Chng 1.

c im cu trc tinh th
thc
Trnh Hn
Ngy Tuyt Nhung
C s ha hc tinh th
NXB i hc quc gia H Ni 2006.
Tr 141 188.
T kho: Tinh th thc, c im cu trc, ng hnh, a hnh, bin dng do.
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
Chng 5 C IM CU TRC TINH TH THC .................................... 3
5.1
CC LOI SAI HNG TRONG TINH TH THC .............................. 3
5.1.1 Sai hng im .................................................................................... 3
5.1.2 Sai hng ng.................................................................................. 4
5.1.3 Sai hng mt ...................................................................................... 4
5.2
NG HNH .......................................................................................... 6
5.2.1
5.2.2
5.2.3
5.2.4

Vect thay th.................................................................................... 7

ng cu trc .................................................................................. 10
Dung dch cng ............................................................................... 11
S phn r ca dung dch cng ........................................................ 14

5.3
A HNH ............................................................................................. 17
5.3.1 Mt s bin th a hnh.................................................................... 17
5.3.2 Trt t khng trt t...................................................................... 20

5.3.3
5.3.4
5.3.5
5.3.6

a dng ........................................................................................... 20
Metamict ......................................................................................... 21
Khong vt khng kt tinh ............................................................... 22
Gi hnh........................................................................................... 22

5.4
BIN DNG DO TRONG KHONG VT TO ........................ 22
5.4.1 Olivin .............................................................................................. 24
5.4.2 Disten (kyannit) ............................................................................... 25
5.4.3 Enstatit ............................................................................................ 25
5.4.4
5.4.5
5.4.6

Amphibol......................................................................................... 26
Mica ................................................................................................ 26
Plagioclas ........................................................................................ 26

5.4.7 Thch anh ........................................................................................ 27

5.4.8 Carbonat .......................................................................................... 28
5.5
C TNH HO L CA TINH TH LIN QUAN VI CU TRC
CA CHNG ....................................................................................... 31
5.5.1
5.5.2
5.5.3
5.5.4

c tnh ho l lin quan vi dng lin kt ho hc trong tinh th..... 31

Tnh cht in .................................................................................. 34
Tnh cht quang ............................................................................... 35
Tnh rn c ca kim loi .............................................................. 37

5.5.5
5.5.6
5.5.7
5.5.8

Tnh ct khai.................................................................................... 38
Cc h s co c, gin nhit............................................................... 39
cng v nhit nng chy ........................................................ 40
nh hng ca dng lin kt hydro n cc tnh cht ho l ............. 43

5.5.9 Hiu ng chn ca ion ..................................................................... 44

5.5.10
ho tan................................................................................... 45
5.5.11
T trng ....................................................................................... 48

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: Fe1XS; st lun thiu ht mt lng no ; Fe2+ lun b trng mt s v
tr ca n trong khoang bt din do lu hunh (S2 xp theo lut ABABAB) to nn.
Phn thiu ht in tch dng to thun li cho mt s Fe3+ vo thay Fe2+ (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

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

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,
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 P6222 chng hn, sau khi chuyn sang pha nhit thp
P3221 (hnh 5.5,c) th cu trc phn li thnh hai phn lin quan vi nhau bng
php quay 180 quanh trc chnh 32. 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 105 cm2 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
KH2PO4 v KH2 AsO4 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
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 CaSO4 v SrSO4, tng t v ho hc,
khng bc l nng lc ng hnh, th hai cp CaSO4NaClO4 v SrSO4KClO4 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 Sr2+ 1,27 ln hn hn ca Ca2+ 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
ClO4 c cng dng t din v cng kch thc nh SO42, ion Na+ (0,98) gn vi Ca2+ v
ln; mc du ho tr khc nhau, CaSO4 v NaClO4 l cp ng hnh. Ion K+ (1,33) ln
hn hn ion Na+ lm cho n khng th i vo cu trc NaClO4 ; nhng ng hnh ca
SrSO4 v KClO4 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:
KAlSi3O8

(orthoclas)

NaAlSi3O8

(albit)

= K Na

= KNa1

S chnh lch gia orthoclas v albit l KNa, m theo php k hiu ca vect thay
th, hiu ny vit thnh: KNa1. 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 NaK1 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
nguyn t bng mt nguyn t, nh KNa1 ni trn. Vect thay th kp th hin s thay
th ca cc cp nguyn t vi nhau. V d: plagioclas;
NaAlSi3O8

(albit)

CaAl2 Si2O8
= NaSi CaAl

(anorthit)
= NaSiCa1Al1

Trong s thay th kp trn, Na+ v Ca2+ 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 Si4+ cp i vi nhau v thay th cho cp Ca2+ v Al3+; 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 FeMg1, 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. FeMn1 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 (CaMg1, CaFe1, CaMn1) 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 (CaMgSi2O6Mg2Si2O6) v
- tremolitMg-cummingtonit (Ca2Mg5Si8O22(OH)2Mg2Mg5Si8O22(OH)2),
u bc l min gin on. Mt solvus tng t cng tng gp trong granat:
gia grosular (Ca3Al2Si3O12) v pyrop (Mg3Al2Si3 O12).
C hai trng hp CaMg1 v CaFe1 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 Fe3+Al1. 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 NaSiCa1 Al1 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

KNa1

Feldspat,
feldspathoid,
mica, amphibol

KAlSi3O8
NaAlSi3O8
Orthoclasalbit

Mi nhm khong u
c min gin on.

FeMg1

Olivin,
pyroxen,
amphibol, mica, talc,
granat, chlorit, serpentin,
staurolit,
chloritoit,
cordierit, carbonat, v.v

Fe2SiO4 Mg2SiO4
Fayalitforsterit

Rt ph bin. Gp trong
mi silicat
Fe-Mg
chnh. Dung dch cng
gn nh lin tc.

Bng 5.1.
Bng lit k nhng vect trao i ph bin trong khong vt to
Vect trao i

Khong vt tiu biu

FeMn1

Ging nh ca FeMg1.
c bit trong granat.
Olivin (th yu), pyroxen,
amphibol,
granat,
carbonat.

CaMg1

Fe Al1

Cr3+Al1

Granat, spinel

F(OH)1

Mica, amphibol,
topaz,v.v

Cl(OH)1
VI

IV

Al Al Mg1Si1
Thay th kiu
tschermak

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

AlmandinSpesartin
Ca3Al2(SiO4)3
Mg3Al2(SiO4)3
GrosularPyrop

Ca2Al3 Si3O12OH
Ca2AlFe2Si3O12OH
Clinozoisitpistacid

talc,

Mg3 Si4O10F2
Mg3Si4O10F2(OH)2
Fluorotalctalc

Pyroxen, amphibol, mica,

talc,
chlorit,
serpentin,v.v

CaAlAlSiO6
CaMgSi2O6
Al-diopsitdiopsit
NaCa2Mg5AlSi7O22

NaAl 1Si1
kiu

Ca2Mg5AlSi8O22

Amphibol, mica.

Edenittremolit.
NaAlSi3 O8
CaAl2Si2O8

IV

NaSiCa1Al1
Thay th kiu
plagioclas

Plagioclas, pyroxen,
amphibol, jadeit.

Albitanorthit

VI

NaAl Ca1Mg1
Thay th kiu
jadeit
hay
glaucophan

Pyroxen, amphibol.

TiAl2Mg1Si2
Thay th kiu
titan-tschermak

Pyroxen, mica,
amphibol, v.v

TiFe2+Fe3+2

Oxit,
v.v

NaAlSi2O6
CaMgSi2O6
Jadeitdiopsit

amphibol,

Ph bin trong hu ht
cc nhm khong. Min
gin on rng gp
trong a s nhm.
Min gin on khng
ln nh CaMg1

Rt c th c min gin
on
trong
epidot,
granat, v.v

MgCr2O4 MgAl2O4
Cromitspinel

IV

Thay th
edenit

Fe3Al2 (SiO4)3
Mn3Al2(SiO4)3

Hedenbergit
Ferosillit

Zoisit, epidot, granat,

pyroxen, amphibol,
spinel.

3+

Ghi ch

CaFeSi2O6
Fe2Si2O6

Olivin (th yu),

pyroxen, amphibol,
granat, carbonat.

CaFe1

V d

CaTiAl2O6
CaMgSi2O6
Ti-tschermakdiopsit
mica,

FeTiO3 Fe2O3
Ilmenithematit

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.

Gp trong mi trng
giu Cl, F.
Al thay th l ch yu
trong hu ht silicat. C
l khng lin tc.
Kim loi kim thay th
trong
amphibol
hay
mica.
Nhiu min gin on;
p sut cao
NaSi bn vng hn
CaAl.

Khng lin tc. NaAl bn

vng p sut cao.

Thay th
silicat.

titan

trong

S thay th titan trong

oxit

10

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 (AlVIAlIVMg1Si1) v phin bn ca n (AlVIAlIVFe1Si1).
Qu trnh thay th ny xy ra trong nhiu silicat, nh pyroxen, amphibol, mica, chlorit,
serpentin v cordierit.
Thay th kiu edenit NaAlIV1Si1 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
IV

NaAl 1Si1

VI

IV

Al Al Mg1Si1

VI

IV

NaAl Al 21Mg1Si2

Bnh thng, amphibolit p sut trung bnh (80 90% tnh a dng ho hc ca Caamphibol) l nm gia actinolit v hornblend dc vect thay th kiu pargasit (hay phin
bn Fe ca n l NaAlVIAlIV 1Fe1Si2).
Bng 5.1 c hai vect thay th: kiu titantschermak
TiAlIV2 Mg1Si2 v TiFe2+Fe3+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. TiFe2+Fe3+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: TiMg2 quan st c trong mica, v TiAl1(OH/F) 1
trong titannit (sphen).
Mt vect quan trng khc l thay th kiu glaucophan hay jadeit: NaAlVICa1Mg1.
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:
VI

NaAl Ca1Mg1

NaSiCa1Al1

VI

IV

Al Al Mg1Si1

Khi nim ng hnh khng tch khi hai khi nim khc: ng cu trc v dung dch
cng.

5.2.2 ng cu trc

11

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 SiO2 (bin th a hnh p sut cao ca silica) v rutil TiO2
cng ng cu trc, c cng nhm khng gian P42/mnm v cation trong c 2 khong vt
(Si4+ hay Ti4+) 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, Mg2+ v Fe2+ 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 Al3+ thay th Si4+, 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 [SiO4 ], Mg2+ c
th b thay th tng phn hay ton b bi Fe2+. Cc thnh phn u v cui ca dy ny l
forsterit Mg2[SiO4 ] v fayalit Fe2[SiO4]. Mt th d khc l dung dch cng (Mn,Fe)[CO3]
nm gia hai khong vt rhodochlrosit Mn[CO3 ] v siderit Fe[CO3]. Chui thay th lin

12

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 A2+X2 cation B3+ thay th cho A2+ th mt trong nhng gii
php nhm duy tr in tch tng l cation C+ cng i vi B3+: 2A2+ = 1B3+ +1C+. S thay
th kp loi ny th hin trong cu trc ca saphir; Fe2+ v Ti4+ th chn 2Al3+ trong
corindon -Al2O3. Dy dung dch cng plagioclas nm gia hai thnh phn u cui l
albit Na[AlSi3O8] v anorthit Ca[Al2 Si2O8] th hin bng thay th kp sau: Na1+Si4+ =
Ca2+Al3+.
Ca2+ thay th Na+ trong cu trc plagioclas, Si4+ s b Al3+ 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
CaMgSi2O6 v jadeit NaAlSi2O6. ng thc thay th kp vit nh sau: Ca2+Mg2+=Na+Al3+.
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, Fe3C. 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 MeX2, v d: LaC2,
ThC2, ZrH2, 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 CaF2 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. WO3 gn ging perovskit CaTiO3 v cu trc.
Nguyn t oxy ca hai cht u phn b nh nhau, volfram phn b nh Ti. Ring v tr

13

ca Ca trong CaTiO3 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
NaWO3 v tr thnh mt hp cht ho hc ging CaTiO3. 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 (WO3)
sang loi khc (CaTiO3). 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 Be3Al2[Si6O18], ch trng ny rng m thnh dng
ng, do cc nhm chc vng su [Si6O18] chng ln nhau to nn. Cc kt qu nghin cu
beryl chng t mt lng ng k ca K+, Rb+, Cs+, H2O v CO2 trong knh dng ng lc
gic y. Phn t H2O v CO2 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: Si4+ = Be2+ + 2R+ v Si4+ = Al3+ + 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 (SiO4) v (AlO4) 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 Pb2+ vo thay cho K+ trong
amazonit, bin th xanh tri pht lc ca microclin K[AlSi3O8] ny phi y hai cation kali
i do nhu cu cn bng ho tr: K+ + K+ = Pb2+ + , 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 :

14

1. Gii ho hc tng a ra nhiu cng thc nh Fe6 S7 hay FenOn +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 Fe1XS,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 Fe2+ 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: Fe2+13X Fe3+2XX 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 Fe2+ v 0,2 Fe3+ trong
cu trc ca pyrrhotin. Ni cch khc, st ba thm nhp cu trc bng s thay th nh sau:
Fe2+ + Fe2+ + Fe2+ = Fe3+ + Fe3+ + .
Mt th d khc ca dung dch cng khuyt tt l maghemit -Fe2O3, mt sn phm
oxy ho ca magnetit Fe3O4 (Fe2+Fe3+2O4). 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: Fe3+Fe3+1,670,33O4, 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 MgAl2O4 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 Al3+ 0,57 so vi ca Mg2+ 0,74); khoang trng t din
nh li cha Mg ln. Trong Ga-spinel MgGa2O4 (rGa = 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

15

dch cng gia hai pha u v cui: Na[AlSi3O8] v K[AlSi3O8]. 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[SiXOY] v B[SiXOY] 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 T4.

16

Dung dch cng gia hai khong vt thnh to nhit T1. 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 Xi) vi mt trnh t xut hin. Ln lt t trn xung, trc ht l pha
ng nht, dung dch cng hnh thnh nhit T1. Sau l ht cha cc phin li khai
song song vi (001) sinh ra nhit T2. Di cng, ngoi cc phin th hn dc (001),
trn ht khong vt mt lot phin song song vi (100) xut hin nhit T4.

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 T1. Vng nm gia T1 v
T4 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 X1 lm v d. Ti vng pha trn min solvus, nhit T1, 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 T2 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 T2 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 T4, c th thy cc tm (A,B)[SiX OY] vi thnh phn X2,nh
hng ng lut tinh th hc (hnh 5.4,b), mc xen trong khong vt ch (B,A)[SiX OY] vi thnh

17

phn X3. Mc du s phn li ion bn trong cu trc silicat bt u T2 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 (SiO2), hnh 5.6 biu trng thi PT
vi cc trng bn vng ca khong vt a hnh SiO2. 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.

18

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 SiO2 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
C

FeS2

CaCO3
SiO2

Tn khong vt

H v nhm khng
gian

cng

T trng

10

3,52

Kim cng

Lp phng Fd3m

Graphit

Su phng P63/mmc

2,23

Pyrit

Lp phng Pa3

5,02

Marcasit

Trc thoi Pnnm

4,89

Calcit

Su phng R c

2,71

Aragonit

Trc thoi Pnam

3,5

2,94

-thch anh

Su phng P3121

2,65

-thch anh

Su phng P6222

Tridymit

Su phng P63/mmc

Cristobalit

Lp phng Pd3m

2,53
7

2,20

6,5

2,20

19

Coesit

Mt nghing C2/c

Stishovit

Bn phng P42/mnm

7,5

3,01
4,3

Hnh 5.6.
Biu trng thi P-T ca cc bin th a hnh SiO2
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 SiO2. Theo bng 5.2, t trng ca chng u t gi
tr thp nht (2,20) trong s cc bin th ca SiO2. 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 SiO2 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 FeS2, ca
C v ca CaCO3 (bng 5.2) cng chng t rng s chuyn i a hnh y l nhng bin
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.

20

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 (KAlSi3 O8). Khung ca nhm
chc (AlSi3O8) 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, Al3+ 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)4O8]
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 Al3+/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[AlSi3O8 ]
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)2Si2O8]

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.
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

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

21

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 Ccm21.
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 2M1.
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 P3112 hay P3212.
Cc loi cu trc mica ph bin nht l 1M (2/m), 2M1 (C2/c) v 3T (P3112) (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
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.

22

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.nH2O 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 Si4+ v Al3+ 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
SiO2.nH2O 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 SiO2.

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
FeS2 c th bin i n limonit FeO.OH.nH2O, 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
CaSO4 c th i thnh thch cao CaSO4.2H2O v galen PbS bin thnh anglesit PbSO4.

5.4

BIN DNG DO TRONG KHONG VT TO

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

23

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
sinh ra t mng ch nh mt bc (trt ct) trt ct n S song song vi mt K1(mt

24

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 K1 v mt K2. Song tinh
cng c th hnh thnh nh bc trt n S song song vi mt trt K2 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 K1 K2 1 2. Di y, trong khi ni n cc trng hp c th,
h song tinh c s dng s gm mt song tinh K1, 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 SiO4 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...

25

Bng 5.3.
Cc h trt chnh trong olivin
(+ ph bin; khng ph bin)
Nhit thp

Nhit cao

(100) [001]+

{110} [001]

{110} [001]

(100) [010]

(010) [100]

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

5.4.2 Disten (kyannit)

Disten l bin th ba nghing ca Al2SiO4O. Cu trc tinh th c t din SiO4 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 SiO4. 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 K1.
(b) Song tinh periclin: Hng song tinh 1 = [010] v chiu dng ca n, v tr ca
mt song tinh K1 ng vi mi thnh phn plagioclas (hm lng anorthit). K1 l mt
ct trc thoi.

5.4.3 Enstatit
Enstatit l Mg-pyroxen trc thoi thuc dy dung dch cng (Mg,Fe)2Si2O6. Cu trc
tinh th (hnh 6.11) gm t din ni nhau qua nh thnh chui dc hng [001]. y l

26

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 SiO4 ghp li (hnh 6.17). Nh th, amphibol lin quan cht
ch vi pyroxen m nhm chc chui cng l nt c trng. Hornblend Ca2(Mg,Fe2+)3
(Al,Fe3+,Ti)2 (Si3 AlO11)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 K2(Mg,Fe)6(Si6Al2O20)(OH)4 v
muscovit K2 Al4(Si6Al2O20)(OH)4.
Chng thuc h mt nghing v c cu trc lp vi nhm chc dng l do t din
SiO4 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
ti. Plagioclas c thnh phn thay i t NaAlSi3O8 v CaAl2Si2O8 v cu trc khung t
din (Al,Si)O4.

27

Theo Borg v Heard (1969, 1970), nhit trong khong t 50 n 800oC 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 800oC 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 An30 n An95 tr An44 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 (An55)

Albit
(lut vung gc)

K1 = (010)

1 = v t
(xem hnh 5.9)

S = 750

Periclin
(lut song song)

K1 = v t,
gn vi (001)

1 = [010]

S = 750

5.4.7 Thch anh

Thch anh SiO2 l silicat c cu trc khung gm cc t din SiO4 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
Mt y

iu kin nhit

H trt
+

{0001}[ 1120 ]

Nhit thp

28

Lng tr bc mt

{ 1010 }[0001]+

Nhit cao

Lng tr bc mt

{ 1010 }[ 1210 ]+

Nhit cao

Lng tr bc mt

{ 1010 }[ 1213 ]

Nhit cao

{ 1120 }[0001]

Nhit cao

{ 1212 }[ 1123 ]

Nhit cao

Lng tr bc hai
Thp bc hai

Thc ra, thch anh lun cha mt lng nc nht nh. Vi cha H2O ti
0,0015% trng lng (104 H/Si) thch anh gi l kh (Griggs, 1967). Tinh th thch anh
nhn to vi hm lng nc ti 8,8.103 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 CaCO3 v dolomit CaMg(CO3)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 ( hk il ) 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].

29

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

r1

[r1 : f2]

( 1011 ) (100)

[(1011) : (2021)]

Ghi ch
Ph bin

[011]
f1

[r2 : f3], [r3 : f1]

( 2021 )
(111)

[(1011) : (0221)]

[(0111):( 2021 )]
[101], [011]

a2

[r1 : f2]

( 1210 )
(011)

[(1011) : (2201)]
[011]

Rt him

30

Hnh 5.13.
Song tinh trong dolomit
Mi tn ch chiu ca trt ct n

Hnh 5.12.
Song tinh trong calcit
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 [f1 : f3] 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

e1

[e1 : a2]

( 012)
(011)

[( 012):( 2 0)]

r1

[r1 : f2]

(10 1)
(100)

[011]

f1
( 021)

S h
tng ng
3

[100]
3

[(10 1):(2 01)]

[f1 : a2]
[( 021):( 2 1 0)]

31

(111)

[211]

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
Dng lin kt
v loi cu trc

Bin th

S phi
tr

Kim cng

ng cc, ba chiu

Rt cng, trong sut, cch in

Graphit

ng cc/van der Waals,

lp

Mm, khng thu quang, mu

en, tnh kim loi

C60

van der Waals, phn t

Mm, mu en, bn dn

~1

Tnh cht

Vng dn, eV

Hnh 5.14.
Ba loi cu trc ca carbon
a) phn t - C60, 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

32

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

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

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

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

Nhit*

ho tan

Ho tan trong dung

mi phn cc thnh
dung dch cha ion

33

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

CaF2, phn ln
khong vt

Kim cng C,
sphalerit ZnS,
phn t O2, 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

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

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

Halit NaCl, fluorit

CaF2, phn ln
khong vt

Kim cng C,
sphalerit ZnS,
phn t O2, 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)

Cu trc

Nhit*

V d

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.

34

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 CaF2
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 nc 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.
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

35

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 0,00033cm2/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 lng 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).

Hnh 5.17.
3+
+
4+
M hnh cu trc thch anh bnh thng(a)v thch anh m khi khuyt tt (b): Al + H thay th Si

36

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

Bn knh,
3
khc x, cm

1,33
2,5

1,36
7,0

Cl
1,81
9,0

Br

Ne

Na+

1,96
12,6

2,20
19,0

1,60
1,00

0,98
0,5

Mg2+
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 (ndichlorobenzen) 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

KBr

36

1,559
} = 0,065

}=8
RbCl

28

1,494

37

KI

1,667

48

} = 0,133

} = 22
CsCl

26

1,534

LiBr

43

1,784

RbF

LiI

54

} = 0,388

} = 40
1,396
1,955

} = 0,507

} = 52
CsF

MgS

65

1,448
2,271
} = 46

CaO

19

CaTe

75

} = 0,433
1,838
2,510

} = 54

} = 0,355

BaS

21

2,155

Hp cht

% mi lin kt ng cc

Gi tr chit sut

KBr

36

1,559

RbCl

28

KI

48

} = 0,065

}=8
1,494
1,667

} = 0,133

} = 22
CsCl

26

LiBr

43

1,534
1,784
} = 40

RbF

LiI

54

} = 0,388
1,396
1,955
} = 0,507

} = 52
CsF

MgS

65

1,448
2,271
} = 0,433

} = 46
CaO

19

CaTe

75

1,838
2,510
} = 54

BaS

21

} = 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
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.

38

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
dhkl 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).
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

39

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 dhkl ln nht ng vi
hnh tm mt (d111 = 0,866 so vi d100 = 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
{111} trong sphalerit

v mt

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 0,3.106 n 4,5.106cm2/kg. Cc oxit kh nng chy cng c gi tr co
cng bc [(0,5 1).106cm2/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
50).106cm2/kg. Bng 5.12 cho thy r nh hng ca loi cu trc ti co ca cc mui
kim loi kim.

40

Bng 5.12.
nh hng ca loi cu trc ti co (cm2/kg) ca cc mui kim loi kim
Hp cht

LiCl

NaCl

KCl

RbCl

CsCl*

2,57

2,81

3,14

3,27

3,57

H s co ( .10 )

3,50

4,18

5,65

7,40

5,90

xp cht ca ion, %

78,66

65,66

65,01

50,16

68,44

A X,
5

* 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 (cm2/kg) ca cc mui halogenur bc v natri
Hp cht

AgCl

A X,
6

H s co ( .10 )

NaCl

AgBr

NaBr

(AgI)

NaI

2,77

2,81

2,88

2,98

2,99

3,23

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

39

40

43

48

.10

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
li tc ng mi; cht b mi mn khi lc lin kt b ph hu. bn vng ca lc lin kt

41

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 sp3, 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 Al2SiO5 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

42

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).
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

CC

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

CaF2

CdCl2*

NaCl

NaCl

NaCl

NaCl

NaCl

Hp cht

SrF2

MgCl2

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

43

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

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 H2TeH2SeH2S (hnh 5.22), c th d bo nhit nng chy ca H2O 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
HF

Nng chy, C
83

Si, C
+20

Hp cht
NH3

Nng chy, C
78

Si, C
33

44

HCl

112

84

PH3

134

88

HBr

88

67

AsH3

116

62

HI

51

35

SbH3

88

17

H2O

+100

CH4

184

162

H2S

86

60

SiH4

185

112

H2Se

66

41

GeH4

166

88

H2Te

51

SnH4

150

22

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 CF4, 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 CF4 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 nhng 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 Sn4+
= 0,67, ca Cl = 1,81, ra : rx = 0,37. Nhit si ca SnCl4 l 114C. Bn ion fluor c
bn knh 1,33 khng th chn hon ton ion thic, hp cht SnF4 si 705C.
So snh cc hp cht halogenur ca nhm v bo cng c th cho kt lun tng t.
Trong hp cht AlCl3, ion nhm kch thc nh b chn bi 3 ion chlor, bi vy nhit
si ca AlCl3 thp (81C). AlF3 si nhit cao hn 1000C v nhm khng b chn hon
ton. Ion bo c kch thc nh (B3+ = 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 SO42) 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 S6+ (0,29), Si4+ (0,39) v
P5+ (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 ra : rx
nm trong gii hn 0,22 n 0,41. Cc ion phc l: [SiO4]4, [PO4 ]3, [SO4]2 .

Tham kho 4.1.4, Tnh phn cc ca ion v quy tc Pauling cui 4.2.1.

45

Ion [SO6]6 v cu hnh [SO6]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 Ag6TeO6 (Te6+ = 0,56, ra : rx = 0,41) v orthoiodic H5JO6, v d Ag5JO6 (bn knh
J7+ Te6+). T s bn knh C4+ (0,2) trn bn knh oxy bng 0,15 tho mn s phi tr 3.
T c th thy, ion CO32 c kh nng tn ti, cn ion CO44th 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.

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
F

Li
Na
K
Rb
Cs

16

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

F
Li
Na
K
Rb
Cs

Br

0,1(18C)

Cation

Anion
Cl

Anion
Cl

Br

11

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=UL
U nng lng mng.

46

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 ra : rx 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.
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

CaF2

BaF2

AlCl3

PrCl3

ThCl4

SnI4

ho tan

1,0

6,1

0,0002

0,009

6,0

4,2

tt

tt

ra + rx

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 (SO4)2, (ClO4),
(PtCl6)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.

47

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 O2 v S2 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 (Pb2+) 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, PbCl2), nhm th hai cu trc phn t v lp d ho
tan (ZnCl2, CdCl2). Cc nguyn t sau cng c th lm kt ta bng S2 nh b sung
dihydro sulfur (v d ZnS).
Bng 5.22.
ho tan ca mt s mui
Ion
Na+

Cl

Br

1,0

6,1

11,3

Ag

14,0

Tl+

3,6

Mg2+
2+

Ca

6.10

4,5.10

9.103

8,5.104

2OH

SO42
10,6
6

1,3.10

6.104
2,19
2

1,3.10

1,5.104
2

2,5.10

48

Sr2+

6.104

3,3.102

Ba2+

6,3.106

2,5.101

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.
Bng 5.23.
S ph thuc t trng vo thnh phn ho hc ca cht kt tinh
Nhm khong vt

Khong vt

Olivin

Forsterit

Granat

Plagiocla

Spinel

Cng thc ho
hc
Mg2SiO4

T trng
3, 22

Fayalit

Fe2SiO4

4, 40

Pyrop

Mg3Al2Si3O12

3, 58

Almandin

Fe3 Al2Si3O12

4,32

Albit

NaAlSi3O8

2,62

Anorthit

Ca Al2Si2O8

2,76

Spinel

MgAl2O4

3,55

Magnetit

FeFe2O4

5.20

Chromit

FeCr2O4

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

49

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.
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 CO3 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 CO3 rng buc vi 2 nguyn t
Ca, v nhm CO3 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 CO3 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 CaCO3 ca calcit
c cc thng s a = 4,9908; c = 17,05951; tng ng, th tch mng c s bng
367,87433; 2 mng c s cha 12 n v cng thc CaCO3 tng ng vi th tch
735,74863. Trong khi mng c s trc thoi cha 4 vct CaCO3 ca aragonit c cc
thng s a = 7,968; b = 5,741; c = 4,959. Tng ng, th tch mng c s bng
226,84593; 3 mng c s cha 12 phn t CaCO3 tng ng vi th tch 680,53783.
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 CaCO3 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 CaCO3 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 CaCO3
Bin th
Calcit
Aragonit

Z
6
4

M, g
600,54
400,36

V, cm3

24

2,710

24

2,930

367,8743 10
226,8459 10

50

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)O4, 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
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 SiO4 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

Chng 6. Ha hc tinh th ca mt s
khong vt to
Trnh Hn
Ngy Tuyt Nhung
C s ha hc tinh th
NXB i hc quc gia H Ni 2006.
Tr 189 290.

T kho: Khong vt to , OLIVIN, GRANAT, silicat, nhm, BIOPYRIBOL,

PYROXEN, MICA, YROPHYLLIT-TALC, khong vt set.
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
Chng 6 HA HC TINH TH CA MT S KHONG VT TO .......3
6.1.
OLIVIN.......................................................................................................3
6.1.1 Cu trc tinh th......................................................................................3
6.1.2 c im ho hc....................................................................................5
6.2.
GRANAT ....................................................................................................8
6.2.1. Cu trc tinh th......................................................................................8
6.2.2. c im ho hc....................................................................................9
6.3.
NHM SILICAT NHM Al2SiO5 ...........................................................14
6.3.1. Silimanit AlIVAlVISiO4O ....................................................................15
6.3.2. Andalusit AlVAlVISiO4O .......................................................................15
6.3.3. Disten AlVIAlVISiO4O ...........................................................................16
6.4.
SILICAT O VNG..............................................................................17
6.4.1. Beryl Al2Be3Si6O18 ...............................................................................17

210

6.4.2. Cordierit (Mg,Fe)2Al4Si5O18.nH2O ........................................................19

6.4.3. Tourmalin
(Na,Ca)(Mg,Fe,Mn,Li,Al)3(Al,Mg,Fe3+)6[Si6O18](BO3)(O,OH)3(OH,F).................20
6.5.
BIOPYRIBOL...........................................................................................22
6.5.1. Tng quan ha hc tinh th micapyroxenamphibol..........................22
6.5.2. Mt s khong vt biopyribol................................................................25
6.6.
PYROXEN................................................................................................25
6.6.1. Cu trc tinh th....................................................................................26
6.6.2. c im ho hc..................................................................................30
6.7.
AMPHIBOL..............................................................................................34
6.7.1. Cu trc tinh th....................................................................................35
6.7.2. c im ho hc..................................................................................35
6.8.
MICA X2Y46Z8O20(OH,F)4.................................................................42
6.8.1. Cu trc tinh th....................................................................................42
6.8.2. Muscovit ...............................................................................................47
6.8.3. Phlogopit - biotit ...................................................................................49
6.9.
PYROPHYLLIT-TALC ............................................................................52
6.9.1. Pyrophyllit ............................................................................................53
6.9.2. Talc.......................................................................................................53
6.10. KHONG VT ST.................................................................................55
6.10.1.
Kaolinit ............................................................................................58
6.10.2.
Illit ...................................................................................................60
6.10.3.
Smectit .............................................................................................63
6.10.4.
Vermiculit ........................................................................................66
6.11. FELDSPAT ...............................................................................................71
6.11.1.
c im cu trc.............................................................................71
6.11.2.
c im ho hc .............................................................................76
6.11.3.
Song tinh ca feldspat.......................................................................79
6.12. THCH ANH, TRIDYMIT V CRISTOBALIT (SiO2)...........................82
6.12.1.
Cu trc tinh th ...............................................................................83
6.12.2.
c im ho hc .............................................................................84
6.13. MT S KHONG VT TO KHC..............................................85
6.13.1.
Calcit................................................................................................85
6.13.2.
6.13.3.
6.13.4.

Aragonit ...........................................................................................86
Barit .................................................................................................87
Apatit ...............................................................................................88

6.13.5.
6.13.6.

Corindon -Al2O3 ...........................................................................89

Spinel ...............................................................................................92

Chng 6
HA HC TINH TH CA MT S KHONG
VT TO
6.1.

OLIVIN
H trc thoi

(+) ()
forsterit Mg2SiO4

fayalit Fe2SiO4

mng

a = 4,75; b = 10,20
c = 5,98

a = 4,82; b = 10,48; c = 6,09

Z=4

Z=4

(Mg,Fe)SiO4

Nhm kh. gian

Pbnm

Pbnm

nh hng

Np = y; Nm = z; Ng = x

Np = y; Nm = z; Ng = x

Mt trc quang

(001)

(001)

dhkl chnh,

4,29 (10); 2,41 (8); 1,498 (7)

2,24 (7); 1,734 (8);

Olivin (Mg,Fe)2SiO4 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 Mg2SiO4 (forsterit) v Fe2SiO4
(fayalit). i lng d130 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
CaOMgOFeOH2O. Lot dung dch cng ph
bin nht ca h ny l FoFa. Tng i him l olivin thuc cc lot monticelitkirschteinit
v fayalittephroit Mn2SiO4.

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 SiO4 khng trng hp nhau, cu trc cho thy chng hng nh v hai pha i nhau dc
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 Mg2SiO4 (forsterit) v Fe2SiO4
(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 CaOMgOFeOH2O. Lot dung
dch cng ph bin nht ca h ny l FoFa. Tng i him l olivin thuc cc lot
monticelitkirschteinit v fayalittephroit Mn2SiO4.
S phn b ca Fe2+ v Mg2+ 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 M1 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 CaMgSiO4, 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 Mg2SiO4
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:
MgVI SiIV O3 MgVI 2 SiIV O4 + SiVI O2
enstatit

olivin

stishovit

MgVI2 SiIV O4 (olivin) MgVI Si2O4 (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,
tng hp thnh cng olivin y vi thnh phn (Fe0,7Mg0,3)2SiO4. 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.

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.

6.1.2 c im ho hc

Hnh 6.3
S chuyn pha olivinspinel
trong h Mg2SiO4 Fe2SiO4 nhit
o
o
800 C v 1200 C (theo Akimoto,
S. et al, 1971)

Hnh 6.4
Tng quan ca khong cch mt mng d130 v
thnh phn trong dy ng hnh forsteritfayalit

Thnh phn ca olivin bin i t Mg2SiO4 (forsterit) sang Fe2SiO4 (fayalit) c s trao
i lin tc gia Mg2+ v Fe2+ (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

SiO2

41,85

32,47

30,09

31,50

29,27

36,63

TiO2

0,07

0,34

0,00

0,00

Al2O3

0,00

0.02

0,00

0,04

0,07

Fe2O3

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

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
3+

0,007

0,000

0,000

Fe

0.004

Mg

1,976

0,602

0,046

0,078

0,098

0,815

Fe2+

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

2,02

2,00

1,99

1,92

2,05

2,02

(tr Si)

Thnh phn nguyn t chnh ngoi silic

Mg
98,0
30,3
2,3
4,0
5,0
Fe
2,0
68,7
97,3
58,0
1,7
Mn
0,0
1,0
0,4
38,0
93,3

74,9
19,2
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 Fe3+
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.
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
Sin Cao

Pn H

khang
SiO2

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
Fe
0,18
0,20
0,27
Mg
1,78
1,97
1,72
Ca
0,00
0,00
0,00
Ni
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
mg #
84,23
83,11
78,00

0,99
0,16
1,84
0,00
0,00

13,47
86,53

1,00
0,15
I,82
0,00
0,00

1,00
0,28
1,70
0,00
0,00

13,01
86,99

22,92
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, Fe2+ v Si tch khi v tr ca chng, m ng cho Fe3+, 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 Fe3+ v nhiu Fe2+ hn. Thnh
phn ca n c chlorit, smectit, goethit v calcit.
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:
2Mg2SiO4 + 3H2O Mg3Si2O5(OH)4 + Mg(OH)2
forsterit

serpentin

brucit

3Mg2SiO4 + 4H2O + SiO2 2Mg3Si2O5(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 CO2 tham gia phn ng th talc v magnesit c th hnh thnh:
2Mg3Si2O5(OH)4 + 3CO2 Mg3Si4O10(OH)2 + 3MgCO3 + 3H2O
v xa hn, phn ng serpentin ho c th nh sau:
6Mg2SiO4 + Mg3Si4O10(OH)2 + 9H2O 5Mg3Si2O5(OH)4

6.2.

GRANAT
H lp phng. Nhm khng gian Ia3d. Z = 8.
dhkl 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 X3 Y2 Z3 O12.
Pyrop
Almandin
Spesartin
Grosular
Andradit
Uvarovit
Hydrogrosular

Cng thc ha hc
Mg3Al2Si3O12
Fe3Al2Si3O12
Mn3Al2Si3O12
Ca3Al2Si3O12
Ca3 Fe2Si3O12
Ca3Cr2Si3O12
Ca3Al2 Si2O8(SiO4)1m(OH)4m

a()
11,459
11,526
11,621
11,851
11,996
11,996
11,85 12,16

Cu trc tinh th gm cc t din ZO4 v cc bt din YO6 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 XO8.
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.

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: CaFe1, CaMg1, CaMn1. Cc
dung dch cng almandin
spesartin vi lng nh pyrop v
grosular thng bt gp trong
phin bin cht cp thp v trung Hnh 6.5. Cu trc tinh th granat chiu trn mt (001)
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
Pyrop
Mg3Al2Si3O12
Almandin Fe3Al2Si3O12
Spesartin Mn3Al2Si3O12

Ugrandit
Uvarovit Ca3Cr2Si3O12
Grosular Ca3Al2Si3O12
Andradit Ca3Fe2Si3O12

10

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 Mg3Cr2Si3O12 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
Pyrop
Almandin
Spesartin Grosular

Granat st
Andradit

Bng 6.3
S liu ho phn tch ca granat
1
2
3

Granat crom
Uvarovit

SiO2

41,33

36,7

36,34

38,96

36,48

36,77

TiO2

0,28

0,75

0,10

0,71

0,50

Al2O3

21,83

21,4

20,25

19,93

6,80

8,36

Cr2O3

1,73

Fe2O3

1,44

0,92

3,43

21,94

5,85

FeO

9,00

29,9

7,30

3,25

3,33

34,51

0,03

0,56

0,22

1,31

0,00

0,27

13,72

MnO

0,44

1,14

MgO

19,60

0,90

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

11

S ion tnh trn 24 oxy

Ion

Si

5,919

5,882

Al

0,081

Al

3,604

5,981

5,918

5,986

5,923

0,118

0,019

0,082

0,014

0,077

3,925

3,909

3,486

1,311

1,510

Cr

0,196

1,747

Fe3+

0,155

0,114

0,392

2,709

0,709

Ti

0,030

0,090

0,012

0,081

0,062

Mg

4,184

0,215

0,297

0,065

Fe2+

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

Thnh phn (% mol) cc khong vt chnh

1

Almandin

17,4

67,4

17,1

Andradit

3,4

1,3

9,5

69,5

18,0

Grosular

2,5

26,3

79,2

21,4

36,2

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

Pyrop

5,8

7,8

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. 15380).
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 Na2O 0,03, K2O0,02, H2O 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. 17782).

12

Nhm t din (OH)4 cng c th thay th cho t din SiO4 (c th coi nh 4H+ thay
th cho Si4+) trong hydrogranat nh hydrogrosular Ca3Al2 Si2O8(SiO4)1m(OH)4m
vi m nm trong khong t 0 n 1. Khong vt cha ti 8,5% H2O.
Cation Ti4+ 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 Hnh 6.7. Thnh phn ca granat bin i theo cc vect trao i
chnh
Al hay Fe3+. Trong
hydrogranat, nhm SiO4 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%
Cr2O3 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 Alm66Gro25Py5Sp4. 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% Y2O3. 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

13

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 And50Gro50. 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
Fe3+ trong v tr bt din, mt phn th chn Si4+ trong khoang t din.
Melanit l Ti-andradit vi Fe3+ > Ti trong v tr bt din. Cn schorlomit (cha khong
15% TiO2) l Ti-andradit vi Fe3+ < 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 Ca3Al2Si2O8(SiO4)1m(OH)4m l khong vt thuc lot ng hnh
3CaO.Al2O3.3SiO2 3CaO.Al2O3.6H2O
vi thnh phn nm gia grosular v hibschit 3CaO.Al2O3.2SiO2.2H2O.
Bng 6.4
S liu ho phn tch ca granat ly t granulit Kan Nak (Kontum) [15]
#
414-S4
414-S4
VN415
VN415
VN415
Nhn

Ra/Bi

Nhn

Ra/Crd2

Ra/Crd2

VN803

VN803

Nhn

Ra/Ilm

SiO2

37,470

37,350

37,990

37,620

37,300

37,77

37,41

TiO2

0,020

0,010

0,040

0,000

0,030

0,06

0,29

Al2O3

21,560

21.460

21,790

21,780

21,940

22,19

21,83

Cr2O3

0,000

0,010

0,010

0,000

0,020

0,04

0,02

Fe2O3

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

Na2O

0,000

0,001

0,000

0,000

0,000

0,01

0,01

K2O

0,010

0,001

0,000

0,000

0,000

0,00

0,00

100,310

100,660

101,630

101,590

101,830

101,18

100,78

Tng

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
3+
Fe
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
Fe2+
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

14

XFe
Xalm
Xpyr
Xgro
Xspe

0,729
0,690
0,256
0,021
0,035

0,766
0,722
0,220
0,028
0,052

0,722
0,660
0,260
0,040
0,040

0,770
0,710
0,210
0,040
0,050

0,890
0,800
0,100
0,040
0,070

0,677
0,64
0,31
0,04
0,01

0,717
0,68
0,27
0,04
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 = Fe2+: (Mg2+ + Fe2+).
Xalm = Fe2+ : (Mg2+ + Fe2+ + Mn2+ + Ca2+);
Xpyr = Mg2+ : (Mg2+ + Fe2+ + Mn2+ + Ca2+)
Xgro = Ca2+ : (Mg2+ + Fe2+ + Mn2+ + Ca2+)
Xspe = Mn2+ : (Mg2+ + Fe2+ + Mn2+ + Ca2+)
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:
X3Y2(XO4)3m(OH)4m. Trong t nhin, cha tng gp khong bin thin thnh phn gia
hibschit v dng thiu silica 3CaO.Al2O3.6H2O. 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 Fe2+ 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 Kfeldspat 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) Fe2+ 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 3CaO3.Al2O3.6H2O 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 Al2SiO5 giu nhm, m cng thc ho tinh th AlIV-VIAlVISiO4O 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

15

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

Mt trc quang:

(010)

Ct khai:

(010)

c s, :

a = 7,48

Nm = y

Ng = z

b = 7,67

c = 5,77

2,49(7)

2,16(8)

Z=4
Nhm khng gian:
d hkl chnh, :

Pbnm
3,32(10)

1,579(7)

1,677(7)

Chui bt din AlO6 song song vi trc c v lin kt vi cc t din SiO4 v AlO4; 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 Fe3+, 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 AlVAlVISiO4O

Mt na lng nhm ca andalusit nm trong phi tr 5 vi cc hnh phi tr gn gin tip
vi nhau bng t din SiO4 (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 SiO4 v AlO5. Khong vt c t khi (17,13/ion
oxy) ln nht trong 3 bin th v nh vy bn vng iu kin p sut thp.
H trc thoi
nh hng:
Ct khai:
c s, :
dhkl chnh, :

()
Np = z
{110}
a = 7,79
Z=4
4,53(10)

Nm = y

Np = x

(110): (1 0) = 89
b = 7,90 c = 5,55
N.K.H: Pbnm
3,96(8) 2,76(9)

MTQ:(010)

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, Fe3+ thay cho Al nhiu nht cng cha t 2%.
Viridin ( phin chlorit-mica, theo Kramm U., 1973) l bin th giu mangan (16,75%
Mn2O3) cng cha n 0,82% Fe2O3. Ngi ta m t pha viridin vi 4,8% Fe3O3 v 19,6%
Mn2O3. Khong vt vi cng thc (Mn3+,Al)AlSiO5 cha 32,2% Mn2O3 cng c bit ti v
kanonait l tn gn cho pha u cui vi cng thc l tng Mn3+AlSiO5.

16

C th tng hp andalusit t kaolinit hay t Al2O3 + SiO2 450 650C v p sut hi

nc gia 0,6 v 2,0kbar. Biu trng thi ca Al2SiO5 (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 AlVIAlVISiO4O

H ba nghing
nh hng:
Ct khai:
Song tinh:
c s:

()
Ng: z trn(100) = 27 32, trn (010) = 5-8
Np:x trn (001) = 0 3; Phn gic nhn (100)
{100} hon ton
(100), trc ST (100) hay //y hay z, (001) a hp
a = 7,12; b = 7,85; c = 5,57; 89,98; 101,12; 106,01

dhkl, :

Z = 4; Nhm khng gian P1

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 AlO6 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 Al2SiO5 ( 25C)
nh sau:
V1, 3:
V2, cm 3/mol:

Andalusit
342
51,5

Silimannit
331
49,9

Disten
293
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 Fe3+ 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.

17

6.4.

SILICAT O VNG

Silicat o vng hay cyclosilicat cha cc vng t din SiO4, 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 BaTiSi3O9. Vng bn c trong vi khong vt rt him, v d
papagoit Ca2Cu2Al2Si4O12(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 Be3Al2Si6O18.

6.4.1. Beryl Al2Be3Si6O18

H su phng
Ct khai:
Song tinh:
c s, :
dhkl, :

Cu trc tinh th

()
{0001} khng hon ton
{31 4 1} {11 2 0} v {40 4 1}
a = 9,200 9,220; c = 9,187 9,249
Z = 2; Nhm khng gian P6/mcc
7,98(9); 4,60(5); 3,99(5); 3,25(10); 2,87(10)

18

Cu trc beryl (hnh 6.9) gm cc

vng su t din (Si6O18) 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, H2O, F, He, cc ion
Rb+, Cs+, Ca2+ 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 kim1+ U Be2+

Hnh 6.9. Cu trc tinh th beryl chiu trn (0001) (a)

v trn mt cha trc c (b)

hay

3 kim1+ + 1Al3+ U 3Be2+.

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 BeO4
v t din SiO4 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.

19

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:
3Be2+ 2Li+ + Si4+, Si4+ Be2+ + 2R+, Si4+ Al3+ + R+ v Be2+ + Si4+ 2Al3+.
Dng hn hp cc oxit SiO2, Al2O3 v BeCO3 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 Be2SiO4 v chrysoberyl BeAl2 O4. c nhiu phng php gip sn xut
emerald tng hp; ngoi cc oxit chnh cn c thm cht t ph gia Cr2O3. 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)2Al4Si5O18.nH2O

H trc thoi
nh hng :
Np Nm Np :
2V :
Ct khai:
a sc:

c s:

(Gi su phng) () (+)

Np = z, Nm = y, Ng = x; MTQ (010)
1,527 1,560; 1,532 1,574; 1,537 1,578
35 106
{100} trung bnh; {001}, {010} khng tt
{110}, {310} n gin, lin phin, dng vng
Mg-cordierit lt dy: Np vng/lc
Nm tm/lam tm, Ng lam nht
Vnh a sc quanh bao th zircon
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 Fe2+ 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

20

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 H2O, CO2, Ar, v.v Hm lng H2O+ 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 Fe2 Al4Si5o18 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 Fecordierit.

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 ()
ne:
no:
Lng chit sut:
T trng:
a sc:
mng c s:
dhkl, :

Dravit
1,612 1,632
1,634 1,661
0,021 0,029
3,03 3,18
Bin i mnh,
a = 15,8 16,0
Z=3
4,24(7); 4,00(7);

Schorl
1,535 1,650
1,660 1,671
0,025 0,035
3,18 3,22
hp ph :
c = 7,1 7,25
Nhm khng gian
3,51(7); 2,98(9);

Elbait
1,615 1,630
1,633 1,651
0,017 0,021
2,90 3,10
no > ne
R3m
2,58(10)

Cu trc tinh th
Tourmalin c cng thc tng qut l XY3Z6B3Si6(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
CdI2, 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
Y3(OH)4Si6O21 s gn vi nhau bng ion Al, B v Na. Ion B phi tr t din, chung mt nh
oxy vi t din SiO4 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

21

y (theo ngun dn). Cu trc tinh th ca tourmalin xydng trn c s cc vng Si6 O18
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 BO3 (khng phi B c phi tr t din). Nhm bt din (Li,Mg,Al)O4(OH)2 lin kt
vng Si6O18 vi nhm BO3. Cc nhm (Al,Fe,Mn)O5(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
XY3Z6B3Si6(O,OH)30(OH,F), trong v tr gip phn bit cc khong vt thnh vin nh
sau:
X

Elbait

Na

Al,Li

Al

Olenit

Na

Al

Al

Dravit

Na

Mg

Al

2+

Schorl

Na

Tsilaisit

Na

Fe

Buergerit

Na

Fe

Lidicoatit

Ca

Li,Mg

Al

Uvit

Ca

Mg

Al,Mg

Feruvit

Ca

Fe2+

Al,Fe3+,Mg

Ca

Mn

Al,Mn

Feridravit

Na

Mg

Chromdravit

Na

Mg

Al,Mn
3+

Al
Al
Al

3+

Fe

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 Fe2+ 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 Fe3+ thay cho Al trong Z khin cho tourmalin cha st ba tin trin thnh feridravit.
Buergerit l thnh vin cha Fe3+ ch yu trong Y, nhng ho tr vn duy tr; l do
(O,OH)30(OH,F) i thnh O30(OH,F). Nh c R+ , OH, F m ion ho tr ba R3+ bin ng.
Gii php nm trong hai trao i sau:
(1) (OH) + R2+ = R3+ + O2 v

(2) R2+ + R+ = R3+ + ;

Al3+ l cation R3+ 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: (Mg2Al)Al6B3Si6O30(OH) l sn phm
tng hp 700 800C. Tourmalin ca Na v Al l sn vt nhn to tip cn olenit l tng:
NaAl3 Al6 B3Si6O30(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.

22

Trong t nhin tourmalin bin i thnh muscovit, biotit hay lepidolit, mica, hoc chlorit
v kookcit LiAl4(Si,Al)4O10(OH)8.
Gi tr chit sut, lng chit sut v trng lng ring tng t l thun vi lng (Fe2 +
Fe + 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 no ln hn theo ne, 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%.
3+

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

Amphibol

M4

M3

M1

M2

T1

T2

(OH)

Mica

M1

M2

(OH)

Phi tr

12

6-8

Cation xp vo
tng v tr
thch hp

Na

Mn

Al

Al

Si

OH

Si

Al

Na
Ca

Ca
Mn

2+

Fe

Mn
2+

Fe

Ti
3+

Mg

Mg

Fe

Fe

Al

Al

Mg

Mg

Ti

Ti

Fe2+

2+

Cl

23

Bng 6.6
Quan h micapyroxenamphibol
2Pyroxen + Mica = Amphibol
2CaMgSi2O6 + Diopsit

Mg3Si4O10(OH) = Talc

Ca2Mg5Si8O22(OH)2
Tremolit

2MgMgSi2O6 + Enstatit

Mg3Si4O10(OH)2 = Talc

Mg2Mg5Si8O22(OH)2
Anthophillit

2NaAlSi2O6 + Jadeit

Mg3Si4O10(OH)2 = Talc

Na2Mg3Al2Si8 O22(OH)2
Glaucophan

2NaFeSi2O6 + Acmit

Fe3Si4O10(OH)2

Na2Fe3Fe2Si8O22(OH)2
Riebeckit

2CaMgSi2O6 + Diopsit

KMg3AlSi3O10(OH)2 = Phlogopit

KCa2Mg5AlSi7O22(OH)2
K-edenit

2CaMgSi2O6 + Diopsit

NaMg3AlSi3O10(OH)2 = Na-Phlogopit

NaCa2Mg5AlSi7O22(OH)2
Edenit

2CaAlAlSiO6+ Ca-tschermak

Mg3Si4O10(OH)2 = Talc

Ca2Mg3Al2Al2Si6O22(OH)2
Tschermakit

= Fe-Talc

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 AlVI, 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 AlVIAlIVMg1Si1 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
AlVI cng c th chim cc v tr M1 v M2 ca mica, M3 v M1 trong amphibol. Vect trao
i plagioclas NaSiCa1Al1 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).
FeMg1 v FeMn1 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.

24

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 > Fe2+ >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.
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.

25

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)10Si12O32(OH4)
v chui kp phc hp xen k gia chui kp 2 v chui kp 3 l:
chesterit

(Mg,Fe)17Si20O54(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.

6.6.

PYROXEN

26

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
nh hng

125 53 125

50 62

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
Nhm khng gian
d hkl,

Z = 16

Z=4

Pbca

C2/c

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 XYZ2O6,
cation X nm trong v tr tinh th hc M2; Y trong v tr M1 (ring Fe2+ tp trung trong v tr
tinh th hc M2 ca pyroxen trc thoi Pbca); Z ch Si4+ 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 Si2O6 ko di theo trc c. Trong
pyroxen thoi, bt din M1 bin dng nhiu hn so vi bt din M2.

6.6.1. Cu trc tinh th

Cu trc pyroxen da trn nhm chc chui n Si2O6 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

27

(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
M2; 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 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 CaMgSi2O6CaFeSi2O6 hedenbergit thuc h mt nghing v

28

enstatit MgSiO3 FeSiO3 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, En80 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 Di50Hs50.
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 En50Wo50 v Wo50Fs50 (ng vi hai trung im
hai cnh ca tam gic). Tng t, Di50Hd50 = Wo50En25Fs25 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 Fe2+) 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 NaFe3+Si2O6 v jadeit NaAlSi2O6. 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 LiAlSi2O6 l pyroxen tng i him, tm thy trong
pegmatit giu liti.
Cc thay th chnh xy ra trong pyroxen th hin bng cc vect:
FeMg1, CaMg1, AlVIAlIVMg1Si1 (tschermak)
Thay th quan trng p sut cao l vect jadeit:
NaAlVICa1Mg1
Ba vect u th hin trn hnh 6.13. Trao i FeMg l ca cc cp diopsithedenbergit
v enstatitferosillit. Cc vect CaMg1 v CaFe1 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.

29

Vect tschermak gp trong c pyroxen FeMg ln pyroxen calci, lm xut hin cc cng
thc u cui FeAlAlSiO6, MgAlAlSiO6 v CaAlAlSiO6; ln lt ng vi cc trao i Fe2+Si
AlVIAlIV, MgSi AlVIAlIV v CaSi AlVIAlIV. 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 Fe2+ c th thay th Mg2+ trong mi t l cho n gn 90% FeSiO3. 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% SiO2. Pyroxen trc thoi cha khng qu 1,5% CaO. Ferrosillit FeSiO3
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
Fe2SiO4 + SiO2
(= 2FeSiO3) l
pha bn vng hn. Trong s pyroxen
mt nghing, cc pha ca dy
clinoenstatit clinoferrosillit vi
cng thnh phn MgSiO3 FeSiO3,
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 CaMg1 v CaFe1
trong pyroxen, nh hnh 6.12 gii
thiu. Biu TX (hnh 6.14) cho
thy phm vi ca min gin on

30

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 CaMg1 t tc dng hn (v min gin on rng hn) so vi vect CaFe1.
Hnh 6.16 gii thiu quan h gia pyroxen natri v pyroxen calci thng qua cc vect thay th
jadeit NaAlVICa1Mg1 v plagioclas NaSiCa1 AlIV1.
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 NaFe3+Si2O6 l pyroxen quan trng khc. N lin quan vi diopsit bng s trao i
NaFe3+ CaMg v vi jadeit bng Fe3+
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 Catschermak 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

Hnh 6.17. Cc vect trao i gia pyroxen calci

(diopsit) v pyroxen natri (jadeit v acmit)

Thnh phn ho hc ca pyroxen c

th biu th bng cng thc tng qut XYZ2O6; trong , X ch Na+, Ca2+, Mn2+, Fe2+, Mg2+
v Li+ trong v tr tinh th hc M2; Y ch Mn2+, Fe2+, Mg2+, Fe3+, Al3+, Cr3+ v Ti4+ trong v tr
M1; ring Fe2+ ch tp trung trong v tr M2 ca pyroxen trc thoi Pbca. Cation X thng ln
hn cation Y. Z ch Si4+ 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)SiO3; khc hn vi pyroxen mt nghing c khong bin thin
rt ln v thnh phn ho hc. Pyroxen c th chia thnh ba ph nhm chnh :

31

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, Fe3+ 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 AlIV 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, Fe3+, 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 Mg1,4Mn0,6Si2O6 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)0,97Ca0,03SiO3.
Cc khong vt diopsit v hedenbergit to dy ng hnh hon ton gia CaMgSi2O6 v
CaFeSi2O6. 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 Fe3+ 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 NaCrSi2 O6 (kosmochlor) hay CaCrSi2O6. 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).

32

Bng 6.7
S liu phn tch ho ca pyroxen
Cu t
1
2
3

SiO2

48,81

52,70

48,18

49.68

49,46

48,02

TiO2

0,01

0,34

0,70

0,56

0,57

0,46

Al2O3

0,74

1,84

1,06

0,78

1,79

13,39

Fe2O3

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

Na2O

0,07

0,49

0,23

0,65

0,23

0,31

K2O

0,02

0,01

0,04

0,15

0,05

0,06

H2O

0,32

0,10

0,20

H2O

0,35

0,00

0,20

0,07

99,40

99,96

100,70

100,04

99,78

99,99

Tng

S ion tnh trn 6 oxy

Ion
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

Al

VI

0,026

0,027

0,000

0,000

0,028

0,338

Fe3+

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

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

0,001

0,000

0,002

0,008

0,003

0,002

2+

=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).

33

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]
Nm Hon

Nm Hon

Cc Pa

Simangkhang

Pn H

Pn H

SiO2

53,80

53,40

92,90

52,80

51,30

54,30

TiO2

0,15

0,20

0,43

0,09

0,27

0,11

Al2O3

1,10

1,11

1,47

1,72

3,96

0,64

Cu t

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

Na2O

0,30

0,37

0,31

0,86

1,11

0,30

Cr2O3

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
Ti
Al

IV

1,96

1,95

1,94

1,96

1,91

1,98

0,00

0,00

0,01

0,00

0,00

0,00

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

AlVI

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 Mn2+/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.

34

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

Np = x

Ng : z = 15 21

Ng : z = 28 10

(010)

(010)

(010)

nh hng
M.T.Q.
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 :

W0-1X2Y5Z8O22(OH,F)2;
vi W: Na+ v K+ v tr A; X: Ca2+, Na+, Mn2+, Fe2+, Mg2+ v Li+ ti v tr M4;
Y: Mn2+, Fe2+, Mg2+, Fe3+, Al3+ v Ti4+ v tr M1, M2 v M3; Z: Si4+ v Al3+ 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 Ca2Mg5Si8O22(OH)2 (hnh 4.5) v hornblendd, P21/m tm thy trong
cumingtonit v mt nhm trc thoi Pnma l ca cc khong vt ca dy anthophillit,
Mg7Si8O22(OH)2Fe2Mg5Si8O22(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,

35

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 Si4O11 (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)4O22(OH)2

36

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 Ca2 Mg5 Si8O22 (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
(Fe2+,Mg)7Si8O22(OH)2 hoc trc thoi nh trong anthophyllit (Mg,Fe2+)7Si8O22(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 Fe3+ tng thch vi M2. i
vi cc v tr nh M1, M2, M3, M4 s tng thch ca Fe2+ thay i tu loi amphibol. Bng
6.9 lit k kt qu phn tch ha hc ca mt s khong vt amphibol.

37

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:
FeMg1 v
Na AlVI Al2IV
1Mg1(Si2)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 AlVI Al2IV 1 Mg1(Si2)1= Na AlIV 1Si1 + AlVI AlIV Mg1Si1
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 Mg7Si8O22(OH)2
(anthophyllit hay Mg-cumingtonit)Fe2+7Si8O22(OH)2 (grunerit hay Fe-anthophyllit)
Ca7Si8O22(OH)2 (thnh phn u-cui gi nh). Cn nh, nhm pyroxen c h tng t l
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 Ca2 Mg5Si8O22(OH)2 v Fe-Actinolit Ca2Fe5Si8O22(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 Mgcumingtonit Mg7Si8O22(OH)2 n gn Fe2Mg5Si8O22(OH)2.
+ Dy cumingtonitgrunerit bao hm cc thnh phn mt nghing v pht trin t gn
Fe2Mg5Si8O22(OH)2 n Fe7Si8O22(OH)2.

38

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
NaAlIV1Si1 v tschermak AlVIAlIVMg1Si1 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 FeMg1, v sau l trao i Fe3+
Al3+ cho dung dch cng glaucophan Na2Mg3Al2Si8O22(OH)2Na2Mg3Fe2Si8O22(OH)2
riebeckit.
Hnh 6.22 khng gii thiu mi lin h ny. Ht thy amphibol natri vi hm lng
Fe3+/Al trung gian u mang tn chung l crosit. Amphibol natri khng c vect thay th
tng t vect pargasit, bi v AlVI v Fe3+ 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 AlVI c
li th r rt so vi AlIV. 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.

39

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

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 NaAlSi2 O6CaAlVIAlIVSiO6 Ca-tschermak (pyroxen nhn to). ng cho ni
tremolit v glaucophan l c ch trao i glaucophan hay jadeit (CaMg Na(M4)AlVI) v
song song vi vect diopsit CaMgSi2O6NaAlSi2 O6 jadeit.
Ni chung, c ch thay th vi s gp mt ca Na(M4) v AlVI thng c xu hng xy
ra p sut cao; cn Na(A) v AlVI 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.

40

Bng 6.9
S liu phn tch ho ca amphibol
4

SiO2

1
58,54

54,73

51,40

50,70

42,70

TiO2

0,21

0,74

0,32

0,45

0,79

1,46

3,88

5,45

18,26

Fe2O3

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

Al2O3

MgO

24,45

17,94

11,22

15,89

8,42

CaO

13,59

12,76

10,17

12,22

10,65

Na2O

0,27

1,44

I,67

2,80

1,42

K2O

0,12

vt

0,09

1,23

0,49

H2O

2,12

2,27

1,90

2,08

2,13

H2O

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 Cr2O3 0,48, NiO 0,06 per cent).
5. Aluminotschermakite: kyanniteplagioclasquartzchlorite
Lukmanier, Switzerland (Leake, B. E., 1971, Min. Mag., 38, 389-407).

schist,

S lng ion tnh trn 24 oxy

Ion

Si

7,918

7,731

7,543

7,284

Al

0,082

0,243

0,457

0,716

1,78

Al

0,044

0,215

0,207

1,35

0,022

0,082

0,035

0,04

Ti

6,21
=8

3+

0,022

0,430

0,196

0,344

Fe

2+

0,042

1,134

2,453

0,792

1,470

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

Na

0,071

0,394

1,599

0,780

0,401

(1,2,3,5)

0,021

0,018

0,225

0,091

3 (4)

OH

1,913

2,139

1,861

1,993

2,069

Fe

Flodalera,

41

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,Mgamphibol, 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)4O10(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).
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, H2O, cation trao i + H2O, 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
TO lin tc
B trng
Kaolinit
H2O+cation trao i
Haloysit
TOT lin tc
B trng
Pyrophyllit
Cation
Mica

Silicat lp ba bt din
Serpentin

Talc
Mica

42

Gin on

H2O+cation trao i

Montmorillonit
Chlorit

H2O zeolit

6.8.

Vermiculit
Chlorit
Paligorskit Sepiolit

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 Mg3(OH)6 (trong phlogopit) hay
gibbsit Al2(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).

43

Cc trnh t ph bin nht l 1M (chu k c gm 1 lp), 2M1, 2M2 (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, 2M1 v 2M2 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.

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, d060 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

Xem thm 5.3.3. a dng.

44

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:
KNa1
FeMg1

AlVIAlIVMg1Si--1
NaAlIV 1Si1

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 MgSiAl1 Al1, ngc vi thay th
tschermak.

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:

45

X2Y46Z8O20(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, Fe3+ v Ti.
Mica hai bt din
Bng 6.11
Cng thc ho hc gn ng ca mica
Mica
ph
bin
Mica gin

Muscovit
Paragonit
Glauconit
Margarit

X
K2
Na2
(K,Na)1,22,0
Ca2

Y
Al4
Al4
(Fe,Mg,Al)4
Al4

Z
Si6Al2
Si6Al2
Si77,6Al1,00,4
Si4Al4

Mica ba bt din

Mica
ph bin
Mica gin

Phlogopit
Biotit
Zinnwaldit
Lepidolit
Clintonit

X
K2
K2
K2
K2
Ca2

Y
(Mg,Fe2+)6
(Mg,Fe,Al)6
(Fe,Li,Al)6
(Li,Al)5 - 6
(Mg,Al)6

Z
Si6Al2
Si65Al23
Si67Al21
Si65Al23
Si25 Al53

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 % H2O+, 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 2M1) 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.

46

Bng 6.12
S liu phn tch ho ca mica
1

SiO2

48,42

49,50

40,95

38,32

34,73

49,76

TiO2

0,87

0,08

0,82

2,89

2,83

0,22

Al2O3

27,16

3,50

17,28

15,21

16,67

25,31

Fe2O3

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

0,01

vt

0,22

1,21

0,42

MnO

MgO

vt

4,90

22,95

13,17

5,95

0,09

CaO

vt

1,16

0,00

0,74

0,00

0,05

4,35

Li2O
Na2O

0,35

0,13

0,16

0,20

0,41

0,61

K2O

11,23

8,58

9,80

8,01

9,35

9,20

0,62

0,91

3,96

4,04

vt

H2O

4,31

5,69

4,23

H2O

0,19

0,61

0,48

99,91

97,86

100,13

O F

97,86

99,87

S ion tnh trn 24 O(OH,F,Cl)

Si
6,597
7,550
5,724
Al
1,403
0,450
2,276
8,000
8,000
8,000

Ca
Na
K

F
OH

2,81
0,33

100,39

101,95

0,39

1,67

100,00

100,00

100,28

5,677
2,323
8,000

5,499
2,501
8,000

6,641
1,359
8,000

100,00

0,26
99,91

Al
Ti
3+
Fe
Fe2+
Mn
Mg
Li

3,01
0,07

2,959
0,089
0.672
0,091

3,811

0,092
1,952
2,044

0,179
0,009
2,433
0,319
0,001
1,114

4,055

0,038
1,670
1,708

0,562
0,084
0,340
0,276

4,776

6,038

0,034
1,746
1,780

0,335
0,322
0,166
1,930
0,028
2,980

5,761
0,117
0,057
1,514
1,688

0,610
0,337
0,417
2,873
0,162
1,404

5,803

0,126
1,889
2,015

2,623
0,023
0,080
0,357
0,047
0,018
2,336
5,484
0.007
0,157
1,567
1,731

3,916
3,916

4,000
4,000

0,278
3,946
4,224

4,000
4,000

0,456
3,179
3,635

1,672
2,503
4,175

1.
Muscovit, low-grade psammitic schist, Inverness-shire, Scotland, UK (Lambert,
R.St.J., 1959, Trans. Roy. Soc.Edingburgh, 63, 553-88).

47

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 P2O5 0,61, CO2 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 P2O5 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 Rb2O 0,67 Cs2O 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
2M1, mt quang trc chia i gc gia cc tia y.

6.8.2. Muscovit
H mt nghing () K2 Al4 [Si6Al2O20](OH,F)4
Np = 1,552 1,576
Ng Np =
c s

Nm = 1,582 1,615

2V = 28 47

0,036 0,049
a5,2; b9,0
Loi 2M1 :
Loi 1M :

nh hng
dhkl,

Ng = 1,587 1,618

Np : z = 0 5;
9,95 (10); 3,37(10);

c20; 93;

Z=2; N.K.G. C2/c

c10; 101;
Nm : x = 1 3;
2,66 (8); 2,45 (8);

Z=1; N.K.G. C2/m

MQT (010).
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 2M1. 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 d002 trong cc hiu ng nhiu x tia X; nhm
thay th silic lm tng hiu ng d060.
c im ho hc

48

Muscovit c s thay th ng hnh ca K bng Na, Rb, Cs, Ca, Ba; ca AlVI bng Mg,
Fe , Fe3+, Mn, Li, Cr, Ti,V v (OH) bng F. (Si6 Al2) c th bin thnh (Si7 Al)
2+

Muscovit hng c thnh phn gn nh l tng vi cha thp ca mangan v liti.

Muscovit vi cha Fe2O3 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 SiO2. 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% Cr2O3. Mica vi hm lng liti
cao l khong vt lepidolit; tuy nhin, Li2O 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 SiO2, MgO,
H2O v mt t K2O.
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 Fe2+ thay th Al trong v tr bt din.
Hydromuscovit c cha H2O cao v K2O thp; K+ c th b thay bng ion (H3O)+. 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 K2OAl2O3SiO2H2O cho thy cc phn ng:
muscovit sanidin + corindon + nc

(1)

muscovit + thch anh sanidin + Al2SiO5 + 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<
lc, lc nht

Nm
lc

<

Ng
lc sm

49

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 ()K2(Mg,Fe2+)64(Fe3+,Al,Ti)02 [Si65Al23O20 ](OH,F)4
c s
Nhm k.g.
nh hng
dhkl,
Np, Nm, Ng
Ng Np

a~5,3; b~9,2; c~10,3; ~100; Z = 1

C2/m
Nm = y; Ng : x = 0 9; MQS: (010)
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)
1,5301,625; 1,5571,696; 1,5581,696
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

K2 Fe4 Al2Si4 Al4O20(OH)4 v

Eastonit

K2Mg4 Al2Si4 Al4O20(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

50

khoang bt din c nh. Cu trc ca phlogopit giu fluor thng cha cc vng trt t gn,
Fe2+ 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 d001 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)5Al v
Si5Al3. 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 Si4+(?). 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
2Al3+ + = 3(Fe2+/Mg)
Sau titan vo ch ca st v magnesi thay cho nhm theo s :
3Ti4+ + 3 = 4Al3+ + 2
Nu nhm b titan thay th ht, th chnh l:
Ti4+ + = 2(Fe2+/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 Fe3+ gi l lepidomelan. Do nguyn nhn

51

cu trc, lng st ng k trong khong vt u-cui annit phi l Fe3+ 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 Fe2+, 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 H2O/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 H2O/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 + 2H2O
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 2M1 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

SiO2

38,13

36,42

37,44

40,67

38,13

40,45

Al2O3

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

TiO2

5,87

2,72

6,77

0,93

4,76

0,92

CaO

0,02

0,06

0,08

Na2O

0,28

0,58

0,58

K2O

0,04
0,62

0,51

0,53

10,18

9,67

9,50

9,39

9,88

9,31

Cr2O3

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

94,77

95,77

94,93

94,44

# Theo Jaques et al, 1986

Thnh phn (%) ca ion tnh trn 20 oxy
(do tc gi sch ny tnh thm)

52

Si
Al
Z
Fe
Mg
Ti
Cr
Y
Ca
Na
K
Ba
X

5,04
2,02
7,06
1,04
3,68
0,58
0,00
5,30
0,00
0,06
1,72
0,02
1,80

5,04
2,06
7,10
1,48
3,76
0,28
0,00
5,52
0,00
0,14
1,70
0,02
1,86

5,00
2,04
7,04
0,92
3,68
0,68
0,00
5,28
0,00
0,14
1,62
1,62
1,76

5,34
2,04
7,38
0,52
4,62
0,08
0,00
5,22
0,00
0,14
1,56
0,00
1,70

5,06
2,08
7,14
1,12
3,70
0,46
0,00
5,38
0,00
0,12
1,68
0,00
1,80

5,24
2,06
7,30
0,46
4,62
0,08
0,16
5,32
0,00
0,12
1,54
0,00
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 Fe2+ v Fe3+. 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

53

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
Al4[Si8O20](OH)4

Mt nghing hay ba nghing

Np, Nm, Ng
Ng Np
nh hng
c s

Nhm k.g.

1,552 1,556; 1,586 1,589; 1,596 1,601

0,050; 2V = 53 62
Ng = y; Nm // x; MTQ (010)
H mt nghing ();
a 5,17; b 8,96
c 18,68; 100
Z=2

C1

dhkl,

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 H2O + 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 ()

Mg6 [Si8 O20](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)

c s

H ba nghing

H mt
nghing

a 5,29

a 5,29

b 9,15

b 9,15

c 9,45

c 18,9

90,5

100

99

54

99
Nhm k.g.

Z=2

Z=1

C2/c hay
Cc

C1

nh hng
dhkl,

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
SiO2
TiO2
Al2O3
Cr2O3
FeO
MnO
NiO
MgO
CaO
Na2O
K2O
+
H2O
Tng

61,71
0,09
0,30

4,09

29,09

95,28

62,5

0,50
0,10
1,32
0,01
0,12
30,08

4,70
100,05

3
62,69

0,49

0,76

29,93
0,30
0,03
0,02
5,48
99,70

S ion tnh trn n v cng thc

Si
7,946
7,945
7,913
Al
0,046
0,055
0,073
7,99
8,00
7,99
Z
Al
0,020

55

Ti
Cr
Mg
2+
Fe
Ni
Mn
Ca
Na
K
OH
Y

0,009

5,582
0,440

4,00
6,03

0,010
5,835
0,140
0,120
0,001

3,99
6,13

5,631
0,080

0,041
0,003
0,003
4,61
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; H2O 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 dhkl ca talc thng ln
hn, chng hn d060 = 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 dhkl.
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:
Mg3Si4O10(OH)2 3MgSiO3 + SiO2 + H2O
Talc c th hnh thnh t hn hp MgO v SiO2, 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.

6.10. KHONG VT ST

56

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 SiO4 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

SiO2

46,20

44,46

51,25

56,59

51,46

50,25

34,04

TiO2

0,09

0,15

0,17

0,06

0,05

0,03

Al2O3

39,20

36,58

23,53

20,06

2,20

4.44

15,37

Fe2O3

0,23

0,36

2,02

3,19

24,70

0,50

8,01

0,07

0,33

FeO
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

Na2O

0,09

0,01

0,05

2,17

1,06

0,76

0,00

K2O

0,21

0,51

7,61

0,45

0,24

0,10

0,00

13,80

13,38

5,87

13,67

15,34

7.25

19,93

H2O+

4,05

5,26

10,76

Tng

99,95

100,12

100,02

100,00

99,80

99,69

99,93

H2O

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

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

Fe

Mg

0,64

Ca

0,006

0,02

0,088

0,100

0,240

0,272

0,023

0,06

1,357

0,079

0,047

0,019

Na

0,015

0,00

0,014

0,578

0,318

0,220

1,46

0,76

0,60

0,51

57

OH

7,980

8,04

4,000

4,000

4,000

H2O

4,00
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 P2O5 0,18).
3. Illite, Aymestry Limestone, Showers End, Worcs, UK (Srodon, J. & Karlinger, M. R.,
1986, Clays and Clay Min., 34,368-78. Includes P2O50,02. 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, 23155).
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)2O5 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

Ca, Na

Mg

Nc xen
lp

Haloysit:
1 lp
Phn t H2O

Mt t trong
hydromica

1 lp H2O
(Na-smectit)/2 lp H2O
(Ca-smectit)

2 lp
phn t
H2O

Thng s
c

7,1
(haloysit:10)

10

Khng xc nh, Casmectit : 15

Khng xc nh,
14,4 khi ngm
nc

Glycol

Ch haloysit
hp ph

Khng tc dng

2 lp pt glycol, 17

1 lp pt glycol, 14

Cng thc

Al4Si4O10(OH)8

KAl4(Si,Al)8

M (Y ,Y )46

3+

2+

2+

3+

2+

M (Y ,Y )4-6

58

ho hc

t bin i

O20(OH)4

(Si,Al)8O20
(OH)4.nH2O

(Si,Al)8O20
(OH)4.8H2O

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

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

Chit sut
Np,
Ng, 2V

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 () Al4 [Si4 O10] (OH)8
Np,Nm,Ng
NgNp; 2V
c s :

1,553 1,565; 1,559 1,569; 1,560 1,570;

0,006; 24 59
a 5,15; b 8,95; c 7,4; 91,8; 104,8; 90.
Z = 1; NKG:

nh hng :
dhkl chnh, :

C1

Nm : x = 1 3,5; Ng = y. MQT (010)

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 (Si4O10)4 hnh thnh t nhng t din SiO4 gn kt thnh l
(do cc vng lc gic ghp li). y cc t din gn nh ng phng, nh ca chng u
hng v pha i. Ti tm lc gic gia 6 ion oxy nh ny c ion OH, cc anion O2 v

59

OH y to nn y ca l bt din dng gibbsit (OH)6Al4(OH)2O4. 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 d001 tng t
7,2 c trng ca kaolinit ln khong 10. Haloysit mt nc c d001 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
d001 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,
rutil v mica. Mc du c mt s khong vt ba bt din, ng cu trc vi kaolinit nh

60

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. AlIV thay th cho Si nhiu hn. Mt na trong
4H2O trong cng thc ca n (Al2O3.2SiO2.4H2O) 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/cm3, 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/cm3 tu
cha nc. T trng ca dickit v nacrit l khong 2,6g/cm3 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 () K1,5 1,0 Al4 [ Si6,5 7,0 Al1,5 1,0 O20 ](OH)4
Np,Nm,Ng :

1,54 1,57

1,57 1,61

1,57 1,61

61

2V < 10

NgNp ~ 0,03
nh hng :
c s (loi 1M) :

Nm ~ (001)
a ~ 5,2;

b ~ 9,0;

d001 ~ 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:
KYAl4(Si8-Y, Ali)O20(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
AlO4(OH)2 kiu gibbsit nm gia hai l t din (Si,Al)O4 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, d001 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 d001 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,Fe2+) thay cho AlIV. Trong
hydromuscovit, lng kali thp hn 2K/vct; in tch m di d s trung ho bng ion
hydroxoni H3O+ xen vo gia cc lp hay bng vic thay th mt s anion O2 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 AlVI; 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

62

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:
d001 =10 ch loi cu trc TOT. d060 xp x 1,50 l ca cu trc hai bt din.
Cng vch I002 > I001:4 cho thy nhm (khng phi st) l cation chnh ca v tr
bt din.

63

Ir = (I001 : I003)mu kh : (I001 : I003)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
1
2

Ba bt din ( Ca,Na)0,7(Mg,Fe,Al)4[(Si,Al)8O20](OH)4.nH2O
H mt nghing ()
Np,Nm,Ng
Ng Np, 2V
nh hng
mng c s,

1,48 1,61; 1,50 1,64; 1,50 1,64

0,01 0,04; hu ht gc nh
Np (001); Nm = y; M.T.Q.(010)
a = 5,2; b = 9,1 9,2;
d001 = 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)O4 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, AlVI 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 Ca2+ hay Na+ xen gia cc lp.
Khong cch d001 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 d001 ln lt bng khong 15,5 n 19. Montmorillonit natri c 1 lp (d001
12,5), 2 lp (d001 15,5), 3 lp (d001 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 d001 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.

64

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 d001 l tng gi tr ca hai thnh phn. Vi trt t tng phn, cu trc c
thng s d001 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 d001 tr
thnh c s ca dng khong vt. Di tc dng ca glicerol, haloysit v vermiculit trng
n, khin cho d001 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, d001 gim cn khong
10. Nung n 500C lm cho d001 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 Fe2+, 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:
Al4YMgY(Si8XAlXO20)(OH)4.XX + 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, Fe3+ v Fe2+ 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 Fe2+ 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

X (cation trao i)

65

Hai bt din
Pyrophyllit

Si8

Al4

Montmorillonit

Si8

Al3,3 Mg0,7

(0,5Ca,Na)0,7

Beidelit

Si7,3Al0,7

Al4

(0,5Ca,Na)0,7

Si7,3Al0,7

3+
Fe4

(0,5Ca,Na)0,7

Talc

Si8

Mg6

Saponit

Si7,2Al0,8

Mg6

Nontronit
Ba bt din

(0,5Ca,Na)0,8

Hectorit

Si8

Mg5,3Li0,7

Sauconit

Si6,7Al1,3

Zn4-6(Mg,Al,Fe )20

(0,5Ca,Na)0,7
3+

(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 Fe2+; 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 Fe3+ trong saponit c
th sinh ra do Fe2+ 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 H2O
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.

66

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, d001 tng t gi tr 12 khi n bo ho K+ v NH4+, 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 d060 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,Fe3+,Al)6,0(Si,Al)8O20(OH)4.nH2O
Np,Nm,Ng:
Ng Np :
nh hng:
c s:

1,520 1,564
0,02 0,03
Np (001)
a 5,3

1,530 1,583
2V = 0 18
M.T.Q. (010).
b 9,25

1,530 1,583

c 14,4

67

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, Fe3+) 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 H2O to mng li gi lc gic. Vermiculit t nhin thng cha 2 mng
li H2O 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 H2O 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 d001 khong
14,3. Trong iu kin m h v nhit tng, Mg-vermiculit ch cn gi c mt lp
phn t nc v d001 gim cn 11,7. iu kin trung gian ng vi d001 13,8 v 90.
Ca-vermiculit v Na-vermiculit vi hai lp phn t nc c d001 ln lt bng 14,9 v 14,8.
Gi tr ln hn ca d001 ( 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 d001 bin ng, l thuc
vo bn cht v s lng ca cation xen lp. Gi tr d001 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 2M1.
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 H2OMg2+H2O 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 AlIV 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 (AlVI,Fe3+) 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

68

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+, NH4+ 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 Fe2+, ri Al, Fe3+, 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)0,60,9Mg4,55,0(Fe3+AlVI)1,51,0Al2,22,6Si5,82,4O20(OH)4.(H2O)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 H2O2, 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 H2O 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.

69

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, d001 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)O2]n. Khi cc t din khng cha nhm, b khung s
trung ho in tch. iu ny hin thc trong nhm khong vt silica SiO2 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) SiO2 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 Si4+ v Al3+ trong silicat khung vi t l thay i:
1/2 (AlO4)/(SiO4) 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
[(Al12Si32)O8](12)
cha cc cation K+, Na+ v Ca2+ 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;

70

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 Na3 K(AlSiO4)4 thuc h su phng. Khung AlSiO4 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 (AlO4) hoc hng dnh xung di (SiO4). 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(AlSi2O6) 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 H2S, NH3, CCl4, 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)O4 do
cation cc loi trung ho nh Ca2+, Na+, K+, Ba2+, Sr2+, Mg2+. Cng thc ho hc ca zeolit
thng p ng t s sau:
(CaO+Na2O+K2O+BaO+SrO+MgO)/Al2O3 = 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 Ca2+
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)5O10 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, Na2Al2Si3 O10.2H2O. H trc thoi.

Mesolit, Na2Ca2(Al2Si3O10)3.8H2O. H mt nghing.

71

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,Na2)Al2Si7 O18..6H2O. H ba nghing.

Stilbit, (Ca,Na2,K2)Al2Si7O18.7H2O. 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, BaAl2Si6O16.6H2O. H mt nghing.

Chabazit, (Ca,Na2)Al2Si4O12.6H2O. H su phng.
Faujasit, (Na2,Ca)Al2Si4O12.6H2O. 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

C1

C2/m

P1

N.K.G.

C1

C1

6.11.1.c im cu trc
Tng t cc bin th a hnh SiO2, cu trc feldspat gm mt khung v hn ca cc t
din SiO4 v AlO4. 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 Si4+ (trn n v
cng thc) b thay th bi mt Al3+, cu trc c th c trung ho bi mt K+ hay mt Na+.
Tng t, khi hai Si4+ (trn n v cng thc feldspat) b Al3+ thay th, in tch ca khung c
th c cn bng bi cation ho tr hai Ca2+. iu ny c th hin nh sau:
Khung Si4O8 Na(AlSi3O8) Ca(Al2Si2O8).
Khung c bn ca cu trc feldspat c th minh ho bng s cu trc ca sanidin, bin
th nhit cao ca KAlSi3O8 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.

72

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 KAlSi3O8, c i xng ba
nghing (nhm khng gian C 1 ) 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 KAlSi3O8 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 C 1 . Albit nhit thp c trt t cao

73

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 C 1 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 KNa1. 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 (NaAlSi3O8KAlSi3O8) 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 San50Al50 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
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

74

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 700oC tr xung

Dung dch cng gia KAlSi3O8 v CaAl2Si2O8 rt hn ch. Mc du vy, cc thnh phn
ca dy plagioclas NaAlSi3O8 v CaAl2Si2O8 v thc cht l cc dung dch cng hon ton
iu kin nhit cao. Cng thc tng qut ca plagioclas vit thnh:
Na1xCax(Si3xAl1+ x)O8,
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).

75

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
thy

nguyn

Hnh 6.33
Biu TX ca feldspat plagioclas
S cc vng gin on cn gy tranh ci

Min gin on peristerit nm ti vng An3An1015, 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
SiO2
TiO2

65,76

64,66

63,68

4
64,46

5*

6*

67,27

66,97

0,08

0,01

0,04

Al2O3

20,23

19,72

19,57

18,55

18,35

18,75

Fe2O3

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

Na2O

8,44

3,42

1,56

0,49

6,45

7,88

K2O

16,07

7,05

5,39

3,29

11,72

14,21

0,37

0,18

0,04

0,08

0,01

H2O

0,08

0,04

0,06

0,08

0,03

Tng

100,35

100,12

100,46

99,94

100,35

100,31

H2O

76

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

0,024

0,011

0,040

0,019

0,124

0,118

3+

Fe
Ti

0,011

0,001

0,005

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

0,748

2,727

3,430

3,797

1,609

1,226

Ba

0,044

0,024

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, 45394).
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 An40 v anorthit An90. Nm ngay trn n
l hai min khc: Boggild (An48--66) v Huttenlocher (An66--87). Khi gim nhit , cc min
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 KAlSi3O8 n
NaAlSi3O8. Nhng thng thng chng cng cha mt lng nh CaAl2Si2 O8 trong dung
dch cng, thng t hn 5% trong vng gia Or100Ab0 v Or60Ab40, nhng cc thnh vin
giu natri cha nhiu An hn. Cc ion khc c th c lng hn ch nh Ba, Ti, Fe2+, Fe3+,
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

77

ln hn 2% Ba, feldspat mi c coi nh feldspat giu bari, y Ba thay th cho K. Tng

t, Fe3+ v Ti thay cho Al; Mg, Fe2+, Sr, Mn thay cho Ca.
Trong orthoclas v microclin thng c t Ti, nhng Fe2O3 c th c mt lng ng
k: c l, i vi feldspat kim bnh thng Fe2O3 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

SiO2

63,89

64,42

63,56

64,19

63,32

63,62

Al2O3

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

CaO

0,12

0,29

0,86

0,07

0,30

Na2O

0,68

0,38

3,90

0,60

3,27

5,23

K2O

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

0,03
0,96

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

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

Na

0,24

0,12

1,36

0,20

Ca

0,00

0,04

0,16

0,00

3,76

3,72

2,48

3,60

2,76

1,88

Ba

0,00

0,00

Sr

0,00

0,00

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

0,00
1,16

1,84
0,16

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 Na2O 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).

78

Bng 6.20
S liu phn tch ho ca plagioclas
1
2
3

SiO2

67,84

67,41

64,10

58,10

52,42

49,06

44,17

TiO2

0,00

0,00

Vt

0,09

Vt

Al2O3

19,65

20,50

22,66

26,44

29,70

32,14

34.95

Fe2O3

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

Na2O

11,07

10,97

9,89

6,48

4,01

2,57

0,79

0,29

0,36

0,05

1,10

0,21

0,17

0,05

0,56

0,15

0,17

0,03

0,13

0,84

0,06

0,06

0,03

0,17

100,37

100,75

100,27

99,65

99,95

100,24

K2O
H2O

H2O

0,30

Tng

99,80

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

0,004

0,009

0,018

0,005

0,049

0,037

0,078

16,05

16,02

15,98

16,00

15,97

15,97

16,00

3+

Mg

0,011

0,026

0,065

0,008

0,022

0,055

Fe

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

2+

Ca

0,152

0,614

1,505

2,467

3,020

3,723

0,066

0,080

0,011

0,252

0,049

0,040

0,012

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

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, 6827).
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).

79

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 NaAlSi3O8 n
CaAl2Si2O8. Mc d vy, plagioclas thng cha mt lng thay i c th ti 5% orthoclas
Na-plagioclas. Nhiu ion
KAlSi3O8, t anorthit n labrador v tng u v pha u
3+
2+
c th c mt mt lng hn ch, nh Ti, Fe , Fe , 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 Fe3+, thay th ng hnh cho Al. Lng Fe2+ 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.

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

80

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.

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

81

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
Trc song
Tn lut
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 )

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)

Song song

a hp

Phc hp
Albit-Carlsbad

(010)

a hp

Albit-Ala

(010)

-nt-

Manebach-periclin

(001)

-nt-

Manebach-Ala

(001)

-nt-

X-Carlsbad

(100)

-nt-

X-periclin

(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
(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.

82

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

2V

40 90

nh hng

Ng Np = 0,003

Np = y; M.T.Q. (100)

T trng
Song tinh

2,65

2,26

2,33

(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

4,913

5,01

5,04

5,03

4,97

7,13

8,74

5,404

5,47

8,24

8,22

6,92

P3121

P6222 hay

C2221

P63/mmc

P41212 hay

Fd3m

c s ()

N.K.G.

P6422

P43212

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.

83

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 SiO4, 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
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

84

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 Al3+ thay cho Si4+. 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 NaAlSiO2 ra i vi 50% trng cha Na. Tng t, ion
Na lp y mt na trng ca cristobalit s lm xut hin pha nhit cao l carnegieit. i
vi NaAlSiO2 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% SiO2. 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

85

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
Li2O
Na2O
K2O
Trong
0,0005
0,0004 0,0002
m khi
0,0004
0,0000 0,0000
Hng
0,0038
0,0011 0,0001
Amethist

Al2O3
0,0008
0,0008
0,0001
0,0001

Fe2O3
0,0000
0,0005
0,0003
0,0216

MnO2
0,00002
0,00002
0,00005
0,00000

TiO2
0,0001
0,0002
0,0015
0,0004

2) Tridymit v cristobalit. Trong t nhin c thnh phn khc so vi cng thc SiO2 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 Al3+ cho Si4+ trong
phi tr t din.

6.13. MT S KHONG VT TO KHC

6.13.1.Calcit
H ba phng
Np, Ng
Ng Np:
Ct khai
Song tinh
c s
dhkl ()

()
1,486 (1,550); 1,658 (1,740)
0,172 (0,190)

{1011} hon ton

{1012} rt thng gp
su phng; a = 4,990; c = 17,061
mt thoi : a = 12,84; = 101,92; Z=8
3,04(10); 2,29(2); 2,10(2); 1,913(2); 1,875 (2)

Anion phc (CO3)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 CO2. Khi c mt ion H+, nhm chc carbonat tr nn khng
bn v d dng phn hu cho CO2 v nc:
2H+ + CO32 = H2O + CO2.
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

86

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 (CO3)2--. Nhm ny nm
trong cc mt phng vung gc vi trc chnh c (= L3). Xen k gia cc mt phng ny l mt
cha cation Ca2+ phi tr 6 vi O2. 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 CO3 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% MgCO3. 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 MnCO3 v thc nghim cho thy con s ny c th t 50%. D Fe2+ 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 (CO3)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, CaCO3 c
hai bin th a hnh vi c hai loi cu trc.

6.13.2.Aragonit
H trc thoi

()

Np: 1,5301,531

Nm: 1,6801,681; Ng : 1,6851,686

Ng Np: 0,1550,156
Np=z, Nm=x, Ng=y; M.T.Q.: (100)
Ph bin, M.S.T.{110}; Gi su phng
a = 4,96; b = 7,97; c = 5,74; Z = 4, N.K.G. Pmcn
3,04(9); 2,71(6); 2,36(7); 1,975(10); 1,880(8)

2V: 18 18,5
nh hng:
Song tinh:
c s:
dhkl ():

c im cu trc
Khi nhm CO3 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.

87

Cu trc aragonit c cc cation Ca2+ 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 CO3 nm thnh lp ti
khong gia cc lp Ca. Cc nhm CO3 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 CO3 u cho
cc mt i xng i qua: mt gng m v mt trt c. Giao tuyn ca chng l trc xon bc
hai 21, n xuyn tm nguyn t carbon ca CO3. Dc trc 21 // z ny cc tam gic CO3 thay
nhau hng nh v pha OY v +OY.
Mc du ion Ca xp theo h su phng, chnh s phn b ca nhm CO3 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 Pbaragonit 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 CaSO4 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
{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 SO4

Np :1,636 1,637;
Ng Np : 0,012
nh hng :
a sc :
c s :
dhkl,

Nm : 1,637 1,639; Ng : 1,647 1,649

2V = 37
Np = z; Nm = y; Ng = x
Hp ph: Ng > Nm > Np
a = 8,88; b = 5,45; c = 7,15; Z = 4; N.K.G. Pnma
3,90(6); 3,44(10); 3,32(7); 3,10(10); 2,12(8)

Cu trc tinh th

88

Barit c cu trc bao gm cc cation ho tr hai c ln phi tr vi anion phc SO4. 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 BaSO4
Anglesit PbSO4
Celestin SrSO4

8,88
8,48
8,36

5,45
5,40
5,35

7,15
6,69
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 BaSO4. 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%
CaSO4 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 H2S 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 BaCl2, 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 SrSO4 t hm lng 50%.

6.13.4.Apatit
H su phng
Np = 1,624 1,666
Mu a sc:
mng c s:
dhkl, :

()
Ng = 1,629 1,667
yu v trung bnh
a = 9,32 9,64;
Z = 2;
2,80(10); 2,77(4); 2,70(6);

Ca5 (PO4)3 (OH,F,Cl)

Ng Np = 0,001 0,007
hp ph : Np > Ng
c = 6,78 6,90
N.K.G. C63 / m
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

89

Khong vt nhm apatit

Fluorapatit Ca5(PO4)F
Chlorapatit Ca5(PO4)3Cl
Hydroxilapatit Ca5(PO4)3OH
Carbonatapatit Ca5(PO4,CO3OH)3(F,OH)

a,
9,36
9,61
9,42
9,32

c,

c/a

6,88
6,78
6,88
6,90

0,735
0,703
0,730
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 (PO4)3 hnh t din vi P5+ ln hn cht t so vi S6+.
Tt c cc phosphat u ly nhm anion phc ny lm n v kin trc c s. Nhng t din
tng t nh (AsO4)3 v (VO4)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 PO4 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 PO4, 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 (PO4)3 v
(CO3OH)3.
c im ho hc
Apatit thuc hng khong vt vi thnh phn ho hc kh gn vi cng thc
Ca5(PO4)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 (SiO4) v (SO4) 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: CO2 v F ti hn 1% mol. ahlit l tn ca mt
apatit khc, ngoi cht t fluor, n cn cha nhiu CO2.Tuy rng vai tr ca dioxit carbon vn
l vn cha ng ng trong cu trc apatit, nhng s thay th (CO32 + F) cho (PO4)3 l s
thay th thng xuyn. CO2 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

90

Ba phng
Np,Ng, NgNp :
mng c s:

()
1,760 1,764; 1,768 1,772; 0,008 0,009
asp = 4,76; csp = 12,98. abp = 5,130; = 5517

dhkl () :

Zsp = 6; Zbp = 2; NKG R 3 c

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 AlO6. Dc theo cc hng
ta OX, OY v OU chng ghp i qua cnh chung, dc OZ l cc bt din AlO6 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 Al3+ c nguyn nhn
ha tr tnh in (xem quy tc Pauling, 4.2.2) hay nng lng ca mi lin kt Al3+ O.
V ion nhm Al3+ c su ion oxy vy quanh, ha tr tnh in ca mi lin kt bng (3:6)
1/2. Mi oxy O2 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 Al3+ bn trong bt din
c xu hng dch khi mt chung, nhm trnh lc y tng h.
-Al2O3 l corindon t nhin, cc bin th khc nh -Al2O3 su phng, c th cha kim
loi kim, Ca v -Al2O3 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
Fe3+ (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 Fe3+ v Fe2+; chng hn mu mu vng (s 5) c n 9,17% Fe2O3 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

SiO2

0,20

0,01

0,137

0,542

0,94

0,028

0,064

0,058

TiO2

0,32

0,03

0,00

0,00

0,37

0,120

0,055

0,029

Al2O3

98,84

99,8

98,8

97,5

89,40

99,023

99,379

98,927

Cr2O3

Vt

0,06

0,945

1,81

0,000

0,000

0,020

Fe2O3

0,14

0,16

0,0147

0.0252

0,000

0,076

0,019

9,17

FeO

0,06

V2O5

0,00

0,0320

0,0582

NiO

Vt

0,00

0,00

0,000

0,000

0,000

MnO

-nt-

0,00

0,00

0,033

0,000

0,000

0,01

91

MgO

0,04

0,01

0,02265

0,0328

0,000

0,027

0,012

CaO
CuO

0,34

0,00
0,00237

0,0016

0,003

0,000

0,001

CdO

0,0168

0,0351

MoO3
Na2O

0,00448

0.0117
0,002

0.013

0,000

K2O

0,018

0,000

0,013

P2O

0,008

0,000

0,019

99,235

99,614

99,098

99,94

100,1

99,97

100,02

99,88

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(CO3)2 + KAl2[AlSi3O10](OH)2 = 3CaCO3 + KMg3[AlSi3O10](OH)2 + Al2O3 + 3CO2
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

92

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 Al2O3 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 TiO2 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

MgAl2O4

Hercynit

8,135

Fe2+Al2O4

Gahnit

8,08

ZnAl2O4

Galaxit

8,28

MnAl2 O4

8,383

MgFe2 O4

Magnesioferrit

3+

2+

3+

Magnetit

8,396

Fe Fe2 O4

Maghemit

8,34

-Fe2 O3

Ulvospinel

8,536

Fe Ti2O4

Franklinit

8,43

ZnFe2 O4

Jacobsit

8,505

MnFe23+O4

Trevorit

8,34

NiFe2 O4

3+

2+

3+

3+

Magnesiochromit

8,334

MgCr2O4

Chromit

8,378

Fe Cr2O4

2+

{111} ph bin

Song tinh
mng

Z=8; NKG Fd3m

dhkl :

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
Mg
Fe
Zn
Mn
Ni

Lot Al
Spinel
Hercynit
Gahnit
Galaxit

3+

Lot Fe
Magnesioferrit
Magnetit
Franklinit
Jacobsit
Trevorit

Lot Cr
Magnesiochromit
Chromit

c im cu trc
Cng thc tng qut ca spinel AB2O4 (hay A8 B16O32, 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

93

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)O4. 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 Al2O3 v Fe32+ O3 vo cc dy dung dch cng, vi cc pha u cui l Al2O3 v - Fe32+ O3 . 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 R2+ v ha tr ba R3+; cng thc tng qut nh sau:
a() = 5,790 + 0,95R2+ + 2,79R3+

c im ha hc
Lot spinel
Spinel, MgAl2O4 l khong vt ph bin nht trong lot ny. T spinel n hercynit
Fe2+Al2O4 l dy ng hnh lin tc (hnh 6.37). y l nhng spinel vi lng Fe2+ thay th

94

cho Mg, vi t s Mg : Fe2+ t 3 n 1, gi l pleonast hay ceylonit. Km c th thay th Mg,

cho dy ng hnh t spinel n gahnit ZnAl2O4;; 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.
Trong s spinel mu sc khc nhau (bng 6.25), mu mu giu Cr2O3 (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 XY2O4 v Y(YX)O4.
Hercynit, Fe2+Al2O4. Cng vi s thay th Fe2+ Mg, mt lng ng k Fe3+ 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
Fe2+Al2O4Fe3O4 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, ZnAl2O4. 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, MnAl2O4. Thnh vin him
hoi nht ca lot spinel ny c c hai c
ch thay th: Mn Fe2+ v Al Fe3+.
Lot magnetit
Magnesioferrit, MgFe23+O4. Trong t
nhin Fe2+ 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, Fe2+ Fe23+O4. 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

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

95

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 vo cu trc tinh th magnetit v hnh thnh dy thnh phn lin tc
gia n vi ulvospinel, Fe2TiO4. 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% Fe2O3; khi h nhit,
pha ny tch ra di dng hematit dc {111} ca magnetit. Nghin cu cn bng pha ca h
ba cu t FeOFe2O3TiO2 cho thy magnetit l pha kt tinh nguyn thy trong khong 0
12% trng lng ca TiO2 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 Fe2O3.TiO2 (trc thoi) FeO.2TiO2,
2) hematit Fe2O3 ilmenit FeO.TiO2 (ba phng) v
3) magnetit FeO.Fe2O3 ulvospinel Fe2TiO4.
Trong dy th ba ny, dung dch cng lin tc tn ti nhit cao, di 600C dung
dch b phn r.
Maghemit, -Fe23+O3. Magnetit c mt s dng cha d Fe23+O3 c xu hng tr thnh
pha u cui trong dy dung dch cng. Trong dy Fe3O4 Fe2O3 ny s ion kim loi tnh trn
32 ion oxy c th nh hn con s l thuyt, tc l < 24, i vi Fe3O4 tinh khit, v i vi
pha u cui maghemit c th l 21,33. Maghemit khng bn v bin i thnh hematit (Fe2O3) khi nung; nhit chuyn pha thay i t 200 n 700C ty thuc vo iu kin sinh
thnh ca mu.
Ulvospinel, Fe22+TiO4. 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 Fe2TiO4 tng hp l 1470C.
Franklinit, ZnFe23+O4. y l oxit ca st
ha tr ba v km, ZnFe23+O4 thng cha t l
ng k Mn2+ ti v tr ca Zn.
Jacobsit, MnFe23+O4. 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, NiFe23+O4. Mt t Mg v Fe2+ c
th thay th ng hnh cho Ni.

Hnh 6.38
H FeO-Fe2O3-TiO2 ng m ch dung dch
cng ch yu. ng nht ni cc pha cng sinh
nhit thp

Lot chromit
Magnesiochromit, MgCr2O4. Khong vt ny lun lun cha mt lng ng k Fe2+.
y l kt qu thay th ng hnh ca st v magnesi, n din ra lin tc cho n tn chromit

96

vi hm lng ca st ln hn so vi magnesi (hnh 6.37). MgCr2O4 cng c kh nhiu Al v

Fe3+ ti v tr ca Cr (bng 6.25, mu 6).
Chromit, FeCr2O4. 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
SiO2
0,28

TiO2
0,02

Al2O3
64,85
60,7
38,18
Cr2O3
0,03

Fe2O3
2,21

FeO
13,70
34,7
10,50
MnO
0,01
0,2
0,08
MgO
18,74
4,3
3,30
ZnO
27,71
CaO
0,1

NiO
Na2O
K2O
P2O
Tng
99,84
100,0
99,77

4
0,27
Vt
0,21

68,85
30,78

6
0,09
0,32
21,6
43,8

19,0
4,3

33,2
43,2

Vt

0,2

6,86
9,26
0,30
17,2

Vt

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

0,005

8,373

0,337

7,263

1,248

Cr
3+

Fe

15,886

Ti

0,003

15,97

16,01

16,01

16,05

5,678

1,434

1,148

0,087

6,199

Fe

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*

Mg
2+

4,154

0,058
15,86

* 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).

97

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]

SiO2

0,029

TiO2

0,199

0,205

0,246

0,206

0,164

0,216

0,006

Al2O3

71,015

69,953

70,857

71,276

71,539

70,948

73,948

Cr2O3

0,514

1,214

0,443

0,163

0,150

0,284

0,234

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

V2O3

0,246

0,038

NiO

0,053

Na2O

0,000

K2O

0,030

P2O

0,024

Tng

99,999

99,999

100,001

S lng ion tnh trn 32 oxy

4+
Si
Ti4+
0,03
0,03
0,04
3+
Al
16,00
15,84
15,92
3+
Cr
0,08
0,18
0,07
3+
V
Tng
16,11
16,05
16,03
2+
Fe
0,16
0,24
0,16
Mg2+
7,68
7,75
7,77
2+
Ca
0,01
0,01
0,01
2+
Mn
0,04
Tng
7,89
8,00
7,94
2+

99,503

99,999

0,03
16,03
0,03

0,02
16,11
0,02

19,09
0,05
7,76
0,01
0,04
7,86

16,15
0,28
7,44
0,02
0,03
7,77

* K c Ni , K v P vi mi ion 0,01.

99,895

0,03
15,94
0,04
0,04
16,05
0,12
7,77
0,02
7,91

99,178

0,00
0,04
16,92
0,00
16,96
0,82
5,71
0,00
0,01
6,57*

Ph lc 2
H thng tun hon nguyn t ho hc vi cc loi cu trc tinh th

IA
1

IIA

C: xp cu lp phng,

I: lp phng tm khi,

K: cu trc vi s phi tr

K = 8 N (N l s hiu nhm)

IIIB

IVB

VB

VIB

VIIB

H: xp cu su phng,

M: cu trc phn t,
L: cc cu trc khc.

VIIIB

IB

IIB

IIIA

IVA

VA

VIA

VIIA

VIIIA

He

K
M
2

10

Li

Be

Ne

11

12

13

14

15

16

17

18

Na

Mg

Al

Si

Cl

Ar

C
3

C
4

19

20

21

22

23

24

25

26

27

28

29

30

31

32

33

34

35

36

Ca

Sc

Ti

Cr

Mn

Fe

Co

Ni

Cu

Zn

Ga

Ge

As

Se

Br

Kr

37

38

39

40

41

42

43

44

45

46

47

48

49

50

51

52

53

54

Rb

Sr

Zr

Nb

Mo

Tc

Ru

Rh

Pd

Ag

Cd

In

Sn

Sb

Te

Xe

H
6

56

57

72

73

74

75

76

77

78

79

80

81

82

83

84

85

86

Cs

Ba

La

Hf

Ta

Re

Os

Ir

Pt

Au

Hg

Tl

Pb

Bi

Po

At

Rn

359 360

55

87

88

89

Fr

Ra

Ac

Ph lc 3
Bn knh hu hiu (tnh bng ) ca cc ion ph bin trong khong vt

I
+

II

III

3+

Li

Be

0.59 (4)
0.74 (6)
0.92 (8)

0.16 (3)
0.27 (4)
0.45 (6)

0.11 (4)
0.27 (6)

2+

3+

IV
C

4+

- 0.08 (3)
0.15 (4)
0.16 (6)
4+

Na

Mg

Al

Sl

0.99 (4)
1.02 (6)
1.18 (8)
1.24 (9)
1.39(12)

0.57 (4)
0.72 (6)
0.89 (8)

0.39 (4)
0.48 (5)
0.54 (6)

0.26 (4)
0.40 (6)

2+

3+

Ca

Sc

1.38 (6)
1.51 (8)
1.55 (9)
1.59 (10)
1.64 (12)

1.00 (6)
1.12 (6)
1.18 (9)
1.23 (10)
1.34 (12)

0.75 (6)
0.87 (8)

2+

3+

4+

Tl

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

5+

3+

2+

Rb

Sr

1.52 (6)
1.61 (8)
1.66 (1)
1.72 (12)

1.18 (6)
1.26 (8)
1.36 (10)
1.44 (12)

2+

Zr

0.90 (6)
1.02 (8)

0.82 (6)
0.78 (7)
0.84 (8)
0.89 (9)

3+

4+

Cs

Ba

La

Hf

1.67 (6)
1.74 (8)
1.81 (10)
1.85 (11)
1.88 (12)

1.35 (6)
1.42 (8)
1.47 (9)
1.52 (10)
1.61 (12)

1.03 (6)
1.16 (8)
1.22 (9)
1.27 (10)

0.71 (6)
0.76 (7)
0.83 (8)

2+

2+

Cr

Mn

Fe

Co

Nl

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

0,62 (6)
Cr4+
0,41 (4)
0,55 (6)
Cr6+
0.26 (4)

0.83 (6)
0.96 (8)

0.74 (6)
0.90 (8)

0.55 (4)
0.69 (6)

Mn

0.63 (4)
0.78 (6)
0.92 (8)

0.65 (6)

Fe

3+
4+

Mn
0.53

4+

2+

5+

4+

3+

4+

Zn

Ga

Ge

0.46 (2)
0.77 (6)

0.60 (4)
0.74 (6)
0.90 (8)

0.47 (4)
0.55 (6)
0.90 (8)

0.39 (4)
0.53 (6)

2+

Cu

3+

2+

Cu

4+

2+

2+

3+

VI
2

VII

- 0.10 (3)
0.13 (6)

1.36 (3)
1.38 (4)
1.40 (6)
1.42 (8)

1.31 (4)
1.33 (6)

5+

Cl

0.17 (4)
0.29 (5)
0.38 (6)

1.84 (4)

1.81 (6)

3+

6+

0.12 (4)
0.29 (6)
2

As

Se

0.58 (6)

1.98 (6)

Br

1.96 (6)

5+

As

0.34 (4)
0.46 (6)

0.57 (4)
0.65 (5)
0.73 (6)

0.65 (6)
0.78 (8)

V
5+

4+

3+

Nb

Mo

Rh

Pd

Ag

Cd

In

Sn

Sb

Te

0.64 (6)
0.78 (7)
0.84 (8)
0.89 (9)

0.65 (6)

0.60 (6)

0.64 (4)
0.86 (6)

1.15 (6)
1.28 (8)

0.58 (4)
0.74 (6)
0.90 (8)

0.62 (4)
0.80 (6)
0.92 (8)

0.69 (6)
0.81 (8)

0.76 (6)

2.21 (6)

2.20 (6)

5+

6+

Mo

0.41 (4)
0.59 (6)
6+

4+

Ta

Re

0.64 (6)
0.69 (7)
0.74 (8)

0.42 (4)
0.51 (5)
0.60 (6)

0.63 (6)

Re

7+

0.38 (4)
0.53 (6)

2+

2+

5+

Sb

0.60 (6)
2+

3+

Ft

Hg

Pb

Bl

0.80 (6)

0.96 (4)
1.02 (6)
1.14 (8)

1.19 (6)
1.29 (8)
1.35 (9)
1.40 (10)

0.96 (5)
1.03 (6)
1.17 (8)