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8/6/2019 3. Nhom Chuc Phan Tich
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NHM CH C PHNTCH
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N i dung bo co
Ph n 1: Nhm ch c phn tch c a Ag
Ph n 2: Nhm ch c phn tch c a CuPh n 3: Nhm ch c phn tch c a ThPh n 4: Quan i m hi n nay v nhm ch c
phn tchPh n 5: Nhm ho t tnh phn tch.
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NHM CH C
Nhm nguyn t c c u t o c tr ngtrong phn t thu c th c tr ng quy t
nh. Ng i ta g i nhm c tr ng ny lnhm ch c phn tch.
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NHM CH C PHN TCH C A Ag
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Nhi u h p ch t h u c ch a nhm aminb c 2 (> NH) ph n ng v i mu i b c. M ttrong nh ng h p ch t y l rodamin.
HN C O
CS H2S
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Rodamin t o v i b c rodaminat b c mu
vng (AgOSC3H2ONS2) trong dung d chaxit. Rodamin c 4 d ng tantomer.
HN C O
CS CH2S
HN C OH
CS CH
S
N C O
CSH CH2
S
N OH
CS CH2
S
C
(I) (II) (III) (IV)
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R= -CH3, -C2H5, R= C6H5-NH=N-,
C6H5-N=NC kh n ng ph n ng v i Ag+ c ng nhrodamin nn khng c c s cho r ng
rodamin ph n ng v i Ag+ d ngtantomer II v IV (nhm OH v SH vn i i trong vng). H p ch t c c u t o
NH
SCS
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L h p ch t khng th no chuy n v n iphn t o nn lin k t i gi a nit vnguyn t cacbon khng ch a l u hu nhtrong vng l u hu nh c ng ph n ngv i Ag+ nh rodamin.
Do rodamin ph n ng v i Ag+ d ngtantomer III c ng khng ng v ng v vv y ch cn c th cng nh n rodamin
ph n ng v i Ag+ d ng tantomer (I).
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P.dimetylaminolanzyliden rodamin l thu cth nh y nh t c a Ag+.Mu i b c t o thnh trong ph n ng c c u
t oV ho c VI. N C O
C
S
A g
N C O
C
S
A g
V
VI
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H p ch t n i ph c vng 4 khng th t nt i.V l i khng ph i t t c nh ng mu i c arodamin, c bi t l mu i Ag+ v c anh ng d n xu t c a n u tan trong dungmi khng n c.
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T ng k t nh ng d ki n th c nghi m
ng i ta cng nh n nhm ch c phn tchc a Ag+ l:S = C NH - C=
N C O
CS CS
CH N
CH
CH
Ag
V y mu i c a Ag+ v i P. dimetylbenzilidenrodamin ph i c cng th c:
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Tnh ch tp- imetylaminobenzyli enro amin
d ng b t k t tinh mu .Nhi t nng ch y: 240 270oCNhi t phn h y t 200oC
N C O
C CS
C NC
C
g
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tan: khng tan trong n c, tan r t t
trong aceton, tan trong r u etylic, ete,clorofom v benzenTan trong cc acid m nh cho mu vng.Ph n ng v i Ag + c mu tm trongmi tr ng acid
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IPHENYLCACBAZONTnh ch t:
L d ng b t k t tinhmu da cam
Nhi t nng ch y157oC
Khng tan trong n c v trong amoniacl ng
Tan trong r u tylic, clorofom, benzen vSO2 l ng.
Khi tc d ng v i Ag+ cho mu
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2- THIO-5X ETO-4- CACBETOX Y-1,3-
IH Y R
OP YR
IMI
INTnh ch t:Tinh th mu da
cam
Nhi t nng ch y276 280oCTan t t trong alilin, phenol v etylenclohydrin nng.t tan trong aceton, acid acetic, bezen nng, clorofom.Khng tan trong n c, cacbontetracloruaDung d ch trung tnh c mu da cam, mi tr ng acid
c mu vng.
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NHMCH C PHN TCH C A Cu
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Nh ng -axyloinoxim c cng th c t ng qut
ch a nhm nguyn tl nh ng thu c th c tr ng c a Cu(II) (ph n
ng x y ra trong mi tr ng amoniac)
R CH C
NOHOH
CH C
NOHOH
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Nh ng h p ch t ny ng vai tr nh m t axitkp v t o v i CuII mu i mu l c khng tantrong n c v c cng th c:
CH C
O
"
N
R
"R
CuO
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Khi nghin c u tc d ng c a axyloinoxim v i CuIIng i ta chia chng ra lm 2 lo i:
- M t lo i bao g m nh ng h p ch t t o mu i v i Cukhng tan trong amoniac (trong nh ng h p ch t ny
ng bo ho ph i t )- M t lo i bao g m nh ng h p ch t t o mu i v i Cu tan
trong amoniac (trong nh ng h p ch t ny ng ch abo ho ph i t )
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Mu i ng t o thnh thu c lo i ny hay lo ikhc l do b n ch t nh ng g c c trong phn tqu t nh: N u trong phn t thu c t c g cth m th mu i ng t ng ng khng tan trongamoniac. N u trong phn t c g c bo th mu i
ng trong nhi u tr ng h p tan trog amoniac.Tr ng l ng c a g c khng nh h ng n tan c a mu i ng trong amoniac.
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Feigl ngh cng th c c u t o mu in i ph c khng tan trong amoniac c a
ng v i a xyloxinin nh sau:
c th dng tan c a mu i thu ctrong dung mi khng n c (v d trongchloro forme) lm c s ng h nghc a Feigl.
N
R
Cu
C
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Mu i c a ng v i 1,2Xyclohexanolonoxim
Khng tan trong n c nh ng tan trongamoniac. i u c gi i thch lcyclohexim b o ho phi t v do khngc kh n ng ph i tr v i ng.
N
Cu
C
O
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Do n u phn t ch a nh ng g c ch a b o ho ph i
tr th
mu i ng t o thnh (do ph i tr n i phn) khngtan trong amoniac. N u nh nh ng g c ny b o hoph i tr th mu i ng tan trong amoniac.C th rt ra k t lu n l khi s d ng nh ng axyloinoxim
lm thu c th cho CuII th mu i t o thnh s khng tann u vng l vng 5.
C
NCu
C
O
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Chnh v v y nn nh ng oxim c amethylaxetonylcarbinol v Cloaxetophenolch a nhm nguyn t .
HO C C C = NOHKhng th t o vng 5 c nn nh ng
h p ch t ny khng th t o mu i ngkhng t o mu i ng khng tan.
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Epharan kh ng nh r ng nhm
Trong phn th m c ng l nhm ch c phn tchc a CuII (v d Salicylaldoxim t o mu i n iph c)
C C
C
NOH
C C
C
OH N
Cu
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Do ng i ta cng nh n 2 c u t o nhm ch cphn tch c a CuII
N m ngoi nhm th m N m trong nhmth m
C C
OH NOH
2HC C
NOH
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V DV d : benzoinxim c hai ion H+ c thb thay th , t o v i Cu2+ h p ch t ph i trc thnh ph n 1:1.
C
CH
2HN
O
Cu
O
OH 2
OH 2
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V D
C
C
Cu
C
C
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V D
Phenyl2pyridylketoxime (2Benzoylpyridineoxime, PPKO)
C NHO N C NOH
N
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V DTrong hai ch t ng phn l p th , d ng ph n ng v i cc ion kim
lo i khc nhau hnh thnh cc ph c c mu v c th chi t b ngdung d ch chloroform.
Ch t ny h u nh khng tan trong n c v c n nh ng l i d tantrong ethanol nng, benzene, chloroform, dioxane, r u izo amylicv cc acid v c long.Thu c th ny d ng r n v l ng u nh y v i nh sng v i khi
ph i trnh nh sng chi u tr c ti pThu c th ny hnh thnh ph c c mu Cu(I) (cam), Cu(II) (xanh)
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NHM CH C PHN TCH C A Th
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Kuz He op ch ra r ng nh ng h p ch t chg c AsO3H2 v nhm hydroxyl v tr OCTO
i v i nhm azo ph n ng v i Th.
Nh ng h p ch t sau y tham gia vo ph n
ng
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N NOH
AsO3H2HO SO3H
SO3H
N N OH
AsO3H2HO
SO3H
(I) (II)
N N
A s O3H 2H O
S O3H
N N
A s O3H 2
H O3S
O H O H
H O3S S O3H
(III) (IV)
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ng th iKuz He op c ng pht hi n cc h pch t nh
H
H HCOOH
OH OH
SO 3H
(V) (VI)
c ng cho ph n ng t ng t v i Th.
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Nh ng h p ch t ch a g c AsO3H2 v tr Para
i v i nhm azo v d :
N N
H O
SO 3 H
N N
A s O 3 H 2 O H O H
H O 3 S SO 3 H
H 2 O 3 A s
H 2 O 3 A s
SO 3 H
m c d t o k t t a v i mu i ThIV nh ng khng gy nn
s i mu
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T t c nh ng iu trnh by trn cho php ch ng
cng nh n nhm nguyn t .
B
: = -, CB: s 3 2, -C
L nhm ch c phn tch i v i ThIV.
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NHM HO T TNH PHN TCH
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Nhm ch c phn tch l nhm nguyn tc tr ng gy nn kh n ng ph n ng
thu c th v i ion v c nh ng khng ph ic cc ch t hu c ch a cng m t nhm ch phn tch l u c gi tr nh nhau v m t phn tch.
nh y v c tr ng c a nh ng png pht hi n m t ion b ng nh ng thu c th
h u c ch a cng m t nhm ch c phn tcc th r t l khc nhau.
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D o ng i ta cng nh n r ng trong phn t thu c th ngoi nhm ch c phntch quy t nh c ch c a ph n ng cc nh ng nhm nguyn t khc khng
nh h ng n b n ch t c ch ph n Chng lm bi n i, tnh c tr ng cs n ph m cu i cng trong m t ch ngm c nh t nh nh tan, c tr
v c ng mu, b n thu phn Nh ng nhm nh v yKu l- e g i lnhm ho t tnh phn tch.
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Thu c th Cng th c Iion
5-(P-dimetylamino benzyliden)-rodamin
Ag+
P-dimetylamino benzeneazophenyl arsenic axit Zr (III)
P-dimetylamino benzene azoanthraquinon
[ nCl6]2-
P-dimetylamino benzene azo beznyliden camphorxin Hg22+
TetrametylP-phenylendiamin
Ag+, Cu2+, Hg2+,Hg22+
P,P Tetrametyldiamindiphenylmetan
Pb2+,Mn2+
Iotmetylat (P- dimetylaminostyril
Zn2+, CN-
NHC
C C
CH
N
H 3 C
H 3 C
NN
H3C
H3C N As H
NN
H 3 C
H 3 C N
NNH3C
H3C N C
HC C CH2
CH
CH
C
CH2H2CCH N
N
H 3 C
H 3 C
N
CH 3
CH 3
N
H3C
H3C
H2C N
CH 3
CH 3
CH
N
H3 C
H3 C
HC
I
N
CH
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Trong nh ng ph n ng t o k t t a, khi nh ng nhm Cl-, r-, CN ,I-, nhn quinolin,nhn pyridin vo phn t thu c th , ho c bi nnhn benzen thnh nhn naphatalen, c ng lmcho nh y c a ph n ng t ng ln.
Nh ng nhm c ng l nh ng nhm hotnh phn tch.
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NNO
ONH 4
NNO
ONH 4
AsO 3 HO
O
AsO 3 H
N CH 3 N CH 3
Cufferon N eocuferon
Phenyl arsonic axit Antraquinon-1- arsenic axit
2 Metyl pyridine 2 metyl quinolin
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QU AN I M HI N NAYV NHM CH C PHN TCH
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Ngy nay, khi nghin cu tc d ngc a thu c th hu c v i ion v c ng i ta ch n 2 iu c b n nh tl c u t o c a thu c th hu c vki n trc i n t c a ion v c .
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Cng nh n cu t o c a thu c th huc v ki n trc i n t c a ion v cquy t nh c ch ph n ng gi a chth chng ta khng th cng nh n c mnhm nguyn t no(trong thu c th huc ) l i ch ph n ng v i m t ion m lkhng c ph n ng v i nh ng ion khcc ki n trc i n t t ng t .
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Trn c s , ngy nay ng i ta
cng nh n c nh ng nhm nguyn tc tr ng cho ph n ng v i m t snguyn t c tnh ch t ho h c g nnhau ngh a l nhm ch c phn tchi v i m t s nguyn t tnh ch tho h c gi ng nhau.
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Chng ta ch c v s ch c nh nthu c th tc d ng v i m t s ion mnhi m v c a nh ng nh phn tch l ph
t o nn nh ng iu ki n c n thi t(lmthay i ho tr , t o ph c, iu ch nh pH,tch . ) cho ph n ng tr thnh
tr ng cho m t ion no c n xc nh.
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V D V NHM CH C PHN TCHNhm ch c nh n bi t Al
Trong dung d ch r u etylic, alizarin ha tan chodung d ch mu vng khi tc d ng v i Al3+ trong mi tr ngNH4OH. Al tc d ng v i NH4OH t o Al(OH)3 r i m i tcd ng v i alizarin.
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V d v nhm ch c phn tch
Nhm ch c nh n bi t Al
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V d v nhm ch c phn tch
Nhm ch c nh n bi t AlNgoi ra cn c h p ch t alizarin S, h p ch t ny tan trong n cv c ng t o mu i ph c c mu c tr ng v i Al trong mitr ng NH4OH.
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T nh ng h p ch t trn c th rt ra k t lu ncho nhm phn tch Al.
Trong :
A: OB: O- , OHC: O- , OH
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Nh ng h p ch t sau y ph n ng v i Fe (II).
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T nh ng i u tr nh by trn cho php ta rt ra k tlu n nhm nguyn t .
L nhm ch c phn tch Fe(II).
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