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TRNG I HC S PHM
L TH MI
Nng, 2008
MC LC
LI NI U
CHNG 1.
1.1. NH NGHA
1.2. U IM CA THUC TH HU C SO VI THUC TH V C
1.3. MT S C TNH C BN CA THUC TH HU C
1.4. HNG NGHIN CU CA THUC TH HU C
1.5. PHN LOI THUC TH HU C
CHNG 2. L THUYT V LIN KT PHI TR
2.1.PHNG PHP LIN KT HA TR (VB
2.2.L THUYT V TRNG TINH TH
2.3. CU TRC PHN T V TAN
2.4. PHC CHELATE (VNG CNG)G
2.5. S N NG KHNG GIAN V CHN LC
2.6. BN CA HP CHT PHI TR
2.7. NG HC CA PHN NG TRONG THUC TH HU C.
CHNG 3 :NHM CHC PHN TCH V NHM HOT TNH
PHN TCH
3.1. NHM CHC PHN TCH
3.2. NHM HOT TNH PHN TCH
CHNG 4: NHNG LUN IM L THUYT V C CH
PHN NG GIA THUC TH HU C V ION V C
4.1.HIU NG TRNG LNG
4.2. HIU NG MU
4.3. HIU NG KHNG GIAN
4.4. THUYT SONG SONG CA KYZHEOB
4.5. S PHN LY CA MUI NI PHC
4.6. S PHN LY CA MUI NI PHC
4.7. LIN KT HYDRO
3
PYROCATECHOL TM
5.3.
CHROMAZUROL S
6.4.
LI NI U
PHN I
L THUYT THUC TH HU C
CHNG 1
Tl
Iodua Tali
Thionalidat tali
61,7
48,6
Thnh phn phn trm ca ion c xc nh thp trong sn phm cui cng lm
gim sai s tnh ton, ngha l lm tng chnh xc ca phng php phn tch. Mt
khc th tch kt ta to thnh bi thuc th v c (khi kt ta 1 lng ion cn xc
nh nh nhau) do nhy ca phn ng tng ln.
3- Sn phm mu ca thuc th hu c vi ion v c, c cng mu ln v trong
nhiu trng hp c cng pht hynh quang ln, do ngi ta c th pht hin
c nhng lng v cng nh ion v c v nh lng chng bng phng php o mu
hoc o hunh quang mt cch thun li.
Thm vo , nhng sn phm mu phn ln l nhng hp cht ni phc nn kh bn
v d chit bng dung mi hu c li l nhng thun li khc rt ng k.
4- Cui cng cn ch ra rng, do s khc bit ca rt nhiu loi thuc th hu c nn
ngi ta c th chn trong mi trng hp ring bit, thuc th thch hp nht v tm
nhng iu kin thun li nht cho phn ng tin hnh v do phn ng phn tch t
nhy v chn loc cao.
1.3. MT S C TNH C BN CA THUC TH HU C
Khi nghin cu cc thuc th hu c ngi ta thng quan tm n cc tnh cht sau
y:
* tinh khit: Tr mt s t thuc th, hu ht cc hp cht hu c trn th
trng l khng tinh khit. Tu theo mi trng hp, c th yu cu c lm sch. V
d: Chloranil nh l mt thuc th dch chuyn in tch vi amino acid nn phi lm
sch trc kh s dng. y l yu cu u tin trong nghin cu cc thuc th hu c.
* tan: tan ca thuc th trong dung mi no s quyt nh phng php
phn tch ca thuc th y. Bit c tan chng ta s ch ng trong nghin cu.
V d: EDTA khng tan tt trong nc (mi trng trung tnh). thay i tan ca
n th cn trung ha bng mt bazo. 8-Hydroxyquinoline tan yu trong nc, n
thng khng tan trong acid acetic dng bng v pha long bng nc, nu phi t
hay phc ca n khng tan trong nc.
*p sut hi: Mt phc c th c p sut hi cao hn cc phc khc. Nhng
dn xut ca metoxy hay etoxy c p sut hi cao hn nhng hp cht b m ca
chng. Da trn s khc nhau v p sut hi ca cc phi t hay phc ca chng, mt
s cht c tch bng phng php sc kh ph.
* bn: Mt s phc chelate rt bn trong dung mi tr khi phc hnh thnh.
Tuy nhin, mt s phc bn vi nhit c tch bng phng php chng ct m
khng b phn hu. Mt vi phc nhy vi nh sng v khng kh th phi c bo
qun cn thn.
* phn cc: phn cc ca mt phn t cho bit tan ca n trong dung
mi. Mt phn t phn cc s c thun li trong dung mi chit. Bn cnh , s tch
8
1.5.
O2N
OH
OH
O2 N
NH2
(I)
NH2
OH
NH2
OH
COOH
COOH
(II)
(III)
(IV)
Nhng dn chng nu trn chng t rng cch phn loi thng dng cho cc
hp cht hu c, th cn c vo cc nhm chc trong phn t thuc th phn loi l
khng hp l.
1.5.2. Phn loi theo phn ng phn tch c thuc th tham gia
Theo s phn loi ny, thuc th hu c c chia thnh 9 nhm. 1- Nhng cht
to phc mu.2 - Nhng cht to mui. 3-Nhng cht c kh nng to nhng hp cht
cng hp t tan hoc c mu c trng. 4-Nhng cht ch th. 5 -Nhng cht mu to
phc hp th (sn). 6-Nhng thuc th gy nn s tng hp hu c trong phn ng,
ng dng vo phn tch. 7 -Nhng thuc th c kh nng to phc vng vi ion kim
loi (vng theo thnh hoc l do lin kt ho tr, lin kt phi t hoc l hn hp c hai
loi ny). 8-Nhng cht oxy ho. 9-Nhng cht kh.
H thng phn loi ny cng mang nhiu mu thun ni ti:
1- Mt cht c th c trong nhng nhm phn loi khc nhau.
V d: Alizarin c th c nhm 5 v nhm 7. Dipyridin cng c th c nhm 1
v nhm 7.
10
H2N
SO4
Cu
Ca
C
CH2
H2N
CH2
SO3Na
H3C
OH2
2HN
Cu
C
H
CH
Cu
OH2
C
H
CHNG 2
3d
dxydxzdyz dx2-y2dz2
4s
4p
F-
F- F- F -
NH3
NH3NH3NH3
4d
F- F-
[Co(NH ) ]
3 6
NH3NH3
2.2.
(2.1)
Trong phng trnh (2.1), q1 v q2 l nhng in tch ca nhng ion tng tc, r l
khong cch gia nhng trung tm ca nhng ion. Ngi ta s dng phng trnh
tng t m t c nhng tng tc ca phn t phn cc khng tch in vi ion.
Php gn ng cho nhng kt qu ph hp kh tt vi nhng gi tr nng lng lin
kt tm c bng thc nghim i vi nhng phc ca nhng kim loi khng chuyn
tip. i vi phc ca kim loi chuyn tip nhng gi tr tnh ton trc thng qu
nh. S khng tng ng s c b chnh li mt cch ng k nu ch ti qu
o ca nhng in t d v gi thuyt v nh hng ca phi t ln nng lng tng
i ca nhng qu o d.
Nm 1930, ln u tin nhng nh vt l (Beta v Vanflek) hon thin l thuyt
tnh in v s dng gii thch mu v t tnh ca cc mui tinh th. L thuyt ny
c gi l l thuyt trng tinh th. Mc d l thuyt ny nu ln trong cng thi
gian hoc l sm hn mt cht so vi phng php lin kt ha tr nhng 20 nm sau
mi c cc nh ha hc bit ti v s dng. Nguyn nhn c th l do thuyt
trng tinh th c vit cho cc nh vt l cn phng php lin kt ha tr th li
cho mt quan nim kh r rng v lin kt gia cc nguyn t.
Nm 1951, mt s nh ha hc l thuyt s dng thuyt trng tinh th mt
cch c lp vi nhau gii thch ph ca phc nhng kim loi chuyn tip. V
phng php t ra c hiu qu nn ngay lp tc hng lot cng trnh nghin cu
c tip tc. Ngi ta lm sng t rng thuyt trng tinh th rt thun li cho
vic gii thch bn nh lng nhiu tnh cht bit ca cc hp cht phi tr.
hiu thuyt trng tinh th cn hnh dung mt cch r rng s nh hng
khng gian ca qu o d (hnh 2.2). Tng tc ca nhng qu o d ca nhng kim
loi chuyn tip vi cc phi t bao quanh, n sn sinh ra hiu ng trng tinh th.
minh ha thuyt trng tinh th, ta hy xt phc bt din [TiF6]2-. Trong ion Ti4+ t do
nm cch bit trong khng gian, hnh dng in t l nh sau: 1s22s22p63s23p6,
khng c in t d. Nm qu o 3d trng trong ion c c trng bng cng mt
mc nng lng. iu cho php gi thuyt rng in t c th nm trn mt trong
s nhng qu o d vi xc xut nh nhau. Nhng qu o tng ng vi cng mt
gi tr nng lng gi l qu o suy bin.
15
ec
Nng lng
0,6 0
0
0,4 0
t2
d
Ion kim loi t do (Ti4+)
Phc gi thuyt vi
cc qu o d suy bin
Hnh 2.2: S mc nng lng ca nhng qu o d ca ion kim loi t do ca phc
gi thuyt trong khng c s tch mc bi trng tinh th v ca phc bt din.
Trong phc [TiF6]2- ion Ti4+ c bao quanh bi 6 ion F-. Do s c mt ca nhng
ion F- , tc dng y ca nhng in tch m ca chng gy tr ngi cho s np in
t vo qu o d ca ion Ti4+. Ni mt cch khc, nhng ion F- (hoc l nhng phi t
khc) khi tin ti gn qu o d lm tng nng lng tng ng ca chng (hnh 2.2).
Nu nh 6 ion F- bao quanh ion Ti4+ trong [TiF6]2- phn b trn cng mt khong cch
ti 5 qu o d ca Ti4+ th tt c cc qu o d c trng ng vi cng mt gi tr
nng lng (chng b suy bin) nng lng tng ng ln hn so vi nng lng vn
c ca ion Ti4+ t do. Phc bt din vi tt c cc qu o d suy bin l phc gi
thuyt. Phc [TiF6]2- c cu to bt din. tin li cho s nghin cu phc chng
ta xem nh 6 ion F- s phn b trn cc trc x, y, z trong h ta Descartes. Trong s
phn b nh vy:
F
z
x
y
F
Cc ion s nm gn cc qu o d x -y v d x nht, l nhng qu o eg . S tht
l cc qu o eg hng thng ti cc phi t F- trong khi th nhng qu o dxy,
2
16
Qu cu bng bt bin
Qu cu bng bt bin di
Qu cu bng bt bin di p
p lc ca lp v hnh cu
lc tc ng vo nhng hng
(phc gi thuyt)
xc nh (phc cht).
S tng nng lng ca nhng qu o d ca ion kim loi hon ton c b tr bng
nng lng to lin kt gia ion kim loi v phi t. Trong trng phi t bt din
nhng qu o t2g v eg ca ion, tng ng vi nhng nng lng khc nhau. Hiu s
nng lng c k hiu l o. C th ni rng, do c im hnh hc ca h bt din,
nng lng tng ng ca nhng qu o t2g nh hn 0.4o. so vi nng lng ca
nhng qu o d suy bin bc 5 ca phc gi thuyt, tc l phc thu c nu nh
khng xy ra s tch mc nng lng trng tinh th (hnh 2.2). Cng do nguyn nhn
, nng lng tng ng ca nhng qu o eg ln hn nng lng ca qu o gi
thuyt suy bin bc 5: 0,6o. Trong phc bt din (v d [Ti(H2O)6+] c mt in t
nm trn qu o d c mc nng lng thp nht. Bng thuyt tnh in n gin th
khng th xc nh c rng trong phc cht nhng qu o d li tng ng vi
nhng gi tr nng lng khc nhau. Do thuyt ny gi thuyt rng in t d cn
phi c mc nng lng ca qu o d suy bin gi thuyt. S tht th qu o d ri
vo t2g c nng lng nh hn nng lng qu o suy bin gi thuyt 0,4o v do
phc s bn hn so vi phc da trn c s m hnh tnh in n gin. C th ni mt
cch n gin rng, in t d v do ton b phc c nng lng nh l do n nm
trn qu o d(t2g) l qu a c th tch xa phi t nht. i vi phc, gi tr 0,4o gi
l nng lng n nh ha bi trng tinh th. Trong bng 1 di y, chng ti s dn
ra nng lng n nh ha bi trng tinh th i vi nhng ion kim loi trong phc
bt din.
Bng 2.1. Nng lng n nh ha bi trng tinh th i vi nhng ion kim loi
trong phc bt din
S in t d
trong ion kim
loi
S in t d
trong ion kim
loi
t2g
t2g
eg
eg
Nng lng
n nh ha
Nng lng
n nh ha
Nng lng
n nh ha
eg
t2g
t2g
eg
Nng lng n
nh ha 0
0,4
0,8
1,2
0,6
1,6
0,0
2,0
0,4
2,4
0,8
1.8
18
1,2
0,6
10
0,0
19
dx2y2
Nng lng
dx2y2
s p
dx2-y2dz2
dz2
dxydxzdyz
e
2
dxy
0
dz
dx -y dz
dxydxzdyz
T din
Bt din
T gic lng
chp
dxz dyz
20
Hnh dung mt cch r rng s tch mc nng lng bi trng tinh th nhng qu
o d i vi cu to t din s gp kh khn hn. Trc ht, cn tng tng hnh t
din v trong khi lp phng (hnh 2.5) sao cho 4 nh ca t din phn b vo 4
nh ca khi lp phng. Nu by gi ta v cc trc x, y, z sao cho chng i qua trung
tm ca khi lp phng v qua cc trung tm ca 6 mt gii hn th c th hnh dung
v tr ca 4 phi t tng i theo cc qu o d ca ion trung tm. Nhng qu o d
nm dc theo h trc Decartes ( d x -y v d x ) cch xa cc phi t hn l nhng qu o
phn b gia cc trc (dxy, dxz, dyz). Do nhng qu o eg ( d x -y v d x ) tng ng
vi gi tr nng lng thp, nhng qu o t2g (dxy, dxz, dyz) c c trng bng gi tr
nng lng cao hn. Ngi ta pht hin ra rng trong trng hp ny c hiu s
nhng gi tr nng lng ca nhng qu o eg v t2g, ngha l b tch mc bi trng
tinh th k hiu l t, ch bng mt na o. Do , hiu ng trng tinh th to iu
kin thun li cho s to phc bt din hn l cho s to phc t din
2
T tnh ca phc nhng kim loi chuyn tip cng c gii thch m mn bng
thuyt trng tinh th. Nhng kim loi chuyn tip c cc mc nng lng ph d mi
ch c in t lp y mt phn, trn nhng qu o theo nh lut Hund s c
nhng in t khng ghp i. V d: ion kim loi c 3 in t d (gi l h d3) c th
c 3 in t khng ghp i
c 2 in t khng ghp i v 3 i in t
[CoF6]3-
[CoF6 ]
0
Co ( NH 3 )6
3+
23
: Cl :
[Fe(H O ) ]
3+
Fe(CN )6
]3
[Cu (NH ) (H O ) ]
2+
3 4
[Ni(CN )4 ]2
[CoCl4 ]2
Trng phi t yu
CO, CN->Phen>NO2>en>NH3>NCS->H2O>F->RCO2>OH->Cl->Br->I gii thch dy cn phi t b m hnh hon ton ch c tnh cht ion tnh in
i vi lin kt trong phc v cng nhn rng y tng tc cng ha tr cng tn ti.
24
100
Xanh
Vng
50
0
0
0.2
0.6
0.4
di nh sng ()
0.8
1
(x 104)
eg
nh sng
5000
t2g
t2g
[Ti(H O ) ]
[Ti(H O ) ]
3+
3+
E =
hc
(2.2)
E =
2, 8 4 * 1 0 5
(2.3)
(2.4)
C s ion ca thuyt trng tinh th cho ta m hnh n gin gii thch nhiu
tnh cht ca kim loi chuyn tip, cu to, bn, ph hp th ca phc. Nhng cn
nhn xt rng m hnh ion n gin ca thuyt trng tinh th khng cho mt khi
26
nim r rng v lin kt trong nhng hp cht ca kim loi chuyn tip. Mt khc,
trong khi nghin cu phc cht, ngi ta thu c nhiu bng chng thc nghim
khng nh vai tr ca c hai loi lin kt: lin kt ion v lin kt cng ha tr. Thuyt
phn nh trung thnh c hai c tnh y trong lin kt ca phc l thuyt qu o phn
t.
2.3.
27
Tr xen ph
Qu o A phn lin kt
Cng xen ph
Qu o lin kt
Tr xen ph
Qu o
kt
Cng xen ph
phn lin
B
Qu o lin kt
Tr xen ph
Qu o A phn lin kt
Cng xen ph
Qu o lin kt
Hnh 2.10. S to thnh qu o phn t theo phng php KAO
T hp nhng qu o nguyn t s cho qu o phn t (sigma). T hp nhng
qu o nguyn t p nh ch r trn hnh 2.10, c th cho hoc l qu o phn t
hoc l qu o phn t . Trong trng hp qu o phn t mt phng qua hai
nhn c xc xut in t tm thy bng khng. in t trong qu o phn t ch
nm trn hoc di trc lin kt.
minh ha vic s dng MO, c th xem biu nng lng MO vi mt s
phn t n gin. Biu nng lng phn t H2 c nu ln hnh 2.11. Trong
nhng nguyn t Hydro ring bit, mi qu o nguyn t ch c mt in t. Trong
phn t H2 c hai in t cng nm trn qu o phn t lin kt c nng lng thp.
Phn t H2 bn hn nhng nguyn t hydro t do bi v c hai in t trong phn t
u nm trn qu o c nng lng thp. Hiu nng lng gia nhng qu o
nguyn t v qu o phn t lin kt ph thuc vo vn l nhng qu o nguyn
t trong phn t xen ph ln nhau nhiu hay t. Xen ph nhiu gy khc nhau ln v
nng lng v do lin kt nhau cht, xen ph t th s khc nhau v nng lng nh
v trong trng hp ny phn t s c gi tr nng lng ch nh hn mt cht so vi
nhng nguyn t ring bit.
28
Nng lng
AO
MO
AO
s *
1s
1s
1s
s
H
H-H
Nng lng
AO
MO
AO
s *
1s
1s
1s
s
H
H : He+
He
MO
2
c
2S
AO
Nng lng
2S
b
1S
A
a
1
AB
1S
B
in t ca A tham gia
vo lin kt
in t ca A tham gia
vo lin kt
1s1
a+b
1s1
1s1
1s1
2a+b
1s2
2a+b
1s2
1s2
1s22s1
1s2
c+d
1s2
1s22s1
1s2
1s22s2
2c
1s22s1
1s22s2
1s22s2
1s22s2
31
3 p*
s*
Nng lng
4p
u *
4s
dXYdyzdxz
3d
Phi t
d1
p
s
Co(III)
AO
Co ( Fe )
6F-
MO
AO
3 p*
s*
Nng lng
4p
u *
4s
3d
2d1
Phi t
p
s
Co(III)
Co ( NH 3 )
6NH
Hnh 2.14. Biu mc nng lng qu o phn t ca phc spin cao [CoF6]3- v
phc spin thp [Co(NH3)6]3+.
32
Nu s khc nhau v nng lng gia nhng qu o t2g khng lin kt v nhng
qu o phn t d* t, th qui lut Hund c thc hin. Phc [CoF6]3- hon ton
ging trng hp ny, nhng in t d phn b theo cc qu o t2g, d*2. Hai in t
nm trn qu o d* lm gim s in t trn qu o lin kt d v do lm yu
lin kt CoF. Nu ln nh [Co(NH3)63+] tt c cc in t c xu th chim qu
o t2g. Nguyn nhn ca s phn b nng lng gia nhng qu o t2g v d* hoc l
eg theo hai thuyt l khc nhau. Theo thuyt trng tinh th th s tch mc nng lng
l hu qu ca tc dng y tnh in ca phi t i vi nhng in t d. L thuyt
qu o phn t th ch yu li qui s tch mc cho s to thnh lin kt cng ha tr.
Nhng qu o eg ca kim loi v qu o ca phi t xen ph ln nhau cng nhiu th
nng lng ca nhng qu o d* cng cao.
L thuyt qu o phn t c th gii thch nh hng ca lin kt n bn
ca phc kim loi v n gi tr tch mc ca trng tinh th gy nn bi nhng loi
tinh th khc nhau. V s gii thch nh lng tng i phc tp nn y ch a ra
s gii thch nh tnh. Trn y nu ln rng, lc tng tc cng ha tr ph thuc
vo mc xen ph nhng qu o nguyn t ca 2 nguyn t lin kt. Trong cc v
d trc ta mi ch nghin cu s xen ph . Trong [Fe(CN)6]4- v trong phn ln
nhng phc khc c ng thi c lin kt v lin kt (hnh 2.15). Trong lin kt
phi t s dng nh l mt baz Lewis v a i in t ca mnh vo qu o trng
eg ( hnh 2.15, d x -y ) dng chung. Trong lin kt ion CN- x s nh l mt acid
Lewis v nhn in t t nhng qu o t2g hon thnh ca kim loi , t qu o
dxy). S c mt ca lin kt cng nh ca lin kt lm tng lin kt kim loiphi
t v lm cho ion [Fe(CN)6]4- bn mt cch c bit. Trong nhng ion cha oxy nh
MnO4- lin kt v cng rt quan trng. Trong trng hp ny phi t (oxy) a
in t to lin kt .
2
Lin kt Fe-CN
Lin kt Fe-CN
34
OH
CO
CO
Be
OH
OH
Thng hng
CO
Fe
CO
OH
T din
O2N
NO2
Co
F
O2N
Bt din
F
Fe
NO2
F
F
F
i lng tr vung
F
Cu trc d on
Ghi ch
d1, d6
Thay i t gic
d2, d7
Thay i t gic
Khng thay i
Spin cao
10
d,d
d,d
d ,d
d6
Khng thay i
d3
Spin thp
2+
+ 2H
+ 2
Cu
OH
AML n
A M A Ln
Y 4-
Y 4-
=
[ H 6 Y ][ H5Y ][ H 4 Y ] H3Y - H 2 Y 2- HY 3- Y 4- [ Y']
[Y4-] nng ion Y4- t do, [Y] l tng nng ca Y trong dung dch.
nh hng ca phi t cnh tranh lm cn bng ca EDTA vi kim loi dch
chuyn sang tri.
M + Y MY
L
ML
nh hng ca phi t ln s cn bng c tnh thng qua M
40
M =
[M]
[ M']
[M] Nng ion kim loi Mn+ t do trong dung dch , [M] tng nng ion kim loi
M trong dung dch. v M c tnh theo cng thc sau:
1
2
3
n
=1+K1 [ L ] +K 2 [ L ] +K 3 [ L ] +......+K n [ L ]
M
[ MY ]
[ M ][ Y ]
m [ Y ] = Y [ Y'] v [ M ] = M [ M']
suy ra: K MY =
[ MY ]
[ M'][ Y'] Y M
K MY Y M =K M'Y' =
[ MY ]
[ M'][ Y']
vy hng s bn iu kin
K M'Y' =
[ MY ]
[ M'][ Y']
41
CHNG 3
C NOH
C NOH
C NH
C NH
CH C NOH thay th
3
V d:
+ Ni 2+ + 2NH3
CH C N
3
OH
phi tr
CH C NO
3
CH C
3
Ni + 2NH
ti OH
CH2
CH2
HN
C
(I)
OH
CH2
CH
OH
SH
CH2
(II)
(III)
(IV)
CHR'
R''
HN
CHR'
CS
O
CH3
C
H
N
CH3
43
Ag
O
CH3
S
Ag
C
H
N
CH3
O
CH3
C
H
VI
N
CH3
O
CH3
C
H
N
CH3
Tng kt nhng d kin thc nghim ngi ta cng nhn nhm chc phn tch ca
AgI l:
S=CNHC=
3.1.2. Nhm chc phn tch ca Cu(II)
Nhng axyloinoxim c cng thc tng qut
R
CH
NOH
OH
CH
NOH
OH
R
CH
R"
"R
N
O
Cu
2 loi:
- Mt loi bao gm nhng hp cht to mui vi Cu khng tan trong ammoniac
(trong nhng hp cht ny ng bo ho phi t)
- Mt loi bao gm nhng hp cht to mui vi Cu tan trong ammoniac (trong
nhng hp cht ny ng cha bo ho phi t)
Mui ng to thnh thuc loi ny hay loi khc l do bn cht nhng gc c
trong phn t quyt nh: Nu trong phn t thuc t c gc thm th mui ng tng
ng khng tan trong ammoniac. Nu trong phn t c gc bo th mui ng trong
nhiu trng hp tan trong ammoniac. Trng lng ca gc khng nh hng n
tan ca mui ng trong ammoniac.
Feigl ngh cng thc cu to mui ni phc khng tan trong ammoniac ca ng
vi xyloxinin nh sau.
R
CH
R"
Cu
HC
Cu
Cu
HO
C N OH
NOH
C
H
OH
trong nhn thm cng l nhm chc phn tch ca Cu(II) (v d salicylaldoxim to
mui ni phc)
C
C
H
OH
N
Cu
OH
NOH
2HC
NOH
AsO3H2
N
SO3H
OH
HO
AsO3H2
N
OH
SO3H
SO3H
(II)
HO
AsO3H2
N
OH
AsO3H2
N
HO3S
HO3S
SO3H
46
OH
SO3H
(III)
(IV)
COOH
OH
HO
AsO3H2
C
H
SO3H
(V)
(VI)
H2O3As
SO3H
SO3H
OH
AsO3H2
H2O3As
OH
HO3S
SO3H
HO
N
Ion phn
ng
Cng thc
O
NH
H3C
N
C
H
H3C
Ag+
H3C
N
AsO3H
H3C
Zr(III)
H3C
pdimethylamino
benzene azo
anthraquinone
H3C
48
[SnCl6]2-
H3C
pdimethylamino
benzene azo
beznyliden
camphorxin
C
H
H 3C
H3C
HON
CH2
H3C
p,p
Tetramethyldiamine
diphenylmetan
CH3
H3C
CH3
H2
C
Pb2+,Mn2+
H3C
Iodidemethylat (p
dimethyl
aminostyril
Ag+,
Cu2+,
Hg2+,
Hg22+
CH3
H3C
Tetramethyl
pphenylendiamine
Hg22+
C CH3
H2
C C CH2
CH3
H3C
N
C
H
H3C
H
C
Zn2+,
SCN-
I
N
CH3
NO
ONH4
NO
ONH4
Cufferon
Neocuferon
O
AsO3H
AsO3H
49
CH3
2 Methyl pyridine
CH3
2 methyl quinoline
50
CHNG 4
Nhng nhm lm tng trng lng khng th hin tc dng slovat ho.
TLPT
nhy
/ml
93
330
143
13
193
173
13
166 (khng k
iodide)
2,5
Cng thc
2methyl pirydin
(-pycoline)
CH3
2methyl quinoline
(Quinadine)
CH3
2methyl5,6
benzoquinoline
CH3
2methyl benthiazol
CH3
N
S
Iodidemethylat 2
methylbenzthiazol
I
N
CH3
C2H5
TLPT
nhy (/ml)
378
SO3H
N
51
SO3H
N
458
100
538
500
SO3H
HO
SO3H
N
SO3H
SO3H
4.2. HIU NG MU
Mu ca phn t thng lin h vi nhng lin kt i trong phn t v vy trc
ht chng ta hy xt c im ca loi lin kt ny.
4.2.1. Lin kt mch lin hp
Lin kt gia 2 nguyn t c to thnh bi nhng orbital S c tnh cht i xng
cn, ch hng theo ng ni lin kt 2 ht nhn ca 2 nguyn t c gi l lin
kt . Lin kt cng c th c to thnh bi nhng electron p v s. V d nh
nhng lin kt HO v HN. Nhng lin kt ny cng l nhng lin kt bi v mt
in tch ca nhng m my in t to lin kt l ln nht trn ng ni lin ht
nhn 2 nguyn t tng ng. Mt cch tng t, lin kt c th c to thnh bi
cc electron sp, min sao mt in t tp trung ln nht trn trc lin kt thng.
c im ca lin kt l rt bn nn t b kch thch. Do , nhng hp cht to
bi lin kt thng khng hp th nh sng trong min trng thy hoc l trong min
quang ph gn t ngoi. Ngoi ra, khi kch thch gc hoc nhng mng khc nhau.
Nh vy, nhng hp cht ch to bi nhng lin kt khng phi l nhng hp cht
ng ch i vi phng php o mu m nhng hp cht quan trng nht phi l
nhng hp cht c ni i.
Ngay c khi ch xut hin mt phn lin kt i cng dn ti kt qu l lm chuyn
cc i hp th v pha sng di.
Ta c th ly ion nitrat lm v d. Khi to thnh ion NO3- c s ghp i cc
52
electron 2px, 2py, 2pz ca nguyn t nit vi mt trong 2 electron p khng ghp i ca
mi nguyn t oxy.
Nh vy l trong hp cht to thnh (NO3-) mi nguyn t oxy cn li mt
electron p cha ghp i.
V O l nguyn t m hn N nn c th cho rng mt trong s 3 electron (ca 3
nguyn t) trng thi t do gy nn in tch m ca ion NO3- cn 2 in t cn li
th ghp i vi nhng in t 2s2 ca N to thnh lin kt th 2.
Nhng do h qu ca hin tng lai to li nn tt c nhng lin kt gia N v O l
nh nhau v phn b trong cng mt mt phng ng thi mi lin kt NO u l
trung gian gia lin kt n v lin kt i. S to thnh mt phn lin kt i dn ti
kt qu l ion nitrat c cc i hp th min t ngoi 305mm.
Trong khi nghin cu v cc phn ng mu, s hp th nh sng ca cc hp cht
hu c c cc ni i c ngha c bit quan trng. Lin kt th hai hoc th ba to
nn bi cc electron p c gi l lin kt . Lin kt ny c nhng c im ring. V
d: trong phn t ethylene CH2=CH2 do lai to sp2 nn cc lin kt nm trong cng
mt mt phng l ng nht v gc gia cc lin kt gn vi 1200. Nh vy, mi
nguyn t carbon cn li 1 in t p. Nhng in t p ny to lin kt nm trong mt
phng thng gc vi mt phng ca lin kt .
N
hc 8mCl2 N
=
=K 2
E
h
N+1
N+1
(4.1)
C2H5
H
C
C
H
C
H
N+
C2H5
Cl-
Khi trong phn t mt cht c cha 2 loi nhm tng mu c c tnh ngc nhau
th nh hng n mu li c bit mnh.
Ta c th minh ha iu ny qua v d sau y:
NO2
NO2
OH
O-
p-Nitrophenol
315nm
Anion p-nitrophenol
400nm
NO2
OH
Bezene
255nm
Phenol
275nm
Nitrobezene
268nm
Nguyn t
Cu, Au, Ti, V(IV)(V), Nb, Cr(III)(IV), Mo, W, U, Pu, Mn(II)(VII), Re,
Fe, Co, Ni, Ru, Rh, Ir.
Cu, Au, In, Sn, Sb, Bi, Mo, U, Fe, Co, Ni, Os.
Cu, Re, Fe, Co, Ni, Ru, Pd.
Cu, Au, Ti, Sb, Bi, Fe, Co, Ni, Ru, Pd, Os, Ir, Pt.
O
n
Men+
HO
Ion
H Ge(IV) Ti (IV) Zr (IV) Anion t do
Bn knh ion kim loi ( A0) 0,50
0,65
0,83
max (nm)
468
508
525
540
560
iu ny c th gii thch bng lc ht tnh in i vi nhng electron t do
cui mch lin hp. Nhng ion c bn knh nh Ge(IV) ht mnh nn max chuyn
mnh v pha sng ngn cn Zr(IV) c bn knh ln nn ht yu. V do max gn vi
max ca dng anion t do ca thuc th.
Khi cation kim loi to phc mu vi thuc th mu acid th cc i hp th mu
ca phc chuyn v pha sng di so vi ph hp th dng phn t (dng acid) ca
thuc th nhng thng s chuyn dch ny khng ln bng khi to thnh anion t do
(mui natri) ngha l:
max dng acid ca thuc th < max phc < max dng anion t do ca thuc th
C s chuyn dch cc i hp th nh vy l v ion kim loi lin kt vi u m
ca mch lin hp ko in t v pha mnh v nh vy l mch lin hp di ra.
V d:
O
OH
O
OH
OH
O-
HA ( Alyzarin )
max=520nm
56
O-
O-
A2 (Alyzarin tm)
max=620nm
Me
Me
O
OH
O2N
OH
Me3+
COOH
O2N
O
Me+
2H+
57
CH3
H3C
N+
CH3
H3C
C
Cl-
CH3
N
CH3
Ngi ta cng quan st thy hiu ng khng gian loi khc. l trng hp
nhng dn xut th 3,3 ca dipyridin. Da vo nhng v tr y nhng nhm c th tch
ln s lm bin dng cu hnh phng ca phi t v dn n kt qu l lm gim s n
nh ho do cng hng v lm xut hin sc cng trong lin kt kim loi phi t.
Hiu ng tng t cng c quan st thy khi a nhng nhm isopropyl hay
fluorbutyl vo v tr 3 ca acetylaceton. Nhng phi t nh th khng to nhng phc
mu bnh thng vi Fe(III) hoc l Cu(II).
R rng l c th gii thch s kin bng tng tc lp th gia nhm isopropyl
v tr 3 v nhm methyl v tr 2 hoc 4 lm cho tnh phng ca vng b ph hu,
gy tr ngi cho s cng hng v ngn cn to phc. N y nhm isopropyl ra xa
mch acetylaceton bng cch t nhm methylene vo gia th s to phc bnh
thng li tr li.
i vi phi t loi nh pocfirin(1) v flaloxyamine(2) kch thc ca nhn trung
tm c nh hng ln n bn ca phc. Nhng ion ln nh Hg2+, Pb2+ khng th
i vo nhn pocfirin, cn i vi nhng ion khng ln th c th d on rng bn
ca phc s gim xung khi bn knh ion gim xung. Do cng ca nhn pocfirin
nn mc xen ph nhng qu o ca ion kim loi c bn knh gim dn v phi t
cng s gim dn.
Tng tc gia Ag+ vi polymethylenediamine l mt v d in hnh khc v nh
hng ca nhng yu t hnh hc n qu trnh to phc.
Thng nhng vng 5 (vng khng c ni i) c hng s bn ln hn so vi
nhng phc tng ng c kch thc khc.
Nhng tt c nhng phc ca Ag+ vi trimethylenedianin, tetramethylenediamine,
pentamethylenediamine c cu to vng tng ng l 6, 7, 8 li bn hn phc vng 5
vi ethylenediamine. iu ny c gii thch nh sau:
Khi kch thc vng tng ln, ho lp th ca lin kt Ag+ c th trong mt mc
ng k tin dn ti dng thng hng l dng thch hp vi s phi t 2.
Do nh hng ca nhng yu t ho lp th nn kh nng to phc ca nhng dng
59
5,2
4,3
60
Ni(II)
6,7
4,6
Cd(II)
6,7
5,4
OH
NaO3S
N N
OH
O3S
N N
O-
33Na
NN
OH
OCH3
-
O3S
N N
OH
22Na
NN
OCH3
(V)
Theo s nh gi bng mt v theo ng cong hp th th mu dung dch ca
nhng hp cht (I), (II) v (V) rt gn nhau.
T chng ta thy rng s thay th hydro trong nhm OH bng nhm methyl
61
trong nhng hp cht chng ta ang bn khng th hin nh hng ln mu trong min
kh kin. iu cng ng trong nhng trng hp thay th hydro bng gc aryl.
Chng ta cng nhn thy mu dung dch ca nhng hp cht c cu to sau y rt
gn nhau:
COOH
NaO3S
N N
OCOC2H5
OH
N N
NaO3S
OH
O
-
O3S
N N
(VI)
Nu chng ta cng nhn quan im trn th s gn nhau v mu sc ca hp cht
(IV) v (VI) l hon ton c th hiu c v c th gii thch d dng sc thi nht
ca phc Ga(VI). Mu ca phc Ga(VI) rt gn vi mu ca monophenolat (IV) l do
trng thi phn ly ni phn ca monophenolat trong mi trng kim. Nhng mu ca
phc Ga cng khng th t ti sc thi hng thm ca diphenolat (II) v thc hin
iu c hai lin kt ca Ga vi nhng nguyn t oxy phi ng thi thc hin. R
rng, iu kin rt kh ng thi thc hin vi chnh iu kin tn ti phc trong
dung dch long.
Nhng iu trnh by trn, cho php chng ta suy lun mt cch hp l l c tn ti
trng thi phn ly ni phn. Da trn khi nim phn ly ni phn chng ta c th:
* Gii thch mu v nh hng ca pH ln mu ca nhng hp cht v phc cht loi
nu trn v nhng loi tng t.
*
R3NH+ + OH-
O
H
H
O
H
H
H
O
H
63
C
H
O
N
H
O
onitrophenol
Do to thnh lin kt hydro ni phn t nn onitrophenol c nhit nng chy
thp (45oC) cn cc ng phn para, meta khng thun li cho lin kt hydro do
nhit nng chy cao hn. (ng phn meta nng chy 97oC, ng phn para nng
chy 114oC).
S to thnh lin kt hydro nh hng r rt n hng s phn ly acid ca cc thuc
th hu c. Cc thuc th cha nhm OH v tr para i vi nhm azo c hng s
64
NaO3S
N N
NaO3S
OH
pK= 8,2
OH
pK= 6,7
HO
N N
NaO3S
N N
NaO3S
pK= 11,2
pK=11,2
N N
NaO3S
OH
SO3H
N N
NaO3S
OH
SO3H
2ON
OH
NH2
H3OS
SO3H
65
Cl
OH
NH2
H3OS
2ON
SO3H
Aso3H
H3OS
SO3H
Be
Cl
Aso3H
H3OS
SO3H
KHA
(4.2)
Hng s phn s :
K HA =
[ HA 0 ]
[ HA ]
(4.3)
[ HA ]
[ HA]
0
(4.4)
Th ph thuc vo K
Thuc th chit thng l acid hu c dng HmR, cc anion ca n to phc chit
c vi ion kim loi M. S phn b ca thuc th chit gia nc v tng hu c
ph thuc vo pH ca dung dch, v rng khng phi tt c cc dng thuc th chit tn
ti trong tng nc iu chuyn c vo tng hu c m ch c mt s dng trong
s chng, s phn b ca chng ph thuc v K, pH ca dng dch nc. Nu thuc
th chit HmR to ra cc dng chit c Hm+1R, Hm-1R,R, th h s phn b ca n
c m t bng phng trnh:
66
DR =
(4.5)
i=1
i=1
i=1
[CM ]0
[CM ]
(4.6)
qn K DM R n Lq [R]n [L]q
p
[R] [L] +
i
ij
j=0
(4.7)
i=0
OH
i
[OH]i
4.7.3. S chit ca cc hp cht ni phc (Cc phc chelate khng tch in)
S chit cation Mn+ bng thuc th chit HR dng hp cht ni phc MRn ho tan
trong dung mi hu c c m t bng phng trnh :
M n+ +nHRO
MR n O+nH +
Kex
(4.8)
Hng s cn bng:
K ex =
[MR n ]0 [H + ]n
[M n+ ][HR]0n
(4.9)
Nu v phi ca phng trnh (4.9) biu din qua hng s bn ca phc chit c
MRn, hng s phn ly acid ca thuc th K a v hng s phn b K D v K D th
HR
MR n
67
HR
(4.10)
MR n
HR
MR n
(4.12)
MR n
MR n
, lc ta nhn c:
D M =K ex [HR]0n /[H + ]n
(4.13)
(4.14)
(4.14)
Cc cn bng xut hin khi chit cc chelate cha cc phn t trung ha ca thuc
th chit, v c bn cng ging nh khi chit cc hp cht ni phc bo ho phi tr,
nhng trong cc cn bng tnh ton cn tnh n thnh phn ca phc chit c, v d
nu to phc MRn(HR)q theo phng trnh:
M n+ +(n+q)HR 0
K ex =
Kex
(4.15)
{MR n } ( HR q )0 {H + }
=K ex M (4.15)
C'M
HR
({ }{ }0(n+q) )
y:
M n+
M =
[ CM ]
68
(4.16)
1
q
pH1/2 = logK ex 1+ {HR}0 logf H+ P (4.16)
n
n
4.7.4.2.
M z+
z + ( n+p ) HR 0 +mA= MR n ( HR ) q A m
( z-m-n )
0
+nH +
(4.17)
V
logDM =logK ex ( n + p ) log [ HR ]0 + mlog [ CA ] + npH + alogf H+
(4.18)
V
1
m
q
pH1/2 = logK ex 1 + log [ HR ]0 log [ CA ] logf H+
n
n
n
(4.19)
mMR n ( 0) +nM m+
II
(4.20)
Ktr
K 'tr =
V rng K ex =
MR n K DMR
K HR
K DHR
(4.21)
M n+
M =
:
[ CM ]
K
'
tr
(
=
(
M I Rn
K DMI Rn MI
M II R m K DM II R m M II
(4.22)
K 'exI
Hay
K 'exII
M R K DM R M
I
(4.23)
M
II R m
K DM II Rm MII
(4.24)
K'exI
(4.25)
K'exII
V iu kin chit tt l:
K 'exI
K 'exII
M R K DM R M
4.8.
(4.26)
M
II R m
K DM II Rm MII
(4.27)
D MI
D MII
(4.28)
Nu nh h s ln hn trong cc h s phn b, v d DM m b hn ng k
I
K DMI , th phng trnh (4.28) c th biu din qua cc hng s iu kin ca s chit:
'
n'-n''
M I K exMI [HR]0
S
= '
+ n'-n''
M II K exMII [H ]
(4.29)
(4.30)
70
PHN II
THUC TH PHI TR O O
5.1. PHENYLFLUORONE
CTPT: C19H12O5
KLPT = 320,30
HO
OH
HO
5.1.1. Tn gi khc
2,3,7Trihydroxy9phenyl6fluorone
2,6,7trihydroxy9phenylisoxanthene3one.
5.1.2. Ngun gc v phng php tng hp
y l thuc th c gi tr v mt kinh t. N c tng hp bi phn ng 1,2,4
benzenetriol vi benzotrichloride.
5.1.3. ng dng trong phn tch
N c dng nh thuc th o quang v nhy, c tnh chn lc vi Ge v Sn;
ngoi ra thuc th cn dng xc nh Co, Fe, In, Mo(VI), Nb, Ti v Zr bng phng
php o quang.
5.1.4. Tnh cht ca thuc th
Phenylfluorone l mt tinh th bt mu cam, c nhit nng chy ln hn 300oC.
Xut hin hunh quang mu hi lc trong dung dch cn pH=8. Trong dung dch
71
pKa1=2.3
Vng
pKa2=5.8
SO3H
vng cam
pKa3=11.3
pKa3=12.3
H2L
HL2L3-
cam hng
Ge ( OH )2 ( H 3L )2 +2H 2
Bng 5.1.
Ion kim loi HCl HCl + H2O2 HCl + oxalate HCl+H2O2 + oxalate
72
Fe (III)
Ge (III)
Hf (IV)
Mo (VI)
Nb (V)
Sb (III)
Sn (IV)
Ta (V)
Ti (IV)
V (V)
W (VI)
Zr (IV)
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
L
L
L
y: S: mu m
L: mu nht
- : t hoc khng mu
Kt qu kho st trn phn ng to mu ca phenylfluorone trong acid HCl cho
thy ch c 12 kim loi c tm thy c kh nng phn ng vi thuc th. Trong
s c mt ca hydrogen peroxide v phi t, s to phc c tnh chn lc cao cho
Ge(IV), Sb(III), Sn(IV).
Trong php xc nh bng phng php o quang, nhy v chn lc gia tng
ng k bng cch chit mi trng acid mnh. c tnh quang ph ca
phenylfluorone chelate c tm tt trong bng 5.2, quang ph hp th ca Ge chelate
c hng dn trong hnh 5.2.
Bng 5.2. c im quang ph ca phc phenylfluorone
Gii hn
cho php
(ppm)
iu kin
T l
max
.104
(nm)
pH 3,0 4,0
pH 9,5 11,0, Triton X100
pH 4,5 5,0; NO2-,
Zephiramine
ML2
ML2X
540
554
6,0
13,5
0 0,2
ML2
645
4,8
~2
Cr(VI)
pH 1,5; 40 EtOH
ML
500
2,1
0,01 1,7
Fe(III)
Ga
ML2
ML2X2
580
570
8,6
11,4
~1
ML2
510
8,7
Ge(IV)
Ge(IV)
In
NaOH 0,001N
pH 8,0 9,0; CPB(X)
HCl 1,2N, gelatin, gm Arabic hoc
polyvinyl alcohol
HCl 0,5N, chit vi benzyl Alcohol
HC l,1 1,5N; CTMAC
pH 5,5; gelatin
ML2
ML2
ML2
505
505
540
14,5
17,1
4,88
0,05 0,5
0,02 0,16
0,2 1,4
Mn(II)
CPC(X)
ML2X2
9,8
Kim
loi
Al
Al
Co(II)
Ge(IV)
73
Mo(VI)
Mo(VI)
Mo(VI)
Nb
Nb
Ni
Sb(III)
Sn(IV)
Sn(IV)
Ta
Ti
Ti
Ti(IV)
Ti(IV)
V(IV)
Zn
Zr(IV)
Zr(IV)
pH 2,0; gm arabic
pH 1,5; CPC
pH 4,5
cyclohexanol
pH 4,6, F- , CPC
ML2
CTMAC:
550
540
9,6
0,33 1,67
0,4 6
518
7,4
0 0,6
520
3,7
525
10,0
0 0,4
620
540
10,4
3,42
0 0,33
510
5,93
~2
505
530
18
6,39
0 0,3
0 0,5
540
9,0
0,05 0,1
550
540
17,1
0,05 10
540
16,3
0 0,2
530
1,7
0,2 2
585
8,0
01
540
13
~1
560
4,6
07
Cetyltrimethylammonium chloride
Cetyltrimethylammonium bromide
74
OH
HO
C
SO3H
H 4L
5.2.1. Tn gi khc
pKa1
+
pKa2 < 1
H4L
H5L
H3L-
pKa3 = 7,82
H2L2Tm
Vng
pKa4 = 9,76
HL3-
pKa5 =11,7
L4-
- tm
77
OH
OH
HO
OH
OH
+H+
C
SO3-
SO3H3L -
H2L2+H+
+ H+
OH
OH
OH+
HO
OH
O-
C
SO3
SO3-
HL3H4L
+H+
+ H+
OH
OH
HO
O-
O-
OH+
SO3-
SO3H
L4-
H5L +
pH
6,5
7,5
5,5
6,5
Mu
Cd(II)
Ce(III)
Co(II)
Cu(II)
Fe(II)
Fe(III)
Ga
In
La
Mg
Mn(II)
8,0
6,5
7,5
5,0
7,5
<2,0
2,5
7,0
9,5
8,5
<3,0
Hng
<1,5 Hi ta
3,5
0,5
<0,3
<1,5 Mu ta
5,0
<3,0
>3,0 Hi ta
6,3
7,0
<1,0 Hi ta
Sb(III)
Sn(II)
Sn(IV)
Th
Ti(IV)
UO22+
WO42WO42Y
Zn
Zr
Mu ta
Hi ta
O-
O
ML2- (xanh tm)
C
SO3-
OH
C
SO3-
M2L- (xanh)
M+
C
SO3-
79
pH
23
HNO3
Cd
10
NH3NH4Cl
Co(III)
9,3
NH3NH4Cl
Cu(II)
Cu(II)
Fe(III)
Ga
56
67
56
3,8
HNO3NH3
Pyridine
Pyridine
Acetate
Mu thay i ti
im kt thc
Xanh Vng
Hi xanh dng
hi ta
Hi xanh dng
hi ta
Xanh Vng
Xanh Vng
Xanh Vng
80
Lu
Fe(III); Hg(II); Th; Zr
c chun cng
Vt ca kim loi nng
khng c ln
Chun chm
Dung dch chun nng
Thm NH2OH
In
Pyridine
Mg
10
NH3NH4Cl
Mn(II)
9,3
NH3NH4Cl
Ni
9,3
NH3NH4Cl
Pb
5
2,5
3,5
Hexamine
HNO3
10
NH3NH4Cl
Th
Zn
Xanh Vng
Hi xanh dng
hi ta
Hi xanh dng
hi ta
Hi xanh dng
hi ta
Xanh Vng
Xanh Vng
Hi xanh dng
hi ta
iu kina
Al(III)
Al(III)
Al(III)
pH 6,0
pH 9,7 10,2, CTAC(X)
pH 10 CPC(X)
(x 104)
0 04
0,27 54
B
Be
Bi(III)
Cd(II)
Co(II)
Cr(III)
Cu(II)
Fe(III)
Fe(II)
Ga
Th
Th
Ti(IV)
Ti(IV)
V(V)
W(VI)
W(VI)
Y(III)
Y(III)
Zn(II)
Zr(IV)
Zr(IV)
-
pH 8,55 8,65
pH 8,0, CPC(X)
pH 3,8, acetate
pH 10 CPC (X)
pH 10, CPC (X)
pH 5,0 6,0, acetate
pH 7
pH 6,2 7
pH 5,0 6,0, CTMAB (X)
pH 6,05 6,4
pH 3,8, acetate
pH 8,0, CTMAB
pH 3,3 3,5, gelatin
pH 2,0, CPC
pH 4,0, Zephiramine
pH 2,0 6,0
pH 1,0, CPC
pH 8,7, H3BO3
pH 8,4 9,0, gelatine
pH 9,0, CPC
pH 3,5 5,0
pH 6,0, CPC
ML
MLX5
MLX5
MLX5
ML2
ML2X2
ML2
ML3
ML2
MLX5
ML3
ML
MLX5
MLX
MLX5
ML2
MLX5
494
680
610
710
720
605
630
610
605
580
480
660
690
745
660
540
670
607
665
690
650
700
0,165
1,5
1,0
1,2
1,1
6,2
13,5
~ 7,3
6,0
7,5
7,5
6,4
1,9
2,59
1,3
3,26
1,3
0,2 2,0
4 24
0,1 7,5
4 24
0 0,6
0 0,35
0,56 3,1
4 24
0,6 4,0
0,06 0,71
0 0,5
16
0-7,8
0 1,8
0 2,0
Ion kim loi c th c xc nh trc tip bng php trc quang trc tip vi
Pyrocatechol tm trong dung dch c dung mi l nc c tm tt bng 5.6. Nh
m t trc y nhy chc chn c ci tin bi s kt hp ca cation cht hot
ng b mt.
Thng thng Pyrocatechol tm khng l thuc th chn lc v b cn tr bi nhiu
nguyn t. Bi vy phng php ny c th p dng sau khi c s tch thch hp hoc
kt hp s dng cht che thch hp.
Phc anion vi Pyrocatechol tm c th c chit vo trong dung mi hu c nh
l mt cp i ion vi cation ring l, nh vy t c nhy v chn lc ca
php xc nh. Xc nh trc quang Sn(IV) vi s kt hp s dng Pyrocatechol tm v
cetytrimethylammonium bromide:
Chuyn 10ml dung dch mu (0,01 0,1mg Sn) v 5ml dung dch Pyrocatechol tm
10 M trong mt beaker 100ml. Thm 2ml cetyltrimethylammonium bromide 0,1% v
pha long n 50ml. Hiu chnh pH ca dung dch n 2,2 bng dung dch ammoniac
long, s dng my pH. Chuyn ton b dung dch vo bnh nh mc 100ml v nh
mc ti vch. Sau 10 pht, o hp thu s dng cuvet 1cm loi tr nh hng nn
bng mu trng 662nm.
-3
5.3. CHROMAZUROL S
CTPT: C23H16O9Cl2S
82
KLPT: 539,34
COOH
COOH
OH
H3C
Cl
Cl
SO3H
5.3.1. Tn gi khc.
3Sulfo2, 6dichloro3,3dimethyl4hydroxyfuchson5,5dicarboxylic acid.
5.3.2. Ngun gc v phng php tng hp
Chromazurol S l tn thng mi ca thuc nhum c sn xut bi tp on
Geigy; loi thuc nhum ny l mt loi thuc th c ng dng rng ri. Chng ch
yu dng mui trinatri. N c tng hp bng s ngng t ca sulfoo
dichlorobenzaldehyde cng 2,3cresotic acid, km theo qu trnh oxi ha.
5.3.3. ng dng trong phn tch
Chromazurol S c dng lm ch th kim loi trong phng php chun phc
cht xc nh Al, Ba, Ca, Fe, Mg, Ni v Th; v cng l mt thuc th trc quang cho
nhiu ion kim loi khc nhau nh l: Al, Be, Ce, Co, Cr, Cu, Fe, Ga, Hf, In, La, Mn,
Mo, Ni, Pd, Rh, Se, Th, Ti, V, Y, Zn, Zr v F-. Theo nhng nghin cu gn y,
phng php trc quang vi nhy cao ca nhng cation k trn trong s hin din
ca cht hot ng b mt cationic.
5.3.4. Tnh cht ca thuc th
Dng thng mi C23H13O9Cl2SNa3.2H2O l bt mu nu . C kh nng ht m
v d ha tan trong nc. Trong dung dch nc, pH = 3 4 c mu cam, pH = 4
c mu vng. Trong mi trng acid pH<0 (HCl 1,2 2,0N) to thnh ta dng t
do H4L v li b ha tan trong dung dch acid hn (HCl 8 9N).
Gi tr hng s phn ly proton c xc nh ( = 0,1 (NaClO4), 25oC) v ph
hp thu trong dung dch nc nhng pH khc nhau c minh ha hnh 5.5
H 5L
+
pKa1
pKa2 = -1,2
pKa3 = 2,25
pKa4 = 4,88
pKa5
H2L2HL3- =11,75
H4L
H3Lcam
vng
COOH
COOH
L4tm
Chromazurol S phn ng c vi nhiu ion kim loi khc nhau nh l: Al, Be, Ce,
Co, Cr, Cu, Fe, Ga, Hf, In, La, Mn, Mo, Ni, Pd, Rh, Sc, Th, Ti, V, Y, Zn, v Zr to
thnh nhng phc chelate tan mang mu. S tng phn gia mu cam hay vng
ca thuc th vi mu xanh tm l gii hn mu ca phc chelate. Nhng gi tr pH
thp nht m quan st c mu ca phn ng th c tm tt trong bng 5.7. T l
gia kim loi v phi t khc nhau ph thuc vo kim loi v cng ph thuc vo iu
kin dung dch nh l pH v t l gia thuc th v kim loi.V d, cu trc ngh
ca ba loi phc chelate Fe(III) c minh ha hnh 5.6.
pH
2,5
2,0
4,0
5,5
7,5
1,0
pH
Al(III)
Acetate
Cu(II)
6-6,5
Acetate
Fe(III)
2-3
Ni(II)
Th(IV)
Thay i mu im
cui
Tm vng
Xanh m xanh
nc bin
chun 80o
chun 80o
Monochloroacetic
acid acetic acid
Pyridine +NH3
1-2
Ch
Xanh tm vng
HNO3-NH3
Tm vng
chun in
th
Aluminon:
Mui ammonium ca acid aurine tricarboxylic.
CTPT: C22H23N3O9
KLPT: 473,43
HO
NH4OOC
COONH4
COONH4
OH
L cht bt mu nu vng, trong sut v d tan trong nc. Sn phm thng mi,
thng c tinh khit khc nhau. tinh khit c th c kim tra bng chy qua
sc k lp mng (TLC) vi silica gel. N to mu lp lnh vi ion Al, Be, Cr, Fe v
nhng ion t him. V th n c s dng trong php o mu xc nh v pht hin
nhng ion ny. Sn mu ny c th tan vi s tr gip ca cht hot ng b mt
nonionic nh l Triton X100 (acetate pH 4,8; 1,5ml Triton 20%; 100oC; bc sng
537nm). nh hng ca Fe c th c loi nh s dng kt hp acid ascorbic v acid
thioglycolic.
-
Erichrome Cyanime R:
2Sulfo3,3dimethyl4hydroxyfuchson5,5dicarboxylic
trisodium (CTPT: C23H16O9S, KLPT: 468,43).
87
acid,
mui
COOH
HO
CH3
COOH
O
CH3
C
SO3H
(1)
OH
C
N
R'
(2)
CH = CH
CH 3
(3)
5.4.1. Tn gi khc
Nhng cht phn ng bao qut trong phn ny c lit k trong bng 5.10, cng vi
nhng ng phn ca chng.
Bng 5.10. NBENZOYLNPHENYLHYDROXYLAMINE v nhng hp cht lin quan
STT
Thuc th
T ng ngha
N-Benzoyl-N-phenylhydroxylamine
N-Cinnamoyl-Nphenylhydroxylamine
N-Benzoyl-N-otolylhydroxylamine
N-Phenylbenzohydroaxamic
aicd, BPA, NBPHA, BPHA
NPhenylcinnamohydroxamic
acid, CPA
N-o-tolyl-benzohydroxamic
acid, BTA
88
Cng thc
phn t
Phn
t khi
C11H13NO2
213,24
C15H13NO2
239,31
C14H13NO2
227,26
89
O
M
O
O
C
nhin, loi acid v c, v tnh acid. Nhng dung mi chit l chloroform, benzene,
v iso amylalcohol, trong dung mi chloroform c a dng hn.
Nng (1) cao hn th cn chit trong acid sulfuric hn l acid hydrochloric.
Trong trng hp acid nitric, s chit tr nn t hiu qu hn vi s gia tng nng
acid, mc d vy nitrate vn c a dng cho vic chit mt s nguyn t.
5.4.6.3 Dng nh cht phn ng trc quang
Nh cht phn ng trc quang, BPA (1) c nghin cu rng ri hn nhng
cht ging nh n. Nhng phc c mu m c chit chn lc t dung dch c
tnh acid.
5.4.6.4 Xc nh Vanadium
Vanadium (V) kt hp vi nhng cht ny qua mt dy rng ca tnh acid, dng
phc c th c chit vi chloroform. Ti pH 2,5, phc mu g c hnh thnh
vi BPA (1) c s hin din ca ethanol, nhng phn ng ny khng c tnh chn lc.
Trong acid hydrochloric 5 9N, chit vi chloroform to phc mu ta, v h mu tun
theo nh lut Lambert Beer bc sng 530nm. Vi s gia tng nng acid hoc
c nh nng ban ngy chiu vo, t trng quang hc ca h s gim.
CPA (2) c ngh l cht phn ng chn lc cho V, nhng n khng c
trng cho V. Sau , (1) c khng nh l chn lc hn, nhng vn phn ng vi
Mo, Ti, v Zr cho phc mu vng n cam nh hng n vic xc nh V dng vt.
Cui cng, BTA (3) dng nh c c tnh chn lc cn thit cho V. Trong acid
hydrochloric 4 n 8 N, (3) l cht phn ng c trng cho V v c th dng phn
tch v nhng cht v c. Phc mu tm c hnh thnh trong dung dch acid
hydrochloric, c chit vi carbon tetrachloride hoc chloroform v o bc sng
510nm. Ch c ion Ti l nh hng nhng c th che n bng fluoride.
* Cc bc xc nh V trong v cc hp cht v c
Phn hy 100g mu dng bt bng cch x l vi acid sulfuric, nitric, v
hydrochloric trong chn Platinum, un cn acid sulfuric trn bp. Nung chy phn cn
trong chn platinum hoc tt nht l trong chn silica vi potassium pyrosulfate v
chit phn nng chy ny vi 10ml nc c cha hai git acid sulfuric 20N. Chuyn
dung dch vo mt ci phu chit v thm tng git potassium permanganate 0,02M
n khi dung dch c mu hng, sau cho d ti thiu 5 git oxy ha V. Th tch
dung dch lc ny nn l 20ml. Thm 2ml dung dch acid sulfamic 0,05M, 2ml dung
dch sodium fluoride bo ha, v 20ml dung dch acid hydrochloride m c. Dng
pipet thm 10ml BTA 0.02% trong carbon tetrachloride hoc chloroform (khng c
ethanol), ng li v lc phu trong khong 30 giy. Sau , c s ngn cch pha, lc
lp di qua mt tm xp vi cotton vo mt ci l nh. o hp thu ca dung dch
i vi mt mu trng bc sng 510nm.
5.4.6.5 Xc nh Titanium
Titanium (IV), nh V(V), hnh thnh dng phc khc vi (1), ty thuc vo tnh
acid v pha nc. Trn pH 1, mu ca phc (TiOL2) th t mnh lit hn so vi mu
thu c ti nhng acid cao hn v mu c tnh chn lc hn i vi nhng thay
i gi tr pH. Khi nng acid hydrochloric tng n 2N, mu ca dng phc TiL4
92
c hnh thnh (max = 355nm, trong CHCl3). Trong dung dch acid hydrochloric
mnh s cho dng phc ML2Cl2 (max = 380nm, trong CHCl3). Mt lng d chloride
gi cho dng ion U (IV) khng phn ng vi (1). Nu ion thiocyanate c thm trc
khi chit Ti t dung dch acid vo trong chloroform, mu sc tng mt cch ng k,
hu nh chc chn l do dng phc ba ML2SCN. Ging nh nh hng c ghi
ch vi (2) v (3).
* Th tc xc nh Ti trong hp kim
mt t l dung dch mu (khng cha nhiu hn 100g Ti) trong phu chit,
thm mt lng va dung dch acid hydrochloric m c acid ha dung dch
cui > 9,6N. Thm 10ml dung chloroform 0.1% BPA vo dung dch ny v lc 1 n 2
pht, lc lp di qua mt giy lc kh v o hp thu ti bc sng 380nm i vi
mu trng.
S hin din ca Fe, Sn, W, V, Zr, v Mo (IV) trn mt vi miligram nu c
gim bng Sn (II) th khng c hi. Phc c hp thu ti a ti 371nm, nhng n
thng c th o 380nm bi v hp thu ca cht phn ng ti bc sng ny thp
hn.
5.4. ACID CHLORANILIC V NHNG DN XUT KIM LOI CA N
CTPT: C4H2O4Cl2
KLPT = 208,99
O
Cl
OH
HO
Cl
O
5.5.1. Tn gi khc
3,6Dichloro2,5dihydroxypbenzoquinone.
5.5.2. Ngun gc v phng php tng hp
Dng acid t do v nhng dn xut kim loi ca n nh Ba, Hg (II), La, Sr, Th v
Zr Chloranilat c th mua c trn th trng. Acid Chloranilic c iu ch bng
cch thy phn cht kim Chloranil. Nhng Chloranilat kim loi c iu ch bng
phn ng ca acid Chloranilic vi mui v c tng ng trong nuc nng.
5.5.3. ng dng trong phn tch
Acid Chloranilic t do c s dng nh cht phn ng to ta cho nhng ion kim
loi nng, a ho tr v cng l cht phn ng ln mu dng trong php o quang cho
nhng ion kim loi da trn c s trn phn ng to ta. Nhng Chloranilat kim loi
c s dng nh l cht phn ng dng trong o quang cho nhng anion da trn s
phn ng ca Chloranilat kim loi to thnh mui kh tan vi anion xc nh v ng
93
nhng dng tinh th khan mu nu c hoc dng bt mu en. Mui Bari c cung
cp (mua) dng kt tinh hydrate, n lp lnh nh sng ging nh kim loi. Mt mu
c nh thng khng ng nht, tu thuc vo iu kin iu ch.
Nhng dn xut kim loi ny th hu ht kh tan trong nc cng nh trong hu ht
cc dung mi hu c, ngoi tr mt s dung mi c s phn cc hn, v d:
ethylenediamine, methyl cellosolve, acid acetic, pyridin, tetrahydrofuran
tan ca Bari Chloranilat trong nc l 2,2.10-4M v trong nc ethanol (1:1) l
5,2.10-6M. Mc d tan ca nhng dn xut kim loi th khng bit c chnh xc,
nhng tan c th gn ng trong nhng nguyn tc chung ca Bari chloranilat.
tan ca Canxi chloranilat trong nuc th tu thuc vo pH, tan nh nht pH
= 4,4. tan 8,1.10-9 pH = 3 v tan 1,8.10-9 pH = 7, c th so snh vi tan
Canxi oxalat.
Khi bc chloranilat kh tan c lc vi dung dch nc cha ion Cl-, kt ta AgCl
v gii phng ion Chloranilat acid c mu ta hi , c biu din nh sau:
Ag2L + 2Cl- + H+ = 2AgCl + HL(rn)
(rn)
(rn)
Du
hiu
Anion
iu kin
PTP
Gii hn
xc nh
(ppm)
BaL
tinh
th
nu
tm
SO42-
pH 4,0 4,6;
trong 50%
ethanol, pH 8
SO42-+ BaL + H+
HL- + BaSO4
0,3 100
BO33-
m NH4Cl
Tartarat
H3BO3+BaL+tartarat
HL- + phc Ba
borat
0,3 10
F-
pH 4, trong isoPrOH
pH 2, trong 50%
methylcellosolve
0,05 200
SrL
Ag2L
HgL
bt
nu
en
bt
xanh
xm
bt
xanh
thm
Cl
Cl-
96
ThL2
bt
nu
en
CuL
bt
nu
La2L3
bt
xm
en
F-
pH 7, trong 25%
Methylcellosolve
0,01 100
S2-
0 10, CN-,
oxalate,
tartarat,
citrat gy
tr ngi
F-
pH 6,5 7, trong
50% Ethanol
hoc trong 50%
methylcellosolve
2 200
pH 7
2PO43- + La2L3 +
3H+ 3HL- + 2LaPO4
3 300
PO43-
5.5. CUPFERRON
CTPT: C6H9N3O2
KLPT: 155,16
5.6.1. Tn ch th v cng thc ha hc
Tn ch th:
Tn ha hc: nNitrosophenylhydroxylamine, mui amoni.
Tn thng thng: Cupferron.
Cng thc ha hc:
Cng thc phn t: C6H9N3O2
Cng thc cu to:
ONH4
N
N O
5.6.2. c im ca ch th Cupferron:
To phc vi cc ion kim loi.
To ta cc ion kim loi.
Chit cc ion kim loi.
5.6.3. Cc tnh cht ca ch th Cupferron:
L bt trong sut mu vng nht, im nng chy t 163 n 164oC, thng hoa trn
97
30oC.
Thuc th ny khng bn di nh sng v khng kh. gim ti thiu nhc
im ny, thuc th thng c cha trong chai mu nu vi mt t ht amoni
carbonat nh l mt cht bo qun.
Acid t do (HL) l mt cht rn khng bn mu trng (im nng chy 51oC) v
t ng phn hy thnh nitrobenzenediazonium, 4,4dinitrodiphenylamine v cc cht
khc. N tan rt t trong nc, nhng d tan trong cc dung mi hu c khc. N l
acid n chc, c pka = 4,16 ( = 0,1 NaClO4, 25oC), KD(CHCl3/H2O) pH > 3 vi HCl
hoc HClO4 = 142 (nhit phng) KD(ethylacetat/nc) = 285,6 v KD(CCl4/H2O) =
2300 (15oC).
5.6.4. Tnh cht chun ca ch th Cupferron:
5.6.4.1. Phn ng to phc v tnh cht ca phc:
Cupferron l phi t hai rng vi cc v tr phi tr ca oxi vi nhm nitroso v oxi
khng mang in tch. Hu ht cc ion kim loi trong bng tun hon c kt ta vi
Cupferron trong dung dch nc. Cng nh mt thuc th phn tch, Cupferron khng
qu chn lc, nhng tnh chn lc hi cao hn trong dung dch c tnh acid mnh so
vi trong dung dch c tnh acid yu. Di iu kin trn, ch Fe(III), Hf, Ga, Nb, Sn,
Ta, Ti, V v Zr kt ta. Kh tnh acid gim, cc ion khc u b kt ta. Nh l cht kt
ta ca kim loi, Cupferrate khng qu bn khi sy kh, chng thng bc chy thnh
oxit trong php phn tch trng lng.
Kim loi Cupferrate khng mang in tch v bo ho phi tr, c th c chit
trong dung mi tr, c minh ha di y:
O
Mn+/n
N
N=O
T
_
Ti
Thp
Fe(III),Mo(VI), Sn(IV),
Ti(IV), V(V), Zr
U(VI)
Bi
Fe
Ga
Th
Actinoids, Am
Pu(III)
iu kin
Dung mi
pH 5,5 5,7,
EDTA,
citrate
4-ethylpentan2-one
Dung dch
kim long,
EDTA,
tartarate, S2pH 5,5,
EDTA, Ce
CHCl3
MIBK
HNO3 0,1N
CHCl3
H2SO4 6N
Iso-AmOH
Acid v c
long
CHCl3, hoc
ethyl acetat
1NHCl
Ti, V, Zn
H2SO4 2N ,
Fe, Ge, Nb,
Ta, Ti, V, Zr
pH 0,3 1,
Hf, La, U(VI)
HCl 0,5
1,5N
CHCl3
CHCl3
CHCl3
Benzene +
iso-AmOH (1
: 1)
CHCl3
U(VI)
iu kin
Ch
H2SO4 2N
pH 4,55,5, EDTA, hn hp
MgO sau khi ng kt ta vi Sn
hoc Ti
H2SO4 610 v/v %
Bi, Fe, Ga, Hf, Mo, Nb, Pa, Po, Sn, Ta,
Ti, V, Zr v actinit ha tr 4
Be v mt lng ln Ti, Zr, F-, CO32-
6N phn ly 50% sau 4 ngy, trong khi Cupferron phn ly trong mt phm vi no
ch trong 65 pht); tan tt trong nc (11,49g/100ml), pKa = 5,58. Phng php to
phc tng t nh Cupferron.
Cc ng ng alkyl khc, nnitrosoncyclooctyl, nnitrosoncyclododecyl v
NnitrosoNisopropylhydroxylamine cng c trnh by.
OH
NaO3S
SO3Na
OH
OH
NO2
NO2
5.7.2.2. c im ca Dinitronaphthalenediol:
To phc vi cc ion kim loi.
Chit cc ion kim loi.
5.7.2.3. Cc tnh cht ca Dinitronaphthalenediol:
Dinitronaphthalenediol c phn t lng bng 250,17.
L bt trong sut mu cam, im nng chy 180o182oC.
Tan t trong nc lnh (dung dch mu cam), tan nhiu hn trong nc nng v tan
trong acid acetic v ethanol.
5.7.2.4. Tnh cht chun ca Dinitronaphthalenediol:
Trong mi trng acid acetic, dinitronaphthalenediol phn ng vi acid boric to
thnh phc anion (ML2-), phc anion ny c th c chit vi thuc nhum cation
nh Brilliant Green to thnh toluene nh mt cp ion (t dung dch HCl, pH 2,5
3,5; max = 637nm, = 10,3.104, 0 0,1 ppm B).
5.7.3. Morin:
5.7.3.1. Tn ch th v cng thc ha hc:
Tn ha hc: 3,5,7,2,4Pentahydroxyflavone.
Tn thng thng: Morin.
Cng thc phn t: C15H10O7.2H2O
Cng thc cu to:
OH
HO
O
HO
OH
OH
5.7.3.2. c im ca Morin:
To phc c mu vi cc ion kim loi.
Chit cc ion kim loi.
5.7.3.3. Cc tnh cht ca Morin:
102
OH
SO3Na
O
5.7.4.2. c im ca Alizarin :
To phc c mu vi cc ion kim loi.
5.7.4.3. Cc tnh cht ca Alizarin :
Alizarin c phn t lng bng 360,27.
Mu dnh cho thng mi l mt mui natri, mui hydrat v bt trong sut mu
vng nu hoc mu vng cam; d tan trong nc to thnh dung dch mu vng, nhng
hu ht khng tan trong dung mi hu c. N tan trong H2SO4 c to thnh dung dch
mu cam; pKa2 (OH) = 5,39 v pKa3 (OH) = 10,72 (25oC, = 0,5). Dung dch
nc cho bit hp thu ln nht ti bc sng 420nm (pH < 3,5) hoc ti bc sng
103
SO3NH4
SO3NH4
OH
CH = CH
HO
N=N
OH
N=N
5.8..2. c im ca Stillbazo:
To phc c mu vi cc ion kim loi.
5.8.3. Cc tnh cht ca Stillbazo:5Stillbazo c phn t lng bng 646,65.
Bt mu nu m, t tan trong nc to ra dung dch mu vng (pH t 3 n 7),
dung dch mu cam (pH 9) hoc dung dch mu (pH 11).
5.8..4. Tnh cht chun ca Stillbazo:
Mc d Stillbazo to phc c mu vi nhiu ion kim loi khc nhau, tm quan
trng ca vic ng dng trong phn tch l c xem nh l cht o quang i vi Al
khi c mt Fe (pH t 5 n 6, = 1,95 n 3,46.104 ti bc sng t 500 n 520nm,
t 0,2 n 1,2ppm). Nng ca Fe (ln n 100 ppm) c th c che bng acid
ascorbic. Khi c mt Zephiramine , c th t c nhy cao hn nhiu (pH 10,
570nm, t 0,08 n 0,64 ppm Al). Cc nguyn t khc, nh l B (pH t 8,9 n 9,1,
= 1340 ti bc sng 414nm, t 0 n 2ppm), Ga, In, Mo, v Sn, cng c xc nh
bng Stilbazo.
104
5.9. -DIKETONE
5.9.1. ng phn:
diketone cng nh ng phn ca chng c xem nh l nhng thuc th quan
trng .
5.9.2. Ngun tng hp v phng php tng hp:
Tt c u c gi tr v thng mi. Chng c chun b bng cch ngng t
Claisen ca ng v alkyl methyl ketone vi ethyl carbonxylate trong baz.
5.9.3. Cc phng php phn tch:
Cc thuc th nh (1) (4), (7), (8), (10), v (11) c dng nh l thuc th chit
c kh nng ha tan trong kim loi v trong mt s trng hp, c dng nh l
thuc th chromogenic trong cc nguyn t chuyn tip. Nhiu kim loi to phc vi
(4)(7), (9), (10) v (11) d bay hi n ni chng c th c phn tch bng phng
php sc k kh hoc phng php thng hoa phn on. t him to phc vi (4),
(5), (6) v (11) c dng nh thuc th shift (thuc th chuyn v) trong nh ph
cng hng t proton.
5.9.4. Tnh cht ca thuc th:
Cc thuc th ny khng th hin bt k tn s hp th no trong vng c th thy
c, nhng ch ra hp th mnh trong vng UV, cng v hnh dng ca thuc
th ph thuc vo bn cht ca dung mi v t s ca keto v dng enol trong hn hp
h bin ln.
R
CH2
CH
O
H
CH
O
M
1/n
Nc
(1)AA
17,3
C th
trn
C th
trn
(2)BzA
3,9.102
63,3
40,5
C
th
trn
30,8
1,3.104
(4)DPM 1,7.102
(5)TAA
(7)TTA 2.10-2
(10)BFA 3.10-1
53,8
40,4
(3)DBM
CCl4
LogKo
Benzene/ CHCl3/nc CCl4/nc
nc
0,57;
1,21
0,50
0,74
3,14
3,44; 3,60
2,82
29,2
5,35
5,40
4,51
0,28
1,62
-
0,53
1,73
-
0,32
1,30
-
qu trnh tch cc nguyn t actinoid v lanthanoid. Gi tr logKex l Am, -7,46; Bk, 6,8; Cf, -9,45; Dy, -7,1; Er, -7,2; Ho, -7,25; Lu, -6,77; Nd, -8,58; Pm, -8,05; Pr, -8,85;
Sm, -7,68; Tb, -7,51;Tm, -6,96; v Yb, -6,72.
Dung dch ca kim loi diketonate cho bit tn s hp th trong vng UV hoc
vng c th thy c, nhng mu ca chng khng r n ni m nhy sng cao
hn khng th c c. nhy cng thp tr phi dng cht che thng dng. Ph
hp th ca Cu(II) v phc uranyl c minh ha tng ng vi v tr hnh 5.10 v
5.11
Hnh 5.10 Ph hp th
ca Cu(II)
Hnh 5.11: Ph hp
th ca phc uranyl
108
OH
OH
O
(1 )
S O 3-
X =H
(2 ) X = B r
cam
Tm
tnh) chuyn sang mu xanh hoc tm khi to phc vi 1 s kim loi nh Al, Cu (II),
Ga (logKgal 5,54), Ge, In, Mo (VI), Sb (V), V (V) v W, i vi PR v Bi, Ge, In, Sb
(v), Th, Ti, UO22+, V (v), v Zr i vi BPR. Khi Chelate cng tan trong nc, PR v
BPR c s dng nh mt ch th kim loi trong phng php chun Chelate v
nh thuc th ca phng php trc quang cho cc kim loi.
Phc 3 cu t tan t trong nc v kt ta 1 phn, nu nng ca dung dch c
trn ln hoc dung dch c s dng lm dung dch chun, phc cng c th c
tch trong Nitrobenzene.
c im phng php trc quang ca PR tng t nh BPR nhng Chelate anion
ca PR v BPR c th c chit trong Alcohol tinh khit hoc dung mi c hng s
in mi cao nh 1 cp Ion vi nhng Cation ln nh Ge(IV), Ti(IV), V(V)....
5.10.5. tinh khit v tinh ch thuc th:
Nhng nguyn liu trong cng nghip thng c tinh khit, nhng c 1
lng c th kt tinh trong nc, thuc th th c th lm sch bng cch ha tan n
trong dung dch kim (Na2CO3 hoc NaOH), sau to kt ta bng cch Acid ha.
Polyhydrate ca PR hoc BPR, bao gm nhng dng si mu , cn thn sy kh n
khi tinh th c mu thm ngm 4 phn t nc.
tinh khit ca PR v BPR c th xc nh bng phng php o quang dung
dch ca n.
PR
Tn thuc th
Danh php
Pyrogallol red
Bromopyrogallol
Red
Pyorgallol sulfonephthalein, PR
5,5 - Dibromopyrogallol sulfonepththalcin, BPR
m
HNO3
NH3-NH4CL
Co (II)
Mg
Mn (II)
Ni
Pb
t him
9,3
10
9,3
9,3
~5
~7
NH3-NH4CL
NH3-NH4CL
NH3-NH4CL
NH3-NH4CL
AcOH-AcONa
AcONa
Xanh
Xanh
Xanh
Xanh
Tm
Xanh
iu kin pH
T l
4,4
HCl 1,0~1,3N
Zephiramine
1M HCL,
CTMAB (X)
5,0 ~5,4
5,6~7,5,
Septonex
ML2
max
(nm)
540
ML
0,17
Nng xc
nh (ppm)
3~7
621
6,5
0,08~1,4
MLX2
610
8,4
0,03~2
ML3
670
680690
4,5
0,16~1,4
Cht cn tr
Cr, Mn, Ti
-
3,3~3,9
0,3~3
x 104
Lu
-
iu
kin
(pH)
Ge(IV)
0,5
4,5
5
Nb
Chit
ML3
550
3,8
Diphenylguanidine
Hexyalxohol
Vng
xc
nh
(ppm)
ML3
610
2,5
di-noctylmethylamine
Isopentylacetate
5,4
t s
113
Amine (X)
Dung mi
Ti(IV)
2,5
MLX4
630
3,75
Ti(IV)
MLX2
610
0,85
V(V)
4(60o) MLX3
114
4Amynoantipyrine
Gelatine hoc
diphenylguanidine
Diphenylguanidine
Isoamyalcohol
Chloroform
(1:1)
0,2
2
CHNG 6
THUC TH O-N
6.1. THUC TH ALIZARIN COMPLEXONE
O
OH
OH
CH2COOH
CH2N
CH2COOH
2 H2O
p K a 1 = 2,40
H3 L
- COOH
vng
p K a 2 = 5,54
2
OH
2-
H2 L
p K a 3 = 10,07
+
N H
3-
HL
p K a 4 = 11,98
1
OH
4-
xanh
115
hp th
Hnh 6.1.
1.4
1.2
1.0
0.8
0.6
0.4
0.2
Quang ph hp th ca ALC cc
pH khc nhau. Hm lng 9.96
ppm trong nc.
(1) pH 4.6;
(2) pH 7.0;
(3) pH 10.0;
(4) pH 11.5;
(5) pH 13.0;
4
2
500
600
700
Bc
sng
(nm)
6.1.2.2. Phn ng to phc v cc tnh cht ca phc:
400
M + HL3- MHL- lgK = 12,19 (Zn), 12,23 (Ni), 12,25 (Co), 14,75 (Cu).
Cn phn ng:
HML- + M2+ M2L + H+ l lgK = 0,8 (Pb) v 3,5 (Cu) ( = 0,1, 20o ).
Cu to ca MHL nh sau:
H
O
O
C
C O
CH2
H2C
O
CH2
OH2
OH2
O
Phc ca cc ion t him pH ~ 4 chuyn thnh mu xanh khi c mt ion Fdo c s to phc MLF. Trong cc nguyn t t him th phc ca La(III) v Ce(III)
c s i mu nhy nht, v phn ng ny c s dng nh mt phng php quang
ph c bit c nhy cao xc nh ion F-.
S kt hp ca F- lm suy yu lin kt O H, do n c th phn ly pH = 4
pH ny ch th t do khng phn ly c.
116
H
O
F
O
OH2
CH2 N
O
hp th
1.4
1.2
1.0
0.8
0.6
0.4
0.2
hp th
0.8
0.6
0.4
0.2
500
550
600
650
700
Bc sng (nm)
Cc hng s cn bng ca h thng LaALC v LaALCF c tm tt trong
bng 6.1.
Bng 6.1. Cc hng s bn ca h thng LAALC v LAALCF 25oC v = 0,1
(KNO3)
Cn bng
Hng s cn bng
117
H thng La-ALC
2M + 2H2L M2L2 + 4H+
lgK202 = 0,28
2M + 2H2L M2HL2 + 3H+
lgK212 = 5,58
H thng La-ALC-F
2M + 2H2L + F- M2HL2F + 3H+
lgK2121 = 9,70
2M + 2H2L + F- M2H2L2F + 2H+ lgK2221 = 14,17
6.1.3. Cch tinh ch v tinh khit ca thuc th:
Hu ht cc mu thuc th bn trn th trng c th s dng cho cc vic phn
tch thng thng khng cn tinh khit. Nhng i vi nhng php phn tch cn
tinh khit th cn phi tinh ch thuc th trc khi dng. Qu trnh thc hin nh sau:
Cn chnh xc 1(g) bt mu cho vo 50ml dung dch NaOH 0,1M, lc dung dch,
ri em chit Alizarin 5 ln bng methylenedichloride. Lm lng ch th t do bng
cch thm tng git acid HCl v khuy u trong mt bn lnh. Lc phn lng trn
mt phu lc thu tinh, ra sch bng nc lnh, v lm kh bng thit b c chn
khng.
tinh khit ca acid t do c th kim tra bng php o kim hoc chun trc
quang vi dung dch chun Al pH = 4.
Cc ng dng phn tch:
6.1.4. S dng phc vi Ce hoc La lm thuc th trong php o quang cho Fluoride:
Khong pH tt nht cho phn ng to mu l t 4,5 4,7, v bn cht ca cc dung
dch m cng nh hng ti nhy ca phn ng. m Succinate c s dng
nhiu nht, hn hp dung dch thuc th lc ny s c n nh trong khong 9
thng. Cn m Acetate th c s dng cho phng php chit trc quang. S c
mt ca dung mi hu c cng lm tng nhy v Acetone (20% 25%) cho kt qu
tt nht. Mu c n nh trong 1 gi. nhy cng c th c tng ln nh dung
mi chit. Vic thm natri dodecysulfate cng lm tng nhy phn ng mu ny.
Cc cation nh Al, Be, Th, Zr, gy cn tr i vi phn ng mu, chng cnh tranh
vi thuc th trong vic phn ng to phc vi F-. Cc cation nh Al, Cd, Co(II),
Cr(III), Cu(II), Hg(I)(II), Fe(II)(III), Mn(II), Ni, Pb, V(IV), Zn, cng gy cn tr,
chng to phc vi Alizarin complexone bn hn so vi cc ion t him. Cc Anion
nh BO3- v PO43- cng gy nh hng, chng to phc bn vi cc ion t him.
6.1.4.1. Qu trnh trc quang i vi fluoride trong dung dch nc.
Dung dch thuc th:
Chuyn mt vi ml dung dch nc cha 47,9 mg Alizarin complexone, 0,1 ml
dung dch ammoniac c v 1 ml ammonium acetate vo bnh nh mc 200 ml cha
sn dung dch c pha t 8,2 g natri acetate v 6ml acid acetic c trong mt lng
nh nc. Thm 100 ml acetone v khuy u. Ri sau thm tip mt dung dch
c pha t 40,8 mg La2O3 trong 2,5 ml HCl 2N. Cui cng, nh mc ti vch bng
nc ct. Dung dch ny c n nh trong 2 tun.
118
Qu trnh xc nh:
Cho mt cht kim yu hoc mu dung dch trung tnh c cha 3 g 30 g F- vo
bnh nh mc 25 ml. Thm 8,00 ml dung dch hn hp thuc th ri nh mc ti
vch. Sau 30 pht em o ph hp thu bc sng 620 nm. Lm mu trng khng c
mu cha F-.
6.1.4.2. Qu trnh chit trc quang i vi Fluoride:
Cho 20 30 ml dung dch mu cha 0,5 10 g F- vo trong phu chit 100 ml.
Ln lt thm 3ml dung dch Alizarin complexone 0,001M, 3ml dung dch m
acetate (pH = 4,4), 8ml acetone, v 3ml dung dch lanthanium chloride 0,01M, ri pha
long hn hp ti 50ml. Chit phc mu xanh bng cch lc dung dch nc vi 10ml
isoamyl alcohol cha 5% n,ndiethylaniline trong 3 pht trn my lc. Sau khi c s
phn chia pha, em o ph hp thu ca pha hu c bc sng 570nm. Lm mu
trng l dung dch khng cha mu. nh lut Beer c p dng ng trong khong
nng ca F- l 0 10 ppm.
6.1.5. Cc ng dng khc:
Alizarin complexone c s dng trong phng php trc quang xc nh cc
ion kim loi nh: Al (pH = 4,1 4,3, = 455nm), Cu(II) (pH = 3,5), Mn(II) (trong
kim, = 570nm), Co(II), Ni(II) (pH = 4,5, = 500nm), V(IV) (pH = 10,3 10,8, acid
ascorbic, CPC).
N cng c s dng nh l mt ch th kim loi trong php chun to phc
ca Co (II), Cu(II), In, Pb, v Zn nhng trong cc trng hp ny dng xylenol da cam
v methyl thymol xanh th tt hn.
6.1.6. Cc thuc th cng h:
6.1.6.1. Sulfonated Alizarin complexon (ALC-5S, AFBS).
Thuc th ny tan trong nc nhiu hn so vi thuc th gc. Hot ng ca phc
La vi F- c nghin cu mt vi kha cnh, v nhn thy thuc th ny c
nhy thp hn so vi thuc th gc.
6.1.6.2. Quinalizarin complexone.
Cng thc phn t: C19H15O10
KLHT = 417,33 vC
Cng thc cu to:
OH
OH
OH
CH2N
OH
CH2COOH
CH2COOH
H
N
O
NH
N
NH
O
O
N
H
ONH4
pKa2=9,2
H4l
pKa=10,9
-
H3L
120
H2L-
O
NH
N
NH
M
N
H
CaH4L
pKa3 =9,5
CaH3L
CaH2L-
Tm
Cu(II) 8
NH3
Vng tm
Co(II) 8
NH3
Vng
Tm
Ni(II) 10
NH3
Vng Xanh tm
6.2.6. ng dng trong phn tch:
Murexid c s dng lm ch th kim loi trong chun EDTA.
Nhng lm ch th tt nht l dng ngay sau khi pha. Dung dch nc ca Murexid
th khng bn, dung dch ethylene glycol 0,1% th c thi gian bo qun di hn dung
dch vi nc. Cn thuc th kh c trn ln vi NaOH hoc KOH khan vi t l
(t 1:100 -1:500) c s dng rng ri hn Murrexid cn c lm thuc th trong
phn tch trc quang ca Ca ( pH = 11,3 bc sng 506nm) trong mu thc.
6.2.7. Hng s bn ca phc Murexide vi mt s ion kim loi(Bng 6.2)
Bng 6.2. Hng s bn ca phc Murexide vi mt s ion kim loi
PH
TT Ion
KL
4
5
6
7
8
9
10
11
12
Ca
2,6
2,8
3,4
4,0
4,6
5,0
Cu(II)
6,4
8,2
10,2
12,2
13,6
15,8
17,9
Ni
4,6
5,2
6,2
7,8
9,3
10,3
11,3
Eu
5,34
5,42
Gd
4,90
5,00
La
4,49
4,55
Tb
4,89
4,98
Gi tr t h quy chiu 3 nhit phng, = ~ 0,1. Gi tr t h quy chiu 4 nhit
25oC 0,1; = 0,1
6.3. HYDROXYLQUINOLINE
Cng thc phn t: C9H7NO
KLPT = 145,16
122
N
OH
HL
431
0,064
251
3,16
Cation (pH 1)
308
1,48
H2L+
319
1,55
252
30,2
Anion (pH 12)
334
2,88
L352
2,82
OXINE 2-Methyloxine
123
1-Butanol
Carbon tetrachloride
MIBK
Toluene
o-Dichlorobenzene
Dichloromethane
Chloroform
45,5
116
136
162
303
377
433
82,6
435
314
557
1003
1248
1670
N
+
O-
O
H
Zwitter
Neutral
Oxine c s dng rng ri nh thuc th tch chit cho nhiu kim loi, v h s
phn b ca oxine trong nhng h dung mi nchu c khc nhau th c tng
hp trong bng 6.4
6.3.5. Nhng phn ng to phc v nhng tnh cht ca phc:
Oxine c xem nh phi t anion ho tr mt to thnh cht khng cnh vi
mt khong rng cc ion kim loi. Nhng cation ca ht mang in tch +n v c s
phi tr l 2n th c gi l phi tr bo ho chelate khng mang in n khng th
ho tan trong nc nhng d dng tan trong nhng dung mi hu c (cu trc (1) ca
Fe(III) oxinate l mt v d). Khi s phi tr ca kim loi ln hn 2n, nhng ni
khng phi tr ca ion kim loi th thng b nc chim ch c minh ho bng cu
trc (2) ca nickeloxinate l mt v d. Mc d loi chelate ny th hon ton khng
tan trong nc, n cng khng d dng tan trong nhng dung mi hu c mc d c s
hin din ca nc phi tr (dung dch ca ZnL2.2H2O trong CHCl3, 2.10-6).
N
OH2
N
Fe
Ni
O
O
O
OH2
V d: khi mt dung dch ca Cd, Zn, Ni, hoc Mg c lc chung vi dung dch
chloroform v oxine ti pH thch hp, nhng kim loi c th c chit dng
chelateML2, nhng trong vi pht chng tr thnh dng hydrad ho v tch ra khi
124
pha chloroform. Tuy nhin, nhng chelate c th c chit thnh cng bi nhng pha
hu c, bng cch thm cht ph tr khng phi t, nh l pyridine, 1,10
phenanthroline, alkylamine, hoc thm d oxine, hoc s dng dung mi phi tr, nh
MIBK hoc amylalcohol, nh mt dung mi chit.
Oxine thuc nhm phenolic l acid yu, mc phn ng to phc vi ion kim loi
th ph thuc nhiu vo khong pH ca mi trng phn ng. Kh nng chit th cng
ph thuc vo khong nng ca oxine trong pha hu c. cc gi tr pH ph hp
c s dng vi nng ca dung dch oxine t 0,001 n 0,01 M. . S chit thng
nhanh hn ti nng oxine cao hn v gi tr pH cao hn.
Mt vi cht khng mang in, cc phi tr bo ho oxinate kh nng thng hoa
di p sut thp, v tnh cht ny c th ng dng tch nhng oxinate kim loi
bng vic thng hoa phn on.
Hng s bn ca oxinate kim loi thng c quan st trong dung mi hu c
dng nc da vo s t tan trong nc.
Dung dch chloroform vi nhng oxinate kim loi thng c mu vng v s lin
kt c biu din bng cc gi tr r rng, oxine cha lin kt th hp thu rt
t. Ngoi tr cc oxinate ca Fe (III) (xanh en) v V (V) ( en) chng c nhng
lin kt rt phc tp. S hp thu quang ph ca mt vi oxinate kim loi trong
chloroform c cung cp trong hnh 6.5. Mc d kh nng hp thu ca chng th
khng c cao, nhng oxine to thnh cc chelate vi rt nhiu ion kim loi, v vy
oxine c xem nh mt thuc th hu c thng thng nht cho vic phn tch kim
loi. Kh nng chn lc c th c ci thin da vo vic chn pH thch hp v vic
che nhng tc nhn trong giai on trch chit.
phn gim chm kh nng hp thu. Nguyn nhn ny c th l gii do s hnh thnh
phosgene trong qu trnh quang phn ca chloroform.
6.3.6. S tinh ch v tinh khit ca thuc th:
Oxine l hp cht hon ton xc nh vi im nng chy r rng.
Oxine th c th c tinh ch da vo ng oxinate bng s phi t trng vi H2S
hoc bng s chng ct hi nc sau khi aicd ho bng H2SO4 im nng chy (73
n 75oC) mt tiu chun rt tt cho vic tinh ch.
6.3.7. ng dng trong phn tch:
Dng nh mt cht chit v quang trc:
L mt cht chit thch hp ca nhiu oxinate kim loi trong h thng nc
chroloform . . S chn la gi tr pH ph hp cho qu trnh chit v vic che nhng tc
nhn th rt cn thit cho vic tng chn lc. Chloroform l dung mi c u tin
nht cho qu trnh chit. nhy ca vic xc nh trc quang ca nhiu kim loi th
khng cao, do phn t gam hp thu trong khong 103 n 104, nhng oxine vn tip tc
hu dng l mt thuc th o quang hu dng v n c ng dng rng ri.
Dng nh mt ch th kt ta:
Nhng thng tin v oxine nh l mt cht phn tch c gii thiu bi Berg nm
1927, trong nhng nm u n c dng ch yu nh l mt tc nhn to ta cho vic
tch v phn tch trng lng xc nh nhng ion kim loi. S to ta vi nhiu
oxinate kim loi cng c th c xc nh bng phng php o th tch. Oxine phn
ng d dng v nh lng vi bromine to thnh 5,7dibromoxine. Nhng oxinate
kim loi c ho tan trong HCl m v c x l bng KBr v dung dch KBrO3 d.
Sau thm KI, bromate d c xc nh bng cch chun iodine thot ra bng
dung dch Na2S2O3 tiu chun.
PFSH (kt ta t dung dch ng th) k thut c gii thiu cho s chun b
oxinate kim loi nhng cht nng hn, d dng lc hn, v t nhim bn hn vi phi
t d v nhng nguyn t thm vo c chun b bng qu trnh c.
Trong phng php PFSH, oxine c to ra bi s thy phn 8acetoxyquinoline
(im nng chy t 56,2 n 6,50) kt ta vi (AlL, BiL3, CuL2, GaL3, InL3, MgL2,
SbOL.2HL, ThL4.HL, UO2L2.HL hoc (UO2L2)2.HL, v dung dch cha oxine, ion kim
loi, v urea (AlL3, BeL2, CrL3, MgL2, NbOL3). Nu ureaza c thm vo trong hn
hp th phn ng c th tin hnh ti nhit phng.
Phng php sc k c dng kim tra nhanh mt s oxinate kim loi trong
mt vi lnh vc nh. Nhng oxinate kim loi c th c tch trong ct hoc trong
lp mng. Ion kim loi cng c th tch trn giy lc vi oxine, thm vi ht silica
c nh oxine, hoc trn cht cao phn t c nhm chc oxine.
6.3.8. Nhng thuc th khc c cu trc lin quan:
6.3.8.1. 2 Methyloxine (8 hydroxyquinaldine):
C10H9NO
126
KLPT = 159,19
CH3
OH
N
OH
dng tinh th bt mu vng. D dng ho tan trong nc; pKa (N+H) = 4,10 v
pKa (OH) = 8,76 ( 0,250). Chelate c tnh tng t nh oxine, nhng chelate
khng ho tan trong nc. Do , thuc th ny c dng nh l thuc th trc
quang (Fe(III), Ta(V) v V) hoc nh mt thuc th hunh quang (Al, Cd, Ce(IV), Ga,
In, Mg v Zn) cho ion kim loi trong dung dch nc. Khi giai on chit khng cn
thit, th qu trnh tng t nh oxine. Hn na, nhy v chn lc c th
c loi tr bng vic loi b giai on chit. Kt qu chelate kim loi trong pha
127
6.4. ZINCON
H 2L
H3 L -
hng hoc
tm
H2L2-
pKa2=7.9(hoac 8.3)
HL3-
pKa3=13(hoac>14)
Vng
128
L4-
tm
Hnh 6.6. Ph hp th ca
Zincon v Cu, cc chelat ZnZincon, nng nng thuc
nhum 4.0x10-3M, ti pH = 9.
1(1): Nhum; (2): chelat Zn;
(3): chelat Cu.
ZnL2 + H +
[ Zn NTA ] + Zincon
mi cht khng chng cho ln nhau, phng php ny c p dng cho tin trnh do
nh sng chy.
6.4.7.2. Xc nh NTA trong nc thi:
Ha tan 31g boric acid v 37g KCl trong 800ml nc ct iu chnh pH trong
dung dch pH = 9,2 vi NaOH 6N v pha long thnh 1000ml.
Dung dch km: ha tan 0,440g ZnSO4 + H2O trong 100ml + thm HCl 2N vo
bnh nh mc dung tch 1000ml v nh mc ti vch
Thuc th ZnZincon: ha tan 0,130g Zincon trong 2ml NaOH 1N, vo bnh
nh mc dung tch 1000ml thm 300ml dung dch m v 15ml dung dch km, nh
mc ti vch. Thuc th ny nn c chun b mi hng tun khng nn dung
dch lu m nn bo qun trong bng ti.
- Cch tin hnh:
Dng pipet ht 25ml vo cc 50ml vi mi mu chng ct v tiu chun l
5ppm NTA, thm xp x 2,5g nha cation traoi i, dng a thy tinh khuy u vo
mi cc. y np bng 1 ci np thu tinh trong v khuy bng my ht chn khng
khong 15 pht. mu lc qua giy lc trc khi lc v khng c ra cht kt ta.
Dng pipet ht tip 15ml cht lc vo cc th 3 c dung tch 50ml, thm 35ml
ZnZincon.
Zincon cng c s dng nh l cht ch th kim loi trong ngh.
6.4.8. Cht phn ng khc c cu trc lin quan:
Nhiu thuc nhum fozmazan c tng hp v c lng nh l thuc th
phn tch, chng c cp nhiu bi bo khc nhau, nhng rt t c ng dng thc
t.
Mui ny c cng thc chung (1) v (2) c th c xem nh l tin thn ca
thuc nhum formazan.
130
131
C16H11O11S2Na2As
KLPT = 592,29
H2O3As
OH
OH
N
NaO3S
SO3Na
OH
Sc
N
H
AsO3H2
SO3Na
SO3Na
Cc nguyn liu t cc k thut cung cp l mui Na1Na5, tinh th dng bt, mui
Na1 ( cam), mui Na5 ( a, ri). N d tan trong nc nhng li khng tan trong
cc dung mi hu c ph bin. Dung dch nc c mu vng cam trong mi trng
acid (max = 510nm, = 1,4.104 ti pH = 1) v mu cam trong mi trng kim(max
= 490nm, = 1,4.104 ti pH = 9 10 ) v c mu trong mi trng acid sunfuric
m c, pKa3 = 3,7; pKa4 = 8,4 (AsO(OH)2), v pKa5 = 11,8 (OH).
134
N to thnh cc chelate c mu trong dung dch acid 0,1N vi Bi (trong dung dch
HClO4 0,02 0,04N max = 535nm, = 9,5.103), Th (pH = 0,5 1,5; ML2 max =
545nm) U(VI) (pH = 3 4; ML2 max = 545nm), Zr v Hf (trong HCl; max = 555nm)
v Pu (IV) (trong HCl; 0,05 0,25N; max = 540nm) cc phn ng th c chn lc
cm quang kh cao vi cc kim loi ny. Thorin cng c s dng trong vic xc
nh bng trc quang ca kim loi khc vng pH cao hn d cc phn ng khng c
tnh chn lc cm quang cao; Be (pH = 10, max = 486nm); Rh (III) (pH = 4; gia nhit
trong 70 giy; max = 550nm) v cho vic xc nh gin tip fluoride qua chelate Zr.
Thorin c th c s dng nh mt ch th kim loi trong php chun chelate
ca Bi v Th (pH = 1 3), ti im cui mu dung dch chuyn t sang vng.V n
cng c s dng nh mt ch th trong chun U (VI) pH = 2,5 bng acid oxalic.
* Rezarson:
2,2,4Trihydroxy3arsono5chloroazobenzene.
C12H10N2O6AsCl
KLPT = 388,60
HO
OH
H2O3As
N
Cl
Rezarson to phc mu theo t l 1:1 vi nhiu kim loi, bao gm Cu, Ga, Ge, Ni,
Pd v Sn trong nc acid trong bnh vi methanol t 50 70 %. N c ngh nh
mt thuc th trong php o trc quang cho Ge v Sn (trong dd HCl, max = 510nm).
Complexon
EDTA
HOOCCH2
CH2COOH
NCH2CH2N
CH2COOH
HOOCCH2
CyDTA
CH2COOH
CH2COOH
CH2COOH
H
N
CH2COOH
GEDTA
HOOCH2C
CH2COOH
NCH2CH2OCH2CH2OCH2CH2N
CH2COOH
HOOCH2C
136
HOOCH2C
DTPA
TTHA
CH2COOH
NCH2CH2NCH2CH2N
HOOCH2C
CH2COOH CH2COOH
HOOCH2C
CH2COOH
NCH2CH2NCH2CH2NCH2CH2N
HOOCH2C HOOCH C
2
HEDTA
CH2COOH CH2COOH
HOCH2CH2
CH2COOH
NCH2CH2N
HOOCCH2
NTA
CH2COOH
CH2COOH
N CH2COOH
CH2COOH
pKa1
pKa2
pKa3
pKa4
pKa5
pKa6
Ag
Al
Ba
Bi
Ca
Cd
Ce(III)
Co(II)
Cr(III)
Cu(II)
Dy
Er
Eu
Fe(II)
Fe(III)
Ga
Gd
Hf
Hg(II)
Ho
TTHA
HEDTA NTA
EDTA CyDTA GEDTA DTPA
(1)
(2)
(3)
(4)
(5)
(6)
(7)
1,99
2,43
2,00
2,08
2,42
2,51
1,89
2,67
3,52
2,65
2,41
2,95
5,31
2,49
6,16
6,12
8,85
4,26
4,16
9,86
9,73
10,26
11,70
9,46
8,60
6,16
10,55
9,40
10,19
logKML
7,32
8,15
6,88
8,70
8,67(13,89)
6,71
5,16
16,13
18,63
13,90
18,4
19,7(28,9)
12,43
9,5
7,76
8,64
8,41
8,63
8,22(11,63)
5,54
4,83
27,9
31,2
23,8
29,7
21,8
10,96
12,50
11,00
10,74 10,06(14,16)
8,14
6,41
16,46
19,23
16,70
19,31 18,65(26,85)
13,6
9,54
15,98
16,76
15,70
20,50
14,11 10,83
16,31
18,92
12,50
18,4
17,1(28,8)
14,4
10,38
23,40
2,54
>10
18,80
21,3
17,8
21,53
19,2(32,6)
17,55 12,96
18,30
19,69
17,42
22,82
23,29
15,30 11,74
18,38
20,20
17,40
22,74 23,19(26,92) 15,42 12,03
17,35
18,77
17,10
22,30
23,85
15,35 11,52
14,33
16,27
11,92
16,50
17,1
12,2
8,84
25,1
28,05
20,5
28,6
26,8(40,5)
19,8
15,87
20,27
22,91
23,0
16,9
13,6
17,0
18,80
16,94
22,46
23,83
15,22 11,54
29,5
35,40
19,08
20,34
21,8
24,30
23,12
27,0
26,8(39,1)
20,1
14,6
18,05
19,89
17,38
22,78
23,58
15,32 11,90
137
In
La
Li
Lu
Mg
Mn(II)
Na
Nd
Ni
Pb
Pr
Sc
Sm
Sn(II)
Sr
Tb
Th
TiO2+
Tl(III)
Tm
UO22+
VO2+
Y
Yb
Zn
Zr
24,95
15,50
2,79
19,65
8,69
14,04
1,66
16,61
18,62
18,04
16,40
23,1
16,7
18,3
8,63
17,81
23,2
17,3
22,5
18,62
25,6
18,77
18,09
18,88
16,50
29,9
28,74
16,75
4,13
20,91
10,32
16,78
2,70
17,69
19,4
19,68
17,23
25,4
18,63
10,54
19,30
29,25
19,9
38,3
20,46
26,9
19,40
19,41
20,80
18,67
20,74
15,79
1,17
17,81
5,21
12,3
1,38
16,28
13,55
14,71
16,05
16,88
23,85
8,50
17,27
17,48
16,82
17,78
14,5
29,0
19,48
22,44
9,3
15,50
21,60
20,32
18,80
21,07
22,34
9,68
22,71
28,78
48,0
22,72
22,05
22,62
18,75
36,9
22,22(25,62)
8,10(14,38)
14,65(21,19)
22,82(26,75)
18,1(32,4)
17,1(28,1)
23,45
23,81
9,26(12,70)
23,61
31,9
23,58
16,65(28,7)
19,74
17,16
13,46
15,88
7,0
10,7
14,86
17,0
15,5
14,61
15,28
6,92
15,32
18,5
15,59
14,65
15,88
14,5
16,9
10,36
2,51
12,49
5,46
7,44
2,15
11,26
11,54
11,39
11,07
12,7
11,53
4,98
11,59
12,4
12,3
18
12,2
9,56
11,48
12,40
10,67
20,8
ng dng
Chit trc quang Cu v Bi
Php xc nh trc quang Ti
Php xc nh trc quang Pd
140
141
142
Gii hn pH v ch th kim loi c xut cho vic chun cc ion kim loi
gii hn pH m ion kim loi chun c,
gii hn pH m
thng thng,
ch th ph hp c th dng c,
gii hn pH m phc ph c s dng lm
cn tr s thu phn ca cc ion kim loi.
6.7.8. Cc ch vit tt ca cc ch th kim loi:
BG:
Bindschedlars Green
PAN: Pyridylazonaphthol
BPR:
Bromopyrogallol Red
PAR: Pyridylazorescocinol
BT:
Eriochrome BlackT
PC:
Phthalein Complexon
Pyrogallol Red
GCR:
PV:
Pyrochatecol Violet
GTB:
Glycinethymol Blue
TAN: Thiaolylazonaphthol
HNB:
Hydroxynaphthol Blue
TAR: Thiaolylazoresorcinol
MTB:
Methylthymol Blue
MX:
Murexide
NN:
XO:
Xylenol Orange
143
OH
HO3S
O2N
HO
OH
OH
N N
HO3S
N N
H3L (1)
HO3S
H4L (2)
HO
OH
HO
OH
COOH
NaO3S
N N
SO3Na
N N
CH3
H3L (3)
H5L (4)
SO3Na
6.8.1. ng phn :
Nhng hp cht azo cng vi ng phn v cng thc phn t c cp trong
chng ny lit k bng 6.9.
6.8.2. Ngun v phng php tng hp:
Cc hp cht trn u c sn trn th trng. Nhng loi thuc nhum azo ny
c tng hp bi cng on chun mc ca phn ng lin hip azo. Chng c gi
t cc tn tng ng sau :
(1) diazo ha 1amino6nitro2naphthol4sulfonic acid v 1naphthol, (2),(3)
v (4) t diazotized 1amino2naphthol4sulfonic acid v 2hydroxynaphthoic
acid, pcresol, 2naphthol3, 6disulfonic acid, tch bit.
6.8.3. Cc ng dng phn tch :
Cc thuc nhum azo loi ny c dng rng ri nh l cht ch th kim loi trong
phng php chelate, c bit cho php chun EDTA ca cc kim loi kim th.
Chng thnh thong c dng nh l thuc th trc quang cho canxi v magie trong
dung dch nc hoc sau khi chit vo trong dung mi khng c tnh trn ln.
6.8.4. c tnh ca thuc th.
Eriochrome Black T (1) lun c cung cp dng mui ca natri dng bt mu
tm m c nh kim loi m nht, d tan trong nc v ru, khng tan trong dung
mi hu c thng thng. Dung dch nc c mu pH < 6, mu xanh pH = 7
11 v mu cam pH =12. Trong dung dch kim d b oxy ha tr thnh khng mu
pKa (H2L-) = 6,3 v pKa (HL2-) = 11,55( = 0,08 ~ 0,008; 18 ~ 200)
(2) thng c cung cp dng acid t do c dng bt mu m, tan nh trong
144
Tn
(1)
Eriochrome
Black
(2)
Cancol
carboxylic
acid
(3)
Calmagite
(4)
Hydroxynaph
thol Blue
ng phn
1(Hydroxy2 naphthylazo)6
nitro2naphthol4sulfonic acid,
mui mononatri; Solochrome
Black T, Mordant Black 11, C.I.
14645, Erio T, EBT, BT
2Hydroxy1(2hydroxyl4sulfo
1naphthylazo)3naphtoic acid Pat
Ton v Reeders dye Cal , HSN,
NANA, HHSNNA, NN
1(1Hydroxy4methyl2
phenylazo)2naphthol4sulfonic
acid
1(1Hydroxy4sulfo1
naphthylazo)2naphthol3,6
disulfonic acid, mui trinatri, HNB
C20H12O7N3SNa,
461,41
C21H14N2O7S,
438,41
C17H14N2O5S,
358,37
C20H11N2O11S3Na3
620,46
Mu
Xanh dng
Hi
Xm Xanh
145
Mu
Cd
Ce(III)
Co(II)
Cr(III)
Cu(II)
Fe(III)
Hg(II)
La
Xm Xanh
Hi
Xm Xanh
Hi
Nu ppt
Xm Xanh dng
Hng m
Os(VIII)
Pt(IV)
Th
U(VI)
V(V)
W(VI)
Zn
Hng
Xm Xanh
Xm Xanh
ti
Xanh dng
Phn ng mu ca (1) vi cc ion kim loi khc nhau c xem xt chi tit v tm tt
li trong bng 6.10. Ph hp th ca Eriochrome Black T v chelate Mg trong namyl
alcohol c th hin trn hnh 6.9.
Hng s bn ca thuc nhum vi nhiu ion kim loi c xc nh hu ht
bng phng php ph quang k. Hng s bn c iu kin (logKML) ca (1), (3) v
(4) pH 10 l cc bo co nh sau: (1); Ca (3,8); Mg (5,4) ; (3); Ca (3,67); Mg (5,69);
(4), Be 3,36); Mg (3,43); Ca (2,82); Sr (2,05); Ba (1,75); La (3,75); Pr (4,03); Nd
(4,13); Sm (4,09); Eu (4,10); Ga (3,76); Tb (3,77); Dy (3,71); Ho (3,68); Er (3,60); Yb
(3,50); UO22+ (4,10 hoc 3,99).
cu v ha l.
(1) c tinh ch bi mui ptoluidinium ca n, l thuc nhum trong dung
dch methanol m 20% c x l vi ptoluidine kt ta mui toluidinium sau khi
lm lnh m cui cng c kt tinh li t nc nng (3) c th c tinh ch bi vic
chit t mu kho vi anhydrous ether .
(4) c tinh ch bi php sc k trn ct bt cellulose vi propanolethyl acetate
nc (5 + 5 + 4) nh l mt cht tch theo cc cng on sau.
Mu th c x l vi ethanol nng loi b cc cht khng tinh khit, sau
ha tan trong dung dch methanol 20%, ri cho qua php sc k. Phn vng tm
pha trn cao c tch na cha thuc nhum tinh khit dng kt ta ca mui
natri trihydate do vic thm HCl m c vo cht tch m c.
6.8.7. Cc ng dng trong phn tch:
6.8.7.1. S dng nh l mt thuc th trc quang:
Thuc nhum azo ca loi ny c dng rng ri nh l cc thuc th trc quang
cho cc ion kim loi khc nhau. Mc d hu ht cc cng on trc quang c thc
hin trong h thng c nc, cc cht chelate mu vn c th c chit vo trong
ru cao hn nh ru izoamyl. Tng t chng c th c chit vo cc cht chlor
ha nh l chloroform hoc 1,2dichloroethane nh l mt cp ion vi chui di ion
amoni thay 4 ln.
Cc v d v ng dng phm nhum azo nh l thuc th trc quang c tm tt
trong bng 6.11.
6.8.7.2. S dng nh l cht ch th kim loi.
Cc thuc nhum azo ny c s dng nh l cht ch th kim loi trong
phng php chelate. Hng s phn ly ca proton cui cng trong (2) v (4) l cao qu
n ni s thay i mu vi Ca c quan st ti vng pH cao hn ( 12 13) mi
Mg kt ta dng Mg(OH)2. V vy chng c xem l cht ch th Ca chn lc trong s
hin din ca Mg. iu kin chun vi cc thuc nhum ny nh sau:
S chun vi: Eriochome Black T (1) (t mu sang mu xanh ti im kt
thc), Ca, Mg, Cd, Zn (pH 10, NH3), Ba, Sr (pH 10, NH3, MgEDTA), Hg(II), In, Pb,
t him (pH 8 ti 10),NH3, tartarate, 100oC), Co(II), Ni(pH 10, NH3, MnEDTA),
Mn(II) (pH 8 ti 10, ascobic acid, 80oC), Sc( pH 7,5 ti 8; NH3; malic acid; 1000),
VO2+ (pH 10, NH3, MnEDTA, ascorbic acid); chun vi Calcon carboxylic acid
(2) (t sang xanh), Ca (pH 12 n 13, KOH); chun vi Calmagite (3) (t
sang xanh), Ca, Mg( pH 10, NH3); chun vi hydroxynaphthol Blue (4) (t sang
xanh), Ca (pH 10 ti 13, KOH) v Mg (pH 10, NH3).
6.8.8. Cc thuc th c cu trc tng t.
6.8.8.1. Gallion
Gallion c s dng nh thuc th trc quang cho Ga (ML, pH = 6, 560nm, =
1,54.104 La, Mn, Pb, Sc, Zn, DCD, t him. S to thnh t 3 phc ca GaGallion
Oxine (MLX; pH = 3; 640nm; = 2,3.104 trong buthanol).
147
Ion
kim
loi
Cd
Co(II)
Co(II)
Mg
iu kin
T l
pH~6; 1,10
Phenalthroline,
ML2X2
chit vi
CHCl3
TPAC, chit
vi CHCl3
pH 5,5~8,2;
SCN-; chit
vi benzene v
Aliquat 336S
pH 10,9 ~
11,3; KCN;
triethanolamin
148
max
(nm)
(x104)
Dy xc
nh
(ppm)
Yy t cn tr
v ghi ch
522
2,2
0,22~5,6
Trong hp kim
Devarda
580
5,0
0,6~18
EDTA,DDTC
cn tr
587
6,62
0,1~ 0,8
Mn,Ni,VO3cn tr
525~30
0,1 ~1
Mg
Mg
Zn
t
him
(2)
(3)
(4)
UO22+
pH 9,5~11,2,
chit v i
545
AmOH hoc
BuOH
pH 11,2 ~
12,2,
690*
Zephiramine,
chit v i
dichloroethane
pH ~ 6; 1,10
Phenalthroline,
ML2X2
522
chit vi
CHCl3
pH 6,35 ~ 6,8;
diphenyl
guanidine;
ML2X2 550~600
chit vi iso
AmOH
Mi trng
kim
pH 8,2~ 8,8;
KCN; EDTA;
Al
chit vi
Aliquat 336S
trong CHCl3
pH 4,2; chit
vi Aliquat
Co(II)
336S trong
CHCl3
pH 11,2~12,2,
Zephiramine,
Mg
chit vi
dichloroethane
pH 11; chit
vi Aliquat
Mo(VI)
336S trong
CHCl3
Kim
loi
pH6; EDTA
kim
th
UO22+
pH 4
2,0
0,5 ~5
Ca,Cd,Ce,Fe,Zn
cn tr
0,03~
0,1
Ca khng cn
tr
2,3
0,64~
3,7
Trong hp kim
Devarda
2,6
~3,5
0,1~ 15
ML2
570
1,36
14 ~ 60
ML3
570
4,2
0,1 ~ 0,5
Cd,Cu,Ni,Pb,Zn
khng cn tr
580
0,8
690
6,3
2~7
Ca khng cn
tr
575
0,6
650
1 ~ 600
ML
530
0,41
0,3 ~
149
t
him
pH 6 ~ 10;
EDTA
ML
65
1 ~ 300
CHNG 7
THUC TH NN
7.1. BIPYRIDINE V CC HP CHT FERROIN KHC
Cc thuc th c cp trong phn ny c lit k bng 7.1 cng vi cc
ng phn ca chng.
Bng 7.1. Bipyridine v cc hp cht ferroin
STT
Tn
ng phn
CTPT
Khi
lng
phn t
(1)
2,2 Bipyridine
, Bipyridyl,
Dipyridyl,2,2
bipyridyl
C10H8N2
156,19
(2)
2,2,2
Terpyridine
2,2,2 Terpyridine
C15H11N3
233,27
(3)
1,10 Phenanthroline
o Phenanthroline,4,5
phenanthroline
C12H8N2.H2O
198,23
Bathophenanthroline
C24H16N2
332,41
Bathophenanthroline
Disulfonic acid,
mui dinatri.
C24H14N2O6S2Na2
536,48
4,7 Diphenyl
1,10
phenanthroline
4,7 Diphenyl
1,10
phenanthroline
(4b)
disulfonic acid, mui
dinatri
(4a)
150
cam
Ag(I)
Ag(II)
Cd
Co(II)
Cr(II)
Cu(I)
Cu(II)
Fe(II)
Fe(III)
Hg(II)
Mg
Mn(II)
Ni
Pb
Ti(I)
Ti(III)
V(II)
Zn
3,7
4,25
6,06
~4
8,0
4,20
4,2
9,64
0,5
2,62
7,13
2,9
9,40
4,91
5,04
2 7,22
2 6,8
3,6
5,36
~ 6,4
2 14,2
5,6
3,70
>5
7,10
2,00
6,88
2 3
6,70
4,67
4,35
iu kin
Nhit
25
0,1(KNO3)
25
2,7
20
0,1(NaNO3)
4,60
20
0,1(NaNO3)
3,5
0,1
25
0,1(KNO3)
3,48
20
0,1(NaNO3)
9,55
25
0,1
25
2 17,06
2,8
20
0,1(NaNO3)
27
0,5(LiClO4)
~ 1,1
25
0,1(KCl)
6,53
20
0,1(NaNO3)
20
0,1(NaNO3)
25
1,0(NaNO3)
25
1,0(NaNO3)
3,85
0,1
3,57
25
0,1(KCl)
Log
K ML3
Cd
Co(II)
Cu(I)
Cu(II)
Fe(II)
Mn(II)
Ni
Zn
5,1
8,4
~9,3
~13,0
7,1
4,4
10,7
6,0
2 18,3
2 20,9
2 21,8
iu kin
Nhit
25
25
25
0,1(K2SO4)
25
0,1(K2SO4)
25
25
25
25
Ag
Ca
Cd
Co(II)
5,02
0,7
5,78
7,25
7,05
5,04
6,70
Log
K ML3
4,10
5,95
153
iu kin
Nhit
25
0.1
20
0,1(NaNO3)
20
0,1(NaNO3)
20
0,1(NaNO3)
Cu(I)
Cu(II)
Fe(II)
Fe(III)
Hg(II)
Mg
Mn(II)
Ni
Pb
Tl(I)
Tl(III)
VO(II)
Zn
9,25
5,86
6,5
1,2
4,13
8,8
4,65
11,57
5,47
6,55
215,82
6,75
5,25
211,4
219,65
3,48
8,3
2 4
6,73
4,22
5,80
5,35
10,03
223,5
3,7
2,7
7,7
5,20
25
20
20
20
20
20
20
20
20
25
25
25
20
0,1(K2SO4)
0,1(NaNO3)
0,1(NaNO3)
0,1(NaNO3)
0,1(NaNO3)
0,1(NaNO3)
0,1(NaNO3)
0,1(NaNO3)
0,1(NaNO3)
1,0(NaNO3)
1,0(NaNO3)
0,082
0,1(NaNO3)
154
Nitrobenzene bo ha nc 3,55.10-2
6,0.10-3
org
OH
HCl
N
Thng dng HCl (H2L.HCl), khi lng mol = 248,67); bt tinh th mu vng
(phn hu 475oC). Cht ny tan nh trong nc pH = 1 8 v trong cc dung mi
hu c, nhng tan mnh trong cc dung dch kim (pH = 8). Dung dch bn trong
nhiu thng thm ch nhit cao, pK1(N+H) = 2,55, pKa2(OH) = 7,28 v pKa3(OH)
= 11,5
Thuc th Snyder l 1 thuc th c bit l th do hnh thnh phc mu vi
Fe(II) trong dd NaOH 6 n 10 N, bc sng = 520nm; = 1,48.104. Hn na,
thuc th ny cn c dng nh mt thuc th trc quang i vi Fe, trong dung dch
kim mnh. Tng t, dn xut ca 2,9dimethyl cng c dng lm thuc th i
vi ion Cu ( = 400nm; = 1,15.104 trong NaOH 0,5 7 N)
7.1.7.2. Phenyl2pyridylketoxime (2Benzoylpyridine oxime, PPKO)
C
HO N
N
OH
Trong hai cht ng phn lp th, dng phn ng vi cc ion kim loi khc nhau
hnh thnh cc phc c mu v c th chit bng dung dch chloroform. Cht ny hu
nh khng tan trong nc v cn nhng li d tan trong ethanol nng, benzene,
chloroform, dioxane, ru izo amylic v cc acid v c long. Thuc th ny dng
rn v lng u nhy vi nh sng v i khi phi trnh nh sng chiu trc tip; pKa1(
H2L*) = 2,84 v pKa2(HL) = 12,19 ( = 0,1NaClO4, 40% acetone, 20oC).
Thuc th ny hnh thnh phc c mu vi Fe(II), (III) (), Cu(I) (cam), Cu(II)
157
(xanh), Au( III), Co(II), Pd(II), Pt( II) v UO22+ (vng), v Cr(III) (khng mu) trong
dung dch trung tnh hoc kim. Trong dd kim mnh (pH, NaOH 5 10 N), Fe(II)
hnh thnh phc mu m (ML2, (max = 545 nm, = 1,52.104, phc ny c th
chit vo ru izo amylic. Hn na, PPKO cng c ngh dng xc nh lng
vt ca Feg trong mu kim. N cng c dng xc nh Au(III), Cu(II) v Pd(II).
7.2. TRIPYRIDYLTRIAZINE(TPTZ) V PYRIDYLDIPHENYLTRIAZINE
X
N
N
N
N
N
N
X
N
(1) L
N N
(2) L, X = H
(3) H 2L, X = SO3H
Tn
(1)
Tripyridyltriazine
(2)
Pyridyldiphenyl
triazine
(3)
Pyridyldiphenyl
triazine, sulfonic
acid, mui natri
Tn gi
2,4,6Tris(2pyridyl)S
triazine, TPTZ
3(2Pyridyl)56
diphenyl 1,2,4triazine,
PDT
3(2Pyridyl)56
diphenyl1,2,4triazine,
sulfonic acid, mui natri,
3(2Pyridyl)56di(4
sulfophenyl)1,2,4
triazine, mui dinatri,
PDTS, Ferrozine (*)
Cng thc
phn t
KLPT
C18H12N6
312,33
C20H14N4
310,36
C20H12N4O6Na2.H2O 486,35
Fe2 + + 3 LH + X
org
([FeL ] X )
3
2 org
+ 3H + + X
Kex
(1)
2,3 Butandionedioxime,
Dimethylglyoxime,
Diethyldioxime, DMG
C4H8N2O2;
116,12
(2)
Furildioxime
C10H8N2O4;
220,18
(3)
1,2 Cyclohexanedione
dioxime, Nioxime
C6H10N2O2;
142,16
STT
CTCT
161
iu kin
Chuyn
mu
Cng thc
ca phc
163
Gii hn
pha long
Bi
NH3
Fe(II)
NH3
Fe(III)
Ni
Pd(II)
Pt(II)
Tc
V(IV)
0.2 N
NaOH
NH3
pH=2 (HCl
hoc
H2SO4 )
Acid, sau
khi kh
Pt(IV)
SnCl2HCl
NH3 c mt
Fe(II)
Mu
vng ppt
, ha
tan
14 g/ml
1:7,0.104
M(HL)2
0,4g/0,05ml
1:1,25.105
Nu ,
M(HL)2
1:3.105
ppt
M(HL)2
0,16g/0,05ml
Vng
M(HL)2
ppt
H(HL)2
Xanh
1:5.105
OH
H
OH
HO
(5)
N OH
(6)
165
R
N
N
H
N
R
R
H2L
L thuc th c nhy cao dng xc nh Cd, Co, Cu (II), Fe(II), Hg (II), Mg,
Mn (II), Ni, Pb, Pd (II), Zn v vi kim loi khc.
7.5. DIAMINOBENZIDINE V NHNG THUC TH TNG T
H2 N
NH2
H2 N
NH2
NH2
(3) X = H
(4) X = Cl
(5) X = NO2
(1)
NH2
(2)
NH2
NH2
7.5.1.Danh php
Nhng odiamine thm bao gm trong phn ny c lit k trong bng 7.9,
chung vi nhng danh php ca chng.
Bng 7.9. Nhng oDIAMINE thm
Thuc
th
(1)
(2)
(3)
(4)
(5)
Diamine
Danh php
3,3
Diaminobenzidine,
tetrahydrochloride
2,3
Diaminonaphthalene
3,3,4,4
Biphenyltetramine,
tetrahydrochloride,DAB
C12H14N4.HCl.2H2O;
396,14
DAN
C10H10N2; 158,20
1,2Phenylenediamine
phenylenediamin
C6H8N2; 108,14
5Chloro1,2
Phenylenediamine
5Nitro1,2
Phenylenediamine
C6H7N2Cl; 142,59
C6H7N3O2; 153,14
H 2N
H 3N +
NH2
NH3+ + H2SeO3
H 2N
H 3N +
Se
N + 2 H 2O
H 3O +
CHNG 8
THUC TH VI CU TRC S
8.1. DITHIZONE V NHNG THUC TH TNG T
CTCT: C13H12N4S
N N
HS
KLPT: 256,32
N N
tan
(g/L,20oC)
Ethanol
0,3
Carbon
tetrachloride
Dioxane
Nc + dioxane
Benzene
Chlorobenzene
Nitrobenzene
Chloroform
max (nm)
1st 2nd
(x103)
1st 2nd
R(t s
peak)
Mu
1,64
Xanh nc
bin
0,512
1,70
Xanh
0,349
1,24
1,43
617
602
622
622
627
19,1
16,4
19,0
18,3
16,7
1,72
1,98
1,80
1,90
1,91
16,9
2,59
Xanh m
Xanh
Xanh nc
bin
446
446
453
452
454
31,9
32,4
34,3
34,8
31,9
170
N N
S
N N
S
N NH
H
N N
(1)
(2)
Bc sng nm
8.1.5. Phn ng to phc v tnh cht ca phc
Dithizone cho phi t S,N, u tin phn ng vi nhng kim loi nh. Nu d thuc
th v trong pha nc l mt acid, cation trong pha ny phn ng vi dithizone ha tan
trong dung mi hu c to mu phc chnh phn b trong pha hu c.
171
H
N
C S
N
N
N
M
N
N
N N
(3)
Nu kim loi d hoc pH cao, cc ion kim loi nh: Cu(II), Ag v Hg, cho phc
ph m cu trc ca chng c cho (4) v (5) cho nhng cation ha tr II v I,
tng ng
N
N
M
C
S
N
N
M
S
C
M
N
(4)
IIa
IIIa
IVa
M
N
N
Ia
Va
(5)
VIa
VIIIa
VIIa
Ib
IIb
IIIb
IVb
Vb
VIb
VIIb
He
Li
Be
Ne
Na
Mg
Al
Si
Cl
Ar
Ca
Sc
Ti
Cr
Mn
Fe
Co
Ni
Cu
Zn
Ga
Ge
As
Se
Br
Kr
Rb
Sr
Zr
Nb
Mo
Tc
Ru
Rh
Pd
Ag
Cd
In
Sn
Sb
TE
Xe
Cs
Ba
La
Hf
Ta
Re
Os
Ir
Pt
Au
HG
Tl
Pb
Bi
Po
At
Rn
Fr
Ra
Ac
Th
Pa
Hnh 8.2. Kim loi c chit bi dithizone v kt ta di dng sulfide t dung dch
nc. Kim loi trong vng m c t en c th tch di dng sulfide t dung dch
nc v khng to thnh phc chit dithizone. Kim loi trong khung cn li c th
chit bng dithizone t dung dch nc.
8.1.6. S tinh ch v tinh khit ca thuc th
172
iu kin
Min kim
Dung dch kim cha CNDung dch kim mnh cha citrate hoc tartrate
Dung dch kim nh cha kp (2-hydroxyethyl)
Dithiocarbamate
Min acid
Dung dch acid nh cha CNPha long dung dch acid cha Br- hoc IPha long dung dch acid cha CN- hoc SCNDung dch acid long (pH=5) cha S2O32Dung dch acid long (pH=4-5) cha S2O32Pha long dung dch cha EDTA
hp th
Trong my quang ph k, hai chm tia sng c bc sng khc nhau c chiu
ln lt qua tng cuvet, v s khc nhau gi tr A gia hp thu c o ti bc
sng 1 v 2. Khi hai bc sng ring bit 1 v 2 c chn 510nm v 663,5nm
Bc sng nm
Hnh 8.3. Ph hp thu ca dithizone v mercury(II) dithizonate [Hg(HL)2]
trong nc.
Dung dch Triton X-100
dithizone;
mercury(II)dithizonate[Hg(HL)2]
tng ng hn hp dithizonate thu ngn v dithizone t do c minh ha trong hnh
8.3, A t l vi nng ca mercury dithizonate, vy trong phng php ny hp
th ca dithizone t do t ng c n b, trnh s dng mu trng.
8.1.8. Chun b dung dch thuc th
Dithizone tan trong kim, nhng khng bn c th khng c s dng cho mc
nh thc t. Nhng dung dch c gii thiu nh carbon tetrachloride hay
chloroform, nhng tinh khit ca nhng dung mi nh hng ln n bn ca
dithzone trong dung dch v hp th trong quang ph ca dithizone. Nng ca
dithizone trong dung mi chit khong 0,001% cho php trc quang v 0,01% cho
chit dung mi.
Dung dch carbon tetrachloride c nh gi l n nh khi che dung dch vi
10% th tch bng acid sulfurous 0,1N v bo qun trong ti v lnh. Trong dung
dch chloroform s dng tt trong vic bo qun trong ti hn l s dng cht kh.
Gn y, dung dch n nh ca dithizoneate kim loi, v d nh Zn(HL)2, th c
gii thiu dng cho khng chit trc quang lng di sng i vi vt nhng ion
kim loi nh: Cu(II), Hg(II) hoc Ag. Dithizonate kim loi tan c vi s tr gip
ca cht c hot tnh b mt nonionic nh l Triton X100 v dithizone l dng phc
ca km, trong situ, acid ha dung dch n pH = 1, m Zn t do th khng nh hng
n vic xc nh. Khong 5mg km dithzonate c x l vi phn nh ca dung
dch Triton X100 20% trong ci m no, thm dung mi tng t c 100 ml.
Dung dch thu c sau khi lc bng mng lc (l 0,45m) thu c dung dch trong
175
do.
Thioxin tan t trong nc (0,67 g/L 20oC, pH = 5,2) nhng d dng tan trong
dung mi hu c nh l l C2H5OH (12,5g/100ml), chloroform, aceton, pyridine,
benzene, toluene. N l dung dch nc mu vng cam trong mi trng trung ha
nhng bin i mu vng ti trong acid hoc trong kim. Trong pyridine, quinoline,
v nhng dung dch khc c mu xanh. Trong benzene v toluene c mu nu.
Hidrochloride hoc mui natri ca n d dng ha tan trong nc, acid HCl cha
nc v dung mi hu c phn cc, nhng n khng ha tan trong dung mi hu c
khng phn cc.
Quinolyl8,8disulfide khng ha tan trong nc hoc dung dch kim nhng d
dng ha tan trong acid.
S phn tch acid ca Thioxin c miu t nh sau:
H 2 L+ h + + [ HL + H + L ]
[HL + H+L-] H+ + LH+ v H+L- ch r s trung tnh (1) v dng ion lng tnh (2) ca thuc th.
Kt
N+
N
S-
SH
(1)
(2)
ha tan trong nc. Mc d cht lng ni trn ca dung dch cha nc thng
xuyn c s dng vi nhng mc ch c th, n c th c lm tinh khit bi s
chim hu ca dung mi xc nh. Tuy nhin cch tt nht Thioxin t c tinh
khit l s tng hp t diquinolyl8,8disulfide.
Ha tan 5,5g disulfide trong hn hp 20 ml acid HCl c v 6 ml acid H3PO4 50%,
un nng dung dch di bnh hi lu trong nit khong 2 gi, lm lnh v lc dung
dch, thm vi git dung dch NaOH trong tin trnh bo ha dng sui nit. Lc kt
ta mu vng ca mui natri (phn kt tinh) mt vi gi trong ru cho n kh.
Mui natri c tng hp trong phng php ny dng tinh th cha mt n
hai phn t nc v n nh nhiu thng di nit.
tinh khit ca Thioxin (dng baz t do, HCl hoc mui natri) c th nghim
bng chun iot ca nhm SH theo phng php tiu chun hoc thun tin hn l
bng phng php TLC vi CCl4isopropyl alcohol (50:3). tinh khit ca
diquinol8,8disulfide c th quan st bng im nng chy.
8.2.7. Nhng ng dng trong phn tch
S dng nh thuc th chit trc quang:
Thioxin c s dng nh l thuc th chit trc quang cho nhng ion kim lai
nh khc. Tnh chn lc c th c ci thin bng s chn lc iu kin phn ng
thch hp (nh acid trong t nhin, tnh acid, tc nhn to phc ph, tc nhn bo v).
Tc nhn bo v thch hp l phi c nghin cu trc tin. Mt dung dch cha
nc 0,2% Thioxin hidrochloride (0,1g trong 50ml HCl 6N) c c, n c c
nh trong bng ti, lnh. Mt dimethanol ca thioxin d dng oxy ha vi disulfide
ngay c trong bng ti, lnh v c chun b mi ngy.
S dng nh l thuc th hunh quang:
Mt s kim lai thioxinates fluorescene trong dung mi hu c v nhng kim lai
tng t c th c xc nh bi php xc nh hunh quang. Cng hunh quang
ph thuc nhiu dung mi s dng. Do vy s la chn tnh cht ca dung mi l
quan trng.
Nhng ng dng khc:
Thioxin c th c s dng nh l thuc th trng lng hoc chun trong
phng php ampe. Giy lc c tm vi thioxin c ngh nh l pha tnh cho
sc k kt ta ca ion kim loi.
Diquinolyl8,8disulfide c th c s dng nh l thuc th sinh mu cho kim
lai nu tc nhn kh l hydroxylamine hoc acid ascorbic.
8.3. NATRIDIETHYLDTHIOCARBAMATE V CC THUC TH TNG
T
S
C2H5
N C
C2H5
SNa
CTPT: C5H10NS2Na.3H2O
KLPT = 225,30
178
hp
th
Bc sng nm
8.3.5. Phn ng to phc v c tnh ca phc
179
S
Cu
N C
S
C N
S
10,5
0,52
12,1
2,79
5,87
3,87
Cc nguyn t chit
pH >11
Cc nguyn t chit
pH = 9
181
Cc
Cc nguyn
nguyn t
t chit
chit pH khng hon
=6
ton
Cc
nguyn t
khc
khng
c lit
k
Fe(III), In(III),
Mn(III), Sb(III) v
Te(IV)
(Sb(III), Te(IV)
khng th bo v
bng EDTA; Fe, In,
Mn(III), Sb(III) v
Te(IV) khng th
bo v bng KCN)
As(III),
Se(IV),
Sn(IV) v
V(V)
Khng th
c chit
pH = 4 11
S
N C
C 2 H5
S(NH2(C2H5)2)
L nhng tinh th khng mu, nng chy 82 83oC, tan trong nc, chloroform,
carbon tetrachloride, v mt s dung mi hu c khc. u im ca thuc th ny
trn natriDDTC l n tan c trong dung mi hu c bi v nhng ion kim loi t
trong dung dch acid v c c th tch ra vi thuc th ny. Trong qu trnh tch, s
lng ca thuc th tng ng vi phc kim loi tn ti trong dung mi hu c vi
dng acid phn li. Kh nng chit t dung dch trung tnh hay baz hu nh tng t
nh cch chit ca mui ca Na.
Ammonium Pyrrolidinedithiocarbamate:
CTPT: C5H12N2S2
KLPT: 164,28
S
CH2-CH2
N
CH2-CH2
C
S.NH4
182
OOCCH2
S
2 NH4+
N C
S-
H3C
C2H5
Ag
N C
C2H5
C2H5
C N
Ag
C2H5
L nhng tinh th mu vng nht, hu nh khng tan trong nc, nhng d dng
tan trong pyridine hoc chloroform. Thuc th ny b nh hng nhiu bi m v
nh sng, v vy n c bo qun trong cc dng c kh c mu ti v ni kh
ro. Nhng mu b nhim bn c th c lm sch bng cch kt tinh trong dung mi
pyridine. Khi c nhng bt kh xut hin trong dung dch pyridine ca AgDDTC,
183
184
Hnh 8.6. Ph hp th
ca sn phm phn ng t
Ag-DDTC v arsine.10g
(+10g Sb).
hp th
0,3 _
0,2 _
0,1_
400
500
600
700
Bc sng nm
Cc cht gy sai s:
S(II) b oxy ha bi acid nitric. Ge, HNO3, v HClO4 b loi b bng s bay hi
lin tip vi HCl. S nh hng bi Cu, Fe, Ni, Sb, Se, Sn, Te, PO43-, v mt s
nguyn t khc c loi tr bi qu trnh tch AsCl3 t dung dch HCl m c vi
pxylene hoc benzene. Nhng ion kim loi chng hn nh Ag, Bi, Cu, Hg, Pb, Pd, Pt
v Sb c khuynh hng lng trn b mt Zn, v ngn nga s ho tan ca Zn, nhng
cng c th che bng KI.
Xanthate:
S
R O C
SK
185
CHNG 9
NH
CH3
(CH3)2N
CH3
2H+, 2e
NH2
(CH3)2N
NH2
NH
Mu
Khng mu
Trong iu kin khng kh t do pH = 5,3 dung dch Neutral Red khng c mu,
sau pht hunh quang mu vng. S hnh thnh ca vt liu hunh quang ny tu
thuc vo pH ca dung dch (xy ra chm pH = 2,7 v gn nh khng xy ra pH =
8,2). Chnh hin tng ny gy ra s thay i tht thng mt cch nhanh chng
ca in th nn Neutral Red ch l ch th khng bn trong dy pH m vt liu pht
quang khng ph hp (Eo = 0,240V, 30oC).
i vi nhng dn xut ca azine c th oxy ho kh qu nh nn n ch c
dng nh cht ch th trong qu trnh chun vi tc nhn kh mnh nh Cr(II),
Ti(III) v V(II).
9.2. BRILLLIANT GREEN
CTPT: C27H29N2Cl.
KLPT = 392,97.
186
H5C2
H5C2
N+
C2H5
C2H5
Cl-
N+
C2H5
C2H5
Cl-
COOH
187
H5C2
H5C2
C2H5
C2H5
C O
C O
Trong dung mi phn cc nh alcohol, acetone hoc nc, vng lacton m hnh
thnh cu trc (R) c mu tm m (max = 553nm; = 1,1.105). c tnh quang ph
ca dung dch Choride (RHCl-), max = 556nm; = 1,1.105 cho RH+ ( pH = 1 3,
c mu tm pht hunh quang mu vng) v ti max = 494nm; = 1,5.104 cho RH22+ (
pH = -1 0, c mu cam).
Rhodamine B to phc vi nhng nguyn t: Au, Ca, Cd, Sb, Si, Mo,
V d: Ta xc nh Au bng phng php chit quang ph, dung mi chit l
benzene, thuc nhum cation l Rhodamine B iu kin HCl 0,8N, NaCl bo ha,
hnh thnh ion i (AuCl4)-R+ , max = 565nm; = 9,7.104.
Cc thuc nhum Rhodamine khc:
Cng thc cu to chung:
X1
N+
X2
X3
C2H5
C2H5
Cl-
COOC2H5
sulfuric: pKa(Rhodamine 6G) = -1,1; pKa(3GO) = -0,4; pKa(4G) = -0,21; pKa(3C) = 0,02.
CHNG 10
CTPT: C21H20O6.
KLPT = 368,39.
OH
CH CH
O C
CH2
O C
CH CH
CH3
OH
10.1.1. Tn gi khc
Mu vng ngh, curcumagelb, diferulonymethane, 1,7bis(4hydroxy3
methoxyphenyl)1,6heptadien3,5dione.
10.1.2. Ngun gc
Trn thng mi, n c trong curcuma, the rhizome ca curcuma longa
L.Zingiberaceae.
10.1.3. ng dng
Pht hin ra: B, Ba, Ca, Hf, Mg, Mo, Ti, V, W, Zr. Phn ng o sng ca B,
cch s dng nh xt ln t giy sc k.
10.1.4. Tnh cht ca thuc th
L bt mu vng ngh, nhit si 183oC, khng tan trong nc, tan t trong ether,
d tan trong methanol, ethanol, acetone, v acid acetic bng. N phn ng vi dung
dch kim cho mu vng.
Mc d thuc th c diketonemoiety trong cu trc ca n,nhng khng d liu
no ph hp cho hng s phn ly ca enolic proton. Hnh 10.1 minh ho ph hp th
ca curcumin iu kin mt vi dung dch khc nhau.
189
190
Khi khng c mt acid oxalic, acid boric phn ng vi curcumin, khi b proton bi
acid v c to thnh dng phc mu (1). Phn ng kh chm v mc d tt nhin
mt lng nc cn thit cho giai on tt ca phn ng, nhng phn ng pha trn
phi c bay hi cho kh phn ng hon ton. Hay l phn ng to mu c thc
hin trong nhng acid khan, nh acid sulfuricacid acetic bng, ni m nc tn ti c
th ph hy bi phn thm vo ca propionyl anhydriceoxalyl chloride. Dung dch (1)
s tr v mu xanh en, khi n to bi cht kim. Mc d curcumin cng phn ng vi
Fe(II), Mo, Ti, Ta, v Zn, nhng phc cht s khng chuyn sang mu en trong
iu kin dung dch kim. Dung dch ethanol ca (1) th c th n nh hon ton v c
th gi trong 5 ngy m khng c s thay i quang ph khi gi nhit 0oC.
Khi c mt acid oxalic, mu 2:2:2 phc (2) c hnh thnh, s bay hi ca
phn ng trn ln n kh th vn cn cho s pht trin mu sc l ln nht. S c mt
ca nc lm tr hon phn ng, nu acid v c c mt th s hnh thnh ng thi ca
(1) cng c mong i.
Quang ph hp thu ca (1) v (2) c minh ha trong hnh 10.2, hp th phn
t ca (2) c ghi nhn l 9,3.104 550nm.
191
545nm.
- Phng php Rubrocurcumin:
Phng php ny c nhy km hn so vi phng php khc, nhng phn ng mu
nhanh v n khng cn H2SO4. Phng php ny thch hp cho mu sau khi pha long.
+ Dung dch thuc th: dung dch acid curcuminoxalic: ho tan 0,4g curcumin v 50g
acid oxalate trong ethanol (> 99%) v nh mc thnh 1l tr trong chai nha, dung
dch phi c gi nhit phng khong mt tun trc khi s dng.
+ Sn xut:
t 2ml mu dung dch cha 0,1 ti 2,0g Bo vochn platin. Sau thm 4ml
dung dch acid curcuminoxalic v trn u. S bay hi ca nc khong 52 58oC,
thm 25ml C2H5OH, lm kh hon ton v trn k.Sau b phn cht khng tan
sau khi lc hoc ly tm, chuyn phn dung dch vo cuvet 1cm v o hp thu ti
bc sng 550nm.
10.2. MONOPYRAZOLONE V BISPYRAZOLONE
O
O
C N
N C
C N
CH CH
N C
C N
CH3 CH3
H2C
C N
H3C
(1)
(2)
C10H10N2O
C20H18N4O2
KLPT: 174,20
KLPT: 346,39
10.2.1. Tn gi khc
(1) 3Metyl1phenyl5pyrazoline5one.
(2) 3,3dimethyl1,1diphenyl4,4bispyrazolin5,5dione.
10.2.2. Ngun gc v phng php tng hp
Trong thng mi, pyrazoline c tng hp t phenylthydrazine v acetoacetic
ester nh l 1 sn phm trung gian ca thuc nhum. Bispyrazolone thu c bng
cch cho chy ngc dung dch ethanol ca Monopyrazolone vi Phenylhydrazine.
10.2.3. ng dng
Hn hp ca Monopyrazolone v Bispyrazolone c dng nh 1 thuc th trc
quang c nhy cao vi CN- v thng khng nhy vi SCN- v OCN-.
10.2.4. Tnh cht ca thuc th
- Monopyrazolone:
L mt cht bt tinh th khng mu, nhit si 128 130oC. Nhng mu thng
mi c mu vng nht nhng c th dng nh thuc th cho CN-, hu nh n khng
tan trong nc, nhng tan kh tt trong Alcohol nng, chloroform, pyridine v cc
193
194
CNChloramine T
CNCl
Pirydine
N+ CN
H2O
CHO
CH2
HC
CH CHO
Monopyrazolone
O
N
HC
H2C
HC
HC
HC
N
CH3
CH3
N
N
O
0,098
0,222
0,155
0,059
0,020
198
763, 1968.
25. Shigematsu, T., Matsui, M., and Utsunomiya, K., Bull. Chem. Soc. Jpn., 42,
1278, 1969.
26. Honjo, T., Imura, H., Shima, S., and Kiba, T., Anal. Chem., 50, 1547, 1978.
27. Heunisch, G. W., Mikrochim. Acta, 258, 1970.
28. Holzbecher, Z., Divis, L., Karal, M., Sucka, L., and Ulacil, F., Handbook of
Oganic Reagents in Inorganic Analysis, Ellis Horwood, Chichester, England,
1976.
29. Dhond, P. V. and Khopkar, S. M., Talanta, 23, 51, 1976.
30. Solanke, K. R. and Khopkar, S. M., Fresenius Z. Anal. Chem., 275, 286, 1975.
31. Savrova, O. D., Gibalo, I. M., and Lobanov, F. I., Anal. Lett., 5, 669, 1972;
Chem. Abstr., 78, 1138n, 1972.
200