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Báo cáo " Nghiên cứu khả năng tạo phức của ortho-este tetra azophenylcalix[4]aren (TEAC) với Th(IV) "
Mô tả tài liệu
Nghiên cứu khả năng tạo phức của ortho-este tetra azophenylcalix[4]aren (TEAC) với Th(IV)
Tóm tắt nội dung
Tgp chi Hoa hgc, T. 47 (6), Tr. 739 - 744, 2009
NGHIEN CQU KHA NANG TAO PHLfC CUA TETRA (TEAC) V6l TH(IV)
Den Tda soan 3-3-2009
TRAN QUANG HIEU', LE V A N T A N ' , NGUYEN NGQC TUAN'
'Bg mon Hoa - Khoa Dai hgc Cong nghe Sdi Gdn
^Trudng Dai hgc Cong Nghiep Tp. Ho Chi Minh
'Wien Nghien cifu Hgt nhdn Dd Lat
A simple, sensitive and selective method was developed for the of
Thorium based on between Tetra azophenyl (TEAC) and
Th(lV). In acid media, TEAC formed a 1:1 complex with Th(IV). Beer's law was obeyed in the
range 2.5x10'- mol.l' of Th(N). The limited of detection was l.OxW" moi i'. This
result could be applied for of Thorium in various samples,
soil and waste samples. Thorium.
I - GlOl THIEU
Trong nhiing nam gan day, ITnh vuc hoa hgc
sieu phan tir phat trien rat nhanh chdng va cd
nhilu ling dung quan trgng trong phan tfch [1,
2]. Mot trong nhirng hudng nghien ciiu dugc cac
nha hoa hgc quan tam la tao ra cac hgp chat
chiia cac nhdm mang miu dua tren chit gdc Tir day, da cd nhilu cdng trinh nghien
cihi dugc cdng bd vl phiic cua cac din xuat vdi cac ion kim loai nhu Ca'* [3]
Ni-"[4], Cr'15, 6], Ba'* [7] hoac chilt cac ion
kim loai bing din xuit [8 - 11].
Tuy nhien, phirc chit ciia din xuit
vdi cac ion ciia nguyen to nhdm dit hiem ft
dugc nghien ciiu.
TTiori la nguyen td phdng xa tu nhien, sd thir
tu 90 trong bang tuin hoan, cd nhilu irng dung
trong linh vuc hat nhan. Ham lugng Tliori trong
cac miu phan tfch dugc xac dinh bing nhilu
phuang phap khac nhau nhu tao phiic miu vdi
thudc thir Asenazo (III) [13, 16], hoac vdi thud'c
thir [19]! I. Hien nay,
phucmg phap phan tfch thudng dugc sir dung la
phan tfch kfch boat natron (NAA) [14, 15], khd'i
phd- cao tan cam iing plasma (ICP-MS) [17, 18]
hoac quang phd phat xa-cao tin cam iing plasma [20].
Trong bai bao nay, chiing tdi gidi thieu kha
nang tao phirc chgn lgc ciia thud'c thir tetra (TEAC) vdi
ion Th(IV) va kha nang irng dung trong phan
tfch.
11 - THUC NGHIEM
1. Hoa chait
Cac hoa chat sir dung trong thf nghiem diu
dam bao do tinh khilt phan tfch.
- Axit nitric HNO3 ndng do 65%; metanol
(MeOH), axeton nitri! (MeCNj, (PA) Merck.
739 (RA) dugc cung cip bdi ca quan
nang luang nguyen tir qud'c t l (IAEA); P^NO,) . (RA); Cr(N03)3; CH3COOH; NaOH rin; NaNOj rin;
axit picric; bromua (RA) Merck.
2. Thiet bj
- May quang phd UV-VIS hai chiim tia
Lambda 25 ciia hang Perkin Elmer (My).
- Miy phd cdng hudng tir 'H-NMR DPX
400 va phd 'C-NMR Bruker
FT-NMR 600 Mz (Diic); Phd FT-IR dugc
do tren may FT-IR 1000 ciia hang Perkin Elmer
(My).
- May cit nudc 2 lin ciia hang Hamilton
(Anh); Can phan tfch Afcoset, do nhay 10"̂ gam
(An Do), may do pH Thermo Orion- 290 (My).
- Cae dung cu thiiy tinh: pipet eac loai tir 1 -
25 ml, dng dong, binh dinh mdc, binh tam giac,
cd'c, pheu chilt cic loai, pheu lgc, chen platin, loai 1 - 25 |il, 50 )al, 100 |rl, 500 î l,
1000 p.\, cac binh, Ig (PE) dung
miu.. . dugc mua tir hang Merck.
3. Pha dung dich chuan
Thud'c thir 5,1
hay ggi theo ten thudng la tetra (TEAC) (xem hinh 1)
dugc tdng hgp bing each cho tac
dung vdi khi cd mat ciia d nhiet do thap. San phim dugc tinh
chi de dat do tinh khilt phan tfch; thanh phin va
ca'u true duac xac dinh bing cac phuang phap FT-lRil2] .
EtO,C' 'CO,Et
I I r
OH OH OH HO Thudc thir TEAC
- Dung dich chudn TEAC: Can chfnh xac
0,1126 gam thudc thir TEAC rdi cho cd'c 50 ml,
them tir tir dung dich hdn hgp gdm MeOH:H20
740
(7:3 vl the tfch) khuay diu. Sau dd chuyin vao
binh dinh miic 100 ml, dinh miic tdi vach thu
dugc dung dich thudc thir cd ndng do 10' M.
- Dung dich chudn Th(IVj: Can chfnh xac
0,5602 g tinh khiet cho vao cd'c
thiiy tinh 100 ml. Sau dd them nudc cit hai lin
rdi hoa tan. Chuyen dinh lugng vao binh dinh
mirc 1000 ml rdi them nudc cit hai lin din vach
ta dugc dung dich chuan Th(IV) 10"̂ M. Cac
dung dich cd ndng do loang han dugc pha tir
dung dich gd'c niy.
- Cic dung dich dem cd pH = 3 - 6 dugc pha
tir dung dich CH3COOH 0,1 M va NaOH 0,1 M.
- Cac dung djch UO2'*; Eu'*; La'*; Pb"*,
Or'*, Ni-*, Fe'*, Sm'*... dugc pha tir mudi nitrat
tucmg ling.
Ill - KET QUA v A THAO LUAN
1. Pho hap thu
- Dung dich thudc thif: Diing cho
200 )il thud'c thir TEAC vao binh dinh mii:c 10
ml, sau dd them 2 ml dung dich dem axetat,
them dung dich hdn hgp (7:3 vl
the tfch) tdi vach, thu dugc dung dich thud'c thir
ndng do 2.10"^M, khao sat phd hap thu ciia dung
dich nay, dung dich so sinh la nudc cit.
- Dung dich nghien cifu: Cho 200 \x\ thudc
thir TEAC lO 'M vao binh dinh miic 10 ml, sau
dd them 2 ml dung dich dem axetat cd pH = 4,5,
d ip tuc cho them 200 |il dung djch Th(IV) 10'
M, dinh miic bing dung dich hdn hcfp (7:3) tdi vach, khi dd ndng dd ciia
TEAC va th(IV) la 2.10-'M. Dung dich chuyin
din tir miu vang sang mau hdng. Sau khi miu
dn dinh, chiing tdi tien hanh do phd hip thu,
dung dich so sinh la nudc cat.
Trong mdi trudng axit, phd hip thu ciia
thud'c thir TEAC dat gia tri cue dai tai budc sdng
385 nm. Gia tri nay phii hgp vdi budc nhiy ciia
electron n -^n vi cua electron n -^n ciia nhdm
-N=N-. Kit qua nay cung rit phii hgp vdi cac
cdng trinh lien quan da dugc cdng bd trudc day
[ 3 - 6 ] . Phd ha'p thu ciia he xuat
hien 2 pic tai cic budc sdng 376 nm va 520 nm
(dudng b). Do ddi pic hip thu cue dai ciia he so
vdi thud'c thir TEAC d dang tu do len de'n 135
nm, la mdt tin hieu td't d l tiln hanh nghien ciiu
cac dilu kien ldi uu. Vi vay, d cac thi nghiem
sau chung tdi do dd hap thu quang tai budc sdng
520 nm.
5 0 0 7 0 0
W a v e l e ng h t (n m )
Hinh 2: Phd cua thudc thir TEAC va he tai pH = 4,5
(a) Phd ciia TEAC 2.10 ' M vai phong so sanh la nudc cat;
(b)Ph6 cua phiic 2.10-M tai pH = 4,5 vdi phong .so sanh la nuoc cat
2. Anh hudng cua pH va dung mdi tdi phd
haip thu ciia he
Chiing tdi khao sat anh hudng ciia pH den
phd hip thu eiia he Gii tri pH
anh hudng rat nhilu den qua trinh tao phiirc ciia
ion kim loai. Trong mdi trudng kiim cac ion
nguyen td dit hilm va phdng xa thudng uu tien
cho qua trinh tao phiic hydroxo hoac tao kit tiia
khi ndng do cac ion dii ldn. Vi vay, chiing toi
chgn mdi trudng axit de nghien ciru.
Chuan bi cac dung dich nghien ciiu tucmg tu
nhu tren va dieu chinh pH ciia he thay ddi tir 2,5
- 6 bing each sir dung dung dich dem natri
axetat, cac gia tri pH diu dugc kiem tra lai bang
may do pH. Do do hip thu quang eiia he tai
budc sdng 520 nm, dung dich so sanh la nudc
cit. Kit qua dugc biiu thi tren hinh 3. Mat do
quang ciia he gia tri cue dai trong khoing pH =
4 - 5. Vi vay, chiing toi ebon khoang gia tri pH
niy de tiln hanh cac nghien ciru tilp theo.
pH
Hinh 3: Su phu thudc ciia mat do quang vao pH
741 toi da tien hinh khao sat phd ha'p thu
ciia he trong nhilu loai dung mdi
khac nhau nhu axeton nitril, tetra hydro furan, hoac cac dung mdi niy vdi nudc. Ke't
qua cho thay trong dung mdi hdn hgp MeOH -i-
H2O vdi ti le 7:3 vl the tfch thi do hap thu quang
ciia he tai budc sdng 520 nm dat gia tri cue dai.
Vi vay, chiing tdi chgn he dung mdi niy de tien
hanh cic nghien cuu sau.
4. Anh hudng cua ndng do Th(IV)
De khao sat inh hudng ciia ndng do ion
Th(IV) de'n phd hap thu ciia he
chiing tdi chuan bi cac dung dich tuong tu nhu
tren nhung giir nguyen ndng do thudc thir TEAC
la 2.10"^ M tai pH - 4,5, cdn ndng do ion Th(IV)
tang tu 0,25.10-5 M- 15 I Q - ' M . Chiing tdi tien
hanh do do hap thu quang eiia he, dung dich so
sanh l i nude cit. Kit qui dugc trinh biy trin
hinh 4. Nhin vao dd thi ta thiy khi tang din
ndng do ion Th(IV) thi mat do quang tai pic tai
520 nm tang din. Tren ca sd dd, chiing tdi da
xay dung dd thi biiu thi khoing tuye'n tfnh cua
ndng do Th(IV) vi do hip thu quang (A) tai
budc sdng 520 nm, bang tfnh toan thdng ke,
dudng bieu dien ed phuang trinh:
A = 0,248x C(10-' mol/1) -^0,020
(R^ = 0,990, n = 7).
Hinh 4: Phd hap thu ciia he TEAC- Th(IV) khi thay ddi ndng do ion 'M
Tir ( a ) ^ (n) : 0; 0,25; 0,5; 0,75; 1; 1,5; 2,0; 2,5; 5,0; 7,5; 10; 12,5; 15
4. Anh hudng cua thdi gian
De khao sat do bin mau ciia he theo thdi
gian, chiing tdi tao dung dich nghien ciiu tuang
tu nhu tren va do do hip thu quang ciia he tai
budc sdng 520 nm, dung dich so sanh la nude
cit trong khoing thdi gian tir 5 - 80 phiit. Chiing
tdi nhan thiy mau ciia he chuyen tir vang sang
hdng dam sau thdi gian khoang 1 phiit va dn
dinh trong khoang thdi gian 5-90 phiit sau khi
cho them ion kim loai vao dung dich thud'c thir.
5. Khao sat thanh phan ciia he
De khio sat thanh phan ciia he, chiing tdi sir
dung phuang phap day ddng phan tir gam:
Chuin bi 9 dung dich nghien ciru vdi cac dilu
kien tdi uu nhu tren, sao cho ndng do TEAC
giam din tir lO'^M - 10'* M cdn ndng dd ion
Th(IV) tang din tir l O ' M - lO'^M, nghla la tdng
ndng do ludn bing 2.10-'M. Gia
tri pH ciia he dugc cd dinh l i 4,5. Sau khi he dn
dinh, do do hip thu quang ciia cac dung dich,
diing nudc cat lam dung dich so sanh tai budc
sdng 520 nm. Kit qua dugc trinh bay tren hinh
5. Tir kit qua niy cho thiy khi =1:1
thi do ha'p thu quang dat gia tri cue dai, tucmg
ung vdi ke't luan la phirc cd thanh phan 1:1.
6. Anh hudng ciia su cd mat cac ion kim loai
khac
Chiing tdi tiln hanh khio sit anh hudng cua
mdt sd ion kim loai khic de'n kha nang tao phirc
ciia TEAC vdi ion Th(IV). Dung dich cac ion
742
dugc pha che tir dung dich mudi nitrat tuang
ling. Sau dd tao dung dich nghien ciiu tai pH =
4,5 tucmg tu tren sao cho ndng do eiia TEAC va
ion kim loai M"* la 2 .10 'M. De dn dinh rdi do
phd hip thu cua timg he. Kit qui dugc trinh bay
d hinh 6. Tir phd nay cho thiy d dilu kien tao
phiic ciia Th(IV), cac ion nhu UO2-*, Eu'*i La'*,
Sm'*... hiu nhu khdng tao phiic vdi thud'c thir.
0 3D - ,
| o 2 5 -
s
< 0.20 -
0.15 -
0 1 0 -
0 05 -
0 . 0
.
0 2
-
0 i 0 6
H
0 8
-
1 .0
Hinh 5: Thanh phin ciia he theo phucmg phap he
ddng phan tir gam vdi [TEAC] -H Th(IV) = 2.10 'M
0.8 - ,
0
1
0.4 -
0.2 -
0.0 - 1 1
3 0 0 4 0 0
^ T E A C - T h ( I V )
/ \ ^ T E A C - U O j * "
(^ / V ^ ^ ^ ^ ^ TEAC-Eu*'
^ ^ , / ^ ^ ^ ' ^ \ ^ ^ ^ T E A C - L a ' '
^ ^ 5 ^ ^ < ^ ^ ^ ^ ' \ ^^^^^^ T E A C - S m ' '
\ ^ ^ ^ ^ ; ^ ^ \ , ^ V \ ^ ^ ' ^ ^ ^ E A C
500 6 0 0 7 0 0
W a v e l e n g h t ( n m )
Hinh 6: Anh hudng cua cac ion kim loai din phii:c TfAC-Th*
Kha ndng tach chiet
La'y 5 binh djnh miic 25 ml, lin lugt cho vao
mdi binh 125 p\ dung dich chuin TEAC 10'M,
them 5 ml dung djch dem axetat cd pH = 4,5.
Sau dd them 125 \x\ dung dich Th(IV) 10 'M,
dinh mirc bing dung mdi hdn hgp
(7:3), ndng dd cua TEAC vi ion Th(IV) khi dd
la E)e yen 5 phiit, chuyen dung dich
vao phlu chiet 100 ml. Cho lin lugt vao mdi
phlu chilt 5ml dung mdi /7-hexan, lae that ki trong 20 phiit. Kit qua cho
tha'y dung mdi chilt khdng thay ddi. Khi dting
mdt lugng du bromua phirc
cung khdng bj chilt. Ngugc lai khi sir dung mdt
lugng axit picric cho vio pheu chiet lic diu thi
dung mdi chie't chuyen sang mau hdng va phd
ha'p thu eiia he sau khi chiet ed hai pic cue dai
tai budc sdng 375 nm va 520 nm. Kit qua niy
kha phu hgp vdi cdng trinh ma Ashok Kumar da
743
cdng bd khi diing ion picrat dl chilt cdng hgp
phiic chit -Rh'* [9].
IV- KET LUAN
1. Da tim dugc phdc chit mdi giira TEAC vi
Th(IV) trong mdi trudng axit ylu, gidi han phat
hiln la LIO'*" mol/1. Phd hap thu ciia phiic cd cue
dai tai budc sdng 520 nm, thanh phin ciia phiic
la 1:1.
2. Do ha'p thu quang tuan theo dinh luat
Beer trong khoang ndng do tir 2,5.10'''
phucmg trinh hdi quy cd dang la A = 0,248 x +0,020 (/?- = 0,995, n = 7).
3. Do bin cua phirc la kha lau, cho phep tie'n
hanh cac nghien ciiu tach
4. Phiic cha't cd the chie't cdng hgp vdi axit
picric bing dung mdi khdng phan cue nhu
CHCI3, CCI4...
T A I LIEU THAM KHAO
1. Xun Guo, Li Zhang, Guo Yuan Lu, Mei
Fang YIN, Fang Liu. Ming Hua Chemical Letters Vol. 16(11), 1543
-
2. C. David Gutsche.
USA, Royal Society of
3. Yunyan Dong, Tae Hyun Kim, Hyun Jung
Kim, Min Hee Lee, Su Yeon Lee, Rakesh
Kumar Mahajan, Hasuck Kim, Jong Seung
Kim. Journal of
XXX 01.015 (2009).
4. Quanli Ma, Huimin Ma, Meihong Su, Zhihua
Wang, Lihua Nie, Shuchuan Liang. Chimica Acta, Vol.439,
5. Lilin Lua, Shufang Zhub, Xingzhong Liua,
Zhizhong Xiec, Xi Yanc. Analytica Chimica
Acta 535,
6. Tae Hyun Kim, Su Ho Kim, Le Van Tan,
Yu Jin Seo, Sun Youn Park, Hasuck Kim,
Jong Seong Kim. Talanta Vol. 71, 1294 -
1297 (2007).
7. Tae Hyun Kim, Su Ho Kim, Le Van Tan,
Yunyan Dong, Hasuck Kim, Jong Seung
Kim. Talanta Vol 74, 1654 - 1658 (2008).
8. Francoise and J.
Chem. Trans. Vol. 2, 575 - 576
(1997).
9. Ashok Kumar, Pratibha Sharma, Lai Kumar
Chandel, Bhagwan Lai Kalal, Sandor
Kunsagi- Mate- J Incl Phenom Macrocycl Vol
10. Deligdz, Mine Sulak Ak, Memon and Mustafa Yilmaz,
Pak. J. Anal. Environ. Chem. Vol. 9(1), 1 -
5 (2008).
11. Deligdz, emin erdem and hasan J. Chem 24, 157 - 163
(2000).
12. Le Van Tan. J. Hue Uni. 30: 34-38 (2006).
13. A. R. Palme, Atomic Energy The Thorium Apans. Complex
A Study, 3, 3 (1958).
14. Kenneth W. Bagnall et al. Can. J . Chem.
Vol.
15. Kim Thomas. The of
Thorium- Nation Academy of Sciences
National Research 5 (1982).
16. David N. Solon A. Gordon.
Michael M. Thommes. J. Am. Chem. Soc,
Vol. 15(6), 945 -946 (1970).
17. Maria Luiza D.P. Godoy, Jose Marcus
Godoy, Renato Kowsmann, Guaciara M.
dos Santos, Rosana Petinatti da Cruz.
Journal of XX,
1-9 (2006).
18. Tatsuya Sekil and Koichi Oguma. J. Flow
Injecdon Anal., Vol . 18(2), 140 - 143
(2001).
19. Linfeng Rao. Acta, Vol. 88,
851
20. Marco Achilli, Giovanni Ciceri, Roberto Daniela Heltai and Waller Analyst, 114, 319 - 323, DOI: (1989).
744