PHN TCH NH TNH Chng 1. MT S VN C BN 1.1.

. Phn tch h thng Hin nay, i vi cc cation, ngi ta tm ra nhiu h thng phn tch, mi h thng c nhng u im v nhc im ring. Hai h thng thng c dng l h thng axit - baz v h thng H2S. Vi cc anion th khng c mt h thng phn tch cht ch no m ch c cc phng php phn tch ring l cho tng anion mt hoc tng nhm nh m thi. H thng cc cation theo phng php H2S: Vic phn chia cc cation thnh tng nhm theo phng php H2S c trnh by trong bng sau: S phn nhm cc cation theo phng php H2S Nhm 1 Thuc th nhm HCl long Cc cation thuc nhm Ag+, Hg22+, Pb2+ Sn phm to thnh sau khi tc dng vi thuc th AgCl, Hg2Cl2, PbCl2 Kt ta cc sunfua. Nhm ny chia thnh hai phn nhm: II H2S trong mi trng axit (pH =0,5) Sn2+, Sn4+, Sb3+, Sb5+, As3+, As5+, Hg2+, Cu2+, Cd2+, Bi3+, (Pb2+) + Phn nhm IIA: Gm cc sunfua tan trong (NH4)2Sx v b oxi ho AsS43-, SbS43-, SbS32+ Phn nhm IIB: gm cc sunfua khng tan trong (NH4)2Sx nh HgS, CuS, CdS, Bi2S3, (PbS) Kt ta Al(OH)3, Cr(OH)3, Fe(OH)3, MnS, CoS, NiS, ZnS. Nhm ny cng chia thnh hai nhm: III (NH4)2S trong mi trng NH3 + NH4Cl Al3+, Cr3+, Fe3+, Mn2+, Co2+, Ni2+, Zn2+ + Phn nhm IIIA: gm cc kt ta tan trong HCl nh Al(OH)3, Cr(OH)3, Fe(OH)3, MnS, ZnS. + Phn nhm IIIB: gm cc kt ta khng tan trong HCl nh CoS, NiS. (NH4)2CO3 IV NaH2PO4 trong mi trng NH3 + NH4Cl Khng c thuc th nhm Ba2+, Sr2+, Ca2+ Mg2+ BaCO3, SrCO3, CaCO3 NH4MgPO4

Na+, K+, NH4+

Phng php phn tch theo ng li H2S c u im l cch phn chia cc nhm v cch tin hnh phn tch rt cht ch, ph hp vi vic trnh by cc s s l thuyt, c bit l vic phn chia cc nhm phn tch c nhiu im ph hp vi vic phn nhm trong bng h thng tun hon Mendelep, do lin h d dng gia cc phn ng hc trong gio trnh ho hc v c vi phn ng phn tch. Tuy nhin, phng php ny c nhc im l H2S c, nn tin hnh phn tch bng phng php ny cn phi c trang thit b bo him tt.

H thng cc cation theo phng php axit - baz: trnh phi tip xc vi cht c H2S, ngi ta a ra phng php khng dng H2S, phng php ny da trn tc dng ca cc cation vi cc thuc th nhm l cc axit v cc baz nh HCl, H2SO4, NaOH, NH4OH. Vic phn chia cc cation thnh tng nhm theo phng php ny c trnh by trong bng sau: Nhm I Nhm axit II Thuc th nhm HCl long H2SO4 long Cc cation thuc nhm Ag+, Pb2+, Hg22+ Ba2+, Sr2+, Ca2+, (Pb2+) Al3+, Cr3+, Zn2+, Sn2+, Sn4+, As3+, As5+ Fe2+, Fe3+, Sb3+, Sb5+, Bi3+, Mn2+, Mg2+ Cu2+, Cd2+, Hg2+, Co2+, Ni2+ Na+, K+, NH4 Sn phm to thnh sau khi tc dng vi thuc th nhm AgCl, PbCl2, Hg2Cl2 BaSO4, SrSO4, CaSO4, PbSO4 AlO22-, CrO42-, ZnO22-, SnO32-, AsO43-

III

NaOHd + H2O2

IV Nhm Baz V

NaOH

Fe(OH)2, Fe(OH)3, Sb(OH)3, Bi(OH)3, Mn(OH)2, Mg(OH)2 Cc phc amoniacat

NH4OH c d Khng c thuc th nhm

Me(NH 3 ) 4 2

VI

Trong phng php ny cc cation c phn thnh 6 nhm ln: - Nhm I gm Ag+, Hg22+, Pb2+, thuc th nhm l dung dch HCl long v ngui. - Nhm II gm Ba2+, Ca2+, Sr2+, c Pb2+ lt xung t nhm I, thuc th nhm l H2SO4 long v ru C2H5OH, thuc th to vi cc cation ny kt ta mu trng. - Nhm III gm Cr3+, Al3+, Sn2+, Sn4+, Zn2+, As5+, thuc th nhm l NaOH d v H2O2. Trong mi trng ny Al3+, Sn2+, Sn4+, to thnh hiroxit lng tnh tan trong kim d: CrO2- s b oxi ho thnh CrO4- mu vng . - Nhm IV gm Fe3+, Bi3+, Mn2+, Mg2+, Sb3+ , thuc th nhm l NaOH d v H2O2. Trong mi trng ny cc cation s dng cc hiroxit khng tan. - Nhm V gm Cu2+, Co2+, Ni2+, Cd2+, Hg2+, thuc th nhm l NH4OH c. Cc cation s to vi thuc th nhm cc phc amoniacat tan c mu. - Nhm VI gm K+, Na+, NH4+, nhng ion ny khng c thuc th nhm bi v chng khng to thnh kt ta kh tan vi mt thuc th no. 1.2. Mt s k thut phn tch nh tnh 1.2.1. Lm sch dng c th nghim Nhng dng c thy tinh nh chai, l, ng nh git, ng nghimtrc khi dng phn tch phi c ra rt sch. Bnh c xem nh sch nu ngn nc trong bnh u n v trn thnh bnh khng cn nhng git nc. Ni chung, cc dng c thy tinh sch, trc khi s dng c ra bng nc my v trng 2, 3 ln bng nc ct. Sau khi s dng phn tch cng phi c ra rt sch, treo ngc trn gi ( y ln trn, ming xung di ) cho ti kh.

 lm sch cc dng c thy tinh, c mt s dung dch ra sau: - Dung dch x phng nng: ha tan mt t x phng trong nc nng. - Dung dch kim pemanganat: ha tan 5g KMnO4 trong 100ml dung dch kim kali 10% nng. - Dung dch hn hp sunfcrmic: ha tan 15g K2Cr2O7 c nghin nh trong 100ml nc nng, lm lnh dung dch ri va khuy lin tc, va thm rt chm 100ml axit K2SO4 c. Dung dch ny c trong l thy tinh c nt nhm, c th s dng trong thi gian di nn sau khi s dng nn gi li. ra cc dng c thy tinh tt nht l s dng dung dch x phng nng v dung dch kim pemanganat c tc dng ph hoi thy tinh, cn hn hp sunfcrmic th khi s dng phi cn thn hn. 1.2.2. un Trong phn tch nh tnh bng phng php ha hc, thng phi un dung dch trong cc ng nghim trn n cn. Khi un, pha ngoi ng phi kh trnh b nt hoc v, mi u nn h nng nh ng nghim bng cch di chuyn trn ngn la, sau mi un nng mnh. Nu un cht lng c cha kt ta th phi khuy u. Thng thng khi un cht lng c cha kt ta nn un trn bp cch thy, khng nn un trc tip trn ngn la v s si d lm ny sinh nhng va chm v cht lng c th bn ra ngoi. Cn ch khi un khng ming ng nghim hng v pha c ngi, v cht lng si thng l axit hoc kim c th b bn mnh ra ngoi. Trong qu trnh phn tch thng cn phi c c dung dch hoc phi lm bay hi n kh, khi ny c th s dng bt s t trn li aming hoc trn bp cch thy. 1.2.3. Kt ta Trong phn tch nh tnh bng phng php ha hc, ta thng kt ta cc cht t dung dch phn tch tch v pht hin cc ion. V vy cn ch n mu v dng bn ngoi ca kt ta. C th phn bit kt ta tinh th v kt ta v nh hnh: kt ta tinh th thng c dng ht to hoc ht nh, thng khng to thnh ngay m cn mt thi gian hnh thnh tinh th; lc mnh v dng a thy tinh c vo thnh ng nghim l nhng ng tc gip cho qu trnh hnh thnh tinh th nhanh hn. Kt ta tinh th thng nhanh chng lng xung y ng nghim, nn vic ly tm tch kt ta cng thun li hn. Kt ta v nh hnh thng xut hin ngay sau khi thm thuc th vo, nhng lng xung y ng nghim mt cch chm chp nn kh quay ly tm tch, chng cng thng d dng to thnh dung dch keo. Vic un nng v thm cht in li l to iu kin ng t chng. Nn kt ta khi un nng dung dch, v khi tng nhit nhng ht kt ta s ln hn, thun li cho vic ra v quay li tm, nhng khng nn un ti si v khi thm thuc th vo c th lm bn dung dch ra ngoi. Nu kt ta dng tinh th th thm t t thuc th kt ta v khuy u, cn nu kt ta dng keo th thm ton b lng thuc th kt ta cn thit. Qu trnh kt ta thc hin nh sau: Ly vo ng nghim quay li tm khong 2-3ml dung dch nghin cu ( nu ng nghim quay li tm loi nh th ly khong 0,5ml ). To mi trng pH ph hp theo hng dn v tng nhit . Kim tra mi trng phn ng bng giy ch th bng cch: t giy ch th ln np knh ng h sch, dng a thy tinh khuy u dung dch ri t u a thy tinh ln giy ch th. Sau khi to mi trng pH ph hp, un nng cn thn ri va khuy va thm thuc th kt ta vo cho n d kt ta hon ton. 1.2.4. Ly tm, tch kt ta, ra kt ta Trong phn tch nh tnh bn vi lng, tch kt ta khi dung dch chng ta thng dng phng php quay li tm bng my quay li tm. Phi lu tun th cch s dng my quay li tm nh hng dn. Thi gian li tm ph thuc vo c tnh ca kt ta, nhng kt ta dng tinh th lng xung y nhanh nn ch cn quay 0,5 n 1,5 pht tc khong 1000 vng/pht; kt ta dng v nh hnh lng chm nn phi quay t 2 n 3 pht tc khong 2000 vng/pht. Sau khi quay li tm, ton b kt ta lng xung y, nc ci trn tr thnh trong sut gi l nc li tm. Cng c khi mt s kt ta khi quay li tm li ni ln trn mt cht lng hoc lng xung rt chm. Gp nhng kt ta ny, mun tch kt ta phi lc qua giy lc.

 kim tra xem qu trnh kt ta hon ton cha, ta th ng nghim va quay li tm bng cch nh vi git thuc th kt ta theo thnh ng ngim v quan st v tr git thuc th ri xung nc li tm, nu khng thy c cc v tr l qu trnh kt ta hon ton. Sau khi quay li tm, kt ta lng cht xung y n mc c th rt d dng nc li tm trn, qu trnh rt nc li tm ra khi kt ta nh vy gi l qu trnh gn. Mt cch khc tch nc li tm ra khi kt ta l: gi ng nghim bng tay tri v tr nghing, tay phi dng ng nh git c ng bp cao su ht nc li tm, ch khi a ng nh git trnh chm vo kt ta, lm c dung dch. Ty thuc vo lng kt ta v tnh cht ca n m s dng nhng dung dch ra khc nhau, ni chung ta ra kt ta bng nc ct, vi nhng kt ta c kh nng chuyn thnh trng thi keo th thm vo nc ra cc cht in li, v d khi ra kt ta st hidroxyt, ngi ta dng dung dch amoni nitrat long. ra kt ta, ta thm vi ml nc ct hoc hoc dung dch ra tng ng, y ng nghim li ri lc hoc t nghing ng nghim kt ta c phn b trn din rng ri khuy, sau quay li tm v b i phn nc ra. Ra kt ta khong 3,4 ln l .

Chng 2. PHN TCH NH TNH CC CATION NHM I Ag+, Hg22+, Pb2+ 2.1. 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. 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+. 2.2. 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+. 2.3. 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 2.4. 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 PbCl 2 hnh vy ng nh rt c trng. Kt ta PbI2 cng d tan trong axit CH3COOH nng.

Chng 3. PHN TCH NH TNH CC CATION NHM II Ba2+, Sr2+, Ca2+ 3.1. 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. nh. Trong cc mui sunfat th BaSO4 v CaSO4 d kt ta nht, SrSO4 kh kt ta hn cn un nng

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. 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 Phn ng vi natri rodisonat Na2C6O6 Natri rodisonat tc dng vi ion Ba2+ trong mi trng trung tnh cho kt ta bari rodisonat mu ti: BaCl2 +

CO CO - CONa CO CO - CONa

CO CO - CONa Ba + 2NaCl CO CO - CONa

Ion Sr2+ cng to kt ta mu nu cn Ca2+ th khng.

Tuy nhin, Stronti rodisonat tan trong HCl long ngui, cn iu kin ny bari rodisonat chuyn thnh hirorodisonat mu ti kh tan. 3.3. 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 Ca 2+ to ra kt ta tinh th CaSO4 mu trng, c tan tng i ln so vi cc sunfat nhm II khc, l 2g/l ( T CaSO4 = 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 3.4. 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.

Chng 4. PHN TCH NH TNH CC CATION NHM III Al3+, Sn4+, Sn2+, Zn2+, As5+, Cr3+ 4.1. 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+, Zn 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:
2+

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 4.2. 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 Al 3+, 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 . 4.3. 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. 4.4. 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]. 4.5. 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 + OHCn 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.

Chng 5. PHN TCH CATION NHM IV Fe2+, Fe3+, Sb3+, Sb5+, Mn2+, Bi3+, Mg2+ 5.1. c tnh chung c tnh chung ca cc cation nhm IV l to vi kim hay amoniac cc hiroxit khng tan: Fe2+ + 2OH- Fe(OH)2 mu trng Fe3+ + 3OH- Fe(OH)3 mu nu Mg2+ + 2OH- Mg(OH)2 mu trng Sb3+ + 3OH- Sb(OH)3 mu trng Sb5+ + 5OH- Sb(OH)5 mu trng Mn2+ + 2OH- Mn(OH)2 mu trng Trong mi trng NaOH d + H2O2 th Mn2+ s b oxi ho thnh MnO2 mu en: Mn(OH)2 + H2O2 MnO2 + 2H2O Trong cc hidroxit ca nhm IV th Sb(OH)3 tan c trong kim d v c trong cacbonat ca kim loi kim, nn antimon khng lt xung nhm III, cn a Sb3+ ln Sb5+ , chnh v vy thuc th nhm vn l NaOH d v H2O2 . Nh vy vi hn hp cation sau khi tch nhm I v nhm II, ta dng NaOH d + H 2O2 tch nhm III, khi ny nhm IV v nhm V dng kt ta hidroxit, ring mangan dng MnO2 . Ta li cho tc dng vi NH4OH d + H2O2, th nhm IV c tch ra dng kt ta, cn nhm V li trong dung dch di dng phc amoniact Sau khi tch ring c nhm IV, ta dng axit ho tan cc kt ta ny, da vo nhng tnh cht ha hc khc nhau ca tng ion tch v nhn bit chng. Cc cation ca nhm IV, c bit l cc cation bitmut, st, antimon u d phn ng vi nc to thnh cc kt ta, cho nn mun cho cc cation ny tn ti trong dung dch th axit ca dung dch phi cao. 5.2. Cc phn ng c trng ca ion Fe3+ v Fe2+ Phn ng vi thuc th nhm Cc dung dch kim to vi Fe3+ v Fe2+ cc kt ta hidroxit khng tan: Fe2+ + 2OH- Fe(OH)2 mu trng Fe3+ + 3OH- Fe(OH)3 mu nu Thuc th nhm l hn hp NaOH d + H2O2 nn Fe(OH)2 mu trng chuyn thnh Fe(OH)3 mu nu: 4Fe(OH)2 + 2H2O2 4Fe(OH)3 lu trong khng kh Fe(OH)2 cng bin i dn t mu trng sang mu sm ri sang mu nu ca Fe(OH)3: Fe(OH)2 + H2O + O2 4Fe(OH)3 Hidroxit st l kt ta v nh hnh, c kh nng hp ph rt mnh cc ion khc c mt trong dung dch. Phn ng vi dung dch kali ferixianua K3[Fe(CN)6]: Kali ferixianua K3[Fe(CN)6] tc dng vi ion Fe2+ to thnh kt ta c mu xanh c trng gi l xanh tuabin Fe3[Fe(CN)6]2, kt ta ny khng tan trong axit nhng b kim phn hy do to thnh hidroxit st ba:

3Fe2+ + 2[Fe(CN)6]3- Fe3[Fe(CN)6]2 Khi nng ca ion Fe2+ qu nh, s khng to thnh kt ta m to thnh dung dch keo mu xanh. Phn ng vi dung dch kali feroxianua K4[Fe(CN)6]: Kali feroxianua K4[Fe(CN)6] tc dng vi ion Fe3+ to thnh kt ta v nh hnh c mu xanh c trng gi l xanh ph hay xanh Prusse Fe4[Fe(CN)6]3 khng tan trong axit nhng b kim phn hy do to thnh hidroxit st ba hoc b cc cht c kh nng to phc bn vi Fe3+ phn hy : 4Fe3+ + 3[Fe(CN)6]3- Fe4[Fe(CN)6]3 Kali feroxianua K2[Fe(CN)6] cng tc dng vi ion Fe2+, nhng to thnh kt ta c mu trng Fe2[Fe(CN)6] hoc K2Fe[Fe(CN)6]: Fe2+ + K4[Fe(CN)6] K2Fe[Fe(CN)6] + 2K+ Hoc: 2Fe2+ + [Fe(CN)6]4- Fe2[Fe(CN)6] lu trong khng kh, kt ta dn dn s ha xanh, c bit khi c mt cht oxyhoas n s bin thnh xanh m rt nhanh v Fe2+ b oxyhoa thnh Fe3+ v to thnh kt ta Fe4[Fe(CN)6]2: Fe2[Fe(CN)6] + 3O2 + 6H2O 2Fe4[Fe(CN)6]2 + 4Fe(OH)3 Phn ng vi dung dch kali hay amoni thioxianat vi ion Fe3+: y l phn ng rt c trng ca ion Fe3+ , to thnh nhng phc cht tan mu mu c thnh phn thay i ( s phi t SCN- thay i t 1 n 6 ) ty thuc vo nng ca ion SCN- trong dung dch. Phn ng ny kh nhy, tuy nhin rt d b nh hng bi cc cht to phc bn vi ion Fe3+ hay cc cht c kh nng to kt ta hay hp cht km phn li vi ion SCN- . Phn ng vi dung dch axit salixilic C6H4(OH)COOH vi ion Fe3+: Axit salixilic vit tt l H2Sal, trong mi trng axit mnh pH ~ 1 to vi ion Fe3+ mt ion phc c mu tm nht, thnh phn ca phc l 1:1, [Fe(Sal)]+; khi tng pH ca dung dch, thnh phn v mu ca phc s thay i: trong mi trng axit yu pH ~ 4 l phc [Fe(Sal) 2]- c mu da cam, trong mi trng kim yu pH ~ 9 l phc [Fe(Sal)3]3- c mu vng. Khi thay axit salixilic bng mt dn xut d tan hn ca n l axit sunfosalixilic th phn ng cng xy ra tng t nhng nhy hn rt nhiu. Phn ng c s dng xc nh st bng phng php o quang, thng c thc hin mi trng kim pH trong khong 9 11 cho hp cht phc c mu vng. 5.3. Cc phn ng ca ion Mn2+ Mangan c th tn ti trong cc hp cht vi nhiu ha tr khc nhau nh 2, 3, 4, 6, 7, trong ion Mn2+ tng i bn, dung dch nc ca ion Mn2+ c mu hng nht, c phn ng axit yu. Phn ng vi thuc th nhm: Khi kim ha dung dch Mn2+ th c kt ta trng tch ra pH > 8,8 ( dung dch Mn2+ 0,01M), kt ta ny d tan trong axit long v mui amoni, tan mt t trong kim d do to thnh phc hidroxo: Mn(OH)2 + 2NH4+ Mn2+ + 2NH3 + 2H2O Mn(OH)2 + OH- Mn(OH)3Kt ta Mn(OH)2 d b oxyha trong khng kh lm cho mu bin i dn gch v cui cng l nu en ca oxit mangan, hoc nu c mt cht oxyha th Mn(OH)2 s b oxyha nhanh hn. Phn ng vi dung dch amoni pesunfat ( NH4)2S2O8 trong mi trng axit y l phn ng rt c trng tm Mn2+ , phn ng xy ra trong mi trng axit v c xc tc bi ion Ag+, to ra ion MnO4- c mu tm rt c trng:

Mn2+ + 5S2O82- + 8H2O 2MnO4- + 10SO42- + 16H+ c ch ca phn ng ny cho n nay vn c nhiu gi thit khc nhau, ph bin nht l theo c ch sau: Ag+ + S2O82- 2Ag2+ + 2SO422Mn2+ + 10Ag2+ + 8H2O 2MnO4- + Ag+ + 16H+ Phn ng vi dioxit ch PbO2 trong mi trng axit: y cng l phn ng rt c trng thng dng nhn bit mangan , ion Mn 2+ khng mu b oxyha thnh ion MnO4- c mu tm. Khi thc hin phn ng phi tin hnh cn thn, nng ion Mn 2+ phi nh, nu dung dch cha lng ln ion Mn2+ th MnO4- mi sinh s tc dng vi Mn2+ d to thnh MnO2 kt ta ln vi PbO2 mu en nn khng nhn c: 2Mn2+ + 5PbO2 + 4H+ 2MnO4- + 5Pb2+ + 2H2O 5.4. Cc phn ng ca ion Mg2+ Dung dch nc ca ion Mg2+ khng mu, c phn ng gn nh trung tnh, pH ca dung dch Mg2+ 0,01M vo khong 7 Phn ng vi thuc th nhm: Khi kim ha dung dch Mg2+ th c kt ta trng tch ra pH = 10 ( dung dch Mg2+ 0,01M) v kt ta hon ton pH = 12,5; kt ta ny d tan trong axit long v mui amoni Mg(OH)2 + 2NH4+ Mg2+ + 2NH3 + 2H2O Phn ng vi Na2HPO4: Dung dch ion Mg2+ khi tc dng vi HPO42- s to thnh kt ta mu trng: Mg2+ + HPO42- MgHPO4 kt ta mu trng Kt ta ny khng hon ton, nu c mt NH4Cl v NH4OH trong dung dch th s to thnh kt ta MgNH4PO4 mu trng hon ton hn, y l phn ng rt c trng, c s dng nhn bit ion Mg2+ khi khng c cc thuc th hu c Vng titan C28H19O6N5Na2 hay Magneson I ( p-nitrobensolazoresocsin ) v Magneson II ( p-nitrobenzolazo--naphtol) tm ion Mg2+ bng cc phn ng c trng.

Chng 6. PHN TCH CATION NHM V Cu2+, Co2+, Ni2+, Cd2+, Hg2+ 6.1. c tnh chung Cc cation nhm ny l cc ion kim loi chuyn tip, v vy tnh cht in hnh ca nhm l kh nng to phc kh mnh, hiroxit ca chng tan trong hn hp NH4+ v NH3 to thnh phc tan amoniacat c s phi t NH3 t 4 n 6. Phc ca ng c mu xanh da tri, ca coban v niken c mu xanh hi xm, ca caimi v thu ngn khng c mu. V vy, thuc th nhm l hn hp NH4Cl + NH3. Cc cation ca nhm V to c cc kt ta sunfua kh tan vi H2S hay (NH4)2S, tan ca cc sunfua ph thuc vo axit ca mi trng, v vy tnh cht ny c s dng tch ring, c lp tng cation trong nhm, sau s dng cc phn ng c trng nhn bit. 6.2. Cc phn ng c trng ca ion Cu2+ Phn ng vi thuc th nhm: Amniac to c vi dung dch ion Cu2+ kt ta mui baz mu xanh lc nht, d tan trong thuc th d. Lc ny dung dch c mu xanh lam m do to thnh ion phc [Cu(NH3)4]2+: 2CuSO4 + 2NH4OH Cu2(OH)2SO4 + 2NH4+ Cu2(OH)2SO4 + 2NH4+ + 6NH3 2[Cu(NH3)4]2+ + SO42- + 2H2O Phn ng vi H2S hay (NH4)2S: H2S tc dng vi Cu2+ to thnh kt ta ng sunfua CuS mu en t cc dung dch axit ca mui ng. CuS khng tan trong H2SO4 , HCl c nhng tan trong HNO3: 3CuS + 8HNO3 Cu(NO3)2 + 3S + 2NO + 4H2O Phn ng vi dung dch kali feroxianua K4[Fe(CN)6]: Kali feroxianua to c kt ta Cu2[Fe(CN)6] mu gch t cc dung dch trung tnh hoc axit yu. y l phn ng kh c trng nhn bit ng, mui ny khng tan trong axit long nhng b kim phn hy thnh ng hidroxit mu xanh hoc tan trong amniac do to phc amniacat: Cu2[Fe(CN)6] + 2OH- Cu(OH)2 + [Fe(CN)6]4Cu2[Fe(CN)6] + 8NH3 2[Cu(NH3)4]2+ + [Fe(CN)6]46.3. Cc phn ng ca ion Cd2+ Phn ng vi thuc th nhm: Mt lng nh amniac kt ta c Cd2+ to thnh hidroxit cadimi, rt d tan trong thuc th d do to thnh ion phc khng mu [Cd(NH3)4]2+: Cd(OH)2 + 4NH3 [Cd(NH3)4]2+ + 2OHDi tc dng ca H2S hoc kim, phc ny b ph hy v to thnh kt ta vng ti CdS hoc Cd(OH)2: [Cd(NH3)4]2+ + 2H2S CdS + (NH4)2S + 2NH4+ [Cd(NH3)4]2+ + 2OH- Cd(OH)2 + 4NH3 Phn ng vi H2S: H2S tc dng vi Cd2+ trong mi trng axit to thnh kt ta cadimi sunfua CuS mu vng ti. y l phn ng rt c trng nhn bit ion Cd2+. Mu ca kt ta ph thuc mi trng, trong mi trng trung tnh n axit yu ( n pH = 0,5 ), cadimi sunfua c mu vng ti, nu mi trng axit mnh hn ( n pH < 0,5 ) v un nng, cadimi sunfua c mu thay i t da cam n nu.

Phn ng vi KCN: Khi thm t t dung dch KCN vo dung dch ion Cd2+, trc tin thy xut hin kt ta Cd(CN)2 nhng sau kt ta tan ngay trong thuc th d to thnh ion phc: Cd2+ + 2CN- Cd(CN)2 Cd(CN)2 + 2CN- [Cd(CN)4]2Phc xyanua ca cadimi l km bn nht trong cc phc xyanua ca cc ion kim loi nhm V, v vy c th dng H2S pht hin ion Cd2+ trong iu kin c cc cation nhm ny nu dng KCN cn: [Cd(CN)4]2- + 2H2S CdS + 2HCN + 2CN6.4. Cc phn ng ca ion Ni2+ Phn ng vi thuc th nhm: Cng ging nh ng v cadimi, lng nh amniac kt ta c Ni 2+ to thnh hidroxit cadimi dng keo, c mu xanh lc nht, rt d tan trong thuc th d do to thnh ion phc [Ni(NH3)4]2+: Ni(OH)2 + 4NH3 [Ni(NH3)4]2+ + 2OHPhn ng vi dimetylglyoxim- thuc th Sugaeep: Trong dung dch amniac, dimetylglyoxim to vi Ni2+ mui ni phc mu hng ti dimetylglyoximat niken, rt t tan trong nc: y l phn ng rt c trng nhn bit niken. Cc cation to hidroxit khng tan trong nc cn tr phn ng. 6.5. Phn tch h thng cation nhm V: xem gio trnh thc hnh

Chng 7. PHN TCH NH TNH CC ANION Thc t ngi ta hay dng bari clorua BaCl2 hoc canxi clorua CaCl2 v bc nitrat AgNO3 lm thuc th nhm phn cc anion thnh 3 nhm nh trong bng di y. Nhm phn tch Cc anion Ion sunfat SO42Ion sunft SO32Ion thiosunfat S2O32I Ion cc bonat CO32Ion phot phat PO42Ion silicat SiO32Ion borat BO2- hay B4O72Ion clorua ClII Ion bromua Br Ion ioua IIon sunfua S2Ion nitrat NO3III Ion nitrit NO2
-

c tnh ca nhm Mui bari ca cc anion ny t tan trong nc nhng tan trong axit long (tr BaSO4)

thuc th nhm

BaCl2 trong mi trng trung tnh hay kim yu

mui bc ca cc anion ny it tan trong nc v trong HNO3

AgNO3 khi c mt HNO3

Mui bari v mui bc ca cc anion ny tan trong nc

Khng c thuc th nhm

Phn tch cc anion c nhng c im ring khc vi cc cation, do cc anion thng khng cn tr nhau. Chnh v vy, i vi nhiu anion, ta c th s dng cc phn ng c trng tm chng ngay trong cc phn ring ca dung dch nghin cu. Vic s dng phn tch h thng ch thc hin trong cc trng hp phc tp khi trong dung dch c mt cc anion ca cc cht kh hay ca cc cht oxi ho. 7.1. Phn tch anion nhm I Nhm I bao gm cc anion SO42-, CO32-, PO43-, SiO32-, hay B4O72-, SO32-, S2O32- Cc anion nhm ny c cc c im l to vi Ba2+ cc mui t tan trong nc, nhng d b ha tan trong cc axit v c long (tr BaSO4), v vy, thuc th nhm bari clorua BaCl2 ch kt ta cc anion ni trn trong mi trng trung tnh hoc yu. Bng 7.1. Mt s phn ng c trng ca cc anion nhm I Thuc th BaCl2 trong mi trng trung tnh hay kim yu SO42Kt ta mu trng BaSO4 SO32Kt ta mu trng BaSO3 Tan v c kh S2O32Kt ta mu trng BaS2O3 Tan v c CO2 CO3 Kt ta mu trng BaCO3 Tan v c CO2 PO43SiO32Kt ta mu trng BaSiO3 Tan v c H2SiO3 tch ra BO2Kt ta mu trng Ba(BO2)2

Kt ta mu trng BaHPO4

Tc dng ca HCl i vi cc mui bari

Khng tan

Tan

Tan

SO2 Hn hp MgCl2 + NH4OH +NH4Cl Dung dch molipat (NH4)2MO4 - HNO3 Cc axit Cc mui NH4+, NH4Cl, (NH4)2SO4 Natrinitropruxua Na2[Fe(CN)5NO] Kt ta MgNH4PO4 mu trng Kt ta mu vng Kt ta mu trng MgSiO3 -

C SO2 v S tch ra -

Kh SO2 Dung dch mu hng Lam mt mu hng -

Kh CO2

Fucxin

Mu ngn la

Xanh lc

Bari clorua BaCl2 kt ta c cc anion ca nhm ny di dng kt ta tinh th mu trng. Trong cc kt ta ny ch c kt ta BaSO4 khng tan trong axit HCl, nh th c th dng phn ng ny tm ion SO42-. Kt ta bari cacbonat BaCO3 tan trong axit HCl, c kh CO2 thot ra cn vi kt ta sunfit v thiosunfat BaSO3 v BaS2O3 th c kh SO2 thot ra. Cc kt ta bari metaborat v bari hirophotphat khi tan trong HCl khng c kh thot ra. Axit HCl phn hu bari silicat v to thnh kt ta ca v nh hnh ca axit silicic. Vi dung dch molipat ch c ion PO33- cho kt ta mu vng amoni photphomoliat. T dung dch silicat, cc mui amoni lm tch ra kt ta v nh H2SiO3 7.2. Phn tch anion nhm II Cc anion nhm II gm Cl-, Br-, I-, S2- v mt s ion khc. Mui ca cc anion ny vi Ag+ khng tan trong nc v trong NH3 khi c mt axit HNO3 long. a s cc anion nhm I cng to vi AgNO3 nhng mui khng tan trong nc. Tuy nhin, tt c cc mui ny u tan trong HNO3 v th chng khng cn tr vic tm cc anion nhm II. Bng 7.2. Mt s phn ng c trng ca cc anion nhm II Thuc th AgNO3 khi c mt HNO3 Clkt ta mu trng AgCl BrKt ta mu vng AgBr IKt ta mu vng AgI S2Kt ta mu en Ag2S

Tc dng ca cc mui bc vi dung dch NH3 Cc cht oxihoa mnh (KMnO4, K2Cr2O7) Nc clo (khi c mt ca benzen) NaNO2 hay KNO2 khi c mt ca H2SO4 H2SO4 Pb(CH3COO)2 CbCO3 Fluorecxon Axit fucxinsunfua Na2[Fe(CN)5NO]

Tan, to thnh [Ag(NH3)2]Cl

Tan r rt, to thnh [Ag(NH3)2]Br Thot ra Br2

Thc t khng b ha tan

Khng tan

Thot ra Cl2

Thot ra I2

Thot ra S

Mu nu Br2

Mu tm I2

Thot ra I2 Tinh th mu vng PbI2 Mu eosin -

Mu hng eosin Mu tm -

Thot ra kh H2S Kt ta vng CbS Mu tm Na2[Fe(CN)5NO]

7.3. Phn tch anion nhm III Ion NO3-, NO2- v mt s cc anion khc thuc nhm III. Mui ca cc anion ny trong c c mui ca bc v ca bari u tan tt trong nc. Anion nhm III khng c thuc th nhm. Bng 7.3. Mt s phn ng c trng ca cc anion nhm III Thuc th FeSO4 trong mi trng axit iphenylamin Antipyrin Cu + H2SO4 Axit long HCl, H2SO4 KI khi c mt H2SO4 KMnO4 khi c mt H2SO4 NO3Vng mu nu ca phc [Fe(NO)SO4] To dung dch mu xanh Mu r ca nitro- antipyrin Tch kh NO2 NO2Vng mu nu ca phc [Fe(NO)SO4] To dung dch mu xanh Mu xanh lc r ca nitrozo antipyrin Tch kh NO2 Tch I2 Lm mt mu tm

Thuc th Grigg un nng vi NH4Cl hay (NH4)2SO4

To dung dch mu Tch N2

Ni chung, vic phn tch tm cc anion thng thc hin trong tng phn dung dch ring, khng nht thit phi theo mt quy trnh nghim ngt. Ngi ta ch s dng cc phn ng tch trong mt s trng hp phc tp, v d nh khi ng thi c mt cc anion Cl-, Br-, I-, hay S2-, SO32-, S2O32- v SO42-. Thng tin hnh th trc cc dung dch phn tch xc nh trong dung dch vng mt cc anion no. Sau , tin hnh tm cc anion ring bit c mt trong dung dch.

BI TP P DNG
1. Gii thch ti sao thuc th nhm ca cc cation nhm I (Ag+,Pb2+ v Hg2+) l dung dch HCl long, ngui m khng phi l HCl long nng, dung dch NaCl hoc HCl c. 2. Vai tr ca C2H5OH khi c s dng vi H2SO4 long lm thuc th cation nhm II? 3. Vai tr ca H2O2 khi c s dng vi NaOH lm thuc th cation nhm III? 4. Trnh by s tch v nhn bit tng cation trong hn hp sau: a/ dung dch A: Pb2+,Ba2+;Al3+,Cr3+,Fe3+,Mg2+ b/ dung dch B : Ag+,Ca2+,Pb2+,Zn2+,Fe3+,Cu2+. c/ Dung dch C: Pb2+,Ba2+,Ca2+,Al3+;Zn2+,Fe3+. 6.Cho 10 ng nghim , trong mi ng ng 1 mL cc dung dch sau: NaCl; CdSO4; Pb(NO3)2; Ba(OH)2 ; Na2S2O3 ; BaCl2; FeSO4 ; KI ; NaHCO3 ; NH4SCN . Ch dng cc vi ng nghim, ng nh git, dung dch HNO3 v dung dch phenolphtalein, hy trnh by cch nhn bit tng ha cht. 7. Cho 9 ng nghim, mi ng c 0,5 mL dung dch cha mi cht sau: NaCl AgNO3 KI HCl Pb(NO3)2 BaCl2 H2SO4 Na2CO3 NaOH Ch dng cc vi ng nghim, cc ng nh git v dung dch phenolphtalein c th nhn bit tng dung dch . Trnh by phng php . Gi cch trnh by: - C 9 ng nghim ng dung dch mu, ln lt c nh s t 1 n 9. - S dng ng nh git trch mi ha cht ra vi ng nghim (khong 5 git) lm mu th, ln lt nh s th t tng ng. Lu khng chm u ng nh git vo thnh ng nghim. - Ln lt nh 1-2 git dung dch phenolphtalein vo tng mu th, mu th no chuyn mu dung dch sang hng l Na2CO3 v NaOH. 8. Cho hn hp cc ion SO42-; SO2-3; S2-;S2O32- v Na+. Trnh by cch nhn bit tng anion trong hn hp . 9.Cho hn hp cc ion SO42-;CO32-;S2-; PO43-; K+. Trnh by cch nhn bit tng anion trong hn hp. 10. Cho hn hp cc ion: Cl-,SO42-; NO3-,CO32- , Na+. Trnh by cch nhn bit tng anion trong hn hp