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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