Bi 1 : i cng v phn tch nh tnh Mc tiu : Nu c nhim v ca phn tch nh tnh, nguyn tc chung, cc phng php phn tch

nh tnh Cc phn ng ha hc s dng trong phn tch nh tnh Cc phng php phn tch h thng Nm s b cc k thut thc hnh trong phn tch nh tnh A. nh ngha nh ngha : Ha phn tch l b mn ca ngnh ha hc nghin cu v thnh phn cu to (nh tnh) v hm lng cc thnh phn (nh lng) ca nhng mu kho st. Ha phn tch thng c chia thnh Ha phn tch nh tnh v Ha phn tch nh lng nhng cng hay c chia thnh Ha phn tch v c v Ha phn tch hu c B. Cc phng php phn tch nh tnh I/. Phng php vt l : Da vo trng thi vt l nh : th lng, rn, hi, mu sc ... 1. Cht rn xc nh cc ch tiu nh : nhit nng chy, thng hoa, tnh tan trong nc hay trong cc loi dung mi khc. Tnh tan : thng thng cht phn cc d tan trong cc dung mi phn cc. Nc l dung mi thng dng nht vi cc hp cht v c. Nc l dung mi phn cc nn d ha tan cc hp cht phn cc cng nh nhiu hp cht ion. Qu trnh ha tan trong nc i khi ta nhit (ha tan NaOH vo nc), i khi thu nhit (ha tan mui sunfat magi) Dung mi phn cc l dung mi c thnh phn l cc phn t phn cc, nh nc chng hn. Phn t nc c hai u phn cc, mt u mang in dng l du cha H+ cn u cn li l u m c cha nhm OH-. Dung mi phn cc thng dng ha tan cc cht v c c kh nng in ly. Ngc li dung mi khng phn cc l dung mi m cc phn t cu thnh n khng c s phn cc hai u phn t. Dung mi khng phn cc th c nhiu v d nh: benzen, du ho, xng, axeton, ... 2. Cht lng xc nh cht cn phn tch dng huyn ph, nh tng, dung dch c ng nht khng ? Huyn ph : l mt h phn tn gm 2 pha lng v rn, trong cc phn t cht rn l ln g trong cht lng (v d : nc vn c) Nh tng : l mt h phn tn gm 2 cht lng khng ha tan vo nhau, mt trong hai cht (gi l pha phn tn) c phn b trong cht kia (gi l mi trng phn tn) II/. PP ha l a. Sc k : l phng php phn tch da vo s phn b khc nhau ca cc cht cn phn tch gia pha ng v pha tnh Pha ng : cc cht dng kh hay dng lng Pha tnh : cc cht dng lng hoc rn Sc k : biu ca sc k 1. Sc k giy : tch cc cht da vo s khc nhau v h s phn b ca chng gia 2 pha lng ; mt pha tnh v pha ng. Pha tnh l nc c sn trong si

cellulose ca giy hoc thnh phn a nc ca h dung mi c ht chn lc vo giy v pha ng l h dung mi thch hp cho s tch. Khi chm dd ca cht cn phn tch , dng micropipet, chm nhiu ln, i git trc kh mi chm tip, ng knh ca vt chm <8mm 2. Sc k bn mng : nhm tch cc cht c tin hnh khi cho pha ng di chuyn qua pha tnh trn t cc cht cn tch. Pha tnh l cht hp ph c chn ph hp, c tri thnh lp mng ng nht. Trong qu trnh di chuyn qua lp hp ph, cc cu t trong hn hp mu c di chuyn theo nhng tc khc nhau. Ta thu c sc k 3. Sc k kh : pp tch trong pha ng l cht kh (kh mang) v pha tnh trong ct l cht rn hoc cht lng ph trn mt cht tr dng rn b. Quang ph : 1. 2. Hng ngoi : bc sng nh sng t > 700nm T ngoi v kh kin : 200 700 nm 3. Hunh quang : so snh cng hunh quang ca cht th vi cng hunh quang ca cht chun o trong cng iu kin 4. Nguyn t pht x v hp th : dng xc nh nng ion kim loi bng php o cng pht x hoc hp th nh sng bc sng c trng bi hi nguyn t ca nguyn t c ha hi t cht cn phn tch c. Cc ch s c trng : 1. Ch s khc x ca mt cht so vi khng kh l t s gia sin ca gc ti v sin ca gc khc x ca chm tia sng t khng kh truyn vo cht ( o bng khc x k) 2. Gc quay cc ca mt cht l gc ca mt phng phn cc b quay i khi nh sng phn cc i qua cht nu l cht lng, hoc qua dung dch cht nu l cht rn (o bng phn cc k) Gc quay cc ring l gc quay cc o c khi chm nh sng D truyn qua lp cht lng b dy 1dm 20oC 3. T trng tng i : l t s gia khi lng ca mt th tch cho trc ca cht v khi lng ca cng th tch nc ct 20oC (dng c o : picnomet) III/. PP ha hc : da trn cc phn ng ha hc c trng ca cht cn xc nh vi thuc th thch hp. Mt phn ng ho hc mun c s dng trong ho phn tch trc ht cn phi tho mn hai iu kin sau: - Phn ng phi xy ra hon ton. - Tc phn ng phi nhanh C 2 phng php phn tch nh tnh : kh v t 1. Phng php kh : a. c im : cht cn phn tch v thuc th u th rn. b. Cc th nghim - t nhit cao, quan st mu ngn la Bng : Mu c trng ngn la khi t Nguyn t Mu ngn la Na Vng sng K Tm Ba Lc Ca gch Sr thm

2. PP t

a.

c im : ha tan mu trong dung mi thch hp (nc, dung dch axit long (HCl, HNO3 ...), axit sunfuric c, HF b. Cc th nghim : xem phn phn tch ring bit v phn tch h thng C. X l mu Mc ch : chuyn mu v dng ph hp vi cc phng php phn tch I/. Phng php 1. Ha tan mu trong nc, axit hay baz - chuyn mu th t dng rn sang dung dch ngi ta c th ha tan mu trong nc, axit v c, hay cc baz (t thng dng hn). - i khi s ha tan c hon ton, ngi ta un nng dung dch n khi pha rn bin mt hon ton 2. t chy mu nhit cao trong mi trng khng kh hoc oxy 3. Nung chy trong mi trng mui nng chy II/. Sai s do x l mu - ha tan khng hon ton cc cht cn phn tch - s mt i mt phn cht cn phn tch do bay hi - a cht bn t dung mi vo cht cn phn tch D. Cc loi phn ng s dng trong phn tch nh tnh (phng php ha hc) Yu cu i vi phn ng trong ha hc nh tnh - Du hiu nhn bit r rng : sn phm to thnh phi l mt kt ta, cht bay hi d quan st hoc mu sc dung dch thay i r rt - Phn ng c nhy cao : ch cn mt lng nh cht cn xc nh tc dng vi thuc th vn c du hiu r rng - c trng ; phn ng ch xy ra vi ion ny m khng xy ra vi ion khc, hoc to kt ta c mu sc hnh dng khc nhau - Mi trng phn ng phi thch hp : I/. Phn ng trung ha : l phn ng ha hc gia axt v baz. Sn phm to thnh l mui v nc. V th n cn c gi l phn ng to nc. V d : NaOH + HCl NaCl + H2O II/. Phn ng oxy ha kh : 1/. Phn ng oxi ha v phn ng kh lun lun i chung vi nhau v to thnh phn ng oxi ha - kh. Th d: Zn - 2e Zn2+ Phn ng oxi ha Cu2+ + 2e Cu Phn ng kh ________________________ Zn2+ + Cu Zn + Cu2+ : phn ng oxi ha - kh 2/. Qui lut din tin ca phn ng oxi ha kh trong dung dch Phn ng oxi ha kh xy ra trong dung dch theo hng gia cht kh mnh vi cht oxi ha mnh to cht oxi ha v cht kh tng ng yu hn. Th d: Phn ng Zn + Cu2+ Zn2+ + Cu xy ra c l do Zn c tnh kh mnh hn Cu v Cu2+ c tnh oxi ha mnh hn Zn2+.

Phn ng Cl2 + 2KBr 2KCl + Br2 xy ra c l do Cl2 c tnh oxi ha mnh hn Br2 v Br- c tnh kh mnh hn Cl-. III/. Phn ng kt ta : da vo cc phn ng to thnh kt ta (hay hp cht t tan) AgNO3 + KCl AgCl + KNO3 Ag+ + NO3- + K+ + Cl- AgCl + K+ + NO3IV/. Phn ng to phc : da vo cc phn ng to phc gia cht cn phn tch v thuc th. N dng nh lng trc tip a s cc cation kim loi v nh lng gin tip mt s anion. Thuc th c dng nhiu nht l cc complexon. Vd : Fe3++ 6SCN- [Fe(SCN)6]3- : mu mu AgCl + 2NH4OH [Ag(NH3)2] + Cl- + 2H2O Cc phn ng mu c trng thng c s dng pht hin cc ion. + Cc phc ca ion kim loi vi amoniac, thioxyanat. + Cc thuc th hu c c dng pht hin ion kim loi kh phong ph Bng : Nhng phc cht ca cation vi NH3 v OHCation
Ag Al3+ Cd2+ Cu2+ Ni2+ Pb2+ Sb3+ Sn4+ Zn2+
+

Phc NH3
Ag(NH ) -Cd(NH3)42+ Cu(NH3)42+ (xanh) Ni(NH3)62+ (xanh) ---Zn(NH3)42+
+ 3 2

Phc OH-Al(OH)4---Pb(OH)3Sb(OH)4Sn(OH) 62Zn(OH)42-

E. Thuc th L cc cht ho hc tinh khit v c hoc hu c dng phn ng vi mt cht cn phn tch. tinh khit ca cc thuc th c phn thnh cc cp (xp theo th t cao dn): tinh khit k thut, tinh khit phn tch, tinh khit ho hc, siu tinh khit. C mt s TT mang tnh c hiu cho tng i tng ring, do chng c tn ring, thng l ly tn ca ngi pht hin: Fis, Mil, Nexl, vv. I/. Yu cu thuc th 1. Tinh khit k thut : lm nguyn liu ban u P : tinh khit th nghim ha hc PA : tinh khit phn tch Ngoi ra cn loi : Tinh khit lm cht chun, tinh khit quang hc 2. Nhy 3. c hiu : iod to mu xanh vi tinh bt (dng tinh bt lm ch th trong phn ng c iod hoc dng iod lm thuc th trong phn ng nh tnh tinh bt) nh tnh hn the (borat) bng giy ngh ; axit ha mu, c hn the giy ngh s chuyn sang mu , chuyn sang mu xanh m trong hi amoniac II/. Phn loi thuc th 1. Thuc th nhm : l thuc th c phn ng cng kiu vi mt nhm ion, nhng khng phn ng vi cc nhm ion khc.

Vd. 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. 2. Thuc th chn lc : l thuc th c tc dng ging nhau trn mt s ion thuc cc nhm phn tch khc nhau Vd : NH3 c th to phc tan v khng mu vi nhiu ion cc nhm phn tch khc nhau 3. Thuc th c hiu l thuc th ch cho phn ng c hiu vi mt ion hoc mt cht III/. Cc loi thuc th thng s dng : Thuc th HCl Cng dng Tng nng H , gim OH , cung cp ClHa tan mui carbonat, cromat, hydroxyt, sunfat khng tan Ph hy hp cht nitroso v phc amoni Kt ta mui clorua khng tan Tng nng H+, gim OHHa tan mui carbonat, cromat, hydroxyt khng tan Ph hy hp cht nitroso v phc amoni Ha tan cc mui sunfua khng tan bng cch oxy ha ion S2L cht oxy ha (un nng) Tng nng OH-, gim H+ To phc hydroxo To ta hydroxyt Tng nng NH3, OH-, gim H+ Ta nhng hydroxyt khng tan To phc amoni To mi trng m vi ion NH4+
+ -

HNO3

NaOH NH3

F.

Phn tch ring bit v phn tch theo h thng I/. Phn tch ring bit : L xc nh trc tip mt ion no trong hn hp bng phn ng c hiu Vd : th ion Fe3+ bng KSCN u im : nhanh, kt qu chnh xc Khuyt im : thuc th khng ph bin, t tin II/. Phn tch h thng Phn tch theo h thng l chia cc ion cn phn tch thnh cc nhm bng thuc th nhm, ri dng cc thuc th c hiu tm tng ion trong nhm phn lp. Vd: Tch cc ion to ta clorua (Ag, Pb, Hg) ra khi hn hp bng cch to ta vi HCl Ly tm, tch ta to thnh Nh thuc th SnCl2 Kt ta chuyn sang mu xm hoc en, chng t c Hg Ag+ + Cl- = AgCl ta trng Pb2+ + 2Cl- = PbCl2 ta trng Hg22+ + 2Cl- = Hg2Cl2 ta trng Hg2Cl2 + SnCl2 = 2Hg en+ SnCl4 u im :

ha cht n gin, ph bin Nhc im mt nhiu thi gian d gy nhim bn do tp cht t thuc th tin hnh nhiu bc, dd b pha long, gy kh khn vi nhng phn ng c nhy khng cao 1/. Phn tch nh tnh cation : a. H thng dng H2S : Nguyn tc : to ta sunfua vi thuc th l H2S, HCl, (NH4)2S v (NH4)2CO3. Theo phng php ny cc cation c chia thnh 5 nhm da vo tnh tan ca sunfua, clorua, carbonat v cc hydroxyt kim loi Nhm 1 2 3 Cation K+, Na+, Li+, NH4+, Mg2+ Ba2+, Ca2+, Sr2+ Thuc th nhm Khng c (NH4)2CO3 trong mi trng kim yu (NH4)2S trong mi trng kim hoc trung tnh c trng Tr Mg cc hydroxyt v mui ca cation nhm 1 d tan trong nc Ta carbonat khng tan trong nc Ghi ch

Dd m amoni (NH4Cl/NH3) pH = 7-9

Al3+; Cr3+; Fe3+; Kt ta sunfua v hydroxyt 2+; 2+ Fe Ni ; khng tan trong nc, tan trong Co2+; Mn2+; axit mnh 2+ Zn Cu2+; Cd2+; H2S trong mi Kt ta sunfua khng tan trong 2+ 3+ Hg ; Bi ; trng axit nc v axit long As3+; As5+; 4a(*) : khng tan trong (NH4)2Sx Sb3+; Sb5+; - thuc th phn 4b(*) : tan trong 2+ 4+ Sn ; Sn nhm (NH4)2Sx (NH4)2Sx + 2+ Ag ; Hg2 ; HCl 2N Mui clorua khng tan trong Pb2+ nc v trong axit long 4a (*) : CuS, CdS, HgS, Bi2S3 4b (*) : As2S3, As2S5, Sb2S3, Sb2S5, SnS, SnS2

pH =0,5

Trnh t thc hin : - Axit ha mu bng HCl n pH =0,5 kt ta hon ton nhm 5 di dng mui clorua - Tch kt ta - Thu c dd cn cation nhm 1,2,3,4 - Sc kh H2S qua dd (mi trng H+), kt ta hon ton cation nhm 4 - Tch kt ta , thu dd cn cation nhm 1,2,3 - Dng thuc th (NH4)2Sx ha tan ta nhm 4b - Tch kt ta nhm 4a, dd cha nhm 4b - DD nhm 1,2,3 c kim ha nh bng m amoni (pH=7-9), tc dng vi thuc th (NH4)2S, kt ta hon ton nhm 3 - DD cn li cation nhm 1,2 - Thm Axit acetic vo dd., gia nhit phn hy (NH4)2S cn d - Thm thuc th (NH4)2CO3 kt ta hon ton nhm 2 ( dd m amoni) - Tch kt ta trong dd cn cation nhm 1 u im : cht ch, kt qu kh chnh xc, pht hin trit cc cation Nhc im : H2S rt c, mi kh chu

b. H thng axit baz : * Nguyn tc : da trn s khc nhau v tan ca cc hidroxit kim loi trong cc axit v bazo kim nh NaOH v NH3 Theo phng php ny cc cation c chia thnh 6 nhm Nhm 1 2 3 4 5 6 Cation Ag+; Hg22+; Pb2+ Ba2+, Ca2+, Sr2+ Al3+; Cr3+; Sn2+; Zn2+ Thuc th nhm DD HCl H2SO4 Dd NaOH hay KOH d Na2CO3 bo ha v NH4OH d NH4OH d Khng c c trng Mui clorua khng tan trong nc v trong axit long Ta sunfat khng tan trong nc v trong axit Hydroxyt lng tnh, tan trong kim d

Mg2+; Mn2+; Fe2+; Fe3+; Hydroxyt khng tan trong kim d 3+ 5+ 3+ Sb ; Sb ; Bi Cu2+, Hg2+, Cd2+, Ni2+ Hydroxyt to phc amoni tan trong NH4OH d + + + K , Na , NH4 , Clorua, sunfat, hydroxyt u tan trong nc * Trnh t thc hin - Cho dd phn tch tc dng vi HCl - Tch ta nhm 1, nc ly tm cn li cha nhm 2, 3, 4, 5 - Cho nc ly tm tc dng vi H2SO4 2N, xut hin ta - Ly tm tch ta nhm 2, nc ly tm cha cation nhm 3,4, 5 - Cho nc ly tm tc dng vi NaOH 2N d - Tch ta cha nhm 4, 5, nc ly tm cha nhm 3 - Ha tan ta cha nhm 4,5 bng HNO3 - Cho dd va thu c tc dng vi Na2CO3 bo ha ti thong c, thm NH4OH d - Tch ta cha nhm 4, nc ly tm cha nhm 5 - Nhm 6 phn tch trc tip bng thuc th c hiu * u im : - t c hi - s dng nhng tnh cht c bn ca cc nguyn t, quan h ca nhng nguyn t ny vi cc acid v base, tnh lng tnh ca cc hydroxyt v kh nng to phc ca cc nguyn t - thi gian thc hin ngn * Nhc im - km nhy hn pp trn c. H thng phn tch photphat - amoniac H thng ny chia cc cation thnh 5 nhm phn tch. Cation
K+, Na+, NH4+, Ba2+, Ca2+, Sr2+, Mg2+, Fe2+, Fe3+, Al3+, Cr3+, Mn2+, Bi3+. Cu2+, Hg2+, Cd2+, Ni2+ , Co2+, Zn2+ As3+, As5+, Sb5+, Sb3+, Sn2+, Sn4+

Nhm
1 2 3 4

Thuc th nhm
Khng c (NH4)2HPO4 trong dung dch amoniac c - DD Phosphat - NH4OH HNO3, un nng Kt ta

c trng

Cc phophat ca chng tan trong dung dch amoniac to thnh cc amoniacat [Me(NH3)6]2+. 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

Ag ; Hg ; Pb

2+

2+

DD HCl

Mui clorua khng tan trong nc v trong axit long

PP ny phc tp, t s dng 2/. Phn tch nh tnh anion : Vi anion thng gp c th chia thnh 3 nhm da vo tnh khng tan ca chng vi Ba, Ag Nhm 1 2 3 anion Cl-, Br-, I-, S2SO42-, CO32-, PO43-, SO32-, AsO33-, AsO43C2O42-, NO3Thuc th nhm AgNO3 trong mi trng HNO3 BaCl2 trong mi trng trung tnh hay kim yu Khng c thuc th nhm c trng To ta khng tan trong nc v HNO3 long To ta khng tan trong nc nhng tan trong axit HCl, HNO3 tr BaSO4

Ti liu tham kho Dc in Vit nam (2002) B y t P.I Vaxcrixenxki . K thut phng th nghim. Nh xut bn i hc v Trung hc chuyn nghip Thc hnh ha hc hu c tp 1 Nh xut bn khoa hc v k thut Gio trnh Ha phn tch PGSTS Nguyn Trng Sn i hc Nng nghip H ni Gio trnh Ha phn tch i hc Cng nghip Ha phn tch. L thuyt v thc hnh PGS. TSKH L Thnh Phc - Nh Xut bn Y hc

I CNG PHN TCH NH TNH

nh ngha Vt l Sc k Cc phng php Ha l Quang ph Ha hc Kh t X l mu

PHNG PHP HA HC PHN TCH NH TNH THUC TH yu cu PHN NG HA HC Yu cu

Phn loi

Nhm Chn lc c hiu

Phn loi

Trung ha To ta Oxy ha kh To phc

PHNG PHP PHN TCH

H THNG Cation

Anion Bng H2S Bng azit baz Phos phat

RING BIT