T P CH KHOA H C V CNG NGH

T p 44, s 2, 2006

Tr. 65-69

T NG H P M T S PH C CH T MANGAN XITRAT DNG LM

CH PH M T O MU CHO GRANIT NHN T O
TR!N TH" #, L TH" H&NG H'I, NGUY+N TH" NG C VINH, NGUY+N H,U #-NH

I. M

Gm granit (cn gi l granit nhn to) l mt loi vt liu xy dng cao cp c c tnh k
thut v thm m cao. Nhu cu v loi vt liu ny nc ta ang tng mnh. Mt vi nh my
u t dy chuyn hin i sn xut granit nhn to. Tuy nhin cc ch phm mu cho gm
granit u phi nhp ngoi vi gi thnh cao.
Axit xitric (HOOC- CH2- (HO)C(COOH)- CH2-COOH ) l mt axit hu c a chc v tp
chc, dung lng phi tr ln, rt d tham gia to phc vng cng vi cc kim loi chuyn tip.
V th c th thay i iu kin tng hp thu c cc phc cht c thnh phn, cu to, tnh
cht p ng yu cu lm ch phm mu.
Bi bo ny trnh by kt qu tng hp, nghin cu tnh cht mt s phc cht Mn(II) xitrat
v th kh nng thm tan, pht mu ca chng trn gm s.
II. TH C NGHI M V K T QU
1. T ng h p ph c ch t
Chng ti tin hnh tng hp phc cht Mn(II) xitrat theo hai s sau:
KMnO4 + H3C6H5O7 + Na3C6H5O7
phc cht P1P5
(1)
phc cht P6.
(2)
MnCl2 + Na3 C6H5O7 + NaOH
thu c phc cht tinh khit, hiu sut cao, tan ln, c trin vng nghin cu ng
dng, chng ti tin hnh kho st cc yu t c nh hng n qu trnh to phc nh cch
tin hnh phn ng, nhit , thi gian, t l cc cht tham gia phn ng. Qua mt lot th
nghim chng ti chn c 6 phc cht sau tip tc nghin cu
Cc phc cht t P1- P5 c tng hp theo s th nht nhng trong cc iu kin rt khc
nhau. Phc cht P1, P2 c tng hp bng cch cho KMnO4, Na3C6H5O7 vo dung dch axit xitric
50 oC - 60oC, vi t l mol KMnO4: Na3C6H5O7: H3C6H5O7 tng ng l 1 : 1 : 2 v 1 : 3 : 2.
Phc cht P3 c tng hp tng t nh hai phc trn nhng vi t l mol KMnO4 :
Na3C6H5O7 : H3C6H5O7 l 1 : 2 : 2, trong iu kin nhit thp 0 2oC v trong bng ti.
Phc cht P4 c tng hp bng cch cho axit xitric, Na3C6H5O7 vo dung dch KMnO4
o
50 C - 60oC. Cn nu tng hp tng t nh phc cht P4 nhng trong iu kin nhit thp 0 oC 2 oC v trong bng ti th thu c phc cht P5. Phc cht P6 c tng hp theo s th hai.
Cc phc cht tng hp c kt tinh li trong dung mi nc hoc ru nc. Quan st
di knh hin vi, cc phc cht thu c sau khi tinh ch u dng tinh th, kch thc, hnh
dng v mu sc khc nhau. Phc cht P1 P5 l nhng tinh th hnh tr c kch thc khc
nhau, mu sc t nu n nu nht cn phc cht P6 li l nhng tinh th mu xanh ru.

65

2. Xc $%nh thnh ph'n, c u t*o cc ph c ch t

Axit xitric (C6H8O5) l hp cht tp chc( HOOC-CH2-(OH)C(COOH)-CH2-COOH). N
c th to phc vi dung lng phi tr 2, 3 v 4. Ngoi ra n c th lm cu ni gia cc ion
kim loi to thnh cc phc a nhn. V vy ph thuc vo iu kin tng hp, phc cht thu
c c thnh phn, tnh cht v cu to rt khc nhau [2, 4]. xc nh thnh phn, tnh cht
v cu to ca 6 phc cht tng hp c, chng ti tin hnh o tan, o dn in phn t,
o ph hp th hng ngoi, ph hp th electron, gin phn hu nhit, xc nh hm lng
ion trung tm ca chng.
dn in phn t ca dung dch cc phc cht c o ti khoa Ho hc trng i hc
S phm H Ni. Kt qu c ch ra bng 1.
B ng 1. Thnh phn v tnh cht cc phc cht

K
H

Cng thc

Hm
lng
Mn (%)
Tm
tnh

P1 H[Mn(C6H5O7) (H2O)2].12H2O
P2 Na4[Mn(C6H5O7)2 (H2O)3]. 6H2O
P3

K[Mn(C6H5O7) (H2O)3]. 2H2O

P4 K4[Mn(C6H5O7)2 (H2O)3]. 9H2O

P5

K[Mn(C6H5O7) (H2O)2]. 4H2O

P6

[Mn(C6H5O7).MnOH(H2O)3].
3H2O

10,55
11,07
7,97
8,00
14,95
14,75
7,03
6,83
14,13
14,07
25,88
25,94

dn

in
phn
tan
t ( -1.
(g/l) cm2. mol-1)

906

171

525

465

336

143

360

481

515

132

429

41

Phn hu nhit (t0C/

m,% tm/ tnh)

Mt nc
kt tinh

Mt nc
phi tr

110 -135

170 -200 310 -700

43,82/43,46
88 -130
17,42/15,72
86 -105
10,51/9,65
86 -120
20,51/20,12
90 -130
17,36/18,41
85 -120

7,00/7,24

Phn
hu

16,20

160 -200 300 -700

9,89/7,86

26,90

128 -195 318 -700

15,45/14,45 31,311
170 -240 291 -700
6,09/ 6,71

28,75

160 -220 314 -700

9,94/9,20

26,76

125 -200 320 -700

13,35/ 12,73 13,65/12,73

22,88

tan ca cc phc cht c xc nh bng phng php trc quang ti khoa Ho hc

trng HSP H Ni. Kt qu cho thy hu ht cc phc cht u tan tt trong nc ph hp
vi mc ch ca ti.
Gin phn tch nhit trong kh quyn N2 c o ti Vin Ho hc, Vin Khoa hc v
Cng ngh Vit Nam. Trn gin phn hu nhit ca tt c cc phc u xut hin hai hiu
ng u tin l hiu ng thu nhit trong khong nhit t 100 oC - 240oC, cng vi s gim
khi lng trn ng TGA v cc tiu trn ng DTG ng vi s mt nc kt tinh v nc
phi tr. Hm lng nc kt tinh v nc phi tr ca mi phc cht theo kt qu thc nghim
v tnh theo cng thc ngh c ch ra bng 1.

66

Hiu ng tip theo l hiu ng to nhit trong khong 300oC - 700oC ng vi qu trnh
phn hu phc cht thnh cc sn phm kh nh CO2, H2O ... km theo cc phn ng t oxi ho
kh v s hnh thnh cc sn phm rn bn nh oxit, cacbonat .... [3]
Hm lng ion trung tm Mn c xc nh bng phng php trc quang vi sai ti khoa
Ho hc, trng i hc S phm H Ni. Kt qu thu c t thc nghim v tnh theo cng
thc ngh c ch ra bng 1.
Ph hp th hng ngoi, ph hp th t ngoi kh kin c o ti Vin Ho- trung tm
KHTN v CNQG v khoa Ho Hc trng HSP H Ni.
Cc vn hp th chnh trn ph hng ngoi, ph hp th t ngoi, kh kin ca cc phc
cht nghin cu c ghi bng 2.
Trn ph hng ngoi ca cc phc cht nghin cu c cc vn hp th c trng cho cc
kdx

dx

, COO so vi nhm
nhm nguyn t trong phn t. S gim mnh tn s ca
cacbonyl t do chng t nhm COO tham gia vo lin kt vi ion trung tm Mn(II) [1].
Trong khi phi t Na3C6H5O7 khng c vn hp th vng trn 200nm th cc phc cht
nghin cu u hp th mnh vng t ngoi gn vi lg > 3,5. S xut hin cc vn ph l
do chuyn mc km chuyn in tch cu phi tr [1].
Cc vn ph chuyn d-d ca cc phc cht nghin cu ch yu nm trong vng kh kin
vi h s hp th mol rt nh, a s < 1. Nguyn nhn sinh ra cc vn hp th ny l do s
chuyn dch electron trong lp v d cha c in y ca ion trung tm Mn2+ (cu hnh d5)
trong trng bt din. Bc chuyn ny b cm khng nhng bi qui tc chn lc Laport m cn
bi qui tc chn lc spin. Do xc sut bc chuyn thp nn cng hp th rt nh [5].
COO

B ng 2. Ph hp th hng ngoi, t ngoi- kh kin ca cc phc nghin cu

Ph hp th hng ngoi, cm-1
K
hiu

OH

CH

kdx

dx

COO

COO

M-O

Ph chuyn
in tch
max/lg

Ph chuyn d-d
max (nm)/

P1

3430 2972 1610 1401

416

232,1 / 3,65 404/ 0,24; 528/ 0,13

P2

3415

1583 1402

410

224,8 / 3,98 362/0,75; 402/ 0,46; 530/ 0,23

P3

3420 2968 1603 1400

415

226,5 / 3,15 365/ 0,38; 410/0,21; 520/0,10

P4

3453 2965 1592 1396

416

224,4 / 4,01 362/0,37; 411/0,27; 437/0,12; 528/0,15

P5

3417 2971 1609 1401

415

224,8 / 3,09 375/0,25; 408/0,14; 440/0,13; 518/0,10

P6

3450 2967 1589 1394

417

225,2 /3,85 410/0,15; 432/0,14; 512/ 0,11

T cc kt qu o dn in phn t, xc nh hm lng ion trung tm, phn tch nhit,

ph hp th hng ngoi, ph hp th electron chng ti s b ngh cng thc cu to ca cc
phc cht nghin cu nh sau:

67

Ph c P1: H[Mn(C6H5O7) (H2O)2].12H2O

Ph c P2: Na4[Mn(C6H5O7)2 (H2O)3]. 6H2O

COONa

COONa

COO

CH2
OH

OH2

CH2

CH2

COO

CH2

OH2

COO

COO

CH2
K HO

C
CH2

OH2

Phc P5: K[Mn(C6H5O7) (H2O)2] . 4H2O

COO
OH

. 2 H2O

CH2

Phc P4: K4[Mn(C6H5O7)2 (H2O)3].9H2O

COOK

COOK
H
CH2 O

OH2

H
O

CH2
C

Mn

C
CH2

OH2

9. H
.8H
O2O
2

CH2

OOC

COO
OH2

COOK

COOK

Phc P6: [Mn(C6H5O7).MnOH ( H2O)3].3 H2O

CH2
HO

Mn

OOC

C
CH2

68

COO
H
O
COO

OH2
Mn

OH2
OH2

OH2
Mn

COO

OH2

COO

COONa

CH2

OH2

. 6 H2 O

CH2

OOC

OH2
Mn

COO

CH2
C

COO

COONa

Phc P3: K[Mn(C6H5O7) (H2O)3] . 2H2O

H
O

Mn

12. H2O

Mn

OH2

H
O OH2

.3H2O

COO

. 4 H2O
OH2

Chng ti tin hnh pha cc phc cht tng hp c thnh cc ch phm khc nhau ri
nh nh lng trn gm mc v nung 1200oC ti cng ty gch Thch Bn, Gia Lm,H Ni.
Sau khi nung gm granit thu c pht mu nu hoc nu . Lp mu t thm su cn thit.
Kt qu cho thy cc ch phm mu ny thch hp vi vic to mu cho granit nhn to.
IV. K T LU:N
tm c iu kin thch hp tng hp 6 phc cht mangan xitrat. Da vo cc kt
qu o dn in phn t, xc nh hm lng ion trung tm, phn tch nhit, ph hp th
hng ngoi, ph hp th electron ngh cng thc cu to ca cc phc cht tng hp c.
Vic th s b cho thy, cc ch phm pha t cc phc cht mangan xitrat c thm su cn
thit v pht mu nu hoc nu trn xng gm, thch hp vi vic to mu cho granit nhn to.
TI LI U THAM KH O
1.
2.

Trn Th , Nguyn Hu nh - ng dng mt s phng php ph nghin cu cu trc

phn t, Nh xut bn Gio dc, H Ni, 1999.
Trn Th , L Phi Thu, Nguyn Hu nh - Tp ch ho hc 39 (1) (2001) 58-62.

3. I.Dranca, Tlupascu, and V.Sofransky - Jour. of Thermal. Analysis 46 (1996) 1403-1412.

4. Sanchez Cabello, H. Sanz Garcia - Chemical abstracts 46 (1952) 8482b.
5. . . . - e . ,
"" e, 1976, c. 254-256.
SUMMARY
SYNTHESIZE SOME COMPLEXES OF Mn(II) CITRATE TO DYE ARTIFICIAL
GRANITES
Nowadays, artificial granites are used widely. But in Viet Nam, water soluble complexes
suitable for coloring artifical granites are rarely studied. So we synthesize some complexes of
Mn(II) citrate to dye artificial granites.
Six citrate complexes of Mn(II) were synthesized starting from KMnO4 or MnCl2 and
citric acid or sodium citrate in various mol ratio and at 0oC 2oC or 50oC 60oC. By using
elemental analysis, thermal decomposition, IR-spectroscopy, UV-Vis and molar conductivity,
structure of the complexes was suggested. Most of them are good dissolve in water. Their
aqueous solutions can be used to dye artificial granites. After firing at 1200oC, they exhibit
brown color and reach necessary penetration.
a ch :

Nh n bi ngy 12 thng 9 n m 2004

Trng i hc S phm H Ni

69