Phan Th Hong Oanh

Tp ch KHOA HC HSP TPHCM

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KHO ST CC PHN NG NG KT TA
CACBONAT, OXALAT Sr - Mn
PHAN TH HONG OANH*

TM TT
Cc phn ng ng kt ta cacbonat v oxalat ca h hai kim loi Sr2+- Mn2+
c nghin cu kho st hiu sut kt ta. iu ch c cc sn phm ng kt
ta cacbonat v oxalat stronti - mangan c t l mol Sr2+:Mn2+ 1 dng cho qu trnh tng
hp gm t SrMnO3 c cu trc perovskite.
T kha: ng kt ta, SrMnO3, cacbonat, oxalat, perovskite.
ABSTRACT
Investigation on the carbonate or oxalate coprecipitation reactions of Sr-Mn system
The coprecipitation reactions of Sr2+-Mn2+ system with carbonate or oxalate agent
were studied in order to investigate the precipitation efficiency. The coprecipitation
products of strontium manganese carbonate and oxalate with the molar ratio of
Sr2+:Mn 2+= 1 were obtained and they are used for the synthesis of ceramic from SrMnO3
which has perovskite structure.
Keywords: coprecipitation, SrMnO3, carbonate, oxalate, perovskite.

1.

M u
Trong nhng thp nin gn y, cng vi s pht trin khng ngng ca cc thit
b k thut v cc phng tin vin thng, nhu cu v vt liu gm in/t cht lng
cao ngy cng ln. Vic tm kim cc phng php mi khc vi phng php gm
sn xut gm cht lng cao, gi thnh h ngy cng thu ht s ch ca cc nh khoa
hc. 2
Cc phng php ng kt ta hay ng to phc (gi chung l phng php
precursor), phng php thy nhit, phng php tch dung mi... rt c quan tm,
c bit l phng php ng kt ta. l v vi phng php ny, cc cation kim
loi s c khuch tn vo nhau n mc nguyn t, khong cch gia cc cation
o

trong h phn ng gim xung ch cn khong vi A , iu ny lm tng kh nng phn

ng ca cc cu t, cho php to c sn phm ht mn, n pha v c ng nht
cao nhit tng i thp.
Tuy nhin, do nh hng ca nhiu yu t nh tch s tan, lc ion, kh nng to
phc ca cc cation kim loi vi cc tc nhn kt ta... , cc kt ta thu c thng
kh c thnh phn xc nh nh mun 1. Trong bi bo ny, chng ti trnh by kt
qu kho st cc phn ng ng kt ta to cacbonat Sr2+- Mn 2+ v oxalat Sr2+- Mn2+.
*

TS, Trng i hc S phm TPHCM

S 43 nm 2013

Tp ch KHOA HC HSP TPHCM

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Khi nhit phn trong iu kin thch hp, cc cacbonat v oxalat s phn hy to
SrMnO3 c cu trc perovskit 3, 4. to c perovskite c cng thc hp thc
SrMnO3, sn phm ng kt ta cacbonat hay oxalat stronti - mangan cn phi c t l
mol Sr2+ : Mn2+ = 1 : 1. Do , chng ti kho st hiu sut kt ta v t l Sr2+: Mn2+
trong cc kt ta thu c.
2.
Thc nghim
Cc ion Sr2+, Mn2+ c ng kt ta di dng cacbonat SrMn(CO3)2 v oxalat
SrMn(C2O4)2. Cc kt ta ny c gi l cc precursor v s c dng lm nguyn
liu cho qu trnh nung kt to perovskite.
2SrMn(CO3)2.nH2O + O2

t 2SrMnO3 + 4CO2 + nH2O

0

2SrMn(C2O4)2.mH2O + 3O2 t 2SrMnO3 + 8CO2 + mH2O

Cc kt ta cacbonat Sr2+-Mn2+ v oxalat Sr2+-Mn2+ c phn tch xc nh
thnh phn xc lp s ph thuc gia t l mol Sr2+ : Mn2+ trong pha rn v t l mol
Sr2+ : Mn2+ trong dung dch ban u, t c th iu ch cc cacbonat Sr2+-Mn2+ v
oxalat Sr2+-Mn2+ c thnh phn nh mun.
Trn th trng, cc ha cht cha ion cacbonat CO32 v ion oxalat C2O42 ph
bin l (NH4)2CO3, Na2CO3, K2CO3, (NH4)2C2O4, Na2C2O4, K2C2O4, v H2C2O4.2H2O.
Nu s dng (NH4)2CO3 v (NH4)2C2O4 lm tc nhn ng kt ta, ion amoni s
to phc cht tan vi cc M2+ nn s lm gim lng kt ta, v vy chng ti khng s
dng hai ha cht ny.
Trong cc hp cht cn li, cc cht c tan ln hn [5] s c la chn, l
Na2CO3 lm tc nhn kt ta cacbonat v K2C2O4 lm tc nhn kt ta oxalat.
Lng cacbonat v oxalat dng kt ta c thay i kho st nh hng ca
lng cht kt ta n hiu sut phn ng.
3.
Kt qu v tho lun
3.1. Kho st hiu sut kt ta
kho st hiu sut kt ta cacbonat, chng ti chun b cc dung dch cha
hn hp cc mui Sr(NO3)2, Mn(NO3)2 c t l mol Sr2+: Mn2+ lun bng 1 v dng
dung dch Na2CO3 thc hin phn ng kt ta. Sn phm thu c l cht bt mu
trng xm, c lc, ra, sy kh 100 oC trong 3 gi; ngui, cn khi lng v tnh
hiu sut kt ta. Kt qu thu c khi thay i lng cacbonat trnh by bng 1.

Phan Th Hong Oanh

Tp ch KHOA HC HSP TPHCM

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Bng 1. Hiu sut kt ta khi thay i lng CO32

Th
nghim
1
2
3
4
5

K hiu
mu
A1
A2
A3
A4
A5

Sr2+: Mn2+: CO32

1 : 1 : 2,0
1 : 1 : 2,2
1 : 1 : 2,4
1 : 1 : 2,6
1 : 1 : 2,8

CO32 d
(% mol)
0
10%
20%
30%
40%

Hiu sut kt ta
(%)
88,57
97,99
97,41
97,35
97,51

Tng t, t cc dung dch cha hn hp mui Sr(NO3)2, Mn(NO3)2 vi t l mol

Sr : Mn 2+ lun bng 1 v dung dch K2C2O4 chng ti thc hin phn ng kt ta
oxalat. Sn phm thu c l cht bt mn mu hng rt nht, c lc, ra, sy kh,
ngui nh trn v cn khi lng tnh hiu sut kt ta. Kt qu thu c khi
thay i lng oxalat C2O42 c trnh by bng 2.
2+

Bng 2. Hiu sut kt ta khi thay i lng C2 O42

Th
nghim
1
2
3
4
5

K hiu
mu
B1
B2
B3
B4
B5

Sr2+: Mn2+ : C2 O42

1 : 1 : 2,0
1 : 1 : 2,2
1 : 1 : 2,4
1 : 1 : 2,6
1 : 1 : 2,8

C2O42 d
(% mol)
0
10 %
20 %
30 %
40 %

Hiu sut
kt ta (%)
89,61
99,63
99,40
99,36
99,56

Bng 1 v 2 cho thy: Nu dng d cht kt ta 10% mol th hiu sut kt ta

tng khong 10% so vi trng hp dng lng cht va . Khi tng lng d cht
kt ta, hiu sut kt ta thay i khng ng k. V vy, chng ti chn dng d 10%
mol tc nhn cacbonat hoc oxalat (ng vi cc mu k hiu A2 v B2).
3.2. Kho st t l Sr2+ : Mn2+ trong cc kt ta A2 v B2
Do nh hng ca tch s tan, lc ion v s to phc trong dung dch, khi kt ta
ng thi cc ion kim loi t dung dch, t l mol ca cc ion kim loi trong kt ta c
th s khc so vi t l mol ca cc ion trong dung dch ban u lm nh hng n
cng thc hp thc ca vt liu cn iu ch giai on sau. Trong phn ny, chng
ti tin hnh kho st t l Sr2+:Mn 2+ trong cc kt ta A2 v B2 qua cc bc:
- Bc 1. Ha tan 1g kt ta bng dung dch HCl 1 M. nh mc thnh 25ml.
Chun xc nh tng Sr2+ + Mn2+ trong dung dch bng EDTA vi cht ch th ET00
trong dung dch m pH = 10. Dung dch s chuyn t mu nho sang xanh lam.
Chun 3 ln, sau ly gi tr trung bnh. Kt qu:
Dung dch t A2 c C( Sr 2 Mn2 ) = 0,145 M.
Dung dch t B2 c C( Sr 2 Mn2 ) = 0,113 M.

Tp ch KHOA HC HSP TPHCM

S 43 nm 2013

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- Bc 2. Dng dung dch H2SO4 m c ko Sr2+ t tng ra di dng kt ta

SrSO4. Lc tch kt ta, sau nh mc dung dch lc v chun bng EDTA vi
cht ch th ET00 trong m pH = 10 (t mu nho sang mu xanh lam). Chun 3 ln
ly gi tr trung bnh. Kt qu:
Dung dch t A2 c CMn 2 = 0,0737 M.
Dung dch t B2 c CMn2 = 0,0581 M.
T tng Sr2+ + Mn2+ v nng Mn2+ bit, s tnh c nng Sr2+ tng
ng trong dung dch A2 l CSr 2 = 0,0689 M v trong dung dch B2 l CSr 2 = 0,0549 M.
Vy trong kt ta A2, t l mol Sr2+ : Mn2+ = 1 : 1,07; v trong kt ta B2, t l mol
Sr : Mn2+ = 1 : 1,05.
Kt qu t l mol Sr2+ : Mn 2+ thu c trong cc kt ta cacbonat v oxalat c sai
lch i cht so vi t l mol ca chng trong dung dch ban u. Sai s mc ny
c th quy cho sai s thc nghim, do trong qu trnh th nghim c tin hnh cc giai
on lc, ra...
Nh vy, iu ch cc precursor cacbonat v oxalat, c th i t cc dung dch
mui nitrat c t l mol Sr2+ : Mn2+ = 1 v dng tc nhn kt ta d 10% mol.
y, mc i vo kt ta ca hai ion Sr2+ v Mn2+ nh nhau, th hin t l
mol ca chng trong kt ta xp x t l mol ca chng trong dung dch ban u, c
gii thch l do cc tch s tan ca chng chnh lch nhau khng nhiu: MnCO3 10 -10,74,
SrCO3 10 -9,96 v MnC2O4 10 -6,3, SrC2O4 10-6,8 .[5]
4.
Kt lun
- nghin cu cc phn ng ng kt ta cacbonat v oxalat ca h hai kim loi
Sr2+- Mn 2+.
- iu ch c cc sn phm ng kt ta cacbonat v oxalat stronti - mangan
c t l mol Sr2+ : Mn2+ 1 dng cho qu trnh tng hp gm t perovskite SrMnO3.
2+

1.
2.
3.
4.

5.

TI LIU THAM KHO

Phan Th Hong Oanh (1996), Nghin cu s hnh thnh ferit Mn-Zn bng phng
php ng kt ta oxalat, Lun n Tin s, H Ni.
Phan Vn Tng (2007), Vt liu V c, Trng i hc Khoa hc T nhin, i
hc Quc gia H Ni.
Robert J. Bell, Graeme J. Miller, John Drennan (2000), Influence of synthesis route
on the catalytic properties of La1-xSrxMnO3, Solid State Ionics, 131 (3-4), pp.211220.
Marjan Marisek, Klementina Zupan, Tanja Razpotnik, Jadran Macek (2007), A
coprecipitation procedure for the synthesis of LSM material, MTAEC9, 41 (2)
pp.8587.
. (1979). . 5e ., .
. .: , .

Tp ch KHOA HC HSP TPHCM

Phan Th Hong Oanh

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(Ngy Ta son nhn c bi: 05-11-2012; ngy phn bin nh gi: 28-11-2012;
ngy chp nhn ng: 18-02-2013)