I HC NNG

TRNG I HC S PHM





L TH MI




BI GING THUC TH HU C TRONG HA
PHN TCH
(Dng cho Sinh vin chuyn Ha i Hc Nng )







Nng, 2008


3




MC LC

LI NI U
CHNG 1. PHN LOI THUC TH HU C
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


4


4.8. TCH CHIT I VI THUC TH HU C
4.8. TCH CHIT CC CHELATE
PHN II GII THIU CC THUC TH HU C V NG DNG
TRONG PHN TCH
CHNG 5. THUC TH PHI TR O O
5.1. PHENYLFLUORONE
5.2. PYROCATECHOL TM
5.3. CHROMAZUROL S
5.4. NBENZOYLNPHENYL HYDROXYLAMINE V NHNG
CHT LIN QUAN
5.5.ACID CHLORANILIC V NHNG DN XUT KIM LOI CA N
5.6. CUPFERRON
5.7. THUC TH HN HP O,ODONATING
5.8. Stillbazo
5.9. -DIKETONE
5.10. PYROGALLOR V BROMOPYROGALLOL
CHNG 6 : THUC TH O-N
6.1. THUC TH ALIZARIN COMPLEXONE
6.2. THUC TH MUREXID
HYDROXYLQUINOLINE
ZINCON
6.3. XYLENOL DA CAM V METHYLTHYMOL XANH
6.4. ASENAZO I V MONOAZO DERIVATIVES OF PHENYL ARSONIC ACID
ACID
6.7. EDTA V CC COMPLEXONE KHC
6.8. HP CHT DIHYDROXYARYLAZO
CHNG 7. THUC TH NN
7.1. BIPYRIDINE V CC HP CHT FERROIN KHC
7.2. TRIPYRIDYLTRIAZINE(TPTZ) V PYRIDYLDIPHENYLTRIAZINE
7.3. Nhng cht dn xut khc ca asymtriazine c nghin cu thay th
cho thuc th ca Fe, Cu, hoc Co (DIOXIME

7.4. PORPHYRIN


5


7.5. DIAMINOBENZIDINE V NHNG THUC TH TNG T
CHNG 8. THUC TH VI CU TRC S
8.1. DITHIZONE V NHNG THUC TH TNG T
8.2. THIOXIN
8.3. NATRIDIETHYLDTHIOCARBAMATE V CC THUC TH TNG
T

CHNG 9. THUC TH KHNG TO LIN KT PHI TR
9.1. THUC TH OXY HA NEUTRAL RED
9.2. BRILLLIANT GREEN
9.3. THUC NHUM CATION RHODAMINE B
CHNG 10. THUC TH HU C CHO ANION10.1.CURCUMIN
155
10.2. MONOPYRAZOLONE V BISPYRAZOLONE
10.3. 2AMINOPERIMIDINE
















6







LI NI U


Thuc th h c c nhiu ng dng trong ho hc phn tch, n c s dng
trong phng php trng lng, chun , trc quang v trong cc php phn tch
cng c khc. Trong phn tch trng lng, vic tm ra thuc th 8-Hydroxyquinoline
v dimethylglioxim l mt v d in hnh. Trong phn tch th tch, thuc th hu c
quan trng nht l EDTA v nhng cht tng t. Trong phn tch quang hc, nhiu
thuc th hu c to sn phm c mu vi ion kim loi, c dng phn tch dng
vt cc ion kim loi. Ngy nay, nghin cu thuc th hu c hu nh c mt khp cc
phng php phn tch. N h tr cho vic tch, chit, ch th v cc chc nng khc
lm tng nhy ca php o.
Do mi cht ch th c tnh cht ring, c trng ring v mu v kh nng to
phcnn nu c nhng hiu bit c bn v thuc th hu c s gip cho ngi lm
cng tc phn tch chn la ng ch th cho php th cng nh tm cc iu kin ti
u cho phn ng. Bit c tnh cht ca thuc th, nh phn tch cng c th nh
hng tng hp cc thuc th mi u vit hn.
Bi ging Thuc th hu c gm 2 phn: phn 1 bao gm ni dung l thuyt ca
Thuc th hu c v phn 2 l phn tra cu cc thuc th hu c v ng dng ca
chng. i vi sinh vin chuyn ngnh phn tch cn thit nghin cu phn 1, khi lm
chuyn v lm kha lun tt nghip phi nghin cu phn 2. Ni dung phn 1 gm
cc phn sau y: M u, Phn loi thuc th hu c, Nhm hot tnh phn tch v
nhm chc phn tch, Nhng lun im c bn ca v c ch phn ng gia ion v c
v thuc th hu c, Lin kt ha hc trong thuc th hu c, D on ph ca thuc
th, Tnh ton mt s hng s ca thuc th hu c v phc ca chng, Phn loi v
gii thiu tnh cht phn tch ca thuc th hu c, cc thuc th quan trng. Ni dung
phn 2 bao gm mt s thuc th hu c quan trng v ng dng ca chng trong
phn tch.g
Chng ti trn trng cm n nhng kin ng gp ca cc bn c gn xa.



7


PHN I
L THUYT THUC TH HU C

CHNG 1
PHN LOI THUC TH HU C

1.1. NH NGHA
Mt hp cht ho hc c s dng pht hin, xc nh hay tch trong qu
trnh phn tch ho hc mt cht hay hn hp ca nhiu cht c gi l thuc th
phn tch.
Do thuc th phn tch bao gm c nhng cht ch th, cht iu chnh pH, dung
dch ra kt ta
Vy mt hp cht cha carbon (tr CO
2
, CO, CaCO
3
) bt k hoc trc tip hoc
gin tip c s dng trong ho phn tch c gi l cht phn ng phn tch hu c
hoc gn hn l thuc th hu c.
Nghin cu phn nh gia thuc th hu c vi ion v c v ng dng n vo phn
tch thc cht l nghin cu qu trnh to phc. S pht trin l thuyt ho hc trong
nhng nm gn y v c bit l s ng dng thuyt trng phi t vo vic nghin
cu cc kim loi chuyn tip v phc ca chng gip cc nh khoa hc ni chung
v phn tch ni ring hiu su sc nhng yu t nh hng n bn ca phc cht,
bn cht ph hp th ca chng v nhng tnh cht qy gi khc.
1.2. U IM CA THUC TH HU C SO VI THUC TH V C
Thuc th hu c c mt s u im ni bt so vi thuc th v c; v vy n c
s dng rt rng ri trong thc t ca ho phn tch.
- Trc ht cn ch n tan rt nh ca hp cht to bi thuc th hu c
v ion v c. V vy, ngi ta c th ra kt ta cn thn tch ht cc cht bn
m khng s mt i mt lng ng k ion cn xc nh. Ngoi ra, hin tng kt
ta theo khi dng thuc th hu c cng ch rt t.
- Thuc th hu c thng c trng lng phn t ln do thnh phn phn
trm ca ion c xc nh trong hp cht to thnh vi thuc th hu c bao gi
cng thp hn trong bt k hp cht no to thnh bi thuc th v c.
V d:
Ion cn
Xc
nh
Hp cht to thnh gia
Ion cn xc nh vi thuc
th
Thnh phn % ca ion
cn xc nh trong hp cht to thnh vi
thuc th

Al
3+

Oxyt nhm
Oxyquinolinat nhm
53,0
5,8


8



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


9


da trn s phn cc hay khng phn cc ca phn t cht c chit c s dng
mt cch rng ri.
1.4. HNG NGHIN CU CA THUC TH HU C
Hin nay, nghin cu thuc th hu c i vo cc lnh vc chnh sau y:
1. Tng hp nhng thuc th hu c mi.
2. Tm cc phng php phn tch mi theo hng n gin, nhy v chn lc.
3. Nghin cu tc ng ca cc nhm chc.
4. Nghin cu cu trc ca thuc th.
5. Nghin cu ng hc phn ng.
6. Phc nha cy hu c.
7. Cc nhm chit.
8. My tnh v chuyn ha furier.
9. Nghin cu phc dch chuyn in tch.
10. Thuc th cho s pht hunh quang v pht quang ha hc.
11. Cht hat ng b mt.
12. Nghin cu trng thi oxy ho.
Thuc th hu c bao gm rt nhiu loi nn cn thit phi h thng ho chng.
1.5. PHN LOI THUC TH HU C
1.5.1. S bt hp l ca cch phn loi trong ho hu c
Ngi ta c th phn loi thuc th hu c theo nguyn tc rt n gin, l
nguyn tc phn loi trong ho hu c (theo cc nhm chc).
S phn loi ny ch thun li khi nghin cu nhng hp cht n gin cn khi
nghin cu nhng hp cht phc tp n t ra khng p ng c yu cu v cn cha
nhiu mu thun.
Theo s phn loi th nhng acid phenol carboxylic trong cng mt nhm cn
nhng dihydroxybenzene thuc v mt nhm khc.
So snh m v ohydroxybenzoic acid vi m v odihydroxybenzene ngi ta
thy rng mhydroxybenzoic acid v mdihydroxybenzene (Resocsin) c rt t tnh
cht phn tch ging vi ohydroxybenzoic acid (salicylic acid) v o
dihydroxybenzene (Pyrocatechin). Trong khi c tnh phn tch ca salixilic acid v
Pyrocatesin li rt gn nhau. S ng nht tnh cht phn tch trong trng hp ny
khng phi l do trong phn t c nhng nhm chc nh nhau m do Pyrocatesin v
salicylic acid cng c kh nng to ni phc ln (nh nhm to phc v nhm to
mui v tr ortho i vi nhau).
V d: cht mu


10


N N
O
2
N
OH


Phn ng vi hydroxide magie trong mi trng kim cn cht mu

Mc d cng loi vi hp cht trn nhng khng cho phn ng y.
Theo tnh cht phn tch th 8oxyquinoline (I) v Anthranilic acid (II) tng i
gn nhau hn so vi 8oxyquinoline (I) v 7oxyquinoline (III) hoc l so vi
antharanilic acid (II) v Paraaminobenzoic acid (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.
N N
OH
O
2
N
OH
NH
2
COOH
NH2
H
2
N
COOH
OH
NH2
(I) (II) (III) (IV)


11


2- Tc dng ca nhng thuc th trong cng mt nhm vi nhng ion v v li c
nhng c tnh khc nhau v nguyn tc.
V d: Theo s phn loi trn th acid oxalic, ethylendiamine dimethylglyoxim phi
thuc v nhm 7 v chng u to vng vi nhng ion kim loi.
Nhng bn cht v c tnh ca oxalat can-xi, triethylendiamino ng sunfat,
dimethylglyoximat Ni li khc nhau rt c bn (mui, mui phc, mui ni phc).
3- S tch ring nhm cht oxy ho v cht kh l khng hp l v mt cht tu
thuc iu kin ca phn ng, c th ng vai tr cht kh hay cht oxy ho.
V d: Methyl da cam.

Trong phn ng vi Chlor ng vai tr cht kh cn trong phn ng vi Sn
2+
li
ng vai tr cht oxy ho.
1.5.3. Phn loi theo Yoe
Yoe chia thuc th hu c thnh 11 nhm ln (theo mc ch s dng) v mi
nhm ln l l li c chia thnh nhiu nhm nh (theo cch phn loi trong nhm hu
c).
Vi d: Nhm ln th nht l dung mi v cht lng ra bao gm nhiu nhm nh:
hydrocarbon, ru, ester, ether, aldehydeketone
Cch phn loi ny thun tin cho vic chn thuc th nhng v c bn n vn
mang nhng khuyt im ca cc cch phn loi k trn.
V d: Pyrogallol, pnitrobenzeneazoresocsin, 8oxyquinoline trong cng mt
nhm nhng c ch tc dng ca mi hp cht vi ion v c li rt khc nhau.
1.5.4. Phn loi theo FEIGL
Feigl chia thuc th thnh 8 nhm. Nhng thuc th to mui. Nhng thuc th
to mui phc. Nhng thuc th to mui ni phc. Nhng thuc th to mui hp
cht hp th. Nhng thuc th dng trong nhng phn ng tng hp hoc phn hu
hu c. Nhng thuc th l h oxy ho kh hu c. Nhng thuc th tham gia phn
ng vi ion v c dng chuyn vi ni phn. Nhng thuc th tham gia vo nhng
phn ng xc tc.
Mc d cha tht hon ho nhng cch phn loi ny c u im c bn l da trn
C
C
O
O
O
O
Ca
Cu
H
2
N
H
2
N
CH2
CH2
3
SO
4
N N SO
3
Na
H
3
C
H
3
C
N


12


c ch phn ng v bn cht sau cng phn loi. Nhng thuc th c xp trong
cng mt nhm khng phi v cng thc ging nhau m v tnh phn ng m n tham
gia ging nhau.
1.5.5. Phn loi theo welcher
Welcher cho rng nhng thuc th hu c c gi tr nht trong phn tch l nhng
thuc th to phc vng cng vi ion phn loi. Cn c vo s ion hydro b ion kim
loi thay th trong mt phn t thuc th trung ha to thnh mt vng cng,
Welcher chia thuc th hu c thnh 3 loi:
Loi 1: Loi 2 ion hydro b thay th. Tham gia vo phn ng phi tr loi ny l ion
kim loi v anion thuc th 2 in tch v do c mi bc phi tr in tch ca phc
s bng in tch ca ion kim loi tr i 2 n v.
Nu s phi tr ca nguyn t kim loi i vi thuc th bng in tch ca ion kim
loi th phc to thnh l phc trung ha v thng khng tan trong nc.
V d: benzoinxim c hai ion H
+
c th b thay th, to vi Cu
2+
hp cht phi tr
c thnh phn 1:1.
Nu s phi tr ca nguyn t kim loi i vi thuc th vt qu in tch ca ion
kim loi th phc anion thng tan trong nc c hnh thnh. C th ly cc phc
tan Oxalate (Fe(C
2
O
4
)
3
), Citrate (CaC
3
H
4
OH(COO)
3
) lm v d. Ngi ta thng s
dng cc phc ny ngn cn kt ta hydroxide trong mi trng kim.
Loi 2: Loi 1 ion hydro b thay th. Phn ng phi tr xy ra gia ion kim loi v
anion thuc th 1 in tch v do c mi mc phi tr in tch tng cng ca phc
kim loi bng in tch ca ion kim loi tr i mt n v. Nu s phi tr ca nguyn
t kim loi i vi thuc th hai ln ln hn in tch kim loi th hp cht trung ho
khng tan trong nc c to thnh v trong a s trng hp, c th chit sn phm
phn ng bng nhng dung mi hu c.
Cn nhn mnh rng, s phi tr thng dng li mc to phc trung ho ngay c
trong trng hp nhng v tr cn cha s dng ht.
iu c gii thch nh sau: s phi tr tip theo i hi thuc th phi phn
ly, v phi ho tan sn phm khng tan. Phn ln thuc th hu c biu l tnh acid rt
yu do s phn ly l khng thun v mt nng lng.
V d: 8oxyquinoline (HX) tc dng vi Mg
2+
to sn phm dihydrat.
Mg(H
2
O
6
)
2
+
+ HX MgX
2
. 2H
2
O + 2H
+
+ 4H
2
O.
S phi tr ca Mg
2+
bng 6 nhng in tch trng thnh trung ho sau khi hai
C
C
H
2HN
O
Cu
O
OH
2
OH
2
C
C
H
N
O
Cu
C
CH O
N


13


phn t thuc th tc dng vi mt ion magie. Cn Al
3+
to 8oxyquinolat khng
ngm nc v s phi tr ca n ng 2 ln ln hn in tch. Phn ln nhng thuc
th hu c c ng dng rng ri trong phn tch iu thuc loi ny: nitroso,
naphtol, dimethylglyoxim, dithizone, v.v
Loi 3: Loi nhng ion hydro khng b thay th. y phn ng phi tr xy ra l
do s thay th nhng phn t nc bng nhng phn t thuc th trung ho. Do sn
phm phn ng l cation c in tch ng bng in tch ca cation kim loi ban u.
Mc d sn phm phn ng thng tan trong nc nhng i khi c th chit bng
nhng dung mi hu c nh cation hu c khi lng ln v nhng anion thch hp.
V d: C th chit phc ca Cu v Fe vi nhng dn xut ca 1, 10-phenanthroline
bng ru cao phn t.
Nhng thuc th to s chelate ln hn vi 1 n phn t thuc th (v d
ethylenediaminetetracetic acid v nhng thuc th ni chung) khng to chelate khng
thuc vo ba loi hp cht k trn.
CHNG 2

L THUYT V LIN KT PHI TR

L thuyt phi tr ca Werner vi quan im ho tr ph cho chng ta mt cch
gii thch thng nht v s tn ti ca phc cht, nh [Co(NH
3
)
6
]Cl
3
. Trn c s ca
thuyt ny, thuyt l nn tng ca ha hc cc hp cht phi tr ngy nay, ta c th gii
thch tnh cht, ha lp th ca nhng cht loi tng t. V l thuyt ca Werner
c nu ln 20 nm trc khi xut hin khi nim v cu to in t ca nguyn t
nn thuyt khng th m t di hnh thc hin i, bn cht ca lin kt ph, hay
l lin kt phi tr nh chng ta thng gi. m t bn cht ca lin kt trong phc
cht, ngy nay ngi ta s dng rng ri 3 thuyt:
- Phng php lin kt ho tr (VB)
- Thuyt trng tinh th tnh in
- Thuyt qu o phn t (MO)
2.1.PHNG PHP LIN KT HA TR (VB)
Phng php lin kt ha tr c gio s Pauling (Hc vin K thut
California) pht trin v nu ln mt cch d hiu trong quyn sch ca mnh Bn
cht ca lin kt ha hc. Ngoi Marie Cuirie, Pauling l ngi duy nht 2 ln c
gii thng Nobel (mt ln v ha hc nm 1954, mt ln v ha bnh nm 1962).
Quan im ca Pauling nh hng rt ln n tt c mi lnh vc ca ha hc. L
thuyt cng ha tr ca ng c kh nng thng nht nhng quan im ca cc nh
ha hc v do c ph bin rng ri. Nh thuyt ny, c th gii thch tt cu to
v t tnh ca phc kim loi. L thuyt ny c th gii thch c nhng tnh cht khc
ca cc hp cht phi tr v d nh quang ph hp th nhng dng nh bng nhng l
thuyt khc c th lm nhng vic ny d dng hn. Do , trong nhng nm gn y


14


nhng nh bc hc nghin cu vn ha hc ca cc hp cht phi tr thch th l
thuyt trng tinh th, trng phi t v l thuyt qu o phn t hn, Chng ta s
ch yu nghin cu cc l thuyt ny.
Trc ht cn nghin cu xem phng php lin kt cng ha tr m t s to
thnh cc phc cht [CoF
6
]
3-
v [Co(NH
3
)
6
]
3+
nh th no v so snh vi nhng quan
im ca l thuyt trng tinh th v l thuyt qu o phn t m chng ta s xt ti
sau y. u tin cn nu ln rng [CoF
6
]
3-
cha 4 in t khng ghp i trong khi
th [Co(NH
3
)
6
]
3+
tt c cc in t ghp i. Mi phi t (theo Lewis l baz) cho
mt i in t to lin kt cng ha tr phi tr. Theo phng php lin kt cng
ha tr, cu to in t ca cc phc trn c minh ha hnh 2.1. Lin kt trong
trng hp ny l lin kt cng ha tr. Nhng t hp tng ng nhng qu o
nguyn t ca kim loi pha ha vo nhau v to thnh dng qu o mi gi l qu
o lai ha. Nhng qu o ny to thnh nhng lin kt cng ha tr bn hn gia
kim loi v phi t.



Trong 6 phi t phi tr, nhng qu o lai ha hnh thnh do s pha ha nhng
qu o nguyn t s, px, py, pz, dx
2
-y
2
v dz
2
. Su qu o lai ha hnh thnh sp
3
d
2

hng ti nhng nh ca bt din. Ta nhn thy rng i vi phc [CoF
6
]
3-
nhng qu
o d cng cng c mc nng lng chnh nh qu o s v p. Phc loi ns np
3
nd
2
gi
l phc qu o ngoi bi v nhng qu o d ngoi tham gia vo s to phc. Mt
khc, nhng qu o d c chc mc nng lng chnh thp hn qu o s v p tham
gia vo s to phc [Co(NH
3
)
6
]
3+
. Nhng phc nh (n-1)d
2
ns np
3
c gi l phc
qu o trong bi v nhng qu o d trong tham gia vo s to thnh chng.
2.2. L THUYT V TRNG TINH TH
Phng php lin kt ha tr v thuyt trng tinh th tnh in khc nhau v bn
cht. Phng php lin kt ha tr xut pht t gi thuyt lin kt phi tr l cng ha
tr cn l thuyt tnh in th hon ton bc b c tnh cng ha tr ca lin kt v gi
thuyt rng lin kt gia ion kim loi v phi t l hon ton ion. C th tnh ton nng
lng ca lin kt phi tr khi ta s dng nhng phng trnh c in ca th nng, c
d
xy
d
xz
d
yz
d
x2
-
y2
d
z2

NH
3
NH
3
3d
F
-
NH
3
4s
F
-
F
-
F
-
NH
3
NH
3
NH
3
NH
3
4p 4d
F
-
F
-


( ) | |
3
6 3
NH Co

Hnh 2.1. S to phc | |
3
6
CoF v [Co(NH
3
)
6
]
3-
theo quan im ca phng php
lin kt ha tr


15


k ti lc ht v lc y gia nhng ht nhn tch in.
Nng lng lin kt = q
1
q
2
/r (2.1)
Trong phng trnh (2.1), q
1
v q
2
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 [TiF
6
]
2-
. Trong ion Ti
4+
t do
nm cch bit trong khng gian, hnh dng in t l nh sau: 1s
2
2s
2
2p
6
3s
2
3p
6
,
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.


16



Ion kim loi t do (Ti
4+
) Phc gi thuyt vi Phc bt din [(TiF
6
)
2-
]
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 [TiF
6
]
2-
ion Ti
4+
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 Ti
4+
. 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 Ti
4+
trong [TiF
6
]
2-
phn b trn cng mt khong cch
ti 5 qu o d ca Ti
4+
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 Ti
4+
t do. Phc bt din vi tt c cc qu o d suy bin l phc gi
thuyt. Phc [TiF
6
]
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:

Cc ion s nm gn cc qu o
2 2
x -y
d v
2
x
d nht, l nhng qu o e
g
. S tht
l cc qu o e
g
hng thng ti cc phi t F
-
trong khi th nhng qu o d
xy
,



0,4
0
0,6
0

0
e
c
t
2
d

N

n
g

l

n
g

F
F
F
F
F
F
z
x
y


17


d
xz
, d
yz
k hiu l cc qu o t
2g
li hng vo gia cc phi t (k hiu e
g
v t
2g
c
s dng trong l thuyt nhm ca ton hc, t ch s suy bin bc 3, e ch s suy bin
bc 2). Do in t kh chim ch trn qu o e
g
hn l trn qu o t
2g
v v vy
nhng qu o e
g
phi c trng bng gi tr nng lng cao hn so vi t
2g
. S phn
chia nh th, nm qu o suy bin ca ion kim loi t do thnh nhng nhm qu o
c trng bng nhng nng lng khc nhau l c im ch yu ca thuyt trng
tinh th. Hin tng c gi l s tch mc do trng tinh th. Nh trnh by
trn, s tch mc nng lng xy ra l do nhng qu o d nh hng khng ng
nht trong khng gian nn nhng nguyn t, ion hay phn t bn cch c th lm bin
i nng lng ca nhng qu o hng ti chng.
Nhiu sinh vin cho rng rt kh quan nim mt cch r rng v thuyt trng tinh
th v quan im tch mc ca thuyt ny. Trn y chng ti trnh by nhng lun
im c bn nht da trn c s nhng m hnh khng gian ca nhng qu o d.
l con ng ng n i ti thuyt trng tinh th. Ta c th dn ra mt hnh nh vt
l nh hnh 2.3. Chng ta hy ch ti hnh 2.3 v gi thuyt rng ion kim loi v lp
v in t ca n c hnh dung di dng qu cu n hi bng bt bin. By gi
chng ta hy xem qu cu bin i nh th no nu b lp v hnh cu cng (tng
ng vi cc phi t) tc dng ln n t bn ngoi. Th tch qu cu b thu nh li v h
s c nng lng cao hn, iu ny c khng nh bi s kin l qu cu n hi t
ln ln chim th tch ban u sau khi tch khi lp v rng buc n. S bin i
nng lng tng ng vi s tng nng lng pht sinh do s y nhau gia nhng
in t trong ion kim loi v in t ca phi t trong phc gi thuyt.

Hnh 2.3. Hiu ng ca trng tinh th c hnh dung mt cch c th nh l p lc
ca lp v hnh cu ln qu cu bng bt bin tt c mi hng v nh l p lc ln
qu cu khi tp trung vo nhng ch xc nh.
Nu by gi lp v cng tp trung lc tc dng ca n vo 6 im ring bit (v d
nh ca bt din chng hn) th qu cu s b lm vo trong nhng im y v li ra
ngoi nhng im gia cc im y. Do kt qu ca sc p , nn h bt bin c
nng lng cao hn 6 im c p lc cao v c nng lng thp hn nhng im
gia chng. iu tng ng vi s tch mc ca trng tinh th v nhng im li
ra tng ng vi qu o t
2g
, nhng im lm vo trong tng ng vi qu o e
g
.
Trc y ta nhn xt rng nng lng tng ng ca nhng qu o d ca ion kim
loi tng ln khi phi t tin gn ti ion. iu t n cho php hnh dung rng, phc
phi km bn hn ion kim loi v phi t t do. Nhng chnh s kin to phc ch r
rng phc l dng c nng lng thp hn sao vi ion kim loi v phi t ring l.
Qu cu bng bt bin
(ion kim loi t do)
Qu cu bng bt bin di
p lc ca lp v hnh cu
(phc gi thuyt)
Qu cu bng bt bin di p
lc tc ng vo nhng hng
xc nh (phc cht).


18


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 t
2g
v e
g
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 t
2g
nh hn 0.4
o
. 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: 0,6
o
. Trong phc bt din (v d [Ti(H
2
O)
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 t
2g
c nng lng nh hn nng lng qu o suy bin gi thuyt 0,4
o
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(t
2g
) l qu a c th tch xa phi t nht. i vi phc, gi tr 0,4
o
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
t
2g
e
g

Nng lng
n nh ha
t
2g
e
g

Nng lng
n nh ha
0

S in t d
trong ion kim
loi
t
2g
e
g

Nng lng
n nh ha
t
2g
e
g

Nng lng n
nh ha
0

1

0,4
2

0,8
3

1,2
4

0,6

1,6
5

0,0

2,0
6

0,4

2,4
7

0,8

1.8


19


8

1,2
9

0,6
10

0,0
Ta nhn thy rng nng lng n nh ha bi trng tinh th c th tnh mt cch
d dng bng cch thm vo gi tr 0,4
o
cho mi in t chim qu o t
2g
v gi tr -
0,6
o
cho mi in t chim in t e
g
. Nh vy, nng lng n nh ha bi trng
tinh th i vi h c 5 in t d:
Hoc l bng: 3*(0,4
o
) + 2*(-0,6
o
) = 0,0
o

Hoc l bng: 5*(0,4
o
) + 0*(-0,6
o
) = 2,0
o

Ngha l ph thuc vo s phn b 5 in t trn qu o t
2g
v e
g

Thuyt tnh in n gin coi ion kim loi nh ht nhn nguyn t c bao quanh
bi m my in t hnh cu. Thuyt trng tinh th ngh m hnh tt hn v
thuyt ny gi thuyt rng nhng in t d to thnh m my in t khng phi
c dng hnh cu do xu hng trnh nhng v tr m phi t chim gi (nhng in
t ny to thnh nhng m my in t khng c hnh dng hnh cu bng cch t sp
xp mt cch la chn vo nhng qu o c gi tr nng lng thp, hng vo gia
nhng phi t). Do , thuyt trng tinh th gii thch mt cch hon ton c th
hiu c nguyn nhn v sao nhng tnh ton tnh in n gin cho ta nhng gi tr
thp hn v bn ca phc v nhng hp cht ca nhng kim loi chuyn tip.
Thuyt tnh in n gin b qua s phn b in t khng theo hnh dng hnh
cu v hu qu pht sinh do hin tng nng lng n nh ha bi trng tinh
th. Mt trong nhng im gy nn s phn i vic ng dng thuyt tnh in n
gin cho lin kt trong phc kim loi l s bt lc ca thuyt ny trong khi gii thch
s to thnh nhng phc phng vung. C th chng minh rng nu 4 in tch m
c gi xung quanh ion trung tm dng ch bng lc tnh in, th nhng in tch
m phi nm nh ca t din. Ch c s phn b nh th, nhng nhm mang in
m mi nm khong cch cc i i vi nhau v chu lc tnh in nh nht. iu
ch ph hp vi thc t trong iu kin, nu ion trung tm c i xng cu. Nhng
s i xng khng in hnh i vi nhng ion ca kim loi chuyn tip bi v in
t nm trn qu o c nng lng thp hng vo gia nhng phi t v do khng
c i xng cu. Trong phn cui ca chng ny, chng ta s nu r, thuyt trng
tinh th cho php gii thch s tn ti nhng phc phng vung cng nh d on tnh
khng bn ca mt s phc bt din.


20



Hnh 2.4. S tch mc nng lng bi trng tinh th nhng qu o d ca ion
trung tm trong nhng phc i xng khc nhau. Ch s ca l k hiu cho nhng
i xng khc nhau.
Nh vy,chng ta nghin cu xong trng hp tch mc nng lng ca trng
tinh th i vi phc bt din, v s xt nhng phc c cu to hnh hc loi khc.
thun tin ta bt u xt s tch mc bi trng tinh th vi cu hnh bt din v theo
di xem s tch mc s bin i nh th no khi hnh hc hnh dng bin i (hnh
2.4). Khi chuyn t cu hnh bt din sang cu hnh phng vung, hai phi t no
vn nm v tr i din trong bt din b tch ra.
Nu nhng phi t trn trc z s nhng v tr nh th no khong cch kim
loi-phi t ln hn mt cht so vi khong cch ca 4 phi t trong mt phng xy th
s thu c cu to t gic (hnh 2.5).
iu kin cho php nhng phi t trong mt phng xy tin gn ti ion trung
tm. Nhng qu o d tng ng trong mt phng xy s chu lc y ca cc phi t
ln hn so vi lc y trong cu to bt din v do nng lng ca nhng qu o
2 2
x -y
d v d
xy
tng ln (hnh 2.5). Trong khi nhng qu o d trong mt phng xy v
yz s chu lc y nh hn ca cc phi t tch xa ra theo trc z thm mt khong
cch no . Hin tng dn ti s gim tng i nng lng ca qu o
2
x
d v
s gim khng nhiu nng lng ca qu o d
xz
v d
yz
so vi dng bt din.
0

p
s
2
dz

dxz dyz
dxydxzdyz
dx
2
-y
2
dz
2

dxydxzdyz
dx
2
-y
2
dz
2

dz
2
dx
2
y
2
dx
2
y
2
dxy

e
N

n
g

l

n
g

T din
Bt din T gic lng
chp


21



Chng ta cng quan st thy hnh nh tng t v s tch mc i vi cu to chp
vung, trong mt phi t nm trn trc z cn 4 phi t cn li v ion trung tm
phn b trong mt phng xy. S tch hon ton hai phi t trn trc z dn ti s to
thnh dng thng vung km theo s tng nng lng ca qu o
2 2
x -y
d v d
xy
v s
gim nng lng ca cc qu o
2
x
d , d
xz
, d
yz
.
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 (
2 2
x -y
d v
2
x
d ) cch xa cc phi t hn l nhng qu o
phn b gia cc trc (d
xy
, d
xz
, d
yz
). Do nhng qu o e
g
(
2 2
x -y
d v
2
x
d ) tng ng
vi gi tr nng lng thp, nhng qu o t
2g
(d
xy
, d
xz
, d
yz
) 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 e
g
v t
2g
, 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
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 d
3
) c th
c 3 in t khng ghp i , cn ion kim loi c 8 in t d c th
c 2 in t khng ghp i v 3 i in t .
Cht c nhng in t khng ghp i b t ht gi l cht thun t (sc ht
tng i yu hn so vi nhng vt liu Ferro t nh st), gi tr lc ht ca t i vi
x
y z
Hnh 2.5. Phc t din, nguyn t trung tm chnh gia


22


mt cht xc nh s in t khng ghp i ca n.
C th o thun t mt cch tng i n gin bng cn. t mu vo trong
ng treo trn cn, ri cn trng lng mu khi c v khi khng c lc tc dng ca t
trng. Nu mt cht l thun t th trng lng ca n s tng ln khi t di tc
dng ht ca t trng. S tng trng lng l s o s in t khng ghp i trong
hp cht.
Ngi ta pht hin rng mt s phc ca kim chuyn tip khng tun theo quy lut
Hund. V d mt s phc ca Co(III) c cu hnh in t d6 nh [Co(NH
3
)
6
]
3+
khng
b t trng ht (nhng phc ny c tnh nghch t). Nhng phc, trong mt s
in t khng ghp i ca ion kim loi trong trng thi kh c ghp i c gi l
nhng phc spin thp. Phc ca Co(III). [CoF
6
]
3-
thun t v c 4 in t khng ghp
i. l v d ca phc spin cao. Trong phc ny, s phn b in t trong nhng
ion kim loi to phc tng t nh khi n trng thi kh. S phn b in t ca
hai phc c th hnh dung nh sau:
v
Cc phc ny c nhiu tn, v d:
[Co(NH
3
)
6
]
3+
: Phc spin thp ni orbital ghp i
[CoF
6
]
3-
: Phc spin cao ngoi orbital.
By gi cn phi hiu v sao in t trong nhng h li phn b trn orbital d
theo nhng cch khc nhau. Trc ht cn phi cng nhn, s phn b in t c
quyt nh bi hai yu t. Th nht, in t c xu hng sp xp nh th no c
th c s in t khng b ghp i cc i, ph hp vi quy tc Hund. cho in t
ghp i cn tiu tn nng lng ln thng lc y ca hai in t trn cng qu
o. Th hai, trong trng tinh th nhng in t d c xu hng chim nhng qu o
c nng lng thp ngha l trnh c cng nhiu cng tt tc dng y ca phi t.
Nh vy, nu bn t c () ln thng s mt i ca bn do s ghp i
in t th in t s ghp i v ta s thu c phc loi spin thp. Khi s tch mc
bi trng tinh th () khng ln th in t gi trng thi khng ghp i ca mnh
v phc spin cao s xut hin.
Hnh 2.6 ch cho ta thy rng gi tr
o
ca [CoF
5
]
3-
nh hn gi tr
o
ca
[Co(NH
3
)
6
]
3+
. Phc c gi tr ln s ch yu l phc spin thp.

0

| |
3
6
CoF


( )
3
3
6
Co NH
+



Phc spin cao Phc spin thp






0

23


Hnh 2.6. Gi tr tng i v tch mc bi trng tinh th (
o
) i vi nhng qu
o d ca phc bt din spin cao v spin thp ca Co(III)
Mt s v d khc v s tch mc bi trng tinh th v s phn b in t trong
phc c dn ra trn hnh 2.7. Nh trnh by trn y, gi tr tch mc bi trng
tinh th quyt nh vic cc in t d trong ion kim loi ghp i hay l tun theo quy
lut Hund. i lng ny nh hng nhiu n tnh cht ca kim loi chuyn tip.
Mc tch mc bi trng tinh th ph thuc vo nhiu yu t. Bn cht ca phi t
gy nn trng tinh th l yu t c bit quan trng. Ph hp vi nhng khi nim
tnh in, nhng phi t c in tch m ln v nhng phi t c th tin gn ti ion
kim loi (nng lng ion nh) gy nn s tch mc ln nht. Nhng ion c in tch
khng ln khi tin gn n qu o d lm cho nhng qu o ny khng thun li cho
in t v mt nng lng. iu ny c khng nh bng thc nghim qua s kin:
nhng ion F
-
c kch thc nh nn gy nn hiu ng trng tinh th ln hn so vi
nhng ion c kch thc ln hn nh: Cl
-
, Br
-
, I
-
. V s tch mc bi trng tinh th l
kt qu ca tng tc mnh ca phi t vi cc qu o hng ti gia chng nn tch
mc ln ch c th t c khi nhng phi t hi t nhng in tch m ca mnh
ln qu o. Ta c th hnh dung d dng rng phi t c mt i in t t do (v d
nh NH
3
) c kh nng hi t ln hn so vi nhng phi t c 2 hoc c mt s i
in t t do ln hn (III) v (IV)


24



Hnh 2.7. S tch mc bi trng tinh th v s phn b in t theo mc nng lng
i vi mt s phc.
Hai phc u tin c cu to bt din, nhng phc khc (t tri qua phi) c cu to
t gic, phng vung v t din . C th s dng tnh cht nu trn gii thch hin
tng, nhng phn t NH
3
trung ha in gy nn s tch mc ca trng tinh th ln
hn trng hp ca nhng phn t nc hoc l ca nhng ion halogen mang in tch
m.
Ni chung, ta s thy kh r kh khn khi s dng m hnh tnh in n gin
gii thch kh nng gy s tch mc ca trng tinh th ca nhng phi t khc nhau.
Ngi ta thy rng, kh nng gim theo trt t dn ra di y:
Trng phi t mnh Trng phi t trung bnh Trng phi t yu
CO, CN
-
>Phen>NO
2
>en>NH
3
>NCS
-
>H
2
O>F
-
>RCO
2
>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.
:

:

Cl
: :













( ) | |
+ 3
6 2
O H Fe
( ) |
3
6
CN Fe
( ) ( ) | |
+ 2
2 2 4 3
O H NH Cu
( ) | |
2
4
CN Ni | |
2
4
CoCl



25


l l do xut hin thuyt trng phi t.
Bin dng ca thuyt trng tinh th l thuyt trng phi t. Theo thuyt ny th
trong phc cht cn tn ti lin kt cng ha tr, t nht th thuyt ny cng c th gii
thch mt cch nh tnh gi tr tch mc bi trng tinh th gy nn bi nhng phi t
khc nhau. Nhng ht nh CO, CN
-
, Phen v NO
2
-
l nhng phi t to nn trng
tinh th mnh nht, chng ta c kh nng to lin kt vi nguyn t kim loi trung
tm. Lin kt c th lm tng mnh s tch mc bi trng tinh th.
Trng thi oxy ha ca ion kim loi v loi cc in t d ca n cng nh hng
n mc tch. Trng thi oxy ha cao ca ion kim loi gy nn s tch mc ln
hn. Phc [Co(NH
3
)
6
]
3+
nghch t v l phc spin thp cn phc [Co[NH
3
)
6
]
2+
li
thun t v l phc spin cao. S tch mc bi trng tinh th trong phc Co(III) gn
hai ln ln hn so vi phc ca Co(II). iu c gii thch bng s ghp i cc
in t. Gi tr
o
ln i vi Co(III) c th gii thch nh sau: V ion kim loi c th
tch nh hn v in tch cao hn nn phi t tin gn hn v do tng tc mnh
hn vi cc in t d cu n. S tch mc bi trng tinh th trong cc phc
[Rh(NH
3
)
6
]
3+
, [Ir(NH
3
)
6
]
3+
, ln hn so vi phc [Co(NH
3
)
6
]
3+
. Ni chung s tch mc
nhng phc c cha cc in t 5d th ln hn cn s tch mc nhng phc c
cha cc in t 3d th nh hn. C th gii thch s kin nh sau: Nhng qu o
5d tri di trong khng gian xa hn v nh vy tng tc vi cc phi t mnh hn.
Thnh tu ln nht ca trng tinh th l gii thch thnh cng mu ca nhng hp
cht ca kim loi chuyn tip. Hiu s nng lng khng ln trong nhng phc kim
loi chuyn tip l hu qu ca chuyn in t t mc nng lng thp ln mc nng
lng cao (gia nhng qu o d khng tng ng: t
2g
v e
g
) c thc hin nh s
hp th nh sng trng thy. l nguyn nhn gy mu ca phc, v d dung dch
nc ca Ti(III) mu tm, mu c gii thch bng ph hp th ca phc [Ti(H
2
O)
6
]
3+

(hnh 2.8). S hp th nh sng ca phc trong vng ph trng thy c gii thch
bng s chuyn in t qu o t
2g
ln e
g
(hnh 2.9).

Hnh 2.8. Ph hp th ca phc [Ti(H
2
O)
6
]
3+
. Dung dch [Ti(H
2
O)
6
]
3+
c mu tm ,
(x 10
4
)
%

n
h

s
a
n
g

b

p

t
h

i

m

u

0
0.2 0.4
0.6
0.8
1
0
50
Xanh Vng
di nh sng ()

100




26


v n hp th cc tia vng cho qua cc tia xanh v .

Hnh 2.9. S chuyn in t d-d gy nn mu tm ca phc [Ti(H
2
O)
6
]
3+

Ph hp th ca nhng phc c s in t d ln hn mt phc tp hn v s cch
chuyn in t nhiu hn.
Phng trnh Plank (2.2) lin h nng lng chuyn in t vi di sng ca
nh sng b hp th.

h c
E

=
(2.2)
h: Hng s plank (6,62 erg/giy).
C: tc nh sng (3,00 cm/giy).
Nng lng c o bng erg trn phn t cn o bng cm. T phng trnh 2.2
c th xc dnh c hiu s nng lng in t i vi nhng qu o d m in t
thc hin b chuyn. Thay nhng gi tr h, C v s dng nhng h s chuyn tng
ng (s Avogadro 6,0210
23
phn t/mol) v hng s Ioule 4,1810
7
erg/kcal) th c
th thu c cng thc (2.3)

5
2, 84 *10
E

=
(2.3)
E: o bng kilocalo/mol v
o
bng . Ngi ta pht hin cc i trong ph hp
th ca [Ti(H
2
O)
6
]
3+
nm = 5000. Cc i tng ng vi gi tr hiu nng
lng gia nhng qu o t
2g
v e
g
khong 57 kilocalo/mol l i lng bc nht vi
nng lng lin kt. Mc d rng, i lng nh khng ng k so vi nhit hydrate
ha ca Ti
3+
(phng trnh 2.4) l 1027 Kcal/mol, i lng ny rt quan trng v cn
thit hiu ha hc ca cc kim loi chuyn tip.
Ti
3+
(trng thi kh)+H
2
O[Ti(H
2
O)
6
]
3+
(trong dung dch nc)+1027Kcal/mol (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
t
2g
( ) | |
+ 3
6 2
O H Ti
nh sng
5000

t
2g



e
g



e
g

( ) | |
+ 3
6 2
O H Ti


27


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. THUYT QU O PHN T (MO)
Thuyt qu o phn t cng ngy cng ph bin i vi cc nh ha hc. Thuyt
ny ch ti c c tnh cng ha tr c c tnh ion ca lin kt ha hc mc d
khng nu ln nhng im ny. Phng php MO xem xt s phn b in t trong
phn t ging nh l thuyt hin i gii thch s phn b in t trong nguyn t.
Trc tin l v tr ca cc ht nhn trong nguyn t v ca cc qu o quay quang
chng c xem nh l xc nh, nhng qu o phn t ny (MO) phn b trong
nhng vng c xc sut tm thy in t ln nht trong khng gian. Thay th cho s
phn b ca mt nguyn t nhng qu o phn t ny tri ra trn ton phn t hoc l
trn mt phn ca n. Di y ch dn ra nhng tnh ton dng qu o phn t cho
trng hp nhng phn t n gin nht.
V s tnh ton da trn c s nhng nguyn tc chung gp nhiu kh khn nn
ngi ta thng s dng phng php tnh gn ng t hp tuyn tnh nhng qu o
nguyn t (KAO). Tt nhin l, MO ca phn t cn phi lm cho ngi ta nh li
nhng qu o nguyn t m t phn t c xy dng ln. Xut pht t nhng
dng bit ca qu o nguyn t c th s b hnh dung cc dng MO c trng.
T hp tuyn tnh cng v tr hai qu o s cho hai qu o phn t c m t
trong hnh 2.10. Mt qu o phn t xut hin do s cng nhng phn xen ph ca
qu o nguyn t. Cn mt qu o khc xut hin do s tr cc vng xen ph ca
AO. Qu o phn t thu c do s cng vng xen ph ca hai qu o s chim vng
khng gian gia hai ht nhn, qu o ny c gi l qu o phn t lin kt. Nng
lng tng ng vi qu o phn t ny thp hn nng lng ca mi qu o
nguyn t s to thnh n. Qu o phn t thu c bng cch tr nhng vng xen ph
ca qu o nguyn t khng chim vng khng gian cha nhng ht nhn, c nng
lng cao hn nng lng ca nhng qu o nguyn t khi u c gi l qu o
phn t phn lin kt. Hiu nng lng ca nhng qu o phn t phn lin kt v
lin kt c th tnh c nu ch rng in t ca qu o lin kt nm di tc dng
ca c hai ht nhn cn in t ca qu o phn t phn lin kt th ch chu tc dng
ca 1 ht nhn.



28



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 H
2
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 H
2
c hai in t cng nm trn qu o phn t lin kt c nng lng thp.
Phn t H
2
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.
P
P
Tr xen ph
Cng xen ph
Qu o
A
phn lin kt
Qu o lin kt
Cng xen ph
A
Qu o
A
phn lin
kt
B
Qu o

lin kt
Cng xen ph
Tr xen ph
Qu o
A
phn lin kt
Qu o lin kt
Tr xen ph


29



Hnh 2.11. Biu mc nng lng qu o phn t ca phn t H
2


Hnh 2.12. Biu mc nng lng qu o phn t ca ion diheli.
Ion He
2+
(ion diheli) l h ba in t, biu mc nng lng ca nhng qu o
phn t ca n c nu ln hnh 2.12. V trn mt qu o ch c th dung np 2
in t nn in t th ba phi i vo qu o phn t phn lin kt *, qu o ny
tng ng vi nng lng cao hn nng lng qu o nguyn t ca nhng nguyn
t Heli ring bit. Nh vy, s np in t vo qu o phn t * c c trng
bng s mt i nng lng v do h to thnh km bn hn. iu ph hp vi
nhng quan st thc nghim. Nng lng lin kt ca He
2+
ch bng 5 Kcal/mol trong
khi nng lng lin kt ca phn t He
2
l 103 Kcal/mol. Phn t He
2
c 4 in t
khng bn hn so vi 2 nguyn t Heli t do.
Biu mc nng lng MO trong trng hp tng qut i vi phn t AB c
AO

MO AO

s
*
1s
1s 1s
H H - H H
N

n
g

l

n
g






AO

MO AO

s
*
1s
1s 1s
H H : He
+
He
N

n
g

l

n
g






30


din t trong hnh 2.13. i vi phn t ny c th c mt s v hn MO c nng
lng cao cng nh nguyn t A v B c th c mt s v hn qu o nguyn t c
nng lng cao, nhng iu ng ch l nhng qu o c nng lng thp, trn
c in t. Nu nh c hai loi nguyn t khc nhau th nng lng qu o nguyn t
cng khc nhau (v d: nng lng tng ng vi nhng qu o 1s ca nhng nguyn
t A v B l khc nhau). Qu o nguyn t nhng nguyn t m in hn c nng
lng thp hn. S khc nhau v nng lng ca nhng qu o nguyn t ca hai
nguyn t (hnh 2.13 nhng i lng b v d) l thc o mc ion ca lin kt.
Trong phn t H
2
, nhng qu o 1s ca hai nguyn t hydro tng ng vi cng mt
gi tr nng lng v do lin kt khng c c tnh ion.

Hnh 2.13. Biu mc nng lng qu o phn t ca phn t AB.
S khc nhau ln v nng lng ca hai qu o nguyn t t hp thnh qu o
phn t c c trng bng tnh ion cao ca lin kt. Trong phn t AB, nng lng
qu o phn t
1
gn vi nng lng ca qu o 1s ca nguyn t B. iu c
ngha l qu o phn t
1
ging qu o 1s ca B nhiu hn so vi qu o 1s ca
A. Nu mi nguyn t A v B u a ra mt in t to thnh qu o phn t th
s dn ti s chuyn in tch t nguyn t A n nguyn t B bi v gi tr nng
lng ca
1
gn vi gi tr nng lng ca qu o nguyn t B hn l ca A. Nhng
i lng a v c cn c rt ng ch trong mt mi quan h khc, chng ph thuc
vo mc xen ph nhng qu o nguyn t ca A v B v l mc cng ha tr
ca lin kt. Trn hnh 2.13: a < c v nh vy c ngha l mc xen ph nhng qu
o ca cc nguyn t A v B trong khng gian khng ln trong trng hp 1s, cn
trong trng hp ca nhng qu o 2s th ln hn v chng tri di ra xa ht nhn
hn. Gi tr nng lng thot ra khi to thnh lin kt AB ph thuc vo s in t v
nng lng in t ca cc nguyn t A v B tham gia vo s to thnh phn t. Bng
2.2 minh ha nhng iu trnh by trn.
Bng 2.2. Nng lng thot ra khi to thnh phn t AB
b
a
a

1
1S

1S

AB

2 c

c

2S

2S

AO

MO

AO

1
a
B A
N

n
g

l

n
g



31


in t ca A tham gia
vo lin kt
in t ca A tham gia
vo lin kt
Nng lng thot ra khi to
thnh phn t AB
1s
1
0 a+b
0 1s
1
A
1s
1
1s
1
2a+b
1s
2
0 2a+b
1s
2
1s
2
0
1s
2
2s
1
1s
2
c+d
1s
2
1s
2
2s
1
C
1s
2
1s
2
2s
2
2c
1s
2
2s
1
1s
2
2s
2
C
1s
2
2s
2
1s
2
2s
2
0
Biu mc nng lng qu o phn t i vi phc kim loi tng i phc tp
hn so vi nhng phn t hai nguyn t n gin. Nhng cui cng da trn biu
nng lng qu o phn t cng c th pht hin kh tt nhng c im bit ca
phc, v d: [Co(NH
3
)
6
]
3+
v [CoF
6
]
3-
(hnh 2.14). Pha bn tri m t nhng qu o
nguyn t 3d, 4s v 4p ca Co
2+
. Nhng qu o nguyn t c nng lng cao hn
hoc thp hn chng ta khng cn ch ti. Khi cng hp 6 phi t th ch cn bn
phi ca biu l khc mt cht so vi nhng biu trnh by trn. y ch
nu ln mt mc nng lng tham gia vo s to thnh lin kt (i khi ngi ta s
dng biu nng lng phc tp hn). V 6 phi t ng nht nn mc nng lng
tng ng vi nng lng qu o ca mi phi t.
Nng lng qu o ca phi t ni chung thp hn nng lng ca kim loi v v
vy lin kt c c tnh ion n mt mc no . Do nhng qu o phn t lin kt
ging qu o phi t hn l ging qu o kim loi v s chuyn in t ca kim loi
vo nhng qu o phn t y dn n s chuyn in tch t ion kim loi n phi t.
Hai qu o d (qu o e
g
:
2 2
x -y
d v
2
x
d ), qu o 4s v 3 qu o p hng dc theo
cc trc x, y v z trn phn b phi t. Do s xen ph qu o kim loi v phi t
dn n s to thnh 6 qu o phn t lin kt v 6 qu o phn t phn lin kt:

s
(1),
p
(3),
d
(2),
d
*(2),
s
*(1),
p
*(3). Nhng qu o t
2g
(d
xy
, d
xz
, d
yz
) khng hng
ti qu o ca phi t v do khng tham gia vo s to thnh lin kt . Nng
lng ca chng khng bin i v chng c gi l nhng qu o khng lin kt.


32



Hnh 2.14. Biu mc nng lng qu o phn t ca phc spin cao [CoF
6
]
3-
v
phc spin thp [Co(NH
3
)
6
]
3+
.

2
d
1

s
Phi t
( )
3
Co Fe




Co(III)
6F
-
4p
4s
3d
*
3p

*
s

*
u

N

n
g

l

n
g











d
XY
d
yz
d
xz
N

n
g

l

n
g

AO MO AO
0

2
d
1

s
Phi t
( )
3
3
Co NH




Co(III)
6NH
4p
4s
3d
*
3p

*
s

*
u















33


Nhng in t ca Co(OH) v phn t nm trn qu o phn t ca phc th
chng lp y 6 qu o lin kt phn t, tng ng vi 6 lin kt kim loi phi t.
Nhng in t cn li phn b trong s nhng qu o phn t khng lin kt (qu o
t
2g
) v qu o phn t
d
* (phn lin kt). Qu o phn t
d
* l kt qu tng tc
nhng qu o dx
2
-y
2
v dz
2
ca kim loi vi nhng qu o ca phi t nhng v
nhng qu o phn t
d
* gn v gi tr nng lng vi nhng qu o
2 2
x -y
d v
2
z
d
ca kim loi, chng khc nhau khng ng k. Do , s phn b nhng in t d
trn cc qu o phn t t
2g
v trong s phn b in t ca m hnh trng tinh th
nu ln trc y cng vi s in t phn b gia nhng qu o t
2g
v e
g
.
Nu s khc nhau v nng lng gia nhng qu o t
2g
khng lin kt v nhng
qu o phn t
d
* t, th qui lut Hund c thc hin. Phc [CoF
6
]
3-
hon ton
ging trng hp ny, nhng in t d phn b theo cc qu o t
2g
,
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(NH
3
)
6
3+
] tt c cc in t c xu th chim qu
o t
2g
. Nguyn nhn ca s phn b nng lng gia nhng qu o t
2g
v
d
* hoc l
e
g
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 e
g
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
e
g
( hnh 2.15,
2 2
x -y
d ) dng chung. Trong lin kt ion CN
-
x s nh l mt acid
Lewis v nhn in t t nhng qu o t
2g
hon thnh ca kim loi , t qu o
d
xy
). 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
MnO
4
-
lin kt v cng rt quan trng. Trong trng hp ny phi t (oxy) a
in t to lin kt .
C th gii thch hiu ng trng tinh th ln to bi nhng phi t nh CN, CO v
cc phi t khc to lin kt cng bng con ng nh vy. Nhng qu o t
2g
ca
kim loi trong phc bt din hng thng theo nhng lin kt . Nh nhn xt
trc y, nhng qu o t
2g
hng ti gia nhng phi t v do khng c th to
lin kt . Trong lin kt vi cc phi t loi CN nhng in t t
2g
mt phn chuyn
ti cc phi t. Qu trnh (tng tc lin kt) h thp nng lng nhng qu o t
2g
.
R rng rng qu trnh h thp nng lng nhng qu o t
2g
phi lm tng
0
.
Tt c nhng iu trnh by trn y ch l phng php n gin ca thuyt qu
o phn t. Phng php ny ch minh ha c mt s lun im c bn v s ch


34


li ca thuyt ny. L thuyt qu o phn t rt c hiu qu tnh ton, s ng gp
ion v cng ha tr vo lin kt kim loiphi t.
Cui cng ta hnh dung mt cch r rng rng c 3 thuyt trong nhng trng hp
tt nht cng ch c mt gn ng m thi. C 3 thuyt trn u c th gii thch
mt cch nh tnh nhiu c tnh ca phc kim loi. Hin nay c 3 thuyt u c s
dng, hoc l thuyt ny hoc l thuyt khc c th thun li i vi mt trng hp
no . Thuyt qu o phn t l linh hot nht v c th l gn ng vi s tht nht.
ng tic l thuyt ny l phc tp nht v khng thun li cho mt khi nim r rng,
c th v mt ha hc i vi nhng nguyn t lin kt.

Lin kt Fe-CN Lin kt Fe-CN
Hnh 2.15. Lin kt v lin kt

trong phc [Fe(CN)

6
]
4-
.
Lin kt c to thnh nh s dng qu o d y in t ca ion Fe
2+
v
qu o phn lin kt ang cn trng ca CN
-
(xem * trn hnh 2.10).
2.4. HNH DNG HNH HC CA CC HP CHT PHI TR
Ngi ta xc nhn rng phc kim loi c cu trc rt l khc nhau. Phc ca Ag
thng l thng hng, phc ca Be thng l t din. St to cc hp cht carbonyl c
cu trc tam gic lng chp, phc ca Co(III) th lun lun l bt din cn ta phi tr
quanh mnh 8 nguyn t F (hnh 2.16). Mc d rng phc kim loi c cu trc v s
phi tr rt khc nhau nhng ngi ta vn thng hay gp s phi tr l 4 hoc 6, chng
thng tng ng vi dng t din v phng vung (i vi s phi tr l 4) v bt
din (i vi s phi tr l 6). Khi nghin cu phc kim loi ta s thy r rng v sao
dng bt din l thng gp nht.
Thuyt lc y ca i in t ha tr cho ta hnh nh gn ng v rt c li
d on cu hnh nhng hp cht ca nguyn t trung tm c s phi tr bit.
H qu rt ra t thuyt ny l kt lun: Nhng phc c s phi tr l 4 v 6 ch yu
c hnh dng t din v bt din. Nhng phc ca kim loi chuyn tip i khi khng
tun theo quy lut y v chng c nhng in t d. Thuyt trng tinh th cho ta s
gii thch n gin nht v nh hng c th c ca nhng in t d n cu trc ca
phc.


35



Hnh 2.16. Nhng hp cht minh ha mt s cu hnh ca phc kim loi.
L thuyt ny khng nh rng nhng qu o d c dng hnh hc v hng trong
khng gian c bit ng thi nhng in t d nm trn nhng qu o xa ht nhn
nht. Nhng in t d trong nhng phc cht c s phi tr l 6 v 4 gy nn s mo
m hnh dng bt din v t din. S mo m cu hnh l do phi t trnh nhng v tr
m nhng in t d chim xung quanh ion kim loi. V d trong phc
[Ti(H
2
O)
6
]
3+
, xung quanh ion Ti
3+
c 6 phn t nc do hy vng rng phi t s
phn b theo hnh bt din.
Nhng cn phi nghin cu nh hng ca nhng in t d ca kim loi n cu
trc ca phc. Nu nh trn mc ph d ngoi c khng, nm (khng ghp i) hoc l
10 in t d th nhng in t ny khng gy nn s mo m cu hnh. Mc ph d
hon thnh 10 in t, th c s i xng in t hnh cu. Nhng ht tch in (v d
phi t) nm trn mt cu c ion kim loi trung tm s chu tc dng ca lc tnh
in ng nht, khng ph thuc vo v tr ca ht trn mt cu. Nu trn 5 qu o d
c mt in t th ion kim loi cng c i xng cu. Nh vy, trong nhng trng
hp ny, nhng in d s khng nh hng g n v tr ca phi t.
Phc [Ti(H
2
O)
6
]
3+
c mt i in t, in t ny s y nhng phi t gn n.
Theo thuyt trng th in t ny nm trn qu o t
2g
c nng lng thp v tri di
ra gia nhng phn t H
2
O. Bi v in t nm trn qu o d
xy
nn s c s thay i
ca cu hnh bt din d on. V qu o d
xy
nm gn 4 phi t trong mt phng
xy nn nhng phi t ny s tch xa ion kim loi hn 4 phi t kia. Hiu ng cng xy
OH
OH
OH
OH
Fe
CO
CO
CO
CO
NO
2
NO
2
O
2
N

O
2
N

Co

Thng hng
T din Tam gic lng chp
Bt din
Fe

F

F

F

F

F

F

F

F

F

i lng tr vung
Be


36


ra tng t nu in t nm trn cc qu o d
xz
hay d
yz
.
V nhng qu o t
2g
hng ti gia nhng phi t nn nh hng ca in t nm
trn mt trong cc qu o s kh nh. S tht khng c nhng bng chng thc
nghim v s thay i t gic cu hnh ca phc [Ti(H
2
O)
6
]
3+
hoc l h d khc. Trong
nhng phc bt din cha 2 hay 3 in t , chng chim cc qu o t
2g
tri di gia
nhng phi t. Mt d c th hy vng s thay i t nhiu cu hnh ca h d
2
bt din
nhng mt ln na iu khng c xc nhn bng d kin thc nghim. Trong
phc d
3
bt din nh [Cr(H
2
O)
6
]
3+
trn mi qu o t
2g
c mt in t. i vi cc
orbital d, mi mt phi t trong s 6 phi t phn b theo hnh bt din, s nm gn 2
in t d v do chu lc y. Trong trng hp ny khng nn ch i mt s thay
i cu hnh no c v iu cng khng c pht hin bng thc nghim.
Phc [Cr(H
2
O)
6
]
3+
l h d
4
spin cao, ba in t u tin ri vo nhng qu o t
2g

v khng gy nn s thay i cu hnh bt din. in t th 4 ri vo mt trong nhng
qu o e
g
hng ti phi t. Nu in t nm trn qu o
2 2
x -y
d th n b 4 phi t
trn mt phng xy y. S tht, ngi ta thy rng nhng phc kim loi d
4
c s
phi tr l 6 c cu to thay i trong tt c mi trng hp c nghin cu. V d
trong phc MnF
3
, mi nguyn t Mn(III) c bao quanh bi 6 ion F, phn b nh th
no cho 4 phi t trong s gn vi ion Mn
3+
hn 2 phi t khc ( hnh 2.17).
By gi cn nghin cu s thay i cu hnh bt din do s c mt ca 0, 1, 2, 3, 4,
5 (khng ghp i) v 10 in t gy nn. Nhng h spin cao d
6
, d
7
, d
8
v d
9
tng t
nh h d
1
, d
2
, d
3
v d
4
tng ng (nm in t u tin cho m my in t i xng
cu, nhng in t cn li gy nn s mo m). nhng phc d
9
c s phi tr l 6 th
s thay i t gic cu hnh c th nhn thy ging nh nhng phc d
4
. Nhng phc
ca Cu (II) thng c ly lm v d. Trong phc [Cu(NH
3
)
4
]
2+
, xy ra s thay i t
gic mnh n l thu c phc phng vung.

Hnh 2.17. V d hiu ng phc An Telep
Nhng cn nhn xt rng nhng phn t dung mi trong dung dch phc loi chim
cc v tr di v trn mt phng. Chng nm xa ion kim loi hn nhng nhm
nm trn mt phng. S thay i cu trc i xng l h qu ca s lp y tng phn
nhng mc nng lng in t (trong nhng trng hp ny l mc ph d) c gi l
hiu ng An Telep.
Cng cn thit phi xt s thay i cu hnh bt din c quan st thy nhng
dng spin thp. Nhng h d
6
spin thp tng t nh nhng h d
3
, 6 in t lp y


37


nhng qu o t
2
.V mi mt trong s 6 phi t u nm gn trc tip 2 trong s
nhng qu o nn s thay i khng xy ra v ngi ta quan st thy cu hnh bt
din u n. Nhng phc d
8
spin thp tng t nh nhng h d
4
. Hai in t cui
cng ri vo mt qu o e
g
v tc dng mnh vi nhng phi t hng v pha qu
o ny. S thay i d nhn thy l trng hp khi hai phi t b tch xa ion trung
tm tng i nhiu so vi 4 phi t khc. S tht l, hu nh tt c nhng phc d
8

spin thp, khng c s ngoi l no u phng lun. S thay i nhng phc bt din
gy nn bi nhng in t d c nu ln trong bng 2.3.
Nh vy, chng ta thy s thay i cu trc bt din do nhng in t d gy nn,
nhng phc kim loi c th c cu trc t din nhng n t ph bin hn phc bt din
v nhng dng bt din thay i. Nu ion kim loi b vy quanh bi 4 phi t th c th
hy vng cu hnh t din. Nhng in t d c th gy nn s thay i t din.
Bng 2.3: S thay i cu hnh bt din do nhng in t d gy nn.
H Cu trc d on Ghi ch
Spin cao
d
1
, d
6

d
2
, d
7

d
3
, d
8

d
4
, d
9

d
5
,d
10


Thay i t gic
Thay i t gic
Khng thay i
Thay i t gic mnh
Khng thay i

Khng quan st thy
Khng quan st thy
Khng nh bng thc nghim
Khng nh bng thc nghim
Khng nh bng thc nghim
Spin thp
d
6

d
3


Khng thay i
Thay i t gic mnh

Khng nh bng thc nghim
Phc di dng vung phng
Cn nhn xt 2 ngoi l, nh thy t 2 v d trn y, nhng phc d
8
spin thp,
phi t 4 l phc phng vung cng nh nhng phc phi t 4 d
9
v d
1
spin cao.
Nhng phc kim loi cha 0, 5 v 10 in t khng ghp i khng gy nn s thay
i ng k nh nhn thy trc y. Trong phc bt din, nhng in t trn
nhng qu o hng ti nhng phi t khng gy nn s thay i ng k. Nh vy,
nhng phc t din d
1
, d
2
, d
6
, d
7
c l l b thay i. Trong nhng h t din d
3
, d
4
, d
8
,
d
9
hiu ng An Telep th hin kh r rng. Nhng nhng v d ca cc hp cht loi
c rt t. Nhng phc t din spin thp khng cn phi bn lun g ti, v nhng v
d v nhng phc cht loi ny khng c l s tch mc bi trng tinh th (
t
) trong
phc t din qu nh khng lm cho nhng in t ghp i.
Mt d rng d on ha tp th ion phc ca ion trung tm vi s phi t bit
l kh chnh xc, nhng d on s phi tr ca ion trung tm l tng i kh khn.
S ht tnh in ca nhng din tch m ca phi t (hay l ca nhng phn t phn
cc) i vi ion kim loi tch in dng l nguyn nhn gy s phi tr cao. L thuyt
lin kt ha tr tin on rng: s ln lin kt gia nhng nguyn t dn ti bn ln


38


ca hp cht to thnh. Xu hng to phc c s phi tr cao mu thun vi nhng yu
t tp th v vi s y nhau tnh in gia nhng phi t (hoc l qui tc Pauli). Cn
nhn xt rng nhng kim loi chuyn tip thng c s phi tr l 6. S phi tr 4 c
quan st thy ch yu nhng phc cht ca nhng anion tng i ln nh Cl, Br, I
v O
2
hoc l ca nhng phn t trung ha c th tch ln. Nhng kim loi chuyn tip
dy th 2, th 3 cng c s phi tr cao, v d l 8.
2.5. CNG TRNG PHI T
Nng lng y electron trong phc kim loi chuyn tip t obitan t
2g
n obitan
e
g
thng trong vng kh kin. S hp th sng bc x c th lm cho nhng electron
dch chuyn. Ph hp th l kt qu ca nhng nng lng y ny.
Cng ca phi t c suy ra t s o ph ca s tch obitan v chng c
sp xp nh sau:
I
-
< Br
-
< SCN
-
< Ce
-
<NO
3
-
< F
-
<NO
2
-
~ OH
-
< HCOO
-
< C
2
O
4
2-
< H
2
O < -NCS
-

<CH
2
(NH
2
)COOH < EDTA
4-
<Pyridin ~ NH
3
< Ethylenediamine ~ diethylenetriamine
< triethylenetetramine < dipyridyl< CN
-
.
2.6. CU TRC PHN T V TAN
Mt trong nhng yu t nn c ch khi chn thuc th ha hu c trong
phng php trc quang, chun v kt ta l tan. tan ca mt phn t trong
nc l c mi lin h vi s phn cc ca cc phn t. Mt phn t cha cc nhm
OH; SO
3
H; COOHrt phn cc, tan nhiu trong nc. Mt phn t cha nhm
bo hoc a nhn th tan t trong nc, nhng tan tt trong dung mi khng phn cc.
Trong phng php trng lng, s kt ta c mi quan h vi tan trong nc.
Nhng cht kt ta l nhng cht t tan trong nc. Trong dung mi chit, nhng cht
chit nn tan t trong nc nhng tan nhiu trong dung mi hu c. tan ca thuc
th hu c rt quan trng trong thuc th phn tch. c trng ca phn ng ca thuc
th hu c trong phn tch ph thuc ln vo s c mt ca cc nhm chc v cu trc
chnh ca phn t. iu ch nhng hp cht vi s chnh sa cu trc ci thin
c trng ca thuc th, bng cch lm tng tan ca chng trong nc hay trong
dung mi hu c hoc lm gim tan ca sn phm phn ng.
Khi mt cht tan trong nc c lc vi mt dung mi hu c khng trn ln,
c s cnh trnh gia hai dung mi. Mt cht phn cc th tan trong dung mi phn
cc, cht khng phn cc th tan trong dung mi khng phn cc.
Mt th d v s chnh sa cu trc phn t c th tm ra s ng dng ca
salinaldehyde nh l thuc th ca hydrazin.
V tr ca nhm OH so vi cc nhm nh l =CO, NO
2
; N=N, nhng nhm
ny to lin kt cho nhn vi nguyn t hydro trong nhm OH, nh hng n tan.
Nhng hp cht cha nhm OH v tr octo th tan yu trong nc so vi cc ng
phn meta hoc para. v tr octo c th do nguyn nhn hnh thnh phc chelate
thng qua lin kt hydro.
tan ca mt cht trong nc lun lun gim khi thay nguyn t oxi bng
nguyn t lu hunh trong phn t, do kh nng to lin kt vi nc ca nguyn t


39


lu hunh yu hn nguyn t oxi.
Nguyn t N trong nhm amine l mt trung tm hot ng to c lin kt vi
nc. Thng qua s proton ha, nhng hp cht th amoni c hnh thnh t nhng
amine. Chng phn cc rt mnh v tan tt trong nc. S proton ha cng c th lm
gim kh nng tan trong nc ca cht hu c. Mt vi cht mang nhm COOH
trong mi trng acid mnh th tan yu hn trong mi trng acid yu.
Trong mi trng trung tnh hoc acid, phenol tp trung ch yu pha hu c sau
khi c lc vi nc. Tuy nhin, trong dung dch baz mnh th phenol chuyn v
dng ion phenolat mang in tch m v kt qu l n c chit t pha hu c vo
pha nc.
Kh nng tan trong nc ca hp cht hu c ph thuc phn ln vo kh nng
phi tr vi phn t nc. S hydrate ha nhng hp cht c khi lng phn t ln
nhn chung khng thay i tan ca chng so vi nhng hp cht c khi lng phn
t b. Khi thay th nhm methyl trong dimethylglyoxim bng hai nhm furyl th lm
tng nhy vi Ni ln ba ln. S thay i cu trc c th gp phn lm tng nhy.
2.7. PHC CHELATE (VNG CNG)
Phi t c hai hoc nhiu nhm nhng electron, c th c nhiu hn mt cp
electron dng chung vi ion kim loi bng 2 hay nhiu hn lin kt phi tr xung
quanh ion kim loi. Nhng phi t nhn chung nh l nhng phi t a lin kt,
thng thng gi l phi t hai rng, ba rng, .... Nhng phi t a lin kt to phc
vi ion kim loi, c dng phc tp v c gi l phc chelate.
Mt nguyn nhn chung l trong phc chelate phi t c cha nhm acid (OH)
hoc nguyn t nhng electron. Mt trong nhng nguyn t nhng electron c bn
l nguyn t N. Trong s hnh thnh phc chelate, nhm acid mt mt proton v tr
thnh anion nhng electron
V d: S to thnh phc chelate vi 8Hydroxyquinoline vi Cu
2+
.
N
OH
N
O
N
O
Cu
Cu
2+ + 2
+ 2H
+


nh hng ca phc chelate: Mt tnh cht ni bt ca phc chelate l bn ca
chng khng n nh. Chng ging vi nhng hp cht thm hu c. Khng phi hp
cht hu c no cng to c phc chelate vi kim loi. Mt phi t trong phc
chelate phi c 2 nhm nhng electron hoc hai nhm acid hoc mt nhm acid vi
mt nhm nhng electron. Hu ht cc nhm c tnh acid hu c u cha cc nhm:
OH; SH; NH. Phi t cha cc nguyn t O, N, S thng to lin kt phi tr vi


40


ion kim loi. Nhng phi t ny phi nh c trong phn t ti nhng v tr m c th
to vi kim loi nhng vng 5 hoc 6 cnh.
2.8. S N NG KHNG GIAN V CHN LC
V s cn tr v khng gian trong cu trc phn t, mt vi thuc th h c c
chn lc cao. S tc ng qua li gia cc phn ging nhau hoc khc nhau c th nh
hng n tc phn ng. N c th lm nh hng n nhng tnh cht vt l nh:
kh nng hp th nh sng, tan, s kt tinh, ...
Hu ht bn ca phc ph thuc vo hnh dng ca chng khi nhng obitan
trng ca ion kim loi c sp xp theo cc hng m ti cc obitan ca phi t s
lp y m khng c s bin dng quan trng. Nhng cu trc ging nhau c th ch
khc nhau s n ng khng gian. Nu nhng phi t khng lin kt c kch thc
ln, th s bao bc xung quanh nguyn t kim loi ca chng s gy cn tr.
2.9. BN CA HP CHT PHI TR
bn ca cc cht trong dung dch c cho bi cn bng sau:
M + nL ML
n

p dng nh lut bo ton khi lng, hng s cn bng c tnh nh sau:
0 n
n n
M L
AML
=
A A

A
M
: hot ca M,
0
n
l hng s cn bng ca phn ng.
V d : nh hng ca pH ln s cn bng ca acid EDTA.
M: ion kim loi, Y l EDTA
4-

M + Y MY
H
+

HY,H
2
Y,H
3
Y....
S nh hng ca hydro ln s cn bng c tnh thng qua
Y

| || || | | |
4- 4-
Y
- 2- 3- 4-
6 5 4 3 2
Y Y
= =
Y' H Y H Y H Y H Y H Y HY Y





[Y
4-
] nng ion Y
4-
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



41


| |
| |
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:
| | | | | | | |
2 3 n
1 2 3 n
M
1
=1+K L +K L +K L +......+K L

k
1
, k
2
....k
n
l hng s bn cc phc ML, ML
2
....ML
n
.
Hng s bn iu kin K
M'Y'
c tnh nh sau:
| |
| || |
M'Y'
MY
K =
M Y
m | | | |
Y
Y = Y' v | | | |
M
M = M'
suy ra:
| |
| || |
MY
Y M
MY
K =
M' Y'

| |
| || |
MY Y M M'Y'
MY
K =K =
M' Y'

vy hng s bn iu kin
| |
| || |
M'Y'
MY
K =
M' Y'


2.10. NG HC CA PHN NG TRONG THUC TH HU
C.
Nhng hn hp phn tch cha mt bn cht giao thoa vi nhau, thng n b tch
hoc b che vi nhng thuc th c thun li hn. Hu ht, nhng phn ng trong ho
phn tch xy ra nhanh nhng mt vi phn ng chm c s dng ph bin trong
ha phn tch.
EDTA phn ng nhanh vi hu ht cc kim loi nhit phng. N cng phn
ng chm vi Cr(III) nhit phng nhng dng tinh khit phc Cr(III) vi EDTA
phn ng nhanh khi c un nng n cng c th c xc tc khi thm mt t
bicarbonate. Crom c th c pht hin chn lc da trn kh nng phn ng ca n
vi EDTA.
Khi phc ca Co(II) vi EDTA hoc Co(II) vi 1(2pyridylazo)2naphthol
(PAN) khong pH = 5 th chng b oxi ho bi H
2
O
2
. Cc phc ca Co rt bn trong
acid mnh.
Chloramin c dng phc dch chuyn in tch vi amino acid pH=9, c un
nng nhit 60
o
C trong khong t 3060 pht phc c hnh thnh v chng bn
trong mi trng acid trung bnh.


42


CHNG 3
NHM CHC PHN TCH V NHM HOT TNH
PHN TCH

3.1. NHM CHC PHN TCH
Kt qu tng tc ca thuc th hu c vi cc ion c quyt nh bi 2
phn trong phn t ca chng:
- Mt phn ca phn t quyt nh s tng tc vi ion ny hay ion khc gi l
nhm chc phn tch (hay nhm nguyn t c trng).
- Mt phn khc c nh hng n sn phm phn ng gi l phn gy hiu ng
phn tch (nhm hot tphn tch).
Khi gn thm vo trong phn t ca mt hp cht hu c (khng c kh nng
phn ng vi ion cho) mt nhm nguyn t c bit th c th lm cho cht
tr nn c kh nng phn ng. S c mt ca nhm l nhm chc phn tch.
Trong nhm chc phn tch c hai nhm nguyn t nm cnh nhau.
- Nhm to mui: trong nguyn t H c th cho cation kim loi thay th
c to lin kt ha tr nh nhm cacboxyl -COOH, nhm oxym =NOH, nhm nol
hydrxyl -OH, nhm sunfo -SO
3
H. nhm amin bc 1 -NH
2
, bc 2 , ...
- Nhm to lin kt phi tr: Trong nguyn t N nh trong =NOH, -NH
2
,
, , ... nguyn t O nh trong -OH, = CO, ... c th to lin kt phi tr v
cc nguyn t cn tha mt hay nhiu cp e
-
t do, lin kt ny thng c biu
din bng mi tn hoc ng chm.
- V d nhm chc phn tch i vi Ni
2+

Sau y chng ta s nghin cu mt s nhm chc phn tch.
3.1.1. Nhm chc phn tch ca AgI
Nhiu hp cht hu c cha nhm amine bc 2 (> NH) phn ng vi mui bc.
N
R
H
C
C NH
NH
v
C
C NOH
NOH
C
C CH
3
CH
3
NOH
N
OH
+ Ni
2+
+
2NH
3
OH
N
CH
3
CH
3
C
C
NO
2
Ni
+ 2NH
+
4
thay th
phi tr
ti
V d:
N
R
H
N


43


Mt trong nhng hp cht y l rhodamine.
HN C
O
C S
CH
2
S

Rhodamine to vi bc rhodaminat bc mu vng (AgOSC
3
H
2
ONS
2
) trong dung
dch acid. Feigl cho rng rhodamine c 4 dng tautomer
HN C
O
C S CH
2
S
HN C OH
C S
CH
S
N C
O
C SH
CH
2
S
N OH
C S CH
2
S
C

(I) (II) (III) (IV)
V nhng dn xut ca rhodamine c cu to tng qut
HN C
O
C S
C
S
CHR'
HN C
O
C R''
C
S
CHR'

R= CH
3
, C
2
H
5
. R= C
6
H
5
NH=N, C
6
H
5
N=N
C kh nng phn ng vi AgI cng nh rhodamine nn khng c c s cho
rng rhodamine phn ng vi AgI dng tautomer II v IV (nhm OH v SH v ni
i trong vng). Hp cht c cu to
NH
S
CS

L hp cht khng th no chuyn v ni phn to nn lin kt i gia nit v
nguyn t carbon khng cha lu hunh trong vng lu hunh cng phn ng vi
AgI nh rhodamine. Do , quan im cho rng rhodamine phn ng vi AgI dng
tantomer III cng khng ng vng. V vy ch cn c th cng nhn rhodamine phn
ng vi AgI dng tautomer I.
Nghin cu nhiu dn xut ca rhodamine Feigl nhn xt rng: p
dimethylaminolanzyliden rhodamine l thuc th nhy nht ca AgI.
HN C
O
C S C
S
C
H
N
CH
3
CH
3

Bozoncenckun cho rng mui bc to thnh trong phn ng c cu to V hoc VI.


44


N C
O
C S
C
S
C
H
N
CH
3
CH
3
Ag
N C
O
C S
C
S
C
H
N
CH
3
CH
3
Ag
V
VI

Nhng d kin ca Feigl v ca mt s tc gi khc hon ton ph nhn nhng
cng thc cu to trn (V;VI). Bi v ngi ta khng th chp nhn s tn ti loi hp
cht ni phc vng 4 nh trn c. Hn na, khng phi tt c nhng mui ca
rhodamine (c bit l mui AgI) v ca nhng dn xut ca n u tan trong dung
mi khng nc. Vy mui ca AgI vi pdimethylbenziliden rhodamine phi c cng
thc:
N C
O
C S
C
S
C
H
N
CH
3
CH
3
Ag

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 C
NOH OH

CH C
NOH OH

c cha nhm nguyn t l nhng thuc th c trng ca Cu(II) (phn ng xy ra
trong mi trng ammoniac). Nhng hp cht ny ng vai tr nh mt acid kp v
to vi Cu(II) mui mu lc khng tan trong nc v c cng thc:
CH C
O
R"
N
R
"R
Cu
O

Khi nghin cu tc dng ca axyloinoxim vi Cu(II) ngi ta chia chng ra lm


45


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.
CH
O
R"
N
R
Cu
C

C th dng tan ca mui thu c trong dung mi khng nc (v d trong
chloroform) lm c s ng h ngh ca Feigl.
Mui ca ng vi 1,2xyclohexanolonoxim khng tan trong nc nhng tan trong
ammoniac. iu c gii thch l cyclohexim bo ho phi t v do khng
c kh nng phi tr vi ng. Do , nu phn t cha nhng gc cha bo ho phi
tr th mui ng to thnh (do phi tr ni phn) khng tan trong ammoniac. Nu nh
nhng gc ny bo ho phi tr th mui ng tan trong ammoniac.
HC
O
N
Cu
C
O

C th rt ra kt lun l khi s dng nhng axyloinoxim lm thuc th cho Cu(II)
th mui to thnh s khng tan nu vng l vng 5.
C
O N
Cu
C
O

Chnh v vy nn nhng oxim ca methylacetonylcarbinol v chloracetophenol
cha nhm nguyn t.


46


HO C C C N OH

Khng th to vng 5 c nn nhng hp cht ny khng th to mui ng
khng tan.
Epharan khng nh rng nhm
C C
H
OH C
NOH

trong nhn thm cng l nhm chc phn tch ca Cu(II) (v d salicylaldoxim to
mui ni phc)
C C
H
O C
OH
N
Cu

Do ngi ta cng nhn 2 cu to nhm chc phn tch ca Cu(II)
C C
OH NOH
2HC
C
NOH

Nm ngoi nhm thm Nm trong nhm thm
3.1.3. Nhm chc phn tch ca Th
KuzHeop ch ra rng nhng hp cht cha gc AsO
3
H
2
v nhm hydroxyl v
tr ortho i vi nhm azo phn ng vi Th. Nhng hp cht sau y tham gia vo
phn ng
N N
OH
AsO
3
H
2
HO SO
3
H
SO
3
H
N N
OH
AsO
3
H
2
HO
SO
3
H

(II)
N N
AsO
3
H
2
HO
SO
3
H
N N
AsO
3
H
2
HO
3
S
OH OH
HO
3
S
SO
3
H



47


(III) (IV)
ng thi KuzHeop cng pht hin cc hp cht nh
N C
H
AsO
3
H
2
HO
N N
COOH
OH OH
SO
3
H

(V) (VI)
cng cho phn ng tng t vi Th.
Nhng hp cht cha gc AsO
3
H
2
v tr para i vi nhm azo v d nh
N N
HO
SO
3
H
N N
AsO
3
H
2
OH OH
HO
3
S
SO
3
H
H
2
O
3
As
H
2
O
3
As
SO
3
H

Mc d to kt ta vi mui Th(IV) nhng khng gy nn s i mu.
Tt c nhng iu trnh by trn cho php chng ta cng nhn nhm nguyn t.
N A
HO B
A: =N, CH B: AsO
3
H
2
, COOH
l nhm chc phn tch i vi Th(IV).
3.1.4. Quan im hin nay v nhm chc phn tch
Ngy nay, khi nghin cu tc dng ca thuc th hu c vi ion v c ngi ta
ch n 2 iu c bn nht l cu to ca thuc th hu c v kin trc in t ca
ion v c. Cng nhn cu to ca thuc th hu c v kin trc in t ca ion v c
quyt nh c ch phn ng gia chng th chng ta khng th cng nhn c mt nhm
nguyn t no (trong thuc th hu c) li ch phn ng vi mt ion m li khng c
phn ng vi nhng ion khc c kin trc in t tng t. Trn c s , ngy nay
ngi ta cng nhn c nhng nhm nguyn t c trng cho phn ng vi mt s
nguyn t c tnh cht ho hc gn nhau ngha l nhm chc phn tch i vi mt s


48


nguyn t tnh cht ho hc ging nhau. Quan im trn chng nhng rt ng n v
mt l thuyt m cn c ngha thc t ln bi v nu cng nhn c nhng nhm
nguyn t c trng ch phn ng vi mt ion th nhng nh phn tch hay ho hc ni
chung s chy theo phng hng tng hp ra nhng thuc th ch phn ng vi mt
ion no m thi m iu v nguyn tc l khng th thc hin c (Trng hp
iodide phn ng vi h tinh bt ch l mt ngoi l c mt khng hai). Chng ta ch c
v s ch c nhng thuc th tc dng vi mt s ion m nhim v ca nhng nh
phn tch l phi to nn nhng iu kin cn thit (lm thay i ho tr, to phc, iu
chnh pH, tch .) cho phn ng tr thnh c trng cho mt ion no cn xc
nh.
3.2. NHM HOT TNH PHN TCH
Trn y, chng ta ni v nhm chc phn tch nhm nguyn t c trng gy
nn kh nng phn ng ca thuc th vi ion v c nhng khng phi tt c cc cht
hu c cha cng mt nhm chc phn tch u c gi tr nh nhau v mt phn tch.
nhy v c trng ca nhng phn ng pht hin mt ion bng nhng thuc
th hu c cha cng mt nhm chc phn tch, c th rt khc nhau. Do , ngi ta
cng nhn rng trong phn t thuc th, ngoi nhm chc phn tch quyt nh c ch
ca phn ng, cn c nhng nhm nguyn t khc khng nh hng n bn cht c
ch phn ng. Chng lm bin i tnh c trng ca sn phm cui cng trong mt
chng mc nht nh.
V d lm bin i tan, c trng, cng mu v bn thu phn
Nhng nhm nh vy KulBe gi l nhm hot tnh phn tch.
V nhm hot tnh phn tch khng nh hng n c ch phn ng (khng gy nn
c ch) nn tc dng c trng ca n phi th hin ng nht trong tt c cc phn
ng da trn cng mt hiu ng phn tch (sinh ra kt ta, to mu hoc l s lin hp
c hai hiu ng y).
Do , s nhm chc phn tch th nhiu nhng s nhm hot tnh phn tch li rt
c hn. Mt s v d minh ho c trnh by trong bng 3.1
Bng 3.1: Nhm hat tnh phn tch
Thuc th Cng thc
Ion phn
ng
5(p
dimethylamino
benzyliden)
rhodamine
NH C
O
C S C
S
C
H
N
H
3
C
H
3
C


Ag
+

pdimethylamino
benzene azophenyl
arsenic acid
N N
H
3
C
H
3
C
N
AsO
3
H


Zr(III)
pdimethylamino
benzene azo
anthraquinone
N N
H3C
H3C
N
O O

[SnCl
6
]
2-



49


pdimethylamino
benzene azo
beznyliden
camphorxin
N N
H
3
C
H
3
C
N C
H
C C CH
2
CH
3
C H
3
C
CH2
H2
C C HON


Hg
2
2+

Tetramethyl
pphenylendiamine
N
H
3
C
H
3
C
N
CH
3
CH
3

Ag
+
,
Cu
2+
,
Hg
2+
,
Hg
2
2+

p,p
Tetramethyldiamine
diphenylmetan
N
H
3
C
H
3
C
H
2
C
N
CH
3
CH
3


Pb
2+
,Mn
2+

Iodidemethylat (p
dimethyl
aminostyril
C
H
N
H
3
C
H
3
C
H
C
I
N
CH
3

Zn
2+
,
SCN
-

T cc dn chng nu trn chng ta d dng nhn thy rng trong tt c cc thuc
th u c cha nhm (CH
3
)
2
N. S c mt ca nhm ny khng phi l ngu nhin.
Mt khc, nhng thuc th nu trn l thuc th c trng nht la chn t mt s
thuc th cha cng mt nhm chc phn tch. Do vy chng ta c th suy lun mt
cch hon ton hp l rng: Nhm pdimethyl aminobenzene l nhm lm cho thuc
th tr thnh c trng hn, nhm l nhm hot tnh phn tch.
Trong nhng phn ng to kt ta, khi a nhng nhm Cl
-
, Br
-
, CNS, I
-
vo nhn
quinoline, nhn pyridin vo phn t thuc th, hoc bin nhn benzene thnh nhn
naphthalen, cng lm cho nhy ca phn ng tng ln.
Nhng nhm cng l nhng nhm hot tnh phn tch (V d: nhy tng (khi
chuyn hp cht bn tri thnh hp cht bn phi)).
N
NO
ONH
4
N
NO
ONH
4

Cufferon Neocuferon
AsO
3
H
O
O
AsO
3
H



50


Phenyl arsonic acid Antraquinone-1- arsenic acid
N CH
3
N CH
3

2 Methyl pyridine 2 methyl quinoline




51


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
Khi tng trng lng phn t thuc th nhy ca phn ng to kt ta tng ln
r rt, nhng iu ch c thc hin khi:
- S lm tng trng lng phn t c thc hin phn ca phn t nhm, nh
hng n c ch ca phn ng.
- Nhng nhm lm tng trng lng khng th hin tc dng slovat ho.
Hiu ng gi l hiu ng trng lng. Sau y chng ta xt mt s v d
minh ho (Bng 4.1).
Bng 4.1. Cc v d v hiu ng trng lng
Thuc th Cng thc TLPT
nhy
/ml
2methyl pirydin
(-pycoline)
N CH
3

93 330
2methyl quinoline
(Quinadine)
N CH
3

143 13
2methyl5,6
benzoquinoline
N CH
3

193 2
2methyl benthiazol
N
S
CH
3

173 13
Iodidemethylat 2
methylbenzthiazol
N
S
CH
3
C
2
H
5
I

166 (khng k
iodide)
2,5
Khi a nhng nhm solvat ho, nh nhm sulfo vo phn t thuc th th
nhy ca phn ng to kt ta gim xung.
Ta ly mt v d minh ha
Cng thc TLPT nhy (/ml)
N N
SO
3
H

378 1


52


N N
SO
3
H
SO
3
H

458 100
N N
SO
3
H
SO
3
H
HO SO
3
H

538 500
(Ni nh vy khng c ngha l khi ta a nhng nhm solvat ho vo phn t
thuc th l lun lun gy kt qu m m ngc li. Trong nhng phn ng o mu,
chng ta cn to nhng sn phm mu tan th cc nhm solvat ho li gip ta rt c
lc).
Nh vy, khi chn nhm lm tng trng lng a vo phn t thuc th cn rt
thn trng. Nhng gc thm, gc bo v nhng nguyn t Halogen l nhng nhm bo
m nht: Nhm th a vo cng cch xa phn xc nh c ch phn ng ca phn t
thuc th cng bo m khng gy hiu qu phn tch m.
Khi a vo phn t thuc th nhng nhm solvat ho thng lm gim
nhy ca phn ng. Nhng nhm ny l: nhm hydroxyl, nhm amino, nhm sulfo
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 NO
3
-
c s ghp i cc


53


electron 2p
x
, 2p
y
, 2p
z
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 (NO
3
-
) 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 NO
3
-
cn 2 in t cn li
th ghp i vi nhng in t 2s
2
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 CH
2
=CH
2
do lai to sp
2
nn cc lin kt nm trong cng
mt mt phng l ng nht v gc gia cc lin kt gn vi 120
0
. 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 .

c im ca lin kt l km bn v do d b kch thch. Ethylene c cc i
hp th 180mm.
Nhng cht mu hp th mnh nh sng trong min trng thy thng c trong
phn t mt s lin kt i, c bit l nhng lin kt i xen k vi nhng lin kt
n to thnh mch lin hp, di tc dng ca nh sng th khng ch nhng electron
ring bit b kch thch m c h mch ni i lin hp b kch thch. Do nh hng
mnh n mu.
C nhiu thuyt gii thch nh hng ca mch lin hp ln mu nh thuyt ph
bin nht l thuyt mu kh in t. Theo thuyt ny th khi in t nm trong nhng
nng lng c di bng di ca mch lin hp. i vi nhng cht mu n gin
c cu to i xng v c mch lin hp thng th c th s dng cng thc sau y
tnh di nh sng ca cc i hp th th nht.

2
N hc 8mCl2 N
= = =K
E h N+1 N+1
(4.1)
h l hng s plank, C l tc nh sng, E l nng lng lng t hp th, m l
khi lng in t, l l di ca mt mt xch ca mch, N l s in t tham gia
vo mch lin hp cng chnh l s mt xch ca mch lin hp. Sau khi thay cc


54


hng s vo ta thu c gi tr ca hng s K=63,7.
Nh vy i vi nhng cht mu mch thng, i xng, di sng ca cc i
hp th trong min trong thy ch ph thuc vo s mt xch N ca mch lin hp.
Di y, dn ra nhng d kin tnh ton v thc nghim i vi nhng gi tr N
khc nhau trong cht mu xyamine i xng c cng thc cu to nh sau
C
2
H
5
N
H
C C
H
C
H
N
+
C
2
H
5
Cl
-

S mt xch ca mch bt u t C
2
H
5
N (bn tri) n =NC
2
H
5
(bn phi) bng
N=102n
S n 0 1 2 3
S N 10 12 14 16
tnh ton (nm) 580 706 834 959
thc nghim (nm) 590 710 820 930
Nhng d kin tnh ton v thc nghim kh ph hp vi nhau. i vi nhng cht
mu khng i xng, s tnh ton tng i phc tp v thng ch c tnh cht nh
tnh, tc l s ph thuc tuyn tnh gia di sng ca cc i hp th vo s mt
xch ca mch lin hp.
Cn nhn mnh rng, phng trnh nu ln s ph thuc ca vo N l hon ton
theo kinh nghim ch cha c chng minh bng l thuyt.
4.2.2. Nhm mang mu, nhm tng mu
c im ca nhng cht mu hu c c dng lm thuc th trong phn tch do
mu xc nh cc kim loi c cha h ni i lin hp. i vi h ni i lin hp th
di tc dng ca nh sng, khng phi ch l nhng in t ring bit m l c h lin
hp b kch thch, do nh hng mnh n mu.
Vy h lin hp l nhm mang mu ph bin v quan trng; nhng mt cht khi ch
cha h lin hp th thng hp th nh sng yu. Cc i hp th s chuyn v pha
sng di v cng hp th s c tng cng nu trong phn t ca cht hp th
nh sng xut hin nhng in tch ion.
Nhng khng phi tt c nhng nhm ion ho (nhm to mui) u c nh hng
n ph hp th nh sng. Nhm sulfo SO
3
H, Cl, F, Br v mt s nhm khc c
in tch in t c nh hu nh khng nh hng.
Ngc li, nhng nhm cha nhng i in t khng phn chia tc l nhng
nhm cho in t nh NH
2
, (NR
2
), OH, SH v nhng dn xut ca n li th hin
nh hng rt mnh. Nhng nhm c in t hoc l nhng nhm nhn in t v d
nh NO
2
> C =ONOCN > SO
2
, N=N v mt s nhm khc cng nh hng tng
t. C hai loi nhm ny c gi l nhm tng mu.


55


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:
Bezene Phenol Nitrobezene p-Nitrophenol Anion p-nitrophenol
255nm 275nm 268nm 315nm 400nm
OH
NO
2
OH
NO
2
NO
2
O
-

Ngi ta quan st thy trt t tng mu ca nhng nhm tng mu nh sau:
CH
3
O < OH < NH
2
< (CH
3
)
2
N < (C
2
H
5
)
2
N < C
6
H
5
NH
Nhng ion v c cng c tc dng mang mu v ng gp phn ca mnh vo mu
sc ca hp cht to thnh gia ion v c vi thuc th hu c (bng 4.2).
Bng 4.2 Nhm mang mu quan trng nht ca cc nguyn t
Nhm mang
mu
Nguyn t
MeO

MeS
MeN
MeHal
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.
4.2.3. Mt s qui lut to phc mu
Trong nhng cng trnh ca mnh KYZHEOB i n kt lun nh sau: Mu ca
nhng phn ng gia thuc th hu c v ion v c l do 2 nguyn nhn:
- Tc dng ca nhm mang mu trong phn t thuc th
- Tc dng mang mu ca ion v c
Nu trong phn t thuc th c cha nhng nhm mang mu th bn thn thuc th
c mu v phn ng mu ch l s bin i (i khi l s tng cng ) mu thuc
th. Nu ion v c c tc dng mang mu (ion c mu) th phn ng mu c th xy ra
gia ion kim loi v thuc th khng mu. Do khng th xut hin phn ng mu
gia thuc th khng mu v ion kim loi khng c tc dng mang mu.
Phn ng ca cc nguyn t c mu ring vi cc cht mu hu c nhy hn nhng
li km la chn hn so vi phn ng mu gia cc ion ny vi thuc th khng mu.
V d: xc nh CuII di dng Amonicacat la chn hn xc nh Cu bng
dithizone. Ag
+
, Zn(II), Cd(II) v cc nguyn t khng c mu ring khng cn tr phn
ng mu gia Cu(II) v ammoniac nhng nhy ca phn ng ny li thp. H s


56


hp th phn t ca amonicat ng khong bng 120.
Xc nh Cu bng thuc th mu nh dithizone, pyridinazoresocsin th nhy hn
(h s hp th phn t ca nhng hp cht y khong 2.104 v ln hn) nhng la
chn ca nhng phn ng ny li thp. Ag(I), Zn(II), Cd(II) v nhng cation khc cho
phn ng mu vi dithizone u cn tr phn ng ny.
Bng con ng thc nghim ngi ta rt ra c kt lun sau y:
max
ca
phc ph thuc vo mc ion ca lin kt kim loiphi t, m ion ca lin kt
tt nhin phi ph thuc vo bn knh ion kim loi.
Do vy, nu so snh nhng ion c cu to lp v in t ging nhau th ta d dng
nhn thy, bn knh ion kim loi cng ln th s chuyn dch
max
ca phc cng tin
gn vi
max
dng anion t do ca thuc th (dng m lin kt c ion ln nht). Ta
c th ly trng hp to phc ca phenylfluoron vi cc cation kim loi ho tr 4
minh ha. Phc c cu to nh sau:
O
HO
HO
O
O
Me
n+
n

Ion H Ge(IV) Ti (IV) Zr (IV) Anion t do
Bn knh ion kim loi ( A
0
) - 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:
OH
O
O OH
OH
O
O O
-

H
2
A ( Alyzarin vng) HA ( Alyzarin )

max
=400nm
max
=520nm


57


O
-
O
O O
-

A
2
(Alyzarin tm)

max
=620nm
OH
O
O O
Me
O
O
O O
Me

Alyzarin kim loi mu (
max
=450520nm)
Nu s to phc xy ra, trong mt mc tng i, l do nhm mch nhnh ca
thuc th v do trng thi in t ca mch lin hp t b ng chm n nn mu
ca phc v ca thuc th t khc nhau. V d nhng cht mu azo, dn xut ca
salixilic acid, khng thay i mu vng ca mnh khi to phc vi Al
3+
v nhng kim
loi tng t.
N N OH
O
2
N
COOH
Me
3+
+


N N O
O
2
N
C
Me
+
O
O
+
2H
+

Mu ca nhng cht nh triarymetan cng khng bin i khi to hp cht vi
nhng phc acid ca kim loi. Cu to mch lin hp ca cation tm tinh th hu nh
khng b bin i d ion ngc du l anion Cl
-
hay anion TaF
6
-
(hoc l nhng cation
tng t khc).


58


C
N
+
N
H
3
C
H
3
C
CH
3
CH
3
N
CH
3
CH
3
Cl
-

Ch c nhng tnh cht khc l bin i: Chloride ca tm tinh th t tan trong
benzene, toluene cn hexafloretanat ca tm tinh th li b cht d dng bng benzene.
Ph hp th nh sng ca phn chit v ca dung dch nc ca chlorua tm tinh th
hu nh ng nht.
Trn y chng ta xt hiu ng trng lng v hiu ng mu ring bit nhng
trong nhng phn ng to sn phm mu kh tan th mt nhm th c th th hin c
hai hiu ng y.
V d: So snh tc dng ca dimethylglyoxim v diphenylglyoxim vi Ni chng ta
thy nhng nhm phenyl, mt mt th hin tc dng mnh mu, ng thi mt khc li
th hin tc dng lm gim tan. Kt qu l chng ta thu c diphenylglyoximat Ni
c mu m hn v c tan nh hn so vi dimethylglyoximat Ni
4.3. HIU NG KHNG GIAN
Nhng phc bn vng l nhng phc c to thnh do s xen ph nhng qu o
lp y ca phi t vi nhng qu o trng ca cation hng ti chng hoc l
ngc li. Tuy vy, nhng cu hnh lp th theo d ton i khi khng c thc hin.
Nu phc c to thnh do s tham gia ca nhiu phi t mt rng v c th tch ln
th nhng kh khn vt l s hon ton gy tr ngi cho s phn b chng xung quanh
ion trung tm.
Vn s tr thnh phc tp hn nu phi t l a rng. S dng nhng m hnh
nguyn t, ta c th bit c tng i nhiu v ho lp th ca nhng phc cht vi
cc phi t hu c.
Bit bn knh ion, di lin kt trung bnh, gi tr gc lin kt thng thng, ta c
th hnh dung cu trc gn ng ca phc, c bit l trong nhng trng hp phi t
phng. Nhng bin i khng nhiu v cu trc ca phi t c th gy nn nhng kh
khn khng gian cho s phi tr.
C th chn 1,10phenanthroline dng xc nh ion Fe(II) v 2,9dimethyl
1,10phenanthroline l thuc th ca Cu(I) lm v d. Phc 1:3 ca Fe(II) vi 1,10
phenanthroline l phc spin thp v c hng s bn ln. Ngoi ra phc cn c mu rt
m. Nhng nhm methyl trong 2,9dimethyl1,10phenanthroline gy tr ngi
khng gian cho s to phc Fe(II) 1:3, cn phc 1:2 th li l phc spin cao v khng
mu. Nhng nhng nhm methyl khng gy tr ngi cho s to phc Cu(I) c t l 1:2.


59


Hiu ng tng nh vy cng c quan st thy trong trng hp ca 6,6
dimethyl hoc l 6,6diamino2,2dipyridin. Kch thc ca ion kim loi cng ng
vai tr quan trng: ion Cu(I) c bn knh ln do phi t nm cch xa nhau v nhng
kh khn khng gian c gim i, ion Al
3+
c bn knh nh nn khng th to phc
vi 2methyl8oxyquinoline v nhng dn xut th tng t ca noridin.
Nhng thuc th ny li phn ng vi nhng ion c bn knh ln nh Cr
3+
, Fe
3+
,
Ga
3+
, Cu
2+
v Zn
2+
.
Thm nhm phenyl vo v tr 2 ca oxyquinoline s gy tr ngi cho s to phc
1:3 ca Al
3+
v Cr
3+
. Khc vi 8oxyquinoline, 2methyl8oxyquinoline khng to
kt ta vi Al
3+
.
S dng thuc th ny c th d dng chit Ga, In v xc nh chng khi c mt
Al
3+
.
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 Hg
2+
, Pb
2+
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


60


ng phn khc nhau ca cng mt thuc th cng khc nhau.
4.4. THUYT SONG SONG CA KYZNHEXOP
Kuznhexp a ra mt hnh tng rt hay d on tnh cht ca thuc th
hu c. Hnh tng l s tng t gia nhng thuc th hu c v thuc th v c
n gin nht.
C th coi s thu phn nh l s biu l ca khuynh hng to lin kt MeOR
di tc dng ca thuc th HOR. Nh vy, hon ton c th xem cc th thuc th
y nh HOR, ch khc l mt nguyn t hydrogen trong phn t c thay th
bng gc hu c R v do c th cng nhn mt cch hp l s tng t ca hai qu
trnh.
nh hng ca pH ln c hai qu trnh rt tng t. Nhng nguyn t no m
mui ca chng b thu phn gi tr pH nh (Sb, Bi,) c kh nng tng tc vi
thuc th hu c cha nhm hydroxylenol nng acid cao. Nhng nguyn t m
mui ca n b thy phn (Th, Al) i hi phn ng trong dung dch acid thp hn.
Nguyn t c mui b thu phn yu hn cn phn ng trong mi trng trung bnh
hay kim yu, cn cc nguyn t nh Ca, Sn ch c kh nng tng tc vi thuc th
loi ang bn, trong dung dch kim mnh.
Trn c s lun im nu trn chng ta c th so snh tc dng ca nhng thuc
th loi RSH vi tc dng ca HSH. KyzHeob khng nh rng nhng thuc th
loi ny ch tc dng vi nhng nguyn t no c kh nng to sunphua trong dung
dch nc. Nh vy Al
3+
, Mg
2+
, Ca
2+
khng phn ng vi nhng thuc th hu c
cha nhm SH. nh hng ca pH ln nhng phn ng vi nhng thuc th y hon
ton tng t nh hng ca pH khi kt ta nhng sulfur.
Nhng arsenic acid RAsO
4
H
2
gn vi acid arsenic v phosphoric v tnh cht
phn tch. Do , nhng ion b kt ta bng nhng acid y trong mi trng acid mnh
vi nhng arsenic acid.
S to phc vi nhng amine n gin nht (v ngay c vi nhng amine phc tp
hn) hon ton tng t vi qu trnh to amonicat. Ngi ta nhn thy rng kh nng
tc dng vi amine ca mt ion tng ln vi s tng bn ca amonicat tng ng,
s dng quan im ny chng ta c th gii thch mt cch hp l nhng quan im
quan st thy khi kt ta mt s ion bng oxim (oxyquinoline). V d: phn ng kt ta
nhng ion to amonicat bn (Cu(II), Ca(II), Zn(II), Ni(II), Cd(II), ) bng oxim xy ra
pH thp hn so vi phn ng kt ta chng vi dng hydroxide. iu c th gii
thch bng s to lin kt phi tr gia nguyn t N ca nhn quinoline vi ion phn
ng. Chng ta dn ra nhng d kin minh ha trong bng 4.3 di y.
Bng 4.3 Cc dng kt ta tng ng cc pH khc nhau
pH bt u kt ta
Ion Dng hydroxide Dng quinolinate
Cu(II) 5,3 2,7
Co(II) 6,8 4,2
Zn(II) 5,2 4,3


61


Ni(II) 6,7 4,6
Cd(II) 6,7 5,4
Tm li, chng ta nu ln s tng t gia phn ng thu phn vi phn ng to
phc ca nhng thuc th hu c cha nhm OH, s tng t gia phn ng to
sunfua vi phn ng to phc ca nhng thuc th hu c ca nhm SH, s tng t
gia nhng thuc th loi RaSO
3
H
2
vi H
3
AsO
4
, s tng t gia nhng phn ng to
ammoniac vi phn ng ca nhng thuc th hu c cha nhm amine. chnh l
ni dung ca thuyt song song.
4.5. S PHN LY CA MUI NI PHC
Trong dung dch nc, mui ca hu ht cc kim loi lun lun in ly kh mnh.
Nhng mui ny l mui ca acid v c cng nh acid hu c trong c c mui ca
nhng acid th nh m, poxyazoenzeic acid.
Ta xt mu ca 3, 4dioxyazobenzene4sulfonic acid (I) trong cc mi trng
khc nhau. Trong mi trng acid v trung ho dung dch acid ny c mu vng. Khi
kim ho do s chuyn hp cht ny thnh phenolat (II) d phn ly nn mu chuyn
thnh hng sm.
N N
OH
OH
NaO
3
S
N N
O
-
O
-
-
O
3
S
3-
3Na

(I) dung dch mu vng (II) dung dch mu hng sm
4Oxy3metoxyazobenzene4sulfo acid (III) trong mi trng acid v trung ho c
mu vng v trong mi trng kim c mu da cam (IV).
N N
OCH
3
OH
NaO
3
S N N
OCH
3
OH
-
O
3
S
2-
2Na

(III) dung dch mu vng (IV) dung dch mu da cam
i chiu mu da cam khng thm ca monophenolat (IV) vi mu hng thm ca
diphenolat (II) chng ta thy rng mu lin quan ti nh hng cong ca hai nhm
phenol phn ly bn cnh nhau trong hp cht (II).
V khng c kh nng tr thnh nhng phenolat 3,4dimetoxyazobenzene4sulfo
acid (V) c mu vng ng nht trong dung dch acid trung ho cng nh kim.
N N
OCH
3
OCH
3 NaO
3
S

(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


62


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:
N N
COOH
OH
NaO
3
S
N N
OCOC
2
H
5
OH
NaO
3
S

Tm li, mu ca nhng phenol t do v mu ca nhng ester ca chng rt gn
nhau. Ch trong nhng este trong nguyn t hydro ca nhm OH c thay th
bng gc aryl hoc alkyl nng, ngi ta mi quan st thy s khc bit v mu sc gia
phenol t do v ester ca n, nhng s khc bit thng khng ln.
Nhng iu trnh by trn y cho php chng ta kt lun rng s ging nhau v
mu ca dung dch phenol v este ca chng lin quan vi s ging nhau v trng thi
khng phn ly ca lin kt OH v OR trong nhng hp cht ny.
Trong dung dch acid yu 3,4dioxyazobenzene4sulfo acid (I) to ni phc vi
Ga. Dung dch phc c mu vng ging nhau nh mu ca monophenolit (IV).
Nu nh c hai lin kt ca nguyn t Ga vi oxy ca nhm OH trong Ga thay
th hydro, l hon ton ng ho tr th tng t vi nhng hp cht alkyl th, mu ca
phc ny phi gn vi mu ca hp cht dimetoxy (V) khng phn ly hoc hp cht
khi u (I) bi v ion Ga khng c mu ring.
Nhng trong thc t li khng nh vy nn c th cho rng trong phc , mt lin
kt GaO mt mc no ion ho ni phn. Chng ta c th m t iu
nh sau:
N N
O
O
-
O
3
S
Ga2+

(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.
* Tm nhng phn ng mu gia nhng nguyn t khng mang mu v thuc th


63


khng mu (v d hn hp c acid ho ca pyrocatesin vi diaosunfanilic acid
dn dn tr thnh khi c mt Zn, Nb, W)
* Thc hin mt s tng hp hu c kh xy ra. V d iu ch cht mu azo t
pyrocatesin bng phng php thng (trong mi trng kim) b tr ngi v ng thi
xy ra hin tng oxy ha pyrocatesin di tc dng ca hp cht diazo.
Khi c mt mui nhm hoc mt s nguyn t khc pyrocatesin phn ng tt v
hin tng oxy ho do hp cht diazo gy nn khng xut hin. Phn ng tng hp
tin hnh ngay c trong mi trng acid.
4.6. LIN KT HYDRO
Do nh hng ca s phn ho cc lin kt nn mt loi lin kt mi c hnh
thnh, l lin kt hydro. T nm 1912 ngi ta a ra ngh v loi lin kt ny
v dng tr li cho cu hi: v sao trong kh ammoniac, methylamine,
dimethylamine v trimethylamine l nhng baz yu m hydroxide ca
tetramethylamine li l mt baz mnh nh KOH?
Ammoniac hoc l nhng dn xut th bt k ca n u c th to vi nc mt
loi lin kt c bit lin kt hydro v phc to thnh c th phn ly mt phn thnh
cation hay anion hydroxyl theo phng trnh:
R
3
N + H
2
O R
3
N ... H O ...H R
3
NH
+
+ OH
-

Mt khc, v ion R
4
N
+
khng c nguyn t H lin kt vi N nn n khng th lin
kt vi ion hydroxyl bng cch ging nh lp hp cht k trn, do hydroxide ca
tetramethyl amoni phn ly hon ton trong dung dch nc ging nh KOH.
Ngi ta cng thu c nhiu d kin thc nghim chng t rng trong nhng
trng hp khc nguyn t H c th lin kt vi hai nguyn t khc, thng l O, N, F,
Mt bng chng hin nhin v s tn ti ca lin kt hydro l nhit si cao bt
thng ca nhng hydrua ca cc nguyn t y. Lc tng tc gia cc phn t ca
mt cht cng ln th nhit si cng cao. nhng iu kin khc nh nhau th ni
chung, phn t lng cng ln, lc tng tc gia cc phn t s cng ln. Do nn
ta thy H
2
O, H
2
Se, H
2
Te nhit si cn tng mt cch n iu. Nhng iu ch
quan st thy cc hydrua ca cc nguyn t nhm IVB (CH
4
; SiH , GeH
4
; SnH
4
).
Cn cc hydrua ca cc nguyn t nhm VB (NH
3
, PH
3
, AsH
3
, SbH
3
), VIB (H
2
O,
H
2
S, H
2
Se, H
2
Te) v VIIB (HF, HCl, HBr, HI) th thnh phn u tin ca dy c
gii thch bng s to thnh lin kt hydro. Do s to thnh lin kt hydro nn nhng
phn t nc ln hn H
2
O n gin.
H
H
O H O
H
H
O
H
O
H
H
O
O
H
H
H
H



64


Lc tng tc gia chng cng ln hn dn n kt qu l nhit si tng ln
nhiu. Hin tng lin hp nh vy trng thi lng gy nn nhng tnh cht bt
thng khc ca cht lng, v nh nc c thm in mi rt cao v t trng cc i
4
o
C.
Bng cch o t trng v s phn b ngi ta chng minh rng nhiu acid
carboxylic cng lin hp thnh dng lng phn trng thi hp trong dung dch
cng nh trong cc dung mi khng nc, v d i vi acid formic ta c dng diner
nh sau:
H C
O
O H O
H O
C H

Nhng iu trnh by trn y chng t rng lin kt hydro l mt loi lin kt c
tht, n lun lin kt hai nguyn t m in X v Y qua nguyn t hydro. Lc ny cc
nguyn t X, Y, H tng i ngn hn so vi khong cch khi m cc nguyn t ny
hon ton khng lin kt vi nhau nhng ln hn khong cch ca hai lin kt trc tip
gia H vi X v Y.
Trong nhiu trng hp nguyn t hydro phn b gn nguyn t X hn Y, c
trng hp khi m 2 nguyn t X v Y l nh nhau. Nhng trong mt s hp cht v
d NaHF
2
(cha ion HF
2
-
) nguyn t H phn b i xng. H to lin kt hydro hon
ton khng c ngha l H c ha tr hai, hai trong s 4 in t lin kt cn phi nm
trn qu o 2s m thc hin c iu ny, nng lng kch thch phi ln hn
nhiu so vi nng lng ph ca lin kt.
Ngy nay, ngi ta chp nhn bn lin kt hydro l do lc tnh in ca cc
lng cc XH v HY gy nn. V X v Y l nhng nguyn t m in mnh v do
vy nhng lng cc XH v YH thng rt ng k. Hn na, nguyn t H khng
c lp v in t trong v th tch ca n li nh nn nhng lng cc c th tin st
gn nguyn t H. Lin kt hydro cng c ngha trong nghin cu thuc th hu c.
Nhiu thuc th hu c tn ti di dng lin kt hydro ni phn t.
N
O
O
O
H

onitrophenol
Do to thnh lin kt hydro ni phn t nn onitrophenol c nhit nng chy
thp (45
o
C) cn cc ng phn para, meta khng thun li cho lin kt hydro do
nhit nng chy cao hn. (ng phn meta nng chy 97
o
C, ng phn para nng
chy 114
o
C).
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


65


phn ly acid ln.
N N OH
NaO
3
S
N N OH
NaO
3
S

pK= 8,2 pK= 6,7
Trong khi thuc th tng t, mang nhm OH v tr ortho so vi nhm azo
nhng li c hng s phn ly acid thp hn nhiu.
N N
NaO
3
S
N N
NaO
3
S
HO
HO

pK= 11,2 pK=11,2
iu ny ch c th gii thch bng s to thnh lin kt hydro ni phn t ca
thuc th ny vi nhm azo, nh v d sau y
N N
NaO
3
S
H
O

i vi nhng thuc th c cha 2 nhm OH v tr o v o i vi nhm azo,
gi tr pK<6 v pK=11. iu chng t ch c 1 nhm tham gia vo cu ni hydro.
N N
NaO
3
S
H
O
SO3H
OH
SO3H
OH

nh hng ca nhm th n bn ca lin kt hydro ni phn t c th thy r
trong trng hp Gallion. i vi Gallion c th thy 2 vng thm gi c to
thnh bi lin kt hydro theo s sau.
N N
O
OH NH2
SO
3
H
2ON
Cl H
H3OS

Nhng nhng d liu thc nghim (pK
1
=4,2; pK
2
=12,4) cho ta c s kt lun
rng ch c mt lin kt hydro hnh thnh


66


N N
OH
O NH2
SO
3
H
2ON
Cl
H3OS
H

bn ca lin kt ny tng ln di tc dng ca cc nhm th NH
2
hoc SO
3
H.
Lin kt hydro cng c hnh thnh trong cc hp cht ni phc lm cho s vng
tng ln v do vy bn tng ln (Hiu ng chelate). V vy, trong khi nghin cu
phc gia kim loi vi thuc th hu c cn ch n loi lin kt ny.
N N
Aso3H
O O
SO
3
H
Cl
H3OS
H
(OH)+
Se

N N
Aso
3
H
O O
SO
3
H
Cl
H3OS
H
Be

4.7. TCH CHIT I VI THUC TH HU C
4.7.1. S phn b ca thuc th
Thuc th HA phn b gia nc v tng hu c :
HA HA
0
K
HA
(4.2)
Hng s phn s :

| |
| |
0
HA
HA
K =
HA
(4.3)
i lng K
HA
khng ph thuc vo pH m ph thuc vo lc ion v nhit .
Cn h s phn b :

| |
| |
0
HA
HA
D =
HA

(4.4)
Th ph thuc vo K
Thuc th chit thng l acid hu c dng H
m
R, 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 H
m
R to ra cc dng chit c H
m+1
R, H
m-1
R,R, th h s phn b ca n
c m t bng phng trnh:


67



m+1 0 m 0 0 R 0
R
m+1 m R
[H R] +[H R] +....+[R] [C ]
D = =
[H R]+[H R]+.....+[R] [C ]
(4.5)
4.7.2. S phn b ca kim loi
S phn b cc kim loi cng nh s phn b ca thuc th gia hai cht lng
khng trn ln xy ra ph hp vi nh lut phn b Nernst, theo nh lut ny th t s
cc hot (hay lc ion c nh) l cc nng cn bng ca mt dng xc nh ca
cht phn b gia dung dch nc v dung dch hu c khng trn ln, nhit hng
nh l mt i lng hng nh.
Gi thit rng cation M chit c t dung dch nc bi mt dung mi hu c
dng cc phc MR, MR
2
, MR
i
vi anion ca thuc th chit H
m
R, thuc th ny cng
chuyn vo tng hu c cc dng HR, H
2
R, , H
i
R. Trong dung dch nc xy ra
s to phc tng nc cc hp cht MR,MR
2
, , MR
n
. Ngoi ra cc cation chit c
M tham gia vo cc phn ng to phc cnh tranh vi ion OH v thuc th che L to
ra cc h cn bng M(OH)
j
v ML
p
. Lc biu thc ca h s phn b c th vit
di dng:

2 n 0 M 0
M j n D
M
i i i
i=1 i=1 i=1
([MR]+[MR ]+...+[MR ]) [C ]
D = =
[C ]
[M]+ [MR ]+ [M(OH) + [ML ]

(4.6)
tan trong tng hu c v thc vy chit c th tng ln bng cch to ra cc
phc hn hp, lc c cc phn t baz hu c khng tch in tham gia vo bu
phi tr bn trong (nh pyridine chng hn ). Khi to ra cc cht hn hp, lm cho gi
tr h s phn b ca phc hn hp chit c MR
n
L
q
c m t bng phng trnh
sau:

M n q
n q
qn D R L
M 0
M p j n
i j OH
M
ij i i
j=0 i=0 1
K [R] [L]
[C ]
D = =
[C ]
[R] [L] + [OH]

(4.7)
4.7.3. S chit ca cc hp cht ni phc (Cc phc chelate khng tch in)
S chit cation M
n+
bng thuc th chit HR dng hp cht ni phc MR
n
ho tan
trong dung mi hu c c m t bng phng trnh :

n+ +
n
M +nHRO MR O+nH


K
ex
(4.8)
Hng s cn bng:

+ n
n 0
ex n+ n
0
[MR ] [H ]
K =
[M ][HR]
(4.9)
Nu v phi ca phng trnh (4.9) biu din qua hng s bn ca phc chit c
MR
n
, hng s phn ly acid ca thuc th
HR
a
K v hng s phn b
MR
n
D
K v
HR
D
K th
ta nhn c mt phng trnh mi lin h cc i lng ny vi K
ex
nh sau:


68



n MR HR HR
n
n
ex MR D D a
K = K /(K /K ) (4.10)
Theo nguyn tc, t (4.10) ta thy gi tr hng s chit ph thuc t l thun vi
hng s bn
n
MR
v hng s phn b ca phc
MR
n
D
K v t l nghch vi hng s
proton ho K
HR
v hng s phn b
HR
D
K ca thuc th chit. Nu bit
MR
n
D
K v
HR
D
K i vi mt dung mi hu c cn so snh th theo gi tr K
ex
i vi mt dung
mi c th tnh ton l thuyt gi tr K
ex
cho dung mi khc. H s phn b D
M
khi ch
chit mt phc duy nht MR
n
c xc nh bng h thc:

n MR HR HR MR
n n
n n+ n+
ex MR D D a M n 0 n D n
K = K /(K /K ) D =[MR ] /(M ]+[MR ])=K /(1+[M ]/[MR ]) . (4.11)
a hng s chit K
ex
vo (4.11) ta nhn c cc i lng D
M
v K
ex
:

MR
n
+ n
M D n 0
1/D =1/K +[H ] /(Kex[HR] ) (4.12)
Trong trng hp, khi DM<<
MR
n
D
K , c th n gin phng trnh (4.12) bng cch
loi t v phi ca n s hng
MR
n
D
1/K , lc ta nhn c:

n +
M ex 0 n
D =K [HR] /[H ] (4.13)
Hay dng logarit:

+
M ex 0
H
logD =logK npH nlog[HR] nlogf + + + (4.14)

+
1/2 ex 0
H
pH = (1/n)logK log[HR] logf (4.14)
4.7.4. Chit cc phc cha bo ha phi tr v cc phc tch in ( dng
cc phc hn hp)
4.7.4.1. Cc phc cha bo ho phi tr :
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 MR
n
(HR)
q
theo phng trnh:

n+
0 n q 0
M +(n+q)HR {MR (HR) } +nH


K
ex
(4.15)

{ }( ) { }
{ }{ }
( )
( )
+
n q
0
ex ex M
0 n+q
MR HR H
K = =K
C'M HR
(4.15)
y:
| |
n+
M
M
M
=
C

V ( ) | | +
M ex
0 H
logD =logK +npH+ n+p log HR +nlogf (4.16)


69


{ } +
1/2 ex
0 H
1 q
pH = logK 1+ HR logf
n n
| |

|
\
P (4.16)
4.7.4.2. Chit phc cation (chit phc tch din)
Phng trnh chit phc cation c m t bng phng trnh .
( ) ( )
{ }
( ) z-m-n
z+ +
z 0 n m
q
0
M + n+p HR +mA= MR HR A +nH (4.17)
V
( ) | | | | +
M ex A
0 H
logD =logK n p log HR mlog C npH alogf + + + + (4.18)
V

| | | | +
1/2 ex A
0 H
1 q m
pH = logK 1 log HR log C logf
n n n
| |
+
|
\
(4.19)
4.7.5. Cn bng trao i khi chit cc phc chelate
Cc phn ng trao i chit c dng tng chn lc trong thc hnh phn
tch. lm cc thuc th chit thng ngi ta dng cc dung dch cc phc chelate
trong cc dung mi hu c, v d dityldithio cacbaminat ch trong chloroform. Khi trn
cc tng th ion cn xc nh (cn tch ) M
1
n+
trong tng nc s y ion M
II
m+

trong phn t phc chelate M
II
R
m
v chuyn vo tng hu c dng M
I
R
n
, ta c:

( ) ( )
n+ m+
I II m II 0 n 0
mM +nM R mMR +nM


(4.20)
Ktr

m
I
II
e'x ' o MII
tr n m
II m o MI ex
K
[mRn] m[C ]
K = =
[M R ] [C ] K'
(4.21)
V rng
n MR
HR
MR D
ex n
HR
D
K
K =
K
K
| |
|
|
\
, phng trnh (4.21) c th vit dng sau nu ch l
| |
n+
M
M
M
=
C

:

( )
( )


I I n I
II m II m II
m
M Rn DM R M
'
tr n
M R DM R M
K
K =
K
(4.22)
y Ktr l hng s chit trao i .
Nh vy, chit trao di hon ton ph thuc vo cc hng s chit iu kin ca
cc phc ring bit, vo cc hng s bn v hng s phn b ca chng.
iu kin chit tt:


70



I II
' '
ex ex
K K (4.23)
Hay
I n I n II m II m II
M R DM R M M R DM R M
K K (4.24)
Nu nh cc ion trao i c din tch nh nhau thnh phn ca cc hp cht chit
nh nhau, cc phng trnh n gin hn, v

I
II
ex '
tr
ex
K'
K =
K'
(4.25)
V iu kin chit tt l:

I II
' '
ex ex
K K (4.26)
V
I n I n II m II m II
M R DM R M M R DM R M
K K (4.27)
4.8. TCH CHIT CC CHELATE
Kh nng v hiu qu ca s tch chit ca nguyn t da trn s khc nhau v cc
h s phn b v cc hng s iu kin ca s chit ca cc phc chelate cn phn
chia. nh gi nh lng hiu qu tch ngi ta dng hai c trng: H s tch S
v h s lm giu S.
H s tch cc ion M
I
v M
II
chit c dng cc hp cht M
I
R
n
v M
II
R
m
c
xc nh bng t s cc h s phn b ca chng:

I
I II
II
M
M M
M
D
S =
D
(4.28)
Nu nh h s ln hn trong cc h s phn b, v d
I
M
D m b hn ng k
I
DM
K , th phng trnh (4.28) c th biu din qua cc hng s iu kin ca s chit:

| |
|
\
M
I
M
II
' n'-n''
ex 0
I
' + n'-n''
II ex
K [HR]
M
S =
M K [H ]
(4.29)
Khi c thnh phn nh nhau ca cc phc chit c (n=n=n) th h s tch c
xc nh bng t s cc hng s iu kin ca s chit cc nguyn t cn tch:

| |
|
\
M
I
M
II
'
ex
I
'
II ex
K
M
S =
M K
(4.30)








71







PHN II
GII THIU CC THUC TH HU C V NG DNG
TRONG PHN TCH

CHNG 5
THUC TH PHI TR O O
5.1. PHENYLFLUORONE
CTPT: C
19
H
12
O
5

KLPT = 320,30

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 300
o
C.
Xut hin hunh quang mu hi lc trong dung dch cn pH=8. Trong dung dch
HO
HO
OH
O


72


kim, thuc th phn ly yu.
t tan trong nc (3.10
-7
M trong 20% ethanol, 25
o
C), t tan trong ethanol lnh,
nhng d tan trong cn b acid ho (HCl v acid H
2
SO
4
). N c th kt tinh li t cn
b acid ho vi s c mt ca ammoniac.Nhng mu thng mi thng c tinh
khit khng tho mn.
Phenyfluorone c xem nh mt cht in ly lng tnh, v s phn ly trong 25%
ethanol c th c xc nh nh di:

Ph hp th ca Phenyfluoronetrong dung dch nc c minh ho trong hnh 5.1

5.1.5. Phn ng to phc cht v tnh cht ca phc cht
Phenylfluorone phn ng vi mt s ion kim loi to thnh chelate c mu
khng ho tan. Trong dung dch acid 0,1M, Ge (IV) to phc c mu vi t l 1:2
xy ra theo phng trnh:
( ) ( ) ( )
3 3 2
4 2 2
Ge OH +2H L Ge OH H L +2H


Hng s cn bng trong dung dch ethanol 20% ti 25
o
C v u = 5 c xc nh
gn bng 8( 4).10
12
. Cu trc phc ca Ge(IV) c biu din nh sau:

Bng 5.1. Phn ng ca phenylfluorone vi 100ug cc kim loi
Ion kim loi HCl HCl + H
2
O
2
HCl + oxalate HCl+H
2
O
2
+ oxalate
pKa
1
=2.3 pKa
2
=5.8 pKa
3
=11.3 pKa
3
=12.3
H
4
L
+

H
2
L
-

SO
3
H
HL
2-
L
3-

Vng vng cam cam hng
Hnh 5.1. Ph hp th ca Phenyfluorone


73


Fe (III) S S
Ge (III) S S S S
Hf (IV) S S
Mo (VI) S L
Nb (V) S
Sb (III) S S S S
Sn (IV) S S L
Ta (V) S L
Ti (IV) S L
V (V) S
W (VI) S
Zr (IV) S 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
Kim
loi
iu kin T l

max

(nm)
.10
4

Gii hn
cho php
(ppm)
Al pH 3,0 4,0 ML
2
540 6,0
Al pH 9,5 11,0, Triton X100 ML
2
X 554 13,5 0 0,2
Co(II)
pH 4,5 5,0; NO
2
-
,
Zephiramine
ML
2
645 4,8 ~ 2
Cr(VI) pH 1,5; 40 EtOH ML 500 2,1 0,01 1,7
Fe(III) NaOH 0,001N ML
2
580 8,6 ~ 1
Ga pH 8,0 9,0; CPB(X) ML
2
X
2
570 11,4
Ge(IV)
HCl 1,2N, gelatin, gm Arabic hoc
polyvinyl alcohol
ML
2
510 8,7
Ge(IV) HCl 0,5N, chit vi benzyl Alcohol ML
2
505 14,5 0,05 0,5
Ge(IV) HC l,1 1,5N; CTMAC ML
2
505 17,1 0,02 0,16
In pH 5,5; gelatin ML
2
540 4,88 0,2 1,4
Mn(II) CPC(X) ML
2
X
2
9,8


74


Mo(VI) pH 2,0; gm arabic 550 0,33 1,67
Mo(VI) pH 1,5; CPC 540 9,6 0,4 6
Mo(VI)
HCl 0,25 0,3M; EtOH, sau khi cho
CHCl
3
, vi BPA(X)
ML
2
X 518 7,4 0 0,6
Nb H
3
PO
4
0,3% ML
2
520 3,7
Nb
H
2
SO
4
0,24 0,48N; Triton X100
1000 trong 90 giy
525 10,0 0 0,4
Ni pH 8,5 10,0; CTMAB, pyridine ML
2
620 10,4 0 0,33
Sb(III) H
2
SO
4
, gelatin, thiourea 540 3,42
Sn(IV)
pH 1,2 2,0 (HCl), tartarate, gum
Arabic, hoc polyvinylalcohol
ML
2
510 5,93 ~ 2
Sn(IV) H
2
SO
4
1,8N, CTMAB 505 18 0 0,3
Ta pH 4,5 530 6,39 0 0,5
Ti
pH 7,0 1,0 (HCl), PB(X), chit
bng CHCl
3
+ AmOH (2:1)
MLX
2
Cl 540 9,0 0,05 0,1
Ti CPA(X), Cl
-
, chit bng CHCl
3
MLX
2
Cl 550
Ti(IV)
Furylvinylacroleyphenyl
hydroxylamine(X), chit bng CHCl
3

ML
2
X
2
540 17,1 0,05 10
Ti(IV)
pH 1,4 2,2; Triton X350 (X) Op
emulsifier (Y)
ML
2
XY 540 16,3 0 0,2
V(IV)
pH 4,0 5,0, 30% EtOH, 0,02%
gelatin
ML
2
530 1,7 0,2 2
Zn pH 7,7 8,2, CPB, pyridine ML 585 8,0 0 1
Zr(IV)
HCl 0,1N, stabilized with
cyclohexanol
540 13 ~ 1
Zr(IV) pH 4,6, F
-
, CPC ML
2
560 4,6 0 7
K hiu cho cationic: CTMAC: Cetyltrimethylammonium chloride
CTMAB: Cetyltrimethylammonium bromide
CPC: Cetylpyridinium chloride
CPB: Cetylpyridinium bromide


75



Hnh 5.2. Quang ph hp th ca Ge chelate
5.1.7. Tinh ch thuc th
Thuc th c th c tinh ch bng cch cho 1 gam mu vi 50ml ethanol trong
thit b Sohxlet, tin hnh chit 10 gi loi b cc cht khng tan.
tinh khit c th c kim tra bng cch o s hp th bc x ca dung dch
nc c nng 5.10
-4
% (1N HCl), ( = 462nm, = 4,06.10
4
)
S c mt ca cc cht khc c th c kim tra bng php in di trn giy vi
dung dch 0,1% c trn ln bi HCl 6N (3ml) ethanol (97ml) dng vi dung dch
c cha 0,05% acid oxalic v 30% acid acetic.
5.1.8. ng dng trong phn tch
- Thuc th trong phng php o quang
Phenylfluorone hu nh c s dng rng ri nh mt thuc th dng o
quang cho Ge. Mt vi ion kim loi Co, Fe, In, Mo(VI), Nb, Ni, Sn(IV), Ta, v Zn
cng c th c xc nh bng thuc th ny. Vic xc nh Ge c th tng nhy
bng cch chit phc Ge cng vi lng d thuc th vo trong mt dung mi hu c
khng trn ln nh benzyl alcohol hoc chit Germanium chloride trong dung dch
HCl vi carbon tetrachloride hoc MIBK, sau , lp tc to thnh phc
phenylfluorone trong pha hu c vi s thm vo ca dung dch alcohol ca thuc
th. Trong s tng phn vi phng php chit, nhy ca phng php o quang
trong pha nc ch bng mt na ca phng php chit, nhng nhy v tc
phn ng c th c thay i bng s kt hp cht hot ng b mt cation chng hn
cetyltrimethylammonium chloride.
Trong vic xc nh thic Sn, tri li thic khng th tn ti hnh thnh mu
thic chelate bi s thm vo dung dch methanol ca phenylfluorone n MIBK c
chit ra t SnCl
4
. Tuy nhin, tin phenylfluorone chelate c to thnh trong dung dch



76


acid pha long, c th c chit ra vi MIBK. Sau khi chit ra mu ca chelate c
khuynh hng nht dn trong dung dch. T l ca s mt mu tng dn vi s gia
tng nng acid trong dung dch c chit ra.
- Xc nh Ge sau khi chit ra vi carbon tetrachloride
Ly 20ml dung dch mu HCl 9N c cha 0,5 n 10 g Ge cho vo mt ng dn
v thm vo 10ml carbon tetrachloride. Sau lc khong 2 pht tch lp hu c
ra. Ly chnh xc 5ml cho vo bnh 10ml v thm vo 1ml thuc th (0,05 g
phenylfluorone cng vi 0,43ml HCl trong 100ml ethanol) v pha long n vi
ethanol. Sau 5 pht o ti bc sng 508nm.
5.2. PYROCATECHOL TM
CTPT: C
19
H
14
O
7
S
KLPT: 386,38

H
4
L
5.2.1. Tn gi khc
3,3,4Trihydroxyfuchsone2sulfonic acid, Catechol sulfonephtalein, Catechol
tm, PV.
5.2.2. Ngun gc v phng php tng hp
C gi tr v mt kinh t. Tng hp t s ngng t ca osulfonephthalein anhydrit
vi pyrocatechol
5.2.3. ng dng trong phn tch
Nh mt ch th kim loi trong phng php chun phc cht chelate ca nhng
kim loi nng. Nh phn ng trc quang cho nhng kim loi khc nhau bao gm: Al,
Bi, Ge, Sn, Y, v Zr. nhy c th c ci tin bng vic thc hin phn ng trong
s c mt cht hot ng b mt cation.
5.2.4. Tnh cht ca thuc th
L loi bt nu thm c nh kim loi mu xanh dng. N rt ht m, v th
nn bo qun tht kn. Sn phm thng mi thnh thong c mi v acid acetic m
khng hon ton loi b c t s kt tinh dung mi. N tan t do trong nc v cn
pha trong nc, t tan trong cn nguyn cht lnh hoc acid acetic bng v khng tan
trong dung mi khng phn cc chng hn: benzene, xylene,
OH
O
OH
HO
C
SO
3
H


77


Dung dch nc ca Pyrocatechol tm c mu vng v mu ca dung dch thay i
theo pH cng nh kt qu tch proton ca thuc th. S tch proton c vit nh
c ch ra di y

S chuyn ha ca thuc th nhng gi tr pH khc nhau c minh ho hnh
5.3 Dung dch nc ca thuc th rt bn trong mi trng acid dn dn b phai mu
pH>7,5.
pK
a1

L
4-

pK
a2
< 1
pK
a3
= 7,82 pK
a4
= 9,76
pK
a5
=11,7

Tm
Vng
- tm
H
5
L
+

HL
3-
H
4
L H
2
L
2-
H
3
L
-



78



Hnh 5.3. S chuyn ha ca pyrocatechol tm nhng gi tr pH khc nhau
5.2.5. Phn ng to phc cht v tnh cht ca phc cht
Pyrocatechol tm to nn cc lin kt mu vi cc kim loi khc nhau, hu ht trong
dung dch acid yu v baz yu c tm tt bng 5.3.
Bng 5.3. Phn ng mu ca pyrocatechol tm vi cc kim loi
Ion kim loi pH Mu Ion kim loi pH Mu
Al 2,5 4,0 Hi ta Nd(III) 6,5
Be 8.0 Ni 7,5
Bi <1,5 Hi xanh ta Pb 5,5
BO
3
2-
6,0 Pr 6,5
OH
O
OH
HO
C
SO
3
-
OH
O
OH
-
O
C
SO
3
-

+H
+
+ H
+
+H
+
H
2
L
2-
H
3
L
-
OH
O
O
-

-
O
C
SO
3
-

OH
OH
+
OH
HO
C
SO
3
-

+ H
+
H
4
L

HL
3-
+H
+

O
-
O
O
-

-
O
C
SO
3
-

OH
OH
+
OH
HO
C
SO
3
H
L
4-
H
5
L
+



79


Cd(II) 8,0 Hng Sb(III) <1,5 Hi ta
Ce(III) 6,5 Sn(II) 3,5
Co(II) 7,5 Sn(IV) 0,5
Cu(II) 5,0 Th <0,3
Fe(II) 7,5 Ti(IV) <1,5 Mu ta
Fe(III) <2,0 UO
2
2+
5,0
Ga 2,5 Mu ta WO
4
2-
<3,0
In 7,0 WO
4
2-
>3,0 Hi ta
La 9,5 Y 6,3
Mg 8,5 Zn 7,0
Mn(II) <3,0 Hi ta Zr <1,0 Hi ta
- Nng ca ion kim loi 5.10
-3
M.
- Mu ca phc kim loi l mu xanh ngoi tr s khc bit ca ch th.
Phc mu xanh c to thnh trn ch th pH. Cc phn ng mu c bn (chnh)
l [ML
2-
]; [M
2
L] v [MHL
-
] M c biu th cho kim loi ha tr 2, c ch ra
sau:



M
O
-
O
O
O
C
SO
3
-
ML
2-
(xanh tm)
OH
O
O
O
C
SO
3
-
M
MHL
-
(xanh tm)
O
O
O
O
C
SO
3
-
M
M
2
L
-
(xanh)
M
+



80


Hng s bn ca mi loi c tm tt trong bng 5.4
Bng 5.4 Hng s bn ca phc chelat ca pyrocatechol tm vi cc kim loi
pyrocatechol tm vi cc kim loi

Ion kim loi Log KML Log KM2L Log KMHLa
Al(III) 19,13 4,95 -
Bi(III) 27,07 5,25 -
Cd(II) 8,13 - 5,86
Co(II) ,01 - 6,53
Cu(II) 16,47 - 11,08
Ga(III) 22,18 4,65 -
In(III) 18,10 4,81 -
Mg(II) 4,42 - 3,67
Mn(II) 7,13 - 5,37
Ni(II) 9,35 - 6,85
Pb(II) 13,25 - 10,19
Th(IV) 23,36 4,42 -
Zn(II) 10,41 - 7,21
Zr(IV) 27,40 4,18 -
Ph chnh thay i theo s hnh thnh ca phc chelate c ch ra hnh 5.4. Mc
d bc sng hp thu cc i nhng cng hp thu khc nhau ph thuc vo ion
kim loi. Ph hp thu tng t c quan st trn nhiu kim loi khc
Trong s c mt ca cht hot ng b mt cation, tuy nhin, s chuyn dch m
mu v s tng cng ca di hp th c quan st th hin r rng.
5.2.6. S tinh khit v tinh ch ca thuc th
Mu thng mi thng khc nhau v cht lng. Nhng mu m khng tinh khit
c th tinh ch bng s kt tinh t acid acetic bng. Dng tinh khit trong m acetate
(pH 5,2 n 5,4) c mu vng chanh (
max
= 445nm, = 1,4.10
4
)
Bng 5.5. Chun phc cht s dng ch th pyrocatechol tm
Ion kim
loi
pH m
Mu thay i ti
im kt thc
Lu
Bi 2 3 HNO
3
Xanh Vng
Cd 10 NH
3
NH
4
Cl
Hi xanh dng
hi ta
Co(III) 9,3 NH
3
NH
4
Cl
Hi xanh dng
hi ta
Cu(II) 5 6 HNO
3
NH
3
Xanh Vng
Cu(II) 6 7 Pyridine
Fe(III) 5 6 Pyridine Xanh Vng
Ga 3,8 Acetate Xanh Vng
Fe(III); Hg(II); Th; Zr
c chun cng


Vt ca kim loi nng
khng c ln

Chun chm
Dung dch chun nng
Thm NH
2
OH


81


In 5 Pyridine Xanh Vng
Mg 10 NH
3
NH
4
Cl
Hi xanh dng
hi ta
Mn(II) 9,3 NH
3
NH
4
Cl
Hi xanh dng
hi ta
Ni 9,3 NH
3
NH
4
Cl
Hi xanh dng
hi ta
Pb 5 Hexamine Xanh Vng
Th
2,5
3,5
HNO3

Xanh Vng

Zn 10 NH
3
NH
4
Cl
Hi xanh dng
hi ta
5.2.7. ng dng trong phn tch
- S dng nh l ch th kim loi trong chun to phc
Ion kim loi, c th c chun bng EDTA s dng Pyrocatechol tm nh l
ch th. Dung dch A 1% c s dng v c th tn tr cho nhiu thng, dung dch c
dung mi l nc th n nh v s thay i mu khng b cn tr bi vt kim loi
nng, n c ngh s dng thch hp ca ch th ETOO hoc Murexit. S thay i
mu vi Bi v Th th rt r rng v th nhng kim loi ny c th c s dng
chun ngc trong chun cc kim loi khc.

Hnh 5.4. Ph chnh thay i theo s hnh thnh ca phc chelate
Bng 5.6: ng dng ca pyrocatechol tm nh thuc th trc quang
Phc chelate kim loi
Ion kim loi iu kin
a

H s
b
Bc sng (x10
4
)
(x 10
4
)
Al(III) pH 6,0 ML
2
580 6,8 0 04
Al(III) pH 9,7 10,2, CTAC(X) ML
2
X
5
670 0,53 0,27 54
Al(III) pH 10 CPC(X) MLX
5
700 3,8



82


B pH 8,55 8,65 ML 494 0,165 0,2 2,0
Be pH 8,0, CPC(X) MLX
5
680 1,5
Bi(III) pH 3,8, acetate 610 4 24
Cd(II) pH 10 CPC (X) MLX
5
710 1,0 0,1 7,5
Co(II) pH 10, CPC (X) MLX
5
720 1,2
Cr(III) pH 5,0 6,0, acetate 605 1,1 -
Cu(II) pH 7 630 4 24
Fe(III) pH 6,2 7 ML
2
610 6,2 0 0,6
Fe(II) pH 5,0 6,0, CTMAB (X) ML
2
X
2
605 13,5 0 0,35
Ga pH 6,05 6,4 ML
2
580 ~ 7,3 0,56 3,1
Th pH 3,8, acetate 480 4 24
Th pH 8,0, CTMAB ML
3
660 6,0 0,6 4,0
Ti(IV) pH 3,3 3,5, gelatin ML
2
690 0,06 0,71
Ti(IV) pH 2,0, CPC MLX
5
745 7,5
V(V) pH 4,0, Zephiramine ML3 660 7,5 0 0,5
W(VI) pH 2,0 6,0 ML 540 1 6
W(VI) pH 1,0, CPC MLX
5
670 6,4
Y(III) pH 8,7, H
3
BO
3
MLX 607 1,9 0-7,8
Y(III) pH 8,4 9,0, gelatine 665 2,59 0 1,8
Zn(II) pH 9,0, CPC MLX
5
690 1,3
Zr(IV) pH 3,5 5,0 ML
2
650 3,26 0 2,0
Zr(IV) pH 6,0, CPC MLX
5
700 1,3
- S dng nh l thuc th trong php trc quang
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
-3
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.
5.3. CHROMAZUROL S
CTPT: C
23
H
16
O
9
C
l2
S


83


KLPT: 539,34
SO
3
H
C
OH
O
COOH COOH
H
3
C
Cl
Cl

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 C
23
H
13
O
9
Cl
2
SNa
3
.2H
2
O 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 H
4
L v li b ha tan trong dung dch acid hn (HCl 8 9N).
Gi tr hng s phn ly proton c xc nh (u = 0,1 (NaClO
4
), 25
o
C) v ph
hp thu trong dung dch nc nhng pH khc nhau c minh ha hnh 5.5






5.3.5. C ch phn ng to phc v tnh cht ca phc
L
4-

pK
a1
pK
a2
= -1,2 pK
a3
= 2,25 pK
a4
= 4,88 pK
a5
=11,75
cam vng
tm
HL
3-
H
4
L H
2
L
2-
H
3
L
-

COOH COOH
H
5
L
+



84


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.

Hnh 5.5. Ph hp thu ca CHROMAZUROL S trong dung dch nc cc gi tr
pH khc nhau:1,2,3,4,5

Bng 5.7: Phn ng mu ca chromazurols vi cc ion kim loi
Ion kim loi pH Ion kim loi pH Ion kim loi pH
Be 2,5
a
Nd 6,5 U (IV) 2,5
Ce (III) 5,0 Ni 7,5 UO
2
2+
2,0
Co (II) 8,5 Pb 6,5 VO
2
+
4,0
Ga 1,5 Pr 6,5 Y 5,5
In 2,5 Sr 11,0 Zn 7,5
La 4,5 Th 1,0 Zr 1,0
Mn (II) 7,5 Ti (IV) 1,0
- K hiu a: ti pH ny phc chelate c mu nho, nhng pH cao hn
phc s chuyn sang mu
tm



85



Hnh 5.6. Cu trc ngh ca ba loi phc chelate Fe(III)
Trong hu ht cc trng hp ca phng php trc quang s dng Chromazurol
S

, dung dch quan st c th l hn hp cn bng ca hai hay nhiu loi phc chelate.
5.3.6. S tinh ch v tinh khit ca thuc th
Hu ht nhng mu thuc th sn c khng tinh khit s dng cho vic
nghin cu ho l, mc d chng c th c s dng nh l thuc th trong phng
php o quang cho nhng kim loi hoc ch th kim loi cho chun phc cht
chelate. Qui trnh c ngh cho qu trnh tinh ch nh sau:
Ho tan 40g mu vo 240ml nc v lc b nhng cht khng tan. Thm 50ml HCl
v lc kt ta. Ra ta vi HCl 2N v lm kh. Ho tan kt ta bng 250ml nc v
lm kt ta hai ln na nhit 70
o
C. Sau khi kt ta ln th ba lm kh sn phm.




86


tinh khit ca Chromazurol S c th c xc nh bng quan st hp thu
ca dung dch ca nng c bit bc sng thch hp (bng 5.8).
Php th chnh xc hn c th dng chun in th ca dng acid t do
(H
4
L.2H
2
O) vi dung dch NaOH.
5.3.7. ng dng trong phn tch
- Thuc th trc quang
Hn 30 ion kim loi c xc nh vi thuc th Chromazurol S. Nhng nm
gn y, hp thu phn t ca phc kim loi c tm thy tng cao n 105 khi
c mt ca mixelle cation; v vy phng php trc quang c nhy cao cho nhiu
ion kim loi khc nhau c bo co. Nhng dng Chromazurol S nh l thuc th
trc quang li thiu tnh chn lc cho nhiu ion kim loi.
Bng 5.8. c im ph ca chromazurols
iu kin
max
(nm) (x10
4
)
HCl 1,0N 540 7,80
pH 79 (acetate, borax) 430 2,24
pH >13(NaOH ~ 1N) 600 7,56
- Xc nh Be bng phng php trc quang
Chuyn ton b dung dch mu c tnh acid nh (180g Be) vo bnh nh mc
25ml. Trn lp nc tch ra, trung ha lng acid d bng NaOH10% bng ch th
methyl da cam, thm 1,0ml acid ascorbic 1%, 2,00ml EDTA10%, 5,00ml m acetate.
Tip tc thm vo hn hp ny mt lng nh trc NaOH10%, v pha long vi
20ml nc. Thm 2,00ml dung dch Chromazurol S

(0,165g trong 100ml nc) v

pha long n th tch trn. o hp thu v loi nh hng nn bng mu trng
569nm.
- Xc nh Be bng phng php trc quang c nhy hn nh s dng cht hot
ng b mt
Chuyn dung dch nc cha t hn 2g Be vo mt beaker v thm 1,00ml EDTA
1% v 5,00ml dung dch perchlorate sodium 5M. Hiu chnh pH ca dung dch n
4,5 vi dung dch m acetate v lm bay hn dung dch cn 510ml. Sau khi lm
lnh nhit phng tip tc thm 1,00ml dung dch Chromazurol S

0,25% v
2,00ml polyoxyethylenedodecylamine 0,5% (ha tan 0,5g trong nc c cha 0,5ml
HCl 5N, sau hiu chnh pH ti 4,5 vi m acetate v pha long ti 100ml). chuyn
ton b dung dch vo bnh nh mc 25ml v nh mc ti vch bng nc ct. Sau
15 pht, o hp thu 605nm v loi tr nh hng bng mu trng. Anion nh l
perchlorate, nitrate, v chloride khng nh hng.
- Ch th kim loi trong phng php phc cht
Chromazurol S c ngh nh l mt ch th kim loi trong phng php phc
cht c tng hp bng 5.9. Mc d mu thay i khng r nt bng Xylenol da
cam, nhng n rt hu dng trong chun Al, Cu v Fe ni m Xylenol da cam v
methyl thymol blue khng hot ng thch hp. Ch th s dng pha trong nc


87


khong 0,10,4% c th trong nhiu thng
Bng 5.9. Chun phc cht ca ion kim loi dng cht ch th chromazurols
Ion kim loi pH m
Thay i mu im
cui
Ch
Al(III) 4 Acetate Tm vng chun 80o
Cu(II) 6-6,5 Acetate
Xanh m xanh
nc bin

Fe(III) 2-3
Monochloroacetic
acid acetic acid
Xanh vng cam chun 80o
Ni(II) Pyridine +NH3 Xanh tm vng
Th(IV) 1-2 HNO3-NH3 Tm vng
chun in
th
5.3.8. Thuc th khc c cu trc lin quan
- Aluminon:
Mui ammonium ca acid aurine tricarboxylic.
CTPT: C
22
H
23
N
3
O
9

KLPT: 473,43

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%; 100
o
C; 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 acid, mui
trisodium (CTPT: C
23
H
16
O
9
S, KLPT: 468,43).
C
NH
4
OOC COONH
4
O
HO
OH
COONH
4


88


CH
3 C
O
HO
SO
3
H
COOH COOH
CH3

Dng bt mu gch, n d dng tan trong nc v alcohol, cho dung dch mu
cam v chuyn sang mu tm khi pH>9. Hng s phn ly acid trong dung dch nc
(pK
n
[n=14]) l 1,79, 4,00, 6,91 v 11,14 (=0,1 NaCl, 2022
o
C). Trong vng acid
hoc trung tnh, n hnh thnh phc tan c mu tm vi Al, Be, Ca, Cu, Fe, Mg, Zr,
... v c bit nh l mt thuc th trc quang xc nh Al (pH 6,0,
max
=535nm).
V cng c nhy cao cho Be khi c mt ca micelle cation (Zephiramine) (pH 6,7
7,2,
max
=595nm, =10
5
, 1855ppb).
5.4. NBENZOYLNPHENYL HYDROXYLAMINE V NHNG CHT
LIN QUAN

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
Cng thc
phn t
Phn
t khi
1
N-Benzoyl-N-phenyl-
hydroxylamine
N-Phenylbenzohydroaxamic
aicd, BPA, NBPHA, BPHA
C11H13NO2 213,24
2
N-Cinnamoyl-N-
phenylhydroxylamine
N-
Phenylcinnamohydroxamic
acid, CPA
C15H13NO2 239,31
3
N-Benzoyl-N-o-
tolylhydroxylamine
N-o-tolyl-benzohydroxamic
acid, BTA
C14H13NO2 227,26

C N
OH
R
O
R
'
CH = CH
CH
3
R R
'
(1)
(2)
(3)


89


5.4.2. Ngun gc v phng php tng hp
Tt c nhng cht phn ng sn c trn th trng (1) v (2) c chun b bi
phn ng ln lt gia phenylhydroxylamine vi benzoylchloride v
cinnamoylchloride. (3) th c chun b bi phn ng gia otolylhydroxylamine vi
benzoylchloride.
5.4.3. ng dng trong phn tch
Nhng cht phn ng ny c lin quan vi Cupferron v mt cu trc, nhng phn
ng ca chng vi ion kim loi l nh nhau, nhng trong nhiu trng hp c th
chng mnh hn Cupferron bi v chng n nh hn trong acid v c. (1) v (3)
thng dng lm nhng cht chit trc quang cho nhng kim loi V(V) v Ti(IV). (3)
th c trng nht cho kim loi V.
Chng cng thng c dng nh l nhng dung mi chit ngn cch nhng
ion kim loi khc nh l nhng cht kt ta hoc nhng cht phn tch trng lng
nh: Al, Cu (II), Ti (IV) v nhng nguyn t khc.
Mt s hp cht c quan h cu trc vi hydroxylamine c thay th c
kim tra v tho lun k trong M
1
, M
2
, R
1
.
5.4.4. Tnh cht ca thuc th
BPA (1) l nhng si kim loi nh, khng mu, im nng chy l 121
o
C n
122
o
C, bn vi nhit , nh sng, khng kh v khng phn hy thm ch trong acid
v c mnh ngoi tr acid Nitric (3N). Hu nh khng tan trong nc, ho tan d trong
cc dung mi hu c, cng ho tan trong nhng acid v c c nc, acid acetic, v
dung dch ammoniac; kh nng tan trong nc: 0,04g/100ml (25
o
C) v trong ethanol
96% l 10,9g/100ml (22
o
C). N l n baz c tnh acid, pKa 8,2 (u = 0,1 NaClO
4
,
25
o
C); 9,13 (20% dioxane), v 10.20 (40% dioxane, 35
o
C).
CPA (2) l nhng tinh th vng xanh sng, im nng chy l 158
o
C n 163
o
C.
Tng t nh nhng tnh cht vt l v kh nng ha tan ca (1); kh nng tan trong
nc: 0,022g/100ml (18
o
C), v trong ethanol nguyn cht l: 0,972g/100ml (18
o
C);
pKa= 11,1.
BTA (3) l nhng si kim loi nh, khng mu, im nng chy l 104
o
C, tng t
nh tnh cht vt l v kh nng ha tan ca (1).
Nhng dung dch nc ca (1) n (3) th khng mu v khng cho hp thu
trong vng kh kin. Ph hp thu ca (1) trong vng cc tm v c biu din hnh
5.7
Nhm cht phn ng ny thng dng chit nhng ion kim loi a ho tr d b
thy phn t dung dch acid kh m c. Trong mi quan h ny, s phn b ca
BPA (1) gia chloroform v acid chlohydric c xem xt k v biu din hnh
5.8. T l phn b ca (1) i vi cc h thng khc c tm tt trong bng 5.11.


90



Hnh 5.7. Ph hp thu ca BPA trong vng cc tm
5.4.5. Nhng phn ng t nhin v tnh cht ca phc
BPA c tng hp u tin bi Bamberger, Ngi ch rng n cho kt ta
mu vi nhm nguyn t chuyn tip. Sau , Shome pht hin ra rng cht ny c
nhng thun li hn Cupferron trong phn tch trng lng (Ksp i vi GaL
3
1,6.
10
34
; InL
3
7,2.10
31
).
Kh nng ha tan ca nhng kim loi c cng trong dung mi hu c cng m
ra kh nng ngn cch ca nhng ion kim loi bng phng php chit dung mi.
Phn ng vi ion kim loi c th vit l:
M
m+
+ nHL = ML
n
m-n
+ nH
+



Hnh 5.8. S phn b ca BPA gia chloroform v acid chlohydric
Bng 5.11. T l phn phi ca BPA
Pha D
CHCl3/H2O 214
CHCl3/HClO4 0,1M 137 5
CHCl3/HClO4 6M 24 1
C6H6/HClO4 1,0M 23, a37b





91


a: Tng nng ca BPA trong benzelne l 1x10-3M
b: Tng nng ca BPA trong benzene l 6x10-3M
Cu trc ca dng lin kt cng ca ML
2
c th c biu din nh sau:


Do kh nng ha tan t ca nhng kim loi to phc nn rt t s liu sn c v
nhng hng s n nh ca nhng cht phn ng ny.
Qu trnh chit thng c tin hnh trong dung dch acid mnh t c
chn lc ca nhng ion kim loi v trnh s thy phn ca nhng ion kim loi a
ha tr. S chit trong dung dch aicd hydrochloric th tt hn l trong aicd Sulfuric.
5.4.6. ng dng ha hc
5.4.6.1 Dng nh l thuc th kt ta v phn tch trng lng
BPA (1) c dng rng ri trong phn tch trng lng cho mt s lng ln
nguyn t. S ngn cch ca chng khi nhng ion kim loi khc c th t c di
nhng iu kin c kim sot bi pH v nhng cht che, nh l EDTA hoc acid
tartaric. . Nhng cht kt ta vi (1) thng c th cn trc tip, nhng trong mt vi
trng hp chng phi c t chy oxi ho trc khi cn.
ng dng quan trng nht ca (1) l xc nh v ngn cch Nb v Ta ln nhau, vic
xc nh trc tip Nb trong dung dch c s hin din ca Ta v mt s ion khc, s
ngn cch Nb, Ta v Ti ln nhau, v vic xc nh Zn trong dung dch c s hin din
ca Nb, Ta, Ti v V.
Tng t nh ng dng xc nh Nb v Ta v ngn cch chng khi nhng ion
khc c bo co cho (2) v (3).
5.4.6.2 S dng nh cht phn ng trong qu trnh chit
Nhng nghin cu rng ri tin hnh trn qu trnh chit c trng v mt vi s
ngn cch mi ca nhng ion kim loi vi BPA (1).
S chit ca nhng ion kim loi vi dung dch (1) trong dung mi khng trn ln
c l mt chc nng ca thi gian lc, nng ca dung dch (1), dung mi t
M
O O
O
O
N C
N C


92


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 (TiOL
2
) 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 TiL
4




93


c hnh thnh (
max
= 355nm, trong CHCl
3
). Trong dung dch acid hydrochloric
mnh s cho dng phc ML
2
Cl
2
(
max
= 380nm, trong CHCl
3
). 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 ML
2
SCN. 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 100ug 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: C
4
H
2
O
4
Cl
2

KLPT = 208,99

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
HO
O
O
OH
Cl
Cl


94


thi l s phng thch ion acid chloranilat (HL
-
) c cng mu cao.
5.5.4. Nhng tnh cht ca acid Chloranilic
Tinh th c mu cam (dng bt) nhit nng chy 283
o
C n 284
o
C. N c
tnh acid baz, pH ca dung dch (nc) bo ho l khong 2, pKa
1
= 0,810,01, pKa
2
=
2,720,05. N c xu hng thng hoa.
N th ho tan rt t trong nc (3,0 g/l nhit phng) cho dung dch mu tm,
mu tng t mu ca dung dch KMnO
4
, d dng ho tan trong dung dch kim hoc
trong nc nng, khng ho tan trong hu ht cc dung mi hu c ngoi tr alcohol.
N phn ng vi nhng ion kim loi a ho tr v ion kim loi nng cho kt ta kh tan
t nu n tm.
Trong dung dch nc c 3 dng (H
2
L, HL
-
, L
2-
), ion acid Chloranilat (HL
-
) phn
b vi mt cao nht trong phm vi pH = 1 2. Hnh 5.9 minh ho cho s hp thu
quang ph ca HL
-
trong min nhn thy c. Peak biu th cng cao nht pH =
1 2, n gim i phn na so vi trc pH = 5 v khng thay i thm na phm
vi pH = 5 12. Ging nh peak c theo di trong min UV (
max
= 332nm).
Trong dung dch th khng bn vi nh sng v phai mu dn. Dung dch cn c
bo qun ni ti, mt v tt nht pH thp.Khi dung dch nc ca acid chloranilic
c trn vi dung dch ion kim loi, c s thay i mu sc do s cu thnh phc
vng cng v trong vi trng hp to kt ta kh tan Chloranilat kim loi, trong
dung dch lc mu tm ca dung dch nht i. Phn ng to kt ta thng dng cho
nh lng v mu ca ta gm nhiu loi khc nhau t nu n tm. Nhng
Chloranilat kim loi nng v a ho tr th s ha tan b hn nhiu so vi acid
Chloranilic. Nhng c trng ny lm nn tng cho s dng trong phn tch kim loi.

Hnh 5.9. Quang ph hp thu ca ion acid Chloranilat (HL
-
)
5.5.5. Nhng tnh cht ca thuc th
Trn th trng c cc loi sn phm Chloranilat ca Ba, Hg (II), La, Sr v Th n



95


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
-4
M v trong nc ethanol (1:1) l
5,2.10
-6
M. 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:
Ag
2
L + 2Cl
-
+ H
+
= 2AgCl + HL
-

(rn) (rn)
Ion Cl
-
t l tng ng vi lng ion chloranilat gii phng ra n c xc nh
bng php o quang
max
= 530nm ( = 200) hoc 332nm. Nguyn tc ny c th
ng dng xc nh nhng anion khc.
Trn phn ng:
ML + X
-
= MX + L
-

(rn) (rn)
y X
-
l anion cn xc nh v ML Chloranilat kim loi kh tan, ML phi ho tan t
hn nhiu so vi MX. Yu cu vic la chn thch hp chloranilat kim loi, h thng
dung mi v pH.
5.5.6. Tinh ch thuc th
Acid chloranilic c tinh khit cao bng s kt tinh t nc nng. sn phm trn
th trng thng c tinh khit cao. Nhng kim loi (tp) c th xc nh c trn
tro sunfat. N c th c th nghim bi mt thit b o acid trong dung dch nc
vi phn tch trng lng ca chloranilat kim loi (v d kt ta mui canxi pH 4,4,
k tip em cn sau khi sy kh 105
o
C).
Chloranilat kim loi dng xc nh anion s i hi nghim ngt trong ho hc
lng php v nhng cht lm nhim nh cation trong mui ho tan th khng vt
qu gii hn v cng khng d acid chloranilic. C th kim tra c khi ra mu, i
theo sau l phn tch nhng cation c trong phn nc lc. Sau cng c th xc nh
theo quy trnh.
5.5.7. ng dng trong phn tch
5.5.7.1 S dng nh l thuc th to ta
Nhng cation to ta c vi acid chloranilic c th xc nh bng phng php


96


trng lng hoc mt vi phng php khc. Mt vi v d c tm tt trong bng
7.21.
5.5.7.2 S dng nh l thuc th trong php o quang cho nhng cation
Ty thuc vo phng php phn tch nh lng, s gim hp thu dung dch
ca acid Chloranilic d c nng bit trc bng to ta khng tan chloranilat kim
loi. S hp thu c o phn cht lng ni bn trn sau khi li tm hoc phn nc
lc sau khi lc.
C th la chn, Chloranilat kim loi khng ho tan tch ra c ho tan tr li
trong acid mnh hoc dung dch kim EDTA v ion chloranilat (HL
-
) c phc hi v
c th xc nh bng my quang ph. Quy trnh ny i hi s chnh xc cao.
Phng php khc thng dng h s hp th ca chelate ho tan c nhum mu
cao ca acid chloranilic vi ion kim loi. Chng hn Zr(IV) hoc Mo(VI)
Dung dch nc ca chloranilic acid hoc chloranilat natri c nng thch hp
thng c s dng o quang, chloranilic acid th n nh hn. Dung dch nn gi
ni ti mt. Dung dch chun cho o quang c pha ch khi cn.
5.5.7.3. S dng nh l thuc th trong php o quang cho nhng anion
Nhng anion c th c xc nh vi s hp thu quang ph, s dng chloranilat kim
loi kh ho tan, c s trn nguyn tc miu t phn trn. Trong nhiu trng hp,
nng ion acid chloranilat t do th o bc sng 530 nm. Nhiu th d v o
quang xc nh nhng anion s dng chloranilat kim loi c tm tt trong bng 5.12
Bng 5.12. CHLORANILAT kim loi v nhng phn ng vi anion
Chloranilat
kim loi
Du
hiu
Anion iu kin PTP
Gii hn
xc nh
(ppm)
BaL
tinh
th
nu
tm
SO
4
2-

pH 4,0 4,6;
trong 50%
ethanol, pH 8
SO
4
2-
+ BaL + H
+

HL
-
+ BaSO
4

0,3 100
BO
3
3-

m NH
4
Cl
Tartarat
H
3
BO
3
+BaL+tartarat
HL
-
+ phc Ba
borat
0,3 10
SrL
bt
nu
en
F
-

pH 4, trong iso-
PrOH
2F
-
+ SrL + H
+
HL
-

+ SrF
2

5
Ag
2
L
bt
xanh
xm
Cl
-

2Cl
-
+Ag
2
L+H
+
HL
-

+ 2AgCl

HgL
bt
xanh
thm
Cl
-

pH 2, trong 50%
methylcellosolve
2Cl
-
+ HgL+H
+
HL
-

+ HgCl
2

0,05 200


97


ThL
2

bt
nu
en
F
-

pH 7, trong 25%
Methylcellosolve
6F
-
+ThL
2
+ 2H
+

2HL
-
+ThF
6
2-
hoc
2F
-
+ ThL
2
+ H
+

HL
-
+ ThLF
2

0,01 100
CuL
bt
nu

S
2-

S
2-
+ CuL + H
+
HL
-

+ CuS
0 10, CN
-
,
oxalate,
tartarat,
citrat gy
tr ngi
La
2
L
3

bt
xm
en
F
-

pH 6,5 7, trong
50% Ethanol
hoc trong 50%
methylcellosolve
6F
-
+ La
2
L
3
+ 3H
+

3HL
-
+ 2LaF
3

2 200
PO
4
3-
pH 7
2PO
4
3-
+ La
2
L
3
+
3H
+
3HL
-
+ 2LaPO
4


3 300


5.5. CUPFERRON
CTPT: C
6
H
9
N
3
O
2

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: C
6
H
9
N
3
O
2

Cng thc cu to:
N
N O
ONH
4

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 164
o
C, thng hoa trn


98


30
o
C.
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 51
o
C) 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 (u = 0,1 NaClO
4
, 25
o
C), K
D
(CHCl
3
/H
2
O) pH > 3 vi HCl
hoc HClO
4
= 142 (nhit phng) K
D
(ethylacetat/nc) = 285,6 v K
D
(CCl
4
/H
2
O) =
2300 (15
o
C).
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:
N
O
N = O
M
n+
/n

V vy, Cupferron c s dng rng ri nh l mt dung mi chit trong phng
php tch cc ion kim loi. Chloroform l dung mi thch hp trong hu ht cc
phng php chit. Phng php chit cc ion kim loi vi Cupferron c nghin
cu tng tn: pH ca phng php chit nh lng, gi tr ca pH
1/2
v nh hng
ca hng s chit ln h chloroformnc....
Khi hu ht cc kim loi Cupferrate khng mu, Cupferron khng c xem nh l
thuc th o quang thit thc xc nh hm lng kim loi.
5.6.4.2. Dng Cupferron nh l dung mi chit :
Cupferron cc k c ch trong vic tch nhm ca Fe(III), Sn(IV), Ti(IV), U(IV),
V(V), Zr(IV) v mt s kim loi khc t cc nguyn t cn li. Trong mt vi trng
hp, cc cu t chnh c tch ra t phng php chit vi Cupferron, cho php tch
c hm lng vt trong php phn tch. Trong mt s trng hp khc, mt lng
nh cc cht cn phn tch c tch t cc cht nn bng phng php chit kim loi
Cupferrate trc khi xc nh. Cc kim loi sau khi chit c thu li bng cch hp
th t (HNO
3
+ H
2
O
2
) cn sau khi lm bay hi dung mi hoc bng cch chit ln


99


na vi dung dch acid mnh hn.
Tnh chn lc ca phng php chit c th c ci thin bng cch chn acid
thch hp trong pha nc v cht che thch hp, nh l EDTA hoc tartarate. y l
phng thc thc hnh ph bin thm dung dch Cupferron lng hoc Cupferron
rn vo dung dch mu trc khi chit vi dung mi hu c. Bng 5.13 tm tt mt
s v d in hnh v phng php tch bng cch chit Cupferron.
Bng 5.13. Mt s v d ca h chit cupferron
Ion kim loi
c chit T
iu kin Dung mi
All,Be,Ce(III), (IV),
Hf, Nb, Sn(II),(IV),Ta,
Ti,U(IV),(VI), V,Zr,
t him
_

pH 5,5 5,7,
EDTA,
citrate

4-ethylpentan-
2-one

Ti

Bi, Cd, Co(II),
Cu,Mn(II),Mo,
Ni,V(V),W,Zn
Dung dch
kim long,
EDTA,
tartarate, S2-
CHCl
3


Ti Thp
pH 5,5,
EDTA, Ce
MIBK
Ag,As(III)(IV), Cd, Co, Hg,
Ni, Pb,Se(VI),Te(IV),
U(VI), Zn
HNO
3
0,1N

CHCl
3

Bi, aFe(III), Ga,
Mo(VI), Sn(IV),
Ti,U(IV), V(V),Zr
Mo, W
Cht liu lm nhng b
phn nhn to trong c th
(sau khi hp th t v
chit dithizon)
H2SO4 6N

Iso-AmOH

Fe(III),Mo(VI), Sn(IV),
Ti(IV), V(V), Zr
U(VI)

Acid v c
long

CHCl
3
, hoc
ethyl acetat

Bi

Ag, Al, As, Cd, Co, Cr, Hg,
Mn, Ni, Pb, Sb, Zn
1NHCl

CHCl
3

Fe Al, Cr, Mn, U Ti, V, Zn CHCl
3

Ga

Al, Cr, In, t him
H2SO4 2N ,
Fe, Ge, Nb,
Ta, Ti, V, Zr
CHCl
3


Th

Kim loi ha tr III

pH 0,3 1,
Hf, La, U(VI)

Benzene +
iso-AmOH (1
: 1)
Actinoids, Am Pu(III)
HCl 0,5
1,5N
CHCl
3

K hiu a: Bi c th c chit li bng H
2
SO
4
2N, da vo cc nguyn t cn li
trong pha hu c.
H chit chloroformCupferron ca Al l ng ch . Theo Sandell, K
ex
ph thuc


100


vo pH v thi gian trc khi chit. K
ex
c tm ra hn ch qu trnh tng pH v
nng ion Cupferron khi qu trnh chit xy ra ngay sau khi thm Cupferron v dung
dch Al. Qu trnh chit Fe(III) vi s c mt ca Al c th xy ra dung dch nc
hoc trong acid HCl 1Mv sau khi thm Cupferron th qu trnh chit c thc hin
ngay lp tc.
trnh tnh khng n nh ca dung dch Cupferron, Fe(III), Cu(II), hoc Al
Cupferrate c dng chit Mo, Nb, Sb, Sn, Ta, Ti, V v Zr, da vo s trao i
ca qu trnh chit.
5.6.4.3. Dng Cupferron nh l cht kt ta:
Bn cnh phng php xc nh kim loi bng phn tch trng lng, Cupferron
c dng nh cht kt ta tch nhm kim loi. Mt s v d v phng php tch
bng cht kt ta c trnh by bng 5.14.
Bng 5.14. Mt s v d ca kt ta cupferron
Ion kim
loi
iu kin Ch
Ga(III) H
2
SO
4
2N Tch t Al, Cr, Sc, U(VI), Zn, t him.
Ga(III)
pH 4,55,5, EDTA, hn hp
MgO sau khi ng kt ta vi Sn
hoc Ti
Ta v hu ht tt c cc ion Be, Ti, U,
PO
4
3-
(trong Nb-Mo), t Nb n Ta
(30:11:30)
Hf(IV)

H
2
SO
4
610 v/v %

Tch t Al, Be, Cr, U, Th l ppt ti pH
18
Ti(IV)

H
2
SO
4
, acid tartaric, EDTAa Si, U, V, W, PC43- gy nh hng
U(IV)

HCl 12 M , HClO
4
hoc H
2
SO
4
,
05o, sau khi gim NH
2
OH
hoc S2O4
Bi, Fe, Ga, Hf, Mo, Nb, Pa, Po, Sn, Ta,
Ti, V, Zr v actinit ha tr 4
U(VI)
pH7, EDTA, tartarat

Be v mt lng ln Ti, Zr, F-, CO
3
2-

a: v tr pha ch Cupferron t phenylhydroxylamine v (NO)NH
4
, KLPT = 205,21).
Bt trong sut mu vng nht, im nng chy t NaNO
2
.
5.6..5. Cc thuc th khc c cu trc tng t:
5.6.5.1. Neocupferron:
Mui amoni ca nnitroso1naphthylhydroxylamine (C
10
H
7
N 125
o
n 126
o
C.
Kh nng tan trong nc (6,0g/100ml 25
o
C). Tnh cht vt l v phng php to
phc tng t nh Cupferron: pKa = 4,1 v K
D
(CHCl
3
/H
2
O) = 1,3.10
3
. N bn hn
Cupferron trong dung dch nc v khi lng ca nhm naphthyl c th c xc
nh bng phn tch trng lng.
5.6.5.2. nNitrosoncyclohexylhydroxylamine:
ng ng cyclohexyl ca Cupferron. Mui amoni c tn l hexahydro
Cupferron; im nng chy 140
o
C v phn ly 250
o
C. N bn hn Cupferron,
trng thi rn tt nh l trng thi dung dch nc (mt dung dch 10
-4
M trong HCl


101


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.
5.6. THUC TH HN HP O,ODONATING
5.7.1. Acid chromotropic:
5.7.1.1. Tn ch th v cng thc ha hc:
Tn ha hc: 1,8dihydroxy3,6acid naphthalendisufonic, mui disodium.
Tn thng thng: Acid chromotropic.
Cng thc phn t: C
10
H
6
O
8
S
2
Na
2
.2H
2
O
Cng thc cu to:
OH
OH
SO
3
Na NaO
3
S

5.7.1.2. c im ca Acid chromotropic:
To phc tan c mu vi cc ion kim loi.
To mu vi NH
3
.
5.7.1.3. Cc tnh cht ca Acid chromotropic:
Acid chromotropic c phn t lng bng 400,28.
L bt trong sut mu vng, khng mi di 300
o
C, d tan trong nc, nhng
khng tan trong dung mi hu c; pKa
3
(OH) = 5,36 v pKa
4
(OH) = 15,6 (20
o
C, u =
0,1).
5.7.1.4. Tnh cht chun ca Acid chromotropic:
Acid chromotropic hp th trong dung dch CuCl2, t 0,05 n 5ppm (520nm) v
formaldehyde (570nm).
5.7.2. Dinitronaphthalenediol:
5.7.2.1. Tn ch th v cng thc ha hc:
Tn ha hc: 2,4Dinitro1,8dihydroxynaphthalen, DNNDO.
Tn thng thng: Dinitronaphthalenediol.
Cng thc phn t: C
10
H
6
N
2
O
6
.
Cng thc cu to:


102


OH
OH
NO
2
NO
2

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 180
o
182
o
C.
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 (ML
2-
), 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, = 10,3.10
4
, 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: C
15
H
10
O
7
.2H
2
O
Cng thc cu to:
OH
O
OH
HO
OH
O
HO

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:


103


Morin c phn t lng bng 338,27.
L bt trong sut khng mu hoc mu vng nht, im nng chy t 285
o
C n
300
o
C; hu ht khng tan trong nc (0,09% 100
o
C), nhng d tan trong dung dch
kim hoc dung mi hu c tr ete v acid acetic. Cht rn chuyn sang mu nu nh
s oxi ha; gi tr pKa t proton u n proton th 5 l 1; 4,8; 7; 9 v 13.
5.7.3.4. Cc tnh cht chun ca Morin:
Morin l mt trong nhng polyhydroxyflavone c xem nh l mt cht phn
tch. Tnh cht quan trng nht l morin l mt loi thuc th hunh quang. Morin cho
ra mt hunh quang mu xanh nht ti pH t 4 n 9, nhng n tng ng k nh to
phc vi cc ion kim loi nh Al (pH 3;
ex
= 440nm;
em
= 525nm); B (HCl long,
365nm, 490nm), Be (NaOH 0,04N, 460nm, 540nm); Ga (pH t 2,5 n 2,9, 400nm,
445nm); Th (HCl 0,01N, 365nm, 404,7nm); Zr; Hf (HCl 2N, 450nm, 502nm); v t
him (pH 2,5; 401nm, 501nm). V vy, cc nguyn t ny c th c xc nh bng
cch o hunh quang. EDTA v DTPA thng c dng nh l cht che.
Morin cng to phc c mu vi cc ion kim loi khc nhau, nh Th (vng), Ga,
In, U v Zr (nu trong dung dch kim NH
3
) v c th c dng nh l mt cht
o quang i vi cc nguyn t ny, nhng xc nh hm lng fluor nhy hn nhiu.
5.7.4. Alizarin :
5.7.4.1. Tn ch th v cng thc ha hc:
Tn ha hc: 1,2Dihydroxyanthraquinone3acid sulfonic, Alizarin S, Alizarin
Carmin, C.I.Mordant Red 3.
Tn thng thng: Alizarin .
Cng thc phn t: C
14
H
7
O
7
SNa.H
2
O.
Cng thc cu to:
O
OH
SO
3
Na
O
OH

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 H
2
SO
4
c to thnh dung dch
mu cam; pKa
2
(OH) = 5,39 v pKa
3
(OH) = 10,72 (25
o
C, u = 0,5). Dung dch
nc cho bit hp thu ln nht ti bc sng 420nm (pH < 3,5) hoc ti bc sng


104


515nm (pH > 3,5).
5.7.4.4. Tnh cht chun ca Alizarin :
Alizarin to phc tan khng tan c mu vi nhiu ion kim loi v c xem nh
l mt cht xc nh Al, F
-
, v BO
3
3-
v nh l mt cht o quang i vi Al (pH t
4,4 n 4,6, = 1,8.10
-4
ti bc sng 490nm, t 0 n 0,8 ppm), Be (pH t 5,4 n
5,6; 480nm; = 4,3.10
3
, t 0,2 n 4,7ppm), Zr (pH t 3,9 n 4,6, trioctylamine, chit
vi toluene, 538nm), v B (pH t 7,7 n 8,2, EDTA, = 1250 ti bc sng 426nm).
Bn cnh cc nguyn t ny, cc ion kim loi di y c xc nh vi Alizarin :
In, Mo, Rh, Zn, v t him.
Nhiu hydroxyanthaquione bao gm quializarin (1,2,5,8tetrahydroxy
anthaquinone, C
14
H
8
O
6
, KLPT = 272,21) c nghin cu nh l thuc th i vi ion
kim loi, c bit l Al, Be v B.
5.8. Stillbazo:
5.8.1. Tn ch th v cng thc ha hc:
Tn ha hc: Stilbene 4,4 bis (1azo) 3,4 dihydroxybenzene 2,2 acid
disulfonic.
Tn thng thng: Mui diamoni.
Cng thc phn t: C
26
H
18
O
10
N
4
S
2
.2(NH
4
).
Cng thc cu to:
HO
OH
N = N
SO
3
NH
4
CH = CH
OH
N = N
SO
3
NH
4
OH

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 3,46.10
4
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.


105


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.
CH
2
C
C
O
O
R
R
CH
C
C
O
O
R
R
H

5.9.5. Phn ng to phc v tnh cht ca phc:
Sau khi loi proton, dng enol ca diketone c xem nh l mt anion ha tr 1,
nh hnh thnh phc kim loi vi cu trc di y:
CH
C
C
O
O
M
1/n
R
R

Tt c cc cu trc tng t ca cc phc diketone ph thuc vo cc phc mang
in tch ng lp bo ha, chng c m t bng im nng chy tng i thp
hn, p sut hi nc tng i cao hn v ha tan tt trong cc dung mi hu c
khc nhau. im nng chy, nhit thng hoa, v cc tnh cht vt l khc ca kim


106


loi diketonate c th c tm thy bng nhiu cch khc nhau: i vi phc AA
(1); i vi phc BzA (2); i vi phc DPM (4); i vi phc TAA (5); i vi phc
HFA (6), i vi phc TTA (7); i vi phc FTA (8); i vi phc PTA (9); i vi
phc BFA (10); i vi phc FOD (11).
Bng 5.15 : Tnh tan v h s phn ly ca Diketone
Tnh tan (g/100ml) LogKo -
Diketone Nc Benzene CHCl3 CCl4 Benzene/
nc
CHCl3/nc CCl4/nc
(1)AA 17,3 C th
trn
C th
trn
C
th
trn
0,57;
0,74
1,21

0,50

(2)BzA

3,9.10-
2

63,3

40,5

30,8

3,14

3,44; 3,60 2,82

(3)DBM 1,3.10-
4
53,8 40,4 29,2 5,35 5,40 4,51
(4)DPM 1,7.10-
2
- - - - - -
(5)TAA - - - - 0,28 0,53 0,32
(7)TTA 2.10-2 - - - 1,62 1,73 1,30
(10)BFA 3.10-1 - - - - - -
Vng pH tt nht ca s hnh thnh phc ph thuc vo bn cht ca cc ion kim
loi v diketone. Trong nguyn tc, phi t c gi tr pKa thp hn to phc vi cc
ion kim loi vng pH thp hn.
Kim loi diketonate thng khng tan trong nc, nhng tan trong cc dung mi
hu c khc nhau. V vy, diketone c chp nhn nh l dung mi cho qu trnh
chit. Trong trng hp khng c in tch, nhng cc phc ng ngbo ha, nh
NiL
2
.2H
2
O hoc CoL
2
.2H
2
O, s hin din ca dung dch ng lp lm gim s phn ly
ca phc vo pha hu c. Tuy nhin, trong mt s trng hp, phn chit v t l chit
c th tn dng bng cch s dng kt hp phi t b tr khng mang in nh l
pyridine hoc 1,10phenanthroline hoc bng cch chn dung mi tng ng nh
MIBK hoc butanol, thay v dng dung mi khng hot ng.
V AA (1) l cht lng, hu ht cc ion kim loi c th c chit bng chnh n
hoc dung dch ca n trong cc dung mi hu c khc nhau (benzene, carbon
tetrachloride, hoc chloroform). Tuy nhin, tnh tan ca mt s kim loi
acetylacetonate khng mang in trong pha nc khng th b qua, c bit l khi
acetylacetone khng pha long c dng nh cht chit, v tnh tan tng i cao
trong nc ca (1) tng so vi tnh tan ca phc trong nc. V vy n c nhiu thun
li hn khi dng dung dch ca n trong dung mi hu c.
S cn bng chit c th nh hng n BzA (2), DBM (3) v TTA (7) chm hn
so vi AA (1). Khuynh hng ny r rng hn so vi TTA v c bit l khi nng
anion thp (trong dung dch acid cao hoc trong tng nng thuc th thp). T l
cng ph thuc vo tnh cht ca kim loi. Tuy nhin, (7) c s dng rng ri trong


107


qu trnh tch cc nguyn t actinoid v lanthanoid. Gi tr logK
ex
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















5.9.6. Tinh ch thuc th nguyn cht:
-Diketone bao gm trong phn ny l cc hp cht hon ton xc nh v c th
c lm sch bng cch chng ct phn on ti p sut thp. Mu th c lm sch
qua phc kim loi ca n nh Cu(II) c th c iu ch d dng bng cch trn dung
dch ng acetat vi dung dch ru ca diketone. Sau khi tinh ch bng cch kt
tinh li, phc ng c to ra v sau lm sch bng cch chng ct.
tinh khit ca diketone c th c kim tra bng cch quan st sc ph kh
ca chng hoc bng cch chun trong dung mi kh (trong methanol vi
(Bu)4NOH 0,1M, dng ch th Crystal Violet).
5.9.7. ng dng vo phn tch:
5.9.7.1. Dng nh l cht chit:
Kh nng tch kim loi bng cch chit dung mi vi diketone c chng
minh bng hc t. Tuy nhin, iu kin chit trong tng trng hp ring bit c th b
nh hng nhiu bi nhiu nhn t, nh khuynh hng thy phn ion kim loi, t l
Hnh 5.10 Ph hp th
ca Cu(II)
Hnh 5.11: Ph hp
th ca phc uranyl


108


chit, nng ca thuc th .v.v
Kh nng chit ca mt s ion kim loi vi acetylaceton (1) nh l mt chc nng
ca pH c minh ha hnh 5.12 v 5.13. Cc ng cong ng dng vi thenoyl
trifluoroaceton (7) c trnh by hnh 5.14.


Hnh 5.12. Kh nng chit ca Be, La, Mo(IV), Sc v Th bng
acetylacetone 0,1M trong mi trng pH ca benzene.
Hnh 5.13. Kh nng chit Al, Cu(II), Fe(III) v Sn(II) bng
acetylacetone 0,1M trong mi trng pH ca benzene.


109



5.9.7.2. Dng nh l cht o quang:
Nh trnh by phn trc, nhn chung diketone khng l thuc th qu nhy
v chn lc thuc th sinh mu i vi kim loi. Tuy nhin, trong mt s trng hp,
chng c dng nh cht o quang cho qu trnh chit . Thenoyltrifluoroaceton (7)
c s dng rng ri cho mc ch ny. Mt s nguyn t t him cng c xc
nh bng cch xc nh hm lng bng php o hunh quang
5.9.7.3. Dng nh thuc th bay hi i vi ion kim loi:
Mt s kim loi diketonate bay hi nhanh n ni m chng c th c tch
bng php ghi sc kh lng hoc bng phng php thng hoa phn on. Cc nguyn
t c kim tra nhanh bng phng php sc k kh l Al, Be, Co, Cr, Fe, Hf, In, Mg,
Mn, Ni, Pb, Rh, Sc, Th, Ti, U, V, Y, Zr v t him. Trong thc tin, phc kim loi
c ha tan trong dung mi hu c d bay hi (t 0,5% n 5%), nh benzene hoc
chloroform, v 0,1 n vi l dung dch c tim vo. Nhit ca b phn tim v
my d c bo qun t 20
o
n 40
o
C cao hn nhit ct. nhy ca my d
phn ln ph thuc vo bn cht ca ion kim loi trung tm hn l ph thuc vo phi
t.
Vic tch phc kim loi bng phng php thng hoa phn on hoc phng php
nu chy vng c nghin cu tng tn.
5.9.7.4. Dng nh NMR thuc th shift:
Mt s lathanide diketonate c bit n nh l thuc th shift NMR m n
di chuyn cc du hiu proton NMR ca cc hp cht hu c khc nhau c cc nhm
chc nng hon ton tri ngc nhau. Vic di chuyn c to ra bi gii hn tip xc
nhn to v s nh hng qua li gia phn t hu c v v tr phi tr cha no ca ion
thun t lathanide ca chelat.
Phc Eropium c bit di chuyn du hiu proton v pha t trng yu hn v
phc Pr v pha t trng cao hn. Cc thuc th ny thng rt d ht m v i khi
Hnh 5.14. Kh nng chit ca Ac, Bi, Pb, Po, Ra, Th v
Tl(I)(III) vi MTTA(7) trong mi trng pH ca benzene.


110


hydrat ha, chng tr nn rt kh tan trong dung mi hu c. V vy, n thch hp hn
trong vic bo qun thuc th trong bnh ht m so vi P
2
O
5
.
Yu cu ca cc phi t tr thnh 1 thuc th shift l:
* Phc phi c hng s to thnh cao so vi kh nng nhn xt phn t hu c.
* Thuc th shift khng phi a ra du hiu proton trong vng quan st.
* Thuc th shift phi c ha tan va trong dung mi hu c i vi php
o NMR
5.10. PYROGALLOR V BROMOPYROGALLOL
O
S O
3
-
X
O
O H O H
H O
X
( 1 ) X = H
( 2 ) X = B r

5.10.1. Danh php (Bng 5.16):
PR: Pyrogllolsulfonephthaline.
BPR: 5,5 dibromopyrogallol sulfonepthaline.
5.10.2. Ngun gc v phng php tng hp:
PR c tng hp bng phng php ngng t osulfobenzoic anhydride vi
pyrogallol.
BPR c to thnh t qu trnh brom ha.
5.10.3. Tnh cht ca thuc th:
PR v BPR: l tinh th dng bt mu sm khi kt hp vi kim loi sng t tan
trong nc, alcohol v trong dung mi hu c khng phn cc.
Trong mi trng acid mnh c mu cam, mu trong mi trng trung tnh,
mu tm trong mi trng kim.
S phn ly dng acid ca thuc th tng t nh Pyrocatechol Violet, v c vit
di dng sau. Hng s phn ly c tng kt trong bng 5.17





5.10.4. Phn ng to phc v tnh cht ca phc cht:
PR v BPR lin kt vi Phenylfluoronl v phc vi mt s kim loi to thnh dung
dch chelate c mu. Dng dung dch ca PR v BPR (mu trong mi trng trung
H
5
L
+
H
4
L H
3
L
-
H
2
L
2 -
HL
3 -
L
4
cam Tm


111


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, UO
2
2+
, 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 (Na
2
CO
3
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 pH 7,9 8,6 (H
2
L
2-
)
max
= 542nm; = 4,3. 10
4

BPR pH 5,6 7,5 (H
2
L
2-
)
max
= 558 nm; = 5,45. 10
4

5.10.6. ng dng trong phn tch:
L ch th kim loi cho qu trnh chun chelate ca Bi, Co (II) , Ni, Pb. Chng
cng c dng nh ch th trong phng php trc quang i vi mt s kim loi
nng.
BPR c s dng rng ri nh l mt thuc th phn tch hn so vi PR. BPR to
thnh phc 3 cu t sm mu vi 1,10phenanthroline v bc c s dng cho vic
xc nh trc quang bc v Ag gin tip dng xc nh cc anion, nh cc hp cht
halogen, cyanide.
5.10.6.1. S dng nh mt ch th kim loi trong phng php chun Chelate:
Nhng Ion kim loi c th c chun bng EDTA, s dng PR hoc BPR nh
cht ch th c lit k trong bng 5.18 v 5.19, dng A 0,05% dung dch ethanol
(50v/v%) , c th bo qun trong nhiu thng m khng b h hng.
5.10.6.2. S dng nh thuc th trc quang:
Nhng Ion kim loi c th xc nh bng phng php trc quang vi PR hoc
BPR trong dung dch c tng hp trong bng 5.20 v 5.21.
Chelate ca kim loi vi BPR c th c chit vi cation thch hp (hoc kt hp
vi acid amine) trong dung mi hu c nh 1 cp ion. Nhng v d c tng hp
trong bng 5.22.


112


Mu phn ng ca h AgphenBPR s bin i khi c mt ca phc anion nh:
cyanide, thiocyanide, sulfile v cc hp cht halogen. Trn thc t, phng php o
quang nh s pht trin cho vic xc nh 1 s anion.
5.10.7. Xc nh Ag bng phng php trc quang, s dng BPR v 1,10
phenanthroline:
Ly khong 40 ml dung dch mu (110 g Ag) cho vo bnh nh mc 50 ml c
cha 1 ml dung dch EDTA 0,1M, 1 ml 1,10Phenanthroline 10
3
M, 1 ml dung dch
ammonium acetate 20% v 2 ml dung dch BPR 10
4
M. nh mc dung dch n 50
ml sau em o quang tc th hoc trong vng 30 pht vi cuvet 4cm bc sng
635nm da vo mu trng.
Nu c Fe(II) trong dung dch th thm va phenanthroline n khi to phc ht
vi Fe(II) v phn ng vi Ag. Khi c mt U(VI), Th, hoc Nb, thm florua hoc
hydrogen peroxide trc khi thc hin phn ng to mu.
Khi c mt ca cht oxi ha, PR d b oxi ha, lm mt mu v tnh cht ny c
s dng cho vic xc nh Ce(IV), Cr(VI), v V(V) bng phng php o quang.
Phn ng mu ca phc PRMo (VI) vi protein (
max
= 600nm, 0 ~ 400 g/10 ml)
c s dng xc nh protein trong nc tiu.
Bng 5.16. Pyrogallol v Bromopyrogallol
STT Tn thuc th Danh php
Cng thc phn
t
KLPT
1 Pyrogallol red Pyorgallol sulfonephthalein, PR C19H12O8S 400,36
2
Bromopyrogallol
Red
5,5 - Dibromopyrogallol sulfo-
nepththalcin, BPR
C19H10O8Br2S 558,15


Bng 5.17. Hng s phn ly
Hp cht pKa2 pKa3 pKa4 pKa5
PR 2,56 6,28 9,75 11,94
BPR 0,16 4,39 9,13 11,27
Bng 5.18. S dng Pyrogallol trong chun chelate nh cht ch th.
Ion kim loi PH m Mu thay i ti im cui chun
Bi 2 ~ 3 HNO3 cam
Co(II) 10 NH3-NH4CL xanh hoc tm
Ni 10 NH3-NH4CL xanh hoc tm
Pb ~ 5 AcOH-AcONa Tm
Bng 5.19. S dng Bromopyrogallol trong chun chelate nh cht ch th.
Ion kim loi PH m Mu thay i ti im cui chun
Bi 2 ~3 HNO3 sm cam
Cd 10 NH3-NH4CL Xanh


113


Co (II) 9,3 NH3-NH4CL Xanh
Mg 10 NH3-NH4CL Xanh
Mn (II) 9,3 NH3-NH4CL Xanh
Ni 9,3 NH3-NH4CL Xanh
Pb ~ 5 AcOH-AcONa Tm
t him ~ 7 AcONa Xanh
Bng 5.20. S dng Pyrogallol nh thuc th o quang
Ion kim loi iu kin (pH) T l max (nm) x 104 Nng xc nh
Ag 7 - 390 1,0 -
Cu (II) 6 ML 582 0,95 0,25~2,3
Ga 4,5 ML 530 1,4 0,28~4,8
Ge 5 ML2 500 - 0,28~2
In 4,7 ML2 580 - -
Mo (VI) 5,0 ~ 5,3 ML3 587 8,15 0,04~0,3
Sb (III) 4,5 ML 520 0,25 0,3~3,0
Sb (V) 2 ~3 (60) ML 500 0,98 -
Ti (III) 2,7 - 610 7,6 0,6~3,12
W (VI) ML 576 6 ~1
Bng 5.21. S dng Bromopyrogallol nh thuc th o quang
Ion kim
loi
iu kin pH T l
max
(nm)
x 104
Nng xc
nh (ppm)
Lu
VO 2+ 4,4 ML2 540 0,17 3~7 -
W(IV)
HCl 1,0~1,3N
Zephiramine
ML 621 6,5 0,08~1,4 -
W (VII)
1M HCL,
CTMAB (X)
MLX2 610 8,4 0,03~2
Cht cn tr
Cr, Mn, Ti
Zr 5,0 ~5,4 ML3 670 4,5 0,16~1,4 -
t
him
5,6~7,5,
Septonex
-
680-
690
3,3~3,9 0,3~3 -


Bng 5.22. Chit cp ion ca cc chelate Bromopyrogallol (2)
Chelate kim loi Chit Ion
kim
loi
iu
kin
(pH)
t s max(nm) (x104) Amine (X) Dung mi
Vng
xc
nh
(ppm)
Ge(IV) 0,5
4,5
ML3 550 3,8 Diphenylguanidine Hexyalxohol

Nb 5 ML3 610 2,5 di-n-
octylmethylamine
Isopentylacetate 5,4


114


Ti(IV) 2,5 MLX4 630 3,75 4-
Amynoantipyrine
0,2
2
Ti(IV)

MLX2

Gelatine hoc
diphenylguanidine
Isoamyalcohol

V(V) 4(60o) MLX3 610 0,85 Diphenylguanidine Chloroform
(1:1)





115


CHNG 6
THUC TH O-N

6.1. THUC TH ALIZARIN COMPLEXONE
CH
2
COOH
CH
2
COOH
2H
2
O
O
O OH
OH
CH
2
N

C
19
H
15
NO
8
.2H
2
O (vit gn: H
4
L)
KLPT = 421,36
6.1.1. Danh php:
Cc danh php thng dng:
3 [Di(carboxymethyl)aminomethyl]1,2dihydroxyanthraquinone.
1,2Dihydroxyanthraquinone3ylmethylamineN.
nDiacetic acid.
Alizarin Complexone.
ALC.
6.1.2. Cc tnh cht ca ch th:
6.1.2.1. Ch th dng t do:
Lun tn ti dng acid t do ngm nc, bt tinh th mu vng nu, nhit
nng chy 190
o
C, hu nh khng tan trong nc, ether, alcohol v cc dung mi hu
c khng phn cc, nhng tan d dng trong dung dch kim. Mu ca dung dch ch
th thay i theo pH v cc nc phn ly ca ch th c trnh by theo s sau ( =
0,1):

Quang ph hp thu ca ch th trong dung dch cc gi tr pH khc nhau c minh
ho hnh 6.1.
H 4L H 3 L
-
H 2 L
2-
H L
3-
L
4
-
p K a
1

=
2,40
p K a
3

=

10,07

p K a
4

=

11,98

p K a
2

= 5,54

- COOH 2 O H
N
+
H 1 OH
vng
xanh


116



6.1.2.2. Phn ng to phc v cc tnh cht ca phc:
Cc ion kim loi to phc mu vi Alizarin Complexone c th c chia thnh 2
nhm. Nhm th nht l cc ion kim loi to phc (MHL) pH = 4,3 4,6, pH
ny ch th t do c mu vng. Nhm th hai l cc ion kim loi to phc tm
(ML) ti pH = 10, pH ny ch th t do c mu .
Nhm 1: Ba, Ca, Cd, Mg, Mn(II), Ni, Sr.
Nhm 2: Al, Cd, Ce(III), Co(II), Cu(II), Fe(III), Ca, Hg(II), In, La, Mn(II), Ni, Pb,
Th, Ti(III) (IV), Zn, Zr, v t him.
Hng s to thnh ca phn ng:
M
2+
+ HL
3-
MHL
-
lgK = 12,19 (Zn), 12,23 (Ni), 12,25 (Co), 14,75 (Cu).
Cn phn ng:
HML
-
+ M
2+
M
2
L + H
+
l lgK = 0,8 (Pb) v 3,5 (Cu) ( = 0,1, 20o ).
Cu to ca MHL nh sau:
O
OH
2
OH
2
O
CH
2
C
O
M
CH
2
O
C
H
2
C
N
O
O O
H

Phc ca cc ion t him pH ~ 4 chuyn thnh mu xanh khi c mt ion F
-

do 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.
400 500 600 700
Bc sng
(nm)
1.0
0.8
0.4
0.6
0.2
1.2
1.4
1
2
3
4
5

p

t
h

Hnh 6.1.
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;


117


O
O O
O M
CH
2
N
F
-
H
OH
2

Quang ph hp th ca phc LaHL v LaLF c minh ho hnh 6.2.
Phc mu xanh c th c chit vi dung mi hu c nu nh nc ion t
him c thay th bng phi t k nc nh alkinamine hay arylamine. Qu trnh
chit da trn tnh cht ca dung mi chit v cc amine, v isobuthanol hoc iso
amylalcohol cha ndiethylaniline 5% N cho kt qu tt nht. Hnh 6.3 minh ho
quang ph hp thu ca dng chit.
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 25
o
C v = 0,1
(KNO
3
)
Cn bng Hng s cn bng
700 400 500 600
Bc sng (nm)
0.2
0.4
0.6
0.8
1.0
1.4
1.2

p

t
h

450 550 650
1
2
3
Hnh 6.2. Quang ph hp th
ca phc La-ALC v phc
La-ALC-F.
(1) LaHL; (2) LaLF;
(3) s khc nhau gia LaHL
v LaLF; nng 0.002M; F
-
, 20g.
500 550 600 650 700
0.4
0.6
0.2
0.8
Bc sng (nm)

p

t
h

Hnh 6.3. Quang ph hp
th ca phc La-ALC-F
trong dung dch iso-
amylalcohol cha 5% N,N-
diethylaniline; F,0.5ppm.


118


H thng La-ALC
2M + 2H2L M2L2 + 4H+
2M + 2H2L M2HL2 + 3H+

lgK202 = 0,28
lgK212 = 5,58
H thng La-ALC-F
2M + 2H2L + F- M2HL2F + 3H+
2M + 2H2L + F- M2H2L2F + 2H+

lgK2121 = 9,70
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 BO
3-
v PO
4
3-
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 La
2
O
3
trong 2,5 ml HCl 2N. Cui cng, nh mc ti vch bng
nc ct. Dung dch ny c n nh trong 2 tun.


119


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: C
19
H
15
O
10

KLHT = 417,33 vC
Cng thc cu to:
O
O
OH
OH
OH
OH
CH
2
N
CH
2
COOH
CH
2
COOH

Phc ca cc nguyn t t him (Ce, Nd, Pr, v Sm) vi thuc th ny hot ng
tng t nh phc ca Alizarin complexone. nhy i vi vic xc nh fluoride
gp 1,5 ln so vi phc ca Alizarin complexone. N to thnh phc mu vi borate


120


trong mi trng H
2
SO
4
m c, v th c dng xc nh boron trong cc hp
cht.
6.2. THUC TH MUREXID
Cng thc phn t: C
8
H
4
O
6
N
5
.NH
4

KLHT = 284,19
Cng thc cu to:
NH
N
H
O
O ONH
4
N
NH
H
N O O
O

6.2.1. Danh php:
5[(Hexanhydroxy2,4,6trioxo5pyrimidinyl)imino]2,4,6(1H,3H,5H)yrimi
dinetrione, mui monoammonium; 5,5nitriloddibarbituric mui amino acid ; amino
acid purpurate; amino purpurate.
6.2.2. Ngun gc v phng php tng hp:
C th mua trn th trng. iu ch bng phn ng ca alloxantine vi ammonium
acetat trong acid acetic si.
6.2.3. Tnh cht ca thuc th:
Murexid l tinh th dng bt c mu ta, c mu xanh sng khi b nh sng chiu
vo. N th khng b nng chy cng nh khng b ph v nhit di 300
o
C.
Dung dch vi nc c mu ta nhng mu b phai nhanh. Murexid tan trong nc
lnh v ethyleneglycol, tan nhiu trong nc nng v khng tan trong alcohol v ether.
Phng trnh phn ly:

pKa
1
=0 pKa
2
=9,2 pKa=10,9
H
5
L H
4
l
-
H
3
L
-
H
2
L
-



121


S hp th quang ph ca H
4
L
-
v H
2
L
-
trong dung dch nc c trnh by hnh
6.4 sau:

6.2.4. Phn ng to phc v tnh cht ca phc:
8.2.4.1. Phn ng to phc:
Trong dung dch trung tnh hoc dung dch kim ion purpurate hnh thnh phc
mu chelate vi cc ion kim loi nh Ca, Cu(II), Co(II), Ni v Zn Mu ca cc
chelate ty thuc vo bn cht ca kim loi v pH ca dung dch.
NH
N
H
O
O O
N
NH
H
N O O
O
M

Trong trng hp chelate ca can xi s cn bng c biu din nh sau:

6.2.4.2. Tnh cht ca phc
Cc chelate ca Cu(II), Ni(II), Co(II) c mu vng v chelate ca Zn Ca th c mu
vng cam.
6.2.5. tinh khit ca thuc th:
Thuc th rn thng thng c cha mt lng nh v phn trm (20%) ca
Murexid (amino acid purpurate) v mt lng ln ca uramil, alloxantine, tuy nhin
pKa
2
=8,2 pKa
3
=9,5
CaH
4
L
+
CaH
3
L CaH
2
L
-

Hnh 6.4. Ph hp th ca murexit v
chelat kim loi murexit; , murexit
(dung dch trung tnh, H
4
L
-
); ---------,
murexit (dung dch km mnh H
2
L
3-
);
, Ca- murexit (CaH
2
L
-
) ti pH =
13; , Cu(II) - murexit (CuH
2
L
-
) ti
pH = 8.


122


t mu khng tinh khit lm cho n tinh khit th cng rt kh khn.
mu c tinh khit cao c th c iu ch t alloxantine tinh khit sao cho
ph hp vi tiu chun.
xc nh cht th trong thuc th tinh khit bng cch chun vi TiCl
3
hoc
c th nh gi bng cch o hp th ca dung dch trong nc (0,5mg/100ml
bc sng 520nm, = 120.10
4
).
TT PH Mi trng Mu thay i
Ca 12 NaOH 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
25
o
C 0,1; = 0,1
6.3. HYDROXYLQUINOLINE
Cng thc phn t: C
9
H
7
NO
KLPT = 145,16


123


N
OH

6.3.1. Danh php: 8Quinolinol, oxine.
6.3.2. Ngun gc v phng php tng hp:
C th tm thy trong cng nghip. Thu c t s sunful ha quinoline, v bng
phn ng kim nng chy.
6.3.3. S dng trong phn tch:
Nh l mt thuc th tch chit, chit trc quang, v l cht to ta cho nhiu
ion kim loi ngoi tr cc cation ho tr mt. chn lc c th c ci thin bng
cch chn gi tr pH thch hp v dng nhng tc nhn che.
6.3.4. Nhng tnh cht ca thuc th:
L tinh th khng mu hoc kt tinh dng bt trong sut, im nng chy t 74
n 76
o
C, im bay hi khong 267
o
C, thng hoa trn 310 (2.10
-2
Torr); hu nh
khng tan trong nc v erther; d dng tan trong nhng dung mi hu c v nhiu
acid nh acetic acid hoc nhng acid v c. S ho tan trong dung mi khan th khng
mu, nhng s c mu vng trong mi trng m. 8Hydroxyquinoline th n nh
th rn cng ging nh trng thi dung dch, nhng nn bo qun ch ti; pKa
(N+H) = 4,85 v pKa (OH) = 9,95 ( = 0,1NaClO
4
, 250).
Bng 6.3: C IM QUANG PH CA OXINE
Dng max

(nm)

(103)
Trung tnh (pH 7.6)
HL
239
305
32,4
2,63
Zwitter ion
HL

270
431
2,84
0,064
Cation (pH 1)
H2L+
251
308
319
3,16
1,48
1,55
Anion (pH 12)
L-
252
334
352
30,2
2,88
2,82
Bng 6.4. S SP XP CC H S CA OXINEV 2 THYLOXINE(25

0.20, = 0.10)
Dung mi hu c OXINE 2-Methyloxine


124


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
Nhng d liu hp thu quang ph ca thuc th trong vng UV c tng hp
trong bng 6.3. Hn na, nhng thay i r rt ca quang ph c quan st trn mi
dng ti nhng vng khc nhau ca proton. Quang ph ca oxine trung tnh trong
nhng dung mi hu c th ph thuc rt nhiu v c tnh ring ca dung mi, t cn
bng di y th c s bin i bi dung mi phn cc.

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 ZnL
2
.2H
2
O trong CHCl
3
, 2.10
-6
).
Fe
N
O
N
O
N
O
Ni
OH
2
O
N
O
N
OH
2
1
2

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
chelateML
2
, nhng trong vi pht chng tr thnh dng hydrad ho v tch ra khi
Neutral
Zwitter
N
O
H
N
+
O -
H


125


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.

Trong chloroform, oxine bn thn n cng c kh nng pht hunh quang yu di
nh sng UV, tuy nhin, nhng oxinate ca ion kim loi nghch t th c kh nng pht
hunh quang mnh trong iu kin tng t. Da trn nguyn tc ny, s xc nh du
hiu hunh quang ca nhng kim loi c a ra. Nhng oxinate kim loi pht hunh
quang mnh cho vic xc nh l Al (
max
= 510nm), Ga (526nm), Nb (580nm),
Sc(533nm), Zn (530nm), v Zr (520nm).
Nhng dung dch chloroform ca nhng oxinate kim loi biu din kt qu quang
Hnh 6.5. Ph hp th ca Al,
Fe(III) v UO
2
oxinates trong
chloroform. (1) Oxine; (2) Al 50
g; (3) Fe(III) 100 g; (4)
UO
2
2+
(100 g nh U).


126


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 H
2
S
hoc bng s chng ct hi nc sau khi aicd ho bng H
2
SO
4
im nng chy (73
n 75
o
C) 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 10
3
n 10
4
, 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 KBrO
3
d.
Sau thm KI, bromate d c xc nh bng cch chun iodine thot ra bng
dung dch Na
2
S
2
O
3
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, BiL
3
, CuL
2
, GaL
3
, InL
3
, MgL
2
,
SbOL.2HL, ThL
4
.HL, UO
2
L
2
.HL hoc (UO
2
L
2
)
2
.HL, v dung dch cha oxine, ion kim
loi, v urea (AlL
3
, BeL
2
, CrL
3
, MgL
2
, NbOL
3
). 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):
C
10
H
9
NO


127


KLPT = 159,19
N
OH
CH
3

Lp nh khng mu, im nng chy t 73 n 74
o
C, nhit nng chy khong
266 n 267
o
C; pKa (N+H) = 4,58 v pKa (OH) = 11,71 (50% dioxane, 250). C tnh
cht vt l hon ton gng nhau v to cnh d dng vi oxine, ngoi l vi Al v Be.
Al khng th to kt ta vi 2methyloxine. iu ny c gii thch bi s b tr
trong khng gian ca nhm methyl trn 2 v tr m khng to thnh cu trc ML
3
loi
chelate vi Al
3+
n th c bn knh ion kh nh. Mc d, 2methyloxine l mt cht
ging nh oxine nhng khi d nhiu vi Al gy tr ngi cho vic xc nh kim loi.
Tuy nhin, theo s vic gn y, Al c tch mt phn vi 2methyloxine trong
m acetate. iu ny cng c th c gii thch v s c mt ca ion acetate vi vic
hnh thnh mt phn ion vi bischelate (AlL
2+
) trong s chit chloroform.
Be c th to ta vi 2methyloxine to thnh BeL
2
, trong khi kt ta ny khng
hon ton vi oxine. Thuc th ny cng c s dng nh mt thuc th chit trc
quang cho mt nhm ion kim loi, gm Mn(II), Pd(II), v V(V).
8Acetoxyquinaldine (im nng chy t 63 n 640) c s dng nh mt tin
thn ca 2methyloxine trong phng php PFHS to ta ThL
4
, CuL
2
v InL
2
.
6.3.8.2. Oxine5sulfonic Acid:
C
9
H
7
NOS
KPPT = 225,22
N
OH
SO
3
H

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


128


nc c th tch ra bi dung mi thm hoc chloroform nh mt cp ion vi mt
chui alkylamine hoc Zephiramine cho trc quang.
Nhiu nguyn t ho hc c xc nh bng trc quang vi oxine: Au, Be, Bi, Ca,
Cu, Fe, Mg v nguyn t t him, nhng hp th phn t ca nhng oxit
khng cao hn 6.10
3
.
Mt vn khc c cp n, oxide kim loi c tch bng chloroform.
6.4. ZINCON

6.4.1. Danh php
o{2[(2Hydroxy5sulfophenylazo)benzylidene]hydrazino}benzoic acid,
2carboxyl2hydroxyl5sulfoformazinbenzene, 5ocarboxylphenyl)1(2
hydroxy5sulfophenyl)3phenylformazan.
6.4.2. Ngun gc v phng php tng hp:
Ch th Zincon c mi ni. N c chun b bng cch: cho 2aminolphenol4
sulfomic tc dng vi nhau.
6.4.3. Cch s dng php phn tch:
u tin n c gii thiu l mt thuc th (cht phn ng) nguyn th cho Cu(II)
v Zn, nhng by gi n cn c s dng l mt cht ch th kim loi v c ng
dng rng ri trong ngnh phn tch.
6.4.4. Tnh cht ca cht phn ng (thuc th):
Thng c cung cp nh l mui mononatri (NaH
3
L). N l cht bt mu tm
m, n ha tan nh trong nc v ethanol, d ha tan trong kim, to ra mt dung
dch m, v n khng ha tan trong cc cht hu c thng thng v nhanh chng
phn hy trong dung dch acid. Cu trc ha hc ca Zincon c lin quan n 1 cht l
diphenylcarbazone v trong dung dch c s cn bng phn ly proton trong dung dch
nc.
S khc nhau mu v gi tr pKa trong qu trnh pha ch c th l do mu mu
th khng trong sch. Ph hp th ca Zincon pH = 9 (HL
3-
) c minh hot hnh
8.6.

hng hoc
tm
Vng
Vng cam hoc
cam
tm
H
2
L H
3
L
-
H
2
L
2-
HL
3-
L
4-
pKa
2
= 4 - 4.5
pKa
3
=13(hoac>14) pKa
2
=7.9(hoac 8.3)


129


6.4.5. Phn ng v tnh cht ca cc hp cht:
Zincon mu vng (H
2
L
2-
) hoc cam (HL
3-
) pH = 5 9 to thnh dng ML mu
xanh l cc chelate tan c vi Co(II), Cu(II), Hg(II), Ni v Zn. H s hp th mol
ca cc chelate Cu v Zn l qu cao (CuL, pH = 5,0 9,0,
max
= 600nm, = 1,9.10
4
;
ZnL pH = 8,5 9,5,
max
= 620nm, = 2,3.10
4
, chnh v vy m Zincon c xem nh
mt thuc th o quang cho nhng kim loi ny, ph quang hp th ca Cu(II) v Zn
c minh ha hnh 6.6.

Cu trc ca kim loi cha c lm sng t, tuy nhin c th xem Zincon nh lm
mt ch th ph bin nht kt hp kim loi st vi 2 oxi (OH, COOH) v 2 Nit
(N=N1NH) khng c s liu no v cng thc ha hc ngoi tr cng thc sau:
3 2 2
HL Zn ZnL H
+ +
+ +


lgK = -1 (hoc -1,8)
6.4.6. Cch lm sch:
Zincon t cc ngun cung cp thng mi c th c s dng m khng cn lm
tinh khit cho cc mc ch phn tch chung. Tuy nhin, kim tra tinh khit cho cc
nghin cu ha l l cn thit, cc cht bn chnh l mui v c c th ly ra bng cch
s dng acid dilute acetic, cc cht bn hu c c th cho chy ngc,
6.4.7. ng dng phn tch:
6.4.7.1. S dng nh l thuc th o quang:
Zincon l mt thuc th o nh sng tng i nhy cm i vi Cu(II) v c bit
l Zn.
iu tr ngi chnh ca Zincon l thiu tnh chn lc v tnh n nh thp ca thuc
th, v vy, php o trc quang vi Zincon c ng dng vi mu th sau khi tch Zn
bng dung mi tch hoc qu trnh trao i anion cc du vt ca NTA (nitrilo triacetic
acid) cc mu trong mi trng nc c th c xc nh bng cch o gim ca
cht ht. Nc Zn, Zincon 620nm da vo phn ng sau:
| | | | NTA Zn Zincon Zn NTA Zincon + +


(pH = 8,5 9,5)
Nu NTA thp hn 0,2ppm th c th xc nh bng phng php ny. S xc nh
ng thi ca Cu, Fe, Zn trong mt mu th l c th c bi v cc nh hp th ca
Hnh 6.6. Ph hp th ca
Zincon v Cu, cc chelat Zn-
Zincon, nng nng thuc
nhum 4.0x10
-3
M, ti pH = 9.
1(1): Nhum; (2): chelat Zn;
(3): chelat Cu.


130


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 ZnSO
4
+ H
2
O 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.

Mui ny thng khng mu nhng d chuyn thnh formazans c mu m cp
formazan v th oxi hokh ca cp mui tetrazolium/tormazan thp v chng c th
chuyn thnh cc dehydrogenase khc nhau. Do mui ny c p dng rng ri
nh l mt thuc th c bit cho vic bo v v xc nh cc cht ln men khc nhau
trong cc mu th sinh hc.


131


6.5. XYLENOL DA CAM V METHYLTHYMOL XANH
6.5.1. Danh php:
6.5.2. Ngun gc v phng php ca s tng hp:
V mt thng mi, XO c iu ch t s s ha c Mannich 2 acid acetic, v
resol vi fomaldehit. Methyl thymol xanh c iu ch t thymol xanh.
6.5.3. ng dng trong phn tch:
Nhn bit nhng kim loai nh: Bi, Cd, Hg, Mn(,) Pb, Sc, Th, Zn, Zr v t him.
Nhng tnh cht ca thc th:
6.5.3.1. Xylenol da cam(XO):
Nhng mu thng mi cha 2 hoc 3 mui natri, l bt tinh th ngm nc mu
sm. Acid t do c th thu c nh dihidrat, n nng chy 286
o
C( cng l nhit
phn hy). Mui kim rt d tan trong nc v tan nhanh trong ru v trong dung
mi hu c khc. Nhng mu thng mi thng l hn hp ca XO v na XO vi
nhng t l khc nhau (c khong 17% ca na XO).
Hng s phn ly acid ca XO gin tip c c th c nhng gi tr khc nhau v
ch tng i chnh xc, i khi bi v mu nghin cu khng tinh khit. Dung dch
nc ca XO c mu vng pH < 6, mu tm pH > 6. Ph hp thu ca dung dch
nc XO trong thang pH ny c minh ha hnh 6.7
6.5.3.2. Methylthymol xanh:
Nhng mu mang tnh thng mi c 1 hoc 2 mui natri, n l bt tinh th mu
tm sm hay en. N ngm nc v tan ngay trong nc nhng khng tan trong ru
ethanol v hu ht nhng dung mi hu c. Dung dch nc c mu xanh (mu hi
ch thong qua) v dung dch rt long c mu vng. Ging trng hp ca XO, nhng
mu thng mi l mt hn hp methylthymol xanh v na methylthymol xanh (na
thymolxanh chim khong 50%) .
Mu ca dung dch chuyn t vng sang xanh khi n mang tnh kim, s thay i
ph hp th trong dung dch theo pH c minh ha hnh 6.7, s thay i ny l do 1
hoc 2 proton c trong chnh thuc th v ph thuc vo kh nng hp thu cc i ca
MTB (XO) theo gi tr pH hay hidro biu din hnh 6.8. Nguyn nhn ca vic thay
i ph l do complexon kt hp vi ion kim loi l hon ton tng ng bi 2 proton
ca thuc th, khong pH ti u o mt quang th hn ch trong khong t 0 n
6 cho XO v MTB.


132



Hnh 6.7. Ph hp th ca Methylthymol xanh Hnh 6.8. Hp th cc i ca MTB
6.5.4. Phn ng complexon v nhng tnh cht ca complexon:
Mu vng ca dung dch thuc th pH = 0, chuyn sang tm pH = 6 (XO) hay
xanh (MTB) khi complexon kt hp vi ion kim loi, c th cn c vo nhng phn
ng khc nhau ca chng vi thuc th.
Nhng ion kim loi m thy phn trong khong pH t 0,0 6,0 khi ch th c
mu vng (phn ng gia ion kim loi vi XO hay MTB thng chm v phi un
nng 60 80
o
C, nhit ny tng ln theo t l ca chng): Ag, Al, Au.
Nhng ion kim loi phn ng vi XO hay MTB trong khong pH t 0,0 6,0,
nhng ch thy phn khi pH > 6 (y l khong pH tt nht cho vic xc nh mt
quang): Cd, Cu, Hg(), Fe().v t him.
Ion kim loi m khng phn ng vi XO hay MTB pH t 0,0 6,0, nhng li
phn ng pH cao hn. Nhng ion kim loi m thuc th khng c ch cho chng bao
gm: Ca, Ba, Sr, Ra. Vi trng hp l MTB, tuy nhin mu ca phn ng l do
complexon cho php phn tch ch dng trong gii hn pH t 11,5 12,5
6.6. ASENAZO I V MONOAZO DERIVATIVES OF PHENYL ARSONIC ACID
C
16
H
11
O
11
S
2
Na
2
As KLPT = 592,29

6.6.1. Danh php:
2(4,5Dihydroxy2,7disulfo3naphthylazo) phenylarsonic acid, mui dinatri,
Neothorin, Neothoion, Uranon.


OH
NaO
3
S
N
OH
SO3Na
N
H
2
O
3
As


133


6.6.2. Ngun gc v phng php tng hp:
Trong k thut thng ph bin l mui dinatri. N c tng hp bng s kt ni
ca acid 2aminophenularsonic c diazo ho vi acid chromotropic.
6.6.3. ng dng:
c s dng nh mt thuc th trc quang cho cc nguyn t: Al, Be, In, Th, Zr,
cc nguyn t t him v cc nguyn t actinoid. N cng c s dng nh mt ch
th kim loi trong chun chelate ca Ca, Mg, cc nguyn t t him v Th; ng
thi n cng l mt ch th trong php chun kt ta.
6.6.4. Tnh cht thuc th:
Mui hai natri l mt tinh th dng bt mu sm, d tan trong nc to thnh
dung dch c mu cam (
max
= 500nm pH = 1 8) v kh tan trong hu ht cc
dung mi hu c. Hng s acid pKa
1
= 0,6; pKa
2
= 0,8; pKa
3
= 3,5; pKa
4
= 8,2; pKa
5
=
11,6; pKa
6
= 15 (u = 0,1; 20
o
C).
6.6.5. Phn ng to phc v tnh cht ca phc:
Arsenazo(I) phn ng vi nhiu loi ion kim loi to thnh cc cht mu chelate
trong dy pH t 1 8. Nhng phn ng xy ra trong dung dch kh acid l nhng thc
t quan trng bi tnh chn lc cao hn ca phn ng. Cc phn ng mu xy ra trong
dung dch acid chlorhydric (HCl) l: Nb (III), Ti (III), Zr (mu tm), Sn (IV), U, cc
nguyn t t him ( cam), Th (xanh tm) v Ta (III) ( tm). Thuc th thng kt
hp theo t l 1:1 vi chelate, chng hn nh biu din bn di:
N
H
N
O
Sc
AsO
3
-
OH HO

Hng s bn ca chelate vi cc ion kim th v La c trnh by nh sau:
logKML vi Mg = 5,58; Ca = 5,09; Sr = 4,41; Ba = 4,15 ( = 0,1 KNO
3
; 25
o
C) v
logKMH
2
L vi La = 28,8.
hp thu quang ph ca cc chelate kim loi trong dung dch nc th ph thuc
vo pH.
Hng s hp th mol ca cc chelate th c s dng tt nng 10
4
, v chng
hn nh cc phn ng mu c th c dng cho vic xc nh trc quang hm lng
vt cc nguyn t.
Cc chelate kim loi th khng mang in tch v c th c chit ra nh mt cp
ion vi mt cation ln chng hn nh diphenylguanidinium
6.6.6. S tinh ch v tinh khit ca thuc th:
Ansenazo I t cc ngun k thut cung cp thng khng tinh khit mc d chng
c th theo nhu cu s dng cho cc mc ch chung nh l mt ch th kim loi. Tuy
nhin chng phi c tinh ch s dng cho mc ch ho l. Thuc th ny c th
c tinh ch bng cch nh chm dung dch nc ca thuc th vo trong cng mt


134


th tch acid chlorhydric m c kt ta cc tinh th vng cam, em lc ton b
kt ta, ra sch bng acetonilite, sy kh 100
o
C trong 2 gi.
Vic tinh ch thuc th c th c xc nh bng cch o hp thu ca dung
dch nc ca thuc th bit trc nng .
6.6.7. Cc ng dng phn tch:
6.6.7.1. S dng nh mt thuc th trc quang:
Arsenazo(I) c s dng trong cc php o trc quang cc ion kim loi trong
dung dch nc v trong php o chit trc quang ca mt cp ion vi ion
diphenylguanidinum. Tuy nhin khi cc thuc th loi disenazon(III) cm quang hn,
cc thuc th Arsenazon(I) by gi c thay th bng cc thuc th hin ti.
ng dng quan trng thc t ca Arsenazon(I) l c th xc nh c Th trong
nhiu loi mu mc d b cc nguyn t Nb, Sn, Ta, Ti cn tr v nh hng ca Zr th
rt ng k.
6.6.7.2. S dng nh mt ch th kim loi:
Arsenazon(I) c xem nh l mt ch th kim loi trong chun phc cht ca
Ca, Mg (pH = 10), Th (pH=1,3 3) v cc nguyn t t him (pH = 5,5 6,5).
Mu sc ti im cui ca php chun trc tip chuyn t mu tm sang mu
cam hoc cam.
N cng c s dng nh mt ch th trong chun kt ta gc SO
4
2-
vi dung
dch chun BaCl
2
(mu chuyn t cam sang tm) nhng dimethylsulfonazo(III) c
bit l mt ch th tt nht.
6.6.7.3. Cc dn xut khc ca thuc th acid phenylarsonic:
* Thorin:
2(2Hydroxy3,6disulfo1naphtylaminlazo) benzennearsonic acid, mui dinatri,
Thoron, Thoronol, Naphtharson, Naphthazarin, APANS, APNS.
N
AsO
3
H
2
N
SO
3
Na
SO
3
Na HO

Cc nguyn liu t cc k thut cung cp l mui Na
1
Na
5
, tinh th dng bt, mui
Na
1
( cam), mui Na
5
( 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, = 1,4.10
4
ti pH = 1) v mu cam trong mi trng kim(
max

= 490nm, = 1,4.10
4
ti pH = 9 10 ) v c mu trong mi trng acid sunfuric
m c, pKa
3
= 3,7; pKa
4
= 8,4 (AsO(OH)
2
), v pKa
5
= 11,8 (OH).


135


N to thnh cc chelate c mu trong dung dch acid 0,1N vi Bi (trong dung dch
HClO
4
0,02 0,04N
max
= 535nm, = 9,5.10
3
), Th (pH = 0,5 1,5; ML
2

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.
C
12
H
10
N
2
O
6
AsCl
KLPT = 388,60
N
OH
N
HO
Cl
H
2
O
3
As

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).
6.7. EDTA V CC COMPLEXONE KHC
6.7.1. Danh php:
Nhng thuc th nm trong phn ny c lit k trong bng 6.5, cng vi nhng
tn gi ca chng.
6.7.2. Ngun gc v phng php ca s tng hp:
Tt c u c th mua v c chun b bi s methyl ho cacboxyl tng ng vi
polyamine, cng do s ngng t kim ca acid haloacetic hoc bng phn ng trung
ho Strecker vi KCN v HCHO (formaldehyde).
6.7.3. ng dng phn tch:
EDTA hu nh dnh ring s dng nh mt dung dch chun trong chun
phc cht. EDTA v cc complexon khc cng c s dng nh nhng tc nhn che
trong nhng trng hp khc ca ho hc phn tch.
6.7.4. Nhng tnh cht ca cc thuc th:


136


Acid t do ca EDTA l bt tinh th c mu trng v hu nh khng tan trong nc
(xp x khong 0,009g/l pH = 1,6) cng nh trong cc dung mi hu c. N tan
trong acid v c hoc trong cc dung dch kim. Cc mu cha mt thuc th phn
tch EDTA thng l mt dihydrate, mui dinatri ca EDTA (Na
2
H
2
L.2H
2
O), m n
c th c tinh ch mt cch d dng bng s kt tinh t nc (11,1g/100g 20
o
C;
27,0g/100g 98
o
C) v thnh 99,5% tinh khit sau khi sy 80
o
C. Sy 100
o
C hoc
cao hn dn n kt qu mt mt phn nc hydrated.
Cc thuc th loi complexon, c hnh dng ca acid t do, l bt tinh th trng v
rt t tan trong nc, cc dung mi hu c thng thng v tan nhiu hn khi kim
ca dung dch tng. Do cc thuc th c tnh lng tnh t nhin, chng cng tan trong
acid v c. Hng s phn ly tng nc ca cc thuc th c tng kt trong bng 6.6.
Ging nh cc acid amino khc, cc complexon tn ti nh ion lng tnh.
6.7.5. Cc phn ng to phc v cc tnh cht ca phc:
Cc thuc th loi complexon t bn v tan chelate vi mt gii hn rng ca cc
ion kim loi, loi tr kim v mt s ion kim loi ho tr 1 khc. c tnh khc l kh
nng chelating ph thuc vo bn pH. T l phi t vi kim loi l 1:1, ngoi tr
TTHA v NTA. Nhng iu ny tr thnh nn tng cho vic s dng complexanes,
c bit l EDTA, nh mt dung dch chun trong vic chun phc cht v nh mt
tc nhn che trong cc phm vi a dng nh ho hc phn tch. Cu trc ca kim loi
EDTA chelate c l c minh ho mt cch ring bit pha di cho 4 s phi tr ca
cc ion kim loi, (a) v (b).
Cc hng s n nh chelate ca cc thuc th ny c tng kt trong bng 6.6.
i vi cht chelate, EDTA c s dng rng ri nht, bi ga c tng i thp
ca thuc th, n ang c sn xut rng ri cho ngnh cng nghip tiu dng.

Bng 6.5. EDTA v cc complexon khc
Complexon Cng thc ho hc
EDTA

HOOCCH
2
NCH
2
CH
2
N
HOOCCH
2
CH
2
COOH
CH
2
COOH

CyDTA

N
N
CH
2
COOH
CH
2
COOH
CH
2
COOH
CH
2
COOH
H

GEDTA

HOOCH
2
C
NCH
2
CH
2
OCH
2
CH
2
OCH
2
CH
2
N
HOOCH
2
C
CH
2
COOH
CH
2
COOH



137


DTPA
HOOCH
2
C
NCH
2
CH
2
NCH
2
CH
2
N
HOOCH
2
C
CH
2
COOH
CH
2
COOH
CH
2
COOH

TTHA

HOOCH
2
C
NCH
2
CH
2
NCH
2
CH
2
NCH
2
CH
2
N
HOOCH
2
C
CH
2
COOH
CH
2
COOH
CH
2
COOH HOOCH
2
C

HEDTA

HOCH
2
CH
2
NCH
2
CH
2
N
HOOCCH
2
CH
2
COOH
CH
2
COOH

NTA

N
CH
2
COOH
CH
2
COOH
CH
2
COOH

Bng 6.6. Hng s phn ly v hng s bn chelate ca cc complexon chn lc

EDTA
(1)
CyDTA
(2)
GEDTA
(3)
DTPA
(4)
TTHA
(5)
HEDTA
(6)
NTA
(7)
pK
a1
1,99 2,43 2,00 2,08 2,42 2,51 1,89
pK
a2
2,67 3,52 2,65 2,41 2,95 5,31 2,49
pK
a3
6,16 6,12 8,85 4,26 4,16 9,86 9,73
pK
a4
10,26 11,70 9,46 8,60 6,16
pK
a5
10,55 9,40
pK
a6
10,19
logKML
Ag 7,32 8,15 6,88 8,70 8,67(13,89) 6,71 5,16
Al 16,13 18,63 13,90 18,4 19,7(28,9) 12,43 9,5
Ba 7,76 8,64 8,41 8,63 8,22(11,63) 5,54 4,83
Bi 27,9 31,2 23,8 29,7 21,8
Ca 10,96 12,50 11,00 10,74 10,06(14,16) 8,14 6,41
Cd 16,46 19,23 16,70 19,31 18,65(26,85) 13,6 9,54
Ce(III) 15,98 16,76 15,70 20,50 14,11 10,83
Co(II) 16,31 18,92 12,50 18,4 17,1(28,8) 14,4 10,38
Cr(III) 23,40 2,54 >10
Cu(II) 18,80 21,3 17,8 21,53 19,2(32,6) 17,55 12,96
Dy 18,30 19,69 17,42 22,82 23,29 15,30 11,74
Er 18,38 20,20 17,40 22,74 23,19(26,92) 15,42 12,03
Eu 17,35 18,77 17,10 22,30 23,85 15,35 11,52
Fe(II) 14,33 16,27 11,92 16,50 17,1 12,2 8,84
Fe(III) 25,1 28,05 20,5 28,6 26,8(40,5) 19,8 15,87
Ga 20,27 22,91 23,0 16,9 13,6
Gd 17,0 18,80 16,94 22,46 23,83 15,22 11,54
Hf 29,5 35,40 19,08 20,34
Hg(II) 21,8 24,30 23,12 27,0 26,8(39,1) 20,1 14,6
Ho 18,05 19,89 17,38 22,78 23,58 15,32 11,90


138


In 24,95 28,74 29,0 17,16 16,9
La 15,50 16,75 15,79 19,48 22,22(25,62) 13,46 10,36
Li 2,79 4,13 1,17 2,51
Lu 19,65 20,91 17,81 22,44 15,88 12,49
Mg 8,69 10,32 5,21 9,3 8,10(14,38) 7,0 5,46
Mn(II) 14,04 16,78 12,3 15,50 14,65(21,19) 10,7 7,44
Na 1,66 2,70 1,38 2,15
Nd 16,61 17,69 16,28 21,60 22,82(26,75) 14,86 11,26
Ni 18,62 19,4 13,55 20,32 18,1(32,4) 17,0 11,54
Pb 18,04 19,68 14,71 18,80 17,1(28,1) 15,5 11,39
Pr 16,40 17,23 16,05 21,07 23,45 14,61 11,07
Sc 23,1 25,4 12,7
Sm 16,7 18,63 16,88 22,34 23,81 15,28 11,53
Sn(II) 18,3 23,85
Sr 8,63 10,54 8,50 9,68 9,26(12,70) 6,92 4,98
Tb 17,81 19,30 17,27 22,71 23,61 15,32 11,59
Th 23,2 29,25 28,78 31,9 18,5 12,4
TiO
2
+
17,3 19,9 12,3
Tl(III) 22,5 38,3 48,0 18
Tm 18,62 20,46 17,48 22,72 15,59 12,2
UO
2
2+
25,6 26,9 9,56
VO
2
+
18,77 19,40
Y 18,09 19,41 16,82 22,05 14,65 11,48
Yb 18,88 20,80 17,78 22,62 23,58 15,88 12,40
Zn 16,50 18,67 14,5 18,75 16,65(28,7) 14,5 10,67
Zr 29,9 20,74 36,9 19,74 20,8
Cc gi tr ca cc kim loi khc; logK
ML
cho Be(9,27); Cs(0,15); K(0,96);
Nb(40,78); Pd(II) (18,5) v Sb(III) (24,8).
- Cc gi tr ngoc n biu din log
ML
.
- Cc gi tr pKa c quan st gi tr trung bnh ca u = 0,1 (KCl hoc KNO
3
)
20
o
C, tr TTHA 25
o
C.
- Cc gi tr logK
ML
c quan st, hu ht cc trng hp, gi tr trung bnh ca u
= 0,1 (KCl, KNO
3
hoc NaClO
4
) 20 25
o
C.
- Cc gi tr cho U(IV).
Cc complexane khc EDTA v NTA th t, vic s dng chng ch gii hn trong
ho hc phn tch v cc mc ch nghin cu khc.
CyDTA to thnh chelate kim loi bn hn so vi EDTA, t CyDTA c tin
c nh mt tc nhn che m ion kim loi khng th c che mt cch c hiu qu vi
EDTA.
GEDTA c bit nhn bit Ca hn l Mg ( logK
CaMg
= 5,79) v Cd hn l Zn
( logK
CdZn
= 2,2) trong vic so snh vi c ch to phc ca EDTA. ( logK
CaMg
=


139


1,9; logK
Cd
Zn 0). Theo , GEDTA c s dng nh mt dung dch chun
chn lc cho Ca v Cd.
DTPA v TTHA c du hiu nh nhng phi t octadentate v decadentate, to
thnh chelate bn hn EDTA, vi cc ion kim loi c 8 phi t hoc cao hn, v kt
qu cc chelate c tnh bn hn i vi s thu phn. Trong cc trng hp ca
TTHA, n cng to thnh M
2
L dng chelate vi Cu(II), Sn(II) (pH t 3 n 4), Al,
Cd, Co (II), Ga, Hg(II), Ni, Pb, Ti (vI H
2
O
2
), Zn (pH t 5 6), Mg v Zn (pH t 9
10).
S tng phn gia Fe(III)EDTA chelate, Fe(III)HEDTA chelate l tnh bn i
vi s thu phn trong dung dch kim n da, v th n c xem nh mt tc nhn
che cho Fe(III) trong dung dch kim mnh.
NTA c xu hng nh mt phi t bn nh, hnh dng cc chelate t bn hn
EDTA. S tn ti lng d ca NTA, n hnh thnh ML dng cng nh ML
2

chelate.NTA c s dng nh mt tc nhn che c hiu qu che cao hn so vi
EDTA v CyDTA khng c nh mong mun.
6.7.6. S tinh ch v tinh khit ca cc thuc th:
Acid t do ca cc complexon c th c tinh ch bng vic ho tan n trong
dung dch kim NaOH, theo s kt ta ca acid t do vi phn thm vo ca acid
sunfuric pha long n pH = 1 2. Kt ta trng c lc v ra bng nc lnh cho
n khi phn nc lc l dung dch cha gc sunfat t do.
Disodium EDTA (Na
2
H
2
L.2H
2
O) c th c tinh ch bi s kt tinh t nc
nng. Phng php tip theo cng c gii thiu thu c mu tinh khit.
Ho tan 10g mu nguyn liu (th) vo trong 100ml nc v thm t t C
2
H
5
OH
vo dung dch ny cho n khi n chuyn sang c. Sau khi lc dung dch, thm mt
lng C
2
H
5
OH c th tch bng vi th tch phn nc lc kt ta mui tinh khit.
Lc mui bng phu, ra bng acetone, tip n l ether. Sau lm kh mui trong
khng kh sut m, sy n 80
o
C trong 4 gi.
Thng thng tinh khit ca cc complexon c xc nh bng vic chun
dung dch Zn tiu chun (ch th XO pH = 5) hoc Cu(II) (ch th PAN pH t 4
5) vi dung dch complexon bit trc nng .
6.7.7. Cc ng dng trong phn tch:
6.7.7.1. S dng nh mt dung dch chun in Chelatometry:
Php tnh h s t lng trong chelatometry c th c vit dng sau:
M
n+
+ H
2
L
2-
ML
n4
+ 2H
+

EDTA l complexon c s dng rng ri nht trong chelatometry, v dung dch
tiu chun ca EDTA 0,01M (3,72g Na
2
H
2
L.2H
2
O/l) c gii thiu cho cc kt qu
tng qut. Cc phng php c th cho vic xc nh mi nguyn t c tm thy
trong cc dng th chelatometry. Tuy nhin, biu gii hn pH c dng trong
vic tm ra iu kin thch hp cho s chun v bn cht ca cc ch th kim loi
nhn c cc kt qu tt. Cc ion v c v hp cht hu c cng c th c xc


140


nh gin tip bng phc cht.
6.7.7.2. S dng nh mt tc nhn che:
Gii hn ca cc ng dng ca complexane nh nhng tc nhn che trong cc phn
ng phn tch rt rng m iu khng thch hp tho lun trong tng v d c
th. Tuy nhin, bng 6.7 tm tt mt vi v d trong vic s dng EDTA nh mt
tc nhn che. Nhng s khc nhau ca cc tnh cht che gia EDTA v CyDTA tri
vi phn ng to phc vi cyanua c trnh by trong bng 6.7 nh mu khc.
xut chi tit trong vic s dng ca cc complexon nh mt tc nhn che c tm
thy trong mt s th khc.
Bng 6.7. Mt vi v d trong vic s dng EDTA
nh mt tc nhn che
Phn ng che ng dng
Fe, Co v Ni vi Natridiethyl-
dithiocarbamate.
Chit trc quang Cu v Bi
Fe(III), V(V) vi Tiron Php xc nh trc quang Ti
Fe, Co, Cu, Ni v Cr vi 2-nitroso-
1 naphthol
Php xc nh trc quang Pd
Al, Cd, Cr, Cu, Ga, Hg, In, Pb, V, Zr
V t him vi PAR
Php xc nh trc quang Ni
(pH = 8,6 10)
Bi, Cd v Cr vI Beryllon IV
Php xc nh trc quang Be
(pH = 7 8)
Fe(II), Ce, Co, La, Mg, Mo, Nd v Pb vi XO
Php xc nh trc quang
Al (pH = 3 3,8)

Mo(V) vi 8 hydroxyquinoline Chit U, W(VI) (pH = 2 3)



141


MT S GII HN CA pH CN LU TRONG QU TRNH CHUN


142




143


Gii hn pH v ch th kim loi c xut cho vic chun cc ion kim loi
thng thng, gii hn pH m ion kim loi chun c, gii hn pH m
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
CuPAN: CuEDTA + PAN mixture PR: Pyrogallol Red
GCR: Glycine cresol Red PV: Pyrochatecol Violet
GTB: Glycinethymol Blue TAN: Thiaolylazonaphthol
HNB: Hydroxynaphthol Blue TAR: Thiaolylazoresorcinol
MTB: Methylthymol Blue TPC: Thylmolphtalein Complexon
MX: Murexide VBB: Variamine BlueB
NN: Calcon carboxylic acid XO: Xylenol Orange
(Patton and Reeders dye)
Bng 6.8 Phn ng ca KCN vi EDTA v CYDTACHELATE kim loi
Kh nng phn ng ca KCN vi
Ion kim loi EDTA chelate CyDTA chelate
Hg(II) Phn ng tc thi Phn ng tc thi
Cu(II) Phn ng tc thi Phn ng tc thi
Pb Khng phn ng Khng phn ng
Bi Khng phn ng Khng phn ng
Cd Phn ng tc thi Hu nh khng phn ng
Ni Phn ng Khng phn ng
Co(II) Phn ng Phn ng chm
Mn(II) Khng phn ng Khng phn ng
Co(III) Khng phn ng Khng phn ng
Zn Phn ng nhanh Phn ng kh nhanh
Fe(II) Phn ng Phn ng chm
Fe(III) Phn ng Khng phn ng

6.8. HP CHT DIHYDROXYARYLAZO
HP CHT DIHYDROXYARYLAZO


144



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 (H
2
L
-
) = 6,3 v pKa (HL
2-
) = 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
OH
N N HO
3
S
O
2
N
OH
OH
N N HO
3
S
COOH HO
H
3
L (1) H
4
L (2)

OH
N N HO
3
S
HO
CH
3
OH
N N NaO
3
S
SO
3
Na
HO SO
3
Na
H
3
L (3) H
5
L (4)


145


nc v ru to ra dung dch mu hng pH < 8. N s chuyn qua mu xanh
pH = 10
-13
v mu hng nht trong dung dch kim mnh pKa (H
2
L
2-
) = 9,26 v (HL
3-
)
= 13,67( = 0,01 KCl; 24
o
C).
Calgamite (3) cng thng c cung cp dng t do, dng bt mu tm m, d
tan trong nc cho dung dch mu ti pH < 7. N s chuyn qua mu xanh pH
= 9,1 11,4 v mu cam nh pH > 13. Cc thuc nhum c lit k bng 6.9
hu ht n nh trong dung dch nc, pKa (HL
2-
) = 7,92 v pKa (HL
2-
) = 12,50 ( =
0,1; KNO
3
; 25
o
C).
Hydroxynaphthol Blue (4) c cung cp dng mui III ca natri, dng bt
ht m mu tm m, d tan trong nc v ru cho dung dch mu tm pH < 6 n
s chuyn qua dung dch mu xanh pH = 7 12 v mu hng pH > 13, pKa (H
2
L
3-
)
= 6,44 v pKa (HL
4-
) = 12,9 (= 0,1; KCl, 24
o
C)
Bng 6.9. DIHYDROXYLAZO hp cht
Thuc
th

Tn

ng phn
Cng thc phn t
v KLPT
(1)
Eriochrome
Black
1(Hydroxy2 naphthylazo)6
nitro2naphthol4sulfonic acid,
mui mononatri; Solochrome
Black T, Mordant Black 11, C.I.
14645, Erio T, EBT, BT
C
20
H
12
O
7
N
3
SNa,
461,41
(2)
Cancol
carboxylic
acid
2Hydroxy1(2hydroxyl4sulfo
1naphthylazo)3naphtoic acid Pat
Ton v Reeders dye Cal , HSN,
NANA, HHSNNA, NN
C
21
H
14
N
2
O
7
S,
438,41
(3) Calmagite
1(1Hydroxy4methyl2
phenylazo)2naphthol4sulfonic
acid
C
17
H
14
N
2
O
5
S,
358,37
(4)
Hydroxynaph
thol Blue
1(1Hydroxy4sulfo1
naphthylazo)2naphthol3,6
disulfonic acid, mui trinatri, HNB
C
20
H
11
N
2
O
11
S
3
Na
3

620,46
6.8.5. Phn ng to phc cht v c tnh ca phc cht:
Khi s th hin ca nhng ion kim loi hn nhng kim loi kim loi tnh mu
xanh ca thuc nhum s chuyn qua nh trong dung dch nc v cc phn ng
mu nh vy c tn dng trong php trc quang cho cc ion kim loi hoc trong
phng php chelate nh l nhng cht ch th kim loi.
Bng 6.10. Phn ng mu ca ERICHROME BLACK T vi ion kim loi ti pH= 9
Ion kim loi Mu Ion kim loi Mu
None Xanh dng Mg
Al Hi Mn(II)
Bi Xm Xanh Nd
Ca Ni


146


Cd Os(VIII) Hng
Ce(III) Xm Xanh Pt(IV) Xm Xanh
Co(II) Hi Th
Cr(III) Xm Xanh U(VI) Xm Xanh
Cu(II) Hi V(V) ti
Fe(III) Nu ppt W(VI) Xanh dng
Hg(II) Xm Xanh dng Zn
La Hng m
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 (logK
ML
) 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); UO
2
2+
(4,10 hoc 3,99).


Hnh 6.9. Ph hp th ca Eriochrome Black T v chelate Mg trong namyl alcohol
(1) trong namyl alcohol
(2) trong namyl alcohol, lc vi dung dch khng cha Mg, pH 11,5
(3) lc vi dung dch cha 0,1ppm Mg, pH 11,5
(4) lc vi dung dch cha 0,2ppm Mg, pH 11,5
6.8.6. S tinh ch v tinh khit ca thuc th:
Cc mu thng mi (trn th trng) l tinh khit cho vic s dng nh l mt
cht ch th kim loi trong phng php chelate. Tuy nhin chng cng cha mt
lng c bn mui hu c v phi c tinh ch khi em s dng trong cc nghin


147


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, NH
3
), Ba, Sr (pH 10, NH
3
, MgEDTA), Hg(II), In, Pb,
t him (pH 8 ti 10),NH
3
, tartarate, 100
o
C), Co(II), Ni(pH 10, NH
3
, MnEDTA),
Mn(II) (pH 8 ti 10, ascobic acid, 80
o
C), Sc( pH 7,5 ti 8; NH
3
; malic acid; 1000),
VO2+ (pH 10, NH
3
, 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, NH
3
); chun vi hydroxynaphthol Blue (4) (t sang
xanh), Ca (pH 10 ti 13, KOH) v Mg (pH 10, NH
3
).
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, =
1,54.10
4
La, Mn, Pb, Sc, Zn, DCD, t him. S to thnh t 3 phc ca GaGallion
Oxine (MLX; pH = 3; 640nm; = 2,3.10
4
trong buthanol).


148


Th cng hu dng cho vic xc nh ca GaLumogallion cng c khuyn co
nh thuc th trc quang cho Al (pH = 5, 576nm) hoc pH = 3,3; 558nm c mt trong
h Antarox CO 890; Ga( pH = 3; 580nm) hoc pH = 3,1 4,3, 553 nm c mt trong
h Antarox. CO 890, In( pH = 2,8 6,5; 500nm; Mo(VI) (510nm

= 1,13.104 ), Nb
(pH = 5,6 7,6; 546nm) Sc (pH = 2; 500nm), Sn(IV) (pH = 1; 510nm) v W (pH = 2,6
3,5; 555nm) hoc nh thuc th hunh quang cho kim loi.
S xc nh chit trc quang cho Fe, Sn v Y thng qua 3 phc cht vi Lu
mogalliondiethylether v Nb thng qua LumogallionBPA c bo co bi 3 phn
phc cht. Ion chelate Lumogallion vi Cu, Fe, Mo(VI), PD, V(IV) v W(VI) c th
cng c chit vi Aliquat 336S trong CHCl3.
6.8.8.2. SPADNS
Bt SPADNS c ngh nh thuc th trc quang cho AL (pH = 4 5;
590nm), Ca (pH = 10; 570nm), Pa (pH = 10 11; 570nm), Mg (pH = 8; 570nm), Pd
(pH = 2,5 4,5; 550nm), Th (pH = 2,6 3,6; 580nm), Zr (HCl 0,5N; 580nm) v t
him ( pH = 5 7,5; 540nm). Anion chelate c th chit nh cp ion vi
diantipymethane cho s xc nh trc quang ca Sc ( ML
2
X
2
, pH = 5,5 8,5; 580nm)
fluoride c th c xc nh khng trc tip trong s bay mu ca chelate Zr (HCl
0,7N, 570nm).
6.8.8.3. BerryllonII
Bt mu tm en gi tr pKa cho 5 bc phn ly 2,9; 4,3; 5,71; 7,01; v 10,88( 20
o
C
n c s dng nh l thuc trc quang cho Be (pH = 12 13,2; 600nm), Mg (pH =
11; 640nm, = 1,03.10
4
), Th (pH = 2; 620nm), Ti(IV) (pH = 4,1; 580nm, = 6.10
4
)
v t him (pH = 7,6; 610nm) v B.
Bng 6.11. ng dng ca phm nhum AZO nh thuc th trc quang
Phm
nhum
azo
Ion
kim
loi
iu kin T l

max

(nm)

(x10
4
)
Dy xc
nh
(ppm)
Yy t cn tr
v ghi ch
(1) Cd
pH~6; 1,10
Phenalthroline,
chit vi
CHCl
3

ML
2
X
2
522 2,2 0,22~5,6
Trong hp kim
Devarda
Co(II)
TPAC, chit
vi CHCl
3

580 5,0 0,6~18
EDTA,DDTC
cn tr
Co(II)
pH 5,5~8,2;
SCN-; chit
vi benzene v
Aliquat 336S
587 6,62 0,1~ 0,8
Mn,Ni,VO
3
-

cn tr
Mg
pH 10,9 ~
11,3; KCN;
triethanolamin
525~30 0,1 ~1


149


Mg
pH 9,5~11,2,
chit v i
AmOH hoc
BuOH
545 2,0 0,5 ~5
Ca,Cd,Ce,Fe,Zn
cn tr
Mg
pH 11,2 ~
12,2,
Zephiramine,
chit v i
dichloroethane
690*
0,03~
0,1
Ca khng cn
tr
Zn
pH ~ 6; 1,10
Phenalthroline,
chit vi
CHCl
3

ML
2
X
2
522 2,3
0,64~
3,7
Trong hp kim
Devarda

t
him
pH 6,35 ~ 6,8;
diphenyl
guanidine;
chit vi iso
AmOH
ML
2
X
2
550~600
2,6
~3,5
0,1~ 15
(2) UO22+
Mi trng
kim
ML
2
570 1,36 14 ~ 60
Sau khi s trao
i ion phn
tch
(3) Al
pH 8,2~ 8,8;
KCN; EDTA;
chit vi
Aliquat 336S
trong CHCl3
ML
3
570 4,2 0,1 ~ 0,5
Cd,Cu,Ni,Pb,Zn
khng cn tr
Co(II)
pH 4,2; chit
vi Aliquat
336S trong
CHCl
3

580 0,8
Mg
pH 11,2~12,2,
Zephiramine,
chit vi
dichloroethane
690 6,3 2 ~ 7
Ca khng cn
tr
Mo(VI)
pH 11; chit
vi Aliquat
336S trong
CHCl
3

575 0,6
(4)
Kim
loi
kim
th
pH6; EDTA 650 1 ~ 600
UO22+ pH 4 ML 530 0,41 0,3 ~ -


150



t
him
pH 6 ~ 10;
EDTA
ML 65 1 ~ 300
Kim loi kim
th, Be, UO
2
2+

cn tr









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
(4a)
4,7 Diphenyl
1,10
phenanthroline
Bathophenanthroline C24H16N2 332,41
(4b)
4,7 Diphenyl
1,10
phenanthroline
disulfonic acid, mui
dinatri

Bathophenanthroline
Disulfonic acid,
mui dinatri.
C24H14N2O6S2Na2 536,48


151



7.1.1. Nguyn liu v phng php tng hp:
Tt c cc nguyn liu c bn di dng thng phm. (1) v (2) c iu ch
t qu trnh hydro ho pyridine vi FeCl
3
hoc c cht xc tc Ziegler 100
200
o
C. (3) c iu ch bng cch un nng. ophenylenediamine vi glycerol,
nitrobenzene, v H
2
SO
4
c hoc bng phn ng Skraup t 8aminoquinoline. (4a)
c iu ch t 8amino4 aminoquinoline bng phn ng Skraup vi
chloropropiophenone. (4b) l 1 sn phm sulfo ho ca (4) vi acid chlorosulfonic sau
l s thu phn.
7.1.2. ng dng trong phn tch:
C 4 cht trn ch yu c s dng nh mt thuc th trc quang xc nh
Fe(II) v cn c dng lm cht che, cht pht hin cc ion kim loi khc. Cc phc
chelate st ca chng cng c s dng nh l cht ch th oxi ho kh.
7.1.3. Tnh cht ca thuc th:
2,2bipyridine (1) l mt cht rn tinh th mu trng, nhit nng chy 702
o
C
v nhit si t 272 275
o
C. N c p sut hi bo ho nhit phng v c
trng l phn no c mi d chu. Cht ny d dng b thng hoa hoc chng ct thnh
hi, tan c trong nc (khong 5g/L) nhit phng. N tan tt trong ru, ether,
benzene, ether du ha, chloroform v acid long. pKa
1
= 0,2 v pKa
2
= 4,4 ( = 0,1
KNO
3
, 25
o
C).
2,2,2Terpyridine (2) l mt cht rn tinh th mu trng, nhit nng chy l
88 89
o
C. N khng bay hi cng vi hi nc v tan hn ch trong nc, nhng tan
d dng trong hu ht cc dung mi hu c v acid long. pKa
1
= 1,6 v pKa
2
= 3,99
v pKa
3
= 3,99 ( = 0,1 K
2
SO
4
, 25
o
C).
1,10phenanthroline (3) l 1 cht bt tinh th mu trng. N ch yu tn ti dng
c ngm nc v khi nng chy 98 100
o
C do qu trnh mt nc. Dng khan nng
chy 117
o
C v d tan trong nc (khong 3,3 g/L nhit phng) v trong benzene
(khong 14g/L nhit phng). N tan tt trong cn (khong 540g/L ), acetone, v
cc acid long.
Bathophenanthroline (4a) l mt cht bt tinh th mu trng hoc c mu vng
nht, nhit nng chy 215 216
o
C v tan nh trong acid long, nhng trong thc t
khng tan trong nc trung tnh hoc nc c tnh kim. N tan d trong cc dung mi
hu c nh cn, acetone, benzene.
Sulfonated Bathophenanthroline (4b) Thng c c dng mui dinatri, c dng
tinh th bt mu vng nht hoc hng sng. Mu ca thuc th ty thuc vo lng vt
ca st nhim bn vo. N l d cht ht m nhng sau khi sy kh 110
o
C trong 2
gi ta thy rng khi lng ca n khng thay i khi tng nhit ln 275
o
C. vng
nh sng UV n c mu xanh hunh quang sng v d tan trong nc nhng kh tan
trong 1 vi dung mi hu c. Acid t do c dng cht lng snh, thu phn cao, v
kh thu c dng rn.
Cc thuc th nhm ny u khng mu v khng c kh nng hp th bt k


152


mt tn hiu no vng kh kin.
7.1.4. Cc phn ng to phc v tnh cht ca phc cht:
Nhng thuc th nhm ny hnh thnh phc c mu bn vi cc kim loi chuyn
tip. Tuy nhin, mt s hnh thnh cc chelate c cng mu khng mnh bng khi
chng tn ti trong dung dch nc. Mt s to chelate gn nh khng mu (Cd, Zn,
Mn(II) v Ag). Cu(I) v Fe(II) l cc ngoi l khi hnh thnh cc vng cng c mu
mnh. Trong cc chelate ny, th (1) v (3) v (4) th hin nh 1 khng mang in tch
to thnh ML
3
v ML
2-
loi phc c ion kim loi (M
n+
) lin kt vi v tr 4 v 6,
theo trnh t nh minh ho hnh 1
Terpyridine (2) th hin nh mt phi t c 3 lin kt, hnh thnh ML
2
n+
, mt loi
phc c ion kim loi lin kt v tr th 6.
Mt s gi tr ca hng s bn c lin quan c dng xc nh cc phc kim
loi ca pyridine, terpyridine v phenanthroline. Cc gi tr ny c tm tt bng
7.2 n 7.4. Cc gi tr ca Bathophenanthroline (4a) l Cu(II), log
3
21,8( 18
o
C, =
0,1; NaCl, 10% ethanol, v i vi sulfonat Bathophenthroline (4b) l Fe(II), log
2

22,3.
Cc thuc th nhm ny c ng dng rng ri xc nh Fe, Cu bi v chng
hnh thnh cc phc c mu mnh vi nhng kim loi ny. Cc c trng quang ph
ca cc phc Co, Cu, Fe, v Ru c lit k bng 7.5, v cc ph hp th ca cc
phc Fe(II) vi (1), (3) v (4a) c minh ha hnh 2. Mt s t cc ion kim loi khc
cng to cc phc c mu tuy nhin quang ph c trng ca chng rt khc so vi cc
phc ca Fe(II) v Cu(I) nn chng khng nh hng n vic xc nh Fe v Cu bng
phng php quang ph.
Tri vi mu cam m ca phc Fe(II) (Ferroin), mu ca phc Fe(III) (Ferriin)
l khng mu hoc mu xanh nht. Cp oxi ho kh Ferroin Ferriin:
FeL
3
3+
+ e FeL
3
2+

khng mu cam
c tnh thun nghch rt cao v p ng tt c cc i hi ca mt cht ch th oxi
ho kh. Th oxi ho kh ca phng trnh c th c m t bng phng trnh
Nerst:
3
3
0
2
3
FeL
E E 0, 059log
FeL
+
+


= +



Gi tr ca E
o
thay i tu thuc vo thnh phn ca dung dch v ph thuc vo
mc nh hng ca h s hot ca cc thnh phn c trong dung dch v bn
ca phc Fe(II) v Fe(III). Bng 9.6 tm tt th ca Ferroin Ferriin cc nng
acid khc nhau, cng vi s thay i mu ca chng. Mt s dn xut quan trng ca
bipyridine(I) v phenanthroline (3) c dng lm ch th oxi ho kh cng c nu
trong bng ny.
Bng 7.2. Hng s bn phc ca BIPYRIDINE


153


iu kin
Ion kim loi Log KML
Log
2
ML
K
Log
3
ML
K

Nhit
Ag(I) 3,7
2
7,22 25 0,1(KNO
3
)
Ag(II)
2
6,8 25
Cd 4,25 3,6 2,7 20 0,1(NaNO
3
)
Co(II) 6,06 5,36 4,60 20 0,1(NaNO
3
)
Cr(II) ~ 4 ~ 6,4 3,5 0,1
Cu(I)
2
14,2 25 0,1(KNO
3
)
Cu(II) 8,0 5,6 3,48 20 0,1(NaNO
3
)
Fe(II) 4,20 3,70 9,55 25 0,1
Fe(III) 4,2 > 5
2
17,06 25
Hg(II) 9,64 7,10 2,8 20 0,1(NaNO
3
)
Mg 0,5 27 0,5(LiClO
4
)
Mn(II) 2,62 2,00 ~ 1,1 25 0,1(KCl)
Ni 7,13 6,88 6,53 20 0,1(NaNO
3
)
Pb 2,9 20 0,1(NaNO
3
)
Ti(I)
2
3 25 1,0(NaNO
3
)
Ti(III) 9,40 6,70 25 1,0(NaNO
3
)
V(II) 4,91 4,67 3,85 0,1
Zn 5,04 4,35 3,57 25 0,1(KCl)



Bng 7.3. Hng s bn phc ca TERPYRIDINE(2)
iu kin
Ion kim loi Log KML
Log
2
ML
K

Nhit
Cd 5,1 25
Co(II) 8,4
2
18,3 25
Cu(I) ~9,3 25 0,1(K
2
SO
4
)
Cu(II) ~13,0 25 0,1(K
2
SO
4
)
Fe(II) 7,1
2
20,9 25
Mn(II) 4,4 25
Ni 10,7
2
21,8 25
Zn 6,0 25
Bng 7.4. Hng s bn phc ca 1,10 PHENANTHROLINE
iu kin
Ion kim loi Log KML
Log
2
ML
K
Log
3
ML
K

Nhit
Ag 5,02 7,05 25 0.1
Ca 0,7 20 0,1(NaNO
3
)
Cd 5,78 5,04 4,10 20 0,1(NaNO
3
)
Co(II) 7,25 6,70 5,95 20 0,1(NaNO
3
)


154


Cu(I)
2
15,82 25 0,1(K
2
SO
4
)
Cu(II) 9,25 6,75 5,35 20 0,1(NaNO
3
)
Fe(II) 5,86 5,25 10,03 20 0,1(NaNO
3
)
Fe(III) 6,5
2
11,4
2
23,5 20 0,1(NaNO
3
)
Hg(II)
2
19,65 3,7 20 0,1(NaNO
3
)
Mg 1,2 20 0,1(NaNO
3
)
Mn(II) 4,13 3,48 2,7 20 0,1(NaNO
3
)
Ni 8,8 8,3 7,7 20 0,1(NaNO
3
)
Pb 4,65 20 0,1(NaNO
3
)
Tl(I)
2
4 25 1,0(NaNO
3
)
Tl(III) 11,57 6,73 25 1,0(NaNO
3
)
VO(II) 5,47 4,22 25 0,082
Zn 6,55 5,80 5,20 20 0,1(NaNO
3
)
Nh trnh by trn, cc cht t (1) n (4a) u th hin nh mt phi t khng
mang in, kt qu ca vic hnh thnh phc cation th vn cn gi li in tch dng
ion kim loi trung tm. Cc phc cation ny c khuynh hng hnh thnh kt ta
khng tan vi cc anion cng knh c ho tr 1 hoc 2, nh l ClO
4
-
, SCN
-
, hoc CdL-
4
2-
. tan ph thuc rt nhiu vo s lin kt ca cc phc gia cc anion v cation,
v phn ng c th c s dng pht hin hay tch cc anion bng phn ng kt
ta. Bng 7.5 tm tt gii hn pha long pht hin cc anion khc nhau bng
Fe(bipy)
3
SO
4
. Mc d cc kt ta ny khng tan trong nc nhng li tan trong cc
dung mi hu c c hng s in mi cao.
Bng 7.5. KT TA CA CC ANION VI [Fe(bipy)
3
]SO
4

Anion Gii hn pha long Anion Gii hn pha long
Cl
-
1:10 Fe(CN)
6
4-
1:5.000
Br
-
1:50 Fe(CN)
6
3-
1:30.000
I
-
1:1.000 Fe(CN)
5
(NO)
2
-
1:20.000
SCN
-
1:5.000 PtCl
6
2-
1:100.000
VO
3
-
1:40.000 BiCl
4
-
1:10.000
Cr
2
O
7
2-
1:6.000 SnCl
6
2-
1:2.000
MnO
4
-
1:12.500 HgCl
4
2-
1:50.000
ReO
4
-
1:1.000 CdI
4
2-
1:1.000.000

tan ca Fe(phen)
3
X
2
(X = ClO
4
-
, I
-
, Br
-
, Cl
-
) trong cc dung mi khc nhau c
tm tt bng 7.6.
Bng 7.6. tan ca Fe(phen)
3
X
2
trong cc loi dung mi khc nhau (mol/l ti 25
o
C)
X
Dung mi
ClO
4
-
I
-
Br
-
Cl
-
SCN
-

Nc
8,8.10
-4
*
7,9.10
-4

6,15.10
-3
5,08.10
-2
2,55.10
-1
3,3.10
-3

Nitrobenzene 2,95.10
-2
6,26.10
-3
6,7.10
-4
6,2.10
-4
6,04.10
-3

Nc bo ha nitrobenzene 4,5.10-4 3,29.10
-3
5,31.10
-2
2,71.10
-1
1,59.10
-3



155


Nitrobenzene bo ha nc 3,55.10-2 6,0.10
-3
1,27.10
-3
2,32.10
-4
6,66.10
-3

V mt s anion c chit vo cc pha hu c nh l 1 cp ion. Mt ln na, h
s chit, li ph thc vo s lin kt ca cc phc cation, cc anion c chit v
dung mi. Cc phc cation c to thnh bi biquinoline v cc ho cht c lin quan
cng c s dng cho mc ch ny.
7.1.5. S tinh ch v qu trnh tinh ch ho cht:
C 4 cht u c nhng tnh cht c trng ca mt tinh th v d dng c tinh
ch bng qu trnh kt tinh li t cc dung mi thch hp, (1) th dung mi l ethanol
long, (2) v (4a) th t benzene, cn (3) th vn cn cha 1 nhm hydrat khi kt tinh
li t benzenenc hay benzene m. Cht khan th c th c iu ch t benzene
hoc ether du ha c loi nc bng qu trnh chng ct.
Khi tinh khit thp, (4b) l 1 cht bt mu nu hoc nu vng v rt kh loi
i mu nhim bn ny. Dung dch (4b)nc rt nhy vi st v vy phi ht sc cn
trng trnh st nhim bn ln nc, ho cht v dng c thu tinh. Mui v c v
mt s cht gy nhim mu c th c loi b bng cch ho tan mu th vo mt
lng nc nh, sau thm vo ethanol kt ta cc cht gy nhim bn, dng tinh
khit ca (4b) c iu ch bng cch cho bc kh dch lc.
Chng ta c th kim tra tinh khit ca (1) n (4a) mt cch d dng bng cch
quan st im nng chy ca chng hoc chun bng acid perchloric trong mi
trng acid acetic vi ch th l naphtholbenzene. Dng phng php ph hp thu
xc nh tinh khit ca (4b). Ho cht m tho mn tinh khit th phi p ng
nhng yu cu sau:
A ( 278,5nm) > 0,70
A ( 535nm) < 0,01
Trong A l hp thu ca dd (4b)10mg/l, cuvet silic 10mm.
7.1.6. Cc ng dng trong phn tch:
71.6.1. Thuc th quang ph:
Mt s thuc th to mu c nghin cu xc nh hm lng vt St,
nhng khng c thuc th no c th snh bng cc thuc th Ferroin.
Bipyridine(1), terpyridine(2) v phenanthroline(3) l c ngh cho cc mc
ch chung m khng cn c nhy cao hay cc iu kin c bit.
Bathophenanthroline(4a) v dn xut xut pht ho (4b) c ngh xc nh hm
lng st cao. Vic xc nh c th c thc hin trong mi trng nc i vi (1),
(2), (3) v (4b). Tuy nhin, i vi (4a) th cn phi chit phc mu bng dung mi
hu c.
Khi s dng (1) n (3) , phc st mu cam hnh thnh mt cch nh lng
trong khong pH t 2 n 9 (tt nht l t 4 6 ). Trong cc tc cht thng dng lm
cht kh chuyn Fe(III) v Fe(II) th hydroxylamineHCl v acid ascorbic l c
ng dng rng ri khong pH ny. Th t cho thm cc thuc th cng rt quan
trng, v th t thng c dng l: cht kh, cht ln mu v m.


156


hp th tun theo nh lut Beer trong khong nng t 0 8 ppm Fe v 5
50g st trong 10 ml dung dch. bn mu trong khong vi thng.
Mc d (1) n (3) c chn lc cao i vi st nhng nu mt vi nguyn t c
nhiu trong mu phn tch cng c th gy nh hng. Mc nh hng ca cc
nguyn t c th gim bt tu thuc vo pH, lng thuc th ln mu v loi thuc th
dng lm cht che v nng ca n. Khi dng citrate v EDTA, khong pH = 5,0
6,5, th t l cc cht c th gy nh hng (t l mol ca ion nh hng/Fe) nh sau
Ag(50), Co (<20), Cu (4.18), Mo (<40), Ni(12,5), Cr (<200), Ru (<30), v W (<7).
(4a) thng c dng khi cn c chn lc v nhy cao, vi thuc th ny
th hm lng ca Fe c th xc nh c l 0,001 0,1 ppm. N cng c chn lc
cao i vi Fe bi v ch c Fe(II) mi hnh thnh phc mu pH = 4 trong dung dch
nc, v phc ny c th c chit vo iso- amyl hay hn hp isoamyl v iso
propylether(1:1). Cu(I) cng hnh thnh phc khng mu c th c chit pH 4
nhng khng gy nh hng n vic xc nh Fe, vi iu kin l lng thuc th to
mu thm vo to phc vi c Fe v Cu.
(4b) hnh thnh phc 3 chelate mu bn trong khong pH = 2
(4b) to phc i vi Fe chn lc yu hn so vi (4a). Mt lng tng i nh
Cu, Co, v Cr cng c th gy nh hng do hnh thnh phc mu , nhng (4b) li
rt thun tin cho vic xc nh Fe thng thng, v giai on chit c th b qua khi
s dng (4b).
7.1.6.2. ng dng lm thuc th hunh quang:
(3) thng dng lm thuc th hunh quang xc nh cc cht nh Ag, Cd, Pd,
Re, Sc, Zn v t him c hm lng vt Nguyn tc ca phng php l da trn s
xut hin ca mu hunh quang trong hn hp to phc c hnh thnh khi c mt
phi t th hai, v d nh acid salicylic, acid 2phenyl4quinolinecarboxyluc, Eosine,
dibromofluorescein hoc TTA.
7.1.6.3. ng dng lm cht che:
Thuc th ca nhm ny thng hnh thnh phc khng mu vi cc ion kim loi
khc nhau v c th c s dng nh lm cht che trong phn ng to phc hay php
o quang.
(4a) cng c ng dng lm cht che loi b cc vt Fe, Cu, v mt s ion kim
loi no c trong dung dch thuc th dng phn tch hm lng vt kim loi.
Sau khi dung dch phn ng vi (4a), phc to thnh v cc cht khng phn ng
c loi b d dng bng cch chit vi dung mi khng tan trong dung dch.
7.1.6.4. ng dng lm cht chit:
Nh trnh by trn, phc cation st c bn cao v cc anion khc c th
c chit vo pha hu c nh 1 cp ion .Trong cc iu kin thch hp, vic chit rt
nh lng, v nng ca anion tng ng trong pha nc c th c xc nh bng
cch o cng ca Ferroin pha hu c, theo phng trnh sau
X ) phen ( Fe X 2 ) phen ( Fe
org
- 2
2
2
aq 3 aq
2
aq 3
+ +
+ +



157


7.1.6.5. ng dng lm cht ch th oxi ho kh:
Nh trnh by trn, phn ng thun nghch Ferroin Ferriin c th c ng
dng lm cht ch th trong phn ng oxi ho kh. Mc d, th dch chuyn ca ch
th m ti c th quan st s thay i mu quan h cht ch vi th hnh thnh, gi
tr c lng ca n phn no bin i tu thc vo cc cu t. Ni chung, v phc
mu cam ca Ferroin mnh hn phc mu xanh nht ca Ferriin, khong 9/10 ca
Ferroin phi c chuyn thnh Ferriin trc khi nhn ra im thay i mu. theo ,
th chuyn dch khong 0,05V(0,0591.log[Ferroin/Ferriin], ln hn th to thnh theo
l thuyt . Ch th c ngun gc t 5nitro1,10phenanthroline l mt ch th l tng
thch hp khi chun Ce(IV) ( perchlorate) trong acid perchloric v dd HNO
3
.
7.1.7. Cc thuc th c cu trc tng t:
7.1.7.1. 4,7dihydroxy1,10phenanthroline (thuc th Snyder)

Thng dng HCl (H
2
L.HCl), khi lng mol = 248,67); bt tinh th mu vng
(phn hu 475
o
C). 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, pK
1
(N+H) = 2,55, pKa
2
(OH) = 7,28 v pKa
3
(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; = 1,48.10
4
. 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; = 1,15.10
4
trong NaOH 0,5 7 N)
7.1.7.2. Phenyl2pyridylketoxime (2Benzoylpyridine oxime, PPKO)

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; pKa
1
(
H
2
L
*
) = 2,84 v pKa
2
(HL) = 12,19 ( = 0,1NaClO
4
, 40% acetone, 20
o
C).
Thuc th ny hnh thnh phc c mu vi Fe(II), (III) (), Cu(I) (cam), Cu(II)
C
N HO N
C
N
OH
N
N N
OH HO
HCl


158


(xanh), Au( III), Co(II), Pd(II), Pt( II) v UO
2
2+
(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 (ML
2
, (
max
= 545 nm, = 1,52.10
4
, 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

7.2.1. Nhng t ng ngha
Nhng thuc th c bao hm trong on ny c lit k trong bng 7.7, cng
vi nhng t ng ngha ca chng .
Bng 7.7. TPTZ V CC HP CHT TNG T
Thuc
th
Tn Tn gi
Cng thc
phn t
KLPT
(1) Tripyridyltriazine
2,4,6Tris(2pyridyl)S
triazine, TPTZ
C
18
H
12
N
6
312,33
(2)
Pyridyldiphenyl
triazine
3(2Pyridyl)56
diphenyl 1,2,4triazine,
PDT
C
20
H
14
N
4
310,36
(3)
Pyridyldiphenyl
triazine, sulfonic
acid, mui natri
3(2Pyridyl)56
diphenyl1,2,4triazine,
sulfonic acid, mui natri,
3(2Pyridyl)56di(4
sulfophenyl)1,2,4
triazine, mui dinatri,
PDTS, Ferrozine (*)
C
20
H
12
N
4
O
6
Na
2
.H
2
O 486,35
(*) Tn thng mi ca cng ty Ho Cht Hach., Lin Doanh.,Ames, Iowa
7.2.2. Ngun gc v nhng phng php ca tng hp
Tt c dng thng phm sn c thng c cung cp nh l tinh th mui mono
hoc dinatri c cha 1 2 phn t nc.
N
N
N
N
N N
N N N
N
X
X
(
1
) L
(
2
) L, X = H
(
3
) H
2
L, X = SO
3
H


159


(1) c iu ch bng cch t c c ca 2cyanopyridine trong s c mt natri
hydroxide.
(2) c iu ch bng phn ng tng giai on ca 2cyanopyridine vi
hydrazine, sau vi benzyl.
(3) l sn phm sulfonate ca (2) vi hi acid sulfuric.
7.2.3. Nhng ng dng trong phn tch.
Nhng thuc th o quang cho Fe(II) v Cu(II). Chng cng c dng o
quang cht xc nh ca cc kim loi khc, nh l Co, Cr, Ni v Ru. (1) v (3) th
thch hp cho vic s dng trong mt h cha nc.
7.2.4. Tnh cht ca thuc th
TPTZ (1) l tinh th hnh kim mu vng sng, im nng chy 245248
o
C, v t
tan trong nc ( 0,03g/100ml), nhng tan nhiu trong ethanol. N d dng tan trong
acid chlorhydric long v khng tan trong dung mi khng phn cc. Gi tr pKa ca
HL
+
l 3,10 (25
o
C, = 0,1 KCl), hoc trong dng khc, gi tr s phn ly nc hai ca
H
2
L
2+
l 2,82 v 2,75 (25
o
C, = 0,23 NaCl). S phn b ca (1) gia dung mi hu
c khc v dung dch acid c nghin cu, v gi tr pH1/2 l 1,93 (nitrobezen),
0,38 (phenylcarbiol, 1,20 (chloroform), 2,16 (dichloroethane), 2,50 (trichloroethylen),
1,72 (nbutanol), v 2,28 (npentanol).
PDT (2) l tinh th hnh kim mu vng sng, im nng chy 191192
o
C v tan t
trong nc, nhng tan nhiu trong alcohol v cc dung mi khc; pKa (LH
+
) = 2,95
(25
o
C).
PDTS (3) l dng bt c mu vng sng hoc vng xanh, nhit phn hy ln hn
350o, n thng c cung cp nh tinh th mui mono hoc dinatri c cha 1 2
phn t nc, v d dng ho tan trong nc to ra dung dch khng mu hoc sng
hng (0,7g/100ml trong NaHL 20
o
C).
Di hp th khng c trng c quan st trong (1),(2) v (3) trn vng kh kin.
7.2.5. Nhng phn ng phc cht v tnh cht ca phc cht
TPTZ (1) ,th hin bng mt phi t c 3 nhnh nh terpyridine,v PDT (2)v
PDTS(3) th hin bng mt phi t 2 nhnh nh bipridine, hnh thnh HL
2-
v HL
3-

loi vng vi ion kim loi c s phi tr bng 6, theo th t. Loi vng vi (1) v (3)
c tnh c trng cho kh nng tan trong nc ca chng. Vng st(II) vi (2)
([FeL
3
]
2+
) c th c chit vo isoamyalcohol, hoc, nu c mt SCN
-
, trong
chloroform hnh thnh pha acid r rt cha nc, tr thnh nn tng cho vic xc nh
vt st trong acid. iu kin hng s cn bng cho phn ng sau
K=K
ex
/[H
+
]
3
.[X
-
], c tnh ton bng (9,00,4).10
11
(trong H
2
SO
4
1M v
NaSCN 0,5M). Hng s bn ca lin kt vng c nh gi trong mt s c gii
hn ca nhng kim loi; TPTZ, log
2
(Co(II)), 9,11; log
2
(Fe(II)); 11,4; PDTS,
( ) | | ( )
2
3 2
org org
Fe 3 LH X FeL X 3H X
+ + +
+ + +


K
ex


160


log
3
(Fe(II)), 15,56 ( iu kin ca hng s pH 3,5 n 4,5).
Quang ph c trng ca vng kim loi c tm tt trong bng 9.13. Ph hp thu
ca FeTPTZ vng (FeL
2
2-
) trong dung dch cha nc c minh ho trong hnh sau:

7.2.6. Tinh ch v tinh khit ca cc thuc th:
TPTZ (1) v PTD (2) c th c tinh ch bng cch lp li qu trnh kt tinh t
dung dch ethanol v ethanolDMF, theo th t, cho n khi nhn c im si chp
nhn.
PDTS (3) c th c tinh ch bng cch kt tinh t nc hoc bng cch ho tan
vi mt t nc, sau thm ethanol vo lng c tinh cht.
Th nghim ca (3) c tin hnh ngoi cch quan st bng hp thu ca vng
vi Fe (2) bc sng 562nm, s dng vt qu 10 ln ca Fe(II) pH 4,5 (m
hydroxylamine acetat) ( = 2,86.10
4
). Mu trng st hin c trong thuc th c xc
nh bng cch o dung dch nc 2,5% bc sng t 500 700nm s dng ng o
1cm. Cch khc trong hp thu gia 502 v 700nm c s dng tnh ton c
cha st.
7.2.7. ng dng trong phn tch
Nhiu dn xut ca triazine, (1), (2), v (3) c pht hin l thuc th ca st
trong hu ht nhng ng dng trong thc t.
Trong nhng ng dng ca (2) c kt hp vi chit xut dung mi, (1) v (3) c
th c s dng trong h thng dung dch nuc. S thun li ca TPTZ l c nh
hp thu xut hin trong khong bc sng tng i rng v thuc th rt r. Tuy
nhin, thuc th khng chn lc i din cho Fe bi v Co, Cu, Cr, Ni v Ru cng hnh
thnh phc mu. Anion nh MnO
4
-
, NO
2
-
, v CrO
4
2-
cng c nh hng rt ln.
PDT v PDTS cng hnh thnh phc mu vi Cu, nhng peak hp thu ca phc
Cu(I) c cng yu hn v xut hin bc sng 488nm, phc ny khng cn tr
khi xc nh st.
TPTZ v TPTS c s dng xc nh Fe trong huyt thanh v sa vi cch
x l s b. Lng nh Cu c th che vi Neocuproine, thiourea, hoc acid
thioglycolic.
7.3. Nhng cht dn xut khc ca asymtriazine c nghin cu thay


161


th cho thuc th ca Fe, Cu, hoc Co (DIOXIME)
7.3.1. Nhng cng thc ng phn:
Dioxime c lit k trong bng 7.8, cng vi ng phn v cu trc cu to ca
n
Bng 7.8. Cc dioxime
STT CTCT Tn gi
Cng thc phn
t
(1)

2,3 Butandionedioxime,
Dimethylglyoxime,
Diethyldioxime, DMG
C4H8N2O2;
116,12
(2)

Furildioxime
C10H8N2O4;
220,18
(3)

1,2 Cyclohexanedione
dioxime, Nioxime
C6H10N2O2;
142,16

7.3.2. Ngun gc v phng php tng hp:
C tnh thng mi. c tng hp t phn ng tng ng ca diketone v
hydroxylamine (ngoi l i vi (1) l c tng hp t methyl ethyl ketone bng
biacetylmonoxime).
7.3.3. Dng trong phn tch:
Dimethylglyoxime (1) l mt trong nhng thuc th hu c chn lc u tin c
ng dng trong ha hc phn tch. Dioximes t (1) n (3) c s dng rng ri nh
mt thuc th kt ta chn lc, thuc th xc nh v thuc th o quang cho cc kim
loi Ni, Pd(II), Pt(II), v mt s ion kim loi khc. Trong s 3 ng phn hnh hc
khng gian, ch c ng phn anti c kh nng to phc chelate vi ion kim loi.


162



7.3.4. Tnh cht ca thuc th:
Dimethylglyoxime 1 l tinh th hnh kim, khng mu, nhit nng chy t 238
240
o
C (c s phn hy), tan rt t trong nc (0,632 g/L 25
o
C) v trong CHCl
3
(0,052
g/L 25
o
C) v hu nh c th ho tan trong C
2
H
5
OH 96% (16,3 g/L 25
o
C) v n d
dng tan trong dung dch kim v trong dung dch acid (pH < 1).
N b thu phn t t nhit phng v thng hoa nhit t 26 68
o
C (2.10
-2

TORR ) t trng D(CHCl
3
/H
2
O) = 0,083 25
o
C pKa (H
3
L
+
) = 8,7; pKa (H
2
L) = 10,6 ;
pKA(HL
-
) =11,9 ( M = 0,01; KIO
4
25
o
C )
Furildioxime (2), mu thng dng nht l hn hp pha trn t hai ng phn anti v
syn theo t l 1:1, tha mn cho hu ht cc ng dng trong phn tch. N l tinh th
khng mu hay c mu vng nht, nhit nng chy t 166 168
o
C (c s phn
hy). ng phn anti tinh khit nng chy 192
o
C v n hu nh khng tan trong
nc nhng tan d dng trong acetone, ru v ether v ho tan t trong chloroform
(10,6 g/L) benzene v ether du ha D(CHCl
3
/H
2
O) = 0,35 (H
2
L) pKa= 11,6 (50%
dioxane 25
o
C).
Cyclohexanedionedioxime (3) l tinh th khng mu nhit nng chy 187
188
o
C (c s phn hy). (3) tan trong nc nhiu hn (1) (8,2 g/L, 21,5
o
C ) v c th
ti kt tinh trong nc nng pKa (H
2
L) =12,0 (50 % dioxane 25
o
C).
7.3.5. Phn ng to phc v tnh cht ca phc:
Dioxime (H
2
L), ng phn anti, to thnh dng phc chelate M(HL)
2
vi nhiu
ion kim loi chuyn tip ho tr 2. Trong vai tr thuc th phn tch, tnh cht quan
trng nht ca (1), (2) v (3) l tnh khng tan trong nc, to phc mu chelate t
din (4) vi Ni, Pd(II), Pt(II). Trong ni phn t, lin kt hydro lm n nh phc
chelate M(HL)
2
, v do hp cht phc ny khng d b solvate. Trong trng hp
phc chelate ca Ni, vic to vi kim loi yu lin kt kim loi trong trng thi rn
cng gp phn lm cho cht khng tan trong nc. Mt khc, phc ca Cu(II) v
Co(II) vi dimethylglyoxime tan t trong nc, v v tr phi tr th 5 hoc 6 ca ion
kim loi trung tm b lin kt vi phn t nc. Trong trng hp ca phc chelate
Pd(II), n khng tan trong dung dch acid hay trung tnh, nhng li tan trong kim yu
v nguyn t trung tm c kh nng to lin kt phi tr vi ion hydroxide. V phc
chelate Ni khng th to lin kt phi tr vi ion hydroxide, thm ch trong mi trng
kim mnh, s khc bit ny trong c ch to phc c th c dung phn tch Ni
v Pd.
C ch to phc ca thuc th (1), (2) v (3) hu nh ging nhau nhng (2) c li


163


th hn (1) chelate kim loi tan nhiu hn trong dung mi hu c, v mu ca phn
ng nhy hn. Mt u im ca (3) so vi (1) l ha tan trong nc ca thuc th
cao hn v phn t khi nng hn c th dng chit trng lng mong mun.
Tht th v nhn thy, trong hu ht cc trng hp, KML/KML
2
1, m ph
thuc vo lin kt hydro ni phn t lm n nh phc chelate M(HL)2 trong dung
dch. S n nh u th ca M(HL)
2
m bo hu nh s to thnh phc M(HL)
2
hon
ton, p ng c u th ng k cho ng dng lm thuc th phn tch.
V phc chelate vi Ni, Pd(II) v Pt(II) c th chit vo dung mi hu c khng
trn ln, chng c th c tch ring tng nguyn t khc nhau bng dung mi chit
v c th xc nh bng phng php o quang. Dung mi thng dng nht dng cho
vic tch chit l CHCl
3
, v hng s phn ly ca phc chelate dimethylglyoxime gia
h dung mi CHCl
3
H
2
O c tnh log K
D
= -9,93 [Cu(HL)
2
]; 1,85 [Pd(HL)
2
] v 2,60
[Ni(HL)
2
].
Phc chelate ca Ni v Pd(II) c mu vng trong CHCl
3
v c th xc nh chng
bng phng php quang ph, tuy nhin kh nng hp th phn t ca phc Ni
dimethylglyoxime trong CHCl
3
khng cao nn t c ngha quan trng trong vic phn
tch hm lng vt trong thc t.
Mt phng php khc nhy hn xc nh Ni vi (1) da trn s to thnh
chelate nu hay trong kim yu, c s hin din ca tc nhn oxy ha nh bromine
hay persulfate. Kt qu thu c l phc chelate Ni(IV) [(NiL
3
)
2-
] v c th chit nh
mt cp ion vi diphenylguanidine. Da theo Zolotov, cu trc ca chelate khng ph
thuc vo tc nhn oxy ha trong t nhin, nhng ph thuc vo mi trng. Mt phc
trung tnh km bn s c to thnh trong dung dch ammoniac, v mt chelate anion
bn s c to thnh trong dung dch NaOH hay KOH.
Dioximme c th to nn phc chelate cu trc t din N
4
ion kim loi c v tr
phi tr trn trc z c th to lin kt c vi nhiu phi t, nh Co(II), (III), Cu(II)
v Fe(II), c th to lin kt vi cc anion (OH
-
, Cl
-
, Br
-
, I
-
v CN
-
) hoc nhng phn t
khng mang in (NH
3
, piridine, ) to thnh hn hp cc phi t ca phc
chelate [M(HL)
2
]X hoc [M(HL)
2
X
2
]. Phc dimetylglyoxime ca Ni, Pd v Pt khng
to lin kt cng ghp hoc c lin kt rt yu. V d khi Co(II) cho phn ng vi KI
mi trng pH = 4, ri phn ng vi (1) mi trng pH = 6 phc to thnh c mu
nu [Co(HL)
2
I
2
]
2-
(
max
= 435; = 1,06.10
4
). Phn ng ny c tnh chn lc cao cho
Co.
7.3.6. ng dng trong phn tch
7.3.6.1. Dng nh thuc th nh tnh
Dimethylglyoxime (1) to thnh kt ta mu hoc phc mu vi mt s ion kim
loi nh vy m chng ta c th s dng cho qu trnh xc nh nhng ion kim loi.
iu ny c tng kt bng 7.8
Bng 7.8. Xc nh kim loi vi dimethylglyoxime (1)
Ion
kim
loi
iu kin
Chuyn
mu
Cng thc
ca phc
Gii hn pht hin
Gii hn
pha long


164


Bi NH
3

Mu
vng ppt
14 g/ml 1:7,0.10
4

Fe(II) NH
3

, ha
tan
M(HL)
2
0,4g/0,05ml 1:1,25.10
5

Fe(III)
0.2 N
NaOH
Nu , M(HL)
2
1:3.10
5

Ni NH
3
ppt M(HL)
2
0,16g/0,05ml
Pd(II)
pH=2 (HCl
hoc
H
2
SO
4
)
Vng M(HL)
2

Pt(II)
Acid, sau
khi kh
Pt(IV)
ppt H(HL)
2

Phc Pd and Pt tan trong
NaOH,nhng Pt cao mu
ta

Tc SnCl
2
HCl Xanh 0,04 g/100 ml
V(IV)
NH
3
c mt
Fe(II)
0.04 g/100 ml 1:5.10
5

7.3.6.2. Dng nh tc nhn tch chit nhng ion kim loi:
Nh c m t trc phc chelate ca dioxime vi Ni, Pd(II), Pt(II) khng
tan trong nc v mt vi kim loi khc v chit c th chit ra bng dung mi hu c
chng ta c th tch nhng ion kim loi t hn hp nhiu kim loi bng phn ng kt
ta hoc hoc chit bng dung mi Ni trong pha hu c c th chit bng dung dch
HCl long.
Dimethylglyoxime (1) hoc cyclohexanedionedioxim (3) l phn ng kt ta c
trng ca Ni trong mi trng NH
3
c mt ca tatrat lm cht che khi c mt ca cc
ion Co(II), Mn(II) hoc Zn. Tuy nhin phn ng kt ta c thc hin mi trng
pH = 5.
Thng thng khi thm alcohol vo trong dimethylglyoxime khi un dung dch
nng s lm cho Ni v phc chelate to thnh kt ta. Tuy nhin khi iu kin dung
dch nng hn 50% lng ta Ni v phc chelate b ho tan trong ru, tan s
khng ng k khi tng ru nh hn 30%. Do trong khi s dng ru vi thuc
th dimethylglyoxime khi thm th tch ru vo khng vt qu mt na th tch ca
dung dch Ni. Trong qu trnh phi km hm nhit si ca ru trong dung dch
trnh dung dch bn ra ngoi v khi bn ra ngoi lm hao ht hm lng lm sai s
trong phn tch trng lng. Trong phc chelate ca cylohexanedioroxime (3). Thuc
th ny tan trong nc, v vy trnh ru thot ra ngoi, y l thuc th c th dng
trong phn tch trng lng i vi Bi. Kt ta n mi trng pH = 12, s c mt
ca EDTA. Bi c th nh lng bng cch kt ta tch ra khi hn hp dung dch
cha hn 30 nguyn t bao gm Ni v Pd.
* Pd(II) phc chelate ca (1) hoc (3) cng c th nh lng kt ta trong khong
bng dung dch acid (HCl hoc H
2
SO
4
) trong iu kin ny nhng ion kim loi khc
khng kt ta.
7.3.7. Dng nh thuc th o quang:


165


Nh tho lun trc y chit quang ca Ni v Pd (2) hu nh rt nhy v phng
php tc dng vi thuc th (2) n gin. S hp th ca phng php o quang ca
Ni trong dung dch kim vi s c mt ca cht oxi ho cng c th chp nhn du
hiu xc nh. Trong phng php ny cng hp th ph thuc rt nhiu vo diu
kin ca phn ng. Vy mi trng chung (NaOH hoc NH
3
) c tc nhn oxy ho sau
mt thi gian phn ng to ra mu y l iu kin dng nhn bit phn ng.
7.3.8. Dng trong iu kin khc:
Nhng thuc th c th dng lm dung dch chun trong chun kt ta ca Ni
bng ampe k.
Xc nh Co
2+
vi thuc th Dymetlyglyoxime chun bng in ct thu ngn v
xc tc H
2
c bc sng xc nh dng xc nh Co
2+
c nhy t (5 20 ppm).
Phc chelate Ni (1) v (3) c th tm thy pha tnh trong sc k lng ca mch
gm cc hydro carbon khc nhau.
7.3.9. Cc monoxime:
Phi t hai nhnh nm trong nhm oxime c a vo 2 v tr ca pyridine, c
tc dng nh thuc th st cho Fe(II), v nhng thuc th nh vy c ni n
trong phn thuc th Ferroin (phn IX).
Mt loi phi t hai nhnh khc c mt nhm oxime, k c salicylaldoxime (5)
(H
2
L, nhit nng chy 50 59
o
C pK = 9,18; 25
o
C) v benzoin monoxime (6) (H
2
L,
nhit nng chy 153 155
o
C pKa = 12, 50% dioxane, 25
o
C), ngi ta cn gi loi
phi t ny l Cupron. C 2 thuc th u to thnh dng phc chelate M(HL)
2
trung
ha in vi Cu(II), v vi mt s ion kim loi ha tr 2, chng c th c chit vo
cc dung mi hu c khng trn ln. V vy chng rt c ch trong vic phn tch cc
kim loi.

Gn y, nhiu dng monoxime dn xut t acetophenone, acenaphthenequione,
, c nghin cu lm thuc th phn tch.
7.4. PORPHYRIN
Porphyrin l tn gi ca hp cht c vng porphin. Cng thc cu to:
OH
C
H
N
OH
C
H
HO
C
N OH
(
5
) (
6
)


166



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

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
Diamine Danh php
Cng thc phn t v
khi lng mol
(1)
3,3
Diaminobenzidine,
tetrahydrochloride
3,3,4,4
Biphenyltetramine,
tetrahydrochloride,DAB
C
12
H
14
N
4
.HCl.2H
2
O;
396,14
(2)
2,3
Diaminonaphthalene
DAN C
10
H
10
N
2
; 158,20
(3) 1,2Phenylenediamine phenylenediamin
C
6
H
8
N
2
; 108,14

(4)
5Chloro1,2
Phenylenediamine
C
6
H
7
N
2
Cl; 142,59
(5)
5Nitro1,2
Phenylenediamine
C
6
H
7
N
3
O
2
; 153,14
7.5.2. Ngun gc v phng php tng hp
NH
2
NH
2
H
2
N
H
2
N
NH
2
NH
2
X
NH
2
NH
2
(
1
)
(
2
)
(
3
) X = H
(
4
) X = Cl
(
5
) X = NO
2
N
N
N N
R
R
R
R
H
H
H
2
L


167


Tt c chng u c gi tr thng mi. Chng c to ra bng cch kh nhng
hp cht nitro lin kt:
(1) t 3,3dinitrobenzidine, (2) t 2,3dinitronaphthalene, (3) t onitroaniline v
(4) t 4chloro2nitroaniline vi Sn/HCl. (5) to ra bi s kh 2,4dinitroaniline vi
(NH4)
2
SO
4

7.5.3. Nhng ng dng phn tch
Nhng thuc th ny c chn lc cao cho Se. (1) v (2) c s dng nh l
nhng thuc th trc quang trong vng kh kin v vng UV, tng ng. (2) c s
dng trong phng php hunh quang. (4) v (5) dng cho trc quang v sc k kh.
7.5.4. Nhng tnh cht ca thuc th
- 3,3Diaminobenzidine (1): thng c cung cp nh tetrahydrochloride

dng
bt tinh th, khng mu, t
o
nng chy 328 330
o
C (c s phn hy). Ho en ngoi
nh sng, do cn c gi ni lnh, ti di kh nitrogen. D tan trong nc
nhng khng tan trong nhng dung mi hu c khng phn cc.
- 2,3Diaminonaphthalene (2): trng thi tinh khit

dng bt tinh th, khng

mu, nhng nhng mu ( sn phm ) thng mi thng c mu vng hoc xm nu v
s oxi ho ca khng kh, to nng chy 190 191
o
C v hu ht khng tan trong nc
lnh, cn nhng s tan kh to > 50
o
C. c bo qun ni lnh v ti.
- oPhenylenediamin (3): dng bt tinh th, khng mu, d ho en trong khng kh, to
nng chy 101 103
o
C v d tan trong nc, cn. Thuc th ny nn c bo qun
ni lnh, ti; pKa
1
(H
2
L
2+
) = 0,86; pKa
2
(HL
+
) = 4,75.
- 5Chlorophenylenediamine (4): dng bt tinh th, khng mu, kh b oxi ho ngoi
khng kh hn (1) v (3), to nng chy 72 74
o
C. D tan trong nc v dng dung
dch th thuc th ny cng bn; pKa
1
(H
2
L
2+
) = 0,11; pKa
2
(HL
+
) = 4,16.
- 5Nitrophenylenediamine (5): dng bt tinh th mu vng sng, kh bn trong
khng kh, to nng chy198 200
o
C. D tan trong nc; pKa(HL
+
) = 3,07.
7.5.5. Phn ng to phc v tnh cht ca phc
+ Phn ng vi ion kim loi
- Nhng odiamin thm ging nh phi t 2 nhnh v tr n,n (chelate c 2 nhm
c kh nng lin kt vi ion kim loi) hnh thnh phc mu vi nhiu ion kim loi.
VD: thuc th (3) tc dng vi Pt(II) to thnh phc chelate loi ML2 (
max
= 703nm,
= 9,8.10
4
) mi trng trung tnh; thuc th (1) tc dng vi V trong mi trng pH =
2 3 to ra phc chelate loi ML (
max
= 470nm; = 3310). Tuy nhin, chng l nhng
thuc th khng c nhiu ng dng thc t quan trng ging nh nhng thuc th to
mu i vi nhiu ion kim loi.
+ Phn ng vi Se(IV)
- u tin tm thy thuc th (1) tc dng vi Se(IV) trong mi trng acid to
phc c mu vng gi l piaselenol, n c th c chit vi dung mi hu c pH
= 6 7 nh l: benzene, toluene, chloroform, butanol, ethylacetate. Phn ng ny c
th c vit:


168



- Kt qu l piaselenol sinh ra mu vng v c th c xc nh bng trc quang
vng kh bin. Sau ny nhiu odiamine thm khc c tm thy hnh thnh
piaselenol v nhng thuc th (2), (5) l nhng thuc th chn lc i vi Se(IV).
Ngc li vi piaselenol ca (1) th hp th cc i ca piaselenol ca (3) nm
vng t ngoi (UV). Trong trng hp ca piaselenol ca (2) th hp thu hunh
quang bc sng di hn so vi dng t do ca thuc th (2) iu ny c th a
ra vic xc nh Se(IV) bng hunh quang vi nhy cao.
- Piaselenol t (3)

(5) d bay hi v vy n c th c phn tch bng sc k kh.

Hm lng siu vt ca paselenol ca (4) v (5) c th c pht hin bng detector
ECD.
7.5.6. Nhng ng dng trong phn tch
- ng dng thc tin ca nhng thuc th ny ch xc nh Se(IV). V s oxi
ho khc th Selen khng phn ng vi nhng thuc th ny, Selen trong mu phi b
kh hoc oxi ho v Se(IV). Mt trong nhng cch thun li oxi ho Se
2-
v So l
s dng dung dch m oxi ho kh (Br/Br
-
) sau khi ph mu t. S kh Se(VI)

Se(IV) ta dng Ti(III).
- Thuc th (1) c ngh cho phng php trc quang trong vng thy c.
iu kin ph hp, thuc th (1) phn ng vi Se(IV) pH = 2 3 50
o
C. Nhng s
cn thit ca phc piaselenol ny phi c thc hin pH = 6 7 bi nh hng ca
s proton ho ca nhm amin t do. S chit nhiu ln ca piaselenol vi toluene l
cn thit t c s tch 1 cch nh lng (t

60% cho ln tch 1). Ion SO

4
2-

gy cn nhiu i vi vic xc nh bi vic to kt ta vi thuc th to ra suffate
khng tan, nhng c th c che y bng cch thm lng d NH
4
Cl. Nhng cation
ph bin c th c che bng EDTA, Fe(III) c th c che bng F
-
, PO
4
3-
v Cu(II)
c th c che bng oxalate.
- Thuc th (3) cng c dng nh thuc th to mu vi Se(IV) nhng trong
vng UV. Tuy nhin, lng tha thuc th khng c chit vo toluene bi v s
chit piaselenol c thc hin pH = 1 2. Hn th na thuc th ny khng b cn
nhiu vi SO
4
2-
v nhy cao gp 2 ln so vi (1).
- Vic xc nh hm lng siu vt ca Se c th t c bng vic s dng
phng php hunh quang vi thuc th (2) hoc phng php sc k kh vi thuc
th (3)

(5). Trong phng php hunh quang, iu quan trng l s dng
diaminonaphthalene (2) tinh ch vi nn hunh quang thp quan st = 520nm.
Trong sc k kh, dung dch mu (pH1) c x l vi lng d thuc th (4) hoc (5)
trong 1h. Phc piaselenol c chit vi 1ml toluene v 5l dd c a vo sc k
kh vi iu kin sau.
- Ct thu tinh c chiu di 1m, c ng knh 4mm, y cht hp ph
chromosorb c kch c li 60 n 80 cha 15% SE 30, nhit ca ct v u d
H
2
N
H
3
N
+
NH
2
NH
3
+
+H
2
SeO
3
H
2
N
H
3
N
+
N
N
Se
+2 H
2
O + H
3
O
+


169


bt in t l 200
o
C, tc dng ca kh mang 20ml/pht He.
- Nhng Cation ph bin,nu khng ln qu gii hn, khng gy nh hng hay
nhng phc khng bay hi. C th xc nh lng nh bng 0,15g Se mi ml
Toluene. Phng php ny c ng dng xc nh hm lng siu vt ca Se
trong acid sulfuric, Telua kim loi, nc bin, nhng mui ng, nguyn liu cy trng
v sa .
7.6. S tinh ch v tinh khit ca thuc th:
- Thuc th (1): cht b h hng nh c th c tinh ch bng cch ho tan vo
nc, sau cho kt ta vi HCl m c. Nhng kt ta ny c lm kh trn
NaOH. Tht khng d dng tinh ch cht ho en.
- Thuc th (2) : dung dch thuc th ny c nn hunh quang thp do nn c
pha hng ngy. Ho cht ny c kt tinh li trong nc 0,05g ho cht (2) ho tan
vo 50ml HCl(0,1N) to 50
o
C. Sau lm lnh (ngui ) ri dung dch ny c chit
2 ln vi 10ml decalin (C
10
H
18
) loi b i nhng g khng tinh khit v a vo li
tm ly ra tinh th ho cht.
- Thuc th (3), (4), (5): nhng thuc th ny c th c tinh ch li bng s kt
tinh li t nhng dung mi kt hp. S tinh khit ca nhng thuc th ny, ngoi tr
(1), c th c c on bng vic quan st to nng chy ca chng.
CHNG 8
THUC TH VI CU TRC S
8.1. DITHIZONE V NHNG THUC TH TNG T

8.1.1. Danh php
Dithizone hay cn gi l 1,5diphenylthiocarbazone, n,ndiphenylC
mercaptoformazane, phenylazothioformic acid 2phenylhydrazide.
8.1.2. Ngun gc v phng php tng hp
c dng trong thng mi. c tng hp bng phn ng gia carbon disulfide
v phenyldrazine, km theo un nng cn thn oxy ha hn hp phn ng.
8.1.3. ng dng trong phn tch
c s dng rng ri trong phng php chit trc quang xc nh cc kim loi
CTCT: C
13
H
12
N
4
S
KLPT: 256,32
HS C
N N
N N
H


170


nng nh: Cd, Cu, Hg, Pd v Zn v c tnh chn lc v nhy cao.
8.1.4. Tnh cht ca thuc th
Dng bt tinh th mu tm en c nh kim, im nng chy 165
o
C n 169
o
C,
thng hoa 40 n 123
o
C (0,02 Torr). Thc t khng tan trong nc pH nh hn 7
(5 n 7,2.10
-5
g/l), nhng tan hon ton trong kim (pH >7, > 20 g/l) c mu vng ca
ion dithizoneate (HL
-
) (
max
= 470 nm, = 2,2.10
4
) v tan trong nhiu dung mi hu c
khc. tan trong nhng dung mi chn lc c lit k trong bng 8.1
Bng 8.1. Ph hp th trong vng kh kin trong cc dung mi hu c ca dithizone

max
(nm) (x10
3
)
Dung mi
tan
(g/L,20
o
C) 1st 2nd 1st 2nd
R(t s
peak)
Mu
Ethanol 0,3 596 440 27,0 16,6 1,64
Xanh nc
bin
Carbon
tetrachloride
0,512 620 450 34,6 20,3 1,70 Xanh
Dioxane 0,349 617 446 31,9 19,1 1,72
Nc + dioxane 602 446 32,4 16,4 1,98
Benzene 1,24 622 453 34,3 19,0 1,80 Xanh m
Chlorobenzene 1,43 622 452 34,8 18,3 1,90 Xanh
Nitrobenzene 627 454 31,9 16,7 1,91
Chloroform 16,9 605 440 41,4 15,9 2,59
Xanh nc
bin
Mc d dithizone c cho l mt diacid (phn ly thiol proton v imino proton),
khng c du hiu ca L
2-
trong dung mi nc. Trong s cc gi tr pKa c bo
co th gi tr pKa = 4,470,25 l tt nht, n c nh gi t bng tan.
H s phn b ca dithizone gia hai pha nc v pha hu c c th c trnh by
v n gin ha nh di y nu trong mi trng l baz vi [H
2
L]
aq
<< [HL
-
]
aq
v
[H
+
] << Ka:
Ph hp th ca dithizone (H
2
L) trong carbon tetrachloride, ion dithizonate (HL
-
)
trong nc, v mercury dithizoneate [Hg(HL)
2
] trong tetrachloride biu din trong hnh
8.1. Ph ca dithizone trong nhng loi dung mi hu c biu din thnh hai di ph
kh r m n c quan h ti hin tng h bin thione (1) v thiol (2), mc d
nhim v ca mi pic th hin vi mt loi tng ng nhng cha dt khot.


171




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.
+ +
+ + nH ) HL ( M L nH M
org n org 2
n

Ion kim loi phn ng vi dithizone c minh ha trong hnh 8.2. Nhng phc
ny tan trong cc dung mi hu nh chloroform hoc carbon tetrachloride. Cu trc
chnh ca dithizonate cho ion kim loi tetracoordinate ha tr II c th trnh by nh
sau (3)
(1) (2)
N N
C S
N
H
NH
N N
C S
N N H
H
Bc sng nm
Hnh 8.1. Ph hp th ca dithizone (H
2
L)
v Mercury(II)dithizonate trong carbon
tetrachloride v ca ion dithizonate (HL
-
)
trong nc. (1) Dithizone (H
2
L) trong
CCl
4
; (2) dithizonate (HL
-
) trong nc; (3)
mercury(II) dithizonate [Hg(HL)
2
] trong
CCl
4
.


172



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

Ia IIa IIIa IVa Va VIa VIIa Ib IIb IIIb IVb Vb VIb VIIb O
H H He
Li Be B C N O F Ne
Na Mg Al Si P S Cl Ar
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb TE I Xe
Cs Ba La Hf Ta W Re Os Ir Pt Au HG Tl Pb Bi Po At Rn
Fr Ra Ac Th Pa U
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
M
C
S
C
M
N
N
N
N
S
N
N
N
N N
C
S
N
N
M M
N
(4) (5)
N
N
C
S
M
N
N
H
N
N
C
S
N
N
H
(3)
VIIIa


173


Dithizone rn bo qun tt trong ti v t lnh trnh khng kh oxy ha , mu
thng mi c tinh khit t 30 n 90%, ph thuc vo iu kin tn tr. Thuc th
rn th c tinh ch bng cch chit Soxhlet vi ether loi cc sn phm oxy ha,
km theo ho tan trong chloroform nng v thm alcohol kt ta.
Phng php tinh ch hiu qu hn vi lng mu nh:
Lc dung dch c ca mu th trong tetrachloride bng phu thy tinh, sau lc
phn lc vi dung dch ammoniac 0,8N chit ion dithizonate. Chit pha nc vi
carbon tetrachloride.
Cui cng acid ha dung dch vi acid sulfuric kt ta dithizone tinh khit. Lm
kh mu trong chn khng. Lng milligram c th c tinh ch bng phng php
sc k vi dung dch benzene, trong ct gm c hn hp silicagel c celite 545 hoc
sc k giy.
tinh khit ca dithzone c th c xc nh bng mt trong nhng phng
php sau:
a. Phng php trc quang
hp th ca dung dch carbon tetrachloride ca nng dithizone c bit o
quang 620nm v lp li tng t vi mu trng. tinh khit c tnh bng cch
da trn hp th ca phn t gam ca dithizone tinh khit ( = 3,4.10
4
620nm).
b. Phng php th tch
Chun dung dch chloroform ca nng dithizone c bit (0,125 mg trong
10 ml) bng dung dch AgNO
3
50.10
-6
(25,0 ml), loi b pha hu c sau mi ln chit.
Chit chun cho n khi phn chit khng cn mu vng, nhng hn hp c mu
vng xanh. tinh khit c tnh t gi tr ca dung dch dithizone b ph hy trong
chun .
c. Phng php t s peak
T s cng ca hai m ph nh ln ca dithizone (
1
= 602 n 617nm,
2
=
440 n 454nm) c th dng o tinh khit bi v dithizone khng tinh khit hp
th di 550nm. Mc d v tr ca hai m ph hu nh khng thay i khi thay i
dung mi, nhng t s cng thay i mt cch ng lu . Gi tr trong chloroform
v carbon tetrachlororide nh sau:
A605/A445(CHCl
3
) = 2,59
A620/A450(CCl
4
) = 1,70
8.1.7. ng dng trong phn tch
Thuc th chit:
Phm vi ca ion kim loi c chit vi dithizone trong dung mi hu c c th
c tnh t K[H
2
L]
org
v pH ca pha nc. S phn li (tch) ca hai hoc nhiu ion
kim loi c th t c nh s la chn pH thch hp ca pha nc v nng
dithizone trong pha hu c. chn lc cho nhiu ion kim loi c th c ci thin
hn bi s kt hp s dng cc tc nhn tr phc (hoc tc nhn che). Mt vi v d


174


in hnh tm tt trong bng 8.2


Bng 8.2. chn lc trong chit DITHIZONE
iu kin
Ion kim loi c
chit
Min kim
Dung dch kim cha CN-
Dung dch kim mnh cha citrate hoc tartrate
Dung dch kim nh cha kp (2-hydroxyethyl)
Dithiocarbamate

Bi, Pb, Sn(II), TL(I)
Ag, Cd, Co, Cu, Ni,
Yl
Zn
Min acid
Dung dch acid nh cha CN-
Pha long dung dch acid cha Br- hoc I-
Pha long dung dch acid cha CN- hoc SCN-
Dung dch acid long (pH=5) cha S2O32-
Dung dch acid long (pH=4-5) cha S2O32-
Pha long dung dch cha EDTA

Ag, Cu, Hg(II), Pb(II)
Au, Cu, Pd
Cu, Hg
CD,Pd, Sn(II), Zn
Sn(II), ZN
Ag, Hg
Thuc th trc quang:
Chit trc quang vi dithizone c th c thc hin bng ba cch: trc quang n
mu, trc quang hn hp mu, v trc quang lng sng.
Trc quang n mu:
Mu dung dch sau khi hiu chnh pH v thm cc cht b tr cn thit, lc lin tc
chia carbon tetrachloride hoc chloroform ca dung dch dithizone n khi tt c kim
loi bt u tch ra. Giai on cui cng ca qu trnh chit, mu ca dung dch
dithizone cn li l mu xanh l cy. Kt hp chit sau khi lc vi vi ammoniac long
chit phn dithizone d, dung dch thu c em o trc quang. Nhiu nguyn nhn
dn n sai s trong phng php ny. Nu trong mi trng ammoniac qu cao, mt
vi kim loi dithizonate c th b phn li, kt qu ph nh sai s. Nu trong mi
trng khng mnh, dithizone khng chit hon ton, kt qu c th sai s.
Dithizone c th c di chuyn d dng trong dung dch carbon tetrachloride hn
trong dung dch chloroform. Bn cnh kh nng thay i phc chnh thnh phc
ph do s ty ra ca kim. V th, trong thc t khng th loi b dithizone tha mt
cch trit khng hnh thnh vi phc ph.
Trc quang hn hp mu:
Trong phng php ny, dung dch hu c cha dithizonate kim loi v dithizone
d c xc nh. Khi peak thu c ca nhiu dithzonate kim loi hin ra mt cch
hn n trong mt vng ni m ng dithizone t do c hp th thp nht, php
trc quang thng xc nh ti gi tr
max
, hp thu dithizone d c n b bng
vic o mu trng. Sai s chnh trong phng php ny c th do mt dithizone b oxy
ha trong qu trnh phn tch, nhng c th lm gim n gi tr nh nht bng mu


175


trng, nhng t c iu ny th qu trnh phn tch cng nh trong bc chit
phi hon ton ging nhau gia mu phn tch v mu trng.
Trc quang lng sng:
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
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
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]

p

t
h

Bc sng nm


176


sut. Bo qun trong ti v lnh.
8.1.9.Mt s thuc th khc c cu trc tng t
Nhng dithizone thay th
Dui y l nhng dithizone thay th c tng hp v tnh cht vt l ca
chng c nghin cu cho vic s dng nh l mt thuc th phn tch.
2,2 (hay o,o) dichlorodithizone,4,4 (hay p,p) dichlorodithsone,2,2
dibromodithizone,4,4dibromodithizone,2,2diioddithizone,4,4
diioddithizone,4,4diflorodithizone, 2,2dimethyldithizone, 4,4dimethyldithizone,
4,4disulfodithizone, , Di(o hay p diphenyl) thiocarbanzone, Dinaphthyl (6) v
dinapthylthiocarbazone
8.2. THIOXIN
CTPT: C
9
H
7
NS.2H
2
O
KLPT: 197,25

8.2.1. Danh php
8Mercaptoquynoline, 8quinolinethiol
8.2.2. Ngun gc v phng php tng hp
Thioxin c gi tr kinh t nh l H
2
hoc HCL. N c to ra bi s kh ca
quinolyl8sunfunylcholoride vi SnCl
2
hoc s phn ng ca diazon ha 8amino
quinoline vi thioure. Bn thn ca thioxin kh khng bn vi s oxy ha ca khng
kh. Diquinolyl88disunfile l sn phm oxy ha ca thioxin, n c dng nh l
mt cht tiu biu, n nh v c gi tr thng mi. Thioxin d dng c iu ch
bng kh disulfide vi H
3
PO
2
3
.
8.2.3. Nhng ng dng trong phn tch
Thioxin l mt sunfua tng t ca 8quinolinol (oxine) v c coi nh mt phi
t cho S, N hnh thnh phc chelate kim loi vi nhng ion kim loi nh nh l Ag,
As, Bi, Cd, Co, Fe, Ga, Hg, In, Ir, Mn, Mo, Ni, Os, Pb, Pd, Pt, Re, Rh, Ru, Sb, Se, Sn,
Te, Tl, V, W v Zn. Thioxine c s dng nh l: php o trc quang, hunh
quang v l dung mi chit trong phn tch cc vt ca nhng nguyn t ny.
8.2.4. c tnh ca thuc th
Mc d bn thn Thioxin l dng du mu xanh ti, nhng dng dihydrat l tinh th
hnh kim c mu ti, nng chy 58 59
o
C v nhit thng hoa l 99 177
o
C
(2.10
-2
Torr). N d dng oxy ha trong khng kh cho ra diquinolyl8,8disulfide.
Disulfide c th c to nn bi s oxi ho vi H
2
O
2
. Disulfide c dng bt trng,
im nng chy 202 204
o
C v rt n nh.
Hidrochloride (HL.HCl) v mui natri (NaL. 2H
2
O) ca n l dng bt mu vng
v nn bo qun di nit trong bng ti, mc d chng n nh hn c thuc th t
HS N


177



do.
Thioxin tan t trong nc (0,67 g/L 20
o
C, pH = 5,2) nhng d dng tan trong
dung mi hu c nh l l C
2
H
5
OH (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:
] L H HL [ h L H
2
+ + +
+ +
[HL + H
+
L
-
] H
+
+ L
-

H
+
v H
+
L
-
ch r s trung tnh (1) v dng ion lng tnh (2) ca thuc th.

C hai dng tn ti nh l hn hp h bin v hng s h bin c th nh sau:
=
t
Ion l ng tnh
K
Trung tnh

8.2.5. Phn ng to phc v tnh cht ca phc
Thioxin phn ng vi ion kim lai nh, dng kt ta khng ha tan hoc l nhng
dung dch mu. Thnh phn ca chelate ph thuc vo tnh cht ca acid v acid
ca dung dch.
Phn ng ca Thioxin vi ion kim lai trong s hin din ca cc tc nhn bo v
khc c u t t m. Hu ht cc tc nhn bo v hiu qu chng li Thioxin l acid
HCL c vi (Ag, Bi,Fe, Hg, Mo, Sb, v Sn), thiore vi (Ag, Au, Cu, Hg, Os, Pt v
Ra), NaF vi (Fe(III) ,Sn(IV), v kim KCl vi (Ag, Cu ,Co, Fe(II), Ir, Ni, Os, Pd, Pt
v Ru). KSCN l mt tc nhn bo v tt nht cho Fe(III) v mt s tc nhn nh l Cd
v Zn.
8.2.6. S tinh ch v tinh khit ca thuc th
Thioxin (dng baz t do) d dng oxy ha trong khng kh (khng d dng oxy
ha vi HCl v mui Na), trong th trng nhng mu oxy ha mt cch khng hon
ton dn n s nhim bn vi diquinolyl8,8disunfile (M
2
S) nhng mu ny khng
N
SH
N
+
S
-
H
K
t
(1)

(2)



178


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 H
3
PO
4
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 CCl
4
isopropyl 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

C
2
H
5
N
C
2
H
5
C
S
SNa
CTPT: C
5
H
10
NS
2
Na.3H
2
O
KLPT = 225,30


179


8.3.1. Danh php
Cupral, mui carbamidat DDTC natri.
8.3.2. Ngun gc v phng php tng hp
C gi tr thng mi, n c to thnh bi phn ng ca diethylamin v carbon
disulfide trong dung dch natrihydroxide.
8.3.3. ng dng trong phn tch
c s dng nh l mt cht to ta v l dung mi thuc th tch chit cc
ion kim loi nh. Cng nh c s dng lm thuc th trc quang cho Bi, Cu, Ni v
mt s kim loi khc.
8.3.4. c tnh ca thuc th
Thuc th ny thng l mt mononatri, mui trihydrate, dng tinh th khng
mu. Dng mui khan nng chy 94 n 96
o
C v tan t do trong nc (35g/100ml ,
20
o
C ) to ra phn ng kim. Mc d thuc th dng rn th bn, nhng trong dung
dch acid th b phn hu rt nhanh. Vi nhng gi tr pH tng dn th dung dch tr
nn bn hn. Mt dung dch c nng 1% c th c gi trong vi tun v dung
dch 0,1% th gi c mt tun. Thi gian mt na dung dch nc tham gia phn
ng ha hc l pH < 2 v pH = 5 l 7 giy n 87 pht tng ng. N hu nh
khng tan trong dung mi khng phn cc (0,006g/100ml trong CCl
4
), nhng tan c
trong ru.
S dng trong vic tch chit th mui diethylammoium thng c dng hn bi
v n tan c trong nc, cng nh tan tt trong carbon tetrachloride, chloroform, v
mt s dung mi hu c khc. Hn na, trong vic tch chit kim loi trong dung dch
acid, mt lng ln dithiocarbamate vn cn li trong dung mi hu c, v th m s
phn hu ca thuc th trong acid c th trnh c.
Acid Diethyldithiocarbamic (HL) l mt acid trung bnh yu, pKa = 3,95 (19
o
C);
K
D
(CCL
4
/H
2
O) = 2,4 n 3,4.10
2
;K
D
(CHCl
3
/H
2
O ) = 2,30 n 2,35.10
3
. Ph hp thu
ca mui natri trong dung dch nc c minh ha trong hnh 8.4.

8.3.5. Phn ng to phc v c tnh ca phc
Hnh 8.4. Ph hp th ca Na-DDTC
trong dung dch nc;

hp
th
Bc sng nm


180


DDTC c xem nh l mt anionic phi t 2 nhnh ha tr mt nhn 2 nguyn t
sulfur, v to thnh nhng kt ta c mu vi hn 30 nguyn t ti pH > 4. Phn ng
xy ra c chn lc hn trong dung dch acid, vi s u tin i vi ion kim loi. Chng
hu ht khng c in tch, dng phc bo ha phi tr v c th tch chit ra bng
dung mi hu c, nh l chloroform hoc tetrachloride. V d, cu trc ca phc
Cu(II) l nh sau :

Mt vi phc c mu nh (Bi, Cu(II), Ni, ...), nhng nguyn t ny c th c xc
nh theo phng php quang ph.
Tnh chn lc cho vic tch chit ion kim loi c th tt hn bng vic chn khong
pH v chn nhng cht che thch hp cho dung dch xc nh.
hng s ca phc DDTC bn, c nhng phng php gin tip da trn phn
ng song song vi mt ion kim loi khc hoc mt phi t khc thng c s dng
thay th trnh xy ra s phn hu phc ca phi t v phc kim loi trong dung
dch acid.
Nh m t trn, mt vi phc kim loi c th c tch trong dung dch
chloroform hoc carbon tetrachloride. Khi phc kim loi c mu cao, n c th d
dng c xc nh theo phng php trc quang sau khi c s tch chit dung mi,
bi v bn thn thuc th khng hp thu trong min kh kin. c im quang ph ca
phc DDTCkim loi c tng kt trong bng 8.3.
Bng 8.3. C IM PH CA PHC MU KIM LOI -DDTC
Trong CCl
4
Trong CHCl
3

Ion kim loi T l Mu
max
(nm) (x10
3
)
Bi ML
3
Vng 366 8,62 370 10,5
Co(III) Xanh
323
367
650
23,93
15,7
0,55


650


0,52
Cu(II) Nu 436 13,0 440 12,1
Fe(III) Nu
335-350
515
600
12,7
2,49
2,05

515

2,79
Ni Vng xanh
326
393
34,2
6,11

395

5,87
Pd(II)
305
345-350
54,8
7,13

Pt(IV) 355 5,87
Sb(III) 350 3,37
Te(IV) 428 3,16
UO22+ nu 380 - 400 390 3,87
S
C
S
N N C
S
S
Cu


181



8.3.6. S tinh ch v tinh khit ca thuc th
Natri diethyldithiocarbamate c th c tinh ch bi s kt tinh t dng nc
t tinh khit cn thit l 99,5%.
Mt mu tinh khit s cho dung dch trong khng mu khi ho tan vo trong nc
hoc ethanol (0,1%). Xc nh hm lng nitrogen bng phng php kieldahl c th
c dng th nghim.
8.3.7. ng dng trong phn tch
S dng nh l mt thuc th dung mi tch chit:
chn lc trong vic tch chit kim loi c th c ci thin bi vic chn la
nhng gi tr pH thch hp ca dung dch v vic s dng nhng cht che. Bng 8.4
tng kt cc iu kin ca s tch chit. Thng th ngi ta cho thm NaDDTC vo
dung dch to ta phc DDTC kim loi, theo s tch chit ca phc vi dung mi
hu c. Trong nhiu trng hp th tc ca s tch chit xy ra rt nhanh. S c
mt ca EDTA s lm gim tc qu trnh tch chit. Do acid ca DDTC khng bn
nn khng nn s dng dung dch acid kh mnh tch chit, mc d c chn lc
cao cho cc ion kim loi nh chng ta mong i. Chng hn nh trong trng hp,
phn ng trao i din ra vi phc DDTC kim loi s c din ra chm hn, hoc
vic s dng diethylammonium diethyldithiocarbamate l ph hp hn.
DDTC thng c s dng nh l thuc th o quang cho Cu(II), v k tip l Bi,
Ni v mt s nguyn t khc.
DDTC khng hp thu trong khong nhn thy c.Tuy nhin, hp thu ca
thuc th c th gy nhiu n ph UV, mc d s tch chit ca HL tr nn khng
ng k pH > 9. V d, Cu(II) (0,002 n 0,03mg) c th c xc nh ti 440nm,
sau tch chit nh CuL2 vi n-butyl acetate ti pH = 9 c EDTA. Cc cation nh
Co, Cr, Fe, Mn v Ni khng gy nh hng.
Zn 11,4 =0,01 22
o
C
Bng 8.4 S chit ca phc chelate kim loiIDDTC vi CCl
4

Cc nguyn t chit
pH >11
Cc nguyn t chit
pH = 9
Cc
nguyn t
chit pH
= 6
Cc nguyn
t chit
khng hon
ton
Cc
nguyn t
khc
khng
c lit
k


182


Ag, Bi, Cd, Co(II),
Cu(II), Hg(II), Ni, Pb,
Pd(II), Tl(I)(III), Zn.
(Ag, Bi, Cu(II), Hg(II),
Pd(II) v Tl(III) khng
th bo v bng EDTA;
Bi, Cd, Pb v Tl(I)(III)
khng th bo v bi
KCN)
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)
Au, Ba, Ir,
Nb(V), Os,
Rh, Ru, Pt
v U(VI)
Khng th
c chit
pH = 4 -
11

8.3.8. Nhng ng dng khc
N tng c s dng nh l thuc th nhn bit Cu (gii hn xc nh l 0,2g
v gii hn pha long 1/5.10
7
), nhng phn ng l khng c tnh chn lc. Thuc th
cn c s dng lm cht to ta trong phng php phn tch trng lng. Phc
DDTC kim loi cng c th c phn li v xc nh bng sc k kh hoc HPLC. Mt
polymer vi nhm chc DDTC hoc ht silicagel lin kt vi phc DDTC c
nghin cu nh l mt ion c la chn lin kt. Nhng ion kim loi c hnh
thnh trc trn b mt knh ni m DDTC c thng k v kim tra bi tia X trong
ph in t vi chn lc v nhy cao.
8.3.9. Mt s loi thuc th khc vi cu trc tng t
Diethylammonium Diethyldithiocarbamate:
CTPT: C
9
H
22
N
2
S
2

KLPT: 222,41

L nhng tinh th khng mu, nng chy 82 83
o
C, 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: C
5
H
12
N
2
S
2

KLPT: 164,28

CH
2
-CH
2
N
CH
2
-CH
2
C
S
S.NH
4
C
2
H
5
N
C
2
H
5
C
S
S(NH
2
(C
2
H
5
)
2
)


183


L APDC, ammonium pyrrolidine-1-carbodithioate; c sn ngoi th trng; l
nhng tinh th khng mu, nng chy 142 144
o
C, d tan trong nc (18,9g/100ml;
200
o
C) v ru, t tan trong chloroform (0,38g/100ml) v carbon tetrachloride
(0,12g/100ml; 200
o
C). Thuc th dng t do l mt acid yu, pK
a
= 3,29 ( = 0,01;
KCl, 25
o
C), KD (CHCl
3
/H
2
O)=1,1.10
3
). Thuc th ny trong dung dch acid th bn
hn DDTC. Chu k bn r pH 1,0, 3,0 v 7,3 theo th t l 63 pht, 175 pht v 170
ngy. V th APDC c dng nh l cht to ta v lm dung mi tch chit cho cc
ion kim loi nng trong dung dch acid.
Nhn chung, phng php tch chit kim loi bng vic s dng thuc th APDC
tng t nh s dng vi diethylammonium dithiocarbamate trong acid hu c v vi
mui natri trong mi trng trung tnh hoc kim yu. tan ca phc APDC kim
loi th thng thp hn so vi DDTC kim loi. Nhng dung mi khng c halogen
ho, chng hn nh MIBK hoc alkyl acetate, th c s dng nh dung mi tch
chit cho s c cn ca mu kim loi nng vi hm lng thp khi chng cho
nhng nguyn t c ph hp thu c dng xc nh hm lng kim loi.
Ammonium N(dithiocarboxy)sarcosine:
CTPT: C
4
H
5
NO
2
S
2
.2NH
4

KLPT: 199,30

L nhng tinh th bt mu trng, d tan trong nc. trng thi lng n c th
c 1 thng. Phn ng vi mt s ion kim loi nng ca hydrogen sulfide v
ammonium sulfide to thnh phc kim loi tan. Nhng ion kim loi m n c th
c che vi EDTA v ch th kim loi l: ti pH 2 3: Bi, Cd, Co, Cu(II), Fe(III), Hg,
In, Mo(VI), Mo(V), Ni, Pb v V(V); ti pH 5 6: Bi, Cd Co(II), Cu(II), Fe(III), Hg, In,
Ni, v V(V); ti pH 9 10: Bi, Co(II), Cu(II), Fe(III) v Ni. Thuc th ny c s
dng nh mt cht che cc ion kim loi nng trong phn tch ca Zn.
Silver Diethyldithiocarbamate:
CTPT: (C
5
H
10
NS
2
Ag)
2

KLPT: 512,26

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,
Ag S
C
S
N
C
2
H
5
C
2
H
5
C
2
H
5
N
C
2
H
5
C
S
S Ag
-
OOCCH
2
N
H
3
C
C
S
-
S
2 NH
4
+


184


phn ng din ra nh sau:
3 3
AsH 6AgL 3B AsAg .3AgL 3L 3HB
+
+ + = + +
3 3
AsAg .3AgL 3B 6Ag AsL 3L 3HB
+
+ = + + +
Trong B l pyridine hoc kh nitrogen khc. Kt qu ca phn ng hn hp trn
l s hnh thnh nhng ht keo c mu hng nht. Phn ng ny c th s dng cho
qu trnh xc nh hm lng nh As trong nhiu loi mu. Mt dung dch chloroform
ca AgDDTC cha mt lng nh nitrogen chng hn nh triethylamin (3.10
-2
M)
c dng mt phn ng trung gian thch hp hn, bi v nhng s nh hng ca
pyridine c th c ngn nga. Nhng gc nitrogen khc cng c a ra thay
th pyridine.
Xc nh As theo phng php trc quang:
Thuc th: dung dch pyridine 0,5% ca AgDDTC. Dung dch pyridine c th
thay th bng dung dch chloroform 0,5% ca AgDDTC, cha 3.10
-2
M triethylamine,
dung dch KI 15% ,dung dch SnCl
2
40% , H
2
SO
4
m c.
Thit b: hnh 8.5

Hnh 8.5. Bnh phn ng xc nh As
Qui trnh: Cho mu dung dch lng cha 4 15g As vo trong bnh phn ng v
pha long thnh 25ml, thm 5ml dung dch H
2
SO
4
m c, 2ml KI 15%, v 0,5ml
dung dch SnCl
2
40% .Tip theo tin hnh trn u trong 15 30 pht vi nhng ln
lc trn khc nhau. Gn cht c ng thu tinh ngp su vo dung dch acetate ch thng
qua vng m bng cao su trn ming bnh lc (trong bnh c cha sn 3ml dung dch
AgDDTC). Cho thm 3g bt kim loi Zn vo trong bnh phn ng v xut hin nhanh
chng du hiu ca s cng hp. Du hiu s kt thc sau 60 n 90 pht v dung
dch trong bnh lc t mu vng nht chuyn sang mu hng. S chuyn i mu ca
dung dch trong khong 10-mm v c o bc sng 540 560nm tu thuc vo
mu trng. ng hp thu mu ca dung dch c trnh by trong hnh 8.6.


185



Cc cht gy sai s:
S(II) b oxy ha bi acid nitric. Ge, HNO3, v HClO
4
b loi b bng s bay hi
lin tip vi HCl. S nh hng bi Cu, Fe, Ni, Sb, Se, Sn, Te, PO
4
3-
, v mt s
nguyn t khc c loi tr bi qu trnh tch AsCl
3
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:

Kali ethyxanthate (R = C
2
H
5
) v kali benzylxanthate (R = C
6
H
5
CH
2
) c ch nh
l thuc th dung mi tch chit cho kim loi tch chit. ng dng ca chng trong
ha phn tch v trong s tuyn ni khong th c xem nh l trong the literature









R O C
S
SK
0,3 _
0,2 _
0,1_
400 500 600

700

p

t
h

Bc sng nm
Hnh 8.6. Ph hp th
ca sn phm phn ng t
Ag-DDTC v arsine.10g
(+10g Sb).


186


CHNG 9
THUC TH KHNG TO LIN KT PHI TR

9.1. THUC TH OXY HA NEUTRAL RED
CTPT: C
15
H
16
N
4
.HCl
KLPT = 288,78.
Tn quc t: 3amino7dimethylamino2methylphenazine hydrochloride.
Neutral Red dng bt c mu xanh m nhng khi ho tan trong nc (4%) v
trong cn (1,8%) s cho dung dch mu (
max
= 533nm, trong 50% ethanol). Ngoi
ra Neutral Red cn tan c trong xenlosolve (3,75%) v ethyleneglycol (3,0%),
nhng khng tan c trong dung mi thm, pKa (NH
+
) = 6,7.
Phn ng oxy ha kh ca Neutral Red c tnh thun nghch v c kh v dng
khng mu bi qu trnh oxy ha kh ca khng kh:

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 (E
o
= 0,240V, 30
o
C).
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: C
27
H
29
N
2
Cl.
KLPT = 392,97.
Mu Khng mu
2H
+
, 2e
N
N
(CH
3
)
2
N
CH
3
NH
2
NH
NH
(CH
3
)
2
N
CH
3
NH
2



187



c im: L mt cht bt mu xanh sng.
Tnh cht: tan trong nc (9,7g/100ml) cho ra mt dung dch mu xanh (
max
=
625nm, = 10
5
). Cc loi monocation (R
+
) m nh hng trong chit sut ion i s
tri hn trong lp trung tnh v n s bin i thnh RH
2+
trong acid cho ra dung
dch mu vng v thnh ROH trong kim. Tuy nhin s bin i ca R
+
thnh RH
2+

v ROH s b chm khi qu trnh chit hu nh kt thc th ta c th bit c
khong pH rng hn (2 8) khi qu trnh chit c thc hin ngay lp tc sau khi
thm vo phm mu alcoholic.
9.3. THUC NHUM CATION RHODAMINE B
CTPT: C
28
H
31
N
2
O
3
Cl.
KLPT = 479,02.

c im: Rhodamine B l cht bt tinh th mu xanh ti mu tm.
Tnh cht: N d tan trong nc (1,2g/100ml), ethanol v cellosolve cho dung dch
mu xanh v pht hunh quang mu vng m.
N tan t trong chloroform, acetone v HCl 1M (0,11g/100ml).
Trong dung dch benzene v ether, Rhodamine B tn ti dng lacton khng mu
v pht hunh quang mu xanh nht.
N O
H
5
C
2
H
5
C
2
C
N
+
C
2
H
5
C
2
H
5
COOH
Cl
-
N
H
5
C
2
H
5
C
2
C
N
+
C
2
H
5
C
2
H
5
Cl
-


188



Trong dung mi phn cc nh alcohol, acetone hoc nc, vng lacton m hnh
thnh cu trc (R) c mu tm m (
max
= 553nm; = 1,1.10
5
). c tnh quang ph
ca dung dch Choride (RHCl
-
),
max
= 556nm; = 1,1.10
5
cho RH
+
( pH = 1 3,
c mu tm pht hunh quang mu vng) v ti
max
= 494nm; = 1,5.10
4
cho RH
2
2+
(
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 (AuCl
4
)
-
R
+
,
max
= 565nm; = 9,7.10
4
.
Cc thuc nhum Rhodamine khc:
Cng thc cu to chung:

- Rhodamine 6G: X
1
= NH(C
2
H
5
), X
2
= X
3
= CH
3
.
L cht bt mu hng hi xanh sng, tan trong nc (5,4g/100ml) cho dung dch
mu ti v pht hunh quang mu xanh.
- Rhodamine 3GO: X
1
= NH
2
, X
2
= CH
3
, X
3
= H, dng bt mu hng sng.
- Rhodamine 4G: X
1
= NH(C
2
H
5
), X
2
= X
3
= H.
- Rhodamine 3C: X
1
= N(C
2
H
5
)
2
, X
1
= X
2
= H, ethylester ca Rhodamine B l cht bt
mu tm, tan trong nc cho dung dch mu tm v pht hunh quang mu
nu.
Thuc nhum ny l dn xut ethylester ca Rhodamine. V trong dung dch nuc
n thng tn ti cu trc R
+
, trong khi Rhodamine B tn ti dng RH
+
trong mi
trng acid (pH < 3). Trong mi trng acid long tng i, mt proton thm vo ion
R
+
s to thnh ion RH
2+
. Gi tr pKa ca RH
2+
c xc nh trong dung dch acid
X
1
X
2
O
C
N
+
COOC
2
H
5
X
3
C
2
H
5
C
2
H
5
Cl
-
N O
H
5
C
2
H
5
C
2
C
N
C
2
H
5
C
2
H
5
C
O
O


189


sulfuric: pKa(Rhodamine 6G) = -1,1; pKa(3GO) = -0,4; pKa(4G) = -0,21; pKa(3C) = -
0,02.
CHNG 10
THUC TH HU C CHO ANION

10.1. CURCUMIN
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 183
o
C, 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.
CTPT: C
21
H
20
O
6
.
KLPT = 368,39.
CH CH
C
CH
2
O
C
CH
O
CH
OH
CH
3
OH
OCH
3


190



10.1.5. Phn ng to phc cht v cu trc phc cht
Curcumin c 2 dng phc tp v mu sc: Rosocyamin (1) v Rubrocurcumin (2),
vi acid boric, ph thuc ch yu vo s c mt acid oxalic.

Hnh 10.1. Ph hp th ca curcumin iu kin mt vi dung dch khc nhau.


191



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 0
o
C.
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 9,3.10
4
550nm.


192



10.1.6. S tinh ch v phn ng tinh khit
Sn phm thng mi th hu ht tinh khit, bng s kt tinh li t ethanol cho ti
khi im tan ti 183
o
C.
10.1.7. ng dng trong phn tch
Curcumin c s dng rng ri nh mt thuc th mu trong phng php so
mu xc nh hm lng vt Bo trong nhng vt liu khc nhau. S hnh thnh phc
mu (1) hoc (2) c s dng trong phng php so mu. Phng php rosocyanin
(1) c nhy cao nhng mu sc phn ng ph thuc rt nhiu vo iu kin phn
ng. Phng php rubrocurcumin c nhy thp nht so vi cc dng khc, nhng
sn phm ca n khng bao qut.
- Phng php rosocyanin:
nhy ca phng php ny cao nhng ph thuc vo s c mt ca nc v
lng d ca curcumin trong trng thi proton. Theo n rt quan trng loi b
nc v s hp th ti thiu khng vt qu gii hn ca phn ng.
+ Dung dch thuc th:
Dung dch curcumin: dung dch phi c tng hp tinh khit trc 1 tun bng
cch ho tan 0,125g curcumin trong 100ml acid acetic bng v phi ng trong bnh
nha.
Dung dch sunfuricacid acetictrn bng nhau nng (H
2
SO
4
98% v acid acetic
bng).
Dung dch mtrn 90ml C
2
H
5
OH 95%,180g CH
3
COONH
4
v 135ml acid acetic
bng, nh mc thnh 1l vi nc.
Anhydric propionie.
Oxaly chloride.
+ Sn xut:
Chuyn 1ml dung dch mu nc cha 0,2 1g Bo vo cc nha, thm 2ml acid
acetic bng, 5ml anhydric propionic v trn u. Thm 0,5ml oxalyl chloride v cho
php phn ng trong 30 pht, nhit phng v thm khong 4ml sunfuricdung dch
acid acetic v 40ml dung dch curcumin, trn u, v yn trong 45 pht. Thm 20ml
dung dch m, trn u v lm lnh ti nhit phng. o hp th bc sng
Hnh 10.2. Ph hp thu ca Rosocyamin (1) v Rubrocurcumin v (2)


193


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 H
2
SO
4
. 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 58
o
C,
thm 25ml C
2
H
5
OH, 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

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 128 130
o
C. 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
N C
O
H
2
C
C N
H
3
C
N C
O
CH
C
CH
3
N
CH
C
O
C
CH
3
N
N
(1)
C
10
H
10
N
2
O
KLPT: 174,20
(2)
C
20
H
18
N
4
O
2
KLPT: 346,39


194


acid. N hnh thnh dng phc mu vi Ag, Co, Cu v Fe.
- Bispyrazolone:
L mt cht bt tinh th khng mu hoc c mu vng xm, nhit si > 300
o
C
v hu nh khng tan trong nc v trong dung mi hu c ni chung ngoi tr
pyridine, cn trong thuc th th tan kh tt.
10.2.5. Phn ng vi ion CN
-

Trong vic xc nh ion CN
-
bng phng php Pyrazolone, dung dch mu c
x l bng chloramine T, sau bng phn ng vi monopyrazolone v bispyrazolone
trong pyridine cho ra dung dch mu xanh o quang. Phn ng lin tc cho n khi
ln mu c trnh by trn hnh 10.3. Kt qu thuc nhum mu xanh c th chit
trong nbutanol c nhy cao.
Vai tr ca bispyrazolone khng chc chn, nhng n khng th thiu trong qu
trnh ln mu ti a. T s ca hn hp khong 12,5:1 th c khuyn dng.
Mi ca Pyridine kh ngi nn c th b loi tr v thay th bng DMF c cha
acid isonicotinic.
Thiocyanur v ammonia gy cn tr nghim trng, chng b oxy ha bi
chloramine T cho ra CNCl v NHCl
2
tng ng. Sn phm sau cng cng c cho
phn ng vi monopyrazolone cho thuc th tm (
max
= 545nm), cht ny c th
chit vi trichloethane sau khi acid ha dung dch nc (mu vng,
max
= 450nm).


195



Hnh 10.3. S chuyn mu ca hp cht Pyrazolone vi CN
-
10.2.6. ng dng trong phn tch
c khuyn dng cho vic xc nh CN
-
nh sau:
- Thuc th:
Dung dch Pyridine pyrazolone: thm Monopyrazolone t 125ml dung dch nc
nng to thnh dung dch bo ha. Lm lnh v lc. lc c, thm 25ml Pyridine
chng ct li c cha 25mg bispyrazolone. Dung dch pyridine v pyrazolone tinh
khit, c trn ln v chun b trc khi s dng.
Dung dch chloramine T 1%: chun b mi mi ngy. m phosphate (pH = 6,8;
14,3g Na
2
HPO
4
v 13,6g KH
2
PO
4
trong 1l nc).
Dung dch Cyanide chun:
Cch lm o quang trc tip: Chuyn t 1 10ml dung dch CN
-
tiu chun
c chia thnh cc phn bng nhau vo ng o th tch n vch 50ml. Thm 5ml
dung dch m v 0,3ml dung dch chloramine T, trn v yn 1 pht. Thm 15ml
dung dch pyridine pyrazolone, pha long n th tch, trn v yn 30 pht. Quan
st hp th bc sng 620nm. i vi mu c cha 1 n 10g CN
-
, trung ha n
CN
-
CNCl
N
+
CN
CH
2
HC
CHO
CH CHO
HC
H
2
C
HC
HC
HC
N
O
N
CH
3
N
N
CH
3
O
Thuc nhum mu xanh (
max
= 620 - 630nm)
Monopyrazolone
H
2
O
Pirydine
Chloramine T



196


v pH = 6 7 bng CH
3
COOH hay NaOH v x l nh cch trn.
Chit trc quang theo di cch lm trn cho ti khi ln mu y . Chuyn
lng mu cng dung dch sc ra cho ti 125ml vo phu chit c cha chnh xc
10ml nbutanol v lc vi pht. Sau khi c s phn chia pha, quan st hp th ca
lp hu c bc sng 630nm. Thiocyanate cn tr nghim trng.
Phng php ny c th ng dng trong vic xc nh thiocyante (620nm, 0
4ppm trong dung dch), cyanate (450nm, 0 5ppm trong CCl
4
), v ammoniac
(450nm, 0 0,5ppm trong trichloroethylene), nh nhng anion ny c tin hnh
nh cyanate. Nitrat c th c xc nh sau khi kh t ammoniac bng alkaline
FeSO
4
. Vic xc nh Vitamin B12 (Cyanocobalamine) bng phng php ny
c tin hnh.
Monopyrazolone cng c th c s dng nh mt cht th cho Ag v Cu.
10.2.7. Mi quan h cu trc vi thuc th khc
Phenazone (2,3dimethyl1phenylpyrazolin5one) va c nghin cu nh mt
cht th i vi NO
3
-
.
10.3. 2AMINOPERIMIDINE
CTPT: C
11
H
9
N
3
.HCl.
KLPT = 219,67.

10.3.1. Ngun gc v phng php tng hp
Sn c trn th trng l hydrochloride v hydrobromide. Cho 1,8
diaminonaphthalene phn ng vi NH
4
SCN.
10.3.2. ng dng
Thuc th kt ta v o c ion sulfate.
10.3.3. Tnh cht thuc th
L cht bt tinh th mu trng hi xm. Tan t trong nc khong 0,5% nhit
phng nhng d dng tan trong nc nng. Thuc th d b oxy ho, thuc th dng
rn t bn nn phi c gi ni mt v ti. Thuc th dng dung dch th n nh
trong mt vi ngy nu c gi trong chai kn v ti. Thuc th c th tinh ch bng
cch un si dung dch bo ho vi than, lc v loi b hydrochloride kt tinh.
10.3.4. Phn ng vi ion sulfate
Cho dung dch c cha ion sulfate vo dung dch thuc th (bo ho ti nhit
phng, 0,5%) th ngay lp tc hnh thnh kt ta snh vn la mu trng ca amine
sulfate.
N
N
H
C NH
2
. HCl


197


Tnh c trng ca kt ta ny l thng khng c nhng ht c nh (< 2m). 2
aminoperimidinium sulfate c tan thp, iu l tng s dng thuc th trong
phng php o c cho ion sulfate. Trong bng 10.1, 2aminoperimidine sulfate
c kh nng ho tan ti thiu gia cc amine sulfate khc nhau. 1ppm sulfare kt ta
c th quan st c v c th thc hin c 0,05ppm sulfate vi th tch o l
10ml.
Bng 10.1. tan khc nhau ca amine sulfate
Benzidine 0,098
1,8-Diaminonaphthalene 0,222
4-Amino-4-chlorobiphenyl 0,155
4,4-Diaminotoluene 0,059
2-Aminoperimidine 0,020
Dung dch 2aminoperimidine hydrochloride c minh ho hnh 10.4 dng
phng php ph hp th UV. Nu vng rng hn ti 305nm ( = 7,23.10
3
) c th s
dng phng php trc quang xc nh cation 2aminoperimidine trong phn dung
dch sau khi kt ta ion sulfate vi lng d thuc th bit. iu ny lm c s cho
phng php so mu gin tip xc nh ion sulfate (4120ppm SO
4
2-
).
Toei ngh s dng thuc th mu, 6(pacetylphenylazo)2aminoperimidine
(pH = 3,4 4,1;
max
= 480nm ; = 6,1.10
3
) cng tng t, nhng vng nhn thy
c ca phng php trc quang nng sulfate t 0 ~ 10ppm.

10.3.5. ng dng trong phn tch
Phng php ny xc nh nng sulfate t 0 ~ 5ppm.
Chuyn 1,0 n 5,0ml dung dch chun sulfate 10ppm vo 5 bnh nh mc. Pha
long vi khong 5ml nc thm 4ml dung dch thuc th 2aminoperimidine
hydrochloride 0,5%. Trn u v loi b huyn ph trong khong t 5~10 pht chuyn
Hnh 10.4. Ph hp th ca dung dch 2aminoperimidine hydrochloride



198


vo trong ng o c v o tn x nh sng ca mi dung dch. Dung dch mu
cng lm tng t.
T 0 n 1ppm hay 0 n 0,5ppm ca sulfate, qu trnh thc hin chnh xc vi
cng mt cch thc nhng phi s dng dng c o c nhy cao.
Cng nh sng truyn qua ti bc sng 600nm cng quan st c thay v o
bng tn x nh sng c cng mnh. Nhng anion gy nh hng c gii thiu
bng 10.2.
Bng 10.2. .nh hng ca nhng anion nhiu
NO
3
-
10 - 100ppm khng b nh hng
Br
-
t 10ppm tr ln khng b nh hng, nhng 100ppm b sai l 20%
I
-
10100ppm b sai l 10%
F
-
, SiF
4
-
1ppm F
-
b sai l 10%, nhng 10ppm b sai l 15%
PO
4
3-
1ppm b sai l 25%
Cl
-
10ppm khng b nh hng, nhng 100ppm b sai t 515%



199


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