TAP CHi HOA HOC T. 50(1) 101-104 THANG 2 NAM 2012
T 6 N G HQP VA NGHIEN CLPU TiNH CHAT HUYNH QUANG
PHLFC CHAT 1,10-PHENANTROLIN TECBI (III) NITRAT
Nguyin Due Vu-gng'', Nguyen Dinh Luyen^ Nguyin Mau Thanh^
'Tnrang Dgi hoc Quctng Binh Trirdng Dgi hoc Sir phgm. Dai hpc Hue
Den Tda soan 8-12-2011
Abstract
Complex of terbium (III) with l,tO-phenanthroline and nitrale has been synthesized and determinated composition by heating-analysis and element analysis. Structure of complex also has been characterized by a variety of modern physical methods such as IR, RAMAN, PL etc. The study showed the molar ratio of central ion and ligand thai efficiency was maximum and most illuminating
Keywords' Synthesized, determinated, characterized, efficiency 1, MO DAU
Phirc chat ciia 1,10-phenantrolin (pben) vdi mpt so nguyen td dat hiem da duoc cac nude tren the gidi nghien ciiu rdng rai trong nhieu nam trd lai day [8], dac biet mdt sd phiic ctia phen vdi Eu, Pr, Sm...cd linh chat quang hgc nen dugc img dung trong nhieu ITnh vuc nhu trong ndng nghiep. khoa hgc vat lieu [3, 4]. Q nude ta, viec tdng hgp cac phirc eua nguyen td dat hiem vdi phen va mdt sd phdi tir khac chua dugc nghien ciru nhieu va mdi dirng lai d* phuc ciia Europi.
Trong bai bao nay, cac ket qua nhan dugc trong qua trinh long hgp phiic chat ciia Tb(lll) vdi phen va phdi Hi nitrat hy vgng se md ra mgt hudng mdi trong viec nghien ciru va irng dung cac phirc chat cua nguyen td dat hiem,
2 THUC NGHIEM 2.L Hoa chat va thiet bi
- Cac hda chat sir dung trong nghien ciru deu loai tinh khiit phan tich: TbjOv, HNO3, d.HsNj.HjO, axelon, cdn.
Phd hdng ngoai ciia phirc chat dugc ghi tren may IMPACT-410-NlCOLET trong vimg 4000-400 cm''.
- Phd Raman dugc ghi tren may Micro Raman LABRAM trong vimg tir 4000-100 cm"' vdi buc xa kich thich 623,8 nm tir laze Heli, phd huynh quang dugc ghi tren may he quang hoc FL 3-22.
- Ham tu'o'ng cac nguyen td C, O, N dugc phan tich tren may phan tich nguyen td Thermo Electron
Eager 1112.
- Ham lugng TbiO: dugc xac djnh bdi gian dd phan lich nhiet TGA dugc phan tich lai Trung tam phan tich vat lieu, Tru'd"ng Dai hgc Bach khoa Ha Ndi.
2.2. Tong hgp phirc chat
- Dung dich mudi Tb(NO-)- dugc dieu che true tiep tir Tb^O? 99,9% (My) bang phuong phap sau, can chinh xac lugng Tb407 da tinh toan irudc khi chuyen vao cdc chju nhiet, tham udl bang nude, them tir tir dung djch axit dac HNO3 (PA) va dun ndng den khi tan bet. Sau dd tien hanh dudi axit tren bip dien nhieu lan vdi nude cat den khi lugng axit du bi loai bd, tiep tuc cd dung dich den muoi am, hda tan bSng nude, lgc dung dich rdi chuyen vao binh dinh mii'c. Them nude den vach va lae deu thu dugc cac dung djch mudi tuang ung cd nong do can pha. Ndng do ciia cac mudi dugc kiem tra lai bang phuang phap chuan do bang DTPA 10"^ M vdi ehi thj la Arsenazo (III) trong mdi trudng dem axelal cd pH = 5-6.
- Phirc chat (phen)2Tb(N03)3 dugc tdng hgp: Lay 4mmol phen hda tan trong 50 m! cdn tuyet doi. sau dd cho phan ung vdi 10 ml dung dich mudi Tb(N03)3 0,2 M, pH = 4.5-6. Hon hgp phan irng dugc dun ndng den sdi va sau dd dugc che hda vdi 150 ml axeton ndng, de yen trong 2 ngay, khi dd cac tinh the cua phiic chat phen-Tb'''-N03" se dugc tach ra dudi dang ket tiia Cac tinh the phiic chat dugc lgc va dugc rira bang axeton Say va bao quan linh the phirc chat d nhiet do SO-SO^C trong vai gid.
TCHH.T 50(1), 2012 3. KET QUA VA THAO LUAN 3.1. Hieu suat tong hgp phirc chSt
1,10-phenantrolin Tecbi (III) nitrat Qua trinh tdng hgp phirc vdi nhiing ty le moi khac nhau giua phdi tu phen va Tb^* la: phen:Nd = L l ; 2:l;3:l; 4:1, ket qua nghien ciiu dugc chi ra d bang 1,
Bdng 1: Hieu suat tdng hgp phirc Tb(III) vdi phen d cac ti le moi khac nhau
TN 1 2 3 4
phen/Tb(III) 1:1 2:1 3:1 4:1
Hieu suat, % 45 78 37 30
(a)
Nguyin Due Virgng vd cdng su Kit qua nghien ciiu thu dugc hieu suat phan img tdng hgp phuc dat gia tri cao nhdt tuong ring vdi ti \%
sd moi phen:Tb la 2:1, tuong tu nhu phirc cua Eu [I], Nd. Ti le nay dugc chgn di tdng hop phiic cho cac nghien ciiu tiep theo. Phiic chit tdng hgp dugc cd mau tim, dang tinh the va dl tan trong axit loang.
3.2. Xac dinh thanh phan phirc
Thanh phSn phiic dugc xac dinh bang phuang phap phan tich nhiet va phan tich ham lugng cac nguyen td C, H, N qua cac gian dd d hinh 2.
Tir gian dd phan tich nhiet va phan tich nguyen td thu dugc cac sd lieu so sanh ham lugng TbjOa sau khi phan hiiy phiic, thanh phan phan tram c4c nguyen td C, O, N trong phiic giiia sd heu tinh loan theo ly thuyet (%LT) va theo kit qua phan tich dugc (%PT) d bang 2.
(b)
Hinh 2: Gian dd phan tich nhiet va phan tich nguyen td ciia phen-Tb^^-NOs"
(a) Gian dd phan tich nhiet (b) Gian dd phan tich nguyen td Bdng 2. Ham lugng TbjOs
Hop chat Phen-Tb'*- NO3
sau khi phan huy phiic va thanh phan C TbiOj, %
LT 26,0
PT 25,3
C, % LT 40,9
PT 39,8
, 0 , N trong phiic 0 , %
LT 20,4
PT 19,9
N, LT 13,9
%
PT 13,4
*LT: % theo ly thuyet; PT: % theo ket qua phan tich.
Tii bang so lieu tren cho thay ket qua giira ly thuyet va thue nghiem tuong duang nhau. Tir dd, ket luan thanh phan phiic tdng hgp dugc phii hgp vdi cdng thirc gia dinh theo ly thuyet la (phen)2Tb(N03)3.
3.3. Xac dinh cau true phu-c chat bang cac phironng phap vat ly hien d^i
3.3.1. Phd hdng ngogi
Phd hong ngoai cua phen, (phen)3Tb(N03)3 va sd sdng dac tnmg dugc dua ra d hinh 3 va bang 3.
Bdng 3. So sdng dac trung pho hdng ngoai cua phen, (phen)2Tb(N03)3
Hgp chat Ci2HsN:.H20 (phen)2Tb(N0j)3
'V-N02(kdx)
TCHH.T. 50(1), 2012 Tdng hap vd nghien cini tinh chdt...
(a)
./v. ,J H\
\f
• •^—_
\f \
(b)
- —,-, ,.
i > i ' i l " ' l
l|i! f'
'?;' ^ \
LTtnh 3: Phd hdng ngoai ciia phen va (phen)3Tb(N03)3 (a) Phd hong ngoai ciia phen (b) Pho bdng ngoai ciia (phen)2Tb(N03)3 Phan tich chi tiet cae phd dao ddng hdng ngoai
cho thay, tren phd IR cua phirc chat khdng cd dao ddng ciia nhdm OH ciia HiO (VQ-H = 3391 em"'), vay phirc chat khdng cd H2O trong phan tu. Kel qua nay phii hgp vdi ket qua phan tich thanh phan nguyen td, Dieu dd chirng td phen da day nude ra khdi eau phdi tri khi lien ket tao phiic.
Phd hap thu hdng ngoai ciia phdi tir phen (C12HSN2.H2O) cd nhieu van phd. Mdt sd van phd quan trgng dugc nhan dang nhu sau: VQ-H = 3391 cm"', Vc-Hj[homi = 3062 cm"', vc=c = 1619 cm"', VC=N = 1584 cm' . Khi hinh thanh phiie chat, van pho vc=c, Vc=N thay ddi (bang 3). Su chuyin djch xudng tan sd thap ehiing td phdi tu phen da lien ket vdi ion trung tam Tb^^, cu the da hinh thanh lien ket phdi tri N(phen)—tTb. Ket luan ve su chuyen dieh tan so dao dpng hda tri cua lien kit C=C, C=N trong phan lu phen xu6ng tan sd thap la do hinh thanh lien ket phoi tri ciia N vdi ion kim loai trung tam. Nhu vay, tren phd hdng ngoai da chi ra dao ddng ciia cac nhdm dac hung cd trong phiic (phen)2Tb(N03)3.
3.3.2 Phd Raman
Pho Raman ciia (phen)2Tb(N03)3 dugc dua ra d hinh 4.
Phd Raman ciia phuc chat (phen)2Tb(N03)3 xuat hien 2 van cd cudng do trung binh 428,3 cm"' va 559,1 cm' irng vdi dao ddng hda tri cua Tb-N va Tb-0. Dao ddng cua hai lien ket nay cao bay thap phu thudc vao do am dien hay phu thuge vao do dai eiia lien ket Tb-0 va Tb-N. Do dai Hen kel nao Idn thi tan sd dao dpng hda tri thap, ngirge lai do dai lien ket ngan Ihi tan sd dao ddng hda trj cao. Do dai lien ket dTi,.() < djij.N, tir dd quy ket dao ddng boa tri ciia lien ket Tb-O cd tan sd vrb-o = 559,1 cm'', va dao dpng hda tri ciia lien ket Tb-N cd lan sd VTIJ-N = 428,3 cm"'.
Tren co sd dd, cdng thiic eau tao eua phirc chat duoc de nghi nhu sau:
Q^./2p^-°
Hinh 4: Phd Raman ciia (phen)2Tb(N03)3
(phcn)2TbCN03)3
4. NGHIEN CU'U TINH CHAT HUYNH QUANG CUA PHUC CHAT
Phd huynh quang ctia phirc chat phen)2Tb(N03)^
dugc Irinh bay d cac hinh 5.
Tren phd huynh quang hinh 5 cho thay, nhung van hep trong phd ciia phirc chat phd nhan dugc bao gdm 4 dinh dac trung tai cac budc sdng 488 nm, 554 nm, 582 nm va 617 nm irng vdi cac chuyen mire 'D;-> 'pfi, ^Di-)- ^Fs, ^Di->- 'F4 va 'Dj -^ 'F? ciia ion Tb* , d budc sdng 554 nm la diem dinh phat xa manh nhat,
Dua tren sa dd nang lugng ciia Tb^'. cd the dua ra CO che truyen nang lugng giira ion Tb"*' nhu sau. eac
r C H H . T 5 0 ( 1 ) . 2 0 ] 2
ion Tb"' a trang thai c a ban, sau khi hap thu photon lai birdc sdng 400 nm se chuyen len mire kich thich ed nang lugng c a o hon, sau dd hdi phuc khdng phat xa ve cac m u c nang l u o n g thap hon (^Dj, j = 2; 3, 4) va cudi ciing la hdi phuc phat xa ve cac mire nang lugng c a ban (^F,, j = 0-6). T r o n g phd kich thich xuat
Nguyin Due Viegng vd cdng su hien cae van pho, d u g c q u y u d c bang ntiung cau binh ben trong d a y chuyen t i i p f-f ciia Tb bang cac lien kit chuyen tiep nhirng nang lugng ciia phan tii phen d i n Tb^^ Ton t^i hieu img c h u y i n chd cua nang lugng lir phan t u phen d i n ion Tb^' thi ion nay cd c u d n g do khuech tan trong viing phd 488-617 nm.
A _
Hinh 5: Phd huynh q u a n g ciia phiic (phen)2Tb(N03)3
5. K E T L U A N
1. Da tien hanh tdng h g p phirc chat cua T b * vdi 1,10-phenantrolin va nitrat, nghien ciiu ve ti le sd moi giira phdi tir phen vdi T b " , ket qua thu d u g c cho thay hieu suat tdng h g p dat gia tri cao nhat irng vdi ti le moi phen T b ' " = 2 : 1 .
2. I hanh phan phiic da d u g c xae djnh bang cac p h u a n g phap phan tich nhiet va phan tich nguyen td C, O, N . Ket qua c d n g thiic phan tir cua phirc la:
(phen)2Tb(NO03
3. c a u triic ciia p h u c (phen)2Tb(N03)3 d u g c xac dinh bang cac p h u a n g phap phan tich vat ly hien dai nhu: IR, Raman.
4. Da xac dinh tinh chat huynh q u a n g ciia phiic (phen)2Tb(N03)3.
TAI LIEU T H A M K H A O
1. Le Ba Thuan, Do Ngpc Lien, Nguyen Diic Vugng, Nguyen Trgng Hiing, Luu Xuan DTnh, Tdng hop nghien cuu mot sd phuc chdt cua Eu(in) vdi IJO- phenantrohn dimg ldm nguyen lieu che tao mdng chuven hoa dnh sdng. Tap chi Hoa hoc va O'ng dung.
59(11), 35-38(2006).
2 Ngu>'en Due Vuang Nghien cim phdn chia tmh che Samari. Europi. Gadolini tic tdng ddt hiem nhdm trung vd irng dung phirc chdt Europi che tgo mdng
chuyen hda dnh sdng. Luan an Tien sT Hoa hoc - Ha Npi (2007).
Pham Ty. Laser trongy hoc va trong phdu thudt than kinh, Nxb. Y hpc. Ha Noi (2010).
DSng Vu Minh. Tinh hinh nghien ciru cong nghe va irng dung ddt hiem, Vien Khoa hpc Viet Nam, Trung tam Thong tin lu lieu. Ha Npi (1992)
A, S. Alikhanyan, I. A. Solonla, and M. N.
Rodnikova. Thermodynamic stability of neodyminum nitrate complex with l.IO-phenanthroline, Russian Journal of Coordination Chemistry, 52(8), 1220-1222 (2007).
Fmelby By. L. R,, N. J. Rose, E. Abramson, and J. C Caris. Synthesis and fluorescence of some trivalent lanthanide complexes, J. Am Chem, Soc, 86(23), 5117-5124(1964).
F A, Hart and F. P. Laming, Complexes of l.IO- phenanthroline with lanthanide clorides and thiocyanates, J Inorg. Nucl Chem,, 26. 579-585 (1964),
Minbo Chen, Zongsen Yu. Rare earth elements and iheir applications. Metallurgical Industry Press, Beijing (1995).
S V, Larionov, \ . L. Varand, R F.Klevtsova, T, G.
Lconova, L. A Glinskaya, and E. M, Uskoy Synthesis of Heterohgand Complex Nd(phen)l(iso- CjH.,).PS2}2(NOi). Crystal Structure of Nd(phen){(iso-CjHv)2PS2j3 and Luminescent Properties of these Compounds. Russian Journal of Coordination Chemistry, 34(12), 931-937 (2008),
Lien he: N g u y e n D i i c V u g n g T r u d n g Dai hgc Q u a n g Binh
Dirdng 312 1 y T h u d n g Kiel. P h u d n g B5c Ly.
Thanh phd D d n g H d i . linh Q u a n g Binh Email: \ u o n g q b u n i @ g m a i l . c o m .
