg
2+
trong v tr M1 v M2 tun theo mt trt t bin i, vi
mt nghch l l cation st ln nm nhiu hn ti bt din M
1
nh. Cc bt din ny gn vi
nhau qua cnh, khin khong cch caion cation co rt; xut hin lc y gia chng. i
ng, cnh chung ca cc bt din ny tr nn ngn li, ni y thu ht thm in tch m, gy
bin dng cc a din (theo Papike J.J. v Cameron M., 1976, xem quy tc Pauling, 4.2.1).
Trong olivin calci, tc l monticelit CaMgSiO
4
, calci chim v tr M2 v magnesi chim M1.

Hnh 6.2
Cu trc tinh th ca olivin
Ti vng p sut tng cao, olivin tip nhn cu trc cht hn ca spinel. Nhit 1000C
v p sut khong 140 kbar, ng vi su 300 n 400 km, xy ra bin i ca Mg
2
SiO
4

sang cu trc loi spinel . T pha sang pha l bin i xy ra khong 170 kbar v
cng nhit nh trn. Trong khong su t 250 n 670km, cc silicat tip nhn cu trc
vi phi tr bt din ca mt phn silic. Cc phn ng xy ra trong i chuyn tip ca manti
c th nh sau

:
Mg
VI
Si
IV
O
3
Mg
VI
2
Si
IV
O
4
+ Si
VI
O
2
enstatit olivin stishovit
Mg
VI
2
Si
IV
O
4
(olivin) Mg
VI
Si
2
O
4
(spinel)
Nm 1969 ngi ta thy olivin (ringwoodit) c cu trc loi spinel trn mnh thin
thch. Trc phng th nghim ca A.E. Ringwood, Trng HQG Australia, Canberra,

Ch s La M ch s phi tr ca ion ng trc. Stishovit c cu trc loi rutil, xem 4.3.2.


V spinel xem 6.13.6.


197
tng hp thnh cng olivin y vi thnh phn (Fe
0,7
Mg
0,3
)
2
SiO
4
. Bin i pha t sang
gii hn phm vi thnh phn vi t l Mg/(Mg+Fe) > 0,85. Tc dng ca p sut cao i
vi cc dung dch cng olivin giu st hn th hin trn hnh 6.3.
6.1.2 c im ho hc


Hnh 6.3
S chuyn pha olivinspinel
trong h Mg
2
SiO
4
Fe
2
SiO
4
nhit
800
o
C v 1200
o
C (theo Akimoto,
S. et al, 1971)
Hnh 6.4
Tng quan ca khong cch mt mng d
130
v
thnh phn trong dy ng hnh forsteritfayalit
Thnh phn ca olivin bin i t Mg
2
SiO
4
(forsterit) sang Fe
2
SiO
4
(fayalit) c s trao
i lin tc gia Mg
2+
v Fe
2+
(bng 6.1 v hnh 6.1) trong cu trc. Tn cc khong vt
fayalit v forsterit ln lt ng vi thnh phn Fo010 v Fo90100. Trung gian l cc
khong vt ferohortonolit Fo1030, hortonolit Fo3050, hialosiderit Fo5070, chrysolit
Fo7090. Ring olivin ly t lamproit Lai Chu (bng 6.2), th tn chrysolit ca n xc
nh bng thnh phn ho hc, hon ton ph hp cc bin th cng loi ca mt s lamproit
in hnh (West Kimberley, LeucitHills, MurciaAlmeria) chn i snh. Trong mt s
mu, olivin chim n 25% thnh phn khong vt (gm olivin, diopsit, phlogopit v sanidin
l thnh t chnh).
Bng 6.1
S liu phn tch ho ca olivin
Cu t 1 2 3 4 5 6
SiO
2
41,85 32,47 30,09 31,50 29,27 36,63
TiO
2
0,07 0,34 - 0,00 - 0,00
Al
2
O
3
0,00 0.02 0,00 0,04 - 0,07
Fe
2
O
3
- 0,18 - - -
FeO 2,05 53,14 69,42 40,33 1,20 8,59
MnO 0,21 0,73 0,28 26,009 65,23 0,44
MgO 56,17 13,22 0,91 1,59 1,98 19,69
CaO 0,00 0,00 0,08 0,05 2,32 34,17
Tng 100,35 100,10 100,78 99,66 100,00 99,61



198
S ion tnh trn 4 oxy
Si 0,988 0,977 1,003 1,038 0,974 0,997
Al 0,000 0,001 0,000 0,001 - 0,002
Ti 0,001 0,007 - 0,000 - 0,000
Fe
3+
- 0.004 - - - -
Mg 1,976 0,602 0,046 0,078 0,098 0,815
Fe
2+
0,040 1,363 1,937 1,112 0,033 0,196
Mn 0,004 0,018 0,008 0,728 1,838 0,010
Ca 0,000 0,000 0,003 0,001 0,083 0,997
(tr Si) 2,02 2,00 1,99 1,92 2,05 2,02

Thnh phn nguyn t chnh ngoi silic
Mg 98,0 30,3 2,3 4,0 5,0 74,9
Fe 2,0 68,7 97,3 58,0 1,7 19,2
Mn 0,0 1,0 0,4 38,0 93,3 0,9
1. Forsterite, serpentine. Douglas Creek. South Irland. New zealand (Cooper, A.F.,1976,
J. Geol. Geophis. New Zealand, 19, 603-23).
2. Hortonolite, ferrodiorite, upper zone a Skaergaard intrusion. East Greenland (Vincent,
E.A.,1964, Amst. Min.,49.805-6).
3. Fayalite, Gunflint Iron Formation. Minnesola- Ontario. USA
(Floran,.R.J. & Papike, J.J., 1978. J. Petr., 19. 215-88).
4. Knebelite, metasomatized limestone. Blue Bell Mine. British Columbia.Canada
(Mossman, D.J. & Pawson, D.J., 1976. Can. Min., 14.479-86).
5. Tephroite, Benallt Mine. Caernarvonshire. Wales. UK (Smith, W.C. etal., 1944.
Min.Mag., 27. 33-46).
6. Monticellite, alnoite. Talnakh. USSR (Nikishov, K.N. et al,. 1978, Abstracts IMA XI
Meeting, Novosibirsk. 56-7).
Mt s cc tinh th t nhin, nht l olivin giu st, c phn nh st v magnesi b
mangan v calci thay th. Nickel v chrom thng c mt trong olivin giu magnesi, ring
chrom th c trong cc phin mng chromit phn r t dung dch cng. Tng t, mt s Fe
3+
cng thng c mt trong nhng ht nh magnetit mc xen (xem li 5.2.4) hoc lin quan n
sn phm bin i do olivin b oxy ho. Mt lng nh calci c trong phn ln olivin (bnh
thng t 0,0 n 1,0% CaO). Phosphor gp trong olivin di dng nguyn t vt (c th t
400ppm), lm xut hin trng trong khoang t din bng thay th sau: P + Si.
Trong chrysolit Lai Chu s c mt ca hai nguyn t vt calci v nickel cng s bin
thin ca chng lin quan n hm lng cc nguyn t to chnh, nht l magnesi, l yu
t c trng cho olivin ca lamproit (Scott, 1979; Jaques et al., Michell, 1986). Kho st vi
thm trn mt s ht olivin phn i (Trn Trng Ho v nnk, 1991) cho thy t trung tm ra
ra ht MgO gim cha ca n th NiO gim theo, trong khi CaO li tng hm lng. So
snh gi tr bn knh ion th thy nickel l nguyn t tng thch, d dng i vo mng tinh
th ca olivin.


199
Bng 6.2
S liu ho phn tch ca olivin ly trong lamproit Lai Chu [12]
Cu t Nm Hon Nm Hon Cc Pa Simang
khang
Sin Cao Pn H
SiO
2
41,26 40,68 40,17 40,86 41,54 40,12
FeO 9,10 9,94 13,13 7,93 7,53 13,58
MgO 48,62 48,91 46,55 50,92 50,33 45,68
CaO 0,09 0,08 0,08 0,09 0,06 0,12
NiO 0,28 0,29 0,26 0,32 0,48 0,25
99,35 99,90 100,19 100,12 99,94 99,75

S ion tnh trn 4 oxy
(do tc gi sch ny tnh thm)
Si 1,01 0,99 0,99 0,99 1,00 1,00
Fe 0,18 0,20 0,27 0,16 0,15 0,28
Mg 1,78 1,97 1,72 1,84 I,82 1,70
Ca 0,00 0,00 0,00 0,00 0,00 0,00
Ni 0,00 0,00 0,00 0,00 0,00 0,00

Thnh phn (%) cc cation chnh
(do tc gi sch ny tnh thm)
fe # 15,77 16,89 12,00 13,47 13,01 22,92
mg # 84,23 83,11 78,00 86,53 86,99 77,08
# fe : FeO / (FeO + MgO + MnO)
mg: MgO / (FeO + MgO + MnO)
(Mg,Fe)olivin to dy dung dch cng lin tc. Vic mt ion bn knh ln thay th lin
tc cho mt ion bn knh nh c tc dng lm gim nhit nng chy. Cation st c cng
ho tr nh magnesi, nhng kch thc ln hn, nn n c lin kt yu hn vi oxy. Cng vi
vic n tham gia ngy cng nhiu vo cu trc, dung dch trung gian ln lt t Fo sang Fa c
nhit nng chy ngy cng thp. Nh vy, ht olivin u tin tch khi th lng (vi thnh
phn cho trc) giu Mg hn so vi ht kt tinh mun. Ion st ngy cng nhiu trong th lng
cn li. Nhit ho tan ca forsterit v fayalit l hm tuyn tnh ca thnh phn ng lng
gam; iu ny cho thy nhit thay th ng hnh bng khng v s cn bng nhit hon ho
c duy tr trong qu trnh st th chn magnesi.
Olivin rt mn cm vi bin i nhit dch, vi tc dng phong ho v bin cht s khai.
Sn phm ca qu trnh kh a dng, bao gm serpentin v hn hp ca idingsit, bowlingit v
chlorophacid. Idingsit nu gm smectit, chlorit v goethit/hematit. C ch bin i c s
khuch tn ion hydro vo cu trc olivin. Ti , chng gn kt nht thi vi ion oxy, khin
cho Mg, Fe
2+
v Si tch khi v tr ca chng, m ng cho Fe
3+
, Al v Ca vo thay th.
Bowlingit l sn phm xanh lc gm smectitchlorit cng vi serpentin v mt t talc, mica v
thch anh. Tng quan gia idingsit v bowlingit ph thuc ch yu vo trng thi oxy ho
ca st (sn phm xanh lc bin thnh sn phm nu khi b t trong khng kh 600C).
Chlorophacid khng khc idingsit my, nhiu mu hn, cha t Fe
3+
v nhiu Fe
2+
hn. Thnh
phn ca n c chlorit, smectit, goethit v calcit.


200
Serpentin ho l dng bin i rng ri nht ca olivin v l qu trnh bin cht ph bin
nht ca cc giu olivin (dunit v peridotit). Sn phm bin i chnh, ni ring ca olivin
giu Mg, l ba bin th a hnh ca serpentin (lizardit, chrisotil v antigorit), cng vi brucit,
talc v carbonat. Qu trnh serpentin ho c th biu din bng cc phn ng:
2Mg
2
SiO
4
+ 3H
2
O Mg
3
Si
2
O
5
(OH)
4
+ Mg(OH)
2

forsterit serpentin brucit
3Mg
2
SiO
4
+ 4H
2
O + SiO
2
2Mg
3
Si
2
O
5
(OH)
4

Phn ng ngc tin hnh bng thc nghim iu kin nhit v p sut ln lt l
375 v 425, 2 v 6kbar. Nu CO
2
tham gia phn ng th talc v magnesit c th hnh thnh:
2Mg
3
Si
2
O
5
(OH)
4
+ 3CO
2
Mg
3
Si
4
O
10
(OH)
2
+ 3MgCO
3
+ 3H
2
O
v xa hn, phn ng serpentin ho c th nh sau:
6Mg
2
SiO
4
+ Mg
3
Si
4
O
10
(OH)
2
+ 9H
2
O 5Mg
3
Si
2
O
5
(OH)
4
6.2. GRANAT
H lp phng. Nhm khng gian Ia3d. Z = 8.
d
hkl
chnh ca pyrop : 2,89 (8); 2,58 (9); 1,598 (9); 1,542 (10); 1,070 (8).
Kh tan trong HF, tr hydrogrosular.
Khong vt nhm granat rt c trng cho bin cht, nhng cng bt gp trong mt s
magma v trong vn trm tch.
6.2.1. Cu trc tinh th
mng c s ca granat cha tm n v cng thc X
3
Y
2
Z
3
O
12
.
Cng thc ha hc a()
Pyrop Mg
3
Al
2
Si
3
O
12
11,459
Almandin Fe
3
Al
2
Si
3
O
12
11,526
Spesartin Mn
3
Al
2
Si
3
O
12
11,621
Grosular Ca
3
Al
2
Si
3
O
12
11,851
Andradit Ca
3
Fe
2
Si
3
O
12
11,996
Uvarovit Ca
3
Cr
2
Si
3
O
12
11,996
Hydrogrosular Ca
3
Al
2
Si
2
O
8
(SiO
4
)
1m
(OH)
4m 11,85 12,16
Cu trc tinh th gm cc t din ZO
4
v cc bt din YO
6
xen k, ni vi nhau qua nh
to nn khung ng thc (hnh 6.5). Bn trong c cc hnh phi tr dng lp phng XO
8
.
Hnh ny c th m t l gm 12 mt tam gic. di a ca cnh mng l mt trong c s
gip xc nh tn ca khong vt granat:
a() = 9,04 + 1,61r(X) + 1,89r(Y)
trong r(Y) v r(Y) l bn knh trung bnh ca cation X v Y.


201
Granat bc l nng lc kt
tinh mnh. Dng quen thng
gp nht l khi mi hai mt
thoi (hnh 6.6, pha trn). Pha
phi l hnh ghp gia n v hnh
tm mt ba t gic (bn tri).
Hnh cho thy quan h gia hnh
thi tinh th granat v thnh phn
ca chng. Phn ln cc granat
sinh ra t qu trnh bin cht u
l dung dch cng ca bn
khong vt almandin, pyrop,
grosular v spesartin (hnh 6.7).
Tt c cc trao i ny u xy
ra trong v tr X phi tr 8.
Nhng thay th trong granat u
tng i hon ho, tr nhng
trao i lin quan ti Ca: CaFe
1
,
CaMg
1,
CaMn
1
. Cc dung dch
cng almandin spesartin vi
lng nh pyrop v grosular
thng bt gp trong phin
bin cht cp thp v trung bnh. Pyrop thng c trong sn phm bin cht p sut cao, nht
l trong tng eclogit. Grosular v andradit ph bin trong silicat calci (trong mi trng giu
calci).
6.2.2. c im ho hc
V tr X trong cng thc tng qut do cation ho tr hai ln hn chim gi, v tr Y dnh
cho cc cation ha tr ba nh hn. T s phn d trong v tr X, granat phn lm hai nhm:
pyralspit l granat vng calci, thay vo l cc cation ha tr hai l magnesi, st,
mangan.
ugrandit l granat cha calci.
Pyralspit Ugrandit
Pyrop Mg
3
Al
2
Si
3
O
12
Uvarovit Ca
3
Cr
2
Si
3
O
12

Almandin Fe
3
Al
2
Si
3
O
12
Grosular Ca
3
Al
2
Si
3
O
12

Spesartin Mn
3
Al
2
Si
3
O
12
Andradit Ca
3
Fe
2
Si
3
O
12

Hnh 6.5. Cu trc tinh th granat chiu trn mt (001)


202

Nu ch nhn nhn n thun l thuyt th nhm granat c th c ti 16 khong vt. Bi
v, mt trong bn kim loi ho tr hai Ca, Mg, Fe v Mn kt hp vi bn kim loi ho tr ba
Al, Fe, Mn v Cr (mi cp cation y li kt hp vi Si phi tr t din). Mt s t hp
cp trn; mt s khc t gp trong t nhin. Knoringit Mg
3
Cr
2
Si
3
O
12
hin c cng nhn l
thnh phn quan trng ca mt s granat trong kimberlit. S thay th ng hnh xy ra rng
ri trong nhm pyralspit cng nh trong ugrandit, nhng gia hai nhm ch c dung dch
cng mc hn ch. Trong s cation ho tr ba, nhm c mt trong granat nhiu nht, th
chn n l st v crom. y cng l cn c phn nhm granat theo cch khc:
Granat nhm Granat st Granat crom
Pyrop Almandin Andradit Uvarovit
Spesartin Grosular


Bng 6.3
S liu ho phn tch ca granat
1 2 3 4 5 6
SiO
2
41,33 36,7 36,34 38,96 36,48 36,77
TiO
2
0,28 0,75 0,10 0,71 0,50 -
Al
2
O
3
21,83 21,4 20,25 19,93 6,80 8,36
Cr
2
O
3
1,73 - - - 13,72
Fe
2
O
3
1,44 - 0,92 3,43 21,94 5,85
FeO 9,00 29,9 7,30 3,25 3,33 -
MnO 0,44 1,14 34,51 0,03 0,56 0,22
MgO 19,60 0,90 1,31 0,00 0,27
CaO 4,40 9,02 0,44 32,52 30,22 34,56
Tng 100,05 99,81 99,86 100,14 99,94 99,75


203

S ion tnh trn 24 oxy
Ion 1 2 3 4 5 6
Si 5,919 5,882 5,981 5,918 5,986 5,923
Al 0,081 0,118 0,019 0,082 0,014 0,077 6
Al 3,604 3,925 3,909 3,486 1,311 1,510
Cr 0,196 - - - - 1,747
Fe
3+
0,155 - 0,114 0,392 2,709 0,709
Ti 0,030 0,090 0,012 0,081 0,062 - 4
Mg 4,184 0,215 - 0,297 - 0,065
Fe
2+
1,078 4,008 1,005 0,413 0,457 -
Mn 0,053 0,155 4,811 0,004 0,078 0,030
Ca 0,675 1,549 0,078 5,293 5,313 5,965 6

Thnh phn (% mol) cc khong vt chnh
1 2 3 4 5 6
Almandin 17,4 67,4 17,1 5,8 7,8 -
Andradit 3,4 - 1,3 9,5 69,5 18,0
Grosular 2,5 26,3 - 79,2 21,4 36,2
Pyrop 70,4 3,7 - 5,0 - 1,1
Schorlomit 0,5 - - 0,4 - -
Spesartin 0,9 2,6 81,6 0,1 1,3 0,5
Uvarovit 4,9 - - - - 44,2
Pyrope, garnet-peridotite xenolith in kimberlite pipe. Matsoku. Lesotho, southern Africa
(Carswell, D.A. & Dawson, J.B., 1970, Contr. Min. Petr., 25. 163-84).
Almandine, chlorit-phengite-biotit-garnet-albit-quartz schist. Dora-Maira massif, western
Italian Alps (Chatterjec, N.D., 1971, Neues Jahrb. Min., 114. 181-215).
Spessartine, single crystal in green mica, Benson no 4 Pegmatit, north Mtoko region.
Zimbabwe (Hornung, G. & Knorring, O. von, 1962. Trans. Geol. Soc. South Africa. 65. 153-
80).
Reddish yellow grossular, crystalline limestone, Liconi, Val dAosta. Itali (Sanero. E.,
1935. Periodico Min. Roma, 6,213-20).
Andradite, hedenbergite-garnet-epidote-plagioclas skarn. Hallinmki borchole,
Virtasalmiarea, eastern Finland (Hivrinen, L., 1969, Bull. Comm. Gol. Finlande. 240. 82
pp. Includes Na
2
O 0,03, K
2
O0,02, H
2
O 0,06).
Uvarovite, quartz- albite- prehnite- uvarovite- pyrrotite, contact zone with nordmakite,
Kalkoven, Grua, north of Oslo, Norway (Prestvik, T., 1974, Norsk. Geol. Tidsskr., 54. 177-
82).


204
Nhm t din (OH)
4
cng c th thay th cho t din SiO
4
(c th coi nh 4H
+
thay
th cho Si
4+
) trong hydrogranat nh hydrogrosular Ca
3
Al
2
Si
2
O
8
(SiO
4
)
1m
(OH)
4m

vi m nm trong khong t 0 n 1. Khong vt cha ti 8,5% H
2
O.
Cation Ti
4+
c th nm
vo v tr Y, km theo l
s thay th ca Na cho Ca
trong v tr X, cho melanit
mu en. Trong granat c
th c nhng thay th ng
hnh nh P thay Si, Ti thay
Al hay Fe
3+
. Trong
hydrogranat, nhm SiO
4
c
th do 4(OH) thay th vi
v tr Si b trng. S liu
ho phn tch ca 6 granat
in hnh trnh by trn
bng 6.3. Granat pyrop in
hnh cha trong bin
cht cao ch c 40 70%,
t khi cha hn 80% cng
thc ny. Chng thng
cha c almandin v
grosular. Pyrop vi 3 8%
Cr
2
O
3
l bin th mang tn
chrompyrop, mu tm pht
lc hay mu ta c trng,
cng sinh ph bin ca chng l vi kimberlit cha kim cng.
Almandin l dng ph bin nht trong nhm granat. N thng cha mt lng ng k
c pyrop ln spesartin, c th c khng t grosular. phin granat mica thuc bin cht khu
vc cha granat thnh phn tiu biu, c th l Alm
66
Gro
25
Py
5
Sp
4
. Thot nhn, nhiu ht
almandin ng nht v mu sc, nhng chng li phn i v ho hc: almandin sn phm
ca bin cht khu vc c th cho thy phn nhn giu mangan, phn ra giu st. Trong nhng
trng hp khc, phn nhn giu calci v mangan, rim th giu st v magnesi hn. Chlorit
l sn phm bin i ph bin ca almandin.
Spesartin c mt khong bin thin rng v thnh phn t khong 97% cng thc
spesartin tr xung. Almandin l thnh phn thay th chnh, nhng mt lng ng k
grosular cng gp . Trong iu kin p sut trung bnh hai thnh phn ny thay th lin
tc cho nhau. V mt a ho, ytri v mangan l hai nguyn t song hnh, cho nn spesartin
c th cha ti hn 2% Y
2
O
3
. Qu trnh bin i v oxy ha b mt lm xut hin hn hp
mu en ca cc oxit v hydroxit mangan.
Grosular c th gp dng thnh phn thun nht; mc du vy, andradit c y v to
thnh lot ng hnh lin tc. Nhiu granat xanh lc do chrom c gi l uvarovit, trong
thc t hm lng chrom tng i nh v chng c gi l Cr-grosular. Mc du gia
grosular v hydrogrosular tn ti lot ng hnh, khng th khng nh rng grosular, sn
phm ca bin cht nhit, c cha lng nc ng k. Andradit kh ph bin vi tinh
Hnh 6.7. Thnh phn ca granat bin i theo cc vect trao i chnh


205
khit ti 90%. Tuy vy, andradit v grosular to hng lot dung dch cng: nhiu andradit
trong skarn bc l tnh phn i v thnh phn (v v mu sc), c s xen k nhau gia cc
i andradit gn sch v And
50
Gro
50
. Gia andradit v spesartin tn ti granat trung gian.
Andradit nguyn sinh trong magma kim c th cha khng t titan. Titan ch yu thay th
Fe
3+
trong v tr bt din, mt phn th chn Si
4+
trong khoang t din.
Melanit l Ti-andradit vi Fe
3+
> Ti trong v tr bt din. Cn schorlomit (cha khong
15% TiO
2
) l Ti-andradit vi Fe
3+
< Ti trong v tr ny. Uvarovit l thnh phn ca lot
ugrandit, nhng him gp di dng sch; grosular cng mt lng nh andradit tham gia
dung dch cng vi uvarovit (xem bng 6.3).
Hydrogrosular Ca
3
Al
2
Si
2
O
8
(SiO
4
)
1m
(OH)
4m
l khong vt thuc lot ng hnh
3CaO.Al
2
O
3
.3SiO
2
3CaO.Al
2
O
3
.6H
2
O
vi thnh phn nm gia grosular v hibschit 3CaO.Al
2
O
3
.2SiO
2
.2H
2
O.
Bng 6.4
S liu ho phn tch ca granat ly t granulit Kan Nak (Kontum) [15]
# 414-S4 414-S4 VN415 VN415 VN415 VN803 VN803
Nhn Ra/Bi Nhn Ra/Crd2 Ra/Crd2 Nhn Ra/Ilm
SiO
2
37,470 37,350 37,990 37,620 37,300 37,77 37,41
TiO
2
0,020 0,010 0,040 0,000 0,030 0,06 0,29
Al
2
O
3
21,560 21.460 21,790 21,780 21,940 22,19 21,83
Cr
2
O
3
0,000 0,010 0,010 0,000 0,020 0,04 0,02
Fe
2
O
3
1,720 1,750 1,840 1,750 0,270 1,42 1,92
MgO 6,430 5,500 6,530 5,320 2,460 7,79 6,78
FeO 30,840 32,190 30,210 31,740 35,470 29,99 30,60
MnO 1,540 1,640 1,900 2,090 2,980 0,58 0,62
ZnO 0,000 0,000 0,000 0,030 0,010 0,04 0,02
CaO 0,720 0,710 1,320 1,260 1,340 0,89 1,28
Na
2
O 0,000 0,001 0,000 0,000 0,000 0,01 0,01
K
2
O 0,010 0,001 0,000 0,000 0,000 0,00 0,00
Tng 100,310 100,660 101,630 101,590 101,830 101,18 100,78

S lng ion tnh trn 12 oxy v thnh phn khong vt ca granat
Si 2,949 2,950 2,947 2,944 2,963 2,945 2,921
Ti 0,001 0,001 0,002 0,000 0,001 0,004 0,017
Al 2,000 1,998 1,992 2,009 2,054 2,019 2,010
Cr 0,000 0,000 0,001 0,000 0,001 0,002 0,001
Fe
3+
0,102 0,104 0,107 0,103 0,016 0,083 0,113
Mg 0,754 0,648 0,755 0,621 0,292 0,896 0,789
Fe
2+
2,030 2,126 1,960 2,077 2,356 1,936 1,998
Mn 0,103 0,110 0,125 0,138 0,200 0,038 0,041
Zn 0,000 0,000 0,000 0,001 0,001 0,002 0,001
Ca 0,061 0,060 0,110 0,106 0,114 0,073 0,107
Na 0,000 0,002 0,000 0,000 0,001 0,001 0,001
K 0,001 0,001 0,000 0,000 0,000 0,000 0,000
Tng 8,000 8,000 8,000 8,000 8,000 8,000 8,000


206

XFe 0,729 0,766 0,722 0,770 0,890 0,677 0,717
Xalm 0,690 0,722 0,660 0,710 0,800 0,64 0,68
Xpyr 0,256 0,220 0,260 0,210 0,100 0,31 0,27
Xgro 0,021 0,028 0,040 0,040 0,040 0,04 0,04
Xspe 0,035 0,052 0,040 0,050 0,070 0,01 0,01
# Alm: almandin, Pyr: pyrop, Gro: grosular, Sp: spesartin.Bi: biotit, Crd: cordierit, Ilm:
ilmenit; Ra/Bi(Crd, Ilm): im tip xc ca granat vi cc khong vt ny;
XFe = Fe
2+
: (Mg
2+
+ Fe
2+
).
Xalm = Fe
2+
: (Mg
2+
+ Fe
2+
+ Mn
2+
+ Ca
2+
);
Xpyr = Mg
2+
: (Mg
2+
+ Fe
2+
+ Mn
2+
+ Ca
2+
)
Xgro = Ca
2+
: (Mg
2+
+ Fe
2+
+ Mn
2+
+ Ca
2+
)
Xspe = Mn
2+
: (Mg
2+
+ Fe
2+
+ Mn
2+
+ Ca
2+
)
Cc khong vt trong khong bin thin thnh phn ny cng gi l hydrogranat, nhng
chng phi c gi l granatoit mi ph hp y vi cng thc tng qut sau:
X
3
Y
2
(XO
4
)
3m
(OH)
4m
. Trong t nhin, cha tng gp khong bin thin thnh phn gia
hibschit v dng thiu silica 3CaO.Al
2
O
3
.6H
2
O. Hydrogrosular khng bn vng v ho hc
nh grosular; n ho tan chm trong acid chlorhidric v acid nitric.
Mi granat granulit Kan Nak (Kontum) ni chung u l almandin-pyrop, ngho grosular
v spesartin v tng i ngho andradit, d cho chng cn bng pha vi silimanit hay
tng phn ng vi n. Mc d thnh phn ho ca granulit bin i ra sao, chng u nm
ht thy trong min p sut t thp n trung bnh. Tuy nhin, y l cc granat phc tp. Khi
phn ng vi biotit hay spinel, trao i Fe
2+
v Mg vi chng, th s phn i ca granat kh
r nt (bng 6.4). Ti ch tip xc ny, granat tng hm lng Fe v do c almandin, cn
Mg th gim theo.
Trong khi , Mn hnh nh khng tham gia vo s trao i, mc d ti ch tip gip vi
biotit Mn tng nh. Khc vi granat, pha biotit tip gip khng c s phn i; biotit khng
ging granat v h s khuch tn Fe v Mg. Khi granat tip xc vi plagioclas, hay vi K-
feldspat mc thp hn, n trao i Ca v Al vi chng, to nn s phn i nh, do
rim grosular gim i cht. Ti vng granat tip xc vi cordierit (ra/crd, VN415) Fe
2+
v
Mg phn i vi bin ln hn. cha Alm tng t nhn ra ra ca ht v ca pyrop gim
theo.
Dy lin tc t grosular v 3CaO
3
.Al
2
O
3
.6H
2
O c th tng hp bng phng php nhit
dch, t th thu tinh vi thnh phn tng ng, iu kin di 500C v 2kbar.
6.3. NHM SILICAT NHM Al2SiO5
Nhm c 3 bin th l silimannit, andalusit v disten. Chng l cc alumosilicat thuc
ph lp nesosilicat ph bin trong bin cht cao v trung bnh. C ba khong vt u l cc
bin th a hnh ca Al
2
SiO
5
giu nhm, m cng thc ho tinh th Al
IV-VI
Al
VI
SiO
4
O th hin
tnh a dng trong phi tr ca cation nhm. Nt c trng ca c ba cu trc l cc bt din
ca nhm lin kt vi nhau qua cnh chung, to nn chui ko di dc trc c. C 3 khong vt
u kh d nhn bit trn mu cc ht th v trung bnh, dng lm khong vt ch th ca cc


207
i bin cht. Silimannit c th dng cho i vi nhit khong 500C v cao hn. Thng
thng tn ca chng dng t cho cc i bin cht. Disten thnh to trong i p sut kh
cao c t trng 3,55 n 3,66 so vi 3,23 ca silimannit. Andalusit, khong vt bn vng
iu kin p sut thp nht, c t trng t 3,15 n 3,20.
6.3.1. Silimanit AlIVAlVISiO4O
H trc thoi (+)
nh hng: Np = x Nm = y Ng = z
Mt trc quang: (010)
Ct khai: (010)
c s, : a = 7,48 b = 7,67 c = 5,77
Z = 4
Nhm khng gian: Pbnm
d
hkl
chnh, : 3,32(10) 2,49(7) 2,16(8) 1,579(7) 1,677(7)
Chui bt din AlO
6
song song vi trc c v lin kt vi cc t din SiO
4
v AlO
4;
cc t
din ny

xen k nhau dc hng c (hnh 6.8,a). Nh vy, trong silimannit ion nhm c mt
na nm trong a din phi tr bt din vi khong cch AlO 1,91 v na kia trong t din
vi AlO 1,77.
Thnh phn khong vt kh n nh n tinh khit. Ion thng xuyn vo thay th trong
cu trc l Fe
3+
, mt s khc c mt di dng tp cht. Nc b hp ph mt lng nh
trong bin th dng si fibrolit. T cc oxit hp phn c th tng hp silimannit nhit v
p sut cao. Khi nung trn 1000C n khng bn vng v bin i thnh mulit + thch anh.
Khi b phong ho n cho muscovit v sericit, pyrophyllit, kaolinit v montmorillonit.
6.3.2. Andalusit Al
V
Al
VI
SiO
4
O
Mt na lng nhm ca andalusit nm trong phi tr 5 vi cc hnh phi tr gn gin tip
vi nhau bng t din SiO
4
(hnh 6.8,b). Mt na nhm cn li c phi tr bt din khng u
n. Chng gn vi nhau qua cnh chung to thnh chui chy dc truc z. Cc chui song
song ny gin tip gn vi nhau qua nhm SiO
4
v AlO
5
. Khong vt c t khi (17,1
3
/ion
oxy) ln nht trong 3 bin th v nh vy bn vng iu kin p sut thp.
H trc thoi ()
nh hng: Np = z Nm = y Np = x MTQ:(010)
Ct khai: {110} (110): (1 0) = 89

c s, : a = 7,79 b = 7,90 c = 5,55
Z = 4 N.K.H: Pbnm
d
hkl
chnh, : 4,53(10) 3,96(8) 2,76(9) 2,17(10) 1,46(10)
Khong vt c thnh phn tng i tinh khit. Ch hai ion ho tr ba l st v mangan c
mt vi hm lng ng k. Thng thng, Fe
3+
thay cho Al nhiu nht cng cha t 2%.
Viridin ( phin chlorit-mica, theo Kramm U., 1973) l bin th giu mangan (16,75%
Mn
2
O
3
) cng cha n 0,82% Fe
2
O
3
. Ngi ta m t pha viridin vi 4,8% Fe
3
O
3
v 19,6%
Mn
2
O
3
. Khong vt vi cng thc (Mn
3+
,Al)AlSiO
5
cha 32,2% Mn
2
O
3
cng c bit ti v
kanonait l tn gn cho

pha u cui vi cng thc l tng Mn
3+
AlSiO
5
.


208
C th tng hp andalusit t kaolinit hay t Al
2
O
3
+ SiO
2
450 650C v p sut hi
nc gia 0,6 v 2,0kbar. Biu trng thi ca Al
2
SiO
5
(theo Bohlen S.R., Montana A. v
Kerrick D.M.,1991) cho thy im kp ba gia silimannit, andalusit v disten nm 530
20C v 4,2 0,3kbar. Andalusit d dng bin i thnh sericit. Chiastolit (bin th ca
andalusit thng cha bao th than; trn mt ct ngang tinh th c th thy hnh ch thp u
n, ti mu; ni y tp trung bao th) rt d b bin i kiu ny dc theo cc tuyn bao th
than. Khi tng nhit v p sut andalusit bin thnh silimannit v disten.
Andalusit thng bt gp cng cordierit trong cha st thuc i tip xc quanh th
magma xm nhp. Khi kiu bin cht ny cn giai on u, andalusit khng c dng a
din. V sau, n sm c dng thi vi mt ct ngang c hnh ch thp mu m, ni cha cc
bao th than; l chiastolit. mc cao hn andalusit tr nn thot khi bao th.
6.3.3. Disten Al
VI
Al
VI
SiO
4
O
H ba nghing ()
nh hng: Ng: z trn(100) = 27 32, trn (010) = 5-8
Np:x trn (001) = 0 3; Phn gic nhn (100)
Ct khai: {100} hon ton
Song tinh: (100), trc ST (100) hay //y hay z, (001) a hp
c s: a = 7,12; b = 7,85; c = 5,57; 89,98; 101,12; 106,01

Z = 4; Nhm khng gian P1
d
hkl
, : 3,18(10); 2,52(4); 2,35(4);1,94(5); 1,37(8)
Trong disten nguyn t oxy phn b theo lut xp cu lp phng bin dng nh. Cng
nh trong silimannit v andalusit, y c cc chui bt din AlO
6
v cc chui (chim mt
na s nhm) ny lin kt vi nhau bng ion Si, Al, O cn li. Silic phi tr t din vi 4 oxy,
nhm phi tr bt din vi 6 oxy (hnh 6.8,c).
Th tch mng c s V1 v th tch mol V2 ca 3 bin th a hnh Al
2
SiO
5
( 25C)
nh sau:
Andalusit Silimannit Disten
V1,
3
: 342 331 293
V2, cm
3
/mol: 51,5 49,9 44,1
R rng, disten c th tch ring nh nht v v vy n l bin th a hnh bn vng
iu kin p sut cao nht trong ba bin th.
Disten rt ging nhng bin th kia ch nguyn t khc l nh Fe
3+
thm nhp vo cu
trc ch vi s lng rt hn ch. i khi Cr c mt mt lng va phi. Mt lng nh Ti
c trong bao th thng bt gp di dng rutil. Nhng nghin cu gn y cho thy hm
lng kim loi kim trong disten khng vt qu 0,06%. Disten nhn to hnh thnh 900C
v 10 40kbar. Khi nung, n bin thnh mulit v mt pha thu tinh. Disten b phong ho th
cho pyrophyllit, muscovit v sericit. iu kin nhit v p sut thay i bin n thnh
silimannit hay l andalusit. Chng hn, trong bin cht khu vc n cho andalusit trong i tip
xc vi grannit mun. Cng vi hai khong vt kia, b nung disten tr thnh vt liu chu la
v c ba khong vt l nhng alumosilicat quan trng nht v phng din ny. Chng cng
thng gp trong nhng m khong tng i ln.


209

6.4. SILICAT O VNG
Silicat o vng hay cyclosilicat cha cc vng t din SiO
4
, c t l Si : O = 1 : 3. Hnh
6.9,a gii thiu mt trong ba cu hnh vng kn ny. n gin nht l vng ba vi v d duy
nht l titansilicat benitoit BaTiSi
3
O
9
. Vng bn c trong vi khong vt rt him, v d
papagoit Ca
2
Cu
2
Al
2
Si
4
O
12
(OH)
6
. Nhng vng su l cu hnh c bn trong cu trc ca cc
khong vt ph bin v quan trng. V d beryl Be
3
Al
2
Si
6
O
18.

6.4.1. Beryl Al
2
Be
3
Si
6
O
18

H su phng ()
Ct khai: {0001} khng hon ton
Song tinh:
{31 4 1} {11 2 0} v {40 4 1}
c s, : a = 9,200 9,220; c = 9,187 9,249
Z = 2; Nhm khng gian P6/mcc
d
hkl
, : 7,98(9); 4,60(5); 3,99(5); 3,25(10); 2,87(10)
Cu trc tinh th


210
Cu trc beryl (hnh 6.9) gm
cc vng su t din (Si
6
O
18
) xp
chng ln nhau thnh cc lp song
song vi {0001}. Cc l ca ion
beryli v nhm nm xen k gia cc
lp ca vng su. Beryli phi tr t
din nm gia hai vng, nhm phi
tr bt din nm gia ba vng. Vng
SiO sp t theo mt trt t ring,
sao cho mi t din c mt cnh
thng ng v c th dng mt
gng ngang ct qua cc ion silic
ca vng su (hnh 6.9,b). Chng sp
t vng n i din vng kia, khin
cho tm im (bn knh ca vng l
2,55) ca chng u nm trn trc
chnh bc su.
Bng cch y chng to nn
cho cu trc nhng knh rng ko
di theo trc chnh. Nhng knh ny
c th cha ng nhiu ion, nguyn
t v phn t. OH

, H
2
O, F

, He, cc
ion Rb
+
, Cs
+
, Ca
2+
v K
+
u nm
trong beryl theo cch y. Vi cc ion
kim loi kim ho tr mt trong knh
nh Na
+
, in tch tng ca cu trc
s trung ho bng c ch thay th:
2 kim
1+
Be
2+
hay 3 kim
1+
+ 1Al
3+
3Be
2+
.
Nc trong knh beryl c 2 loi: phn t nc loi I nh hng trc i xng ca n
vung gc vi trc z, trong khi phn t nc loi II xoay 90 do ion kim loi kim k cn tc
ng ln u m ca phn t nc lng cc.
Mc du beryl l thnh vin ca silicat vng su, nu nhn nhn vai tr ca t din BeO
4
v t din SiO
4
ngang bng nhau trong cu trc, th v ton cc c th nhn thy cu trc nh
mt khung ba chiu. V l do y, beryl cng c th xp loi vo ph lp silicat khung
(tectosilicat).
c im ho hc

Tng hm lng kim loi kim trong beryl c th ln ti khong 5 7%. Cng vi natri
v liti, cc ion kim c ln cng gp mt nh kali v cesi, nhng rubidi th t gp hn. S liu
phn tch ho cho thy (theo W. A. Deer, R.A. Howie & J. Zussman, 1992), beryl c th xp
hng theo hm lng kim nh sau:
Beryl khng kim: tng hm lng kim nh hn 0,1% trng lng.
Beryl kali ngho kim v beryl kali natri: K tri hn, 0,5 1,0% trng lng.
Beryl natri: natri tri hn, 0,5 1,0% trng lng.
Hnh 6.9. Cu trc tinh th beryl chiu trn (0001) (a)
v trn mt cha trc c (b)


211
Beryl liti natri: Na trong khong 0,0 2,0% trng lng, liti < 0,6% trng lng.
Beryl cesi liti: cesi > 0,5% trng lng.
Vy s c mt ca kim loi kim trong beryl r rng v vi mt lng ng k. Chng
chim gi cc knh rng, in tch dng chng mang n c th cn bng; bng c ch thay
th trong cu trc. S thay th c th nh sau:
3Be
2+
2Li
+
+ Si
4+,
Si
4+
Be
2+
+ 2R
+,
Si
4+
Al
3+
+ R
+
v Be
2+
+ Si
4+
2Al
3+
.
Dng hn hp cc oxit SiO
2
, Al
2
O
3
v BeCO
3
c th tng hp beryl bng phng php
nhit dch p sut thay i t 400 n 1500bar; 400C xut hin bt trng mn beryl cng
vi mt t phenakit Be
2
SiO
4
v chrysoberyl BeAl
2
O
4
. c nhiu phng php gip sn xut
emerald tng hp; ngoi cc oxit chnh cn c thm cht t ph gia Cr
2
O
3
. Mt trong nhng
phng php trng yu l qu trnh nhit dch ca Line c ph gia tr dung tng i n
gin.
Thng thng, beryl bin i thnh kaolinit, i khi c thm lng nh muscovit. Cc
khong vt khc nh bavenit, bertrandit, phenakit, epididymit v milarit cng l sn phm
bin i ca n. Vic beryl cha kim loi kim l yu t ch yu nh hng ti tnh cht
quang hc ca n. Hm lng kim lm tng gi tr chit sut v c lng chit sut mc
thp hn.
6.4.2. Cordierit (Mg,Fe)
2
Al
4
Si
5
O
18
.nH
2
O
H trc thoi (Gi su phng) () (+)
nh hng : Np = z, Nm = y, Ng = x; MTQ (010)
Np Nm Np : 1,527 1,560; 1,532 1,574; 1,537 1,578
2V

:

35 106
Ct khai: {100} trung bnh; {001}, {010} khng tt
{110}, {310} n gin, lin phin, dng vng
a sc: Mg-cordierit lt dy: Np vng/lc
Nm tm/lam tm, Ng lam nht
Vnh a sc quanh bao th zircon
c s: a 17,1; b 9,7; c 9,3; Z = 4; N.K.G. Cccm
Cu trc tinh th
Cordierit c bin th a hnh nhit cao l indialit, ng cu trc vi beryl, trong
nhm phn b ngu nhin trong vng su. Bin th nhit thp ph bin hn thuc h trc
thoi (gi su phng). Trong , vng su c 2 t din cha nhm, to nn cu trc trt t
o vng. Nhng, Al/Si phi tr t din (nh Be) lin kt cc vng ny theo chiu ngang v
chiu dc. V vy, theo G.V. Gibbs, cordierit tr thnh silicat khung vi Mg v Fe
2+
phi tr
bt din ging nh Al trong beryl. Cc phn t nc v ion kim loi kim gp trong khong
vt quy m thay i v nh v ln lt trong ch rng v hp ca knh do cc vng su to
nn.
Trong indialit t din trong vng su u tng ng v giu silic, cn ngoi vng su
th chng giu nhm. Cordierit c trt t cao ca silic v nhm khp ni trong cu trc; nhng
s trao i ion cng nh hng ti iu ny.
c im ho hc


212
Hu ht cordierit cha Mg vt tri trong v tr bt din, cordierit cha Fe hn 1 ion/n
v cng thc th him gp v c xu hng hn ch trong pegmatit. So snh vi cc khong vt
st magnesi nh biotit, granat, pyroxen thoi v spinel, cordierit thng giu magnesi hn st.
T l Si : Al khng thay i nhiu hn 5 : 4, tng ng vi nhu cu ca cu trc. Vng
su c 4Si + 2Al, bn ngoi c 1Si + 2Al. Thng cordierit ca pegmatit giu beryli th hm
lng nhm thp hn, hm lng silic v/hay ion kim cao hn. Cng vi kim, vng su
cha H
2
O, CO
2
, Ar, v.v Hm lng H
2
O
+
ca khong vt cordierit t 2,8% trng lng
tng ng khong mt phn t trn n v cng thc.
Cordierit hay bin i; sn phm thng gp nht l pinit pht lc; l hn hp
muscovit vi chlorit hay serpentin v oxit st. Thc nghim cho thy Mg-cordierit khan nng
chy bt chnh dung 1465C thnh mulit v cht lng. Fe-cordierit Fe
2
Al
4
Si
5
o
18
nng chy
bt chnh dung 1210C cho mulit, tridymit v cht lng. T thc nghm c th kt lun rng
nhit bin i cordierit t trc thoi sang su phng gim t 1450C i vi Mg-cordierit
xung khong 700C i vi thnh phn trung gian v tng n gn 900C i vi Fe-
cordierit.
6.4.3. Tourmalin(Na,Ca)(Mg,Fe,Mn,Li,Al)3(Al,Mg,Fe3+)6[Si6O18](BO3)(O,OH)
3(OH,F)
Ba phng () Dravit Schorl Elbait
n
e
: 1,612 1,632 1,535 1,650 1,615 1,630
n
o
: 1,634 1,661 1,660 1,671 1,633 1,651
Lng chit sut: 0,021 0,029 0,025 0,035 0,017 0,021
T trng: 3,03 3,18 3,18 3,22 2,90 3,10
a sc: Bin i mnh, hp ph : n
o
> n
e
mng c s: a = 15,8 16,0 c = 7,1 7,25
Z = 3 Nhm khng gian R3m
d
hkl
, : 4,24(7); 4,00(7); 3,51(7); 2,98(9); 2,58(10)
Cu trc tinh th
Tourmalin c cng thc tng qut l XY
3
Z
6
B
3
Si
6
(O,OH)
30
(OH,F). V tr Y nm trong
khoang bt din gia cc ion oxy v hydroxil. Ba bt din vy quanh trc i xng bc ba;
mi bt din chung cnh vi mt trong hai bt din kia, theo ng trt t ca lp brucit (hay
CdI
2
, xem 4.3.2, cu trc dng lp). Su nguyn t silic u c phi tr t din vi oxy. Su t
din ghp vng vi nhau; mi ci c hai oxy chung vi hai ci k bn; 2/4 oxy ny tr nn
trung ho in tch. Khng ging beryl, cc t din ca vng u hng nh oxy vi in
tch 1 cha trung ho v pha cc bt din. Phn ct li ca cu trc vi thnh phn
Y
3
(OH)
4
Si
6
O
21
s gn vi nhau bng ion Al, B v Na. Ion B phi tr t din, chung mt nh
oxy vi t din SiO
4
ca vng su. iu ny cho thy nguyn nhn ti sao Al khng vo thay
chn Si trong vng su. Bi v cu oxy ni AlOSi qu yu so vi SiOSi; n s b tiu
bin khi k cn l mi lin kt vn yu l BOSi. Ion Al (v tr Z) phi tr su vi oxy,
nm trong bt din mo m; mi i chung cnh vi mt bt din Mg cng trn mt phng.
Ion Na (v tr X) lin kt vi 3 nguyn t oxy v mt nhm hydroxil c phi tr t din.
Thnh phn ho hc ca tourmalin rt phc tp, cho n gn y cng thc c s ca n
vn cha xc nh (Deer W.A., 1992). Cu trc tinh th cng khng trnh khi tnh trng ny.
M hnh a ra sau y (Cornelis K. & nnk, 1993) cng c chi tit khc so vi m hnh trn


213
y (theo ngun dn). Cu trc tinh th ca tourmalin xydng trn c s cc vng Si
6
O
18

nm ngang; mi t din c hai oxy trung ho in tch ghp t din thnh vng. Hai oxy
kia vn cn d 50% in tch. Cc t din u hng mt trong hai ion ny v mt pha, lm
cho vng su tr nn c cc (ging nh m hnh trn). Ti tm ca chng, Na
+
v

OH

xen k
nhau dc trc ng ( y khng ni Na c phi tr t din). Xen gia cc vng su l lp
tam gic BO
3
(khng phi B c phi tr t din). Nhm bt din (Li,Mg,Al)O
4
(OH)
2
lin kt
vng Si
6
O
18
vi nhm BO
3
. Cc nhm (Al,Fe,Mn)O
5
(OH) ghp cc ct vng su vi nhau.
c im ho hc
Thnh phn ho hc ca tourmalin c th biu din bng cng thc tng qut nh dn
XY
3
Z
6
B
3
Si
6
(O,OH)
30
(OH,F), trong v tr gip phn bit cc khong vt thnh vin nh
sau:
X Y Z
Elbait Na Al,Li Al
Olenit Na Al Al
Dravit Na Mg Al
Schorl Na

Fe
2+
Al
Tsilaisit Na Al,Mn Al
Buergerit Na Fe
3+
Al
Lidicoatit Ca Li,Mg Al
Uvit Ca Mg Al,Mg
Feruvit Ca Fe
2+
Al,Fe
3+
,Mg
Ca Mn Al,Mn
Feridravit Na Mg Fe
3+
Chromdravit Na Mg Cr
Ti v tr X, Na c th b K hay Ca thay th nu tho mn c iu kin ho tr; chng
hn uvit c s thay i NaAl CaMg. Ti Y ion vt tri l Fe
2+
nh trong schorl, l Mg
nh trong dravit, hay l Al,Li nh trong elbait; mt s ion khc c th vo v tr ny, l Zn,
Cu, Ba, Mn (nh trong tsilaisit) v V hay Cr nu tho mn c iu kin ho tr.
Ion Fe
3+
thay cho Al trong Z khin cho tourmalin cha st ba tin trin thnh feridravit.
Buergerit l thnh vin cha Fe
3+
ch yu trong Y, nhng ho tr vn duy tr; l do
(O,OH)
30
(OH,F) i thnh O
30
(OH,F). Nh c R
+
, OH

, F

m ion ho tr ba R
3+
bin ng.
Gii php nm trong hai trao i sau:
(1) (OH)

+ R
2+
= R
3+
+ O
2
v (2) R
2+
+ R
+
= R
3+
+ ;
Al
3+
l cation R
3+
ch yu. C ch (1) gii thiu mt dung dch cng vi pha cui l
hydroxilbuergerit.
Vic tng hp tourmalin thc hin bng phng php nhit dch trong khong t 400
700C v 1 2kbar. Tourmalin tin gn ti u cui: (Mg
2
Al)Al
6
B
3
Si
6
O
30
(OH) l sn phm
tng hp 700 800C. Tourmalin ca Na v Al l sn vt nhn to tip cn olenit l tng:
NaAl
3
Al
6
B
3
Si
6
O
30
(OH), l Al-buergerit sinh ra 450 600C v 1kbar. Tuy vy, nhiu cng
trnh thc nghim i xa hn cho thy s cn thit phi xc lp ranh gii cho thnh phn ca
tourmalin.


214
Trong t nhin tourmalin bin i thnh muscovit, biotit hay lepidolit, mica, hoc chlorit
v kookcit LiAl
4
(Si,Al)
4
O
10
(OH)
8.
Gi tr chit sut, lng chit sut v trng lng ring tng t l thun vi lng (Fe
2
+
Fe
3+
+ Mn + Ti). Tnh a sc thay i vi cng ln, nhng rt mnh tourmalin cha st.
Kh nng hp ph nh sng lun lun phn bit; theo n
o
ln

hn theo n
e
, kt qu l hp ph ti
a xy n khi trc z nm vung gc vi phng dao ng trong Nicol phn cc. i vi
schorl tia thng c tc xuyn thu vt 10%.
6.5. BIOPYRIBOL
Danh t ny phn nh s lin quan v ho hc tinh th gia silicat lp (vi BIOtit l tiu
biu), silicat chui (vi PYRoxen) v silicat chui kp (vi amphiBOL). Mica, pyroxen v
amphibol c th l nhng nhm khong vt lin quan nhau v mt ho hc tinh th
(Thompson, 1978, 1981).
6.5.1. Tng quan ha hc tinh th micapyroxenamphibol
T pyroxen sang amphibol ri n mica c th l s chuyn ho lin tc, kt qu ca
trnh t trng hp nhm chc chui n sang chui kp 2, chui kp 3, v sau cht l
chui kp . Khng nhng th, amphibol c th xem nh c dng nn t nhng modul
ca pyroxen v ca mica. Quan h cu trc gia ba nhm khong vt biu din trn hnh 6.10.
C th ni, cu trc ca amphibol dng nn t nhng gii bng t dinbt dint din vi
mt ct ngang hnh ch I. Phn gia ca gii bng amphibol tng ng vi modul mica v
cu trc, vch hai bin ca n dng nn t cu trc ca modul pyroxen. C th nhn thy rng
mt vi v tr tinh th hc trong amphibol nh v tr A ly t modul mica v v tr M4 ly t
M2 ca modul pyroxen.
Chng l A v tr ca nguyn t kim, M (tc l M1, M3 v M4) ca nguyn t kim loi
khc v T v tr t din ca Si. By v tr cation ca amphibol c th coi nh xut pht t
modul mica (A, M3, M1, T1) v t modul pyroxen (M4, M2 v T2). V tr M4 v M2 ca
amphibol ln lt ng vi M2 v M1 ca pyroxen, M3 v M1 ca amphibol ng vi M1 v
M2 ca mica. Bng 6.6 cho thy by cng thc ca amphibol; chng l sn phm kt hp ca
pyroxen v mica. Khng phi tt c cc dng gi nh y u l nhng khong vt bn vng.
Bng 6.5
i chiu cc v tr tinh th hc trong pyroxen, amphibol v mica
Khong vt Cc v tr
Pyroxen M2 M1 T O
Amphibol A M4 M3 M1 M2 T1 T2 O (OH)
Mica A M1 M2 T O (OH)
Phi tr 12 6-8 6 6 6 4 4
K Na Mn Mn Al Al Si OH
Na Ca Fe
2+
Fe
2+
Ti Si Al F
Ca Mn Mg Mg Fe
3+
Cl
Cation xp vo
tng v tr
thch hp
Fe
2+
Al Al Mg
Mg Ti Ti Fe
2+



215

Bng 6.6
Quan h micapyroxenamphibol
2Pyroxen + Mica = Amphibol
2CaMgSi
2
O
6
+

Diopsit Mg
3
Si
4
O
10
(OH) = Talc Ca
2
Mg
5
Si
8
O
22
(O
H)
2
Tremolit
2MgMgSi
2
O
6
+ Enstatit Mg
3
Si
4
O
10
(OH)
2
= Talc Mg
2
Mg
5
Si
8
O
22
(O
H)
2
Anthophill
it
2NaAlSi
2
O
6
+ Jadeit Mg
3
Si
4
O
10
(OH)
2
= Talc Na
2
Mg
3
Al
2
Si
8
O
22
(OH)
2
Glaucoph
an
2NaFeSi
2
O
6
+ Acmit Fe
3
Si
4
O
10
(OH)
2
= Fe-Talc Na
2
Fe
3
Fe
2
Si
8
O
22
(OH)
2
Riebeckit
2CaMgSi
2
O
6
+ Diopsit KMg
3
AlSi
3
O
10
(OH)
2
= Phlogopit KCa
2
M
g
5
AlSi
7
O
2
2
(OH)
2
K-edenit
2CaMgSi
2
O
6
+ Diopsit NaMg
3
AlSi
3
O
10
(OH)
2
= Na-Phlogopit NaCa
2
Mg
5
AlSi
7
O
22
(OH)
2

Edenit
2CaAlAlSiO
6
+ Ca-tschermak Mg
3
Si
4
O
10
(OH)
2
= Talc Ca
2
Mg
3
Al
2
Al
2
Si
6
O
22
(OH)
2
Tscherma
kit
C th thy, trong bng 6.5 cation xp theo mc thch hp vi tng v tr tinh th hc
ca biopyribol. Cc v tr M4, M2 v T2 trong amphibol c cc tp hp rt ging nh ca cc
v tr tng ng M2, M1 v T trong pyroxen. Cng c th ni nh vy v cc v tr A, M3,
M1 v T1 ca amphibol v A, M1, M2 v T ca mica. Mt s trng hp c bit: v d,
M1v M2 trong mica cha Al
VI
, trong khi nhm phi tr su ny li tp trung ti M2 ca
amphibol v M1 ca pyroxen. Calci khng bao gi nm trong v tr kim (A) ca amphibol,
nhng mt s mica nh margarit v xanthophyllit li cha calci trong A.
Vect thay th tschermak Al
VI
Al
IV
Mg
1
Si
1
bao qut v tr M2 phi tr su trong amphibol
v M1 trong pyroxen cng nh cc v tr t din. Vect ny c mt trng hp c bit l
Al
VI
cng c th chim cc v tr M1 v M2 ca mica, M3 v M1 trong amphibol. Vect trao
i plagioclas NaSiCa
1
Al
1
gm vic thay th ca Na cho Ca ti M4 ca amphibol

hay M1
ca pyroxen v s thay th trong v tr t din ca Si cho Al. Mica l trng hp c bit
y; v s thay th ny xy ra trong v tr A ca mica (chng khng c v tr tng ng vi
M4 ca amphibol).


216
FeMg
1
v FeMn
1
l nhng vect trao i c trong tt c cc v tr bt din M ca
biopyribol. Tuy nhin, cation khng th thch hp nh nhau i vi tng v tr, bi v khng
phi tt c cc v tr u c kch thc nh nhau.


Hnh 6.10
S cu trc tinh th chiu dc trc c ca (a) pyroxen, (b) amphibol v dc
trc b ca (c) mica cho thy nhng nt tng ng
C th coi cu trc ca amphibol dng ln t modul pyroxen v modul mica. T gc nhn
ho hc tinh th, v tr M4 v M2 ca amphibol tng ng M2 v M1 ca pyroxen, M1, M3
v A ca amphibol ln lt tng ng M1, M2 v A ca mica. Px = pyroxen, T = t din, B =
bt din.
V tng quan kch thc th cc v tr xp theo th t nh sau:
trong amphibol M4 > M3 = M1 > M2;
trong pyroxen M2 > M1 v trong mica M1 = M2.
Cn cation th xp theo th t gim bn knh ion: Ca > Mn > Fe
2+
>Mg. Cho nn Ca, Mn
v Fe thch hp vi v tr M4 ca amphibol v M2 ca pyroxen; cn Mg th thch hp vi M2
amphibol v M1 pyroxen.
T gc a cht, silicat lp c tm quan trng ln, trong mica l thnh phn chnh
ca phin v magma. Hnh thnh nhit thp hn so vi pyroxen v amphibol,
chng thng sinh ra do kt qu ca phn ng thay th khong vt thuc hai lp sinh sm y
bng bin i nhit dch. Chng hn, talc l sn phm ca s thay th trc tip t pyroxen thoi
dc khe nt m Veblen D.R. v Buseck P.R. (nm 1981) quan st c di knh hin vi
in t phn gii cao. y l qu trnh bin i phc tp v mt ho hc v tinh th hc.


217
Nhiu sn phm trung gian ca qu trnh ny pht hin c mi y. Chng l kt qu
ca hydrat ho trn cc silicat chui enstatit v anthophillit.
6.5.2. Mt s khong vt biopyribol

Hnh 6.11
a) S chui n v chui kp (mt ct ngang) ca pyroxen, amphibol v
biopyribol;
b) S ch hng ca cc phn ng gi nh nhm bin i pyroxen thnh silicat
lp.
Cc ch s ch chui kp: kp 2 trong amphibol, kp 3 trong biopyribol, do cc chui
n 1 ca pyroxen trng hp nn. T suy ra s trng hp cao nht ca chui n,
vi sn phm l silicat lp (theo Veblen D.R. v Buseek P.R., 1981)
Nm 1977, Veblen D.R. bt gp nhng pha rn mi, mang tn chung biopyribol. Hai
trong s pha rn mi tm c c cu trc c trng (hnh 6.11,a) ca nhm chc chui kp
ba (do s trng hp ca 3 chui n) l:
jimthomsonit (Mg,Fe)
10
Si
12
O
32
(OH
4
)
v chui kp phc hp xen k gia chui kp 2 v chui kp 3 l:
chesterit (Mg,Fe)
17
Si
20
O
54
(OH)
6
Nhng pht hin sau (1983) ca cng tc gi cho thy s c mt ca chui kp bn
trong mt sn phm cng loi. Chng xut hin giai on chuyn tip ca s pht trin cu
trc tinh th t silicat chui, tc l pyroxen (khong vt nhit cao, khng cha nc) sang
silicat lp, tc l mica (khong vt nhit thp, cha nc) theo s trn hnh 6.11,b.
Di knh hin vi in t, cc tc gi cn cho thy biopyribol vi cu trc mch kp ba
nm gia mt bn l th st (cha b bin i) ca augit vi bn kia l talc. Vy, biopyribol l
sn phm trung gian trong lot phn ng :
pyroxen silicat mch kp ba talc.


218
6.6. PYROXEN

Enstatit (+)
H trc thoi
Diopsit (+)
H mt nghing
Np 1,650 1,768 1,664 1,732
Nm 1,653 1,770 1,672 1,730
Ng 1,658 1,788 1,694 1,755
Ng Np 0,007 0,020 0,031 0,024
2V 125 53 125 50 62
nh hng Np

= y; Nm=y; Ng

: z = 3848
Mt trc quang (100) (010)
mng c s a =18,2218,43 a = 9,75 9,85
b = 8,81 9,08 b = 8,90 9,0
c = 5,17 5,24 c = ~5,3
= 104,8 105,8
Z = 16 Z = 4
Nhm khng gian P b c a C 2 / c
d
hkl
, 3,17(10);2,94(4);2,87(9); 3,23(8);2,98(10);2,94(7);
2,53(4); 2,49(5) 2,53(4);1,748(4)
Inosilicat bao gm pyroxen vi nhm chc chui n v amphibol vi nhm chc chui
kp. Gia chng c nhiu im tng ng. Hu ht khong vt ca chng u thuc h mt
nghing, nhng c hai u c nhng khong vt trc thoi. Thng s mng c dc chui n
hay chui kp u c ln khong 5,2. Thng s b ca chng cng gn nh nhau. Duy
thng s a th amphibol c nhm chc chui kp nn a c di ln gp i so vi a ca
pyroxen.
Hai bn u c nhng cation cng loi trong thnh phn. Nhng nhm hydroxil (OH) ch
c mt trong amphibol. Mc d cc khong vt ca hai pha c biu hin nh nhau v mu
sc, v nh, v cng; nhng nhm (OH) trong amphibol lm cho t trng v chit sut
ca chng thp hn so vi ca pyroxen. Tinh th ca chng c dng quen ko di dc theo
hng ca chui. Tuy vy, lng tr ca pyroxen thng ngn, dng thi. Tinh th ca
amphibol l lng tr di, hnh kim. Mt ct khai theo {110} phn bit r rt v gi tr gc c
th lin quan trc tip n mt ct ngang ca cu trc chui.
Thnh phn ho hc ca pyroxen c th biu th bng cng thc tng qut XYZ
2
O
6
,
cation X nm trong v tr tinh th hc M2; Y trong v tr M1 (ring Fe
2+
tp trung trong v tr
tinh th hc M2 ca pyroxen trc thoi Pbca); Z ch Si
4+
nm trong tm cc t din ca chui.
C th thy rng cation X thng ln hn cation Y, tng ng vi kch thc ca cc v tr
M2 v M1. Cu trc pyroxen da trn nhm chc chui n Si
2
O
6
ko di theo trc c. Trong
pyroxen thoi, bt din M1 bin dng nhiu hn so vi bt din M2.


219
6.6.1. Cu trc tinh th
Cu trc pyroxen da trn nhm chc chui n Si
2
O
6
ko di theo trc z (xem li hnh
4.24 v 4.38), do t din silicoxy gn vi nhau ti hai nh. Chu k tun hon dc chiu di
ca chui ng vi hai t din v bng khong 5,2. Gi tr ny l thng s c ca mng c
s. Cc chui ghp vi nhau nh lp cation X v Y: X gn chng vi nhau pha y t din
(1/3 oxy d 1), Y gn chng pha nh vi mi oxy in tch d 1 (xem cc hnh 6.10,a
v 6.11,a).
So snh thng s mng ca diopsit mt nghing v enstatit trc thoi (xem bng trn), c
th thy chng tng ng v cc thng s b v c, cn a (ca pyroxen trc thoi) th gn bng
2asin (mt nghing).

Hnh 6.12
S cu trc pyroxen mt nghing chiu trn mt vung gc trc c (a)
Ct khai dc lng tr trc thoi lin quan ti chui Si-O vi mt ct ngang dng ch I (b)
Trong pyroxen mt nghing (hnh 4.24, 6.11), v tr M2 l a din khng u n ca s
phi tr 8 (theo Prewitt C.T. v Burnham C.W., 1966). Chnh ni y, cc t din hng mt
y trung ho 2/3 in tch ca chng li vi nhau, cnh l cc cation in tch thp ca
M
2
; lin kt yu bin ni y thnh khu gic cha s min gin on
D tch gin ca cu trc chui. Trn thang nguyn t, mt ct khai ln sng, lch
gia cc chui SiO v ct qua cc mi lin kt ca v tr M2.

Hnh 6.13
Cc vect trao i cho thy nhng lin quan v thnh phn ho hc
gia cc pyroxen trong t gic enstatitferosillithedenbergitdiopsit vi


220
nhau v vi cc pyroxen nhm
Pyroxen c th chia thnh mt s nhm, ph bin nht trong s th hin trn phn t
gic DiHdFsEn ca h trn hnh 6.13. Phn t gic ny bao gm cc thnh phn ca dy
ng hnh ph bin l:
diopsit CaMgSi
2
O
6
CaFeSi
2
O
6
hedenbergit thuc h mt nghing v


221

enstatit MgSiO
3
FeSiO
3
ferrosillit thuc
h trc thoi enstatit.
V mt danh php, trc y thnh phn
trung gian ca dy tng c tn; nh bronzit
v hipersthen l cc thnh phn ca dy trc
thoi, salit v ferosalit l ca dy mt nghing.
iu ny tri vi quy nh ca danh php
hin i (theo Morimoto et al., 1988).
Ngoi tn ca cc pha u-cui nh trn
hnh dn, thnh phn trung gian s din t
bng phn trm ca khong vt gn hn trong
hai khong vt u v cui dy. V d, En
80
n
nh cho khong vt ca dy trc thoi hai cu
t, n c 80% phn t enstatit v 20% phn t
ferrosillit trong thnh phn. Tng t, mt pha
trong dy diopsit hedenbergit c th biu th bng phn trm phn t, chng hn Di
50
Hs
50
.
Cn ni thm rng t gic DiHdFsEn chnh l mt phn ca h ba cu t Wo
(wolastonit)En (enstatit)Fs (ferosillit). Theo , diopsit hay hedenbergit (hai nh Di v Hd
ca t gic va ni) c thnh phn ln lt l En
50
Wo
50
v Wo
50
Fs
50
(ng vi hai trung im
hai cnh ca tam gic). Tng t, Di
50
Hd
50
= Wo
50
En
25
Fs
25
v bt c thnh phn no tng
qut hn nm trong lng t gic u din t bng phn trm phn t ca h ba hp phn.
Augit lin quan cht ch v thnh phn vi cc thnh vin ca dy DiHd, nhng vi mt s
thay th, nh Na thay cho Ca trong M2, Al cho Mg (hay Fe
2+
) trong M1. Pigeonit c trng
thnh phn ca cc dung dch MgFe, nhng vi cha Ca phn no cao hn so vi dy
enstatitferosillit; thnh phn Pgt tng ng mt phn ca trng pyroxen trc thoi. Pyroxen
cha Na l aegirin NaFe
3+
Si
2
O
6
v jadeit NaAlSi
2
O
6
. Mi khong vt trong cp y to vi
augit mt dy ng hnh: aegirinaugit v jadeitaugit. Omphacit l mt trong nhng thnh
vin ca dy th hai. Spodumen LiAlSi
2
O
6
l pyroxen tng i him, tm thy trong
pegmatit giu liti.
Cc thay th chnh xy ra trong pyroxen th hin bng cc vect:
FeMg
1
, CaMg
1
, Al
VI
Al
IV
Mg
1
Si
1
(tschermak)
Thay th quan trng p sut cao l vect jadeit:
NaAl
VI
Ca
1
Mg
1

Ba vect u th hin trn hnh 6.13. Trao i FeMg l ca cc cp diopsithedenbergit
v enstatitferosillit. Cc vect CaMg
1
v CaFe
1
cho ra i cc i enstatitdiopsit v
ferosillithedenbergit. Quan h pha trong t gic pyroxen c phn phc tp, do va c min
solvus trong pyroxen va c bin i pha trong vng ngho calci ca h. Vng nhit thp
(hnh 6.14) c min gin on gia pyroxen trc thoi (Opx) v pyroxen mt nghing (augit)
v min ny tri rng khp t gic (hnh 6.15,a). Gia 800 v 900C pigeonit tr nn bn
vng trong h khng c Mg (hnh 6.15,b), bi v solvus co rt v pha vng MgCa.



222

Vect tschermak gp trong c pyroxen FeMg ln pyroxen calci, lm xut hin cc cng
thc u cui FeAlAlSiO
6
, MgAlAlSiO
6
v CaAlAlSiO
6
; ln lt ng vi cc trao i Fe
2+
Si
Al
VI
Al
IV
, MgSi Al
VI
Al
IV
v CaSi Al
VI
Al
IV
. Nhng thay th ny ch xy ra trong
phm vi hn hp ca pyroxen bin cht. Tr li vi c ch thay th chnh ca pyroxen, c th
nhn xt rng Fe
2+
c th thay th Mg
2+
trong mi t l cho n gn 90% FeSiO
3
. Tuy vy,
trong cc pyroxen trc thoi ph bin t l Fe : Mg him khi vt 1 : 1. Enstatit tinh khit cha
40,0% MgO v 60,0% SiO
2
. Pyroxen trc thoi cha khng qu 1,5% CaO. Ferrosillit FeSiO
3
tinh khit him gp trong t nhin; bi v trong cc khong nhit v p sut quan st c
chnh t hp fayalit + thch anh
vi thnh phn tng ng tc l
Fe
2
SiO
4
+ SiO
2
(= 2FeSiO
3
)
l pha bn vng hn. Trong s
pyroxen mt nghing, cc pha ca
dy clinoenstatit clinoferrosillit
vi cng thnh phn MgSiO
3

FeSiO
3
, nhng km bn vng hn
v bn vng nhit cao hn, do
t ph bin hn, so vi cc pha
tng ng ca orthopyroxen.
Min gin on v min mc
xen. Trong pyroxen min gin
on rng ln gia augit v
pyroxen trc thoi (khng phi l
solvus, v hai pha ny khng ng
cu trc; solvus thc s ch c
augit v pigeonit) tn ti dc cc
vect CaMg
1
v CaFe
1
trong
pyroxen, nh hnh 6.12 gii thiu.


223
Biu TX (hnh 6.14) cho thy phm vi ca min gin on trong mt h khng c st.
Hnh 6.15 gii thiu cc mt ct ng nhit v ng p ca t gic pyroxen.
iu ny m ra trng cng sinh ba pyroxen: augit, pigeonit v pyroxen trc thoi. Nhit
tng, solvus tip tc co rt v vng MgCa, cho n khi pigeonit tr nn bn vng trong
h khng c st nhit khong 1300C (hnh 6.15,c). Gia 950 v 1000C pyroxen trc
thoi bin thnh protoenstatit (hnh 6.14). S kt hp gia s chuyn i cu trc (mt nghing
sang trc thoi) v vng gin on lm xut hin s mc xen rt phc tp khi pyroxen ngui
dn.
Nhn xt: Calci ho tan trong pyroxen trc thoi t hn hn so vi s ho tan ca Fe+Mg
trong v tr M2 ca augit. Min gin on vng giu st thu hp hn so vi vng giu Mg, v
vect trao i CaMg
1
t tc dng hn (v min gin on rng hn) so vi vect CaFe
1
.
Hnh 6.16 gii thiu quan h gia pyroxen natri v pyroxen calci thng qua cc vect thay th
jadeit NaAl
VI
Ca
1
Mg
1
v plagioclas NaSiCa
1
Al
IV
1
.
C th thy, tam gic diopsithedenbergitCa-tschermak xut hin c hai hnh 6.13 v
6.16. Ni chung, jadeit l pyroxen tiu biu ca vng p sut cao v c th ca phin lam
hay tng eclogit. Omphacit l bin tng ca pyroxen, tc l thnh phn trung gian gia
jadeit v diopsithedenbergit (hnh 6.17). N l pha tng gp trong t nhin, nm gia
tremolit v glaucophan, ti min gin on dc vect jadeit.
Acmit NaFe
3+
Si
2
O
6

l pyroxen quan trng khc. N lin quan vi diopsit bng s trao i
NaFe
3+
CaMg v vi jadeit bng
Fe
3+
Al. Acmit l pyroxen ph
bin trong mi trng p sut cao
cng nh trong magma kim. Cn
nhn mnh nng lc ca vect trao
i y. V d, s lin quan gia
dung dch cng ca pyroxen v
plagioclas, m thot nhn c th cha
thy. Nhng t hnh 6.16, gia Ca-
tschermak v jadeit chnh l vect
trao i kiu plagioclas. Nh vy,
mt thay i bt k trong t l
tschermak/jadeit ca pyroxen cng c
th c phn nh bng mt thay i
anorthit/albit ca plagioclas trong
cng loi .
6.6.2. c im ho hc
Thnh phn ho hc ca pyroxen c th biu th bng cng thc tng qut XYZ
2
O
6
; trong
, X ch Na
+
, Ca
2+
, Mn
2+
, Fe
2+
, Mg
2+
v Li
+
trong v tr tinh th hc M2; Y ch Mn
2+
, Fe
2+
,
Mg
2+
, Fe
3+
, Al
3+
, Cr
3+
v Ti
4+
trong v tr M1; ring Fe
2+
ch tp trung trong v tr M2 ca
pyroxen trc thoi Pbca. Cation X thng ln hn cation Y. Z ch Si
4+
trong t din ca chui.
Pyroxen gm cc khong vt thuc h trc thoi v h mt nghing (ortho- v clinopyroxen).
Pyroxen trc thoi ch yu thuc lot thnh phn ho hc n gin: (Mg,Fe)SiO
3
; khc hn
Hnh 6.17. Cc vect trao i gia pyroxen calci
(diopsit) v pyroxen natri (jadeit v acmit)


224
vi pyroxen mt nghing c khong bin thin rt ln v thnh phn ho hc. Pyroxen c th
chia thnh ba ph nhm chnh :
pyroxen magnesi-st: y ngoi Mg v Fe, cc cation khc chim cha ti 10%
cc v tr M1,M2; khong vt thuc ph nhm ny ch yu l cc pyroxen trc
thoi, hai ph nhm sau l cc pyroxen mt nghing;
pyroxen calci: calci chim hn 2/3 v tr M2;
pyroxen natri: natri chim v tr M2, cc cation nh Al, Fe
3+
hay Cr chim M1,
vi cc v d ln lt l jadeit, aegirin v kosmochlor.
Ngoi ra, hai ph nhm nh l pyroxen calci-natri, tiu biu l omphacid v aegirin-augit
v pyroxen liti nh spodumen. Cc bng 6.7 v 6.8 gii thiu s liu ho phn tch ca mt s
pyroxen trong v ngoi nc. Kt qu tnh ton sau nhm xc lp cng thc ho hc cho
mi khong vt.
Nhng ch khuyt do Si b li trong v tr T c ion Al
IV
lp vo, b sung cho hai v
tr t din trn n v cng thc. C th thy y khng t dy thay th ng hnh. Dy
enstatitferrosillit ch yu l nhng metasilicat ca magnesi v st ho tr hai. Nhng cation
khc nh Al, Mn, Fe
3+
, Ca, Ti, Cr v Ni thng xuyn c mt, nhng trong hu ht cc
(Mg,Fe)-pyroxen tt c cc thnh t ny cng li khng vt qu 10% ng lng gam.
Chrom v nickel thng gp trong enstatit giu magnesi ca metabasic v basic. Mangan
vi cha cao thng gii hn n ferrosillit trong magma v cc h tng st bin cht
trao i.
Donpeacorit l Mnpyroxen thoi c thnh phn Mg
1,4
Mn
0,6
Si
2
O
6
v kanoit l thnh vin
ca dy clinoenstatit clinoferrosillit cha 31,2% th tch ca MnO. cha ca nhm c
th t 0,5 Al n v cng thc gp trong enstatit ca bin cht trnh cao ch yu thuc
tng granulit. cha ca Ca thng nh; gi tr cao nht nm trong cng thc
(Mg,Fe)
0,97
Ca
0,03
SiO
3
.
Cc khong vt diopsit v hedenbergit to dy ng hnh hon ton gia CaMgSi
2
O
6
v
CaFeSi
2
O
6
.

Nhm c mt trong hu ht cc khong vt ca dy, nhng s trao i Si Al
thng cha ti 10%. Trong mt s diopsit lng Fe
3+
khng vt qu 0,25 ion trn n v
cng thc. Chrom thng xuyn c trong diopsit ca basic v metabasic; diopsit chrom l
khong vt cha mt lng ng k NaCrSi
2
O
6

(kosmochlor) hay CaCrSi
2
O
6
. cha
mangan thng thp (cha n 0,25% trng lng MnO) trong thnh vin giu magnesi ca
dy DiHd, nhng khong vt giu st ca dy c Mn nhiu hn (hedenbergit cha ti 4%
trng lng MnO).


225

Bng 6.7
S liu phn tch ho ca pyroxen
Cu t 1 2 3 4 5 6
SiO
2
48,81 52,70 48,18 49.68 49,46 48,02
TiO
2
0,01 0,34 0,70 0,56 0,57 0,46
Al
2
O
3
0,74 1,84 1,06 0,78 1,79 13,39
Fe
2
O
3
0,79 2,12 1,46 3,29 1,65 2,09
FeO 1,54 5,42 26,08 18,15 25,51 3,11
MnO 22,58 0,16 0,53 0,59 0,81 0,07
MgO 2,29 15,15 3,52 16,19 10,94 8,18
CaO 21,87 21,58 18,90 9,90 8,57 24,03
Na
2
O 0,07 0,49 0,23 0,65 0,23 0,31
K
2
O 0,02 0,01 0,04 0,15 0,05 0,06
H
2
O
+
0,32 - - 0,10 - 0,20
H
2
O
-
0,35 - - 0,00 0,20 0,07
Tng 99,40 99,96 100,70 100,04 99,78 99,99

S ion tnh trn 6 oxy
Ion 1 2 3 4 5 6
Si 1,990 1,947 1,941 1,905 1,945 1,760
Al
IV
0,010 0,053 0,051 0,034 0,055 0,240 =2
Al
VI
0,026 0,027 0,000 0,000 0,028 0,338
Fe
3+
0,024 0,059 0,036 0,033 0,049 0,058
Ti 0,000 0,009 0,021 0,016 0,017 0,012
Mg 0,139 0,834 0,211 0,925 0,641 0,447
Fe
2+
0,053 0,167 0,879 0,582 0,839 0,095
Mn 0,780 0,005 0,019 0,019 0,027 0,002
Ca 0,955 0,854 0,816 0,407 0,361 0,944
Na 0,006 0,035 0,017 0,048 0,018 0,022
K 0,001 0,000 0,002 0,008 0,003 0,002 2
Johannsenite. Aravaipa mining district, Arizona, USA (Simons, F.S. & Munson,
E.,1963, Amer. Min, 48, 1154-58).
Augite, pyroxen diorite, Feather Fiver area,.northern Sierra Nevada, USA
(Heitanen,A.,1971,Contr. Min. Petr., 30. 161-76).
Ferroan augite, ferrodiorit, Skaergaard, east Greenland (Brown, G. M., 1960, Amer. Min.,
45. 15-38).
Ferroan augite, hipersthene-augite basalt. O-sima Island, Japan (Kuno, H., 1955, Amer.
Min., 40. 70-93).


226
Ferroan pigeonite, dolerite, Yamagata Prefecture, Japan (Aoki, K., 1962. J. Japonese
Assoc. Min. Petr., Econ., Geol., 47, 41-5).
Aluminian diopsit, eclogite, Knockorman, ayrshire, Scotland, UK (Bloxam, T. W. &
Allen, J. B., 1960. Trans, Roy. Soc. Edingburgh,64. 1-27).
Bng 6.8
S liu phn tch ho ca pyroxen ly t lamproit Lai Chu [12]

Cu t


Nm Hon

Nm Hon

Cc Pa
Simang-
khang

Pn H

Pn H
SiO
2
53,80 53,40 92,90 52,80 51,30 54,30
TiO
2
0,15 0,20 0,43 0,09 0,27 0,11
Al
2
O
3
1,10 1,11 1,47 1,72 3,96 0,64
FeO 3,36 4,57 5,67 6,93 7,13 3,85
MnO 0,00 0,15 0,17 0,26 0,22 0,14
MgO 17,23 16,79 16,55 14,22 13,49 18,74
CaO 23,70 23,39 21,96 22,42 21,57 20,89
Na
2
O 0,30 0,37 0,31 0,86 1,11 0,30
Cr
2
O
3
0,42 0,15 0,29 0,04 0,03 0,21

S ion tnh trn 6 oxy
(do tc gi sch ny tnh thm)
Si 1,96 1,95 1,94 1,96 1,91 1,98
Ti 0,00 0,00 0,01 0,00 0,00 0,00
Al
IV
0,00 0,00 0,00 0,00 0,01 0,00
Z* 1,96 1,95 1,95 1,96 1,92 1.98
Al
VI
0,02 0,04 0,06 0,07 0,16 0,02
Fe 0,10 0,09 0,17 0,21 0,22 0,11
Mn 0,00 0,00 0,00 0,00 0,00 0,00
Mg 0,93 0,91 0,90 0,79 0,75 1,02
Ca 0,92 0,91 0,86 0,89 0,86 0,81
Na 0,01 0,02 0,02 0,06 0,08 0,02
Cr 0,00 0,01 0,00 0,00 0,00 0,00
XY* 1,98 1,98 2,01 2,02 2,07 1,98
* Z l tng cation (phi tr 4: Si, Ti v Al) nm trong v tr Z; XY l tng cation
trong v tr X (phi tr 68) v Y (phi tr 6).
Tuy nhin, Mn c th thay th (Mg,Fe) vi lng ln hn v rt c th c dy ng hnh
hon ton diopsithedenbergitjohansenit. Phn ln johansenit c cha Mn bin thin
trong khong 0,8 v 0,95 Mn
2+
/n v cng thc. Phn ln dung dch cng ca dy diopsit
hedenbergitjohansenit cha lng km rt nh, diopsit km v hedenbergit km vi 0,3 n
v cng thc tm thy trong m khong km Franklin, New Jersry. Zn l cation chnh ti v
tr M1 ca pyroxen km (0,37 n v cng thc) mang tn petedunit.


227
Cn c dy hp phn v danh php ca h CaMgFe (Morimoto M., 1988), pyroxen mt
nghing ca lamproit Lai Chu c thnh phn ho hc ng vi diopsit v diopsit augit. i
chiu vi lamproit in hnh (West Kimberley, Leucit Hills, Murcia Almeria) c th thy
clinopyroxen ny thuc loi giu nhm v ngho titan: s ion trn n v cng thc ln lt l
> 0,10 v < 0,01 so vi 0,002 0,026 v 0,01 0,058. Ring v hm lng st th
pyroxen ca lamproit Lai Chu kh ph hp vi cc s liu i chng.
Pyroxen l nhm silicat Fe-Mg to quan trng nht v c mt nh nhng pha bn
vng trong hu ht cc loi magma. Chng cng c trong nhiu loi vi thnh phn
thay i, hnh thnh trong iu kin bin cht khu vc v tip xc.
6.7. AMPHIBOL
Anthophyllit ()(+)
H trc thoi
Cummingtonit
(+)
H mt nghing
Tremolit ()
H mt nghing
Np 1,587 1,694 1,630 1,696 1,599 1,688
Nm 1,602 1,710 1,644 1,709 1,610 1,697
Ng 1,613 1,722 1,652 1,730 1,620 1,705
Ng Np 0,013 0,029 0,020 0,045 0,027 0,017
nh hng Np = x Ng : z = 15 21 Ng : z = 28 10
M.T.Q. (010) (010) (010)
Nhm K.G. Pnma C2/m C2/m
mng a ~ 18,6 a = 9,5 9,6 a ~ 9,85
b ~ 17,9 b = 18,1 18,4 b ~ 18,1
c ~ 5,2 5,3 c = 5,30 5,35 c ~ 5,3
~102 ~ 105
Z = 4 Z = 2 Z = 4
Thnh phn ho hc ca amphibol vit di dng tng qut nh sau :
W
0-1
X
2
Y
5
Z
8
O
22
(OH,F)
2
;
vi W: Na
+
v K
+
v tr A; X: Ca
2+
, Na
+
, Mn
2+
, Fe
2+
, Mg
2+
v Li
+
ti v tr M4;
Y: Mn
2+
, Fe
2+
, Mg
2+
, Fe
3+
, Al
3+
v Ti
4+
v tr M1, M2 v M3; Z: Si
4+
v Al
3+
v tr ca t
din. Thay th ng hnh hon ton xy ra gia cc ion natri v calci ti A, gia magnesi, st
ho tr ba v mangan M4. Thay th ng hnh hn ch l s trao i gia st ho tr ba v
nhm, gia titan v cc ion ti M1, M2, M3. Thay th ca nhm cho silic trong v tr ca t
din l s thay th ng hnh tng phn, xy ra nhiu trong amphibol hn l trong pyroxen v
c th t ti 1/3. Thay th tng phn ca fluor, oxy v hydroxil cng ph bin trong
amphibol.
Phn ln amphibol c th lit vo mt trong ba nhm khng gian; hai nhm mt nghing
l C2/m nh tremolit Ca
2
Mg
5
Si
8
O
22
(OH)
2
(hnh 4.5) v hornblendd, P2
1
/m tm thy trong
cumingtonit v mt nhm trc thoi Pnma l ca cc khong vt ca dy anthophillit,
Mg
7
Si
8
O
22
(OH)
2
Fe
2
Mg
5
Si
8
O
22
(OH)
2
v ca gidrit (anthophyllit cha Al v Na). Vic cc
cation c nh nm trong M4, M3, M2, M1 khin mt s amphibol c xu hng chuyn sang
h trc thoi, v v tr M4 khng ph hp cation nh. mng c s trc thoi lin quan vi
mt nghing l do hai gii bng t-o-t ca amphibol mt nghing ghp i (kiu song tinh,


228
di tc dng ca mt gng). Kt qu l thng s a ca trc thoi gn bng 2asin ca
mt nghing. Tng t, quan h v kch thc mng gia amphibol ca hai h gp trong
pyroxen.
Vic nhm OH c mt trong cu trc lm cho amphibol km chu nhit so vi pyroxen.
iu ny gy phn hu amphibol, bin n thnh pha khan (thng l pyroxen) nhit thp
hn im si. V mt ha hc tinh th, amphibol, pyroxen v mica lin quan cht ch vi
nhau (xem 6.5).
6.7.1. Cu trc tinh th
Cu trc tinh th ca amphibol da trn c s chui kp Si
4
O
11
(cc hnh 4.5, 4.36; 6.10,a
v 6.18), l kt qu kt ni dc hng [010] ca tng cp chui n kiu pyroxen. Chui kp
ny chy dc hng [001], lp li theo chiu di ca n sau mi on 5,3. on ny ly lm
thng s c ca c s. Ti ch cc chui n ni nhau, hnh thnh vng su t din SiO; n
cha mt nhm (OH)

chnh gia 6 anion oxy trung ha in tch m.
Nhm chc chui kp ny c hai mt khc nhau v in tch: mt y t din vi phn
ln oxy trung ho in tch m v mt nh t din vi O

(cc ion ny cng vi OH

xp
cht thnh mt lp cu anion). Cc chui kp ny chy dc hng [001], ghp ln u ui
vi nhau theo hng [010] v [100] v phn thnh lp dc (100). Chng xp sng i nhau,
hng nh t din vi O

vo trong. in tch m ny do cc cation Y ho tr hai v ba (ti
M1, M2, M3) trung ho (hnh 6.18). Cc cation W ti A v X ti M4 nm gia hai mt y
cc t din SO v trung ho in tch m cn st ti y.
V tr A do 10 n 12 vi oxy v hydroxil to nn v l ni ca natri l chnh, ri n
kali. V tr M4 hnh thnh do phi tr 6 v 8 v l ca cation loi X. Cc hnh bt din M kt
ni vi nhau qua cnh to nn gii bng bt din song song vi c. Cc v tr M1 v M3 l do 4
anion oxy v 2 nhm anion (OH,F) to nn, cn M2 do 6 anion oxy phi tr m c (hnh
6.18,a, theo Papike J.J. v nnk,1969).
Ging nh pyroxen (hnh 6.12,b & c), trong amphibol ct khai hon ton theo {110}.
Mt ct khai i qua gia cc mch chui kp v gia cc anion oxy in tch trung ho v
cc cation in tch ho tr thp trong v tr A v M4 (hnh 6.18,b & c). Cc n v cu trc
gii t-o-t vi mt ct ngang dng ch I ca amphibol c chiu rng (dc theo b) gp i so vi
gii tng t trong pyroxen, l do chui kp do 2 chui n ghp li. V vy, amphibol c
gc ct khai {110} in hnh l 56 v 124; cn cc gi tr tng ng trong pyroxen l 87
88 v 9293.
V kch thc ca c s gia hai h mt nghing v trc thoi hai nhm khong vt ny
c s tng ng; ngha l amphibol ca hai h c ln bng nhau ca cc thng s b v c,
nhng a ca amphibol trc thoi th xp x gp i v bng 2asin trong amphibol mt
nghing.
6.7.2. c im ho hc
Cng thc cu trc ca amphibol l:
A(M4)
2
(M1)
2
(M3)
1
(M2)
2
(T1)
4
(T2)
4
O
22
(OH)
2


229
Kch thc ca cc cation trong M1, M2, M3 v M4 xc nh cch phi tr ca chng vi
cc oxy ca chui kp silic-oxy v chnh iu ny li xc nh v tr ca cc chui kp ghp
i vi nhau. Trong hu ht cc trng hp, cc chui kp u xp theo cch ca mng mt
nghing, nh trong tremolit Ca
2
Mg
5
Si
8
O
22
(OH)
2
vi M1 = M2 = M3 ca Mg v M4 ca Ca.
Trong amphibol vi M4 cha (Mg,Fe) l chnh, khng phi cation c ln (Ca,Na), cch
ghp i ca chui kp c th cho hai kt qu. l mt nghing nh trong cummingtonit
(Fe
2+
,Mg)
7
Si
8
O
22
(OH)
2
hoc trc thoi nh trong anthophyllit (Mg,Fe
2+
)
7
Si
8
O
22
(OH)
2
.
Trong tremolit v cummingtonit v tr A thng b trng. Nhng trong mt s amphibol,
v tr ny cng b chim mt phn hay hon ton. Amphibol c th cha ti hai ion (Ca, Na,
K) trong n v cng thc.

Trong amphibol, s c mt ca hng lot v tr cng loi (m khng nh nhau), v d bt
din M1, M2 v M3, t din T1 v T2 (hnh 6.18,a). iu ny chng t cation phn b ti cc
loi v tr khng phi theo cch bt k; mi cation c s tng thch ring i vi tng v tr.
Trong t din, Al tng thch vi T1; trong bt din, Al cng Fe
3+
tng thch vi M2. i
vi cc v tr nh M1, M2, M3, M4 s tng thch ca Fe
2+
thay i tu loi amphibol. Bng
6.9 lit k kt qu phn tch ha hc ca mt s khong vt amphibol.


230

Amphibol chia thnh ba loi
trn c s cation trong v tr M4
(pyroxen chia theo cation trong
v tr tng ng l M2):
Amphibol st-magnesi thuc
h trc trc thoi v h mt
nghing vi Fe v Mg trong M4.
Amphibol calci;
Amphibol natri.
Hai loi sau u thuc h
mt nghing v cha Ca/Na
trong M4.
Amphibol trc thoi
(orthoamphibol). Amphibol st
magnesi c cu trc ca h trc
thoi v thnh phn ho hc bin
i theo hai vect trao i:
FeMg
1
v Na Al
VI
Al
2
IV

1
Mg
1
(Si
2
)
1
(trao i kiu pargasit, hnh 6.18). Nh li rng trao i kiu pargasit l s kt
hp ca hai kiu edenit v tschermak:
Na Al
VI
Al
2
IV

1
Mg
1
(Si
2
)
1
= Na Al
IV

1
Si
1
+ Al
VI
Al
IV
Mg
1
Si
1
Gia hai amphibol trc thoi, anthophyllit (ngho natri v nhm, giu silic) v gedrit (giu
natri v nhm, ngho silic) c vng gin on (y thc s l solvus) ti vng nhit thp
hn 600C, nh thy trn hnh 6.19. Gedrit ngui dn s cho v s tm mc xen song song
vi (010).
Amphibol st-magnesi mt nghing (Fe-Mg-clinoamphibol). Mt s dy ng hnh ph
bin ca amphibol c th cho thy thnh phn ca chng trong h Mg
7
Si
8
O
22
(OH)
2
(anthophyllit hay Mg-cumingtonit)Fe
2+
7
Si
8
O
22
(OH)
2
(grunerit hay Fe-anthophyllit)
Ca
7
Si
8
O
22
(OH)
2
(thnh phn u-cui gi nh). Cn nh, nhm pyroxen c h tng t l


231
WoEnFs (hnh 6.13); phn ct li ca n l t gic DiHdFsEn, ni tp trung nhng hp
phn quan trng ca pyroxen. Biu tam gic amphibol cng cha t gic tng t:
TremolitFe-ActinolitGruneritMg-Cumingtonit (hnh 6.20). N c cc dy ng hnh chnh
sau:
+ Tremolit Ca
2
Mg
5
Si
8
O
22
(OH)
2
v Fe-Actinolit Ca
2
Fe
5
Si
8
O
22
(OH)
2
vi cc thnh vin
thuc h mt nghing. Actinolit l nhng khong vt thng gp v gn lin vi cc thnh
vin giu Mg ca dy ny.
+ Anthophyllit tng ng khong thnh phn ca cc amphibol trc thoi, t Mg-
cumingtonit Mg
7
Si
8
O
22
(OH)
2
n gn Fe
2
Mg
5
Si
8
O
22
(OH)
2
.
+ Dy cumingtonitgrunerit bao hm cc thnh phn mt nghing v pht trin t gn
Fe
2
Mg
5
Si
8
O
22
(OH)
2
n Fe
7
Si
8
O
22
(OH)
2
.

Nhng min gin on tri rng gia anthophyllit v dy tremolit-actinolit, cng nh
gia dy cumingtonitgrunerit v cc Ca-amphibol. Cc min gin on ny tm thy dn
chng trong thc t. l tng cp anthophyllittremolit v cumingtonitgrunerit, cng nh
kin trc mc xen kiu phn r dung dch cng gia cc khong vt ca dy MgFe v
amphibol cha Ca.
Amphibol calci. Amphibol calci c mt nhiu trong tng phin lc v tng amphibolit.
Cng nh trong amphibol trc thoi, amphibol calci c s trao i kt hp gia vect edenit
NaAl
IV

1
Si
1
v tschermak Al
VI
Al
IV
Mg
1
Si
1
t s 1/3, cho ra i dung dch cng gia
actinolit v hornblend. Nhng trao i ny th hin trn hnh 6.21, ch khc hnh 6.19 ch
cation trong M4 khng phi Fe hay Mg, m Ca. Hnh ny cng c min gin on gia
actinolit v hornblend. Nhiu tranh ci xy ra xung quanh s tn ti min mc xen ny. Trong
thc t, t hp cng sinh ca tng amphibolit nhit thp thng cha
actinolit v hornblend trong cng loi .
Amphibol natri. Nt c trng ca amphibol natri l s c mt ca natri trong v tr M4.
Chng c dung dch cng hon ton lin quan ti vect FeMg
1
, v sau l trao i Fe
3+



232
Al
3+
cho dung dch cng glaucophan Na
2
Mg
3
Al
2
Si
8
O
22
(OH)
2
Na
2
Mg
3
Fe
2
Si
8
O
22
(OH)
2

riebeckit.
Hnh 6.22 khng gii thiu mi lin h ny. Ht thy amphibol natri vi hm lng
Fe
3+
/Al trung gian u mang tn chung l crosit. Amphibol natri khng c vect thay th
tng t vect pargasit, bi v Al
VI
v Fe
3+


chim v tr M2. Glaucophan thng c mt
trong cc t hp cng sinh p sut cao, v iu kin p sut ny nhm s phi tr cao Al
VI
c
li th r rt so vi Al
IV
. Glaucophan c mu lam; nn tng phin xanh lam mang tn n.
Riebeckit gp trong cc t hp khc nhau, k c cc thnh to qung st v magma kim nhit
cao.











Hnh 6.23 gii thiu mi lin h gia cc pha u cui ca amphibol calci v natri. Ging
nh t gic vch bin ca hnh 6.21, y ca biu lng tr ny c 4 nh l tremolit, edenit,
pargasit v tschermakit. Trc ng l trao i kiu plagioclas; ging nh albitanorthit hay l
jadeit NaAlSi
2
O
6
CaAl
VI
Al
IV
SiO
6
Ca-tschermak (pyroxen nhn to). ng cho ni
tremolit v glaucophan l c ch trao i glaucophan hay jadeit (CaMg Na(M4)Al
VI
) v
song song vi vect diopsit CaMgSi
2
O
6
NaAlSi
2
O
6
jadeit.
Ni chung, c ch thay th vi s gp mt ca Na(M4) v Al
VI
thng c xu hng xy
ra p sut cao; cn Na(A) v Al
VI
lin quan n nhng thay th xy ra nhit cao. Nh
vy, cc thuc tng phin lc, bin cht thp thng cha actinolit; phin xanh p sut
cao, nhit thp cha glaucophan; phun tro bin cht thuc tng amphibolit p sut v
nhit trung bnh thng cha hornblend pargasit.

Hnh 6.22. Biu tam gic tremolit (Ca-amphibol) tschermakit
glaucophan (Na-amphibol), tng t biu ca pyroxen (hnh 6.12)


233

Bng 6.9
S liu phn tch ho ca amphibol
1 2 3 4 5
SiO
2
58,54 54,73 51,40 50,70 42,70
TiO
2
0,21 0,74 0,32 0,45
Al
2
O
3
0,79 1,46 3,88 5,45 18,26
Fe
2
O
3
0,22 0,00 3,90 1,81 3,14
FeO 0,37 9,60 14,91 6,59 12,07
MnO vt 0,16 0,33 0,17 0,75
MgO 24,45 17,94 11,22 15,89 8,42
CaO 13,59 12,76 10,17 12,22 10,65
Na
2
O 0,27 1,44 I,67 2,80 1,42
K
2
O 0,12 vt 0,09 1,23 0,49
H
2
O
+
2,12 2,27 1,90 2,08 2,13
H
2
O

0,00 0,00 0,04 0,05 0,00
100,47 100,57 100,25 99,80 99,80
1. Tremolit, marble, Gouverneur, New York State, USA, (Shido,F., 1959, Geol. Soc.
Japan J. 65,563-9).
2. Actinolit, hornblendde clinozoisit schist, Salcome Estuary, south Devon, UK (Tilley,
C. E., 1938, Geol. Mag., 75,497-511).
3.Ferro-actinolite, albite stilomelan actinolite schist, New Zealand (Hutton, C. O.,
1940, Dept. Sce. And Ind. Res., New Zealand, Geol. Mem., 5,90pp).
4. Edenite, amphibolite, Kushalnagar, Coorg. Districk, Mysore, India (Leake, B. O.,
1971, Min. Mag., 38, 389-407. Includes Cr
2
O
3
0,48, NiO 0,06 per cent).


234
5. Aluminotschermakite: kyanniteplagioclasquartzchlorite schist, Flodalera,
Lukmanier, Switzerland (Leake, B. E., 1971, Min. Mag., 38, 389-407).
S lng ion tnh trn 24 oxy
Ion 1 2 3 4 5
Si 7,918 7,731 7,543 7,284 6,21
Al 0,082 0,243 0,457 0,716 1,78 =8
Al 0,044 0,215 0,207 1,35
Ti 0,022 0,082 0,035 0,04
Fe
3+
0,022 0,430 0,196 0,344
Fe
2+
0,042 1,134 2,453 0,792 1,470 5
Mg 4,928 3,777 0,040 3.402 1,827
Mn 0,019 1,830 0,021 0,009
Ca 1,970 1,932 0,474 1,881 1,662 2
Na 0,071 0,394 1,599 0,780 0,401 (1,2,3,5)
K 0,021 0,018 0,225 0,091 3 (4)
OH 1,913 2,139 1,861 1,993 2,069 2
Khong vt thuc nhm amphibol gp trong nhng trng P T rng ln v ph bin
trong cc magma v bin cht. Chng c mt trong tt c cc nhm chnh ca magma,
t siu mafic n acid v kim; nht l trong thnh phn trung gian ca cc dy ng hnh
calcikim. Chng l nhm khong vt c hu trong su v thng t gp trong phun
tro. Amphibol tm thy trong cc loi khc nhau ca bin cht khu vc, hnh thnh trong
nhng iu kin ca cc tng t phin lc n granulit nhit thp. Chng khng c nhiu
trong mi trng bin cht tip xc, nhng khng phi l t ph bin trong i tip xc vi
vi, dolomit v trm tch giu calci.
Gia Ca-amphibol v Fe,Mg- amphibol c th c chnh lch ln v kch thc cation ti
v tr Y. iu ny dn ti s thiu vng dung dch cng gia hai nhm v kh nng xut hin
cc tm mc xen ca pha thuc nhm ny trong khong vt nhm kia. V d, cummingtonit
trong actinolit hay hornblend. iu tng t cng thy gia amphibol kim v Fe,Mg-
amphibol, gia hai pha ngho hn v giu hn v Al+Na l anthophyllit v gedrit. Bng 6.9
gii thiu s liu phn tch ho hc ca mt s khong vt amphibol.
SILICAT LP
Silicat lp hay phyllosilicat u c chung nhm chc vi cng thc (Si,Al)
4
O
10
(OH)
2
tri
rng theo mt y (001). L t din ny c hai pha khc nhau v in tch: mt pha l 3/4
oxy (nm gia 2 silic) trung ho in tch, phn b dc y ca cc t din; pha kia l 1/4
oxy in tch 1 d (sau khi lin kt vi silic trong t din) v nhm hydroxil nm ti tm lc
gic do 6 oxy to nn. Cc l t din (T) ny ghp vi cc l bt din (O), do oxy v hydroxil
xp kht to nn; trong , mt na hay ton b l xut pht t l t din T.
Cc l t din v bt din lin kt vi nhau theo 2 cch: TO v TOT.
Trong TO, l bt din (O) hnh thnh t mt pha l cc ion OH


xp cht v mt pha l
oxy + hydroxil ca l t din T. Trong TOT, l O hnh thnh t oxy+hydroxil xut pht t 2
l T. Gia hai l T ny c s x dch tng i theo hng nm ngang (song song vi mt l).


235
iu ny l cn thit nhm t c s cht kht ca cc l vi nhau, nhng li lm gim tnh
i xng ca TOT t su phng xung mt nghing.
Trong l O, v tr bt din c 3 loi: 1 v tr M1 m hnh bt din c 2 nhm OH nm
cc nh i (xuyn tm) ca n v 2 v tr M2 vi 2 nhm OH lin k ( 2 u ca 1 cnh
ca bt din). Da vo t s v tr bt din do cation chim, c th phn bit:
Silicat lp ba bt din hay dng brucit (xem cu trc CdI hay brucit, hnh 4.19):
3/3 v tr do cation ho tr hai (magnesi, st) chim.
Silicat lp hai bt din hay dng gibbsit (tham kho cu trc gibbsit trn hnh
4.19): 2/3 v tr M2 b chim bi cc cation ho tr ba (nhm, st).
Cc lp TO hay TOT xp chng dc theo [001], s phn cch nhau bng mt lp trung
gian b trng hoc cha cation, H
2
O, cation trao i + H
2
O, hoc bng mt lp bt din. Da
vo , silicat lp chia thnh cc nhm nh sau (bng 6.10).
Bng 6.10
Bng phn loi silicat lp (theo Baronnet A., 1988)
Cc loi lp Lp trung gian Silicat lp hai bt din Silicat lp ba bt din
TO lin tc B trng Kaolinit Serpentin
H
2
O+cation trao i Haloysit
TOT lin tc B trng Pyrophyllit Talc
Cation Mica Mica
H
2
O+cation trao i Montmorillonit Vermiculit Gin on
Chlorit Chlorit
H
2
O zeolit Paligorskit Sepiolit
6.8. MICA X2Y46Z8O20(OH,F)4
Nhm khong vt mica rt a dng v mt ho hc v vt l hc. Nhng ht thy chng
u c tinh th dng tm, c ct khai hon ton theo {001} v y l h qu ca cu trc tinh
th dng lp. Trong s cc mica ph bin nht, bn khong vt sau c ngha kinh t:
muscovit, paragonit, phlogopit v lepidolit.
6.8.1. Cu trc tinh th
c im cu trc c s ca mica l lp TOT. Hai l t din biu hin trn hnh 6.24.
Bn tri, tt c t din u hng nh ln, bn phi t din hng nh xung. Hai l ny xp
chng, ghp vi nhau bng mt l cation phi tr bt din, nh th hin trn hnh 6.25 v 6.26.
Khi ghp thnh lp TOT, cc l T u hng nh t din vo trong, tp trung in tch ca
nhm chc cho l O. Cu trc c th coi nh c l O brucit Mg
3
(OH)
6
(trong phlogopit) hay
gibbsit Al
2
(OH)
6
(trong muscovit). Bn trong su ion (OH) ca chng thay bng 4 oxy, chia
u cho hai l T. Cc ion (OH) cn li nm ti tm cc lc gic to bi oxy nh.
Nh vy, mi lc gic lin quan vi lc gic k tip bi php quay 0 hay bi ca 60.
Php quay ny kt hp vi bc chuyn a/3 do cation Y nh ot (nh trn ni), dng ln
cch sp xp nguyn t trong cc mng k tip nhau. Cc lp xp ln nhau theo nhng trnh
t khc nhau, khi trnh t y lp li u n chng s to nn mng c s vi mt, hai, ba
lp hay nhiu hn (hnh 6.27).


236

Cc trnh t ph bin nht l 1M (chu k c gm 1 lp), 2M
1
, 2M
2
(chu k c u gm 2 lp)
thuc h mt nghing, 3T vi 3 lp v i xng ba phng

. Hnh 6.27 cho thy 1M v 2O (2


lp, trc thoi) gm bc chuyn theo mt phng x, 2M
1
v 2M
2
theo hai phng x, 2T v
6H theo c ba phng x. (Trong h su phng OX, OY v OU l cc phng tng ng).
Nhng sai khc so vi cc trt t trn khng phi khng c trong t nhin.







Xem thm 5.3.3. a dng.




237
















Trong cc mica ph bin nh muscovit, phlogopit v biotit, cation phn b khng trt t.
V d, (Fe,Mg) trong v tr bt din v (Si,Al) trong t din. Thng s mng ca mica chu
nh hng ca s thay th ion: thng thng mica hai bt din v ba bt din phn bit nhau
bng v tr ca hiu ng (060) trn biu nhiu x tia X. i vi hai loi mica trn, d
060
ln
lt bng 1,50 v 1,53 1,55. Nhng cu trc mica m t trn l m hnh l tng. Trong
thc t, cc t din SiO gn vi nhau thnh l vi tam gic kp, tc l vi i xng ba
phng (khng phi su phng). Sai khc ca l t din ko theo s bin dng ca l bt
din: khong cch gia cc oxy nh phn no km ph hp vi kch thc ca cnh bt din.
Cu trc hai bt din c nhiu sai hng hn so vi cu trc ba bt din (xem di y).
Mi vect thay th c trong amphibol cng gp trong mica. Nhng vect chnh l:
KNa
1
Al
VI
Al
IV
Mg
1
Si
--1
FeMg
1
NaAl
IV

1
Si
1
Muscovit v paragonit l nhng mica hai bt din ph bin nht. Muscovit thng gp
trong phin st bin cht thp v trung bnh. Thay th tschermak thng xy ra trong c hai
mica, mc du mica thay th ny thng mang tn phengit. Thng thng mica phengit cha
nhiu magnesi v silic, bi v thay th phengit l MgSiAl
1
Al
1,
ngc vi thay th
tschermak.


238









Hnh 6.27
S dch chuyn tng i ca l t din xp chng Cc t din hng nh vo nhau,
nhng khng i nh. Chng x dch tng i a/3 theo mt hay nhiu vect
6.8.2. c im ho hc
Thnh phn ho hc ca mica biu th bng cng thc tng qut sau:
X
2
Y
46
Z
8
O
20
(OH,F)
4

trong , X l K, Na hay Ca, Ba, Rb, Cs, v.v; Y l Al, Mg, hay Fe, Mn, Cr, Ti, Li,
v.v; Z l Si hay Al, Fe
3+
v Ti.
Mica hai bt din
Bng 6.11
Cng thc ho hc gn ng ca mica
X Y Z
Mica Muscovit K
2
Al
4
Si
6
Al
2
ph Paragonit Na
2
Al
4
Si
6
Al
2

bin Glauconit (K,Na)
1,22,0
(Fe,Mg,Al)
4
Si
77,6
Al
1,00,4
Mica gin Margarit Ca
2
Al
4
Si
4
Al
4


239
Mica ba bt din
X Y Z
Phlogopit K
2
(Mg,Fe
2+
)
6
Si
6
Al
2

Mica Biotit K
2
(Mg,Fe,Al)
6
Si
65
Al
23

ph bin Zinnwaldit K
2
(Fe,Li,Al)
6
Si
67
Al
21

Lepidolit K
2
(Li,Al)
5 - 6
Si
65
Al
23

Mica gin Clintonit Ca
2
(Mg,Al)
6
Si
25
Al
53

Mica chia ra hai lot: mica hai bt din v mica ba bt din vi lng cation trong v tr Y
tnh trn n v cng thc ln lt l 4 v 6 tu ho tr (+3 hay l +2). Mi lot li chia tip
tu bn cht ca ion chnh trong v tr X. Trong mica ph bin, X thng cha K hay Na,
nhng trong ci gi l mica gin X thng c Ca. Mica cn c phn chia chi tit hn,
da vo cc thnh phn trong X, Y v Z; iu ny th hin bng cng thc gn ng trong
bng 6.11. i vi muscovit v paragonit, khi t l Si/Al vt qua 6 : 2 th in tch dng di
d s c cn bng; bi v v tr Y s c s thay th tng ng ca cation ha tr hai cho
nhm ha tr ba.
Phn ln mica c c im l cha nc trong thnh phn; s liu phn tch ha cho thy
cha ny nm trong khong 4 5 % H
2
O
+
, ngoi nhng mica vi cha fluor cao (bnh
6.12).
Tnh cht vt l
Cc khong vt mica u c quang du m v Np gn vung gc vi mt ct khai hon
ton (001). Lt mng vung gc vi mt ct khai cho thy du ko di dng. Hu ht cc
mica u l tinh th hai trc quang; mica hai bt din c gi tr gc 2V trung bnh, mica ba bt
din c gi tr gc 2V nh; s t mica l tinh th mt trc quang r rt. Trong mt (001) ca
bn mica c lng chit sut rt yu, nhng trong mt vung gc vi (001) th gi tr ny ln
hn.
Mica mu c tnh a sc mnh v hp ph mnh nht l i vi sng sng dao ng
song song vi mt ct khai, tr nhng bit l him hoi. Mica hai bt din thng c mt
quang trc vung gc vi (010), mt s khc (tr vi ba biotit vi loi cu trc 2M
1
) c mt
quang trc song song vi (010). Mi mica u bc l song tinh (lut song tinh mica) vi
mt phn cch {001} v trc song tinh [310]. Tinh th hon thin thng cho thy cc mt
{110} v do vy chng u c mt ct ngang (// mt ct khai) gi lc gic.


240

Bng 6.12
S liu phn tch ho ca mica
1 2 3 4 5 6
SiO
2
48,42 49,50 40,95 38,32 34,73 49,76
TiO
2
0,87 0,08 0,82 2,89 2,83 0,22
Al
2
O
3
27,16 3,50 17,28 15,21 16,67 25,31
Fe
2
O
3
6,57 21,20 0,43 1,49 3,50 0,80
FeO 0,81 2,50 2,38 15,58 21,70 3,20
MnO 0,01 vt 0,22 1,21 0,42
MgO vt 4,90 22,95 13,17 5,95 0,09
CaO vt 1,16 0,00 0,74 0,00 0,05
Li
2
O 4,35
Na
2
O 0,35 0,13 0,16 0,20 0,41 0,61
K
2
O 11,23 8,58 9,80 8,01 9,35 9,20
F vt 0,62 0,91 3,96
H
2
O
+
4,31 5,69 4,23 4,04 3,01 2,81
H
2
O

0,19 0,61 0,48 0,07 0,33
99,91 97,86 100,13 100,00 100,39 101,95
O F 0,26 0,39 1,67
99,91 97,86 99,87 100,00 100,00 100,28

S ion tnh trn 24 O(OH,F,Cl)
Si 6,597 7,550 5,724 5,677 5,499 6,641
Al 1,403 0,450 2,276 2,323 2,501 1,359
8,000 8,000 8,000 8,000 8,000 8,000
Al 2,959 0,179 0,562 0,335 0,610 2,623
Ti 0,089 0,009 0,084 0,322 0,337 0,023
Fe
3+
0.672 2,433 0,340 0,166 0,417 0,080
Fe
2+
0,091 0,319 0,276 1,930 2,873 0,357
Mn 0,001 0,028 0,162 0,047
Mg 1,114 4,776 2,980 1,404 0,018
Li 2,336
3,811 4,055 6,038 5,761 5,803 5,484
Ca 0,117 0.007
Na 0,092 0,038 0,034 0,057 0,126 0,157
K 1,952 1,670 1,746 1,514 1,889 1,567
2,044 1,708 1,780 1,688 2,015 1,731
F 0,278 0,456 1,672
OH 3,916 4,000 3,946 4,000 3,179 2,503
3,916 4,000 4,224 4,000 3,635 4,175
1. Muscovit, low-grade psammitic schist, Inverness-shire, Scotland, UK (Lambert,
R.St.J., 1959, Trans. Roy. Soc.Edingburgh, 63, 553-88).


241
Glauconite, pellets in calcareous mudstone submarine continental shelf 31 27
/
N, 10 24
/

w 750 m (Buckley, H.A., Bevan, J. C., Brown, K.M. & Johnson, L.R. 1978, Min. Mag., 42,
373-82. Includes P
2
O
5
0,61, CO
2
0,59).
Phlogopit, marble, New Zealand (Hutton, C.O., 1947, Trans. Roy. Soc. New Zealand, 76,
481-91. Includes BaO 0,03).
Biotit, granulite facies gneiss, Warriup Hill, southern Western Australia (Stephenson, N.
C. N., 1977, Lithos. 10,9-27. Includes P
2
O
5
0,13).
Biotit, porphiritic biotit grannite. Dinkey Lakes, central Sierra Navada, Calafornia, USA
(Dodge, F. C. W., Smith, V. C. & Mays, R.E., 1969, 10, 250-71. Includes Cl 0,05).
Lepidolite in apjite dyke. Meldon. Devon. UK (Chaudhry, M. N. & Howie, R. A., 1973,
Min. Mag., 39, 289-96. Includes Rb
2
O 0,67 Cs
2
O 0,17).
C th nh hng cho bn mica bng mt tc ng c hc. Ti im va p trn bn
mica s cho xut hin hnh to tia, cc tia cch nhau 60. Trong , mt tia ni bt song song
vi (010). Nh vy, mica M1 c mt quang trc song song vi mt trong cc tia; i vi mica
2M
1
, mt quang trc chia i gc gia cc tia y.
6.8.2. Muscovit
H mt nghing () K
2
Al
4
[Si
6
Al
2
O
20
](OH,F)
4

Np = 1,552 1,576 Nm = 1,582 1,615 Ng = 1,587 1,618 2V = 28 47
Ng Np = 0,036 0,049
c s a5,2; b9,0
Loi 2M
1
: c20; 93; Z=2; N.K.G. C2/c
Loi 1M : c10; 101; Z=1; N.K.G. C2/m
nh hng Np : z = 0 5; Nm : x = 1 3; MQT (010).
d
hkl
, 9,95 (10); 3,37(10); 2,66 (8); 2,45 (8); 2,18 (8).
Muscovit l mt trong nhng mica ph bin nht v hnh thnh trong nhng mi trng
a cht a dng. c im cch in v cch nhit ca n lm cho muscovit tr thnh vt liu
quan trng cho cng nghip. Tnh ct khai hon ton vi cc phin bn chc, tnh thu quang
cao nht trong cc mica, thng bt gp di dng bn kh rng, c cha st tng i
thp, khng c sai hng cu trc v bao th (trc ht l bao th oxit st) lm nn gi tr kinh
t ca nhng mica nh muscovit v phlogopit.
c im cu trc
Nh m t trn, trong muscovit nguyn t nhm phn b mt cch ngu nhin cng
vi silic trong phi tr bn, t l Al : Si = 1 : 4. Nguyn t kali chim ht v tr vi phi tr
12 gia cc lp TOT; gn kt cc lp ny theo trnh t kiu 2M
1
. Mt s mu ht mn trong
trm tch v a bin cht trnh thp c cu trc kiu 1M v 1Md ( trt t thp).
Nguyn t natri th ch ca kali lm gim d
002
trong cc hiu ng nhiu x tia X; nhm
thay th silic lm tng hiu ng d
060.

c im ho hc


242
Muscovit c s thay th ng hnh ca K bng Na, Rb, Cs, Ca, Ba; ca Al
VI
bng Mg,
Fe
2+
, Fe
3+
, Mn, Li, Cr, Ti,V v (OH) bng F. (Si
6
Al
2
) c th bin thnh (Si
7
Al)
Muscovit hng c thnh phn gn nh l tng vi cha thp ca mangan v liti.
Muscovit vi cha Fe
2
O
3
ng k tng c cng b (xem bng 6.12, pt 1). Mt s
khc c bit ti vi cha FeO cao thng i km vi SiO
2.
Hu ht muscovit cha di
1% MnO, nhng vi mu ta v xanh tri n thng cha trn 2% MnO. Crom ch dng
nguyn t vt, nhng muscovit crom l fuchsit cha ti 6% Cr
2
O
3.
Mica vi hm lng liti
cao l khong vt lepidolit; tuy nhin, Li
2
O c ti 3,6% trong muscovit. Trong F-muscovit
nhn to ion OH do F thay th ht, nhng khong vt F-muscovit thng ch cha khong
0,6% fluor.
Sericit l thut ng ch mica trng (muscovit v paragonit) ht nh. Thnh phn ho hc
ca chng khng nht thit phi khc, nhng chng thng c cha cao ca SiO
2
,

MgO,
H
2
O v mt t K
2
O.
Phengit l danh t dng m t muscovit, m trong Si : Al ln hn 3:1 v khi lng
Si tng thng km theo hin tng Mg v Fe
2+
thay th Al trong v tr bt din.
Hydromuscovit c cha H
2
O cao v K
2
O thp; K
+
c th b thay bng ion (H
3
O)
+
. Illit
(xem 6.10. Khong vt st) c th l thut ng thng p dng cho khong vt mica. S liu
ho phn tch cho thy mt s Al b Si th chn, lm tng t l Si : Al, km theo s gim kali.
Cc kt qu thc nghim trong h K
2
OAl
2
O
3
SiO
2
H
2
O cho thy cc phn ng:
muscovit sanidin + corindon + nc (1)
muscovit + thch anh sanidin + Al
2
SiO
5
+ nc (2)
Phn ng (2) xy ra nhit thp hn 30C so vi phn ng (1). Mc du phn ng ny
c biu hin s phn hu ca muscovit trong t nhin, nhng phn ng khc vi s tham
gia ca muscovit v s hnh thnh feldspat cng c th xy ra. Hn na, s thay th ng hnh
trong muscovit t nhin s to nhng iu kin rt khc nhau cho s phn hu muscovit.
Muscovit c th b phong ho, qua illit v hydromuscovit, ti montmorillonit, v cui
cng l kaolinit, vi kali bt i v nc, silic thm vo.
Tnh cht vt l
Muscovit c xu hng chung l ch s khc x tng khi cha st (c bit st ho tr
ba) v mangan tng v khi cha nhm gim. Muscovit vi hm lng Mg v Fe thp nht
thng c gi tr 2V ln nht. V d muscovit mu hng c ch s khc x thp hn gi tr
trung bnh ca muscovit, nhng gc 2V t gi tr cao hn.
Mc du mu ca muscovit hng tng t mu ca lepidolit, nhng khng c tng quan
no gia mu sc v hm lng liti. Mu hng trong hai mica ny l do mt lng nh ca
mangan gy ra, c th mangan ho tr ba, s vt tri ca n so vi st ho tr hai, v s thiu
vng ca st ho tr ba. Mu lc nht hay nu ca muscovit l nh hm lng thay i ca
st ho tr hai v st ho tr ba. S c mt ca crom sinh mu lc; mu a sc ca fuchsit nh
sau:
Np < Nm < Ng
lc, lc nht lc lc sm


243
Ch s khc x ca chng tng cng vi cha ca crom.
Li-muscovit c ch s khc x thp, nhng tnh cht quang hc ca chng chu nh hng
ca st v mangan hn l ca liti. Ch s khc x ca phengit, illit v hydromuscovit cao hn
ca muscovit bnh thng bi s thay th ca silic cho nhm phi tr bn v ca st ho tr
hai hay magnesi cho nhm phi tr su.
Hin tng mc xen gia muscovit v biotit khng phi l khng ph bin v trong hu
ht trng hp mt quang trc ca chng lch nhau 60. cng ca muscovit thng l 2,5
n 3, nhng nh vn thng thy i vi cc khong dng lp, cng thay i theo hng:
t 2,5 theo hng song song (001) n 4 theo hng vung gc.
Du hiu phn bit
Muscovit khc vi phlogopit v biotit ch n c mt quang trc vung gc vi (010).
Hng [010] xc nh bng tc ng va p trn bn mica (xem trn) v thm nh bng
nhiu x tia X. Biotit thng rt m mu. Muscovit thng c gc 2V ln hn ca
phlogopit, biotit v talc; iu ny gip phn bit muscovit v talc. Lng chit sut ca
muscovit gip phn bit n vi kaolinit, chlorit v cc silicat lp khc. Ring pyrophyllit c
2V ln hn. Biu nhiu x tia X c th dng phn bit mica hai bt din vi mica ba bt
din v phn bit cc bin th a hnh khc nhau ca muscovit.
6.8.3. Phlogopit - biotit
H mt nghing ()K
2
(Mg,Fe
2+
)
64
(Fe
3+
,Al,Ti)
02
[Si
65
Al
23
O
20
](OH,F)
4
c s a~5,3; b~9,2; c~10,3; ~100; Z = 1
Nhm k.g. C2/m
nh hng Nm = y; Ng : x = 0 9; MQS: (010)
d
hkl,
Phlogopit: 10,13(10); 3,53(4); 3,36(10); 3,28(4); 2,62(10)
Biotit: 10,1(10); 3,37(10); 2,66(8); 2,54(8); 2,18(8)
Np, Nm, Ng 1,5301,625; 1,5571,696; 1,5581,696
Ng Np 0,0280,08; 2V = 025
Biotit (v phlogopit) l nhng mica ba bt din quan trng. Mc du phlogopit l danh t
cho thnh phn ca pha u cui giu magnesi, gia n v biotit khng c s phn bit r
rt. Khong vt tng t giu st l annit. Phlogopit v annit u khng c nhm trong v tr
Y, nhng trong hu ht biotit t nhin u c mt lng ng k Al thay cho (Mg,Fe); km
theo l Al thay cho Si trong v tr t din cn bng ho tr. Thay th tschermak ny dn
n khong vt giu st:
Siderophyllit K
2
Fe
4
Al
2
Si
4
Al
4
O
20
(OH)
4
v
Eastonit K
2
Mg
4
Al
2
Si
4
Al
4
O
20
(OH)
4
c im cu trc
Trong cu trc ca phlogopit v biotit, v tr bt din (v l thuyt, chng u b chim ht) b
b trng t 5,6 ti 6 tnh trn n v cng thc. Ph bin nht l bin th a hnh 1M, nhng 2M
v 3T cng thng gp. Cu trc 1Md c cc lp TOT sp xp km.
St ho tr hai v magnesi phn b ngu nhin trong khoang bt din c ln. Silic v
nhm cng khng trt t trong khoang t din. St ho tr ba l ion thng gp nht trong


244
khoang bt din c nh. Cu trc ca phlogopit giu fluor thng cha cc vng trt t gn,
Fe
2+
i km OH v Mg vi F.
Do bt din ca st ho tr hai v magnesi ln hn ca nhm, cc t din trong biotit b
xon vn nhiu hn so vi trong muscovit. Cng nhiu nhm th chn silic th hin tng ny
cng pht trin, cho ti khi s gim tng ng ca d
001
t gii hn.
S thay th ca st ho tr hai cho magnesi trong biotit lm cho thng s b tng. Nhng
khng th dng t l Fe/Mg xc nh thng s mng; v nhng thay th ca st ho tr ba,
nhm v fluor cng nh hng ti kch thc ca c s.
c im ho hc
Bng 6.11 gii thiu cc cng thc ho hc ca mica. Trong t nhin thng him c
phlogopit v biotit ch c st trong v tr Y. S thay th ca nhm cho st/magnesi v cho silic
(km theo cn bng in tch) khng th vt qu cc gii hn tng ng (Mg,Fe)
5
Al v
Si
5
Al
3
. Trong mica giu magnesi cc thay th ny thng t ph bin hn. Thay th ca nhm
cho st v magnesi cng c th cn bng bi s xut hin ca cc trng trong v tr Y (xem
di). Phlogopit ca lamproit thuc loi giu Mg, ring ca lamproit Lai Chu hm lng
nguyn t ny trong khong 3,68 4,62 nguyn t trn n v cng thc. S liu tnh ton
cho thy (bng 6.12) s nguyn t Al c mt ch nm trong khong 2,02 2,08, ni cch khc
y hu nh khng c s thay th ca nhm. Mc d vy, s nguyn t Si y mc
thp nht (5,04 5,34 Si trn n v cng thc), tc l trong anion phc thiu xp x mt
nguyn t silic; c th c mt trng gi nh cho Si
4+
(?). Trong khi , titan c th dng
ht s lng nguyn t (0,08 0,68 trn n v cng thc) thay th nhm ti v tr ca
st/magnesi. Nh ni trn, s thay th ca nhm trong v tr Y phi sinh trng
2Al
3+
+ = 3(Fe
2+
/Mg)
Sau titan vo ch ca st v magnesi thay cho nhm theo s :
3Ti
4+
+ 3 = 4Al
3+
+ 2
Nu nhm b titan thay th ht, th chnh l:
Ti
4+
+ = 2(Fe
2+
/Mg).
Di y l nhng thay th khc.
a) Thay kali trong v tr gia cc lp bng natri, calci, bari, rubidi v cesi. Trong ,
natri c th c mt vi hm lng cao hn, nhng khng vt qu 0,5 nguyn t tnh trn n
v cng thc. S ny trong phlogopit ca lamproit Lai Chu l 0,06 0,14 (bng 6.13). Bari v
calci gp trong phlogopit Lai Chu thng xuyn hn, cn mangan th ch c trong phlogopit
ca cc lamproit i chng (West Kimberley, Leucit Hills, Murcia Almeria).
b) Thay th trong v tr bt din Y gia cc nguyn t nh mangan, titan, st ho tr ba v
liti. cha mangan t khi vt qu 0,2 nguyn t tnh trn n v cng thc; phlogopit giu
mangan c tn manganophillit. Ion liti ho tr mt c th c trong v tr Y ti ch ca st v
magnesi. in tch dng thiu ht s c b sung bng nhm phi tr su v bng s thay
th ca silic cho nhm phi tr bn, nh vn thng xy ra trong lepidolit v zinwalit. Titan
c mt trong v tr bt din, thng trong trng hp ny n thay th nhm. in tch dng
d s trung ho bng nhm thay silic v bng s xut hin trng. Nhit tng to thun li
cho qu trnh thay th ny. St ho tr ba thay th nhm cng quy m tng t, nhng qu
trnh ny ph thuc iu kin oxy ho. Biotit giu Fe
3+
gi l lepidomelan. Do nguyn nhn


245
cu trc, lng st ng k trong khong vt u-cui annit phi l Fe
3+
v iu ny minh
chng bng php phn tch ph Mssbauer.
Biotit in hnh khng bao gi t c lng tng l thuyt ca ion Y l 6 trn n v
cng thc. Gi tr ny nm trong khong t 5,6 n 5,9 (xem bng 6.11). Gia Li-muscovit v
lepidolit tn ti mt lot thnh phn trung gian ca mica cha liti. Montdorit l mt mica
him c. Cu trc ca n cha mt trng trong 6 v tr Y, cc v tr cn li do Fe
2+
, Mn v
Mg chim. Cn lp li s trung ho in tch, v tr trong khoang t din ht thy u l
ca silic.
Ni n cc anion fluor v sau l chlor c mt trong biotit thay cho OH, th khi
lng ca chng tng cng vi t l Mg/Fe. Hm lng ca fluor trong biotit gim cng vi
nhit v t l H
2
O/Hf ca cht lng ang cn bng vi n. cha ca fluor c th gip
xc nh mt trong cc thng s ny, nu bit thng s kia (v d H
2
O/HF t bao th lng).
Phlogopit c th tng hp bng phng php nhit dch t nhng nguyn liu khc nhau.
Sau y l phn ng phn hu nhit dch ca mica ny :
2 phlogopit = leucit + kalsillit+ 3 forsterit + 2H
2
O
Tnh cht vt l
Ch s khc x ca cc khong ny tng theo hm lng st, v cc nguyn t thay th
cng nh hng ti ch s ny; v d chng tng t l thun vi hm lng mangan v titan, v
t l nghch vi hm lng fluor. Cho nn khng th dng phng php quang hc xc
nh t s Fe/Mg.
Hu ht biotit (loi cu trc 1M) c mt trc quang song song vi (010), nhng i vi
cu trc 2M
1
th

mt trc quang vung gc vi (010). Phn gic gc nhn xp x vung gc
vi (001), vy muscovit quang m cho thy ko di dng trn mt ct vung gc vi ct khai
(001).
Bng 6.13
S liu phn tch ho ca phlogopit ly t lamproit Lai Chu [12]
Cu t Nm Hon Nm Hon Cc Pa Simang-khang Sin Cao # Pn H
SiO
2
38,13 36,42 37,44 40,67 38,13 40,45
Al
2
O
3
12,94 12,68 13,07 13,21 13,28 13,60
FeO 9,56 12,89 8,39 4,81 10,24 4,34
MgO 18,71 18,29 18,57 23,68 18,67 23,96
TiO
2
5,87 2,72 6,77 0,93 4,76 0,92
CaO 0,02 0,06 0,08 0,04
Na
2
O 0,28 0,58 0,58 0,62 0,51 0,53
K
2
O 10,18 9,67 9,50 9,39 9,88 9,31
Cr
2
O
3
0,10 0,05 0,04 0,90 0,07 1,62
BaO 0,51 0,49 0,16 0,19 0,19
96,00 93,65 94,44 94,77 95,77 94,93
# Theo Jaques et al, 1986
Thnh phn (%) ca ion tnh trn 20 oxy
(do tc gi sch ny tnh thm)


246
Si 5,04 5,04 5,00 5,34 5,06 5,24
Al 2,02 2,06 2,04 2,04 2,08 2,06
Z 7,06 7,10 7,04 7,38 7,14 7,30
Fe 1,04 1,48 0,92 0,52 1,12 0,46
Mg 3,68 3,76 3,68 4,62 3,70 4,62
Ti 0,58 0,28 0,68 0,08 0,46 0,08
Cr 0,00 0,00 0,00 0,00 0,00 0,16
Y 5,30 5,52 5,28 5,22 5,38 5,32
Ca 0,00 0,00 0,00 0,00 0,00 0,00
Na 0,06 0,14 0,14 0,14 0,12 0,12
K 1,72 1,70 1,62 1,56 1,68 1,54
Ba 0,02 0,02 1,62 0,00 0,00 0,00
X 1,80 1,86 1,76 1,70 1,80 1,66
Mu sc ca biotit ni chung m hn so vi ca phlogopit v thng lin quan vi thnh
phn, trc ht l vi hm lng ca st ho tr ba, st ho tr hai v titan. Biotit ngho Ti
thng c mu t xanh lam xanh lc n vng hay lc nu v nu khi hm lng st tng.
Biotit giu Ti thng c mu nu pht , khng ph thuc cha st.
Mt s phlogopit cha bao th hnh kim ca rutil, v i khi ca tourmalin, nh theo
hng ring: vung gc vi (010) v cch nhau 60. y l nguyn nhn ca hin tng nh
sao khi c nh sng xuyn qua l phlogopit.
Biotit bc l tnh a sc r rt vi hin tng hp ph cao i vi dao ng sng sng
dc theo (001). Hin tng ny tng theo hm lng st, nht l khi c mt st ho tr ba; ti
min gip ranh ca cc bt din xy ra trao i in t gia Fe
2+
v Fe
3+
. Biotit thng cho
thy nh ho quang a sc, lin quan n s c mt ca bao th zircon hay cc khong cha
nhng nguyn t dy phng x URa v ThAc.
Biotit thng thnh to dng quen hon thin bn rng {001} v hnh gi lc gic. Hnh
to tia do tc ng c hc c th th xc nh hng tinh th hc, tuy vy thc nghim ny
khng phi lun d dng thc hin v gii thch i vi mi khong vt mica.
Du hiu phn bit
Phlogopit c 2V nh hn ca muscovit, c ch s khc x thp so vi biotit giu st hn,
nn phn bit c vi chng. Biotit thng ti mu hn, a sc mnh hn v c ch s khc
x cao hn so vi cc mica khc. Do c gc 2V ln hn, nn c th phn bit n vi
muscovit. Vermiculit c ch s khc x v lng chit sut thp hn, cn chlorit c lng
chit sut thp nhiu so vi phlogopit.
Lepidolit c mu nht hn, nn c th phn bit vi biotit. N c th tng t phlogopit
v b ngoi v cc tnh cht quang hc. Dng ng thi ngn la i vi liti v nhiu x tia X
l cn thit c th phn bit hiu qu. Nhiu x tia X nn s dng thng xuyn i vi hai
lot khc nhau l mica ba v hai bt din.
6.9. PYROPHYLLIT-TALC
Ging nh mica, hai khong vt ny cng c cu trc tinh th gm cc lp TOT. Tuy
nhin, nu trong muscovit/biotit cation K
+
ng vai tr trung ho in tch m d do nhm
ho tr ba cng thay th silic ha tr bn cng, th trong pyrophyllit-talc khng c thay th
ng hnh khc ho tr ny. Do vy, cc lp TOT gn vi nhau bng lin kt tn d (Van der


247
Waals) yu hn. D thy y nguyn nhn ca cng thp v s lch lc trong trnh t
chng xp cc lp TOT vi nhau.
Mt trong nhng khc nhau ca hai khong vt ny l thnh phn cation. L bt din
trong pyrophyllitc dng hydrargillit (cation nhm chim 2/3 s khoang), trong talc n c
dng brucit (magnesi chim ht s khoang bt din).
6.9.1. Pyrophyllit
Mt nghing hay ba nghing Al
4
[Si
8
O
20
](OH)
4

Np, Nm, Ng 1,552 1,556; 1,586 1,589; 1,596 1,601
Ng Np 0,050; 2V = 53 62
nh hng Ng = y; Nm // x; MTQ (010)
H mt nghing ();
c s a 5,17; b 8,96
c 18,68; 100
Z = 2
Nhm k.g.
C1
d
hkl
,
Tng t muscovit, trong pyrophyllit l brucit gia hai l t din silic oxy (xem hnh
4.21) to nn lp TOT trung ho in tch. Pyrophyllit thng c cu trc hai lp mt
nghing 2M, t gp pyrophyllit mt lp ba nghing 1Tc.
Pyrophyllit cho thy i cht sai st nh so vi thnh phn quy nh trong cng thc ho
hc: thm mt t nhm phi tr bn thay cho silic, bt mt t nhm phi tr su do b magnesi,
st ho tr hai, st ho tr ba v titan th ch. Mt lng nh calci, natri v kali c th hin
din. Ngoi ra, phn no OH b F th ch, ri OH thay cho O lm xut hin lc hydro yu lin
kt cc lp vi nhau. Thc nghim DTA cho thy pyrophyllit c th mt nc khong nhit
t 450C, sinh ra pha pyrophyllit khan gi bn, do phn ng 2OH H
2
O + O
Trong t nhin pyrophyllit thng gp dng vy nh, dng kim to tia v i khi ht
nh kt khi cu c tr. So vi talc v muscovit, pyrophyllit c gc 2V ln hn. Lng chit
sut ca n c gi tr ln hn ca kaolinit.
6.9.2. Talc
Ba nghing hay mt nghing () Mg
6
[Si
8
O
20
](OH)
4
Np,Nm,Ng 1,539 1,550; 1,589 1,594; 1,589 1,600;
Ng Np 0,05; 2V = 0 30
nh hng Ng = y; Nm~//x; MQT (010)
H ba nghing H mt
nghing
c s a 5,29 a 5,29
b 9,15 b 9,15
c 9,45 c 18,9
90,5 100
99


248
99 Z = 1 Z = 2
Nhm k.g.
C1
C2/c hay
Cc
nh hng
d
hkl,
9,34 (10); 4,66 (9);
3,12 (10); 2,48 (7);
1,870 (4).
Talc l khong vt th sinh hnh thnh t s bin i cc silicat magnesi, nh olivin,
pyroxen v amphibol; n c th bt gp dng gi hnh ca cc khong ny. Steatit hay x
phng, dng khi c xt, gm ch yu t talc ht mn, sn phm bin cht ca giu silicat
st/magnesi. N lun c cm gic trn nhn, nh ngc trai hu ht dng tn ti v cng 1
c chn lm chun cho thang Mohs. Talc nguyn khi dng lm vt liu cch in, cch
nhit; n cng dng lm nguyn liu trong sn xut s gm, giy, sn, v.v...
c im cu trc tinh th
Talc c cu trc tinh th tng t ca pyrophyllit, v tr trong khoang bt din do magnesi
chim, thay ch ca nhm v khng c ch trng (ba bt din thay cho hai bt din). Cng
nh trong pyrophyllit, cc lp u trung ho din tch, xen gia chng khng c cation trao
i v chng lin kt vi nhau bng lc rt yu. iu ny dn n cng rt thp v khut
tt trong trnh t cc lp ca talc.
Cn thy rng khi cc lp TOT chng ln nhau th cc vng su t din ca chng khng
i nhau trc din, m lch nhau mt khong bng 1/3 cnh a ca c s. Mt khc, vng
su t din khng i xng su phng, m ba phng kp do cc t din t xoay mt gc
quanh trc ng. Vy, talc c nhng loi cu trc nh 1Tc (mt lp ba nghing), 2M (hai lp
mt nghing) v 2O (2 lp trc thoi).
Bng 6.14
S liu phn tch ho ca talc
1 2 3
SiO
2
61,71 62,5 62,69
TiO
2
0,09
Al
2
O
3
0,30 0,50 0,49
Cr
2
O
3 0,10
FeO 4,09 1,32 0,76
MnO 0,01
NiO 0,12
MgO 29,09 30,08 29,93
CaO 0,30
Na
2
O 0,03
K
2
O 0,02
H
2
O
+
4,70 5,48
Tng 95,28 100,05 99,70

S ion tnh trn n v cng thc
Si 7,946 7,945 7,913
Al 0,046 0,055 0,073
Z 7,99 8,00 7,99
Al 0,020


249
Ti 0,009
Cr 0,010
Mg 5,582 5,835 5,631
Fe
2+
0,440 0,140 0,080
Ni 0,120
Mn 0,001
Ca 0,041
Na 0,003
K 0,003
OH 4,00 3,99 4,61
Y 6,03 6,13 5,76
1. Talc, talcchloritoidchlorit schist, Gran Paradiso, Cogne, Itali (Chopin, C., 1981, J.
Petr., 22, 62850. Probe analisis : all Fe as FeO).
2. Talc, contact-metamorphosed antigorite schist, south-west Alpe Zocca, Itali
(Tromsdorff, V. & Evans,B. W., 1972, Amer. J. Sci., 272. 423-37. Probe analisis : all Fe as
FeO; H
2
O assumed).
3 Talc orebody, Trimouns, French Pyrnes (Noaack, Y., Decarreau, A. & Manceau, A.,
1986, Bull. Min., 109, 253-63).
Khoang bt din c hai loi, chng ch khc nhau cht t v kch thc; php phn tch
ph Mossbauer cho thy khi st thay th ng hnh cho magnesi n thng chim khoang
M2. Hai khong vt c biu nhiu x tia X tng t; nhng gi tr d
hkl
ca talc thng ln
hn, chng hn d
060
= 1,52, trong khi ca pyrophyllit l 1,49. Gia cc lp TOT khng c
cation trao i, cng khng c cc phn t nc; bi vy, tc dng ca dung mi hu c v
ca nhit 700 khng nh hng ti gi tr d
hkl.

c im ho hc
Talc thng ch c cht t bin i trong thnh phn ho hc (bng 6.14); i khi mt
lng nh nhm v titan thay cho silic, mt lng nh mangan hay nhm v mt lng trung
bnh ca st (ho tr hai v ho tr ba) c th thay th magnesi. Tuy vy, mt s mu cha ti
hai nguyn t st trong n v cng thc.
Talc cha hm lng tng i nh ca calci v kim; chng c th thay th cho
magnesi, nhng cng rt c th chng nm xen lp hay di dng tp cht. Vi ba s liu
phn tch cho thy cha nc cao khc thng, nhng mt s c l duy tr dng nc
hp ph.
Talc b phn hu nhit khong 800C cho enstatit v cristobalit:
Mg
3
Si
4
O
10
(OH)
2
3MgSiO
3
+ SiO
2
+ H
2
O
Talc c th hnh thnh t hn hp MgO v SiO
2
, nhit di 800C v p lc hi
nc gia 0,5 v 2kbar. Talc thng cng sinh vi forsterit, t hp ny thay bng enstatit
nhit cao (cng vi serpentin p sut cao). Tp hp talc + enstatit l tng ng vi
anthophillit, sn phm ca p sut cao v nhit thp. Vic thm FeO s gy tc dng r rt
i vi nhng phn ng ny: n lm gim nhit bn vng ca talc.




250
6.10. KHONG VT ST
Phn ln, khong vt st thng gp di dng tp hp ht mn. Khi hp ph nc,
chng tr thnh vt liu vi do thay i. Ht st c dng vy; chng c th tn ti trng
thi v nh hnh. Kch thc ht thng nh, c th thay i t c ht keo cho n gn gii
hn ca phn gii ca knh hin vi. V cu trc tinh th, khong vt st hnh thnh t cc
lp TO v TOT gm l t din SiO
4
ghp vi l bt din kiu brucit/gibbsit.
Da trn nhng c trng khc nhau, trc ht l ln ca c (thng s chui mng
thng gc vi mt lp) khong st chia thnh 4 nhm chnh: kaolinit (7), illit (10), smectit
(15) v vermiculit (14,5).
Bng 6.15
S liu ho phn tch ca khong vt st
1 2 3 4 5 6 7
SiO
2
46,20 44,46 51,25 56,59 51,46 50,25 34,04
TiO
2
0,09 0,15 0,17 0,06 0,05 0,03
Al
2
O
3
39,20 36,58 23,53 20,06 2,20 4.44 15,37
Fe
2
O
3
0,23 0,36 2,02 3,19 24,70 0,50 8,01
FeO 0,07 0,33
MnO 0,03 0,03 0,02
MgO 0,07 0,18 3,32 3,10 3,27 23,81 22,58
CaO 0,06 0,19 0,59 0,68 1,45 1,70 0,00
Na
2
O 0,09 0,01 0,05 2,17 1,06 0,76 0,00
K
2
O 0,21 0,51 7,61 0,45 0,24 0,10 0,00
H
2
O
+
13,80 13,38 5,87 13,67 15,34 7.25 19,93
H
2
O

4,05 5,26 10,76
Tng 99,95 100,12 100,02 100,00 99,80 99,69 99,93

S ion tnh trn 18 (O,OH)
Si 3,981 4,01 7,163 7,776 7,950 7,513 5,44
Al 0,019 0,837 0,224 0,050 0,487 2,56
4,00 4,01 8,00 8,00 8,00 8,00 8,00
Al 3,962 3,89 3,040 3,026 0,351 0,296 0,32
Ti 0,006 0,01 0,018 0,006 0,006 0,003
Fe
3+
0,015 0,02 0,212 0,330 2,872 0,056 0,96
Fe
2+
0,01 0,039
Mn 0,003 0,004 0,003
Mg 0,009 0,02 0,692 0,635 0,753 5,306 4,72
3,99 3,95 4,00 4,00 3,99 5,67 6,00
Mg 0,64
Ca 0,006 0,02 0,088 0,100 0,240 0,272
K 0,023 0,06 1,357 0,079 0,047 0,019


251
Na 0,015 0,00 0,014 0,578 0,318 0,220
1,46 0,76 0,60 0,51
OH 7,980 8,04 4,000 4,000 4,000 4,00
H
2
O 8,64
1. Kaolinit, St. Austell, Cornwall, UK; Contain 1-2 per cent mica (Jepson, W. B. &
Rowse, J. B., 1975, Clays and Clay Min., 23, 310-17).
2. White halloysite, Bedford, Indiana, USA (Kerr, P. F.,Hamilton, P.K. & Pill, R. J.,
1950, Reference clay minrrals. Amer. Petrolium Inst. Res. Proj., 49, Columbia Univ., New
york, Includes P
2
O
5
0,18).
3. Illite, Aymestry Limestone, Showers End, Worcs, UK (Srodon, J. & Karlinger, M. R.,
1986, Clays and Clay Min., 34,368-78. Includes P
2
O
5
0,02. Containes 7 per cent smectit
layers).
4. Montmorillonite, Creme, Recoaro Terme, Vicenza, Itali (Brigatti, M. F., 1983, Clay
Min., 18, 177-86).
5. Nontronite, Andreasberg, Germany (Brigatti, M. F., 1983, Clay Min., 18, 177-86).
6. Saponite, Ballarat, Inyo Co., California, USA (Post, J. G., 1984, Clays and Clay Min.,
32, 147-53. Includes NiO 0,07).
7. Vermiculit, Kenya (Mathieson, A. McI.. & Walker, G. F., 1954, Amer. Min., 39, 231-
55).
Tuy vy, thng s ny c th thay i gi tr: tng (trng n) do nc hay dung mi hu
c b hp ph, nm chn vo gia cc lp; gim (co rt) do mt c nc hp ph v nc cu
trc. Khong vt st ht thy u l silicat ngm nc, nhit cao sau khi mt nc, chng
bin thnh vt liu chu la.
Nhng trang sau s cp n cc khong, tr nhm nm. Tuy c nhiu im chung nh
cc khong dng lp, paligorskit v sapiolit c dng si mnh. Cu trc ca chng cng c
nhm chc (Al,Si)
2
O
5
dng l, nhng cc bt din (Al, Mg, Fe) khng kt thnh lp m thnh
chui, li cc knh cha cc phn t nc v cht hu c.
Bng 6.16
Mt s c trng chnh ca cc nhm khong vt st
Kaolinit Illit Smectit Vermiculit
T : O 1 : 1 2 : 1 2 : 1 2 : 1
L
bt din
Hai
bt din
Hu ht hai
bt din
Hai v ba bt din Hu ht ba
bt din
Cation
trao i
Khng c

K Ca, Na Mg
Nc xen
lp
Haloysit:
1 lp
Phn t H
2
O
Mt t trong
hydromica

1 lp H
2
O
(Na-smectit)/2 lp H
2
O
(Ca-smectit)
2 lp
phn t
H
2
O
Thng s
c
7,1
(haloysit:10)

10 Khng xc nh, Ca-
smectit : 15
Khng xc nh,
14,4 khi ngm
nc
Glycol Ch haloysit Khng tc dng 2 lp pt glycol, 17 1 lp pt glycol, 14


252
hp ph
Cng thc
ho hc
Al
4
Si
4
O
10
(OH)
8

t bin i
KAl
4
(Si,Al)
8
O
20
(OH)
4
M
+
(Y
3+
,Y
2+
)
46

(Si,Al)
8
O
20
(OH)
4
.nH
2
O

M
2+
(Y
3+
,Y
2+
)
4-6

(Si,Al)
8
O
20
(OH)
4
.8H
2
O
Nung
200C
Haloysit co rt,
c = 7,4
Khng bin i Co rt,
c = 10
Phn lp,
c gim
Nung
650C
Kaolinit
Metakaolinit,
c 7
c 10 c 9,6 10 Co rt
c n 9
Chit sut
Np,
Ng, 2V

1,55 1,56
1,56 1,57
24 50

1,54 1,57
1,57 1,61
< 10

1,48 1,61
1,50 1,64
Khng xc nh

1,52 1,57
1,53 1,58
<18
Khong vt st phn bit nhau cch chng mt nc, cch chng phn r v bn cht
ca sn phm phn hu. Thnh phn ho hc (xem bng 6.15) bin ng tu thuc quy m
trao i ca Si, Al v Mg vi cc cation khc, tu thuc bn cht v s lng ca cation v
nc chng hp ph.
Khong vt st l thnh t chnh ca mt loi trm tch, m sau khi lng ng v kt cht
sn sinh phin st hay st. Chng thng l sn phm ca phong ho v bin i nhit
dch, loi hnh thay i tu thuc iu kin ho l v bn cht ca m; v d feldspat, mica,
phun tro thu tinh hay cc khong vt fema. Khong st ng vai tr quan trng trong kin
trc v tnh cht ca t trng.
Khong vt st tp hp trong cc nhm sau:
Nhm kaolinit, gm kaolinit, dickit, nacrit v haloysit.
Nhm illit, gm illit, hydromica, phengit, bramalit, glauconit v celadolit.
Nhm smectit, gm montmorillonit, beidelit, nontronit, hectorit, saponit v sauconit.
Vermiculit
Nhm paligorskit, gm paligorskit v sepiolit.
6.10.1. Kaolinit
H ba nghing hay mt nghing () Al
4
[Si
4
O
10
] (OH)
8
Np,Nm,Ng 1,553 1,565; 1,559 1,569; 1,560 1,570;
NgNp; 2V 0,006; 24 59
c s : a 5,15; b 8,95; c 7,4; 91,8; 104,8; 90.

Z = 1; NKG: C1
nh hng : Nm

: x = 1 3,5; Ng

= y. MQT (010)
d
hkl
chnh, : 7,15 (10); 3,57 (10);
2,55 (8); 2,49 (9); 2,33 (10); 2,33 (10).
c im cu trc
Vi T : O = 1 (bng 6.16), kaolinit c n v cu trc gm hai l TO; l t din v l bt
din dng gibbsit. Nhm chc (Si
4
O
10
)
4
hnh thnh t nhng t din SiO
4
gn kt thnh l
(do cc vng lc gic ghp li). y cc t din gn nh ng phng, nh ca chng u


253
hng v pha i. Ti tm lc gic gia 6 ion oxy nh ny c ion OH

, cc anion O
2
v
OH

y to nn y ca l bt din dng gibbsit (OH)
6
Al
4
(OH)
2
O
4
. Ti y, Al ch chim
2/3 s khoang bt din (hnh 6.28).
Cc lp TO ca kaolinit xp chng ln nhau, sao cho ion oxy mt di ca lp ny kt
ni vi ion hydro mt trn ca lp kia (bng mi lin kt hydro). mng c s h ba nghing
ca cu trc tinh th kaolinit hnh thnh nh vy. N ch gm mt lp duy nht (hnh 6.28,b).
Dickit v nacrit c thnh phn ho hc ging ca kaolinit, nhng cc lp ca chng sp
t theo nhng trnh t khc nhau. Dickit v nacrit c mng c s mt nghing vi b dy c
ln lt gm hai lp v su lp.
Trong khng gian gia cc lp, haloysit cha mt lp phn t nc; lm cho d
001
tng t
7,2 c trng ca kaolinit ln khong 10. Haloysit mt nc c d
001
khong 7. Trt t
xp lp to nn c s hai lp v d cho phn t nc sp xp c v hp l bng dng lin
kt hydro, cu trc haloysit vn bc l s khng trt t. Cc lp c xu hng cun thnh dng
ng hay dng cu. iu , cng vi tnh trng khng trt t, lm cho hiu ng nhiu x ca
haloysit c dng tri rng v khng i xng. Nc xen lp c th thay bng glycol lm cho
d
001
t 10 ln khong 11. Cc khong vt khc trong nhm c th trng n, khng phi do
nc, m do mt s hp cht hu c c bit.

Hnh 6.28
Cu trc tinh th kaolinit
a) Cu trc l tng ca lp TO chiu trn mt (001);
b) Cu trc nhn dc trc [010] v [100] cho thy cc lp chch nhau
c im ho hc
Thnh phn ho hc ca kaolinit t bin ng. Mt lng nh cation nh Fe, Cr, Ti, Mg
v K c mt, nhng khng phi trong cu trc khong vt, m di dng tp cht nh anatas,


254
rutil v mica. Mc du c mt s khong vt ba bt din, ng cu trc vi kaolinit nh
serpentin, amesit, berthierin, cronstedtit, nhng thay th ng hnh trong kaolinit ca (Mg, Fe)
cho Al l khng ng k: kaolinit vn l cu trc hai bt din.
Haloysit c thnh phn bin ng hn. Al
IV
thay th cho Si nhiu hn. Mt na trong
4H
2
O trong cng thc ca n (Al
2
O
3
.2SiO
2
.4H
2
O) tn ti di dng ion OH

v s cn li c
mt gia cc lp di dng cc phn t lin kt yu. Hu ht chng b thi loi ngay nhit
trong phng, ti mi trng khng bo ho nc.
Nng lc trao i cation ca kaolinit ch bng 1/20 ca illit, 1/40 ca haloysit v 1/100
ca smectit. c bit, kaolinit c nng lc trao i anion mnh hn so vi hu ht cc khong
vt st. Xen gia cc lp c cc ion OH

d b thay th.
Tnh cht vt l
Ct khai {001} rt hon ton cho cc tm mm do, nhng khng n hi v i khi c
kch thc kh ln. Kaolinit khng chu tc ng ca cc dung mi hu c, trong khi cc
khong st khc c th thay i ch s chit sut khi tinh th c cc cht ny thm nhp vo.
i vi cc mu ht mn ch c th o gi tr trung bnh ca chit sut. Chit sut ca haloysit
(khong 1,530) thp hn ca kaolinit. Trn nh hin vi in t phn ln cc ht kaolinit c
dng cnh thng v i khi dng tm di vi gc ca cc cnh l 60.
Halloysit thng c dng ko di, dng phng cu v dng khng u n. Trn nh hin
vi in t si halloysit c dng ng, dng cun ko di dc trc y. Halloysit cng c dng tm
v kaolinit cng c dng si.
T trng ca khong vt st c l khng d xc nh; ln ca n bin thin cng vi
trng thi hydrat ho. Kaolinit c t trng khong 2,63g/cm
3,
trong khi gi tr ny t thay i
th t trng ca halloysit dao ng t 2,55 i vi trng thi mt nc n 2,0g/cm
3
tu
cha nc. T trng ca dickit v nacrit l khong 2,6g/cm
3
v bin thin cho ti gi tr l
thuyt.
Khi trng thi ngm nc, kaolinit v cc khong vt st thng c tnh do, tuy nhin
iu ny cha c gii thch tng tn. c do ti a, chng i hi mt lng nc
hp l. Bng chng cho thy, cc phn t nc phn b trong cu trc ca tinh th khong st
phi theo mt trt t nht nh. C l lin kt hydro l lc gn chng vi nhau, vi nguyn t
oxy v vi ion hydroxil mt ngoi ca lp TO.
Du hiu phn bit
Cc tnh cht quang hc c th s dng phn bit kaolinit vi dickit v nacrit. Dickit
quang dng c ch s khc x thp, v gc tt Nm : x = 1420. Nacrit quang m v gc tt
ny c gi tr ln hn. Montmorillonit c ch s khc x thp so vi sericit, c hai khong ny
u c lng chit sut ln hn. Khi phn bit cc khong kaolinit ht mn vi nhau v vi
cc khong vt st khc cng nh vi cc silicat lp (khng phi l st), cn s dng phng
php nhiu x tia X i vi cc mu nguyn, mu nung, mu x l glycol; cn kt hp vi
phng php DTA, vi x l mu v vi cc thc nghim khc. Kaolinit thng khng chu
tc ng ca HCl long, nhng serpentin v chlorit d dng b acid ny phn hu.
6.10.2. Illit
H mt nghing () K
1,5 1,0
Al
4
[ Si
6,5 7,0
Al
1,5 1,0
O
20
](OH)
4



255
Np,Nm,Ng : 1,54 1,57 1,57 1,61 1,57 1,61
NgNp ~ 0,03 2V < 10
nh hng : Nm ~ (001)
c s (loi 1M) : a ~ 5,2; b ~ 9,0; d
001
~ 10; Z = 1
c im cu trc tinh th
V cu trc tinh th, illit cng vi smectit v vermiculit l nhng khong st ging mica,
nhng illit cn c thm nt ca mica l cha kali, cation xen lp chnh. Hu ht illit u n
v cu trc c s TOT, hai bt din ging muscovit, mt s khc ba bt din ging biotit.
Cng thc tng qut ca illit l:
K
Y
Al
4
(Si
8-Y
, Ali)O
20
(OH)
4

trong , y < 2 v thng xp x 1,5. Vy, illit khc muscovit v ho hc l c nhiu silic
v t kali hn; cn v vt l hc l kch thc ca ht st < 2m.
Vi T : O = 2 : 1, n v c s ca cu trc tinh th illit l lp TOT. L bt din
AlO
4
(OH)
2
kiu gibbsit nm gia hai l t din (Si,Al)O
4
hng nh vo trong; n ging n
v c s ca pyrophyllit (xem li hnh 4.21). Cc lp ny lin kt nhau bng lp cation K xen
gia.
Hu ht illit cha t cation xen lp so vi muscovit, cho nn cc lp lin kt vi nhau yu
hn, km u n hn. Illit c th nhn bit bng hiu ng 001 mnh ca nhiu x tia X. Illit
cha t hoc khng cha nc hay dung mi hu c, d
001
khng thay gi tr, d c x l nhit
hay khng.
Illit t nhin cha cc lp smectit, xen k u n hoc ngu nhin. Thnh phn khong
vt st phong ph nht ca trm tch l tp hp cc lp illit/smectit (I/S). Khi n v cu
trc c s ca smectit xen vi illit th thng s mng d
001
tng gi tr v mu khong vt mang
thm nhng c trng ca smectit; chng hn trng n khi x l glycol, co rt khi x l nhit,
cation K c th thay bng Na khi x l NaCl. T l smectit trong mu I/S c th nh lng
c.
c im ho hc
L bt din ca illit cha 4 Al trong n v cng thc, ging nh trong muscovit. L t
din s c d in tch do illit c t s Si/Al cao hn. S lng ion K tuy nh (< 2K/vct,
bng 6.15, pt 3), cng trung ho in tch m d ny. Khong vt phengit cng c t s
Si/Al cao v in tch dng d s trung ho bng vic (Mg,Fe
2+
) thay cho Al
IV
. Trong
hydromuscovit, lng kali thp hn 2K/vct; in tch m di d s trung ho bng ion
hydroxoni H
3
O
+
xen vo gia cc lp hay bng vic thay th mt s anion O
2
OH

. Mt
s illit l hn hp ca hai loi: mt vi khong 2K/vct, mt vi khong 1,1K/vct, cho thnh
phn trung bnh khong 1,55K/vct.
Thut ng sericit thng dng m t mica trng ht mn, c th l muscovit hay
paragonit. i khi, n cng c p dng cho mt th st vi thnh phn bin i t
muscovit theo mt trong nhng cch ni trn. Illit thng cha mt t Ca, Na thay cho K
cng nh Mg, Fe thay cho Al
VI
; nhng ion ny c th va nm xen lp va nm trong lp
illit.
V nng lc trao i cation, illit xp hng cao hn kaolinit, nhng thp hn hn so vi
haloysit, smectit v vermiculit. D sao, trong t illit cng thng l dng b phong ho thiu


256
kali v c th bin i thnh smectit hay vermiculit. Cc dng khong ny c nng lc hp
ph mnh kali t phn bn v c nh n.
Illit hai hay ba bt din u mt nc theo tng giai on. Nc hp ph trn b mt cc
ht v c th c mt t nc xen lp u bc ra nhanh chng nhit di 110C, s cn li
chm hn v thot ra trong khong t 110 n 350C. Nc thnh to t ion OH

s b o
thi sm, gia 350 v 600C, thi nt s t st li cn nung tip.
Illit v tp hp illit/smectit l nhng khong vt st phong ph trong trm tch v c
th hnh thnh t nhng nhm khc nhau nh muscovit, kaolinit v feldspat. Nhng khi
lng chnh ca chng l sn phm ca qu trnh thnh hay bin cht thp (do vi lp) tc
dng ln smectit. Qu trnh illit ho cng xy ra trong mi trng nhit dch, v d trong cc
trng a nhit hay quanh cc m qung. Nhit tng th qu trnh pht trin v sn phm
chnh sinh ra l bin th 1M.
Ti phn di ca cc i phong ho, feldspat b sericit ho cho ra i illit v
illit/smectit. Cc khong vt ny cng sinh ra do smectit bin i khi chu tc dng ca vng
tun hon ma ma ma kh.
Tnh cht vt l
Khong vt illit c gi tr chit sut thay trong khong rng. l do nhiu kh nng
thay th ng hnh (ch s khc x tng cng vi cha st), do mc hydrat ho, do cu
trc c xen cc lp ca khong vt khc. So vi cc mica tng ng l muscovit v biotit, illit
c chit sut thp hn cht t. S dng tnh cht quang hc phn nh cc khong vt ny
i hi chun xc cao, do kch thc rt nh ca cc ht illit. Di knh hin vi in t illit
cho thy hnh thi a dng, nh vy mo m v lc gic u n, thanh hp di v si mnh.
Cc si ny thng gp trong cc l hng ca ct kt rng v c th nh hng tiu cc ti
vai tr ca chng trong vic thu hi du m.
Illit tinh khit th khng mu, nhng cc tp cht nh oxit v hydroxit st ht mn c th
lm cho n nhim mu vng, xanh hay nu, v.v..., v c th bc l tnh a sc nh. Cng nh
chit sut, t trng khng th o chnh xc bi v n chu nh hng ca s hydrat ho v s
c mt ca tp cht ht mn. Thng thng, cc khong vt illit c t trng hi thp so vi cc
mica tng ng.
Du hiu phn bit
Bn cht ht mn ca cc illit gy nhiu kh khn cho vic nhn bit chng bng phng
php quang hc. Chit sut trung bnh ca chng xp x bng chit sut ca mica tng ng,
nhng 2V thng nh so vi muscovit. nhn bit chng, c th p dng phi hp cc php
phn tch ho vi DTA v nhiu x tia X i vi cc mu trc v sau khi x l nhit v dung
mi hu c.
Mt s c im trn biu nhiu x tia X c th gip phn bit illit v cc silicat lp
khc:
d
001
=10 ch loi cu trc TOT. d
060
xp x 1,50 l ca cu trc hai bt din.
Cng vch I
002
> I
001
:4 cho thy nhm (khng phi st) l cation chnh ca v tr
bt din.


257
Ir = (I
001
: I
003
)
mu kh
: (I
001
: I
003
)
mu x l glycol
= 1 cho thy mu khng trng n. Ch s
Ir thng ln hn 1 khi cu trc cha cc lp smectit.
6.10.3. Smectit
Ba bt din (
1
2
Ca,Na)
0,7
(Mg,Fe,Al)
4
[(Si,Al)
8
O
20
](OH)
4
.nH
2
O
H mt nghing ()
Np,Nm,Ng 1,48 1,61; 1,50 1,64; 1,50 1,64
Ng Np, 2V 0,01 0,04; hu ht gc nh
nh hng Np (001); Nm = y; M.T.Q.(010)
mng c s, a = 5,2; b = 9,1 9,2;
d
001
= 10 15, tu cha nc.
Khong vt chnh l nhng silicat lp vi T : O = 2 : 1, gm c: montmorillonit, beidelit
v nontronit (hai bt din) vi cng thc chung v saponit, hectorit v sauconit (ba bt din).
V mt ho hc tinh th, hai nhnh ny lin quan ln lt vi pyrophyllit v talc.
c im cu trc tinh th
Cu trc c s ca tinh th smectit l pyrophyllit (hnh 4.21). Vi T : O = 2 : 1, n v c
s ca cu trc tinh th l lp TOT gm 3 l: nm gia hai l t din (Si,Al)O
4
i nh l l
bt din:
kiu gibbsit Al(OH)
3
(smectit hai bt din, vi 2/3 bt din do Al chim), hay
kiu brucit Mg(OH)
2
(vi tt c cc bt din u do Mg chim, smectit ba bt din) trong
2/3 nhm OH

thay bng anion oxy thuc mng lc gic ca nhm chc silic-oxy. Trong
c hai mica ng cu trc vi smectit, l pyrophyllit v talc, Si, Al
VI
hay Mg khng b thay
th ng hnh. Thnh ra, lp TOT trung ho in tch v khng cn c cation xen gia
chng. Trong khi, smectit li c s thay th ng hnh c v tr trong bt din (Al hay Mg)
ln v tr trong t din (Si). in tch di d t s c trung ho bng mt lng nh
cation Ca
2+
hay Na
+
xen gia cc lp.
Khong cch d
001
trong pyrophyllit v talc ln lt xp x bng 8,9 v 10. Smectit cho
thy thng s ny bin thin trong phm vi rng vi gi tr nh nht 9,6 (ng vi trng thi
co rt ti a). Lng cation xen lp ch cn bng in tch m ca cc lp TOT v do
chng khng lp y cc v tr sn c, khng ging K trong muscovit. C th, chng xp
theo trt t xen k gia chui c cation v chui b trng. Khi thm nhp vo khng gian gia
cc lp, cc phn t nc khng xp thnh lp lin tc, m bao bc thnh v quanh cc
cation. V tr cc cation v phn t nc phn no phn nh bng lin kt hydro.
Bn cht cu cation xen lp nh hng phn no ti s lp ca phn t nc.
Montmorillonit calci (thng gp trong t nhin) thng c t 2 n 3 lp trong phm vi
mng v d
001
ln lt bng khong 15,5 n 19. Montmorillonit natri c 1 lp (d
001

12,5), 2 lp (d
001
15,5), 3 lp (d
001
19) hay nhiu hn trong mng. Khong vt c
th cha mng hn hp vi cha nc ca mi mt khc, cho nn thng s d
001
c cc
gi tr bin i lin tc gia 10 v 21 v c th bin i theo m v bn cht cation trao
i. Sau khi b mt nc, montmorillonit v saponit th hin nng lc nhiu x trn biu
Roentgen tng t nh pyrophyllitv talc.


258
Smectit thng bc l s chng xp lp khng trt t, sinh ra trn biu nhiu x tia X
nhng hiu ng tri rng thay cho nhng vch r nt. Mt s smectit hai lp bc l trt t
tng phn, sn sinh trn biu mt s hiu ng sc nhn bn cnh cc hiu ng khng r.
Smectit tri qua vng x l kh t k tip vi dung dch cha K c th cho cu trc trt t
tt (C2/m, 10) vi cation K c nh ti khng gian gia cc lp.
Smectit kt hp vi cc silicat lp khc theo nhng trt t khc nhau, thng gp nht
l illit/smectit v chlorit/smectit. Mt s tn khong vt ra i dnh cho cc cu trc trt t
cao, v d rectorit (illit/smectit), tosudit (chlorit/smectit), alietit (saponit/talc). Cu trc vi
trt t hon ho c d
001
l tng gi tr ca hai thnh phn. Vi trt t tng phn, cu trc c
thng s d
001
nm gia cc gi tr ca hai thnh phn. Cng c th gp hn hp cc lp ca
hai khong vt smectit (montmorillonit v beidelit).
Bn cnh nc v cc cation trao i, mt s ion hu c nh akylammon v cht lng
hu c nh glycol v glicerol cng c mt trong khng gian gia cc lp. Cc lp cht ny
nh v y theo s nguyn, gp phn duy tr trt t chung ca cu trc, lm cho d
001
tr
thnh c s ca dng khong vt. Di tc dng ca glicerol, haloysit v vermiculit trng
n, khin cho d
001
tng ln ln lt n 11 v 14.Cn i vi smectit, kt qu l 17.
Khi nung nhit gia 100 v 200C, smectit mt nc xen lp, d
001
gim cn khong
10. Nung n 500C lm cho d
001
gim tip, cn t 9,6 n 10 tu bn cht ca cation xen
lp.
c im ho hc
Thnh phn ho hc ca tt c cc smectit u ging nh ca pyrophyllit hay talc. Mi
s thay th ca ion ho tr thp hn vo cc v tr bt din v t din u c km theo s b
sung tng ng ca cation trao i. Quy m trung bnh ca s thay th ny i hi b sung
khong 0,7 cation ho tr mt (hay tng ng) tnh trn n v cng thc v nhng cation
ny thng c th trao i.
Nhm smectit c nhiu s khc nhau v thay th ng hnh (trnh by c phn l tng
ho, bng 6.17). Chng hn, montmorillonit v hectorit hu ht thay th trong v tr Y, trong
khi beidelit v saponit ch yu trong Z. Ngoi nhng thay th gii thiu trong bng, smectit
c nhiu trng hp thng gp khc. V tr Y c th cha mt lng nh Fe
2+
, Mn v Ni.
Khng nhng th, trong t nhin cng tn ti trng hp trung gian vi cc c im ca hai
hay nhiu khong vt ca nhm smectit. V d, montmorillonit c mt phn Si b thay th bi
Al, ri beidelit v nontronit c mt t Mg. Nh th, montmorillonitbeidelitnontronit l mt
chui dung dch cng (bng 6.15, mu 4, 5 v 6). Chui montmorillonitbeidelit c th biu
th bng cng thc:
Al
4Y
Mg
Y
(Si
8X
Al
X
O
20
)(OH)
4
.X
X + Y
trong , X l s cation xen lp ho tr mt v ho tr hai. i vi montmorillonit y > x,
i vi beidelit y < x. Trong smectit nhm ny, lng trung bnh tnh trn n v cng thc
ca Al, Mg, Fe
3+
v Fe
2+
trong bt din ln lt bng 3,0; 0,7; 0,4 v 0,4 v Al trong t din l
khong 0,4/vct. Cn lng Fe
2+
trong nontronit thng ln hn 3, trong
montmorillonit/beidelit nh hn 3 nguyn t tnh trn n v cng thc.
Bng 6.17
Thnh phn cation trong smectit, pyrophyllit v talc vi s thay th ng hnh
Z Y X (cation trao i)


259
Hai bt din
Pyrophyllit Si
8
Al
4

Montmorillonit Si
8
Al
3,3
Mg
0,7
(0,5Ca,Na)
0,7
Beidelit Si
7,3
Al
0,7
Al
4
(0,5Ca,Na)
0,7
Nontronit Si
7,3
Al
0,7
Fe
4
3+

(0,5Ca,Na)
0,7

Ba bt din
Talc Si
8
Mg
6

Saponit Si
7,2
Al
0,8
Mg
6
(0,5Ca,Na)
0,8

Hectorit Si
8
Mg
5,3
Li
0,7
(0,5Ca,Na)
0,7

Sauconit Si
6,7
Al
1,3
Zn
4-6
(Mg,Al,Fe
3+
)
20
(0,5Ca,Na)
0,7

Trong smectit ba bt din, Mg l cation chnh ti Y, nhng n c th b thay th hon
ton bi Fe
2+
; lm ny sinh saponit st. Saponit (bng 6.14, pt 7) thng cha mt s cation
ho tr ba trong v tr Y v tng ng s c thm Al thay cho Si. Mt t Fe
3+
trong saponit c
th sinh ra do Fe
2+
nguyn sinh b oxy ho. Hectorit thng cha thm F do n vo thay cho
OH.
Tng lng ion Y trong smectit thng nm trong khong t 4 4,5 n 5,7 6 v mc
d c l khng c thnh phn trung bnh, vn c th gp nhiu hn hp lp ca cation ho tr
hai v ha tr ba.
Cation trao i thng gp nht l natri, cesi, stronti, magnesi, hydro, v nhng cation
xen lp khc; chng c mc trao i khc nhau. Chng c l hin din sn trong
khong vt, khi n thnh to. Chng cng c th sinh mun, do qu trnh trao i v sau.
Nng lc trao i ph thuc vo kch thc ca ht khong, vo bn cht ca cation. Nng
lc ny tng theo trnh t sau:
Li < Na < K < Rb < Cs, cho cation ho tr mt v
Mg < Ca < Sr < Ba, cho cation ho tr hai.
Ni chung, vi ho tr cng cao cation c nng lc thay th cng ln, kh nng b thay th
cng nh. V d, Ca kh b thay th hn Na. Phn tch ho ca smectit hai bt din cho thy
tng lng ion ti Y vt qu 4 nguyn t/vct. Dng nh mt s ion Mg chim ch ti
khng gian gia cc lp, gp phn vo nng lc trao i cation ca khong smectit
Phn t xen lp: Lng phn t nc thm nhp vo khng gian gia cc lp bin i
tu theo chng loi smectit, theo bn cht ca cation ti ch v theo iu kin t nhin. Chng
hn, smectit calci thng hp ph hai n ba lp phn t nc ti mi khong cch lp. Trong
khi smectit natri lin tc thay i kh nng hp ph nc v thng bc l s trng n
mnh. Nc xen lp c th c dng i km cation ti ch, to lp v gm cc phn t H
2
O
bao bc chng.
Cc phn t hu c khc nhau cng c th hin din trong khong khng gia cc lp. V
vy, smectit c dng nhiu trong vic ty mu, ty du m, tinh ch du m. Mt lot hp
cht hu c nh cn, keton, amin, urea v amit bm cht cc ion kim loi ti ch. Ni chung,
i vi cc cht hu c, cation Na, Ca v Mg hp dn hn K v trong nhiu trng hp, c s
tham gia ca dng lin kt hydro nh cc nhm (OH) v (NH). Chnh nh vic a nhng
cation (kimloi hu c) bn vng loi ny vo cu trc lp ca smectit, rng v tnh
nng xc tc ca khong st c tng cng.


260
Hiu ng nhit: Smectit mt hu ht phn nc xen lp khi b nung nhit t 100 n
250C, nhng phn st th cn li n gn 300C, ti nhit ny nc cu trc (OH) bt u
thot dn. T khong 500C tr i, nc (OH) thot nhanh v mt ht nhit chng
750C. Qu trnh mt nc ca montmorillonit din ra thng km theo mt phn s thu hi,
cho ti khi mt ht. Thm ch, khi nung n 600C, phn no nc xen lp dn dn quay tr
li. Ngay nhit thp hn cht t, saponit v smectit cha nhiu st co rt hn, mt c
nc (OH). Nung tip, chng s chuyn i thnh pha nhit cao, nh cristobalit, mulit,
cordierit hay hp cht dng spinel.
Tnh cht vt l
Smectit thng gp dng tp hp cc ht mn hnh su, hnh tm hay hnh cu. i khi,
cc ht ca tp hp nh hng tt v to dng v ca nhng tinh th hon thin. Tuy nhin,
quan st di knh hin vi in t mi thy ht c s l cc vy rt mnh. B ngoi, hu ht
chng u mo m, mt s c dng lc gic hay hnh thoi. Ht dng gii, si cng ph bin.
Mu sc ph bin nht ca montmorillonit l mu hng, mu da b, mu xm hay mu
nu nht, i khi c c mu trng. Nontronit thng c mu lc ti. Nhng khong vt c
mu thng bc l tnh a sc; cc mu ca nontronit l mu lc dc (001), mu vng theo
hng vung gc (001). Do tnh cht quang hc ca chng chu nh hng ca bn cht ht
mn, ca hydrat ho, ca dung mi hu c v ca s thay i thnh phn, nhng thng s
quang hc o c cho smectit khng c chnh xc cao.
Ch s khc x ph thuc nhiu vo cha st v ch lin quan rt t vi s thay th silic
nhm v nhm magnesi, nhng gc 2V th bin thin trong mt khong rng. Chit sut
tng cng vi s tht thot ca nc trao i, cn t trng th ph thuc vo mc hydrat
ho.
Du hiu nhn bit
Smectit c ch s chu nhit bnh qun tng t nh ca illit v kaolinit, nhng khong
vt ca nhm kaolinit c lng chit sut thp hn ca hu ht cc smectit, illit li c lng
chit sut cao hn. Montmorillonit v saponit khan v t st thng tng ng vi
pyrophyllit v talc v ch s chu nhit; nhng li c lng chit sut thp hn ca chng.
Khng th nhn bit smectit nu ch s dng phng php quang hc. Trong phn tch pha
ny, cn kho st nhiu tnh cht ca n, thng qua ng cong DTA, ng cong mt nc,
biu nhiu x tia X trc v sau khi x l nhit v dung mi hu c.
i vi smectit, d
001
tng t gi tr 12 khi n bo ho K
+
v NH
4
+
, t 15 vi Ca hay
Mg, t 17 vi glycol. Khong ny gim cn 10 khi nung n 150C (250C i vi
sapolit). Montmorillonit v beidelit c d
060
bng khong 1,5 v sapolit bng khong 1,53.
Nontronit v saponit d dng b acid phn hu, nhng montmorillonit v beiderit l nhng
khng th i vi acid.
6.10.4. Vermiculit
H mt nghing () (Mg,Ca)
0,60,9
(Mg,Fe
3+
,Al)
6,0
(Si,Al)
8
O
20
(OH)
4
.nH
2
O
Np,Nm,Ng: 1,520 1,564 1,530 1,583 1,530 1,583
Ng Np : 0,02 0,03 2V = 0 18
nh hng: Np (001) M.T.Q. (010).
c s: a 5,3 b 9,25 c 14,4


261
97 Z = 1 N.K.G. C2/m
Vermiculit mang nhiu nt ca mica v smectit ba bt din, nhng cng c nhiu c
trng ring.
Cu trc tinh th
Vermiculit c cu trc loi phlogopit, l trung tm c Mg, Fe trong thnh phn. Thay th
Al cho Si sinh in tch m d v c trung ho mt phn bi thay th khc (Al, Fe
3+
) cho
Mg trong l trung tm, mt phn bi cation Mg xen lp.
Khc phlogopit, vermiculit cha phn t nc ti khong cch lp. Cng vi cation Mg,
cc phn t ny chim nhng v tr xc nh v gn vi nguyn t oxy ca l t din bng lin
kt hydro. V tr ca H
2
O to mng li gi lc gic. Vermiculit t nhin thng cha 2 mng
li H
2
O trong mi khong cch lp. Lin kt hydro duy tr cc phn t nc vi nhau trn
cng mt phng; ri cc mng phng ny li ghp i song song vi nhau nh lp cation
trung gian. Bng cch , cation c lp v bc do phn t H
2
O to nn. Thc ra, trong iu
kin bnh thng ca kh quyn, nhiu phn t nc b v tr, khng tham gia bao bc cation.
Chng tr thnh phn t khng b rng buc, nhanh chng bc hi nhit nh hn 110C.
Trong iu kin nhit v m bnh thng, Mg-vermiculit c khong cch d
001
khong
14,3. Trong iu kin m h v nhit tng, Mg-vermiculit ch cn gi c mt lp
phn t nc v d
001
gim cn 11,7. iu kin trung gian ng vi d
001


13,8 v 90.
Ca-vermiculit v Na-vermiculit vi hai lp phn t nc c d
001
ln lt bng 14,9 v 14,8.
Gi tr ln hn ca d
001
( 18,9) c th gp trong Mg-vermiculit trng n, gi tr nh nht
l ca cu trc co rt ti a.
Glycol v glicerol c th nm xen vo cu trc vermiculit khin d
001
bin ng, l thuc
vo bn cht v s lng ca cation xen lp. Gi tr d
001
ca vermiculit bo ho Mg c th t
14,3.
Cc lp ca vermiculit c th xp theo trnh t u n, nhng bn trt t vn thng gp
hn s dch chuyn u n a/3 v a/6 dc x v ngu nhin l b/2, b/3, b/6 dc hng y.
Thng thng, cu trc s trt t hn, khi trong khong khng gia cc lp c in tch ho
tr cao v lng phn t nc chng lin kt cht thnh lp. Mc du vy,
vermiculit khng cha nc v bo ho kali th li c trt t cao v thuc loi cu trc ca
phlogopit. Cu trc ca hu ht vermiculit, d khng trt t, c lit vo cu trc ca mica
1M, mt s khc c nhiu nt ca 2M
1
.
So vi cu trc ca chlorit, cu trc Mg-vermiculit c nhiu nt tng ng, tr nt khc
l khong khng gia cc lp TOT c nhiu v tr b trng. Trong cu trc, i khi nm th
ch ca l trung tm dng brucit l lp H
2
OMg
2+
H
2
O khng lin mch. Khong st c gp
di dng lp hn hp vermiculit/chlorit v vermiculit/mica (dng ny cn c tn khng
chnh thc v d gy nhm ln l hydrobiotit).
c im ho hc
Vermiculit l khong tng ng vi phlogopit v saponit. Phlogopit c s thay th ng
hnh ca Al
IV
cho Si v, cn bng in tch, cation kali thm nhp vo khong khng gia
cc lp TOT. Trong vermiculit, s thay th tng t c cn bng mt phn bi mt thay
th khc (Al
VI
,Fe
3+
) Mg trong l bt din, mt phn bi cation Mg (khng phi K) xen vo
gia cc TOT. S thay th ng hnh trong l t din khng c trng cho saponit, v th nhu


262
cu cn bng khng ln: s thay th ng hnh trong l bt din v s xen lp ca Ca v Na
(khng phi Mg hay K) xy ra yu t.
Tuy trong vermiculit t nhin (v d trn bng 6.14, mu 8), Mg l cation trao i thng
gp nht, nhng Ca v him hn l Na cng c trong v tr X. in tch ho tr gia cc lp
TOT tng ng 0,7 cation ho tr hai tnh trn n v cng thc; so vi 0,7 cation ho tr
mt trong smectit. Tng ng, nng lc trao i cation ca vermiculit (gia 1,2 hay 2,4
mcq/g) ln gp i ca smectit v thc ra, l cao nht trong tt c cc khong vt st.
Trong cu trc tinh th vermiculit, cc cation Mg, Ca, Na, K, Rb, Cs, Ba, Li, H
+
, NH
4
+

c th
d dng tham gia vo qu trnh trao i trong khong khng gia cc lp TOT. Mc du v tr
bt din Y cha Mg l chnh; n cn cha thm c mt s cation Fe
2+
, ri Al, Fe
3+
, ri mt
lng nh cation khc nh Ti, Li, Cr v Na. Vermiculit hai bt din khng ph bin, tuy
nhin n cng c gp trong t.
Khc vi lng nc xen lp ca smectit, lng nc do vermiculit hp ph thng t
bin ng. Nhiu nht l nc di dng hai lp phn t ti mi khong gia hai TOT. Phm
vi trao i cation xy ra trong hu ht vermiculit t nhin c th hin cng thc sau:
(Mg,Ca)
0,60,9
Mg
4,55,0
(Fe
3+
Al
VI
)
1,51,0
Al
2,22,6
Si
5,82,4
O
20
(OH)
4
.(H
2
O)
7,09,0
Vermiculit cng bc l nng lc hp ph vo khong gia hai TOT i vi cht lng hu
c. Hin tng phn hu i khi xy n vi vermiculit, khi b nung t ngt n khong
300C v cao hn: nc thot thnh tia cng ph cu trc, lm cho n phn li thnh lp. Hiu
ng tng t cng thng c, khi x l vermiculit bng peroxit hydro H
2
O
2
,

lm cho cu trc
m rng ti 30 ln dc phng vung gc vi mt ct khai.
ng cong DTA ca Mgvermiculit cho thy hiu ng ni nhit khong 140C v
240C, ln lt tng ng vi chuyn ho t hai lp H
2
O sang mt v t mt lp n mt
hn. Cc t thot nc ny u l phn ng thun nghch xy ra n tn 550C. Nhng
nhit cao hn, cu trc phn hu do ion OH

b thi loi v do phn ng ni nhit thng


bt u khong 800C.
Tnh cht vt l
Mc du vermiculit l mt thnh t ca t, thng c kch thc ht nh; n cng gp
di dng tm tinh th ln, ch yu khi n l sn phm bin i ca biotit. Tnh cht quang
hc c th xc nh d dng hn so vi cc khong vt st khc. Tuy th, qu trnh hydrat ho
bin ng v cha cation thay i dn n sai s ln trong cc php o cc thng s quang
hc. V tnh cht quang hc, vermiculit gn ging phlogopit; nhng nu n c ch s khc x
ln hn, th l do n cha mt lng st ng k. Cng v vy, 2V ca n lun c xu
hng t gi tr cao so vi phlogopit.
Du hiu phn bit
Vermiculit thng c ch s khc x thp hn so vi biotit hay hydrobiotit v cao hn so
vi chlorit. Lng chit sut ca n nh hn ca biotit hay ca talc. phn bit n vi
montmorillonit v chlorit, hy s dng biu nhiu x tia X ca khong vt ny, sau khi
x l glicerol. Nhng khc nhau chnh gia vermiculit v smectit c th tm tt nh sau:
Vermiculit thng c c ht ln hn.
N c nng lc trao i cation cao hn v c th tip nhn nhm thay th cho silic nhiu
hn.


263
N ch c th cha mt lp phn t glicerol, cn smectit th cha ti 2 lp phn t dung
mi ny. Sau khi x l glicerol, d
001
ca cc khong vt ny ln lt bng 14 v 17.
Smectit mt nc d dng, cn vermiculit thu hi nc nhanh hn.
N hnh thnh ch yu t cc tm biotit ln.
Nhng iu phn bit trn khng phi lun xc thc. Mt s smectit nh saponit cng c
vi c im ca vermiculit.
SILICAT KHUNG
Silicat khung hay tectosilicat c cu trc gm cc t din gn kt nhau thnh b khung ba
chiu vi cng thc tng qut [(Si,Al)O
2
]
n
. Khi cc t din khng cha nhm, b khung s
trung ho in tch. iu ny hin thc trong nhm khong vt silica SiO
2
kt tinh. Khi cc t
din cha nhm, in tch m pht sinh trong khung m ng cho cc cation c ln ca kim
loi kim, kim th. Chng nm trong nhng khong rng sn c trong khung. l trng
hp ca nhm feldspat, feldspathoid v zeolit.
Silica (kt tinh, khng cha nc) SiO
2
c nhiu bin th a hnh: thch anh , thch anh
, tridymit, cristobalit, coesit v stishovit (xem hnh 5.5 v 5.6 vi ch gii i km). Ti iu
kin p sut kh quyn, nhng bin i a hnh chnh ng vi cc nhit xc nh: 573C
(thch anh thch anh ), 867 (thch anh tridymit), 1713C (tridymit
cristobalit ).
Feldspat. Thnh phn ca feldspat ph bin th hin biu trng thi ba hp phn:
orthoclasalbitanorthit (xem hnh 5.3). Nhng dung dch cng c th c s thay i phm vi
ca chng, tu thuc iu kin nhit . Khi nhit trn 660C, cp orthoclasalbit c
dung dch cng lin tc. Di nhit ny, h hai hp phn c mt min gin on (solvus),
ng vi s phn r perthit. Do natri v calci rt gn nhau v kch thc ion, h albitanorthit
c phm vi dung dch cng kh ln. Phm vi ca min gin on trn h ba hp phn cho
thy c th xp thnh phn cc feldspat theo hai lot: feldspat kim hay feldspat kali natri v
feldspat plagioclas hay feldspat natri calci.
Cc nt chung v cu trc tinh th
T din ca Si
4+
v Al
3+
trong silicat khung vi t l thay i:
1/2 (AlO
4
)/(SiO
4
) 1/3
lin kt vi nhau bng tt c 4 anion oxy chung. Khung y c th xem nh s gn kt ca
cc di bng ln sng ko di dc theo [100]. Hnh thnh t nhng vng 4 t din k tip
nhau, cc di bng ny gn vi nhau theo [010] v [001], ln lt a oxy nh vo dng
chung (hnh 6.29 v 6.30). Nhng lin kt gia cc di bng ny kh lng lo, lm ny sinh
hai hng ct khai (010) v (001) di gc vung trong feldspat mt nghing (orthoclas) hay
gn vi gc vung trong feldspat ba nghing (plagioclas). Khung ca nhm chc alumosilicat
[(Al
12
Si
32
)O
8
]
(12)
cha cc cation K
+
, Na
+
v Ca
2+
trong cc khoang trng rng, do nhu cu trung ho in
tch m.
Cc feldspat c quan h trt tkhng trt t ca Al-Si khi chng thay nhau lp y
khoang t din. Khi kt tinh hoc b nung nhit thp, feldspat thng c trt t cao;


264
khi nhit cao chng thng c t trt t hn. Tng ng vi qu trnh ca Al-Si i vo
trng thi trt t l s h gim i xng ca feldspat: feldspat nhit cao h mt nghing tr
nn ba nghing.
Feldspathoid l nhng alumosilicat c thnh phn tng t, nhng khng giu silica nh
feldspat. Cu trc tinh th ca chng c khung t din gn vi khung ca bin th silica
(tridymit v cristobalit) hn l vi khung ca feldspat. Hy quan st hai i din chnh ca
chng l nephelin v leucit.
Nephelin Na
3
K(AlSiO
4
)
4
thuc h su phng. Khung AlSiO
4
l cc lp t din trong
(0001) ging ca silicat lp (phillosilicat), nhng cc t din lin k ca vng su th thay
phin nhau, hoc hng nh ln (AlO
4
) hoc hng dnh xung di (SiO
4
). Cc anion oxy
nh ra (ti nh) dng lm cu ni cc lp lin li thnh khung. Trong s cc khong trng hnh
thnh c n 75% l dnh cho natri, 25% cn li l v tr ca kali.
Leucit K(AlSi
2
O
6
) c hai bin th a hnh. Di 625C bin th bn vng l thuc h bn
phng, phn na hnh 4/m, gi su phng vi a = 13,04; b = 13,85. Trn nhit ny l
bin th lp phng, ton hnh m3m, a = 13,43. Bin i a hnh ny khng lm bin dng
nhiu s cu trc. N bao gm cc vng su t din gn vi nhau thng qua cc vng bn
t din. Cng nh nephelin, leucit c nhm v silic phn b vi trt t cao.
Nhm zeolit thuc cc tectosilicat vi khung t din rt a dng. Trong cu trc thng
c nhng hang ln thng vi nhau bng ng ng rng; v d, morddenit v chabasit (xem
hnh 5.25 v 5.26). Ti y, c cc phn t nc t gn vi khung silicat (nc zeolit). Chng
c th thot ra, ri nhp tr li; tu thuc s bin ng ca p lc ring phn ca hi nc
hay ch nhit ca mi trng. Cc phn t nc ny c th b cc phn t hay nguyn t
th chn, nh kh H
2
S, NH
3
, CCl
4
, Ar, Xe, Ne, v.v hay kim loi nh Hg. T , zeolit dng
lm tm by phn t trong bm chn khng, lm tm ry phn t tch lc cc phn t
kch c khc nhau.
y l nhng alumosilicat cha nc, m in tch m ca khung t din (Al,Si)O
4
do
cation cc loi trung ho nh Ca
2+
, Na
+
, K
+
, Ba
2+
, Sr
2+
, Mg
2+
. Cng thc ho hc ca zeolit
thng p ng t s sau:
(CaO+Na
2
O+K
2
O+BaO+SrO+MgO)/Al
2
O
3
= 1.
Nm trong h ng ng, nhng cation ny va lin kt vi khung t din va lin kt
vi cc phn t nc bng lc lin kt tng i yu. Chng d dng trao i ln nhau; v d:
cation calci trong dung dch d dng thay ch ca cation natri trong cu trc theo s Ca
2+

2Na
+
. T , zeolit dng lm cho nc cng. Trong ng dng cng nghip, chng
hn trong cracking hydrocarbur, zeolit nhn to thng c dng ngy cng nhiu.
Da vo cu trc v dng quen tinh th zeolit chia lm 3 loi :
Zeolit dng si: Vng nm t din (Al,Si)
5
O
10
gn kt nhau thnh chui di dc
theo [010] hay [001] lm cho tinh th c dng kim, dng si. Chng lun thnh to
cc tp hp si to tia:
Natrolit, Na
2
Al
2
Si
3
O
10
.2H
2
O. H trc thoi.
Mesolit, Na
2
Ca
2
(Al
2
Si
3
O
10
)
3
.8H
2
O. H mt nghing.


265
Zeolit dng phin: B khung t din vi lc lin kt ln hn dc theo cc mt
song song trong cu trc l nguyn nhn ca hin tng ct khai hon ton theo
(010). y l zeolit dng l:
Heulandit, (Ca,Na
2
)Al
2
Si
7
O
18.
.6H
2
O. H ba nghing.
Stilbit, (Ca,Na
2
,K
2
)Al
2
Si
7
O
18
.7H
2
O. H mt nghing.
Zeolit dng ng thc: Cc vng t din gn vi nhau bng lc lin kt ng
hng lm nn b khung ng thc. Cu trc cha nhng hang ln ni vi nhau
bng knh ng. i xng gi lp phng hay lp phng:
Harmotom, BaAl
2
Si
6
O
16
.6H
2
O. H mt nghing.
Chabazit, (Ca,Na
2
)Al
2
Si
4
O
12
.6H
2
O. H su phng.
Faujasit, (Na
2
,Ca)Al
2
Si
4
O
12
.6H
2
O. H lp phng.
6.11. FELDSPAT
Feldspat kim
c s Microclin
nhit thp
Albit
nhit thp
Albit
nhit cao
Sanidin
nhit cao
Anorthit
a() 8,590 8,138 8,160 8,604 8,17
b() 12,966 12,785 12,873 13,029 12,87
c() 7,223 7,158 7,110 7,176 14,17
90,65 94,26 93,52 90 93,1
115,96 116,60 116,43 116,02 115,9
87,65 87,68 90,27 90 91,3
Z 4 4 4 4 8
N.K.G.
C 1 C 1 C 1
C2/m
P 1
6.11.1. c im cu trc
Tng t cc bin th a hnh SiO
2
, cu trc feldspat gm mt khung v hn ca cc t
din SiO
4
v AlO
4
. Trong , t din vn ch cha Si (nh trong cc dioxit silic), nay (khi
chuyn sang feldspat) mt s t din cha Al thay cho Si. Cng vi vic c thm Al, cu trc
phi nhn Na
+
(hay K
+
hay Ca
+
) vo nhng hang hc ca n. Khi ch c mt Si
4+
(trn n v
cng thc) b thay th bi mt Al
3+
, cu trc c th c trung ho bi mt K
+
hay mt Na
+
.
Tng t, khi hai Si
4+
(trn n v cng thc feldspat) b Al
3+
thay th, in tch ca khung c
th c cn bng bi cation ho tr hai Ca
2+
. iu ny c th hin nh sau:
Khung Si
4
O
8
Na(AlSi
3
O
8
) Ca(Al
2
Si
2
O
8
).
Khung c bn ca cu trc feldspat c th minh ho bng s cu trc ca sanidin, bin
th nhit cao ca KAlSi
3
O
8
vi nhm khng gian C2/m (hnh 6.29). Trong cu trc ny,
nguyn t nhm v silic phn b khng trt t, hon ton ngu nhin trong hai v tr tinh th
hc ring bit, T1 v T2. Ion K
+
lin kt vi 9 oxy gn nht, trong mt khong rng v ti v
tr c bit trn mt i xng gng vung gc vi trc y.


266
Khung t din SiAl gm cc vng bn t din (gn vi nhau qua nh chung). Cc vng
bn ny gn vi nhau thnh chui song song vi trc x (hnh 6.30). Chui dng khi vung
vn gi cc mt ct khai di gc vung v dng quen gi bn phng c trng ca
feldspat.
Cu trc ca microclin, bin th a hnh nhit thp ca KAlSi
3
O
8
, c i xng ba
nghing (nhm khng gian C1 ) v thiu mt gng cng trc xoay bc hai so vi sanidin
nh trn hnh 6.30.

Ni cch khc, cu trc ca n c i xng thp hn v khng cn v tr c bit cho
cation K
+
na. S phn b ca AlSi tr nn hon ton trt t trong microclin nhit thp.
Orthoclas l bin th ca KAlSi
3
O
8
m v trt t trong cch phn b AlSi n v tr trung
gian gia sanidin v microclin. Orthoclas, vi nhm khng gian C2/m, kt tinh nhit
trung bnh.
Khi nhit h thp, liu feldspat nhit cao c duy tr cu trc khng trt t hay s
chuyn i thnh cu trc nhit thp, trt t hn. Vn ny ph thuc nhiu vo tc
h gim nhit ca qu trnh. Hnh 6.31 gii thiu bng s ca cc cch gim nhit
cho feldspat. Microclin rt c trng cho su v pegmatit, orthoclas cho xm nhp thnh
to nhit trung bnh v sanidin cho phun tro, cho ni la nhit cao.
Cu trc chung ca dy plagioclas kh ging vi cu trc ca microclin. Albit l thnh
vin Na, i xng ba nghing vi nhm khng gian C1 . Albit nhit thp c trt t cao


267
trong cch phn b AlSi. Albit nhit cao, h mt nghing v AlSi phn b km trt t,
gi l albit mt nghing (monalbit). Anorthit l Ca-plagioclas nhit thp, cng h ba
nghing vi nhm khng gian C1 v trt t hon ho ca Al-Si trong cu trc. Nhit
tng cao lm cho cu trc anorthit c mng tm khi vi nhm khng gian I 1 .
Ti vng nhit trong khong 300 v 800C, s thay th ng hnh xy ra rt hn ch
trong feldspat KNaCa (xem hnh 5.3 v ch gii). c tnh ny cn r nt hn, khi p sut
tng cao. Bi vy, feldspat c th kho st trn hai h hai hp phn: albitK-feldspat v
albitanorthit.

Hnh 6.30
Cu trc tinh th feldspat

a) Vng bn t din kt ni thnh chui dng sng song song trc OX; b) S gn kt
cc chui dng sng, oxy khng th hin trn hnh
S thay th gia cc feldspat kim biu th bng vect KNa
1
. N cho thy min gin
on nh trn hnh 6.32. Nhng chuyn ho v cu trc ca chng, lm xut hin hng lot
bin th:
Feldspat kali: microclin nhit thp microclin nhit va sanidin nhit thp
sanidin nhit cao;
Feldspat natri: albit nhit thp albit nhit va albit nhit cao.
Dy feldspat kim (NaAlSi
3
O
8
KAlSi
3
O
8
) l dung dch cng lin tc ch nhit cao.
Th d, cc thnh phn ca dy sanidinalbit cao bn vng iu kin nhit cao, nhng
khi nhit h dung dch y tr thnh hai pha ring bit bn vng: albit thp v microclin.
Hnh 6.32 cho thy khong thnh phn rt hp ca hai pha ny. Nu chm ri h nhit ca
pha feldspat ng nht San
50
Al
50
vi ion K
+
v Na
+
phn b ngu nhin, th n s b phn r;
cc ion kali v natri s phn d, bi v khi nhit h s chnh lch v bn knh ion tr nn


268
khng thch hp so vi yu cu ca cu trc v kch thc tr nn cht ch. Ion Na
+
s
khuch tn to nn nhng min giu natri v K
+
s li khai lp thnh min giu kali. S
phn r ny sinh ra kin trc mc xen mang tn perthit; cc tm albit mnh nm dc {100}
trong pha ch K-feldspat. Hin tng mc xen him gp l albit cha cc tm K-feldspat.
nh ca min mc xen ph thuc vo p sut; khi P = 1kbar, n khong 670C; P =
5kbar, n khong 715C. Biu hai cu t ca feldspat ny bc l hai c im l min
mc xen rng ln ca feldspat v s thay i trng thi cu trc ca chng xy ra cng vi s
bin thin nhit . Hai c im c s dng xc nh nhit bin cht. V nguyn
tc, mi gi tr nhit v p sut ca mi trng ng vi thnh phn ca mt trong hai
feldspat giu K v giu Na.
Trong trng hp ny, thnh phn feldspat (nn) i khc do qu trnh phn r dung dch
cng. iu ny c th dn n kt qu sai khi nh gi nhit . Cho nn, c d liu xc
thc v thnh phn th ngoi feldspat phn nn, cn tnh n c tng tm mc xen.
Vi s h tr ca k thut vi thm (microsond) iu ny thc thi kt qu v feldspat
kim c s dng nh a nhit k hu hiu. Trng thi cu trc ca feldspat cng c khai
thc nhm mc tiu ny. Bi v, khi nhit tng th ni chung cu trc ca feldspat kali tr
nn km trt t hn. Trng thi cu trc c th xc nh bng phng php quang hc v bng
nhiu x tia X. y l cch tin li nhm nh gi nhit trong vng gneis thch anh
feldspat.
Al: albit
San: sanidin
Mi: microclin
hAb: albit nhit
cao
hSan: sanidin nhit
cao
hMi: microclin nhit
cao
mAb: albit nhit
va
mSan: sanidin nhit
va
mMi: microclin nhit
va
lAl: albit nhit
thp
lSan: sanidin nhit
thp
lMi: microclin nhit
thp
Hnh 6.32
Biu TX ca feldspat kim
Dy dung dch cng c vng gin on rng ln t khong di 700
o
C tr xung


269
Dung dch cng gia KAlSi
3
O
8
v CaAl
2
Si
2
O
8
rt hn ch. Mc du vy, cc thnh phn
ca dy plagioclas NaAlSi
3
O
8
v CaAl
2
Si
2
O
8
v thc cht l cc dung dch cng hon ton
iu kin nhit cao. Cng thc tng qut ca plagioclas vit thnh:
Na
1x
Ca
x
(Si
3x
Al
1+ x)
O
8
,
vi x bin thin t 0 n 1.

Quan h pha trong plagioclas l rt phc tp; bi v khng th
bin i albit thnh anorthit bng thay th lin tc CaAl cho NaSi, m khng thay i cu
trc. Vn ny lin quan ti trt t ca Al/Si trong v tr t din (tham kho 5.3). V
vy, feldspat c nhiu trng thi cu trc khc nhau v mt s min gin on (hnh 6.33, theo
Smith, 1974).
Ab: albit
monAb: albit mt nghing
hAb: albit nhit cao
mAb: albit nhit va
lAb: albit nhit thp
Pg: min gin on
Peristerit
Hg: min gin on
Huttenlocher
Vg: min gin on Voll
I-An: anorthit mng tm khi
P-An: anorthit mng
nguyn thy

Hnh 6.33
Biu TX ca feldspat plagioclas
S cc vng gin on cn gy tranh ci
Min gin on peristerit nm ti vng An
3
An
1015
, thng quan st c trong bin
cht mc thp (t tng phin lc sang amphibolit thp) vi albit v oligoclas cng tn ti.
Ni chung, albit gp trong tng phin lc v lin quan vi oligoclas bi tng amphibolit.
iu ny gip phn nh ranh gii ca hai tng trn.
Bng 6.18
S liu ho phn tch ca feldspat kali
1 2 3 4 5 * 6 *
SiO
2
65,76 64,66 63,68 64,46 67,27 66,97
TiO
2
0,08 0,01 0,04
Al
2
O
3
20,23 19,72 19,57 18,55 18,35 18,75
Fe
2
O
3
0,18 0,08 0,29 0,14 0,92 0,88
FeO 0,24
MgO 0,10 vt 0,05 0,00 0,00 0,00
BaO 0,63 0.34
CaO 1,19 0,34 0.40 0,17 0,15 0,36


270
Na
2
O 8,44 3,42 1,56 0,49 6,45 7,88
K
2
O 3,29 11,72 14,21 16,07 7,05 5,39
H
2
O
+
0,37 0,18 0,04 0,08 0,01
H
2
O

0,08 0,04 0,06 0,08 0,03
Tng 100,35 100,12 100,46 99,94 100,35 100,31




S ion tnh trn 32 ion oxy
Si 11,719 11,794 11,730 11,938 12,030 11,932
Al 4,249 4,240 4,249 4,050 3,868 3,938
Fe
3+
0,024 0,011 0,040 0,019 0,124 0,118
Ti 0,011 0,001 0,005
Z 16,00 16,04 16,02 16,01 16,02 15,99
Mg 0,027 0,014
Na 2,916 1,209 0,557 0,176 2,236 2,722
Ca 0,227 0,066 0,078 0,033 0,029 0,069
K 0,748 2,727 3,430 3,797 1,609 1,226
Ba 0,044 0,024
X 3,96 4,00 4,05 4,01 3,87 4,02
Or, % 20,0 68,1 83,1 94,8 41,5 30,5
Ab, % 73,6 30,2 13,7 4,4 57,7 67,8
An,% 6,4 1,7 3,2 0,8 0,8 1,7
1. Sodium-rich orthoclase cryptoperthite, ijolite-nepheline-syenite, Mogok, Burma
(Tilley, C. E., 1954, Amer. J. Sci., 252, 65-79).
2. Orthoclase microperthite (moonstone), Ceylon (Spencer, E., 1937, Min. Mag., 24, 453-
94).
3. Microclin microperthite, charnockite, St. Thomas Mt, Madras, India (Howie, R. A.,
1955, Trans. Roy. Soc. Edinburgh, 62, 725-63).
4. Low microclin, pegmatit in grennaite, Norra Ktt, Sweden (MacKenzie, W. S.,1954,
in. Mag.,30, 354-66).
5. Sanidine, rhiolite, Michell mesa, Texas, USA (Tuttle, O. F., 1952, Amer. J. Sci.,
Bowen vol., 553-67).
6. Anorthoclase, Grande Caldeira, Azores (Tuttle, O. F., 1952, Amer. J. Sci., Bowen vol.,
553-67).
Min gin on Voll rng ln nm gia andesin An
40
v anorthit An
90
. Nm ngay trn n
l hai min khc: Boggild (An
48--66
) v Huttenlocher (An
66--87
). Khi gim nhit , cc min


271
gin on ny l nguyn nhn ny sinh tng mng vi tinh mc xen kh ln xn; c th quan
st nh k thut hin vi in t.
6.11.2. c im ho hc
a) Feldspat kim ch yu l cc dung dch cng trong khong t KAlSi
3
O
8
n
NaAlSi
3
O
8
. Nhng thng thng chng cng cha mt lng nh CaAl
2
Si
2
O
8
trong dung
dch cng, thng t hn 5% trong vng gia Or
100
Ab
0
v Or
60
Ab
40
, nhng cc thnh vin
giu natri cha nhiu An hn. Cc ion khc c th c lng hn ch nh Ba, Ti, Fe
2+
, Fe
3+
,
Mg, Sr v Mn.
Bng 6.18 & 19 gii thiu s liu ho phn tch ca feldspat kim. Nh nhng tnh ton
k tip, cc bng ny lit k s lng ion cc loi ng vi 32 nguyn t oxy. Vi hm lng
ln hn 2% Ba, feldspat mi c coi nh feldspat giu bari, y Ba thay th cho K. Tng
t, Fe
3+
v Ti thay cho Al; Mg, Fe
2+
, Sr, Mn thay cho Ca.
Trong orthoclas v microclin thng c t Ti, nhng Fe
2
O
3
c th c mt lng ng
k: c l, i vi feldspat kim bnh thng Fe
2
O
3
d tha (khong 0,5%) tn ti dng tp
cht hay dng sn phm phn r khi nhit gim (st trong cc ht khong vt thng lm
cho vng ranh gii ht v mt ct khai bin mu). Feldspat aventurin l bin th cha bao th
hematit.
Bng 6.19
S liu ha phn tch ca sanidin ly trong lamproit Lai Chu [12]
Cu t Nm Hon Nm Hon Cc Pa Simang-khang Pn H Pn H
SiO
2
63,89 64,42 63,56 64,19 63,32 63,62
Al
2
O
3
18,93 18,17 19,53 18,73 18,99 20,05
FeO 0,32 0,35 0,03 0,42 0,32
MgO 0,08 0,10 0,03
CaO 0,12 0,29 0,86 0,07 0,30 0,96
Na
2
O 0,68 0,38 3,90 0,60 3,27 5,23
K
2
O 15,88 15,73 10,52 15,28 11,56 8,09
BaO 0,13 0,27
SrO 0,13 0,10
100,16 99,81 98,40 98,87 97,89 98,27

S ion tnh trn 32 oxy
(Do tc gi sch ny tnh thm)
Si 11,80 11,96 11,72 11,92 11,80 11,68
Al 4,12 3,96 4,24 4,08 4,16 4,32
Z 15,92 15,92 15,96 16,00 15,96 16,00
Fe 0,04 0,04 0,00 0,04 0,04
Mg 0,00 0,00 0,00
Na 0,24 0,12 1,36 0,20 1,16 1,84
Ca 0,00 0,04 0,16 0,00 0,16
K 3,76 3,72 2,48 3,60 2,76 1,88
Ba 0,00 0,00


272
Sr 0,00 0,00
X 4,00 3,88 4,00 3,80 3,92 3,88
San,% 94,00 95,87 62,00 94,73 70,40 48,45
Ab,% 6,00 3,09 34,00 5,20 29,59 47,42
An, % 0,00 1,03 4,00 0,00 4,12
Mg t c trong feldspat kim, nhng BaO i khi c th t hm lng 1% v hn na.
Mt lng nht nh Na
2
O cng vi CaO thng c trong microperthit hay perthit, bi v pha
plagioclas hu nh thng xuyn c mt mc khc nhau. Hm lng CaO thng di
1%, nhng trn 1% trong feldspat giu natri v c th t 3 4% trong anorthoclas. Sanidin
trong lamproit Ty Bc Vit Nam (bng 6.19) c nt c trng l giu natri v ngho st hn
so vi sanidin cc vng chn so snh (West Kimberley, Leucit Hills, Murcia Almeria).
Bng 6.20
S liu phn tch ho ca plagioclas
1 2 3 4 5 6 7
SiO
2
67,84 67,41 64,10 58,10 52,42 49,06 44,17
TiO
2
0,00 0,00 Vt 0,09 Vt
Al
2
O
3
19,65 20,50 22,66 26,44 29,70 32,14 34.95
Fe
2
O
3
0,03 0,07 0,14 0,04 0,36 0,27 0,56
FeO 0,02 0,17 0,15 0,13 0,08
MgO 0,04 0,10 0,25 0,03 0,08 0,20 0,00
CaO 0,00 0,81 3,26 7,84 12,65 15,38 18,63
Na
2
O 11,07 10,97 9,89 6,48 4,01 2,57 0,79
K
2
O 0,29 0,36 0,05 1,10 0,21 0,17 0,05
H
2
O
+
0,56 0,15 0,17 0,03 0,13 0,84
H
2
O

0,30 0,06 0,06 0,03 0,17
Tng 99,80 100,37 100,75 100,27 99,65 99,95 100,24

S ion tnh trn 32 ion oxy
Si 11,964 11,785 11,267 10,413 9,540 8,990 8,237
Al 4,085 4,225 4,695 5,586 6,373 6,942 7,683
Fe
3+
0,004 0,009 0,018 0,005 0,049 0,037 0,078
Z 16,05 16,02 15,98 16,00 15,97 15,97 16,00
Mg 0,011 0,026 0,065 0,008 0,022 0,055
Fe
2+
0,003 0,025 0,023 0,020 0,012
Na 3,785 3,718 3,370 2,252 1,436 0,913 0,285
Ca 0,152 0,614 1,505 2,467 3,020 3,723
K 0,066 0,080 0,011 0,252 0,049 0,040 0,012
X 3,87 3,98 4,08 4,04 4,01 4,03 4,03
Ab, % 98,0 93,5 82,5 56,0 35,7 22,7 7,1
An, % 0,3 4,5 17,2 37,7 63,1 76,3 92,6
Or, % 1,7 2,0 0,3 6,3 1,2 1,0 0,3


273
Albite, pegmatit, near Court House, Amelia Co., Virginia, USA (Kracek, F. C. &
Neuvonen, K. J., 1952, Amer. J. Sci., Bowen vol., 293-318).
Albite, with quartz and sphene in crevice in amphibolite, Val Devero, Itali (Azzini, F.,
1933, Atti Accad. Sci. Veneto-Trentino-Istriana, 23, 45-65).
Glassy oligoclase, pegmatit, Kioo Hill, Kenya (Game, P. M., 1949, Min. Mag., 28, 682-
7).
Andesine antiperthite, two-pyroxen granulite, charnockite series, Madras, India (Howie,
R. A., 1955, Trans. Roy. Soc. Edinburgh, 62, 725-68).
Gem-quality labradorite megacryst in cinders in basaltic pyroclastic deposits, Crater
Elegante, Sonora, Mexico, (Gutman, J. T. & Martin, R. F., 1976, Schweiz. Min. Petr. Mitt.,
56, 55-64. Includes SrO 0,105).
Bytownite, norite, Rustenburg platinium mines, Transvaal (Kracek, F. C. & Neuvonen,
K. J., 1952, Amer. J. Sci., Bowen vol., 293-318).
Anorthite, olivine norite, Grass Valley, California, USA (Kracek, F. C. & Neuvonen, K.
J., 1952, loc.cit.).
b) Plagioclas l alumosilicat Na v Ca, lot dung dch cng bin thin t NaAlSi
3
O
8
n
CaAl
2
Si
2
O
8
. Mc d vy, plagioclas thng cha mt lng thay i c th ti 5% orthoclas
KAlSi
3
O
8
, t anorthit n labrador v tng u v pha u Na-plagioclas. Nhiu ion
c th c mt mt lng hn ch, nh Ti, Fe
3+
, Fe
2+
, Mn, Mg, Ba v Sr.
Bng 6.20 gii thiu s liu ho phn tch ca plagioclas. Mi s liu u quy i thnh
s lng ion tnh trn n v cng thc, hay trn c s 32 nguyn t oxy. Trong , hu ht
lng st u l Fe
3+
, thay th ng hnh cho Al. Lng Fe
2+
rt nh, tn ti di dng tp
cht hay thay th Ca. Antiperthit thng pht trin trong oligoclas v andesin (mu 4), t ph
bin trong albit v him c trong labrador v Ca-plagioclas.
6.11.3. Song tinh ca feldspat
a) Hnh thi
V i xng feldspat ba nghing khng khc nhiu so vi feldspat mt nghing, cho
nn mt s dng quen c trng u ph bin i vi cc khong vt thuc c hai h.
Dng tinh th pht trin dc trc z. y l mt trong nhng dng quen thng gp
nht. N gm cc hnh n pht trin tt, nh {001} v {010}, cng vi hnh n
{110} thm vo, chng sinh ra mt i ni bt song song vi trc z.
i khi, tinh th ko di dc trc x v i vt tri s bao gm cc hnh n
{010} v {001}. V d, tinh th orthoclas v microclin c mt trong hai dng quen
in hnh k trn.
Dng tinh th pht trin ng thi dc hng x v z. l tinh th hnh tm vi
cc mt pht trin nht ca hnh n {010}. Sanidin thng c dng quen ny.
Dng tinh th pht trin dc trc y. N c i vt tri song song hng ny v
i khi y hnh thi ca albit. Mc du n cng kt tinh dng tm kiu sanidin.


274
Dng quen adularia. Khong vt adularia c b ngoi ca tinh th h trc thoi, v
{001} v {101 } to nhng gc gn bng nhau vi trc z.
Ngoi ra, feldspat giu natri nhit cao anorthoclas thng c tinh th hnh mt thoi.
Ct khai hon ton ca nhm khong vt ny l {001} v {010} thng lm vi nhau gc
vung trong bin th mt nghing; nhng tinh th ba nghing th gc ny khng vung.
b) Hin tng song tinh
Song tinh l mt trong cc hin tng mc xen theo quy lut tinh th hc, y l mc xen
i xng ca hai (hay nhiu) tinh th thuc cng mt cht. Hai hay nhiu c th ca tp hp
song tinh lin quan bng yu t i xng thng khng c trong mi c th ring bit. Yu t
i xng mi (yu t song tinh) c tc dng a c th ny ti trng vi c th kia. Cn phi
phn bit song tinh vi cc tp hp ngu nhin, cn s dng cc phng tin nghin cu hnh
thi (bng gic k phn x) v cu trc tinh th (bng nhiu x tia X). Yu t song tinh bao
gm ba thao tc i xng: (1) phn chiu qua mt gng, gi l mt song tinh; (2) xoay 180
quanh mt hng tinh th hc chung cho c hai c th, gi l trc song tinh; (3) nghch o
qua mt im gi l tm song tinh.
Lut song tinh quy nh yu t no trong ba thao tc l c trng cho mt song tinh v
trc hay mt song tinh nh hng ra sao. Hng ca trc song tinh biu th bng k hiu trc
ca i, th d [001]. Mt song tinh k hiu bng ch s Miller, chng hn (010). Hai c th
gn kt vi nhau qua mt b mt chung, gi l mt ghp song tinh. Mt ny thng l mt
song tinh, nhng iu ny khng phi l bt bin. Nu lut song tinh c th xc nh ch bng
mt song tinh, mt ny lun song song vi mt mt tinh th gi nh, nhng khng bao gi
song song vi mt mt i xng. Trc song tinh l trc i hay l php tuyn ca mt mt
(mng) tinh th; nhng khng th l trc i xng bc chn.
Song tinh tip xc c mt ghp song tinh xc nh v n c mt song tinh; v d (111 )
trong spinel. Mt (111 ) ch l mt trong 4 hng c th c v tng ng v tinh th hc
trong hnh n bt din {111} ca h lp phng. Song tinh xuyn ct do cc c th xuyn v
lng vo nhau. N c mt ghp song tinh khng u n, nh trong fluor, pyrit hay orthoclas.
Lut song tinh y thng xc nh bng trc song tinh, chng hn l [001] trong orthoclas.
Song tinh a hp l do ba hay nhiu phn lin kt i xng v theo cng mt lut song
tinh. Nu tt c cc mt ghp k tip u song song th kt qu l song tinh lin phin. Th d,
song tinh ca albit, calcit. Trong trng hp cc mt ghp ny khng song song, th y l
song tinh dng vng, nh trong chrysoberyl, rutil hay aragonit. Khi song tinh lin phin do
nhng phin mng to nn, mt tinh th hay mt ct khai s c kha sc; l do mt ny
giao ct mt ghp v do cc c th lin k ngc nhau (i xng nhau di tc dng ca yu
t song tinh) v nh hng.
Tp hp song tinh thng c i xng cao hn so vi i xng ca tng c th; bi v
mt hay trc song tinh l nhng yu t b thm cho n.
c) Lut song tinh
Song tinh trong khong vt nhm feldspat hnh thnh theo ba cch khc nhau:
Song tinh xy n nh bin c trong khi tinh th pht trin.


275
Song tinh xy ra do bin dng
trt.
Song tinh din ra trong phn ng
chuyn pha sang i xng thp
hn (xem thm 5.1.3).
Lin kt song tinh l hin tng rt ph
bin trong feldspat v nhng lut ph bin
nht (bng 6.21) chia lm ba nhm: trc
giao, song song v phc hp. Trong lut
trc giao trc song tinh vung gc vi mt
mt gi nh ca tinh th v mt ny li song
song vi mt (mt ghp) phn cch hai c
th. Trong trng hp tinh th i xng tm,
trc song tinh ny tng ng vi php
phn chiu qua mt ghp song tinh. Lut
song song quy nh ly mt cnh gi nh
(tc l trc ca i) lm trc song tinh, mt ghp song tinh song song vi trc ny v lut
khng c mt gi nh xc nh.
Bng 6.2
Cc lut song tinh ca feldspat
Tn lut
Trc song
tinh
Mt ghp song tinh Nhn xt
Trc giao
Albit (010) (010) a hp,ch c h ba nghing
Manebach (001) (001) n gin
Baveno (phi) (021) (021) n gin,him c plagioclase
Baveno (tri)
( 021) ( 021)
n gin,him c plagioclas
Lng tr (phi) (110) (110)
Lng tr (tri)
(1 0)
(110 )

Song song
Carlsba [001] (trc z) (hk0), thng (010) n gin
Periclin [010] (trc y) (h0l) a hp,ch c h ba nghing
Ala [100] (trc x) a hp
Phc hp
Albit-Carlsbad z (010) a hp
Albit-Ala x (010) -nt-
Manebach-periclin y (001) -nt-
Manebach-Ala x (001) -nt-
X-Carlsbad z (100) -nt-
X-periclin y (100) -nt-
Gi d, c th B ghp song tinh vi c th A bng mt trong nhng lut trc giao, c th
C vi c th B bng lut song song vi cng mt mt ghp song tinh nh ca lut trc giao


276
(hnh 6.34). Hai c th C v A s lin quan vi nhau bng mt trong nhng lut phc hp.
Trc song tinh ca lut phc hp ny nm trong mt ghp song tinh v trc giao vi mt cnh
gi nh, tc l vung gc vi trc song tinh ca lut song song. C th trung gian B lin quan
vi A v C bng cc lut n, nhng c th n khng c mt.
Cc lut Carlsbad, Baveno v Manebach tn ti trong c hai loi feldspat ba nghing v
mt nghing, ch yu vi song tinh ghp i, i khi vi ghp ba, bn hay su. Cc lut albit v
periclin rt thng gp trong feldspat kim ba nghing, d lut albit ph bin hn. Cu trc ca
feldspat ba nghing khng sai khc nhiu so vi i xng mt nghing, mt (010) hay trc y l
mt song tinh hay trc song tinh ca chng.
Trong song tinh albit [lut trc giao; trc vung gc (010); mt song tinh (010)], ti ch
ghp i cc c th song tinh, (010) thc s l mt gng lin kt hai cu trc ba nghing vi
nhau. Trong song tinh periclin [lut song song; trc // y; mt ghp (h0l)], ti ch ghp ni, y
thc s l trc bc hai lin kt hai pha ca cu trc ba nghing. Feldspat mt nghing khng
th c song tinh albit hay periclin, bi v i vi chng trc song tinh [vung gc (010) hay y]
trng vi trc bc hai c sn trong cu trc tng c th.
6.12. THCH ANH, TRIDYMIT V CRISTOBALIT (SiO2)
-Thch anh
Ba phng (+)
-Tridymit
Trc thoi (+)
-Cristobalit
Bn phng ()
Np = 1,544 Np = 1,469 1,479 Np = 1,487
Ng = 1,553 Nm = 1,470 1,480 Ng = 1,484
Ng = 1,473 1,483
Ng Np = 0,009 Ng Np = 0,002 0,004 Ng Np = 0,003
2V 40 90
nh hng Np = y; M.T.Q. (100)
T trng 2,65 2,26 2,33
Song tinh (1) Trc song tinh z Mt song tinh {110} Kiu spinel {111}

(2) Mt song tinh {1122 }


(3) Mt song tinh {1120 }


-Thch anh -Tridymit -Cristobalit
- - - - - -
Ba phng Su phng Trc thoi Su phng Bn phng Lp phng
c s ()
A 4,913 5,01 5,04 5,03 4,97 7,13
B 8,74
C 5,404 5,47 8,24 8,22 6,92
Z 3 3 8 4 4 8
N.K.G. P3
1
21

P6
2
22 hay C222
1
P6
3
/mmc P4
1
2
1
2 hay Fd3m
P6
4
22 P4
3
2
1
2


277
Thch anh l mt trong nhng khong vt phong ph nht v l thnh phn chnh trong
trong nhiu magma, trm tch v bin cht. N cng l khong vt ph v th sinh trong
mch v trong m khong bin cht trao i.
Cc bin th chnh ca silica tn ti di dng bn vng nh sau:
Thch anh : bn vng nhit kh quyn cho n 573C.
Thch anh: bn vng t 573C n 870C, v gi bn t trn 870C.
Tridymit : c th tn ti nhit kh quyn cho n 117C, nhng khng phi l dng
bn vng trong iu kin y.
Tridymit : c th tn ti trn 117C v l dng bn vng t 870C n 1470C. Trn
nhit ny c th tn ti dng gi bn. Nng chy 1670C.
Cristobalit: c th tn ti nhit kh quyn v n tn 200 275C, nhng khng
phi l dng bn vng.
Cristobalit: c th tn ti trn 200 275C v bn vng t 1470 cho n im si
1713C.
Coesit: pha p sut cao sinh ra 450 800C v p sut 38kbar, gp ti ch b va p
mnh vi thin thch v trong xenolit ca kimberlit.
Stishovit: dng t trng cao (4,3) ca silica, sinh ra 130kbar v trn 1200C.
Silica thu tinh: c th tn ti nhit kh quyn v cho ti 1000C.
Silica n tinh (chalcedon): bin th rn chc cha tinh th thch anh rt nh.
6.12.1. Cu trc tinh th
Ba bin th chnh ca silica (thch anh, tridymit, cristobalit) c cu trc tinh th hon
ton khc nhau, mi dng c mt trng bn vng xc nh di iu kin cn bng. Tuy
nhin, s chuyn ho t dng ny sang dng khc xy ra hi chm chp; cho nn khong vt
nhit cao, nh tridymit v cristobalit, c th tn ti gi bn di nhit bin i a
hnh.
Mi dng k trn li c hai bin th nhit thp v nhit cao, t tn ln lt l v
. Trong mi trng hp, cu trc dng t nhng t din SiO
4
, mi oxy u l nh chung
ca mt i hnh bn mt ny (oxy phi tr vi 2 silic). Gc ho tr SiOSi bin i trong
khong t 160 n 180 tu cu trc ca tng bin th, nu s bin i a hnh khng km
theo s gin on ca lin kt SiO.
Thch anh
Thch anh c i xng su phng v thuc v lp tinh th 622 phitri. Cu trc l
tng ca n trn Hnh 5.5,b l hnh chiu trn mt y (0001). Cc t din tp hp to nn
vng xoy ba phng v su phng, to z ca nguyn t silic th hin bng phn s ca
thng s c (0; 1/3; 2/3). Vng xoy t din phi hay tri u c mt trong cu trc ca mi
dng phitri ca thch anh.
Thch anh c i xng ba phng v thuc v dng i xng phitri 32. Cu trc
ca n gn ging ca thch anh , nhng t din ca n km u n v xoay vn cht t so


278
vi v tr l tng (hnh 5.5,c). S bin i - xy ra vi s chuyn di khng ng k ca
nguyn t, khng c s ph b lin kt ho l, nguyn t khng hon v.
Khc vi tridymit v cristobalit, thch anh c s sp t ca t din rt cht v s phn
b ca nguyn t oxy khng tun theo lut xp cu no. Thch anh c thng s mng n
nh, d mu khong vt ly u v th o c l ai; cho nn tinh th ny tng dng
lm cht chun trong phng php nhiu x Roentgen. Tuy vy, phng php o lng chnh
xc gip tm ra nhng sai khc c ngha, c l lin quan ti s trao i ion.
Tridymit
Tridymit thuc h su phng v cu trc l s lin kt ca cc lp song song vi
(0001). Lp l do cc t din ni nhau vi oxy lm cu, to nn mng li gm cc vng lc
gic rng m (hnh 5.5,a). y tam gic ca mi t din u nm trn mt (0001), nhng nh
ca chng th thay nhau hng v hai chiu i, +z hay z. Cc lp t din song song k nhau
th chung nhau oxy nh v i qua cc nh chung ny l mt i xng gng. Trong cu trc
l tng, thng s c ln gp bn ln chiu cao ca t din, cn thng s a ln gp i cnh t
din, vy t s c/a = 1,633.
Tridymit thuc h trc thoi, nhng cu trc ca n ch c nhng thay i nh so vi
bin th nhit cao. mng nh nht ca n l trc thoi tm y v c th coi l thuc
mng gi su phng. Bi v ln ca a v b gn bng ln ca hai ng cho y thoi
ca su phng.
Cristobalit
Cristobalit l bin th lp phng vi cu trc c nhiu chi tit ging nh ca tridymit
.
Cu trc l s lin kt ca cc lp song song vi (0001). Lp l do cc t din ni nhau
vi oxy lm cu, to nn mng li gm cc vng lc gic rng m. T din cc lp k
nhau cng gn vi nhau bng lin kt SiOSi vung gc vi (0001). Nhng y t din i
xng nhau khng qua mt gng nh trong tridymit, m qua tm nghch o (hy tng
tng : mt trong hai y ny xoay 60 quanh trc ca lin kt SiOSi). Li ni v cc
lp oxy, tuy cc qu cu oxy ny khng xp cht, nhng s phn b ca chng trong tridymit
v cristobalit cng tun theo quy lut ca hai lut xp cu su phng v lp phng. V i
snh hai cu trc th chng khng khc cp bin th ca ZnS l vurtzit v sphalerit. Cu trc l
tng ca cristobalit thc s l ca h lp phng vi tm n v cng thc trong mng.
T , cu trc ny c th coi nh ging cu trc kim cng (hnh 4.14): nguyn t silic phn
b ti v tr ca carbon, oxy ti im gia khong SiSi ngn nht.
Nhng bin ng trong kch thc mng c th do cc mu t nhin c cha nhiu tp
cht. Bi v trong cu trc ca chng, tridymit v cristobalit u rng m cho cc ion l thm
nhp. Cristobalit thuc h bn phng, nhng v cu trc n rt gn vi cristobalit .
Cu trc rng m ca tridymit v cristobalit c th duy tr c nhit cao do dao
ng nhit. S d chng c th tn ti gi bn v duy tr cu trc nhit thp, c th l
nh nh hng ca cc cation l. in tch dng do cc cation ny mang n s ko theo
mt c ch thay th vi vai trung ho in tch; l Al
3+
thay cho Si
4+
. S thay th cao nht,
khi Al vo thay mt na lng Si, s ko theo lng cation Na
+
tng ng thm nhp vo
tridymit, th cu trc ca nephelin NaAlSiO
2
ra i vi 50% trng cha Na. Tng t, ion


279
Na lp y mt na trng ca cristobalit s lm xut hin pha nhit cao l carnegieit. i
vi NaAlSiO
2
y khng th l cu trc thch anh, bi v thch anh khng h c ch trng
cho Na thm nhp.
Trong khi s bin i gia cc bin th v xy ra trong s x dch hn ch ca
nguyn t, dn n s thay i gi tr ca gc ha tr SiOSi trong thch anh, th s chuyn
ho gia thch anh, tridymit v cristobalit km theo s ph b v s ti to. Mc du vy,
trong trng hp chuyn pha gia tridymit v cristobalit, c hai bin th u c lp t din
[song song ln lt vi (0001) v vi (111)] lm c s cho cu trc, th qu trnh bin i c
l ch dng li s thay i gi tr ca gc ha tr OSiO; tc l chuyn ng xoay quanh
trc [0001]/[001] ca b ba nguyn t oxy trn y t din.
6.12.2. c im ho hc
1) Thch anh. Thnh phn thch anh thng rt gn 100% SiO
2
. Kt qu phn tch ho
hc cho thy mt lng nh cc oxit khc v mt s cht; chng c mt di dng bao th
khong vt khc hay cht lng lp y l hng trong lng thch anh (bng 6.22). S thay th
ca Al cho Si xy ra c km theo s xut hin ca ion kim nh Li
+
hay Na
+
. Lng nhm vt
tm thy trong thch anh l hnh thnh trong mi trng bo ho nhm. Vic ny c th dng
lm nhit k a cht, bi v cha nhm thay i cng vi nhit kt tinh, tng vi tc
1 phn triu/3,6C. Trong bin cht trao i, thng s mng tng khi nhit bin cht
gim; l do hm lng tp cht tng. Hai khuynh hng i nghch ny tt dn n s ng
vc i vi hiu lc ca a nhit k nhm.
Bng 6.22
S liu phn tch ho ca thch anh
Li
2
O Na
2
O K
2
O Al
2
O
3
Fe
2
O
3
MnO
2
TiO
2

Trong 0,0005 0,0004 0,0002 0,0008 0,0000 0,00002 0,0001
m khi 0,0004 0,0000 0,0000 0,0008 0,0005 0,00002 0,0002
Hng 0,0038 0,0011 0,0001 0,0001 0,0003 0,00005 0,0015
Amethist 0,0001 0,0216 0,00000 0,0004
2) Tridymit v cristobalit. Trong t nhin c thnh phn khc so vi cng thc SiO
2
v
cha lng ng k nhm v kim. iu ny lin quan ti cu trc tng i rng, c ch cho
cc cation kim c ln. in tch thp ca chng trung ho bi s thay th Al
3+
cho Si
4+
trong
phi tr t din.
6.13. MT S KHONG VT TO KHC
6.13.1. Calcit
H ba phng ()
Np, Ng 1,486 (1,550); 1,658 (1,740)
Ng Np: 0,172 (0,190)
Ct khai
{ }
1011 hon ton
Song tinh
{ }
1012 rt thng gp
c s su phng; a = 4,990; c = 17,061
mt thoi : a = 12,84; = 101,92; Z=8
d
hkl
() 3,04(10); 2,29(2); 2,10(2); 1,913(2); 1,875 (2)


280
Anion phc (CO
3
)
2
l n v cu trc bn vng, chng gn kt gin tip vi nhau thng
cc cation loi khc. N cng l n v cu trc c s ca mi carbonat v l cn nguyn ca
cc c im ring ca chng. Mc du lin kt C O l tng i mnh, nhng khng th so
vi lin kt cng ho tr trong CO
2
. Khi c mt ion H
+
, nhm chc carbonat tr nn khng
bn v d dng phn hu cho CO
2
v nc:
2H
+
+ CO
3
2

= H
2
O + CO
2
.
y cng l phn ng dng acid nhn bit carbonat.
Carbonat khan c ba khong vt l calcit, aragonit v dolomit. Ngoi ra, carbonat ng
thuc h mt nghing l azurit v malachit vi OH

trong thnh phn. Cng nhm v ng
cu trc vi calcit (xem hnh 4.18) c 4 c th phn bit bng thnh phn cation: magnesit
(Mg), siderit (Fe), rhodochrosit (Mn) v smithsonit (Zn).
c im cu trc
Calcit c cu trc dn xut t cu trc halit (xem cc hnh 4.18, 5.11), nhng khng thuc
h lp phng t nht l do dng tam gic phng ca n v cu trc (CO
3
)
2--
. Nhm ny nm
trong cc mt phng vung gc vi trc chnh c (= L
3
). Xen k gia cc mt phng ny l mt
cha cation Ca
2+
phi tr 6 vi O
2
. Mi oxy phi tr vi 2 calci v 1 carbon. Nh vy anion
oxy dng ht ho tr tnh in d, sau khi tham gia to thnh nhm chc.
Carbonat calci c hai loi cu trc vi s phi tr khc nhau ca calci l 6 trong calcit (ba
phng) v 9 trong aragonit (trc thoi). T l bn knh Ca : O (= 0,714) trong carbonat ph
hp vi phi tr 6 (0,732) v i khi 8. mng vi a = 6,42 v = 101,92 cha 4 n v
cng thc khng phi l mt thoi Bravais; dc cnh , cc nhm CO
3
k tip nhau c hng
ngc nhau. Vy, mng ch thc phi l a (2 6,42) v = 101,92 cha 8 n v cng
thc, vn ph hp vi ct khai ph bin ca calcit
{ }
1011 .
c im ho hc
Mc d nhiu cation ho tr hai c th phn no thay th calci trong calcit, nhng thnh
phn ho hc ca n kh ph hp vi cng thc l thuyt. Calcit cha ti 20% MgCO
3
. Nu
Mg c nh d dng vo ch ca Ca th Ca c ln kh hp vi v tr Mg trong cu trc
magnesit. y l mt trong nhng dung dch cng quan trng trong t nhin. Calcit cha ti
42% mol MnCO
3
v thc nghim cho thy con s ny c th t 50%. D Fe
2+
thay th cho
Ca, nhng dolomit vn cha st nhiu hn so vi calcit. Lng Fe c th t 5 10% mol
trong cc mu t nhin. Ion Sr vo th ch ca Ca mt lng nh, nhng cation c ln ny
d dng vo ch Ca phi tr 8 ca aragonit. Trong khi ti kt tinh, aragonit ch chuyn thnh
calcit nu loi c Sr trong cu trc.
Nhm chc kh bn vng (CO
3
)
2
c nng lc ho hp vi hng lot cation ho tr hai,
cho cc hp cht t nhin vi bn vng mc khc nhau. Ni chung, bn knh ion kim
loi l yu t quan trng xc nh loi cu trc. Carbonat ca kim loi vi bn knh ln hn
1 thng c cu trc loi aragonit. Bi v Ca c bn knh gn gi tr ti hn y, CaCO
3
c
hai bin th a hnh vi c hai loi cu trc.
6.13.2. Aragonit
H trc thoi ()


281
Np: 1,5301,531 Nm: 1,6801,681; Ng : 1,6851,686
2V: 18 18,5 Ng Np: 0,1550,156
nh hng: Np=z, Nm=x, Ng=y; M.T.Q.: (100)
Song tinh: Ph bin, M.S.T.{110}; Gi su phng
c s: a = 4,96; b = 7,97; c = 5,74; Z = 4, N.K.G. Pmcn
d
hkl
(): 3,04(9); 2,71(6); 2,36(7); 1,975(10); 1,880(8)
c im cu trc
Khi nhm CO
3
ho hp vi cation c bn knh ln hn 1, kch thc ny tr nn khng
ph hp vi s phi tr 6 na, cu trc phi chuyn t ba phng sang trc thoi. l loi
cu trc aragonit vi nhm khng gian Pmcn. Mc du cation calci hi ln so vi s phi tr 6
ca calcit, n li hi nh i vi phi tr 9 trong aragonit. Carbonat ca cc cation ho tr hai
c ln nh Ba, Sr v Pb d c cu trc ca aragonit, khc khong vt ny, chng li bn vng
iu kin kh quyn, ging nh calcit.
Cu trc aragonit c cc cation Ca
2+
nm trong mt i xng nh trt n, song song vi
{001} v phn b theo lut xp cu su phng ABABAB vi khong A B co rt
i cht so vi A A hay B B. iu ny tng phn vi lut xp cu ca Ca trong calcit v
ct ngha i xng gi su phng ca aragonit. Trong calcit, nhm CO
3
nm thnh lp ti
khong gia cc lp Ca. Cc nhm CO
3
vung gc vi trc c ging calcit. Nhng y
chng nm trong tng cp mt phng xen gia cc lp cation calci. Cc tam gic CO
3
u cho
cc mt i xng i qua: mt gng m v mt trt c. Giao tuyn ca chng l trc xon bc
hai 2
1
, n xuyn tm nguyn t carbon ca CO
3
. Dc trc 2
1
// z ny cc tam gic CO
3
thay
nhau hng nh v pha OY v +OY.
Mc du ion Ca xp theo h su phng, chnh s phn b ca nhm CO
3
lm cho i
xng ca aragonit gim xung trc thoi. Tuy vy, i xng gi su phng ca aragonit vn
bc l s o gc nh din ca mt lng tr {110} v gia chng vi {010} ca tinh th v
song tinh phc hp dng vng.
c im ho hc
Phn ln aragonit l khong vt tng i tinh khit; thnh phn ph hp vi cng thc l
tng. Nguyn t stronti c mt vi lng nh nhng ng k trong aragonit. V gi tr bn
knh nguyn t, n kh gn vi Ca. Ch cng vo thay th cho calci trong aragonit cho Pb-
aragonit mang tn tarnowitzit.
Dng dung dch carbonat trn vi dung dch cha ion calci v c cch kim sot nhit
ngi ta tng hp c aragonit. Ni chung, aragonit kt tinh thun li nhit 50
80C v khi c thm mui ca Sr, Pb, hay Ba, hay CaSO
4
trong dung dch. Biu P T xc
lp bng thc nghim cho thy nhit trong phng v p sut 1 at aragonit tn ti trng
thi gi bn.
Aragonit thng bin i thnh calcit. Trong thn san h c th gp c hai bin th
carbonat; trong phn aragonit hm lng Sr thng 2 ln ln hn trong phn calcit. iu
cho thy nguyn t ny cn tr s bin i ca aragonit thnh calcit iu kin t nhin. qu
trnh chuyn pha ny ch xy ra khi loi b phn ln lng Sr trong h.
Tnh cht quang hc ca aragonit thng bin thin trong phm vi nh, tr cc bin th
giu Sr v Pb. Khi Sr thay th Ca th aragonit c ch s khc x v gc 2V h gim, s c mt
ca Pb li gy hiu ng tri ngc. Vi mt song tinh {110} v mt ghp song tinh cng l


282
{110}, ba c th aragonit mc xen cho song tinh dng lng tr gi su phng vi y {001}
chung. Trong lt mng vung gc vi [001] c th thy cc c th song tinh phn b theo
mi, vi mt trc quang ca cc c th ct nhau di gc gn 60.
6.13.3. Barit
H trc thoi (+) Ba SO
4

Np :1,636 1,637; Nm : 1,637 1,639; Ng : 1,647 1,649
Ng Np : 0,012 2V = 37
nh hng : Np = z; Nm = y; Ng = x
a sc : Hp ph: Ng > Nm > Np
c s : a = 8,88; b = 5,45; c = 7,15; Z = 4; N.K.G. Pnma
d
hkl
, 3,90(6); 3,44(10); 3,32(7); 3,10(10); 2,12(8)
Cu trc tinh th
Barit c cu trc bao gm cc cation ho tr hai c ln phi tr vi anion phc SO
4
. Nhm
t din tng i u n ny c mt gng (vi to y = 0 v 1/2) i qua ion lu hunh v
hai ion oxy; hai ion oxy kia nm hai pha ca mt gng v cch u n. Ion Ba cng nm
trn mt gng v phi tr vi 12 oxy. Khong vt khc c cu trc tng t nh ca barit l:
Thng s mng a () b () c ()
Barit BaSO
4
8,88 5,45 7,15
Anglesit PbSO
4
8,48 5,40 6,69
Celestin SrSO
4
8,36 5,35 6,87
c im ho hc
Barit to dung dch cng lin tc cng vi celestin, mc du cc mu khong vt ny
thng c thnh phn ho hc rt gn vi cng thc BaSO
4
. Nhng pha cha Ba nhiu nht
trong lot ng hnh ny mang tn strontiobarit; pha u cui Sr l baritoselestin. Nhng ion
khc nh Pb, Ca c th thay Ba vi mt lng khng ng k. Trong t nhin, ch khong 6%
CaSO
4
c th thm nhp vo dung dch cng ca cu trc barit. ho tan ca barit trong
nc rt nh, tng khi un nng v vi s c mt ca cc chlorur. Khi t nh, mt vi ht
barit phn hu v cho H
2
S bay hi.
Mt trong nhng du hiu phn bit barit ngun gc bin hay lc a l hm lng Th.
Chng hn, barit trong trm tch bin su cha khong 34 ppm, trong khi cc mu t lc a
ch c khong 0,1 ppm Th.
Khi bin i barit cho witherit BaCl
2,
nn n thng b carbonat, sulfat v sulfur thay th
gi hnh. ho tan rt thp ca n cho thy nu c s kt ta barit trong t nhin, th nguyn
nhn d bo l do trong dung dch cha Ba xy ra oxy ho, khin sulfur bin thnh sulfat.
Barit thng gp di dng tinh th hon thin, cng gp di dng tp hp ht ng
thc, si, l v.v Cc tinh m barit dng tm cha ct, li c mu hng, thng gi hoa
hng sa mc. Barit thng khng mu hoc trng khi tinh khit. Tp cht oxit, hydroxit st
v.v... lm cho n c mu vng v nu. Do c nhng nt tng ng vi Ba nn Ra c mt
trong barit, gy tc ng phng x, lm cho khong vt c thm mu lam. Ch s khc x v
lng chit sut gim nh do Sr thay th Ba v tng ln do Pb thay th. Gc trc quang tng
cng do nhng thay th ny v tng cc i khi SrSO
4
t

hm lng 50%.


283
6.13.4. Apatit
H su phng () Ca
5
(PO
4
)
3
(OH,F,Cl)
Np = 1,624 1,666 Ng = 1,629 1,667 Ng Np = 0,001 0,007
Mu a sc: yu v trung bnh hp ph : Np > Ng
mng c s: a = 9,32 9,64; c = 6,78 6,90
Z = 2; N.K.G. C6
3
/ m
d
hkl
, : 2,80(10); 2,77(4); 2,70(6); 1.84(6); 1,745(3)
Thnh vin ca nhm apatit l nhng khong vt ph ph bin trong hu ht cc
magma v cng gp trong cc trm tch v bin cht. Chng l khong vt cha phosphor
di do nht. Ph bin hn c l cc thnh vin ca dy ng hnh sau (bng 6.23).
Bng 6.23. Thnh vin ca nhm apatit


284

Khong vt nhm apatit a, c, c/a
Fluorapatit Ca
5
(PO
4
)F 9,36 6,88 0,735
Chlorapatit Ca
5
(PO
4
)
3
Cl 9,61 6,78 0,703
Hydroxilapatit Ca
5
(PO
4
)
3
OH 9,42 6,88 0,730
Carbonatapatit Ca
5
(PO
4
,CO
3
OH)
3
(F,OH) 9,32 6,90 0,740
Trong , fluorapatit ph bin nht, i khi n cng gi l apatit.
c im cu trc tinh th
Trong cu trc apatit c anion phc (PO
4
)
3
hnh t din vi P
5+
ln hn cht t so vi S
6+
.
Tt c cc phosphat u ly nhm anion phc ny lm n v kin trc c s. Nhng t din
tng t nh (AsO
4
)
3
v (VO
4
)
3
gp trong arsenat v vanadat. Cc cation ho tr 5 l
phosphor, arsen v vanadi u c th thay th cho nhau trong nhng anion phc ny. Calci
phi tr vi oxy ca nhm PO
4
hai v tr khc nhau; trong phi tr 9 v phi tr 8. Chng nm
trn cc trc bc ba v lin kt vi cc t din PO
4
, to nn chui phc tp chy dc trc c.
Gia cc chui ny l ng knh ln cha anion fluor (hay chlor, hay OH) nm trong tm
tam gic ca 3 calci khc. Cc anion ho tr mt ny xp dc trc bc ba khc loi. Kch
thc khc nhau ca cc anion ho tr mt dn n vic thay i thng s mng trong cc
pha apatit (bng 4.25). Trong carbonatapatit cn c s trao i gia cc anion (PO
4
)
3
v
(CO
3
OH)
3
.
c im ho hc
Apatit thuc hng khong vt vi thnh phn ho hc kh gn vi cng thc
Ca
5
(PO
4
)
3
(OH,F,Cl). Mc du trong c s thay th ln nhau ca anion ho tr mt, ca
anion phc hp nh ni trn. Ngoi ra, mt t (SiO
4
) v (SO
4)
cng c th c mt do c ch
trao i y. C th c min gin on gia pha u l OHF-apatit vi 10% mol Cl-apatit v
pha cui chlorapatit tng i tinh khit. Ca c th b Mn thay th phn no v mt t l
Mn/Ca = 1 : 8 khng phi khng thng gp. Sr v t him, ch yu l Ce, cng c th thay
th cho Ca mt phm vi ng k v fluorapatit c bit n vi hn 11% mol SrO. S liu
phn tch ho ca mt s apatit cho thy mt lng ti 5 hay 6 phn trm mol trong
francolit l khong vt apatit cha c hai th: CO
2
v F ti hn 1% mol. ahlit l tn ca mt
apatit khc, ngoi cht t fluor, n cn cha nhiu CO
2
.Tuy rng vai tr ca dioxit carbon vn
l vn cha ng ng trong cu trc apatit, nhng s thay th (CO
3
2
+ F

) cho (PO
4
)
3
l s
thay th thng xuyn. CO
2
c mt trong apatit khng phi di dng tp cht calcit hay
aragonit, m nh mt b phn ca cu trc apatit.
V tnh cht vt l, apatit quang m thng l tinh th mt trc quang, tuy vy cng c
nhng bin th hai trc vi gc trc quang t ti 20. Francolit l apatit cha carbonat vi
tnh cht quang hc d thng. Ni chung, chlorapatit c ch s khc x cao nht, h xung
khi OH vo thay th v gim na nu ion vo l F. Khi C thay tng phn P thng lm cho
chit sut gim theo. S c mt ca Mn lm cho c chit sut v t trng cng tng ln. Lng
chit sut cng bin ng cng vi s trao i gia OH, F v Cl; thp nht l ca chlorapatit
(0,001), trung bnh cho fluorapatit (khong 0,004) v cao nht l hydroxilapatit (0,007).
6.13.5. Corindon -Al2O3


285

Ba phng ()
Np,Ng, NgNp : 1,760 1,764; 1,768 1,772; 0,008 0,009
mng c s: a
sp
= 4,76; c
sp
= 12,98. a
bp
= 5,130; = 5517
Z
sp
= 6; Z
bp
= 2; NKG R 3 c
d
hkl
() : 2,54(6); 2,08(9); 1,738(5); 1,599(10); 1,374(7)
Cu trc tinh th
Nguyn t oxy xp gn vi lut xp cu su phng. Nguyn t nhm nm ti 2/3 s
khoang tm mt, 1/3 bt din trng nm xen gia cc i bt din AlO
6
. Dc theo cc hng
ta OX, OY v OU chng ghp i qua cnh chung, dc OZ l cc bt din AlO
6
ghp i
qua mt chung. Kch thc mng c s ca corindon nhn to thng tng tuyn tnh cng
vi cha chrom. S c mt ca 1/3 khoang bt din trng vng ion Al
3+
c nguyn nhn
ha tr tnh in (xem quy tc Pauling, 4.2.2) hay nng lng ca mi lin kt Al
3+
O.
V ion nhm Al
3+
c su ion oxy vy quanh, ha tr tnh in ca mi lin kt bng (3:6)
1/2. Mi oxy O
2
chung cho 4 bt din cha nhm, ngha l nng lng ca n chia u cho 4
mi lin kt (2 : 4 = 1/2). Trn mt {0001} ch thy hai mi lin kt t mi oxy, tc l hai bt
din nhm chia nhau mt oxy ti nh (hnh 6.35,a). Trn mt thng ng {10 0} c th thy
tng cp bt din nhm chung nhau mt tam gic (hnh 6.35,b). Cation Al
3+
bn trong bt din
c xu hng dch khi mt chung, nhm trnh lc y tng h.
-Al
2
O
3
l corindon t nhin, cc bin th khc nh -Al
2
O
3
su phng, c th cha kim
loi kim, Ca v -Al
2
O
3
h lp phng u l cc sn phm tng hp. Khi nung chng u
bin i thnh corindon. Ruby mu v saphir nhiu mu l nhng corindon qu.
c im ha hc
Mc du corindon thng tinh khit, n c th cha mt lng nh cc ion khc, nh
Fe
3+
(bng 6.24). Ruby cha mt lng chrom va phi (xem mu 3,4), trong khi mu ca
saphir lin quan ti s c mt ca st v titan. Corindon mu vng v mu lc cha mt lng
thay i ion Fe
3+
v Fe
2+
; chng hn mu mu vng (s 5) c n 9,17% Fe
2
O
3
v khng c
FeO. Corindon Lc Yn phn ln c mu ta v hng, dng quen gm lng tr su phng v
thp i su phng. Trong hoa, corindon thng i km vi calcit, phlogopit v margarit;
ring mu LI-1 c thm pargasit, clinochlor v graphit; mu AP-12 thm pargasit, clinochlor
v spinel; mu LI-108 thm pyrit.
Bng 6.24
S liu ha phn tch ca corindon vi cc mu ly t hoa Lc Yn [7]
1 2 3 4 5 LI-1 LI-108 AP-12
SiO
2
0,20 0,01 0,137 0,542 0,94 0,028 0,064 0,058
TiO
2
0,32 0,03 0,00 0,00 0,37 0,120 0,055 0,029
Al
2
O
3
98,84 99,8 98,8 97,5 89,40 99,023 99,379 98,927
Cr
2
O
3
Vt 0,06 0,945 1,81 0,000 0,000 0,020
Fe
2
O
3
0,14 0,16 0,0147 0.0252 9,17
FeO 0,06 0,000 0,076 0,019
V
2
O
5
0,00 0,0320 0,0582
NiO Vt 0,00 0,00 0,000 0,000 0,000
MnO -nt- 0,01 0,00 0,00 0,033 0,000 0,000


286
MgO 0,04 0,01 0,02265 0,0328 0,000 0,027 0,012
CaO 0,34 0,00 0,003 0,000 0,001
CuO 0,00237 0,0016
CdO 0,0168 0,0351
MoO
3
0,00448 0.0117
Na
2
O 0,002 0.013 0,000
K
2
O 0,018 0,000 0,013
P
2
O 0,008 0,000 0,019
99,94 100,1 99,97 100,02 99,88 99,235 99,614 99,098
Dark blue corundum, contact altered marble, Urals (Gavrusevich, B.A.,1941, Doclady
Acad.Sci. USSR, 31, 686-8).
Corundum, South Africa (Carswell, D. A., Dawson, j.b. & Gibb,F. G. F., 1981, Min.
Mag., 44, p. 79-89).
Natural gem ruby, light in colour (Alexander, A. E., 1948, J. Gemmol., 1, no. 8, 4-8).
Natural gem ruby, dark in colour (Alexander, A. E., 1948, ibid).
Yellow iron-corundum, metamorphosed lithomarge (porcellanite) in dolerite plug.
Tievebulliagh, Northern Ireland (Agrell, S. O. & Langley, J. M., 1958, Proc. Roy. Irish Acad.,
59, B. 93-127, 1.785, 1.794).
Nh thy, tt c cc mu u c phlogopit bn cnh corindon. y l kt qu ca phn
ng gia carbonat v vt liu st trong qu trnh bin cht. Phn ng sinh ra corindon ny c
th vit nh sau:
CaMg(CO
3
)
2
+ KAl
2
[AlSi
3
O
10
](OH)
2
= 3CaCO
3
+ KMg
3
[AlSi
3
O
10
](OH)
2
+ Al
2
O
3
+ 3CO
2
dolomit muscovit calcit phlogopit corindon
Ni c nhiu dolomit th corindon bin mt; phn ng gia hai khong vt ny lm ny
sinh spinel.

Nguyn liu sn xut corindon vi khi lng ln l oxit nhm, gibbsit, boehmit,
diaspor hay bauxit. Khi nung n trn 450C chng cho corindon bn vng. Cng vi nhng


287
sn phm nhn to nh carbur silic, n dng lm bt mi thay cho corindon t nhin. T nm
1912, ngi ta s dng phng php Verneuil tng hp n tinh th ruby v saphir.
Bt Al
2
O
3
nung trong ngn la hydro oxy, sau khi ngui s cho n tinh dng thi.
Mt lng nh chrom hay ion st ha tr ba thm vo s cho mu thch hp. Nm 1947, Linde
Air Products USA dng nguyn t titan lm ph gia v cch x l nhit thch hp, khin
cho dung dch cng phn r v Ti tch ra di dng bao th rutil TiO
2
hnh kim. Chng nh
hng song song cc trc ta ngang, nhn dc trc OZ n tinh th ruby v saphir cho hiu
ng quang hc di dng hnh sao su cnh.
6.13.6. Spinel
H lp phng
a () Cng thc
Spinel 8,103 MgAl
2
O
4

Hercynit 8,135 Fe
2+
Al
2
O
4

Gahnit 8,08 ZnAl
2
O
4

Galaxit 8,28 MnAl
2
O
4

Magnesioferrit 8,383 MgFe
2
3+
O
4

Magnetit 8,396 Fe
2+
Fe
2
3+
O
4

Maghemit 8,34 -Fe
2
3+
O
3

Ulvospinel 8,536 Fe
2+
Ti
2
O
4

Franklinit 8,43 ZnFe
2
3+
O
4

Jacobsit 8,505 MnFe
2
3+
O
4

Trevorit 8,34 NiFe
2
3+
O
4

Magnesiochromit 8,334 MgCr
2
O
4
Chromit 8,378 Fe
2+
Cr
2
O
4

Song tinh {111} ph bin
mng Z=8; NKG Fd3m
d
hkl
: 2,44(9); 2,02(9); 1,552(9);
1,427(10); 1,053(10)
Nhm spinel c th phn ra ba lot theo thnh phn cation ha tr ba:
Cation ha tr hai Lot Al Lot Fe
3+
Lot Cr
Mg Spinel Magnesioferrit Magnesiochromit
Fe Hercynit Magnetit Chromit
Zn Gahnit Franklinit
Mn Galaxit Jacobsit
Ni Trevorit
c im cu trc
Cng thc tng qut ca spinel AB
2
O
4
(hay A
8
B
16
O
32
, theo dung lng ca c s; a =
8,08 8,54,z = 8). Loi cu trc ny c c s l lut xp cu lp phng ca nguyn t oxy;
tm cation A c phi tr t din, 16 B nm trong khoang bt din. Nh vy, 3/4 khoang t
din v 1/2 khoang bt din cn b trng. a din phi tr cc loi tp hp thnh hai loi lp


288
vung gc vi trc i xng bc ba: 1) lp bt din v 2) lp bt din t din (hnh 6.36,a).
Lp 1 tp hp ti 75% tng s bt din B, 2/3 s ny gn vi nhau qua cnh chung thnh
chui, 1/3 s cn li gn cc chui ny thnh lp (hnh 6.36,b). Lp 2 gm tt c s t din A,
nh hng ngc nhau dc trc bc ba v 25% bt din B cn li (hnh 6.36,c).
Trong s hp cht ca nhm ny, mt s c cu trc vi cc cation hon i v tr: 8/16
cation B chim tm t din; sinh ra cng thc ca cu trc B(BA)O
4
. Phn ln spinel c
ngun gc t nhin thng cho thy s phn b cation theo nhng s trung gian gia hai
loi cu trc trn. S a dng v cu trc tinh th ca spinel cn th hin ch chng c th
tip nhn cc oxit Al
2
O
3
v
3
2 3
Fe O
+

vo cc dy dung dch cng, vi cc pha u cui l -
Al
2
O
3
v -
3
2 3
Fe O
+
. Maghemit vi cu trc lin thng ny c s thiu ht cation trong cc
v tr.
Kch thc a ca c s thuc cc thnh vin trong nhm spinel ph thuc gi tr bn
knh ion ha tr hai R
2+
v ha tr ba R
3+
; cng thc tng qut nh sau:
a() = 5,790 + 0,95R
2+
+ 2,79R
3+
























289



c im ha hc
Lot spinel
Spinel, MgAl
2
O
4
l khong vt ph bin nht trong lot ny. T spinel n hercynit
Fe
2+
Al
2
O
4
l dy ng hnh lin tc (hnh 6.37). y l nhng spinel vi lng Fe
2+

thay th
cho Mg, vi t s Mg : Fe
2+
t 3 n 1, gi l pleonast hay ceylonit. Km c th thay th Mg,
cho dy ng hnh t spinel n gahnit ZnAl
2
O
4;
; nhng spinel cha km ny gi l
gahnospinel. Ion Al c th b Cr thay th, dn n magnesiochromit trong lot chromit: picotit
thu hp vng hercynit vi s thay th CrAl ng k, khi cha st ha tr hai picotit l
pleonast hay Fe-Cr-spinel.


290
Trong s spinel mu sc khc nhau (bng 6.25), mu mu giu Cr
2
O
3
(1,214%), mu
mu hng giu FeO (1,754%), spinel mu nu cha nhiu CaO (0,108%). Ngoi ra, s bin
thin t l nghch v hm lng gia thnh phn oxit nhm v oxit chrom cng gp phn lm
cho mu sc ca spinel thay i theo [8]. Spinel trong cc mu hoa ca vng m qu
Lc Yn c hai mu c trng. Spinel vi mu ca ruby c mt cng vi pargasit mu lc
emerauld, spinel mu ta n tm thng lin quan vi calcit, dolomit, forsterit v humit hay
vi pargasit mu nu. Ngoi ra, ni no trong vng corindon xut hin thng khng c
spinel. Ring trong mu AP12 [7], spinel giu st c mt mt lng nh v cng sinh vi
saphir hng. Theo cng thc l thuyt, trong mu spinel AP12 (vi tng 23,53 cation so vi
24) c th thy v tr bt din tha cation (16,92 so vi 16), cn v tr t din li thiu (6,57 so
vi 8).
Nh ch trn, i vi spinel s hon i ion gia cc v tr t din v bt din l bnh
thng v c th gi nh rng AP12 c du hiu ca mt pha trung gian gia hai loi cu
trc XY
2
O
4
v Y(YX)O
4
.
Hercynit, Fe
2+
Al
2
O
4
. Cng vi s thay th Fe
2+
Mg, mt lng ng k Fe
3+
cng trao
i vi Al; mc du hai c ch ny khng th dn n s ra i ca magnetit. Ring thay th
lin tc Al Cr ny lm nn dung dch cng hon ton gia hercynit v chromit: picotit
cng l bin th ca hercynit vi lng nhm ln hn chrom v t l Fe : Mg t 3 n 1. H
Fe
2+
Al
2
O
4
Fe
3
O
4
c nghin cu thc nghim: trn 858C h cho dung dch cng hon
ton, nhng di nhit ny n cho xut hin hai pha, vng phn r m rng khi nhit
h.
Gahnit, ZnAl
2
O
4
. Bng
6.25 cho thy s thay th ca
Fe v Mg cho Zn. Gia
gahnit v spinel c th c
dung dch cng hon ton.
Galaxit, MnAl
2
O
4
. Thnh
vin him hoi nht ca lot
spinel ny c c hai c ch
thay th: Mn Fe
2+
v Al
Fe
3+.

Lot magnetit
Magnesioferrit,
MgFe
2
3+
O
4
. Trong t nhin
Fe
2+
thng thay cho Mg. S
liu phn tch ha ca khong
vt thng him c, v n hay
gp di dng mc xen v
cng sinh cht ch vi
hematit.
Magnetit, Fe
2+
Fe
2
3+
O
4
. Mu s 4 (bng 6.25) cho thy nhng s liu gn vi thnh phn
l thuyt ca pha u cui. Nhm c mt lng nh thay th cho st ha tr ba; cc ion ha tr
hai nh Ca, Mn v Mg thay th st ha tr hai nhng t l tng ng; mc du Mg v Fe
thng trao i lin tc cho n Magnesioferrit (hnh 6.37). Titan c th thm nhp ng k

Hnh 6.37
Lng tr a cu t ca spinel
Mt y gm cc spinel thng, nh l spinel
vi cu trc lin thng


291
vo cu trc tinh th magnetit v hnh thnh dy thnh phn lin tc gia n vi ulvospinel,
Fe
2
TiO
4
. Mu s 5 l mt ulvospinel; i vi khong vt ny cation ha tr ba nh nhm, st
thay th ng hnh cho titan, magnesi thay cho st ha tr hai; tng s cation 23,48/n v
cng thc v in tch vn c cn bng.
im si ca magnetit l 1594C, 1452C n c th cha ti 30% Fe
2
O
3
; khi h nhit,
pha ny tch ra di dng hematit dc {111} ca magnetit. Nghin cu cn bng pha ca h
ba cu t FeOFe
2
O
3
TiO
2
cho thy magnetit l pha kt tinh nguyn thy trong khong 0
12% trng lng ca TiO
2
vi nhit nng chy 1594C h n gi tr nh nht l 1524C.
H c ba dy dung dch cng (hnh 6.38):
1) pseudobrookit Fe
2
O
3
.TiO
2
(trc thoi) FeO.2TiO
2
,
2) hematit Fe
2
O
3
ilmenit FeO.TiO
2
(ba phng) v
3) magnetit FeO.Fe
2
O
3
ulvospinel Fe
2
TiO
4
.
Trong dy th ba ny, dung dch cng lin tc tn ti nhit cao, di 600C dung
dch b phn r.
Maghemit, -Fe
2
3+
O
3
. Magnetit c mt s dng cha d Fe
2
3+
O
3
c xu hng tr thnh
pha u cui trong dy dung dch cng. Trong dy Fe
3
O
4
Fe
2
O
3
ny s ion kim loi tnh trn
32 ion oxy c th nh hn con s l thuyt, tc l < 24, i vi Fe
3
O
4
tinh khit, v i vi
pha u cui maghemit c th l 21,33. Maghemit khng bn v bin i thnh hematit (-
Fe
2
O
3
) khi nung; nhit chuyn pha thay i t 200 n 700C ty thuc vo iu kin sinh
thnh ca mu.
Ulvospinel, Fe
2
2+
TiO
4
. Trong t nhin
cha thy ulvospinel vi thnh phn tinh
khit, khong vt ch bt gp di dng tinh
th mc xen do phn r dung dch cng
(bng 6.25, mu 5). Ulvospinel trong basalt
mt trng c thnh phn gn vi cng thc l
thuyt. Nhit si ca Fe
2
TiO
4
tng hp l
1470C.
Franklinit, ZnFe
2
3+
O
4.
y l oxit ca
st ha tr ba v km, ZnFe
2
3+
O
4
thng
cha t l ng k Mn
2+
ti v tr ca Zn.
Jacobsit, MnFe
2
3+
O
4
. Khong vt qung
tng i him ny cha kh nhiu mangan
ha tr ba ti ch ca st v magnesi thay
cho mangan ha tr hai.
Trevorit, NiFe
2
3+
O
4
. Mt t Mg v Fe
2+
c th thay th ng hnh cho Ni.
Lot chromit
Magnesiochromit, MgCr
2
O
4
. Khong vt ny lun lun cha mt lng ng k Fe
2+
.
y l kt qu thay th ng hnh ca st v magnesi, n din ra lin tc cho n tn chromit

Hnh 6.38
H FeO-Fe
2
O
3
-TiO
2
ng m ch dung dch
cng ch yu. ng nht ni cc pha cng sinh
nhit thp


292
vi hm lng ca st ln hn so vi magnesi (hnh 6.37). MgCr
2
O
4
cng c kh nhiu Al v
Fe
3+
ti v tr ca Cr (bng 6.25, mu 6).
Chromit, FeCr
2
O
4
. Chromit t nhin hu ht cho thy magnesi thay th st ha tr hai,
thng cha kh nhiu nhm v mt lng t hn ca ion st ha tr ba. Chromit cha km
cng bt gp trong t nhin.
Bng 6.25
S liu ha phn tch ca spinel
1 2 3 4 5 6
SiO
2
0,28 0,27 0,09
TiO
2
0,02 Vt 19,0 0,32
Al
2
O
3
64,85 60,7 38,18 0,21 4,3 21,6
Cr
2
O
3
0,03 43,8
Fe
2
O
3
2,21 68,85 33,2 6,86
FeO 13,70 34,7 10,50 30,78 43,2 9,26
MnO 0,01 0,2 0,08 0,30
MgO 18,74 4,3 3,30 Vt 0,2 17,2
ZnO 27,71
CaO 0,1 Vt
NiO
Na
2
O
K
2
O
P
2
O
Tng 99,84 100,0 99,77 100,11 99,9 99,6

S ion tnh trn 32 oxy
Si 0,057 0,083 0,022
Al 15,564 16,01 16,01 0,077 1,473 6,159
Cr 0,005 8,373
Fe
3+
0,337 15,886 7,263 1,248
Ti 0,003 4,154 0,058
15,97 16,01 16,01 16,05 15,86
Mg 5,678 1,434 1,148 0,087 6,199
Fe
2+
2,332 6,492 2,049 7,896 10,502 1,873
Zn 4,775
Mn 0,002 0,038 0,015 0,061
Ca 0,024
8,01 7,99 7,99 7,896 23,48 8,17*
* K c Ni 0,037
1. Ferroan spinel, sapphirine phlogopitetaaffciteapatite metasomatic rosk in pyroxenite.
Musgrave Rangers, Central Australia (Wilson, A. F. & Hudson, D. R., 1967, Chem. Geol., 2,
20915).
2. Hercynite, corundumspinelilmenite rock. Plossberg, northern Bavaria (Propach, G.,
1971, Neues Jahrb. Min., 115, 120 2).


293
3. Gahnite, Archacan iron formation, Malene supracrustal belt. Godthab area, western
Greenland (Appel, P. W. V., 1986, Min. Mag., 50, 175 77. Microprobe analisis).
4. Magnetite, Lovers Pit, Mineville, New York State (Newhouse, W. H. & Grass, J. J.,
1936, Econ. Geol., 31, 699 711).
5. Fquant ulvospinel in skeletal pseudobrookite in rapidli quenched dyke, White
Mountain batholith, New Hanpshire (Rice, J. M., Dickey, J. S. & Lions, J. B., 1971, Amer.
Min., 56, 158 62. Microprobe analisis).
6. Magnesiochromite, komatiite, Gorgona Island, Colombia (Echeverria, I. M., 1980,
Contr. Min. Petr., 73, 253 66. Microprobe analisis. Include NiO 0,191).
Bng 6.26
S liu phn tch ha ca spinel ly t Lc Yn, Yn Bi [8]
Cu t Tm Hng Vng Lam Nu AP12 [7]
SiO
2
0,029
TiO
2
0,199 0,205 0,246 0,206 0,164 0,216 0,006
Al
2
O
3
71,015 69,953 70,857 71,276 71,539 70,948 73,948
Cr
2
O
3
0,514 1,214 0,443 0,163 0,150 0,284 0,234
V
2
O
3
0,246
FeO 1,018 1,501 1,012 0,292 1,754 0,755 5,081
MgO 26,972 27,064 27,374 27,289 26,127 27,338 19,725
CaO 0,059 0,062 0,069 0,057 0,071 0,108 0,010
MnO 0,222 0,220 0,194 0,038
NiO 0,053
Na
2
O 0,000
K
2
O 0,030
P
2
O 0,024
Tng 99,999 99,999 100,001 99,503 99,999 99,895 99,178

S lng ion tnh trn 32 oxy
Si
4+
0,00
Ti
4+
0,03 0,03 0,04 0,03 0,02 0,03 0,04
Al
3+
16,00 15,84 15,92 16,03 16,11 15,94 16,92
Cr
3+
0,08 0,18 0,07 0,03 0,02 0,04 0,00
V
3+
0,04
Tng 16,11 16,05 16,03 19,09 16,15 16,05 16,96
Fe
2+
0,16 0,24 0,16 0,05 0,28 0,12 0,82
Mg
2+
7,68 7,75 7,77 7,76 7,44 7,77 5,71
Ca
2+
0,01 0,01 0,01 0,01 0,02 0,02 0,00
Mn
2+
0,04 0,04 0,03 0,01
Tng 7,89 8,00 7,94 7,86 7,77 7,91 6,57*
* K c Ni
2+
, K
+
v P
+
vi mi ion 0,01.


294
Ph lc 2
H thng tun hon nguyn t ho hc vi cc loi cu trc tinh th
C: xp cu lp phng, I: lp phng tm khi, H: xp cu su phng, M: cu trc phn t,
K: cu trc vi s phi tr K = 8 N (N l s hiu nhm) L: cc cu trc khc.
IA IIA IIIB IVB VB VIB VIIB VIIIB IB IIB IIIA IVA VA VIA VIIA VIIIA
1 1
H
K
M
2
He
2 3
Li
I
C
4
Be
H
5
B
L
6
C
K
7
N
M
8
O
M
9
F
10
Ne
3 11
Na
I
C
12
Mg
H
13
Al
C
14
Si
K
15
P
K
16
S
M
17
Cl
M
K
18
Ar
4 19
K
I
20
Ca
H
C
21
Sc
C
H
22
Ti
C
H
23
V
I
24
Cr
I
H
25
Mn
C
26
Fe
I
C
27
Co
C
H
28
Ni
C
29
Cu
C
30
Zn
H
31
Ga
M
32
Ge
K
33
As
K
34
Se
K
35
Br
M
K
36
Kr
5 37
Rb
I
38
Sr
I
H
39
Y
H
40
Zr
I
H
41
Nb
I
42
Mo
I
43
Tc
H
44
Ru
H
45
Rh
C
46
Pd
C
47
Ag
C
48
Cd
H
49
In
C
50
Sn
L
K
51
Sb
K
52
Te
K
53
I
M
K
54
Xe
6 55
Cs
I
56
Ba
C
57
La
C
H
72
Hf
H
73
Ta
I
74
W
I

75
Re
H
76
Os
H
77
Ir
C
78
Pt
C
79
Au
C
80
Hg
C
81
Tl
C
H
82
Pb
C
83
Bi
K
84
Po
L
85
At
86
Rn
7 87
Fr
88
Ra
89
Ac



295
Ph lc 3
Bn knh hu hiu (tnh bng ) ca cc ion ph bin trong khong vt
I II III IV V VI VII
Li
+
0.59 (4)
0.74 (6)
0.92 (8)
Be
+
0.16 (3)
0.27 (4)
0.45 (6)

B
3+
0.11 (4)
0.27 (6)
C
4+
- 0.08 (3)
0.15 (4)
0.16 (6)
N
5+
- 0.10 (3)
0.13 (6)
O
2
1.36 (3)
1.38 (4)
1.40 (6)
1.42 (8)
F

1.31 (4)
1.33 (6)
Na
+

0.99 (4)
1.02 (6)
1.18 (8)
1.24 (9)
1.39(12)
Mg
2+
0.57 (4)
0.72 (6)
0.89 (8)


Al
3+
0.39 (4)
0.48 (5)
0.54 (6)
Sl
4+
0.26 (4)
0.40 (6)
P
5+
0.17 (4)
0.29 (5)
0.38 (6)
S
2
1.84 (4)
S
6+
0.12 (4)
0.29 (6)
Cl

1.81 (6)
K
+
1.38 (6)
1.51 (8)
1.55 (9)
1.59 (10)
1.64 (12)
Ca
2+
1.00 (6)
1.12 (6)
1.18 (9)
1.23 (10)
1.34 (12)
Sc
3+
0.75 (6)
0.87 (8)
Tl
4+

0.42 (4)
0.61 (6)
0.74 (8)


V
5+
0.36 (4)
0.46 (5)
0.54 (6)

Cr
3+
0,62 (6)
Cr4+
0,41 (4)
0,55 (6)
Cr6+
0.26 (4)
Mn
2+
0.83 (6)
0.96 (8)
Mn
3+
0.65 (6)
Mn
4+
0.53
Fe
2+
0.63 (4)
0.78 (6)
0.92 (8)
Fe
3+
0.65 (6)
0.78 (8)
Co
2+
0.74 (6)
0.90 (8)
Nl
2+
0.55 (4)
0.69 (6)
Cu
+
0.46 (2)
0.77 (6)
Cu
2+
0.57 (4)
0.65 (5)
0.73 (6)
Zn
2+
0.60 (4)
0.74 (6)
0.90 (8)
Ga
3+
0.47 (4)
0.55 (6)
0.90 (8)
Ge
4+

0.39 (4)
0.53 (6)
As
3+
0.58 (6)
As
5+
0.34 (4)
0.46 (6)
Se
2
1.98 (6)
Br

1.96 (6)
Rb
+

1.52 (6)
1.61 (8)
1.66 (1)
1.72 (12)
Sr
2+
1.18 (6)
1.26 (8)
1.36 (10)
1.44 (12)
Y
3+
0.90 (6)
1.02 (8)
Zr
4+
0.82 (6)
0.78 (7)
0.84 (8)
0.89 (9)
Nb
5+
0.64 (6)
0.78 (7)
0.84 (8)
0.89 (9)
Mo
4+
0.65 (6)
Mo
6+
0.41 (4)
0.59 (6)

Rh
4+
0.60 (6)
Pd
2+
0.64 (4)
0.86 (6)
Ag
+
1.15 (6)
1.28 (8)
Cd
2+
0.58 (4)
0.74 (6)
0.90 (8)
In
3+
0.62 (4)
0.80 (6)
0.92 (8)
Sn
4+
0.69 (6)
0.81 (8)
Sb
3+
0.76 (6)
Sb
5+
0.60 (6)
Te
2
2.21 (6)
I

2.20 (6)
Cs
+
1.67 (6)
1.74 (8)
1.81 (10)
1.85 (11)
1.88 (12)
Ba
2+
1.35 (6)
1.42 (8)
1.47 (9)
1.52 (10)
1.61 (12)
La
3+
1.03 (6)
1.16 (8)
1.22 (9)
1.27 (10)
Hf
4+
0.71 (6)
0.76 (7)
0.83 (8)
Ta
5+
0.64 (6)
0.69 (7)
0.74 (8)
W
6+
0.42 (4)
0.51 (5)
0.60 (6)
Re
4+
0.63 (6)
Re
7+
0.38 (4)
0.53 (6)

Ft
2+
0.80 (6)

Hg
2+
0.96 (4)
1.02 (6)
1.14 (8)

Pb
2+
1.19 (6)
1.29 (8)
1.35 (9)
1.40 (10)
Bl
3+
0.96 (5)
1.03 (6)
1.17 (8)



296





297
VIT TT

n v ngstrom (10
8
cm)
A (B, C) ion kim loi
X (Y, Z) ion kim
A B khong cch gia hai ion kim loi thuc cc nguyn t khc nhau
A X khong cch gia ion kim loi v ion kim
a thng s (cnh) mng theo phng OX
b thng s (cnh) mng theo phng OY
c thng s (cnh) mng theo phng OZ
d
hkl
khong cch gia cc mt mng thuc h (hkl)
DTA phn tch nhit vi sai
vct n v cng thc
Eh th nng ion ha
MTQ mt trc quang
NKG nhm (i xng) khng gian
n
o
tia thng, ch s khc x ca n
n
e
tia d thng, ch s khc x ca n
Ng ch s khc x ln, tia vi vn tc ln, phng dao ng ca n
Nm ch s khc x va, tia vi vn tc va, phng dao ng ca n
Np ch s khc x nh, tia vi vn tc nh, phng dao ng ca n
Ng Np lng chit sut
T l t din trong cu trc silicat lp
O l bt din trong cu trc silicat lp
TO tp hai l trong cu trc silicat lp
TOT tp ba l trong cu trc silicat lp
t-o-t n v cu trc dng ch I trong pyroxen v amphibol
x, y, z trc tinh th hc
Z s n v cng thc trong mng
2V gc trc quang ca tinh th hai trc
, , gc gia hai chiu dng ca OY v OZ, OX v OZ, OX v OY




Acmit, 230, 238.
Actinolit, 150, 167, 246 9.
Aegirin, 236, 239.
Albit, 162 6, 169, 172, 183 5, 205, 218, 238, 2478, 281, 283 7, 291 4.
Amphibol, 91, , 109, 154, 164 7, 172 4, 184, 196, 229 34, 242 9, 252, 264,
287, 292.
Andalusit, 221 4.
Apatit, 128, 152 3, 301 3, 311.
Aragonit, 149 50, 166, 167, 186, 188, 206 207, 250, 291, 298 300, 302.
ch dn tra cu


298
Augit, 233, 235, 237 42.

Bn knh hiu dng, 78, 88.
Barit, 89, 151, 300 1.
Beidelit, 269, 274 76, 278.
Beryl, 87, 170, 224 7, 292.
Bin dng do, 180 1, 186, 194 5.
Biopyribol, 229, 231 3.
Biotit, 167 8, 184, 218, 220 1, 227, 229, 252, 254, 256, 258 62, 271, 273, 279
80.
Boehmit, 145 7, 305.
Bravais,
k hiu mt, 22, 186, 188;
k hiu nhm im, 38 9, 47;
mt tinh th, 18 9, 22, 55, 59, 195;
mng khng gian, 14, 47, 52, 57, 83, 111, 298.

Calcit, 11, 57, 86, 103, 106, 148 50, 162, 176, 181, 186 88, 206 207, 214, 292,
298 300, 302, 304 5, 308.



Ct khai, 12, 16 7, 19, 22, 61, 86, 105, 108, 123, 151 2, 179, 185 6, 190 1,
195 6, 209, 222 4, 226, 234 5, 243 4, 250, 254 6, 261, 270, 279, 281 3,
289, 291 2, 298.
Carbonat, 86, 89, 106, 133, 147 50, 152, 164 5, 186, 206, 214, 298 303, 305.
Chabasit, 208, 282.
Chesterit, 233.
Chiastolit, 223.
Chlorit, 87, 150, 165 6, 214, 218 9, 222, 227, 229, 250, 258, 262, 265, 271, 275,
279 80.
Chlorur cadimi CdCl
2
, 86, 107, 129, 131 2, 135, 199, 205.
Chlorur cesi CsCl, 58, 82, 85, 88, 104, 116, 129 31, 194, 197, 203.
Chromit, 104, 133 4, 141 2, 205, 213, 306, 308, 310 1.
Co c, gin nhit, 108, 196.
Coesit, 157, 176 7, 280, 295.
Cordierit, 165 6, 220 1, 223, 226 7, 277.
Corindon, -Al
2
O
3
, 105 6, 136 9, 141 2, 169, 257, 303, 308.
Corindon Lc Yn, 304 5.
Cummingtonit, 164, 242, 244, 249.
Cuprit, 18 9, 137.

Dng i xng, 33 5, 37, 41, 51, 295.


299
Dng quen, 22, 54 61, 102, 108 9, 150 1, 153, 215 6, 234, 262, 282 3, 291,
304.
Danh php ca pyroxen, 235, 242.
D cc, 89, 128, 147, 151.
D hng, 13 18, 27, 105 6, 108, 150, 165, 198.
Dung dch cng, 112 3, 116 7, 123, 126, 134, 141, 143, 158 9, 165, 167, 168
74, 183, 209 11, 213, 215 6, 299, 229, 238, 242, 266 7, 249, 275, 281, 285
6, 288, 291, 299, 301, 305, 307 10.

a dng, 178, 252.
a din phi tr, 82 83, 88, 90, 306.
a hnh, 175, 177.
i lng i xng, 41.
Diaspor, 146 7, 305.
nh lut cc i (Veis), 23.
nh lut Goldschmidt, 77, 86.
nh lut Groth, 55.
nh lut Hauy, 21.
Disten, 182 3, 188, 198, 221, 223 4.
cng v nhit nng chy, 197.
ha tan, 148, 190, 202 5.
Dolomit, 149 50, 186 8, 249, 298 9, 305, 308.
ng cu trc, 122 3, 127, 142 3, 167.
ng hnh, 163, 167 8, 171 2.

Fayalit, xem Olivin.
Feldspathoid, 157, 165, 207, 280 1.
Feldspat, 87, 154, 157, 162, 165, 172, 177, 181, 184, 207, 221, 257, 268, 272 3,
280 1, 283 94.
Fluorit, 16, 81, 104, 120 1, 128 9, 131, 135 6, 138 9, 159, 162, 180, 190 2.
Forsterit, xem Olivin.

Gi hnh, 179 80, 264, 301.
Gibbsit, 146, 178, 250 1, 266, 269 70, 272, 274, 305.
Gii hn bn vng ca s phi tr, 80 2.
Granat, 55, 58, 139, 143, 164 6, 177, 205, 214 21, 227.
Granat Kan Nak, 220 1.
Grosular, xem Granat.

Halit, 19, 32, 61, 80, 82, 85, 87 88, 103 4, 106, 120 1, 123 7, 129 31, 135
139, 141, 145, 148, 162 3, 167, 169, 190, 298.
Halogenur, 55, 82, 85, 103 4, 107, 127 32, 135, 191, 197, 201 3.
Loi cu trc:
chlorur cadimi CdCl
2
, 131.


300
chlorur cesi CsCl, 130.
fluorit CaF
2
, 131.
halit NaCl, 130.
iodur cadimi CdI
2
, 131.
rutil TiO
2
, 131.
Haloysit, 250, 268, 270, 272, 275.
Hng tinh th, 42, 54.
Hematit, Fe
2
O
3
, 106, 133 4, 137, 141, 150, 166 7, 214, 289, 309 10.
Hercynit, xem Spinel.
H im quy tc (tng ng), 53 4, 71, 74, 114, 168, 171, 173, 177, 179.
H tinh th, 37, 41, 51, 55.
H trc tinh th hc, 40.
Hiu ng chn, 201, 201.
Hnh n, 22, 33 5, 41 47.
Hnh thi tinh th, 27, 33, 41, 56, 61, 150, 188, 215.
Ha tr tnh in, 88 90, 101, 151, 298, 303.
Hp cht hu c, 55, 87, 117, 149, 190, 196 8, 270, 277.
Hydroxoni (oxoni), 133 4, 272.
Hydroxit, 107, 133 4, 144 6, 219, 273, 303.
Loi cu trc:
diaspor -AlO(OH), 146 7;
gibcit, 107;
brucit Mg(OH)
2
(iodur cadimi CdCl
2
), 107, 145, 178;

Illit, 257 8, 266 8, 270 3, 275, 277.
Iodur cadimi (CdI
2
), 86, 106, 121 2, 126, 129, 131 2, 145 46, 199.

Kaolinit, 107, 222 3, 226, 250, 258, 263, 266 72, 277.
Khong vt khng kt tinh, 171.
K hiu mt, 20 23, 25 6.
K hiu nhm im, 38, 40.
Kim cng, 97, 100 3, 105, 123, 137, 176, 188 90, 193, 195 6, 198 9, 206,
219, 296.
Kim loi v hp kim, 87, 110.

Lin kt ha hc trong cu trc tinh th, 86, 98.
Lin kt v c tnh ho l, 189.
Loi cu trc, 100.
Lp tinh th, xem dng i xng.

Maghemit, 171, 306 7, 309 10.
Magnesit, 11, 148 50, 214, 298 9.
Magnesiochromit, 306, 308, 310 1.


301
Magnesioferrit, 104, 142, 306, 309.
Magnetit, 32, 104, 133 4, 137, 141 2, 171, 205, 213, 306, 308 9, 311.
Mng khng gian, 17 20, 47 8, 77, 83, 139, 160 1.
Mt tinh th, 13, 16 20, 22, 24, 27, 56 60, 64, 162, 292.
Mica, 87, 128, 154, 165 7, 178 9, 184, 214, 218 219, 222, 229 33, 243, 250
60, 262, 267 8, 270 4, 278 9.
Min gin on (solvus) 164 7, 173, 237 8, 245 7, 281, 285 8, 302.
Molybdenit, 82, 98, 101, 120, 122 3.
Montmorillonit, 222, 250, 258, 267, 269, 271, 274 8, 280.
Muscovit, 107 8, 167, 184, 222, 224, 226 7, 229, 250 2, 254, 25662, 271 4,
305.

Nacrit, 268, 270 1.
Nng lng mng, 92 3, 99, 202 4.
Nephelin, 281 2, 288, 297.
Nguyn l xp cu, 93 4, 117.
Nhm chc, 53, 86, 89 90, 98, 102, 106 9, 147 9, 153, 170, 177, 184, 229 233
4, 243, 249, 251, 267, 269, 274, 281, 298 9.
Nhm im, xem Dng i xng.
Nhm khng gian, 47, 49, 51 4.
Nickelin, 109, 120 4, 127, 159.
Nontronit, 267, 269, 274 8.

Olivin, 105, 153, 165, 168, 182, 205, 209 14, 264.
Olivin Lai Chu, 211, 213.
Oxit, 133 44.
Loi cu trc:
corindon, -Al
2
O
3
, 136;
fluorit CaF
2
, 135, 138;
halit NaCl, 136;
oxit mangan Mn
2
O
3
, 133;
perovskit CaTiO
3
, 139;
spinel MgAl
2
O
4
, 142.
mng c s, 47, 54, 689, 72 3, 111.
trng, 166 7, 170, 213, 259 60, 297.

Pentlandit, 124.
Perthit, 172, 281, 285, 288, 290 1.
Phn cc ca ion, 82 4, 86.
Phn r dung dch cng, 172 4.
Phengit, 218, 253, 257 8, 268, 272.
Phng php phn tch cu trc, 61, 78.
Phlogopit, 107 8, 167, 211, 230, 250 2, 254, 256 62, 278 80, 304 5, 311.
Phlogopit Lai Chu, 260.


302
Phosphat, 87, 147, 152 3, 302.
Pigeonit, 235 8, 241.
Plagioclas, 154, 164, 166 7, 169, 183 5, 218, 221, 231, 238, 247 8, 281, 284,
286 7, 290 1, 293.
Pyralspit, xem granat.
Pyrit, 18 9, 54, 103, 123 4, 126 7, 176, 180, 292, 304.
Pyrop, 164 5, 205, 214 22.
Pyrophyllit, 107, 167, 222, 224, 250, 258, 262 5, 272, 274 7.
Pyrrhotin, 109, 123, 159, 171.
Pyroxen, 109, 154, 164 7, 169, 172 4, 183 4, 196, 227, 229 47, 291.
Pyroxen Lai Chu, 241 2.

Quy tc Pauling, 88, 151.

Radical, xem nhm chc.
Rhodochrosit, 149, 298.
Rutil, 108, 129, 131, 134, 136 7, 139, 143 5, 157, 167 8, 223, 262, 270, 292,
305.

Sai hng trong cu trc tinh th, 16, 109, 159 3, 180, 252, 256.
Sanidin, 162, 177, 211, 257, 283 6, 289 91.
Sanidin Lai Chu, 289.
Serpentin, 165 6, 212, 214, 227, 250, 266, 270 1.
Sphalerit, 85, 97, 103, 120 1, 123, 125 9, 151, 178, 190, 192, 195 6, 199, 205.
Siderit, 11, 149 50, 168, 211, 298.
Silimanit, 188, 221 2, 224.
Smectit, 15, 214, 266 80.
Smithsonit, 149, 298.
Song tinh, 17, 108, 160 2, 181 5, 187 8, 223 4, 243, 254 5, 291 4, 298
300, 306.
S bi, 53 4, 114 5, 117 8.
S phi tr, 80 83, 85.
Spesartin, xem Granat.
Spinel, 86, 89, 104, 125 26, 134, 136 7, 139, 141 4, 148, 165 6, 171, 205,
210 1, 221, 227, 277, 292, 294, 304 6, 308 12.
Spinel Lc Yn, 308, 312.
Stishovit, 108, 157, 168, 176 7, 206, 211, 280, 295.
Sulfur v mui sulfur, 114 22.
Loi cu trc:
halit NaCl, 120 1;
fluorit CaF
2
, 120 1;
iodur cadimi, 122;
marcasit FeS
2
, 124;
nickelin NiAs, 120;


303
pyrit FeS
2
, 123;
sphalerit ZnS, 125;
vurtzit ZnS, 125.
T trng, 205.
Tnh cht in v quang, 191.
Tnh rn c ca kim loi, 194.
Tinh th lng, 13, 15.
Tourmalin, 128, 227 8, 262
Trt tkhng trt t, 177.
Trevorit, xem Spinel.
Tridymit, 143, 157, 175 7, 206, 227, 280 1, 294 7.
Trt ct n, 181 2, 187.

Ugrandit, xem Granat.
Ulvospinel, xem Spinel.
Uvarovit, xem Granat.

Vect thay th, 163.
Vermiculit, 250, 262, 266 9, 271 3, 275, 278 80.
V nh hnh, 13 7, 145, 179, 206, 266.

Yu t i xng, 27, 31, 35, 47.

Zeolit, 55, 170, 207, 250, 280, 282