Tgp chi phdn tich Hoa, Ly vd Sinh hgc - Tap 19, So 4/2014
TONG HOP VA NGHIEN CUtJ TINH CHAT PHlTC CHAT MQT SO NGUYEN TO DAT HIEM NANG V d l AXIT 2-PHENOXYBENZOIC
Din tda sogn 1 - 6 — 2014 Nguyin Thj Hien Lan, Nguyen Quynh Giang Khoa Hoa hgc, truang DH Su Phgm - DH Thdi Nguyin
SUMMARY
PREPARARION AND STUDY ON CHARACTERIZATION OF COMPLEXES OF SOME HEAVY RARE-EARTH ELEMENTS WITH 2- PHENOXYBENZOIC ACID
The complexes of heavy rare earth ions with 2-phenoxybenzoic acid have been synthesized. The characteristics of the rare earth complexes Ln(Pheb)3 (D^*: Tb'*, Dy , Ho , Yb ; Pheb; 2-phenoxybetrzoate) have been performed by elemetal analysis, IR, thermal analysis and mass-spectroscopy methods. IR spectra of the complexes showed that carboxyl of 2-phenoxybenzoic acid coordinated to earth ions. Mass- spectroscopy showed that the 2-phenoxybenzoates are monomes Ln(Pheb)3. TG- curves indicate that the complexes are stable up to a temperature of about 403-488 C.
The thermal separation ofthe 2-phenoxybenzoates was supposed as follows:
Tb(Pheb)3 "'-'^'•'^ > TbzOa Dy(Pheb)3 " - " • ' ^ ) Dy203 Ho(Pheb)3 "'-""'" > H02O3 Yb(Pheb)3 '"°'' > Yb203
1 Mri DATT Vdi muc dich gdp phin nghien Cliu vao
>n-. • u-~ .- u t.-. •!.• • u ' linh vuc cac cacboxylat thom ciia dat Nho co nhieu tinh chat quy bau ma phuc , -^
, i , , . tt. • . . .i hiem, trong cdng trinh nay chiing tdi chat caboxylat thom cua cac nguyen to ' ? ° . J a
. ( , . ; , . , . , - , . , . trinh bay ket qua tdng hgp va nghien Cliu dat hiem luon thu hut duac su quan tam / T © . r o-
, . . . , . u - i u i . n i tinh chat phiic chat 2-phenoxybenzat ciia nghien ciru cua cac nha khoa hpc [1,2, , ^ , , ,
, , ^ , , , . i . . . .* . mdt sd nguyen td dat hiem nang.
3], Cac phuc chat nay dugc ung dung ' " v ^ " B / . s rdng rai trong nhilu Hnh vuc khac nhau ^^ "^^^ NGHIEM
nhu: chl tao cac vat lieu tir, vat lieu sieu ^- ^ " " 8 h?P "^f P"*'^ ^hat 2- dln, vat lieu phat huynh quang...[4, 5, 6]. phenoxybenzoat 4at hiem
Cac 2-phenoxybenzoat dit hilm dugc tdng hgp md phdng theo tai lieu [7]: Hda tan mdt lugng xac dinh axit 2- phenoxybenzoic (HPheb) trong dung djch NaOH 0,1M theo ti le moi HPheb : NaOH = 1:1, hdn hgp dugc khuiy tren may khuay tir trong khoang 1,5 gid cho din khi thu dugc dung dich natri 2- phenoxybenzoat (NaPheb) trong sudt.
Them tir tir mgt lugng dung dich LnCls 0,1M (Ln: Tb, Dy, Ho, Yb) vao dung dich natri 2-phenoxybenzoat theo ti le moi LnCl3 : NaPheb = 1 : 3. Hdn hgp dugc khuiy tren bep khay tir d 60 C, pH = 6. Sau khoang 2 gid. tinh thi phiic chit tir tit tach ra. Lgc, nia va lam khd phirc chit trong binh hut am den khdi lugng khdng ddi. Hieu suat tdng hgp dat 80-85 %. Cac phiic chit cd mlu dac tnmg cua ion dat hiem.
2. Cac phuong phap nghien ciru Ham lugng dit hiem dugc xac dinh bang phuang phap chuan dp complexon vdi chit chi thi Arsenazo III.
Phd hip thu hdng ngoai dugc ghi tren may Impact 410 - Nicolet (My), trong
viing 400+4000 c m ' . Mlu dugc che tao bing each nghien nhd va ep vien vdi KBr, thuc hien tai Vien Hda hpc, Vien Han Lam KH va CN Viet Nam Gian dd phan tich nhiet dugc ghi tren may DTG 60H trong mdi trucmg khdng khi. Nhiet do dupc nSng tit nhiet dp phdng din 800°C vdi tdc dp ddt ndng lO'C/phut, thuc hien tai Khoa Hda Hgc, Trudng Dai Hpc Su Pham Ha Ndi.
Phd khdi lugng dugc ghi tren may LC/MS Xevo TQMS, hang Water (My), ngudn ion: ESL nhiet do khi lam khd 325°C, ap suit khi phun: 30 psi, thuc hien tai Vien Hda hgc, Vien Han Lam KHvaCN Viet Nam.
3. KET QUA VA T H A O LUAN Ket qua phan tich nguyen td, phd hap thu hong ngoai, phan tich nhiet va phd khoi lugng cua cac phiic chat dugc trinh bay d cac bang 1, 2, 3 va 4 tuong iimg. Hnh 1 la phi hdng ngoai ciia HPheb va Tb(Pheb)3, hmh 2 la gian dl phan tich nhiet cua Ho(Pheb)3 va Yb(Pheb)3, hinh 3 la pho khoi lugng ciia Ho(Pheb)3 va Yb(Pheb)3
Bdng 1. Kit qudphdn tich hdm lugng kim logi trong cdc phirc chdt stt
1 2 3 4
Cdng thiic gia dinh cua cac phirc chat
Tb(Pbeb)3 DY(Pheb)3 Ho(Pheb)3 Yb(Pheb)3
Ham lugng ion kim loai trong cac phiic chat Ly thuyet (%)
19,95 20,26 20,55 21,31
Thuc nghiem (%) 19,88 20,31 20,63 21,63 Cac ket qua d bang 1 cho thay ham
lugng dat hiem trong cac phiic chat xac dinh bang thuc nghiem tucmg ddi phii hgp vdi cdng thirc gia dinh.
Trong phd hdng ngoai cua cac phiic chat deu xuat hien cac dai cd cudng dp manh d vimg (1531H-1585) cm"', dai nay dugc quy gan cho dao dgng hda tri bit ddi xiing
cua nhdm -COO'. Cac dai nay da dich chuyen vl vimg cd sd sdng thip ban so vol vi tri tugng iing ciia nd trong phd hap thu hdng ngoai cua HPheb (1688 cm ). Dieu dd chiing td, trong cac phiic chat khdng cdn nhdm -COOH tu do, ma da hinh thanh sir phdi tri cua phdi til vdi ion dat hilm qua nguyen tu oxi
cua nhdm -COO' lam cho lien ket C=0 trong phiic chat bi ylu di. Trong phd hap thu hdng ngoai ciia cac phirc chit gia tri
Av(Av=v _ - v -,)vao khoang
^ as(coo ) s(coo ) ' ^
IOO cm', chiing tdi gia thiet khuynh hudng phdi tri vdng hai cang la dac trung trong cac 2-phenoxybenzoat dit hilm [8].
Bdng 2. Cdc ddi hdp thu dgc trung trong pho hdp thu hdng ngogi cua cdc hgp chdt (v, cm') Stt
1
2 3 4 5
Hffp chat
HPheb
Tb(Pheb)3
Dy(Pheb)3
Ho(Pheb)3 Yb(Pheb)3
VfCOOHl
1688
- - - _
VastCOO-)
1585 1534 1585 1531 1583 1536 1582
Vs(COO-)
1481 1411 1480 1410 1481 1412 1483
•"fCH)
3064 2823 2653 3067 3076 2934 3081 3064
M^z^.j
(a)
x_
(b) FTinh 1: Phd hdp thu hong ngogi cua
a) HPheb b) Tb(Pheb)3
Cac dai hip thu trong viing (1410 1483) cm'' dugc quy gan cho dao dgng hda tri ddi xiing cua nhdm -COO". Dac tnmg trong pho hdng ngoai cua cac 2- phenoxybenzoat dit hilm la hien tach dai phi tuong iing vdi cac dao dgng hda
tri bat ddi xiing va ddi xiing cua nhdm COO'
Cac dai trong viing (2934 -;- 3081) cm'' thugc vl dao ddng hda tri cua nhdm -CH tiong vdng benzen.
%
^ Hlnh 2. Gidn do phdn tich nhiet cita cdcphuc^dt a) Ho(Pheb)3
b) Yb(Pheb)3
Bdng 3. Ket qudphdn tich nhiet cua cdc phiec chdt
stt
1
2
3 4
Phirc chat
Tb(Pheb)3
Dy(Pheb)3
Ho(Pheb)3 Yb(Pheb)3
Nhiet do tach cau tir
("C) 403 446 479 420 472 481 474 451 488
Hieu img nhiet
Tda nhiet Tda nhiet Tda nhiet Tda Nhiet Tda Nhiet Toa nhiet Tda Nhiet Tda Nhiet Toa nhiet
C l u t u tach
Phan buy va chay
Phan buy va chay Phan buy
va chay Chay
Phan cdn lai
Tb203
Dy203
H02O3 Yb203
Phan tram mat khoi lirgng thuyet
(%)
77,06
76,75
76,49 76,26
Thuc nghifm
(%)
80,97
80,60
77,37 76,94
Nghien ciru gian dd phan tich nhiet cua bdn phiic chit thiy ring, d dudi 403°C khdng xult hien hieu ling thu nhiet tren dudng DTA va hieu ling mit khdi lugng tran dudng TGA. Kit qua nay hoan toan phil hgp vdi dir lieu phd hip thu hdng ngoai ring cac phiic chit diu d trang thai khan, khdng chira nudc. Tir (403 - 488 C) la cac hieu ung tda nhiet tuang ling vdi cac hieu iing giam khdi lugng tren dudng TGA. Cac hieu iing nhiet nay ling vdi qua trinh chay ciia cac phiic chit
tao ra san pham cudi cimg la cac oxit dit hilm LnzOs. Tir bang 3 cho thay phan tram mat khdi lugng tinh theo ly thuyet phil hgp vdi kit qua thuc nghiem.
Tir dd cd thi gia thilt sg dd phan buy nhiet cua cac phiic chat nhu sau:
-> Tb203 Tb(Pheb)3
Dy(Pheb)3 " " " ' ^ > Dy203
Yb(Pheb)3 ? ^ Yb203
Htnh 3. Pho khdi lugng cua:
a) Ho(Pheb), b) Yb(Pheb),
Bdng 4. Cdc mdnh ion gid thiit trong phd khdi lugng ctia cdc phtic chdt
TT
1
2
3
4
Phiic chat
Tb(Pheb)3 (M=797)
Dy(Pheb)3 (M = 801)
Ho(Pheb)3 (M = 803)
Yb(Pheb)3 (M = 812)
m/z
798 702 691 625 584 490 802 695 629 616 587 529 509 804 697 631 617 590 510 377 813 705 640 621 597 514 382
Manh ion
[Tb(Pheb)3+ IT]"
[Tb(Pheb)2(Pheb-C6H50) + VT]"
[Tb(Pheb)(Pheb-0)(Pheb-C6H50)+H"]"
[Tb(Pheb)(Pheb-C6H5)(Pheb-C6HjO)-H*]"
[Tb(Pheb)2 +IVY
[Tb(Pheb)(Pheb-C6H50)+II*]*
[Dy(Pheb)3 +H*]*
Py(Pheb)(Pheb-0)(Pheb-C6H50)+H*[*
[Dy(Pheb)(Pheb-C6H5)(Pheb-C6H50)-H*]*
[Dy(Pheb)(Pheb-C6H;0)2+H*]"
Py(Pheb)2 + H*]*
Py(Pheb-C6H50)3 - H*]*
[Dy(Pheb)(Pheb-C6H5) - H*]"
[Ho(Pheb)3+ir]*
[Ho (Pheb)(Pheb-0) (Pheb-CsHsO) +H*J*
[Ho(Pheb)(Pheb-C6H5) (Pheb-CsHsO) - 2Lr]*
[Ho(Pheb)(Pheb-C6H50)2 - H*]*
[Ho(Pheb)2]*
[Ho(Pheb)(Pheb-C6H!) - 3H*]*
[Ho(Pheb)]*
[Yb(Pheb)3 + H*]*
[Yb(Pheb)(Pheb-0)(Pheb-C6H50) + H*]*
[Yb(Pheb)(Pheb-C6H5)(Pheb-C6H;0)]*
[Yb(Pheb)(Pheb-C6H50)2 - H"]' [Yb(Pheb)2]*
[Yb(Pheb)(Pheb-C6H5) - 5H*]*
[Yb(Pheb) - 4 i r ] *
Tan suat
(%)
44 14 73 12 62 14 85 41 16 28 11 100 85 65 70 17 22 13 51 13 64 34 13 32 6 80 14
Gia thiet ve cac manh ion dugc tao ra trong qua trinh ban pha cua cac phvrc chat dua tren quy luat chung vl qua trinh phan manh ciia cac cacboxylat dat hilm [9].
Tren phd khdi lugng ciia cac phiic chit deu xuat hien pic cd m/z ldn nhat lln lugt bing 798, 802, 804 va 813 tuang ling vdi cac pbuc chit 2 - phenoxybenzoat cua Tb'*, Dy'', Ho'* vaYb'*. Cac gia tti nay ling diing vdi cdng thiie phan hi [Ln(Pheb)3 + H*]* (Ln'*: Tb'*; Dy'";
Ho'*; "Yb'*; Pheb': 2-phenoxybenzoat) ciia cac phiic chit. Dieu dd chiing td, trong dieu kien ghi phd, cac phiic chit tdn tai d ttang thai monome vdi cdng thiic phan hi Ln(Pheb)3.
Tren phd khdi lugng ciia cac phiic chat, cac pic ion phan tu cd cudng do tuang ddi ldn, dieu dd chiing td cac ion phan tir la tucmg ddi ben ttong dilu kien ghi phd.
Nghien ciiu phd khdi lugng ciia cac phiic chat thiy ring thanh phan pha hoi cua bdn phiic chit la tuong tu nhau, diu gdm su xult hien cua ba ion manh cd cdng thiic chung:[Ln(Pheb)(Pheb-0)(Pheb-C6H50) +H*]"; [Ln(Pheb)2+H*]* va [Ln(Pheb)(Pheb-C6H5)(Pheb-C6H50)-H*]*
(Ln'*: Tb'*, Dy'*, Ho'*, Yb'*). Trir phiic chit tecbi 2-phenoxybenzoat, ttong pha hai ciia ba phirc chit cdn lai ciing deu xuat Men ion manh [Ln(Pheb)(Pheb-0)2 + H*]
(Ln'*:Dy'*,Ho'*,Yb'*).
Tuy nhien, trong mdi phiic chat tin suat cd mat cua cac loai ion manh la khac nhau. Ddi vdi phiic chat tecbi 2- phenoxybenzoat va dysprozi 2- phenoxybenzoat, ttong pha hoi, chiem tin suit ldn nhit la ion manh
[Tb(Pheb)(Pheb-0)(Pheb-C6H50)+H*]*
va ion manh [Dy(Pheb-C6H50)3-H*]*
Cdn ddi vol phiic chat honmi 2- phenoxybenzoat va ytecbi 2- phenoxybenzoat ion phan tu [Ho(Pheb)3+H*]* va ion phan tii [Yb(Pheb)3+H*]* cd tin suit ldn nhat trong pha hoi.
4. K^TLUAN
1. Da tdng hgp dugc cac phiic chit 2- phenoxybenzoat cua 4 nguyen td dat hilm, cac phirc chit cd cdng thiic chung:
Ln(Pheb)3 (Ln**: Tb**, Dy*, Ho'*, Yb'*;
Pheb': 2-phenoxybenzoat)
2. Da nghien cuu cac san pham bang phuong phap phd hdng ngoai, ket qua xac nhan Pheb' da tham gia phdi tri vdi cac ion dat hiem qua oxi cua nhdm - COO' va cac phiirc chat tdng hgp dugc deu d ttang thai khan.
3. Da nghien cliu cac phirc chat bang phuang phap phan tich nhiet, ket qua cho thiy, cac phirc chit diu kem ben nhiet va da dua ra so dd phan buy nhiet cua chiing.
4. Da nghien ciiu cac phiic chat bang phuang pbap phd khdi lugng, ket qua cho thiy, cac phiic chit tdn tai d dang monome Ln(Pheb)3. Thanh phan pha hai ciia cac 2-phenoxybenzoat dat hiem la tuong tu nhau.
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