TIU LUN CHNG 7 CC PHN NG ION TRONG DUNG DCH NC I) Nhng du hiu c trng ca phn ng ion trong dung

dch nc

Cc phn ng dng trong phn tch nh tnh c mt s du hiu c trng, ta cn c vo nhn bit mt ion no c mt hay vng mt trong dung dch. Nhng phn ng nh th gi l phn ng c trng ca ion kho st, cn thuc th tng ng gi l thuc th c trng. Nhng du hiu quan trng nht l: II) Xy ra s thay i mu sc ca dung dch. Xut hin mt pha mi : to ra kt ta hoc thot ra cht kh. Bin mt mt pha: ha tan kt ta. Mu sc ca cht kh thot ra. Mi c trng ca cht kh thot ra. Vn tc ca qu trnh phn ng. Cc h thng phn tch cation v anion trong dung dch nc Thuc th nhm : thuc th c phn ng cng kiu vi mt nhm ion, nhng

Mt s khi nim : khng phn ng vi cc ion khc. V d : axit clohiric (HCl) l TTN cho nhm cc ion Ag+, Pb2+, Hg2+; H2SO4 l TTN cho nhm cc ion Ba2+, Sr2+, Ca2+, vv. Nh cc TTN, ngi ta tch c tng nhm cc ion ra khi hn hp nhiu ion. Thuc th chn lc : l thuc th tc dng ging nhau trn mt s ion m cc ion Thuc th c trng hay thuc th ring: l thuc th ch cho phn ng c hiu

ny c th thuc cc nhm phn tch khc nhau. vi mt ion hoc mt cht xc nh. Cc h thng phn tch cation v anion trong dung dch nc gm c phn tch h thng v phn tch ring bit.
1

1)

Phn tch h thng

Phn tch h thng l tin hnh xc nh cc ion theo mt th t nht nh. Mun phn tch hn hp nhiu ion ngi ta thng dng cc thuc th nhm chia cc ion thnh nhiu nhm, mi nhm c th c chia thnh cc phn nhm v cui cng c tch ring thnh cc ion ring bit xc nh. C nhiu phng php phn loi cc cation thnh cc nhm phn tch ph bin hn c l phng php phn loi da ch yu trn s khc nhau v tnh cht ca cc sunfua kim loi v phng php da trn s khc nhau v tnh cht ca cc hidroxit ngoi ra cn da vo h thng photphat amoniac. *Phn tch nh tnh cation H thng dng H2S: nguyn tc da vo tan khc nhau ca sunfid kim loi i. ii. Nhm 1: cc kim loi kim NH4+, Li+, Na+, K+, Rb+, Cs+,Fr+. Nhm 2 : cc kim loi kim th Ba2+,Sr2+,Ca2+,Mg2+ Sunfua nhm 1 v 2 tan trong nc iii. Nhm 3 : Be3+,Al3+,Cr3+,Mn2+,Fe2+,Fe3+,Co2+,Ni2+,Zn2+,Ga3+,In3+, Sunfua (hoc cc hidroxit) khng tan trong nc nhng tan trong cc acid mnh. iv. Nhm 4 : Ag+,Pb2+,Hg2+,Cu+,Au+, Sunfua khng tan trong nc v acid long: v. Nhm 5 : As(III),As(V),Sb(III),Sb(V),Sn(IV),Au(III),Ge(IV),V(V),W(VI),Mo(VI).Sunfua tan trong cc sunfua kim v cc bazo mnh u im : kh cht ch, kt qu kh chnh xc, pht hin trit cc cation Nhc im : H2S rt c, mi kh chu, hay gp dung dich keo ca S. H thng dng acid- base : da trn s khc nhau v tan ca cc hidroxit kim loi trong cc acid v bazo kim nh: NaOH, NH3. Cc cation c phn thnh 6 nhm : i. ii. Nhm 1: cc kim loi kim : Li+,Na+,K+,Rb+,Cs+,Fr+,(NH4+). Nhm 2 : cc kim loi kim th : Ba2+,Sr2+,Ca2+,(Ra2+).
2

Cc cation c phn thnh 5 nhm :

iii. iv.

Nhm 3 : cc ion to c mui clorua t tan : Ag+,Pb2+,Hg22+, (Ti+, Cu+, Au+) Nhm 4 : cc cation to c hidroxit tan trong NaOH d : Be2+,Al3+,Cr3+,Zn2+,Sn2+, Sn4+,Sb(III),Sb(V),As(III),As(V),Ga3+,In3+, cation ca ( V, Mo, W)

v.

Nhm 5 : cc cation c hidroxit tan trong NH3 hoc trong hn hp NH3+NH4Cl do to phc amin : Cu2+,Co2+,Ni2+,Cd2+,Hg2+. Nhm 6 : cc cation to c cc hidroxit t tan trong nc tan trong axit : Fe3+,Fe2+,Mg2+,Mn2+,Bi3+(cc cation ca nguyn t t him Ti,Zr,Th,U,Nb,Ta)

vi.

u im t c hi hn h thng dng H2S S dng c nhng tnh cht c bn ca nguyn t : quan h cc nguyn t ny

vi cc acid v base, tnh lng tnh ca cc hidroxit v kh nng to phc ca cc nguyn t. Thi gian thc hin ngn hn t 30% - 40% so vi h thng H2S H thng photphat amoniac : gm c 5 nhm cation Nhc im : phn chia nhm khng cht ch bng h thng dng H2S * Phn tch nh tnh anion Do khng c thuc th nhm r rng nn cng khng th phn chia mt cch cht ch ton b cc anion thnh nhng nhm ring phn tch h thng ging nh cc cation. Da theo tc dng thuc th nhm anion c th c phn loi theo bng TT Thuc th nhm Nhm anion Sn phm hoc du hiu phn ng CO32-; CN-; S2-;SO3; S2O32-; NO2-; ClOTo cc kh tng ng: CO2 (khng mu, lm c nc vi trong); HCN(mi hnh
3

HCl 2N hay H2SO4

nhn); H2S(mi thi); SO2 (mi sc mnh); SO2 v S;NO v NO2 (mu nu , kh th); Cl2 (mu vng lc, kh th) AsO33-; AsO43-; CrO42-; ClO-; MnO4; SO42-; PO43-; BrO3; IO3-; F- ; To kt ta tng ng: Ca3(AsO3)2 trng; Ca3(AsO4)2 trng; BaCrO4 vng; Ba(MnO4)2 ; BaSO4 trng; Ca3(PO4)2 trng; Ba(BrO3)2 trng;Ba(IO3)2 trng; CaF2 trng: SCN-;Cl-; Br-; ITo kt ta tng ng: AgSCN trng; AgCl trng; AgBr vng nht; AgI vng r AsO43-; PO43To kt ta tng ng: MgNH4AsO4 trng; MgNH4PO4

BaCl2 + CaCl2 trong mi trng trung tnh

AgNO3 + HNO3 2N

Hn hp Mg (NH4OH + NH4Cl + MgCl2)

trng. CrO42-; AsO33BrO3-; IO3-; NO2-

KI + H2SO4 2N

Gii phng I2 (Nhn trong dung dch nc hoc trong cloroform, hoc th bng h tinh bt).

;MnO4-; ClO-; ClO3-; bit iod bng mu

Dung dch I2

S2-; SO32-; S2O32-;

Lm mt mu I2

Dung dch KMnO4 + S2-; SO32-; S2O32-; H2SO4 2N AsO33-; NO2-; Cl;Br-: I-; CN-; SCN-

Lm mt mu KMnO4

Khng c thuc th nhm

NO3-; ClO4-

2)

Phn tch ring bit

L xc nh trc tip mt ion no trong hn hp nhiu ion bng mt phn ng c hiu (phn ng ch xy ra vi ring mt ion). C th ly tng phn ring dung dch phn tch th ring tng ion, khng cn theo mt th t no V d: tm Bi3+ bng thuc th thioure c mu vng ti, Fe3+ vi KSCN c mu c trng.

Trong nhiu trng hp khng s dng c phng php phn tch ring bit v khng phi tt c cc ion u c phn ng tht c hiu. III) Phn tch cation nhm 1,2,3 trong dung dch nc theo h thng acid base Phn tch nh tnh cation nhm I c tnh chung ca nhm : Nhm 1 cation gm: Ag- ; Hg2+ ; Pb2+, cc nguyn t ny nm trong cc nhm khc nhau ca h thng tun hon. Chng c hoc 18 electron lp ngoi cng hoc (18 + 2) electron 2 lp ngoi cng, l nguyn nhn ti sao chng li tc dng ging nhau i vi cc ion halozenua. Xc nh cc cation nhm 1 ( Ag+, Pb2+, Hg22+)

Dung dch phn tch + HCl long; Li tm

Kt ta 1 + H2O un si, lc nng

Nc lc 1

Nc lc 2 + KI (hoc K2CrO4)

Kt ta 2 + NH4OH

PbI2 vng (hoc PbCrO4 vng)

Kt ta en xm Hg + NH2HgCl

Nc lc 3 + HNO3

AgCl trng

Phn tch nh tnh cation nhm II c tnh chung ca nhm: Nhm 2 cation gm: Ca2+, Sr2+, Ba2+ l nhng nguyn t thuc nhm hai trong h thng tun hon, chng c y s electron lp ngoi l 8, l c s chng c nhng tnh cht inh tnh gn ging nhau. Hot tnh ho hc ca chng tng t Ca n Ba. Cc ion ca chng trong dung dch nc u khng ging nhau. Xc nh cc cation nhm 2: Ba2+, Sr2+, Ca2+ L1 + H2SO4 long + ru etylic, li tm, lc gn

Kt2 + MeSO4 chuyn thnh MeCO3 bng Na2CO3 bo ha

Kt MeCO3 + CH3COOH n va tan ht + K2CrO4, li tm, lc L + Na2CO3 SrCO3 + CaCO3, li tm, ly kt ta, ra sch bng nc

Kt + NaOH lc k, li tm

BaCrO4 vng

Nc lc + Na2S

Kt + CH3COOH n va tan ht, chia thnh 2 phn

PbS en

Phn t + CaSO4 bo ha

Phn nhiu + (NH4)2SO4, li tm, lc

Phn t + CaSO4 bo ha
7

SrSO4 trng CaC2O4 trng

Phn tch nh tnh cation nhm III c tnh chung ca nhm : Cation nhm 3 gm Al3+, Zn2+, Cr3+ tng ng vi nhng nguyn t l nhng kim loi lng tnh, khi tc dng vi dung dch kim to thnh cc hydroxyt lng tnh kt ta. Cc kt ta ny tan trong dung dch kim c d. Xc nh cc cation nhm 3: Al3+, Cr3+, Zn2+, Sn2+, Sn4+, As3+, As5+

L2 + NaOH d + H2O2, un k, li tm, b kt ta

L3 + NH4Cl, un si k, li tm

Kt3,1

L3,1 chia lm 2 phn

Lc mnh, un nng vi (NH4)2S

P1: + H2O2 + ru amylic + H2SO4

P2: + Na2S

Nc lc c SnS32- + CH3COOH SnS2 vng

Kt ra sch + CH3COOH n tan + alizarin + NH4OH Kt son

Lp ru c mu xanh ca H3CrO8

ZnS trng

IV) -

Ti liu tham kho Gio trnh Ha Phn Tch Trng i Hc Cng Nghip TP H Ch Minh. Ha Hc Phn Tch Phn II : Cc phn ng ion trong dung dch nc, NXB Gio Dc, tc gi Nguyn Tinh Dung. Bi ging ha phn tch trng i hc cng ngh ng Nai ging vin Li Th Hin. Ni dung Gio trnh ha phn tch nh tnh 2012 ging vin Dc Trung Cc trang web s dng : tailieu.vn, thuvien247.net, google.com.vn,