2. Cc h thng phn tch cation v anion trong dung dch nc 2.1.

Thuc th trong cc phn ng nh tnh Yu cu ca thuc th trong phn tch: Phi tinh khit, nhy v c hiu. tinh khit l yu cu quan trng nht, cc thuc th ha hc xp theo tinh khit tng dn nh sau: Loi k thut thng lm nguyn liu ban u. Loi tinh khit th nghim ha hc ni chung. Loi tinh khit phn tch. Loi tinh khit ha hc lm cht chun. Loi tinh khit quang hc dng trong phn tch quang ph. Thuc th theo tc dng phn tch: gm hai loi Thuc th nhm: L thuc th c tc dng ging nhau ln mt nhm cc ion. + 2+ V d: HCl l thuc th ca nhm Ag , Pb , Hg2+. Thuc th chn lc: l thuc th c tc dng ging nhau trn mt s ion m cc ion ny c th thuc cc nhm phn tch khc nhau. V d: NH3 c th to phc tan v khng mu vi mt sion nhiu nhm phn tch. Thuc th c hiu hay thuc th ring: l thuc th ch cho phn ng c hiu vi mt ion hoc vi mt cht. V d: H tinh bt cho mu xanh chvi iod, dimethyglyoxim trong mi trng amoniac to thnh ch vi ion Ni2+ mt kt ta mu hng. 2.2. Phn tch ring bit v phn tch h thng 2.2.1. 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 i vi ring mt ion). C th ly

tng phn ring dung dch phn tch th ring tng ion, khng cn theo mt th t nht nh no. 3+ 3+ V d: Tm Bi bng thuc th thioure c mu vng ti, Fe vi KSCN c mu 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. 2.2.2. Phn tch h thng L tin hnh xc nh cc ion theo mt th t nht nh. Mun phn tch h thng mt hn hp nhiu ion, ngi ta thng dng cc thuc th nhm chia cc ion thnh nhiu nhm, mi nhm c th li c chia thnh cc phnnhm v cui cng c tch ring thnh ion ring bit xc nh. C hai h thng phn tch cation: H thng dng H2S. H thng dng acid base. H thng photphat amoniac.

2.3. Phng php nh tnh cc cation 2.3.1. H thng phn tch H2S Nguyn tc: to ta vi cc thuc th nh : HCl, H2S, (NH4)2S/ NaOH, (NH4)2CO3. tan ca cc sunfua, clorua v cacbonat l c s ca h thng ny. Theo h thng ny, cc cation c chia lm 5 nhm phn tch (trong quyn Cc c s ho hc phn tch ca A. P. Kreskov trnh by y h thng phn tch ny). - Nhm 1 gm cc cation kim loi kim v NH4+, Mg . 2 2+ 2+ - Nhm 2 gm cc cation kim loi kim th (Ba , Sr , Ca ). Nhm ny b kt ta bi thuc th nhm - amoni cacbonat trong dung dch m amoniac di dng cc cacbonat khng tan trong nc. Nhm 2 khng b kt ta bi amoni
2+

sunfua v H2S. 3+ 3+ - Nhm 3 gm hai phn nhm l phn nhm ca Al , Cr v phn nhm 2+ 2+ 2+ 2+ 2+ 3+ ca Mn , Fe , Fe , Ni , Co , Zn . Nhm ny khng b kt ta di dng sunfua t dung dch acid. 2+ 2+ 2+ 3+ 3+ 5+ Nhm 4 gm Cu , Cd , Hg , Bi , As , As , Sb 5+ , Sb 3+ , Sn 2+ , bng H2S

4+ Sn . Nhm ny b kt ta bi H2S di dng cc sunfua trong mi trng acid pH = 0,5. Cc sunfua ca chng thc t khng tan trong nc v trong cc dung dch acid v c long. Thuc th chng l H2S trong HCl. + - Nhm 5 gm Ag , Hg
2+

, Pb

2+

. Cc clorua ca nhm ny khng tan trong

nc v trong cc acid long. Thuc th ca nhm l HCl 2N. 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 dch keo ca S. 2.3.2. H thng phn tch acid bazo Nguyn tc: Cc cation to ta hay to phc vi cc acid HCl, H2SO4 hoc vi cc base nh NaOH, NH4OH. H thng ny chia cation thnh 6 nhm: - Nhm 6 gm cc cation kim loi kim v NH4+. Cc clorua, sunfat v hydroxyt ca chng u tan trong nc. Chng khng c thuc th nhm.

Cc hp cht c mt nhm ny u c th tan to thnh dung dch. - Nhm 1 gm Ag+, Hg22+, Pb2+. Cc clorua ca nhm ny khng tan trong nc v trong cc acid long. Thuc th ca nhm l HCl 2N. - Nhm 2 gm Ba 2+ 2+ 2+ 2+ , Sr , Ca , Pb . Sunfat ca chng khng tan trong

nc v trong cc dung dch acid. Thuc th ca nhm l H2SO4 2N 3+ 3+ 2+ 3+ 5+ 3+ 2+ 4+ - Nhm 3 gm Al , Cr , Zn , As , As , Sb , Sn , Sn . Cc hydroxyt ca chng u lng tnh tan trong dung dch kim d. Thuc th

thng dng l NaOH 4N v KOH 4N d. - Nhm 4 gm Mg2+, Mn2+, Fe2+, Fe3+, Bi3+, Sb5+, Sb3+. Cc hydroxyt chng u khng tan trong dung dch kim d. Thuc th thng dng l dung dch NH3 25% d. - Nhm 5 gm Cu2+, Cd2+, Hg2+, Co2+, Ni2+. Cc hydroxyt chng to ra cc amoniacat tan. Thuc th l dung dch NH3 25% d. Phn nhm cc cation theo phng php acid bazo STT nhm I II III Cc cation + 2+ Ag , Pb , Hg22+ 2+ 2+ Sr2+, Ba , Ca 3+ 2+ Cr , Al , Zn
3+

ca

Thuc th HCl 6M H2SO4 3M/ cn 90 NaOH d o

Kt qu Ta clorua Ta sulfat Hydroxyt tan/ kim d

Hydroxyd khng tan/ IV V VI 3+ 3+ 2+ NaOH, NH4OH + H2O2 Bi , Fe , Mg 2+ 2+ Cu , Hg + + Na , K , NH4+ NH4OH Khng c kim d Phc tan/ NH4OH d

u im ca h thng ny l: t c hi hn h thng dng H2S S dng c nhng tnh cht c bn ca cc nguyn t: quan h ca cc nguyn t ny vi cc acid v base, tnh lng tnh ca cc hydroxy v kh nng to phc ca cc nguyn t. - Thi gian thc hin phn tch ngn hn t 30 40% so vi h thng H2S Nhc im l cn gii hn v s lng cc cation, cc tnh cht ca cc hydroxyt ca cc cation nhm 4 v 5 cha c nghin cu k, cng nh cc iu kin tch, to kt ta ca chng. 2.3.3. H thng phn tch photphat - amoniac

H thng ny chia cc cation thnh 5 nhm phn tch. - Nhm 1 gm cc cation kim loi kim v NH4+. Khng c thuc th c trng cho nhm. - Nhm 2 gm Ba2+, Sr2+, Ca2+, Mg2+, Fe2+, Fe3+, Al3+, Cr3+, Mn2+, 3+ Bi . Nhm ny b kt ta bi thuc th (NH4)2HPO4 trong dung dch amoniac c. - Nhm 3 gm Cu2+, Cd2+, Hg2+, Co2+, Ni2+, Zn2+. Cc phophat ca chng tan trong dung dch amoniac to thnh cc amoniacat [Me(NH3)6]2+. - Nhm 4 gm: As3+, As5+, Sb5+, Sb3+, Sn2+, Sn4+. Cc ion thic v antimon khi un nng vi HNO3 th to thnh kt ta khng tan l acid metastanic v acid metaantimon (H2SnO3, HSbO3). Cc hp cht asen (III) khi un nng vi HNO3 th b oxy ho thnh H3AsO4. - Nhm 5 gm Ag+, Hg2+, Pb2+ b kt ta bi acid HCl di dng cc clorua t tan. 2.4. Phn tch nh tnh cc anion Phn tch nh tnh l mt mt trong cng tc phn tch, c nhim v xc nh thnh phn phn t ca cht hoc thnh phn phn t ca cc cht trong hn hp hoc cc ion c trong dung dch. Thng c tin hnh bng cc phng php nh phng php ho hc (dng phn ng ho hc chuyn cht cha bit thnh cc cht mi c tnh cht c trng, ri mi xc nh cht cn tm), phng php vt l, nhm - amoni hydro phophat

phng php ho l (da vo l tnh v ho tnh ca cc cht, phng php ny ch yu dng my nn chnh xc cao v cho kt qu nhanh). 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 ca thuc th nhm anion c th c phn loi theo bng sau:

TT

Thuc th nhm

Nhm anion

Sn phm hoc du hiu phn ng To cc kh tng ng: -CO2 (khng mu, lm c nc vi trong);

CO32- , CN-, S2-, SO3, - HCN (mi hnh nhn); 1 HCl 2N hay H2SO4 S2O32-, NO2- , ClO - 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-, To kt ta tng ng: Ca3(AsO3)2 trng; Ca3(AsO4)2 trng; ClO- ; MnO4-, SO42-, BaCrO4 vng; Ba(MnO4)2 ; PO43- ; BrO3-; IO3-; F- BaSO4 trng; Ca3(PO4)2 trng; Ba(BrO3)2 trng; Ba(IO3)2 trng; CaF2 trng: AgNO3 + HNO3 3 2N Hn hp Mg 4 (NH4OH +NH4Cl + Mg Cl2) CrO42-; AsO33-; MnO4-; 5 KI + H2SO4 2N ClO- ; ClO3-; BrO3-; IO3-; NO26 7 Dung dch I2 S2- ; SO32- ; S2O32-; Gii phng I2 (Nhn bit iod bng mu trong dung dch nc hoc trong cloroform, hoc th bng h tinh bt). Lm mt mu I2 AsO43- ; PO43To kt ta tng ng: MgNH4AsO4 trng; MgNH4PO4 trng. SCN- ;Cl- ; Br - ; ITo kt ta tng ng: AgSCN trng; AgCl trng; AgBr vng nht; AgI vng r

BaCl2 + CaCl2 2 trong mi trng trung tnh

S2-; SO32-; S2O32- ; Dung dch KMnO4 + AsO 2- ; NO -; Cl- ; Br- ; 3 2 H2SO4 2N I; CN- ; SCN-

Lm mt mu KMnO4

Khng c thuc th nhm

NO3- ; ClO4-

3. Phn tch cation nhm 1, 2, 3 trong dung dch nc theo h thng acid - bazo 3.1. Phn tch h thng cation nhm 1 (Ag+, Hg22+, Pb2+) 3.1.1. c tnh chung Cc cation nhm I bao gm Ag+, Hg22+, Pb2+, chng to vi anion Cl- thnh cc mui clorua AgCl, Hg2Cl2, PbCl2 t tan. V vy, ngi ta dng HCl long, ngui lm thuc th nhm tch cc cation Ag+, Hg+, Pb2+ ra khi cc cation khc c trong dung dch phn tch. Khng dng HCl c hay NaCl bi cc kt ta clorua ca cc cation ny tan trong HCl c v dung dch c cha Cl- vi nng ln v to phc, cng khng dng thuc th nng v nhit cao tan ca PbCl2 tng mnh, nh hng n qu trnh phn tch. Cc mui AgCl, Hg2Cl2, PbCl2 c nhng tnh cht chung v ring nh sau: - u l kt ta mu trng. - AgCl v Hg2Cl2 c tan nh hn PbCl2. - PbCl2 tan nhiu trong nc nng, do dng cch un nng tch Pb2+ ra khi Ag+ v Hg22+. - AgCl tan trong NH3 long to thnh phc [Ag(NH3)2]+. Li dng tnh cht ny tch Ag+ ra khi Pb2+ v Hg22+. Khi tc dng vi NH3 th Hg2Cl2 t mu trng bin thnh mu en v phn ng sinh ra Hg kim loi, phn ng ny dng nhn bit Hg22+. 3.1.2. Mt s phn ng c trng ca ion Ag+ Phn ng vi HCl v KCl HCl long v c nhng clorua tan tc dng vi cc dung dch mui bc u to ra kt ta AgCl trng : Ag+ + Cl- AgCl

AgCl b nh sng phn hu gii phng ra bc kim loi, kt ta c mu tm, sau s ho en. Kt ta AgCl khng tan trong HNO3 nhng d tan trong HCl c v trong cc dung dch KCl, NaCl c do to thnh nhng phc [AgCl3]2- v [AgCl4]3- tan. AgCl + 2HCl H2[AgCl3] AgCl + 3HCl H3[AgCl4] Cc phc ny khng bn nn khi pha long vi nc, kt ta AgCl s li c to thnh v tch ra khi dung dch. H2[AgCl3] AgCl + 2HCl AgCl tan trong amoniac, trong cc mui amoni, xianua v trong natri thiosunfat to thnh cc ion phc. AgCl + 2NH4OH [Ag(NH3)2]Cl + 2H2O AgCl + 2KCl K[Ag(CN)2] + KCl Khi thm HNO3 vo dung dch [Ag(NH3)2]Cl n phn ng axit th dung dch s ho c ri tip kt ta trng AgCl li c tch ra: [Ag(NH3)2]Cl + 2HNO3 AgCl + 2NH4NO3 Ngi ta s dng tnh tan ca AgCl trong NH4OH tch Ag+ ra khi Hg22+. 3.1.3. Mt s phn ng c trng ca ion Hg22+ Phn ng vi HCl HCl long lm kt ta t cc dung dch mui ca ion Hg22+ kt ta bt Hg2Cl2 mu trng, khng tan trong thuc th d nhng tan trong HNO3 (y l im khc vi kt ta AgCl). Hg2(NO3)2 + 2HCl Hg2Cl2 + 2HNO3

3Hg2Cl2 + 8HNO3 3HgCl2 + 3Hg(NO3)2 + 2NO + 4H2O Hg2Cl2 b phn hu mt phn theo: Hg2Cl2 HgCl2 + Hg

V axit HNO3 ho tan c Hg kim loi nn lm cn bng chuyn dch hon ton sang phi, do ho tan c kt ta Hg2Cl2.

Khi cho NH4OH tc dng vi kt ta Hg2Cl2 ta s c NH2HgCl mu trng v Hg kim loi mu en tch ra di dng bt: Hg2Cl2 + 2NH3 NH2HgCl + Hg + NH4Cl

Kt ta tan c trong HNO3 c, nng v c trong nc cng thu: 3NH2HgCl + 3Hg + 14 HNO3 6Hg(NO3)2 + 2NO + 3NH4Cl + 4H2O Phn ng vi KI Hg2I2 rt kh tan, c iu ch bng cch cho KI tc dng vi dung dch mui Hg(I). Hg22+ + 2I- Hg2I2 (mu vng lc) Nu d nhiu thuc th, Hg2I2 s b phn hu. Hg2I2 HgI2 + Hg

Phn ng vi K4[Fe(CN)6] v K3[Fe(CN)6] Hg22+ to vi kali feroxianua kt ta keo Hg4[Fe(CN)6] mu vng nht, cn vi kali ferixianua to kt ta Hg3[Fe(CN)6] mu vng lc. S kh Hg22+ n thu ngn kim loi Nhng kim loi hot ng mnh hn y thu ngn ra khi hp cht ca n: Cu + Hg2(NO3)2 2Hg + Cu(NO3)2

Ion Hg22+ cng c kh n thu ngn kim loi khi cho mui thu ngn (I) tc dng vi thic (II) clorua: SnCl2 + Hg2(NO3)2 Hg2Cl2 + Sn(NO3)2 Sau : Hg2Cl2 + SnCl2 2Hg + SnCl4

3.1.4. Mt s phn ng c trng ca ion Pb2+ Phn ng vi HCl HCl long y c t cc dung dch mui ch ra mt kt ta trng. Pb2+ + 2Cl- PbCl2

Kt ta ny khng hon ton v PbCl2 c tan ln nn khi un si vi nc, kt ta s tan ht, sau khi ngui s thy c tinh th PbCl2 hnh kim xut hin. Ch clorua tan trong HCl c to thnh phc H2[PbCl4]. PbCl2 + 2 HCl H2[PbCl4] Phn ng vi KI KI tc dng vi dung dch mui Pb2+ cho kt ta PbI2 vng, kt ta ny tan trong thuc th d: Pb2+ + 2I- PbI2 PbI2 + 2I- [PbI4]2Kt ta PbI2 tan hon ton nu un si trong nc, sau khi ngui s thy c tinh th PbCl2 hnh vy ng nh rt c trng. Kt ta PbI2 cng d tan trong axit CH3COOH nng.

Hnh 3.1. S phn tch dung dch cation nhm I

3.2. Phn tch h thng cation nhm 2 (Ba2+, Sr2+, Ca2+) 3.2.1. c tnh chung Cc cation nhm II, c th bao gm c ion Pb2+ t nhm I lt xung, to vi ion SO42+ trong ru thnh cc mui BaSO4, SrSO4, PbSO4, CaSO4 khng tan. Vi vy, ngi ta dng H2SO4 long v C2H5OH lm thuc th nhm tch cc cation Ba2+, Sr2+, Ca2+, Pb2+ ra khi cc cation khc c trong dung dch phn tch. Khng dng H2SO4 c v s to thnh cc sunfat axit Me(HSO4)2 tan. Trong cc mui sunfat th BaSO4 v CaSO4 d kt ta nht, SrSO4 kh kt ta hn cn un nng nh. CaSO4 c tan ln nht, rt kh kt ta, v vy ngi ta thng thm ru vo gim bt tan ca n, khi CaSO4 d kt ta hn. Trong tt c 4 kt ta sunfat ch c PbSO4 ho tan trong NaOH to thnh phc PbO22- hoc tan trong CH3COONH4, v to phc Pb(CH3COO)3-, ta li dng tnh cht ny tch ch ra khi hn hp cation nhm II. Cc kt ta sunfat ca Ba2+, Sr2+, Ca2+ khng tan trong cc axt v c long, tch chng ra khi nhau, chng ta li phi chuyn cc sunfat thnh hp cht tan, mun vy un kt ta sunfat vi dung dch Na2CO3 bo ho nhiu ln chuyn kt ta sunfat thnh kt ta cacbonnat ri ho tan cc kt ta ccbonat bng axit CH3COOH, cc cation ca nhm II li tr v trng thi ion trong dung dch. Trong mi trng CH3COOH, khi thm cromat hoc dicromat vo th ch c Ba2+ kt ta di dng BaCrO4 mu vng, ta li dng tnh cht ny tch Ba2+ ra khi hn hp Sr2+ v Ca2+, sau dng dung dch ny tm Ca2+ v Sr2+. 3.2.2. Mt s phn ng c trng ca ion Ba2+ Phn ng vi H2SO4 v (NH4)2SO4 Axit sunfuric long v cc mui sunfat tan u lm kt ta Ba2+ di dng tinh th trng BaSO4, khng tan trong cc axit v c. Ba2+ + SO42- BaSO4 Phn ng vi (NH4)2CO3, K2CO3, Na2CO3

Cc thuc th ny u to vi Ba2+ kt ta tinh th trng, tan trong axit: Ba2+ + (NH4)2CO3 BaCO3 + 2NH4+ BaCO3 + 2H+ Ba2+ + H2O + CO2 Phn ng vi K2Cr2O7; K2CrO4 Kali cromat tc dng vi dung dch cha ion Ba2+ cho kt ta vng BaCrO4, tan trong HCl v khng tan trong CH3COOH Ba2+ + CrO42- BaCrO4 Khi dng K2Cr2O7 chng ta cng thu c kt ta BaCrO4 mu vng. Phn ng vi (NH4)2C2O4 Amoni oxalat tc dng vi dung dch Ba2+ cho kt ta BaC2O4 mu trng, tan trong cc axit v c long v tan c trong axit axetc: Ba2+ + (NH4)2C2O4 BaC2O4 + 2NH4+ Phn ng vi Na2HPO4 Thuc th Na2HPO4 to vi ion Ba2+ mt kt ta v nh hnh BaHPO4 Ba2+ + HPO42- BaHPO4 Kt ta tan trong axit HCl, HNO3 v CH3COOH 3.2.3. Mt s phn ng c trng ca ion Ca2+ Cc phn ng c trng ca ion Ca2+ cng tng t nh ca ion Ba2+ Phn ng vi H2SO4 v cc dung dch mui sunfat Axit sunfuric long v cc dung dch sunfat tc dng vi dung dch c cha ion Ca2+ to ra kt ta tinh th CaSO4 mu trng, c tan tng i ln so vi cc sunfat nhm II khc, l 2g/l ( TCaSO4 = 2.10-4 ). Ca2+ + SO42- CaSO4 Khc vi cc kt ta SrSO4 v BaSO4 , kt ta CaSO4 tan c trong dung dch amoni sunfat do to thnh phc tan theo phn ng sau:

CaSO4 + 2 (NH4)2SO4 (NH4)2[Ca(SO4)2] V vy, ta cng c th dng (NH4)2SO4 kt ta Ba2+ v Sr2+, tch ra khi Ca2+. Phn ng vi (NH4)2C2O4 Amoni oxalat tc dng vi dung dch Ca2+ cho kt ta tinh th CaC2O4 mu trng, tan trong cc axit v c long nhng khng tan trong axit axetc, y l im khc so vi cc oxalat nhm II khc, nn phn ng ny c dng nhn bit ion Ca2+ : Ca2+ + C2O42- CaC2O4 3.2.4. Mt s phn ng c trng ca ion Sr2+ Phn ng vi H2SO4 v (NH4)2SO4 Axit sunfuric long v amoni sunfat tc dng vi dung dch c cha ion Sr2+ nng to ra kt ta tinh th SrSO4 mu trng: Sr2+ + SO42- BaSO4 Sr2+ + (NH4)2SO4 SrSO4 + 2NH4+ Phn ng vi (NH4)2CO3 Khi cho (NH4)2CO3 tc dng vi dung dch trung tnh cha ion Sr2+ ri un nng, ta c kt ta SrO3 mu trng tan trong axit v c v axit axetic: Sr2+ + (NH4)2 CO3 SrCO3 + 2NH4+ SrCO3 + 2H+ Sr2+ + H2O + CO2 Phn ng vi (NH4)2C2O4 Amoni oxalat tc dng vi dung dch Sr2+ cho kt ta SrC2O4 mu trng, tan trong cc axit v c long v tan c trong axit axetc: Sr2+ + (NH4)2C2O4 SrC2O4 + 2NH4+ Mu ngn la: y l phn ng kh c trng nhn bit cc cation nhm II, cc mui d bay hi ca bari trong ngn la kh khng mu to thnh ngn la mu vng lc; mui canxi c mu gch, mui stronti coa mu cacmin.

Hnh 3.2. S phn tch dung dch cation nhm II

3.3. Phn tch h thng cation nhm 3 (Al3+, Sn4+, Sn2+, Zn2+, As5+, Cr3+ ) 3.3.1. c tnh chung Hiroxit ca cc ion Al3+, Cr3+, Sn4+, Zn2+ c tnh cht lng tnh, kt ta hidroxit ca chng tan trong axit cng nh trong kim mnh nh KOH, NaOH, v vy khi thm dung dch NaOH d vo hn hp cc hidroxit th c th tch c cc cation ny khi cc cation nhm sau: Al(OH)3 + NaOHd AlO2- (aluminat) Cr(OH)3 + NaOHd CrO2- (cromit) Sn(OH)4 + NaOHd SnO22- (stanit) Zn(OH)2 + NaOHd ZnO22- (Zincat) Cn ch rng ion cromit CrO2- thng kt hp vi mt s cation nh Mn2+, Fe3+, Mg2+, Zn2+ to thnh nhng kt ta MnCrO2, MgCrO2, ZnCrO2 kh tan trong mi trng kim d. V vy nu ch dng ring NaOH d lm thuc th th mt phn Cr3+ c

th vn cn li trong kt ta vi hiroxit ca nhm sau. Do , hn hp NaOHd + H2O2 c dng lm thuc th nhm, khi Cr3+ s b oxi ho thnh CrO42- theo phn ng: 2Cr3+ + 3H2O2 + 10 OH- 2 CrO42- + 8H2O Ngoi ra cng cn lu rng, cc ion Pb2+ ( nhm II ), Sb3+ ( nhm IV ), Cu2+ ( nhm V ) cng to thnh mui tan trong kim d: Pb(OH)2 + 2 NaOH Na2PbO2 + 2H2O ( natri plombit ) Cu(OH)2 + 2 NaOH Na2CuO2 + 2H2O ( natri cuprit ) Sb(OH)2 + 2 NaOH Na2SbO2 + 2H2O ( natri stibit ) Cc cation nhm III sau khi tch khi cc cation khc bng thuc th nhm u nm dng mui tan AlO2-, CrO2-, SnO32- ( anion stanit SnO22- b oxiha thnh stanat SnO32- ), ZnO22- . Ta c th dng NH4+ l mt axit yu, ly bt OH- i th Al(OH)3 v Sn(OH)4 s kt ta tr li, cn km s dng cation phc tan amoniacat [Zn(NH3)42+] v crom vn dng anion cromit CrO2- , nh vy s tch c nhm III thnh 2 phn: AlO2- + NH4+ Al(OH)3 + NH4OH SnO32- + 2 NH4+ Sn(OH)4 + 2NH4OH ZnO2- + 4NH4+ Zn(NH3)42+ + NH4OH 3.3.2. Mt s phn ng c trng ca ion Al3+ Phn ng vi thuc th nhm Thm t t tng git dung dch kim long vo dung dch cha ion Al3+, kt ta v nh hnh dng keo hidroxit Al(OH)3 mu trng c hnh thnh: Al3+ + 3OH- Al(OH)3 Tnh axit v tnh baz ca hidroxit nhm u yu, Al(OH)3 H3AlO3 HAlO2. H2O, trong mi trng axit: Al(OH)3 + 3H+ Al3+ + 3H2O Cn trong mi trng kim: Al(OH)3 + OH- AlO2- + 2H2O

Mun cho kt ta Al(OH)3 tan hon ton to thnh AlO2- thi phi thm d OH- , mi trng pH = 11, qu trnh chuyn l hon ton, ngc li mun chuyn AlO2- thnh kt ta Al(OH)3 th phi ly bt OH- trong dung dch, mun vy ta thm mt axit yu l NH4+ v un nng dung dch NH3 bay i, cho cn bng chuyn mnh v pha to kt ta. Phn ng vi thuc th hu c alizazin S Trong mi trng NH3, ion Al3+ to vi thuc th hu c alizazin S mt kt ta mu thm gi l sn nhm, y l phn ng rt c trng v nhy pht hin ion nhm nhng khng phi l phn ng chn lc v cc ion Sb3+, Sn4+, Zn2+ cng to c vi alizazin cc kt ta mu xm, da cam v vng nn phn ng phi thc hin rt cn thn nh sau: nh 3- 5 git dung dch alizazin 0,1% pha trong ru vo dung dch th, sau thm dung dch NH4OH long n khi c phn ng kim, un si 2-3 pht, quay li tm kt ta lng xung y ng nghim. Nghing ng nghim v nh tng git axit CH3COOH long theo thnh ng nghim axit ha nh phn dung dch cho n khi mt mu tm ca alizazin S d s chuyn thnh mu vng, nu c Al3+ ta c kt ta mu son ti rt p, nu t Al3+ th dung dch nhum mu . 3.3.3. Mt s phn ng c trng ca ion Cr3+ Phn ng vi thuc th nhm Thm t t tng git dung dch kim long vo dung dch cha ion Cr3+, kt ta v nh hnh dng keo hidroxit Al(OH)3 mu lc xm c hnh thnh: Cr3+ + 3OH- Cr(OH)3 Cng tng t nhm hidroxyt, tnh axit v tnh baz ca hidroxit crm u yu, Cr(OH)3 H3CrO3 HCrO2. H2O, trong mi trng axit: Cr(OH)3 + 3H+ Cr3+ + 3H2O Cn trong mi trng kim: Cr(OH)3 + OH- CrO2- + 2H2O

Ion crmit c mt s tnh cht c bit m khi phn tch ta cn lu : - Ion crmit rt d phn ng vi nc, nht l khi un nng:

CrO2- + H2O Cr(OH)3 + OHCr(OH)3 sinh ra trong phn ng ny th li khng tan trong kim d c. - Ion crmit kt hp vi cc ion Mn2+, Fe3+, Mg2+, Zn2+ to thnh nhng kt ta kh tan nn khng th tch hon ton nhm III khi nhm IV. Mt khc, nu c mt Fe3+ khng th dng kim d tch nhm III tch nhm III v trong iu kin ny s hnh thnh Fe(OH)3 v Cr(OH)3 s cng kt cng vi Fe(OH)3 , khi s khng b tan trong kim d na. Chnh v vy, tch hon ton nhm III khi cc nhm sau, ta dng hn hp NaOH v H2O2 chuyn crm v dng ion crmat tan. Phn ng c trng ring bit tm ion crm Phn ng c trng nht tm crm chnh l phn ng oxiha Cr3+ thnh thnh CrO42- mu vng hay Cr2O72- mu da cam v phn ng ca Cr2O72- vi H2O2 trong mi trng axit to thnh axit pecromic H2CrO6 c mu xanh lam: Cr2O72- + 4H2O2 + 2H+ = 2H2CrO6 + 3H2O Phn ng c thc hin nh sau: Trong mi trng NaOH + H2O2, Cr3+ b oxi ho thnh CrO42-; sau tm ion ny, phi axit ho dung dch bng H2SO4 hoc HNO3 (khi CrO42- s chuyn sang dng Cr2O72-); thm vo y 5-7 git dietylete (hay ru amylic) v 1 git H2O2 3% ri lc u mnh, trn lp ete (hoc lp ru amilic) l axit H2CrO6 c mu xanh lam. 3.3.4. Mt s phn ng c trng ca ion Zn2+ Phn ng vi thuc th nhm Thm t t tng git dung dch kim long vo dung dch cha ion Zn2+, kt ta v nh hnh dng keo hidroxit Zn(OH)2 mu trng c hnh thnh: Zn2+ + 2OH- Zn(OH)2 Km hidroxit l cht in li lng tnh, tan trong axit v trong kim d: Zn(OH)2 + 2H+ Zn2+ + 2H2O Zn(OH)2 + 2OH- ZnO22- + 2H2O

Ta c th thm vo dung dch zincat mt axit th ly li c kt ta Zn(OH)2, nhng khc vi nhm v thic, khng th dng NH4+ v s to thnh phc tan ca km: Zn(OH)2 + 2OH- + 4NH4+ [Zn( NH3)4]2+ + 4H2O Phn ng c trng ring bit tm ion km Trong mi trng axit long, ion Zn2+ to vi thuc th (NH4)2[Hg(SCN)4] khi c mt ca Co2+ vi nng rt nh ( khng vt qu 0,02% ) mt kt ta tinh th mu lc rt c trng c thnh phn l Zn[Hg(SCN)4]. Co[Hg(SCN)4]. Nu thay ion Co2+ bng ion Cu2+ ( nng khng vt qu 0,1% ) th to thnh kt ta tinh th mu tm Zn[Hg(SCN)4]. Cu[Hg(SCN)4]. Phn ng ny b cn tr bi cc ion Co2+, Cu2+, Mn2+, Pb2+, Ag+, khi nng ca chng vt qu nng ca ion Zn2+ nn phi thc hin phn ng cn thn nh sau: Ly 0,5ml dung dch nghin cu vo ng nghim sch, thm vi git H2SO4 long to mi trng axit, thm 0,5ml dung dch 0,1% Cu2+ hoc 0,02% Co2+ v mt vi git dung dch thuc th (NH4)2[Hg(SCN)4]. Nu trong dung dch nghin cu c mt ion Zn2+ th s c kt ta tinh th mu tm Zn[Hg(SCN)4].Cu[Hg(SCN)4] hoc kt ta tinh th mu lc Zn[Hg(SCN)4]. Co[Hg(SCN)4]. 3.3.5. Mt s phn ng c trng ca ion Sn2+, Sn4+ Phn ng vi thuc th nhm Thm t t tng git dung dch kim long vo dung dch cha ion Sn2+, kt ta v nh hnh dng keo hidroxit Zn(OH)2 mu trng c hnh thnh: Sn2+ + 2OH- Sn(OH)2 Sn(OH)2 tan trong trong kim d to thnh anion stanit SnO22- : Sn(OH)2 + 2OH- SnO22- + 2H2O lu v khi un nng, SnO22- phn ng vi nc: SnO22- + H2O HSnO2- + OHTrong mi trng kim long, HSnO2- b phn hy to thnh kt ta oxyt mu en SnO: HSnO2- SnO + OH-

Cn trong mi trng kim c, HSnO2- b phn hy to thnh Sn: 2HSnO2- Sn + SnO32- + H2O - Sn(OH)4 c tnh cht tng i c bit, kt ta keo Sn(OH)4 mi hnh thnh cn gi l axit - stanic d tan trong axit v trong kim d: Sn(OH)4 + 4H+ Sn4+ + 4H2O Sn(OH)4 + 2OH- SnO32- + 3H2O Nhng nu lu v un nng th c s trng hp, tch bt mt s phn t H2O chuyn thnh H2SnO3, gi l axit - stanic, khng tan c trong axit v trong kim, khi ny thic s b ln xung cc nhm sau. - Sn(OH)4 th hin c tnh baz v axit yu nn cc ion axit Sn4+ v ion baz SnO32- c kh nng phn ng vi H2O: Sn4+ + 4H2O Sn(OH)4 + 4H+ SnO32- + 3H2O Sn(OH)4 + 2OHNh vy, cng ging nh AlO2-, mun chuyn SnO32- thnh kt ta Sn(OH)4 ta c th dng 4NH4+: SnO32- + H2O + 2NH4+ Sn(OH)4 + 2NH3 Dng phn ng ny c th tch thic v nhm ra khi crm v km. Phn ng c trng ring bit tm ion thic Phn ng vi FeCl3 trong mi trng axit: 2FeCl3 + SnCl2 2FeCl2 + SnCl4 Nh vo dung dch ny my git imtyl glixim th s to mui ni phc mu hng vi ion Fe2+. Phn ng ny b cn tr bi mt s ion nh Mn2+, Co2+, Ni2+, Fe2+, Cr3+. Phn ng vi K3[Fe(CN)6]: 2[Fe(CN)6]3- + Sn2+ Sn4+ + 2[Fe(CN)6]4Sau nh vo dung dch ny my git Fe3+ s to thnh Fe4[Fe(CN)6] c mu xanh c trng.

Hnh 3.3. S phn tch dung dch cation nhm III