Phân Tích Kim Lo I

Phn tch kim loi
Chng 1: Phn tch kim loi en
MC LC
M U .........................................................................................................................3 MC CH MN HC .............................................................................................3 YU CU MN HC ...............................................................................................3 CHNG 1 PHN TCH KIM LOI EN ..................................................................4 I. I CNG V KIM LOI EN .........................................................................4 1. Phn loi..............................................................................................................4 1.1. Gang ..........................................................................................................4 1.2. Thp ..............................................................................................................5 2. nh hng ca cc nguyn t n tnh cht ca thp .........................................5 II. PHNG PHP LY MU..................................................................................5 1. Ly mu u tin .................................................................................................5 1.1. Ly mu dng sn phm tm, thanh, thi .....................................................6 1.2. Ly mu ngay l nung ...............................................................................6 2. Chun b mu ......................................................................................................6 III. NI DUNG PHN TCH ......................................................................................6 1. Xc nh Silic (Si) ................................................................................................6 1.1. Phng php khi lng ..............................................................................6 1.2. Phng php so mu ....................................................................................8 2. Xc nh phospho (P) ........................................................................................11 2.1. Phng php th tch molybdate ................................................................11 2.2. Phng php so mu ..................................................................................14 3. Xc nh Mn bng phng php persulfat bc ................................................16 4. Xc nh Crm trong thp hp kim ...................................................................19 4.1. Phng php Iod ........................................................................................19 4.2. Phng php persulfat bc .........................................................................21 4.3. Phng php so mu ..................................................................................23 5. Xc nh Carbon bng phng php o th tch kh ........................................24 6. Xc nh lu hunh (phng php t trong l in) ......................................29 7. Xc nh Ni trong thp hp kim ........................................................................32 7.1. Phng php khi lng dioximat .............................................................32 7.2. Phng php so mu ..................................................................................34 8. Xc nh Wonfram (W) bng phng php chun acid-baz ......................35 9. Xc nh ng trong thp bng phng php chit trc quang ......................36 IV. CU HI N TP V BI TP ......................................................................38 CHNG 2 PHN TCH KIM LOI MU ...............................................................43 I. PHN TCH HP KIM NG .............................................................................43 1.1. Xc nh Pb trong hp kim ng bng phng php cromat ....................43
Khoa CNHH Chuyn ngnh Ha phn tch http://www.ebook.edu.vn
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Phn tch kim loi
1.2. Xc nh ng thi Pb, Cu, Zn, Fe cng mt lng cn bng phng php kt hp in phn phc cht ...........................................................................47 1.3. Xc nh Sn trong hp kim ng bng phng php Iod ..........................51 1.4. Xc nh km trong hp kim ng bng phng php Ferocyanur...........54 II. PHN TCH HP KIM NHM ...........................................................................56 1. Xc nh ng trong hp kim nhm bng phng php iod .............................56 2. Xc nh Fe bng phng php KMnO4 ...........................................................58 III. XC NH KM OXIT CNG NGHIP ..........................................................59 1. Xc nh ZnO trong ZnO cng nghip ( Phng php chun kt ta) ........60 2. Xc nh PbO trong ZnO cng nghip ( Phng php th tch cromat) ..........60 3. Xc nh ng thi ZnO v PbO ( phng php EDTA) ..................................62 IV. CU HI N TP V BI TP .......................................................................63
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Phn tch kim loi
M U
Phn tch kim loi l mt mn hc thuc nhm mn hc chuyn ngnh thuc chuyn ngnh Ha Phn Tch ca Cng Ngh Ha hc. Hin nay, ti liu Phn Tch Kim Loi phc v cho cng tc ging dy, nghin cu, tham kho cho gio vin, cng nh nhu cu hc tp sinh vin chuyn ngnh Phn tch cha c mt gio trnh hon chnh, ri rc v cha thng nht. p ng c nhu cu , bi ging Phn Tch Kim Loi c bin son. Bi ging cp n ni dung phn tch cc ch tiu ha l ca cc i tng kim loi ang s dng rng ri trong cc lnh vc cng nghip mi nhn ca nc ta nh lnh vc xy dng, lnh vc c kh ch to, lnh vc luyn kim Mi mt ch tiu phn tch, bi ging trnh by y , chi tit cc phn: Nguyn tc, cc phn ng ha hc, cc iu kin k thut khi xc nh, thit b, c ch cc qu trnh, qui trnh phn tch hon chnh v tnh ton, x l kt qu. Trong mi ch tiu, c trnh by cc gii hn cht lng phc v cho vic nh gi cng nh tnh ton iu kin phn tch ph hp, cc phng php phn tch khc nhau v cch la chn phng php sao cho ti u trong iu kin p ng ca phng th nghim. Cui mi chng c cu hi n tp gip sinh vin h thng ha li kin thc hc v bi tp rn luyn k nng phn tch v c bit l k nng tnh ton l mt yu rt cn thit ca ngi cn b phn tch. Mc d rt c gng, nhng bi ging vn cn nhiu thiu st. Rt mong kin ng gp, xy dng ca tp th gio vin ca khoa Cng Ngh Ho Hc v cc bn c. Xin ghi nhn v chn thnh cm n
MC CH MN HC
Sinh vin c trang b cc kin thc c bn v k thut v k nng phn tch cc thnh phn ha hc ca kim loi. Rn luyn nhn cch c th ca ngi cn b phn tch.
YU CU MN HC
Sinh vin nm vng k thut x l mu ca kim loi en v kim loi mu; nm c trnh t cng vic; hiu c cc iu kin xc nh ca qui trnh phn tch khi phn tch mt ch tiu ha hc; bit s dng cc thit b c bn trong phn tch kim loi v x l s liu thu c sau khi phn tch. Sinh vin hnh thnh c k nng phn tch cc ch tiu trong kim loi en v kim loi mu. Khoa CNHH Chuyn ngnh Ha phn tch http://www.ebook.edu.vn Trang 3
Phn tch kim loi
CHNG 1 PHN TCH KIM LOI EN

I. I CNG V KIM LOI EN
1. Phn loi Kim loi thng c chia lm 2 nhm l kim loi en v kim loi mu. Kim loi en chnh l st v cc hp kim ca st, trong st chim 95.7 99.8%, C chim 0,2 4,3%. Ngoi ra cn c Si, P, S, Mn.Kim loi en l vt liu ch yu nht dng trong cc ngnh cng nghip, nht l ngnh c kh v xy dng. Cc thnh phn C, S, P, Mn l nhng thnh phn c sn trong nhin liu hoc c thm vo trong qu trnh luyn gang, thp, hp kim. Nhng cht ny tuy hm lng khng ln nhng nh hng rt ln n tnh cht c l ca kim loi, hp kim. Cn c vo hm lng C cao hay thp m ngi ta chia kim loi en thnh gang v thp. 1.1. Gang 1.1.1. c im chung L hp kim ca Fe v C cng mt s nguyn t khc vi hm lng nh. Trong gang hm lng C > 2%, nhng trong thc t thng dng gang c hm lng C =1.7 6.6%. c im chung ca gang l thng c mu nu, xm, d nt rn khi chu tc dng ca lc c hc nhng d c, d gia cng. Gang c nhiu loi nhng c chia thnh 3 loi chnh: Gang thng dng: Cn gi l gang ph thng bao gm gang xm v trng. - Gang xm: L hp kim ca Fe v C trong phn ln C trng thi t do c hm lng 2.8 3.5% v mt s nguyn t khc do qu trnh luyn gang a vo. Gang xm c bn c hc km, nhng d gia cng, gi thnh r nn c dng nhiu. - Gang trng: Cng, gin, kh gia cng hn gang xm. Hm lng C t 2,54,5% v tn ti ch yu dng Fe3C, hm lng Si<1%. Gang trng thng dng luyn thp, ch to ni hi, thit b ha cht. - Gang c bit: c ch to theo cc phng php c bit ci tin cht lng ca cc sn phm bng gang nh gang bin tnh, gang cu, gang ngui - Gang hp kim: Ngoi thnh phn chnh l Fe, C ngi ta a vo thm mt s nguyn t khc nh Mn, Si, P, S, 1.1.2. nh hng ca cc nguyn t n tnh cht ca gang - Carbon: Hm lng C cng cao th mu ca gang cng xm, bn c hc, do, tnh dn nhit gim xung. Silic: Lm gang xm, d to bt bn trong khi gang lm gang d rn nt. Trang 4 http://www.ebook.edu.vn Khoa CNHH Chuyn ngnh Ha phn tch
Phn tch kim loi
- Mangan: Lm tng tnh mi mn, tng bn ca gang nhng hm lng Mn cao d chuyn gang hp kim thnh gang trng. Ngoi ra Mn cn c tc dng kh S l mt thnh phn c hi cho gang. - Phospho: Lm mu ca gang xm, cng nhng rt gin, lm cho gang d nng chy, lm tnh linh ng ca dung dch gang trng thi nng chy cao nn d c. - Lu hunh: Lm gang cng, dn, d nt cc b, l mt nguyn t rt c hi cho gang. 1.2. Thp 1.2.1. c im chung L hp kim ca st c iu ch t gang bng cch lm gim hm lng C xung cn 0.2 1.7%, ng thi a thm mt s nguyn t khc nh Cr, Ni, Vanai, W v lm gim hm lng Si, P, S, Mn nhm lm tng tnh c l cho thp. Tng cc nguyn t tp cht khng qu 2%. c im chung ca thp l c bn cao, chu c lc ko, un, c tnh n hi v bin dng tt. V vy thp c s dng rng ri v c c bit s dng nhiu trong ngnh c kh, c nhiu loi thp sau: - Thp carbon: Thnh phn thng l C: 0.07 0.63%, Mn: 0.35 0.85%, Si : 0.12 0.35%, S : 0.055 0.06, P : 0.05 0.07%. - Thp hp kim: Ngoi Fe, C. Khi luyn thp, ngi ta cn a vo cc nguyn t nh Cr, W, Ni, V, tng tnh c l ca thp. 2. nh hng ca cc nguyn t n tnh cht ca thp - Carbon: hm lng C cho php trong thp t 0.1 0.8%. Khi hm lng C cng nhiu th s lm tng cng, sc bn ko, un xon, n hi cng tng nhng khi hm lng C > 95% th sc bn gim, do gim, v kh gia cng. - Silic v Mangan: Nu t l thnh phn ca 2 nguyn t ny tng th thp s tng bn c hc v cng. Ring Si lm cho tnh n hi ca thp cao, c thm t cao nn c dng lm li ca my bin th. Mn lm tng tnh mi mn ca thp. Hm lng cho php ca Si t 0,1 0,35%, Mn: 0,2 0,8%. - Phospho: P l nguyn t c trong thp do ln t qung khi luyn gang a vo v luyn thp khng kh ht. P lm tng bn, cng, lm tng tnh linh ng ca thp lng trong l luyn. Nhng nu hm lng P ln lm thp dn, chu va chm c hc km, khng bin dng tt khi thp ngui. Hm lng P cho php 0.05 0.07%. - Lu hunh: L thnh phn c hi thng c do qu trnh luyn gang v luyn thp khng kh ht lm thp cng, dn, nng cc b, hm lng cho php l < 0,06%. Cc nguyn t khc nh Cr, W, V, Ni, Mo ty hm lng khc nhau v ty theo yu cu k thut m chng c nh hng rt ln n tnh cht c l ca thp nh Cr tng cng, mi mn, chu nng khi ma st.
II. PHNG PHP LY MU

1. Ly mu u tin Khoa CNHH Chuyn ngnh Ha phn tch http://www.ebook.edu.vn Trang 5
Phn tch kim loi
Kim loi hay hp kim thuc loi mu rn, thnh phn ha hc khng ng nht, thng nhiu dng khc nhau nh dng qung, dng nung luyn trng thi lng, dng sn phm nh tm, thi, phoi, bnvi cc kch thc khc nhau. V vy vic ly mu u tin rt quan trng v phi ly mu ng quy cch. 1.1. Ly mu dng sn phm tm, thanh, thi Trc khi ly mu phi lm sch v lm mt lp oxit kim loi trn b mt bng cch dng bn chi thp chi. - Ly mu t thanh thi hnh tr, hnh hp, ng th phi khoan nhiu l trn ton b thanh kim loi . Chiu su ca mi khoan phi vo gia tm kim loi. Khi kim loi c dng ch L th phi khoan c 2 thnh. H mi khoan t t thu c mt phoi nh. - Ly mu dng bn mng th dng ko ct theo chiu ca tm kim loi vi b rng 5cm, mi mnh gp li thnh nhiu lp, sau bo 2 u s c nhng dy kim loi, sau dng ko ct vn. 1.2. Ly mu ngay l nung Trong phn tch kim tra cng ngh, ngi ta thng ly mu trc tip ngay l nung. Trc ht gt b lp trn ca khi kim loi nng chy b lp x. Dng c ly mu c bit l go thp hoc xng thp. Nhng dng c ly mu vo khi lng nng chy, ly ra ngui, mu s c tch ra khi dng c ly mu, sau dng phng php c hc chuyn mu thnh dng mt, phoi hoc ht nh. Ly mu dng mt, phoi: c ly v ry qua ry c 50 60 l/cm2. 2. Chun b mu Mu u tin c x l v ly mu rt gn, sau khi trn u, chia theo vung, ri ry qua ry c 1400 l/cm2. Sau ly 5080g x l bng cn v ete, sy kh ri cho vo chai mu nu, c nt nhm, ct phn tch dn.
III. NI DUNG PHN TCH

1. Xc nh Silic (Si) Trong gang thp Si tn ti ch yu dng FeSi, FeSi2, MnSi v mt phn dng Silicat: 2FeO.SiO2, 2MnO.SiO2 Trong thp hm lng Si t 0.11%, trong gang th Si : 0.1 4%. Ty theo hm lng Si thp hoc cao m dng phng php trng lng hay phng php so mu. 1.1. Phng php khi lng 1.1.1. Nguyn tc Mu gang thp s c ha tan bng HCl vi s c mt ca HNO3 trong iu kin un nng, Si s chuyn thnh SiCl4, sau thy phn thnh orthosilicat SiO2.2H2O di dng keo ng t tch ra khi mu, lc v ra, nung 95010000C thu c SiO2. Cn lng SiO2 thu c t tnh ra hm lng Si c trong mu. Khoa CNHH Chuyn ngnh Ha phn tch http://www.ebook.edu.vn Trang 6
Phn tch kim loi Cc phn ng:
FeSi + HCl + nH2O t SiO2. nH2O + FeCl2 + H2
1000 C SiO2. nH2O 950 1.1.2. iu kin xc nh

a. iu kin ph mu
SiO2 + nH2O
- HCl c nng c tc dng ha tan mu, ng thi to mui SiCl4, khi thy phn cho mui orthosilicat H2SiO3 (SiO2.nH2O). FeSi + 6HCl SiCl4 + FeCl2 + 3H2 SiCl4 + (n+2)H2O SiO2. nH2O + 4HCl - S c mt ca acid HNO3 lm cho mu tan nhanh hn, c tc dng chuyn Fe2+ Fe3+. 3FeCl2 + HNO3 + 3HCl 3FeCl3 + NO + 2H2O - Ngoi ra do l phng php trng lng v vy nu c C (b than) v W (khng tan trong acid HCl) th s gy ra sai s rt ln, v vy phi lc b. W + 2HNO3 H2WO4 + NO - Acid H2WO4 c loi b cng than ch, cn SiCl4 dng mui tan. Qu trnh lc b b than v H2WO4 c tin hnh khi dung dch nng khi cha tin hnh c kh mu. - Do HNO3 phn ng to kh NO, phn ng xy ra mnh li cun HCl m c theo, lm gim vai tr ca HCl trong qu trnh ha tan mu v nh hng n qu trnh keo t SiO2 sau ny, v vy phi cho HCl trc, un nh cho mu tan gn ht, sau mi thm tng git HNO3 vo. Lng cn mu: ty thuc hm lng Si m lng cn s ly khc nhau. %Si mmu(g) 0.5 3 0.51 2 12 1 23 0.5 3 0.2
b. iu kin c kh mu v ng t keo SiO2
- Do SiCl4 chuyn sang SiO2 khi nng pH ln bng cch c kh ui HCl, lc phn ng thy phn xy ra. - Cn phi c kh 3 ln nhm y nhanh qu trnh keo t v lm n nh cu trc ht keo, c trn bp cch thy, nhit tt nht l 1051100C. Nu nhit cao th FeCl3 cng b thy phn theo phng trnh: FeCl3 + 2H2O Fe(OH)2Cl + 2HCl - Qu trnh trn lm tng trng lng kt ta nn s mc sai s d. Trong qu trnh c khng c khuy nhiu trnh keo SiO2 b nt s lc chm v ra khng sch. C th lm tng kh nng ng t keo bng cch thm gelatin hoc ru polivinylic. Khoa CNHH Chuyn ngnh Ha phn tch http://www.ebook.edu.vn Trang 7
Phn tch kim loi

c. iu kin ch ha kt ta,nung v cn
- Cn lc nng, ra keo lc u bng HCl 1% lm chc kt ta, sau ra bng nc ct nng cho n ht sch ion Cl-, nung 8500C, cn nhanh v SiO2 d ht m. Khi c ln Fe2O3 th cn x l bng HF c biu din bi cc phng trnh sau: SiO2 + 4HF SiF4 + 2H2O Fe2O3 + 6HF 2FeF3 + 3H2O 2FeF3 + 3H2SO4 Fe2 (SO4)3 + 6HF Fe2(SO4)3 900 C
0
Fe2O3 + 3SO3
Sau khi x l bng HF xong , lng kt ta cn li trong chn nung chnh l Fe2O3. em cn xc nh khi lng Fe2O3. Khi lng SiO2 c tnh nh sau: m(SiO2) = m(SiO2 + Fe2O3)- m(Fe2O3) 1.1.3. Qui trnh xc nh Cn lng mu thch hp (ty theo hm lng Si c trong mu) vo trong mt becher 250ml hoc bnh nn 250ml chu nhit, t mt phu thy tinh sau thm t t 3040ml HCl m c, un nh trn bp in c li aming cho n khi mu tan ht, nu cn mt t cn th thm 510 git HNO3 c cho mu tan hon ton. Nu c b gang (do b than v H2WO4) th tin hnh lc nng, dng HCl 1:1 ra k b gang, tp trung dch lc, dch ra v nc ra khong 100150ml, thm tip 10ml HCl m c, khuy u ri c n kh trn bp cch ct hoc bp cch thy, khi gn kh phi khuy nh, u. Tm cn kh bng 10ml HCl 1:1, thm 78 git gelatin 1% (hoc ru polivinylic), khuy u, thm 100ml nc si, em lc kt ta qua giy lc nh lng bng , ra 23 ln bng HCl 1% nng, sau ra bng nc ct nng n ht ion Cl- (th bng AgNO3 0.1N/CH3COOH 1%). Chuyn giy lc + keo silic vo mt chn s bit trc khi lng, nung 8509000C khong 1 gi. Ly chn ra ca l nung ch ngui xung khong 1502000C, cho vo bnh ht m 30 pht, sau em cn. T khi lng kt ta SiO2, tnh c hm lng Si c trong mu. 1.1.4. Tnh kt qu %Si = Vi: a - khi lng SiO2 m - khi lung mu f= 1.2. Phng php so mu 1.2.1. Nguyn tc
a 100 f m
MSi MSiO
= 0,4672
2
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Phn tch kim loi
Mu gang, thp c ph mu bng HNO3 c, ton b Si trong mu chuyn v dng H4SiO4 (orthosilicat). Dng orthosillicat s c to phc vi thuc th amonimolybdate trong mi trng HNO3, sau dng mui Morh (Fe2+) kh phc silisomolybdate thnh phc silicomolybden xanh, hp thu cc i bc sng 680750nm. Bng cch dng k thut ng chun c hm lng Si t 0,05mg0,35mg nu nh c mu gang thp chun hoc dng phng php thm chun nu nh khng c mu gang thp tiu chun. Cc phn ng: FeSi + 2H+ NO
3
Si4+ + Fe3+ + H2O + NO2
Si4+ + 4H2O H4 SiO4 + 4H+ H4SiO4 H2 SiO3 + H2O H2SiO3 + 12(NH4)2MoO4 + 21HNO3 21NH4NO3 + (NH4)3H5[Si(Mo2O7)6] + 9H2O
(NH 4)3H 5[Si(Mo2O 7)6] Fe
2
4H +
(NH 4)3H 5 Si
Mo2O 5 (Mo2O 7)5
Fe3+
2H 2O
Phc mu xanh 1.2.2. iu kin xc nh iu kin ph mu Do cn Si tn ti trng thi ion sau khi ph mu thc hin qu trnh to phc nn phi dng HNO3 m c m khng dng HCl. V HNO3 m c ngui th ng vi Fe nn cn phi un nng trong qu trnh ph mu. Kh sinh ra trong qu trnh ph mu l kh NO2 (c), v vy cn phi tin hnh trong t ht, c th dng HNO3 1:3 cng ph mu. Mt s hp cht cacbua kim loi kh tan trong HNO3, y nhanh qu trnh oxi ha mu cn b sung thm cht tr oxi ha mnh nh (NH4)2S2O8. Khi ph mu cn un nng nh khng c qu 800C, trnh tnh trng Si chuyn sang dng keo mt phn gy ra sai s rt ln. Lng cn mu phi ly ph hp, nu sau khi ph mu v c nh mc n 100ml th lng cn c ly theo bng sau: Hm lng Si (%) Lng cn (g) iu kin xy dng ng chun Trng hp c mu chun gang thp trong sn xut: khi xy dng ng chun vi s im chun l 8 im, dung dch chun Si4+ c chun l TSi = 0,1mg/ml. c pha t SiO2 tiu chun hay t Na2SiO3. Khong nng xy dng ng chun l 0,050,35mgSi/100ml dung dch o. Cc dung dch chun ny c thnh phn nn ging nh mu phn tch. Khoa CNHH Chuyn ngnh Ha phn tch http://www.ebook.edu.vn Trang 9 0,05 0,05 0,050,1 0,25 0,10,15 0,2
Phn tch kim loi
Trng hp khng c mu tiu chun gang thp: Khi cn phi s dng k thut thm chun nhm trnh sai s nn. Dung dch chun c thm cng chnh l dung dch tiu chun TSi =0,1mg/ml TSiO =0,2741mg/ml.
3 _2
Mi trng i vi chun l mi trng HNO3 1:3 iu kin loi tr nh hng Do trong gang thp thng c P, trong cng iu kin th c Si4+ v PO43- cng to phc vi thuc th amonimolybdate c mu vng, hn na do dng HNO3 lm acid ph mu, s c mt ca Fe3+ cng c mu vng ru, v vy khng th o quang phc mu vng bc sng 410nm. khc phc cn phi chuyn phc silicomolybdo ln phc silicomolybden ng thi phi ph hy phc ca P vi thuc th molybdate. Bng cch dng acid oxalic, th phc ca phospho vi thuc th b ph hy. Do oxalat to phc vi molybdate bn hn so vi P to phc vi molybdate , trong khi phc oxalate vi molybdate li km bean hn so vi Si. Mt khc chuyn phc molybdo ln phc molybden ngi ta dng tc nhn kh l Fe2+ (mui Morh), nhm trnh a ion l vo nh Sn2+, hydroxylamin - iu kin o mu v chun: Mu trng chnh l nc ct v HNO3 1:3 bng ng lng HNO3 theo ng t l pha long. - Trc khi o chng ta cn qut tm max. C 2 vng qut sng: 650750, 770880nm. T quyt nh chn vng v max. - Sau khi to phc xong em o sau 510 pht. 1.2.3. Qui trnh xc nh - Chuyn lng cn mu vo cc chu nhit loi 100ml, thm 1015ml HNO3 1:3 un nh cc trn bp cch thy cho mu tan ht, sau thm 2ml (NH4)2S2O8 (100g/l), oxi ha cc hp cht cacbua kim loi. Khi mu tan ht un tip cc 1015 pht. Khi ph mu trn bp cch thy ch un 80 0C, nu nhit cao Si s chuyn sang dng keo lm sai kt qu phn tch. Sau khi ph mu, ngui, lc dung dch vo bnh nh mc 100ml, dng nc ct ra cn mu, dng nc ct nh mc ti vch, lc trn u, rt ra 510ml cho vo bnh nh mc 100ml, thm 10ml H2SO41%, 5ml thuc th amonimolybdate (50g/l), lc u 3 pht, thm tip 20ml dung dch H2C2O4 1:3, lc u, sau 2 pht thm dung dch mui Morh (40g) n vch nh mc, lc u, em o max. Mu trng l nc ct. ng chun c dng t dung dch c TSi =0,1mg/ml. (TSiO32-=0,2741mg/ml). S th t ng 100 (ml) V ml dung dch Si (0,1mg/ml) Hm lng Si (mg) 1 0,5 0.05 2 1 0,1 3 1,5 0,15 4 2 0,2 5 2,5 0,25 6 3 0,3 7 3,5 0,35
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Phn tch kim loi
- Nu dng phng php thm chun th thm 23ml dung dch chun TSi = 0,1mg/ml vo bnh mu ri mi dng mui Morh nh mc v em o. 1.2.4. Tnh kt qu Tnh theo phng php ng chun hay phng php thm chun (xem gio trnh phn tch dng c). 2. Xc nh phospho (P) - Cng nh S, P trong gang thp nhn chung l thnh phn c hi, thng lm gim tnh ma st, tnh n hi, kh bin dng khi dp ngui. Trong hp kim st, P thng tn ti di dng phosphur Fe2P, Fe3P v mt phn dng x phosphur kim loi khc. Trong gang %P = 0,1 0,5% v c th cao hn, trong thp th %P=0,013%. xc nh P trong gang thp hoc trong cc hp kim, phi oxi ha cc dng P trong mu thnh PO43- ri dng mt trong nhng phng php xc nh Phng php th tch Molybdate thng dng cho mu gang c%P 0,5% Phng php so mu thng dng cho mu gang thp c %P=0,01 0,05.
2.1. Phng php th tch molybdate 2.1.1. Nguyn tc Mu gang hp kim c ph bng HNO3 hoc hn hp cng thy vi s c mt ca KMnO4 trong iu kin un nng. Loi b tp cht khng tan v keo Si thu c dung dch cha PO43-. Kt ta ion ny di dng kt ta vng phosphomolybdate bng thuc th (NH4)2MoO4 trong HNO3, dung dch nng, lc, ra kt ta n khi ht acid, sau ha tan kt ta bng dung dch kim NaOH tiu chun d chnh xc. Chun lng kim d bng dung dch chun HCl vi ch th PP. im tng ng nhn c khi dung dch mt mu hng. Cc phn ng: 3Fe3P + 14HNO3 3H3PO4 + 9Fe(NO3)3 + 14NO + 16H2O H3PO4 +12(NH4)2MoO4 + 21HNO3 21NH4NO3 + (NH4)3H4[P(Mo2O7)6] + 10H2O. 2(NH4)3H4[P(Mo2O7)6] + 46NaOH 2(NH4)2HPO4 + 23Na2MoO4 + (NH4)2MoO4 + 26H2O. 2.1.2. iu kin xc nh iu kin ph mu NaOH d + HCl NaCl + H2O
Ph mu bng HNO3 c, nng (hoc h cng thy), cn thm cht oxi ha mnh nn qu trnh ha tan mu, chuyn Fe2+ Fe3+ lm mu tan nhanh. Sau khi mu tan, phi un si k ui ht kh NO, NO2. Khng dng HCl trnh bay hi phosphurhydro 2Fe3P + 12HCl 2PH3 + 6FeCl2 + 3H2
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Phn tch kim loi
Cn thm mt lng d cht oxi ha mnh KMnO4 oxi ha H3PO3 H3PO4 (P P+5)
+3
Fe3P + 13HNO3 H3PO3 + 3Fe(NO3)3 + 4NO + 5H2O 5H3PO3 + 2KMnO4 + 6HNO3 5H3PO4 + 2Mn(NO3)2 + 2KNO3 + 3H2O. Khi un nng lng d KMnO4 phn hy to thnh kt ta MnO2 mu nu khng tan trong HNO3. 4KMnO4 + 4HNO3 t 4MnO2 + 4KNO3 + 3O2 + 2 H2O Kt ta MnO2 nh hng n giai on sau ca qu trnh phn tch nn c loi tr bng NaNO2 hay KNO2 MnO2 + NaNO2 + 2HNO3 Mn(NO3)2 + NaNO3 + H2O Phi un si k dung dch ui ht NO v lc b than ch, b x gang khi ph mu. - iu kin kt ta: Kt ta (NH4)3H4[P(Mo2O7)6] l mt kt ta tinh th ht mn, c tnh acid, rt d hp ph cc ion l v vy cn phi tin hnh kt ta trong iu kin dung dch nng. Mi trng kt ta l mi trng acid 23N. Khi kt ta cn a thm cht in li mnh NH4NO3 vo nhm to hiu ng ion chung. Khi cho thuc th vo, khuy nh, trnh khuy mnh, nhiu, s lm nt kt ta. kt ta to ht, chc cu trc nn lng 12h. - iu kin lc ra kt ta: Do phng php xc nh l phng php trung ha nn kt ta phi ra ht acid, trong qu trnh ra, trnh ta tan. Mun vy phi ra ta bng dung dch in li mnh trung tnh KNO3 3%. Cn thit phi kim tra sch acid ca ta bng giy qu hoc tt nht l th mt git cui cng bng mt git NaOH vi ch th pp (khng mt mu hng). Do kt ta tinh th nn phi lc gn, giy lc bng xanh. - Do kt ta vng molybdate rt d thm thu (hin tng leo kt ta) ln giy lc v vy khi chuyn kt ta ln giy lc, khng c rt qu phu lc. Kt ta vng cng bm 1 lp ln a thy tinh khi lc, v vy khi ha tan, cn ngm a thy tinh trong dung dch ha tan NaOH. iu kin chun Dng dung dch NaOH tiu chun d chnh xc ha tan kt ta, tuy nhin khng c dng d nhiu NaOH s lm cho mui (NH4)2HPO4 b tan ra gy sai s, ng thi tn nhiu dung dch chun v ko di thi gian chun . Do trong dung dch c mui (NH4)2HPO4 nn pH tng ng t 89 dng ch th pp l thch hp. Khi ha tan kt ta, trnh lm nt giy lc v s lm dung dch xn mu, kh nhn mu v s chuyn mu chm. Acid HCl c nng 0,050,2N l ph hp Khoa CNHH Chuyn ngnh Ha phn tch http://www.ebook.edu.vn Trang 12
0
Phn tch kim loi
iu kin pha ch dung dch (NH4)2MoO4 15%: ha tan 150g (NH4)2MoO4 trong 0,5 lt nc ct 2 ln, khuy cho tan ht, sau 1 ngy rt t t dung dch ny vo 0,5lt HNO3 1:1 trn u, sau 1 tun em lc qua giy lc bng xanh, thu dch qua lc vo bnh cha mu nu c nt nhm, bo qun ni mt v trnh nh sng. 2.1.3. Qui trnh xc nh
a. Xc nh P trong gang
Cn chnh xc khong 1,0000 + 0,0002g mu gang chuyn vo cc thy tinh chu nhit 250ml, thm t t khong 2030ml HNO3 1:1, y np cc, un nh trn bp cch ct, nu mu si nhanh, cn a ra khi bp. Sau khi mu tan ht (khng cn nhng ht gang), un tip khong 30 pht cho mu gn kh (cho n khi ui ht khi nu), ri thm khong 3040ml H2O ct em lc b than ch trn giy lc dy. Dng nc ct nng ra cn b. Dung dch lc v nc ra khong 7080ml tp trung vo cc thy tinh chu nhit 250ml. em c cn dung dch ti khong 50ml (nu thy H2SiO3 xut hin th thm khong 78 git HF 30%, un si 10 pht ri thm 34 git Na2B4O7 5% un nh 5 pht ui HBF4). Thm tng git KMnO4 4% vo dung dch mu cho ti khi dung dch c mu tm nht, un si dung dch 5 pht, ngui, nh tng git dung dch NaNO2 15% cho ti khi dung dch c mu vng chanh (mu ca Fe3+) trong sut, un k ui ht NO, ngui ri dng NH4OH 10% trung ha t t cho n khi xut hin kt ta nu (Fe(OH)3), dng HNO3 1:1 cho n khi kt ta Fe(OH)3 va tan ht, sau thm d 5ml HNO3 1:1. Thm 5ml NH4NO3 20% (hoc 1g NH4NO3), un nng dung dch n 50600C, rt t t 2530ml dung dch (NH4)2MoO4 15% + 3 git NH4OH 10%, khuy k 510 pht, lng 2 gi. Lc kt ta qua giy lc bng xanh, tm t giy lc bng NH4NO3 20%, ra lng gn kt ta bng NH4NO3 1%, sau dng KNO3 1% ra n ht acid (th bng cch cho 12 git NaOH 0,1N + 2 git pp, hng git nc ra cui cng, nu khng mt mu hng l sch acid). Chuyn kt ta v cc va kt ta, thm 56 git ch th pp 1%. Dng dung dch NaOH 0,1N ha tan kt ta n khi dung dch ha hng, thm d chnh xc 5ml NaOH na. em chun lng d NaOH bng dung dch chun HCl 0,05N ti khi mt mu hng. Ch khi chun th thm 50ml nc ct v trnh dm nt giy lc. a. Xc nh P trong thp Ty theo hm lng P trong thp m ly lng cn t 12g, chuyn lng cn vo cc chu nhit 250ml, thm t t nhiu t HNO3 1:1, mi ln 6070ml, un si nh cc trn bp cch ct, sau khi mu tan ht, un tip 30 pht, ngui, thm tng git KMnO4 4% ti khi dung dch c mu hng, sau tip tc nh qui trnh xc nh P trong gang. 2.1.4. Cng thc tnh %P = Vi: mgp= 23OHKhoa CNHH Chuyn ngnh Ha phn tch http://www.ebook.edu.vn Trang 13
m P [( NV )OH- _( NV ) H+ ] 100 m
31 do 2(NH4)3H4[P(Mo2O7)6] 2P 46NaOH 1P 23.10 3
Phn tch kim loi m(g): khi lng mu. 2.2. Phng php so mu
Phng php ny thng p dng khi hm lng P<0,2% cho cc mu thp hp kim. 2.2.1. Nguyn tc Ph mu thp bng hn hp acid v c, c mt KMnO4 trong iu kin dung dch nng, loi b tp cht khng tan, keo v cc thnh phn tr ngi, trong dung dch cha ion PO43-. Lm hin mu PO43- bng thuc th (NH4)2MoO4 trong mi trng pH thch hp 0.18 0.36 to phc mu vng. Kh phc mu vng thnh mu xanh bng mt h kh thch hp nh h SnCl2/ HCl, hay h Fe3+/Na2SO3 hay h SnCl2/acid ascobic. em o mt quang bc sng 680nm hay 880nm. Da vo th chun c xy dng t mu thp tiu chun xc nh hm lng P c trong mu. Cc phn ng: 3Fe3P + 41HNO3 = 9Fe(NO3)3 + 3H3PO4 + 14NO + 16 H2O Fe3P + 13 HNO3 = 3Fe(NO3)3 + H3PO3 + 4NO + 5H2O 2KMnO4 + 5H3PO3 + 6HNO3 = 2Mn(NO3)2 + 2KNO3 + 5H3PO4 + 3H2O
2KNO3 + 2MnO2 + 2KMnO4 + 2HNO3 t
0
3 O2 + H2O 2
MnO2 + NaNO2 + 2HNO3 = Mn(NO3)2 + NaNO3 + H2O H3PO4 + 12(NH4)2MoO4 + 24HNO3 24NH4NO3 + H7[P(Mo2O7)6] + 10H2O Vng
H7[P(Mo2O7)6] + 2SnCl2 + 4HCl H7 P Mo2O5 (Mo2O7)5 + 2SnCl4 + 2H2O
Hoc Fe(NO3)3 + Na2SO3 + H2O Na2SO4 + Fe(NO3)2 + HNO3

H7[P(Mo2O7)6] + 3Fe(NO3)2 + 4HCl H7 P Mo2O5 (Mo2O7)5 + Fe(NO3)3 + 2H2O
2.2.2. iu kin xc nh - Ph mu loi b keo Si v b hp kim: Si v As l 2 nguyn t tr ngi nht v chng c kh nng hnh thnh phc tng t nh P lm mt quang tng. Khi ph mu bng HCl asen c loi tr do bay hi di dng H3As, cn Si c chuyn thnh keo H2SiO3 c loi b. Cn P chuyn thnh H3PO4. Phn KMnO4 dng oxi ha H3PO3 ln H3PO4 c loi tr bng Na2SO3 v un nng, cng c th loi tr bng NaNO2. - iu kin phc mu molypdate: hnh thnh phc mu vng molypdat th lng thuc th (NH4)2MoO4 d mi trng acid H+ = 0,180,36N, iu kin ny th Khoa CNHH Chuyn ngnh Ha phn tch http://www.ebook.edu.vn Trang 14
Phn tch kim loi
phc phosphomolybdat bn, trnh c nh hng ca Si v cc thnh phn khc, iu chnh mi trng ngi ta dng NH4OH hoc HCl. iu kin kh phc vng thnh phc xanh: Do mu cha nhiu ion Fe3+, phc vng molypdate li km bn hn phc xanh molybden, trnh hin tng cng mu v phc bn hn trong qu trnh o, nn thng phi kh phc vng molypdat ln phc xanh molypden. Vic s dng cc h kh thch hp kh phi ph hp, c bit nu dng h SnCl2 th phi ch n pH v Sn2+ v Sn4+ rt d b thy phn gy c dung dch, ngoi ra c th a thm NaF vo che Fe3+, Al3+. - iu kin v xy dng chun: loi tr c sai s nn khi xy dng chun, ngi ta dng cc mu thp tiu chun c hm lng P=0,020,06%, s mu thp c s dng l 3 mu. Thp %P=0,02: cn 0.3g, thp chun %P=0,4: cn 0,6g v thp %P=0,033 th trn 2 th tch ca 2 mu thp 0,02 v 0,04 theo t l 1:1. 2.2.3. Qui trnh xc nh a. Qui trnh xc nh 1 Cn khong (1.0000 0.0002)g mu thp vo bnh nn chu nhit 100ml, t mt phu thy tnh nh v rt qua phu 5ml HCl m c + 23ml H2SO4 m c, un nh trn bp cch ct cho n khi tan ht, nu mu kh tan thm 34 git HNO3 m c, un nh n gn kh, thm tip 5ml HCl m c, c kh nh, thm 20ml nc ct nng, lc b keo SiO2 v than ch, ra b bng nuc nng, dch qua lc c tp trung v c thm tng git KMnO4 4% n khi c mu tm, un nh n khi c MnO2, dng dung dch Na2 SO3 5% kh n khi dung dch trong sut (hoc dung dch NaNO2 5%), un si nh 5 pht, lm ngui thm 6ml HCl 1:2 to mi trng, thm tip 4ml (NH4)2MoO4 5% lc mnh dung dch, chuyn ton b dung dch vo bnh nh mc 100ml, thm nc ct n vch nh mc 100ml, sau 1 pht em o =680nm. So snh mt quang vi ng chun, t tnh ra hm lng P. Qu trnh tin hnh xy dng chun c tin hnh tng t nh mu thc. b. Qui trnh xc nh 2 - Cn khong 1.0000g mu cho vo becher 100ml, ha tan bng 10ml HNO3 1:3, un nh (trnh si) n khi mu tan hon ton, khi mu tan xong, un si 1 pht ui ht NO, nh tng git dung dch KMnO4 2% n khi dung dch c mu tm nht. Sau thm tng git NaNO2 n khi dung dch trong sut, un si 1pht, thm 5ml dung dch (NH4)2MoO4 5%, va thm va lc, sau thm 20ml dung dch kh (dung dch ny c pha ch: 2,4g NaF + 2g SnCl2 + 10g acid ascobic + H2O thnh 1 lt) lc u v chuyn vo bnh nh mc 100ml, dng nc ct nh mc ti vch, lc u, sau 1 pht em o bc sng 680nm. - Mu chun: cn 1.0000g mu thp tiu chun P loi 0,02% hoc 0,03%, 0,04%. Ri tin hnh tng t nh mu tht. %P=
Ax Cc Ac
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Phn tch kim loi Vi
% P: l hm lng phn trm ca P c trong mu xc nh

C c : % P c trong mu tiu chun A
x
: Mt quang mu
A c : Mt quang ca chun
3. Xc nh Mn bng phng php persulfat bc Mn trong thp tn ti ch yu dng MnS hoc Mn3C, khi % Mn<0,2% th kim loi d ti luyn v c rn cao. Khi % Mn 0,2 th rn gim, khi ng c th co rt nhanh, km bn. Trong gang khi %Mn=0.51, trong thp % Mn=0.20.5 th thng c xc nh bng phng php persulfat bc. Phng php ny thng c p dng khi % Mn=0.26%, nhng nu %Mn=0.050.1% th dng phng php so mu. 3.1. Nguyn tc Ph mu gang thp bng hn hp H2SO4, HNO3, H3PO4 trong iu kin dung dch nng chuyn Mn trong hp kim thnh Mn2+, sau dng persulfat S2O82- c mui Ag lm xc tc trong iu kin nng v mi trng acid oxi ha Mn2+ MnO4-. Chun MnO4- sinh ra bng mt h kh tiu chun nh mui Morh hoc mui Na3AsO3. T th tch ti im cui tnh c hm lng Mn c trong mu. 3.2. iu kin xc nh - iu kin ph mu: Ph mu bng hn hp acid, HNO3 va ng vai tr ha tan mu kim loi, va ng vai tr oxi ha Fe2+ Fe3+ lm mu tan nhanh, H2SO4 ng vai tr lm dung mi ho tan, vi H3PO4 th c vai tr ha tan MnO2 trong mu v MnO2 khng tan trong HNO3, H2SO4. 3MnO2 + 4H3PO4 Mn3(PO4)2 + 6H2O - Hn hp H2SO4 + H3PO4 cn c tc dng lm cho si n nh, lm cho qu trnh ph mu c trit hn. Cn thit phi ui ht thnh phn kh NO sau khi ha tan mu, v n s nh hung n qu trnh oxi ha Mn2+ MnO4-. - iu kin oxi ha Mn2+ MnO4-: Oxi ha Mn2+ thnh MnO4- bng lng d S2O82- c AgNO3 xc tc. Nu khng c xc tc AgNO3 d sinh ra: Mn2+ + S2O82- + 3H2O MnO(OH)2 + 2SO42- + 4H+ - Nhng khi c AgNO3 xc tc th trnh c kt ta sinh ra. C ch xc tc c gii thch nh sau: 2AgNO3 + (NH4)2S2O8 Ag2S2O8 + 2NH4NO3 - Nhng Ag2S2O8 km bn, d b thy phn sinh ra Ag2O2 c tnh oxi ha cao. (E0Ag2+/Ag+ = 1, 98 V) Ag2S2O8 + 2H2O Ag2O2 + 2H2SO4 Khoa CNHH Chuyn ngnh Ha phn tch http://www.ebook.edu.vn Trang 16
Phn tch kim loi
Chng 1: Phn tch kim loi en Ag2O2 Ag2O + [O]
Chnh [O] l tc nhn oxi ha Mn2+ MnO45Ag2O2 + 2Mn(NO3)2 + 6HNO3 2HMnO4 + 10AgNO3 + 2H2O C th oxi ha Mn2+ ln MnO4- bng NaBiO3/HNO3 hoc KIO4/HNO3. Tuy nhin vic s dng 2 h ny lm tc nhn oxi ha thng gp kh khn giai on loi tr lng d ca chng v cng on loi tr l cng on bt buc do giai on sau chun MnO4- bng h kh tiu chun. V vy h ny thng c s dng trong phng php so mu. 2Mn(NO3)2 + 5NaBiO3 +16HNO3 5Bi(NO3)3 + 5NaNO3 + 7H2O + 2HMnO4 Hoc 2Mn(NO3)3 + 5KIO4 + 3H2O 4HNO3 +5KIO3 +2HMnO4 - Loi b lng d ca (NH4)2S2O8 v xc tc AgNO3 bng cch un si k dung dch n ht bt kh O2: S2O82- SO42- + SO3 + 1 O2 2
Loi xc tc AgNO3 bng lng d NaCl, dung dch ngui Nu dung dch nng c nguy c MnO4- b tht thot do phn ng: MnO4- + +2Cl- + H+ Cl2 + Mn2+ + 4H2O iu kin chun :
AgNO3 + NaCl AgCl + NaCl
Nu chun bng h kh Na3AsO3 th mi trng acid va phi, mc ch lm tng tnh oxi ha ca dung dch MnO4- v tng c tnh kh AsO33- lm cho phn ng chun hon ton. 5AsO33- + 2MnO4- +6H+ 5AsO43- + 2Mn2+ +3H2O Nu thiu acid th phn ng s sinh ra MnO2 trung gian lm phn ng chun khng hon ton: AsO33- + MnO4- + 2H+ AsO4 3- + MnO2 + H2O khc phc thng thm thnh phn cht kh NaNO2. Khi phn ng chun trit l: MnO2 + NO2- + H+ Mn2+ + NO3- + H2O V vy phng trnh tng qut l: AsO33- + MnO4- + NO2- +2H+ AsO43- + Mn2+ + NO3- + H2O - Nu chun bng mui Morh (Fe2+) th thc hin trong mi trng acid H2SO4 6N c thm H3PO4. kt thc chun chnh xc, giai on cui c th s dng ch th diphenylamin hoc ch th acid phenylantranilic. Khoa CNHH Chuyn ngnh Ha phn tch Trang 17
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Phn tch kim loi
- Nu trong mu thp c Cr3+ th nu s dng cc h oxi ha trn th Cr3+ cng c kh nng b oxi ha ln Cr2O72- v cng c chun bng cc h kh tiu chun. V vy nu ly mu thp c Crom th cn phi loi tr Crm di dng Cr(OH)3 trc khi tin hnh oxi ha. Cr3+ c kt ta pH=3.54 bng NH3 1:1 c thm cht tr lng huyn ph ZnO. 3.1.3. Qui trnh xc nh
a. Xc nh Mn trong thp (khng loi crm)
Ty theo hm lng Mn m ly lng cn ph hp: %Mn lng cn (g) 0,5 1 0,50,8 0,5 0,81,0 0,3 1,02.0 0,25
Thng cn chnh xc 0,5 0,0002g mu gang chuyn vo bnh nn 250ml chu nhit, thm 30ml hn hp acid (150ml HNO3 m c + 80ml H3PO4 m c + 750ml H2O ct), un mu n khi gn tan ht, thm 1ml HNO3 m c un cho n tan ht, un si 15pht ui ht kh NO. Thm khong 25ml nc ct nng, lc nng qua giy lc bng vng, dng nc ct nng ra b trn lc, tp trung dch lc, nc ra n khong 100ml, thm 10ml AgNO3 2,5%, thm 20ml (NH4)2S2O8 loi 150g/l, un si nh dung dch cho n khi xut hin mu tm r, n nh, tip tc un si 5 pht loi tr (NH4)2S2O8, thm 10ml H2SO4 6N, ngui, thm 5ml NaCl loi 150g/l, em chun bng dung dch Na2AsO3 0,02 N hoc bng dung dch chun Fe2+ 0,05 N, ti mu tm nht, thm 23 git ch th diphenylamin, chun ti mu xanh lc.
b. Xc nh Mn trong thp (c loi crm)
Cn chnh xc khong 1 0,0002g mu thp, chuyn vo cc chu nhit 250ml, thm khong 40ml H2SO4 1:1, un nh mu trn bp cch ct, khi mu tan gn ht, thm tng git HNO3 m c (khong 34ml) cho mu phn hy hon ton. Nu vn cn cn khng tan th c gn cn n bc khi trng, sau thm nc ct ri thm tip acid un nng cho n khi tan ht. Chuyn dung dch vo bnh nh mc 250ml, dng NH3 1:1 trung ha cho n mu hng sm, nh tng git huyn ph ZnO (150g/l) ti khi thy huyn ph ZnO lng xung y bnh, lc u, lc b kt ta qua giy lc bng xanh. B 1020ml dung dch u. Ly chnh xc 100ml cho vo bnh nn, thm 10ml AgNO3 3,5g/l + 20ml (NH4)2 S2O8 150g/l ri tip tc lm nh qui trnh xc nh Mn trong gang.
c. Qui trnh xc nh Mn trong li thp
Cn 0,1g mu thp cho vo bnh nn 250ml, thm tip 15ml H3PO4 m c. un nng t t n khi bc khi trng, ngui, thm 2g (NH4)2S2O8, un nh n khi dung dch c mu tm n nh, lc u, lm lnh, thm 100ml H2O ct + 5ml H2SO4 1:1, lm lnh. Chun bng dung dch mui Morh (Fe2+) 0,05N n mu nht, thm 3 git ch th phenylantranilic 0,2% (pha trong nc) v tip tc chun cho n khi c mu xanh sng.
d. Qui trnh xc nh Mn bng phng php so mu
Khoa CNHH Chuyn ngnh Ha phn tch
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Phn tch kim loi
- Mu: Cn 0,1g mu cho vo becher 100ml, thm 10ml hn hp acid (100ml HNO3 m c + 100ml H3PO4 m c + 800ml H2O + 4g AgNO3), gia nhit ti khi mu tan gn ht, un tip ui khi nu, thm 5ml (NH4)2S2O8 20%, un si n mu tm r, ly ra ngui v chuyn vo bnh nh mc 50ml, thm nc ct ti vch, lc trn u, em o cng vi chun bc sng 550nm 555nm. - ng chun: Chun b 6 becher 100ml, thm ln lt vo cc becher 1, 2, 3, 4, 5ml dung dch Mn2+ tiu chun 0,1mg/ml (c pha t MnSO4.5H2O: cn 0,4338g MnSO4.5H2O pA + 100ml H2O + 5ml H2SO4 m c + H2O = 1lt). Sau thm cc ha cht lm tng t nh vi mu. Ch : C th thay (NH4)2S2O8 bng 0,1g KIO4/1 bnh, trong hn hp acid ph mu khng c 4g AgNO3. 3.1.4. Tnh ton kt qu
m Mn ( NV ) c 100 % Mn = m
vi mMn =
54,91 5 103
Nu dng phng php so mu th dng k thut tnh ton t ng chun hoc phng php so snh, thm chun tnh hm lng Mn c trong mu. 4. Xc nh Crm trong thp hp kim Crm trong thp hp kim tn ti ch yu dng Cacbur Cr4C hoc Cr3C2. Trong thp hm lng Crm dao ng t 0.10.2%. Crm c nh hng ln n tnh cht ca kim loi, n lm tng cng, gim tnh bin dng, tng kh nng chu mi mn, kh nng chu nhit. Ty theo hm lng Crm m c nhiu phng php xc nh: Phng php chun iod Phng php persulfat bc Phng php so mu quang in
4.1. Phng php Iod 4.1.1. Nguyn tc Mu c ph bng hn hp HNO3 + H2SO4 trong iu kin nng, Crm t hp cht carbur chuyn thnh ion Cr3+. Ion Cr3+ c chuyn thnh ion CrO42- trong mi trng kim, loi b thnh phn tr ngi, dung dch cn li cha ion CrO42- c xc nh theo phng php chun iod vi k thut chun th. Cc phn ng xy ra: 2Cr3C2 + 9H2SO4 3Cr2(SO4)3 + 9H2 + 4C Cr2(SO4)3 + 2KMnO4 + 4Na2CO3 2Na2CrO4 + MnO2 + K2SO4 + 2Na2SO4 + 4CO2. 2CrO42- + 2H+ Cr2O72- + H2O Cr2O72- + 6I- + 14H+ 2Cr3+ + 3I2 + 7H2O 2Na2S2O3 + I2 2NaI + Na2S4O6 Khoa CNHH Chuyn ngnh Ha phn tch Trang 19
Phn tch kim loi 4.1.2. iu kin xc nh
- iu kin ph mu: Dng hn hp acid v c mnh HNO3 + H2SO4 ph mu. HNO3 c vai tr ha tan mu, ph v cu trc mng tinh th v lin kt carbur kim loi, oxi ha Fe2+ Fe3+, t lm cho mu tan nhanh, trit hn. H2SO4 lm dung mi ha tan mu. iu kin oxi ha Cr3+ CrO42-: Trong mi trng kim th th chun ca CrO42- v MnO4- l:
E0 CrO 4 2 _ ,OH_ / Cr3+ = _ 0.13V ; E0MnO 4 2 _ ,OH_ / MnO 2 = 0.6V

= 0,6 + 0,13 = 0,73V phn ng xy ra nh lng. Trong khi nu thc hin trong mi trng acid th:
E0 CrO 4 2 _ / Cr 3+ =1.36V ; E0 MnO 4 2 _ ,H+ / Mn2+ =1.51V

= 1,51 1,36 = 0,15V phn ng xy ra gia MnO4- + Cr3+ khng nh lng. Mt khc nu thc hin trong mi trng kim th s km theo vic kt ta c ion Fe3+ di dng Fe(OH)3 m ion Fe3+ l mt ion gy tr ngi cho phng php iod. Trong mi trng kim lng KMnO4 d s chuyn thnh MnO2 do phn ng: MnO4- + 2H2O MnO2 + 4OH- + O2 Nh vy ion gy nh hng l ion Fe3+, MnO4- d c loi tr trit bng k thut lc. iu kin loi tr ion gy tr ngi: nh cp iu kin trn, Fe3+ MnO4phi c loi tr di dng Fe(OH)3 v MnO2. Lng d MnO4- phi c loi tr trit bng cch thm C2H5OH ri un nng 900C.
C KMnO4 + C2H5OH 90 CH3CHO + MnO2 +
0
1 O2 + H2O 2
CH3CHO +
1 O2 2
t CH3COOH
- iu kin chun : c thc hin theo cc iu kin chun ca phng php iod (xem phn tch nh lng). 4.1.3. Quy trnh xc nh Cn chnh xc khong 0,50.1 0,0002g mu c x l ht acid v du m, chuyn vo cc chu nhit 250ml, thm 4050ml H2SO4 1:4 v thm 12ml HNO3 m c, ly phu chn v un trn bp in c li aming cho n khi mu tan hon ton (ch c cn hoc b l b than), lc ny dung dch c mu xanh trong ca Cr3+. Tip tc un si ui ht kh NO (ht khi nu NO2), c gn cn n khi c khi mu trng bc ra, ngui, thm nc ct v chuyn ton b vo bnh nh mc 250ml, dng nc ct nng ra v nh mc ti vch, lc u, lc b b than v H2WO4 (kt ta trng). Ly 100ml dung dch qua lc chuyn vo cc chu nhit 250ml, dng NaOH trung ha s b, sau dng Na2CO3 loi 400g/l trung ha ti khi Khoa CNHH Chuyn ngnh Ha phn tch Trang 20
Phn tch kim loi
xut hin vn c khng tan (pH= 6, ht kh CO2 bay ra). Sau thm tng lng nh KMnO4 loi 40g/l ti khi dung dch c mu tm nht, thm C2H5OH 900 n khi mt mu tm, sau un si nh 5 pht chuyn CH3CHO CH3COOH. Lc nng dung dch qua giy lc bng vng, dng nc nng ra kt ta trn giy lc cho ti khi dch qua lc ht mu vng. Dung dch lc v nc ra tp trung vo bnh nn 250ml, thm H2SO4 1:4 trung ha n pH = 34 (ht bt kh CO2 bay ra), thm d 12ml H2SO4 6N na, thm 10ml KI 10%, cho vo ti 5 pht, ly ra chun bng Na2S2O3 0,02N ti mu vng nht, thm 5 git h tinh bt 5%, chun ti mt mu xanh en ca dung dch. Ghi th tch Na2S2O3 0,02N (hoc 0,05N) tiu tn. 4.1.4. Cng thc tnh % Cr =
m Cr ( NV )S O 2
2 3
mm
100 f vi:
mCr = 52,01 3
3.10
mm - khi lng mu, (g)
f - h s pha long
( NV)
S2O 32
- s mili ng lng ca dung dch chun Na2S2O3 s dng.
4.2. Phng php persulfat bc Trong phng php ny ngoi vic xc nh c Crm cn xc nh c V (Vanai). 4.2.1. Nguyn tc Ph mu hp kim c cha Cr v V bng hn hp H2SO4 v HNO3 trong iu kin nng. Cr v V s chuyn thnh Cr2+ v VO2+. Oxi ha ring Vanai bng KMnO4 iu kin thng chuyn VO2+ VO3-, chun lng VO3- bng dung dch chun Fe2+ vi ch th ferroin trong mi trng acid. Dung dch sau khi xc nh V, c xc nh Cr3+ bng cch oxi ha Cr3+ Cr2O72- bng cht oxi ha (NH4)2S2O8 c mt ca xc tc AgNO3. Sau chun Cr2O72- bng dung dch chun tng t nh Vanai. Cc phn ng xy ra: 2Cr3C + 9H2SO4 3Cr2(SO4)3 + 9H2 + 4C 3V + 3H2SO4 + 4HNO3 3VOSO4 + 4NO +5H2O 5VOSO4 + KMnO4 + 6H2O 5HVO3 + MnSO4 + 3H2SO4 + KHSO4 5HVO3 + 2FeSO4 + 3H2SO4 2VOSO4 + Fe2(SO4)3 + 4H2O Cr2(SO4)3 + 3(NH4)2S2O8 + 7H2O H2Cr2O7 + 3(NH4)2SO4 + 6H2SO4 Cr2O72- + 6Fe2+ + 14H+ 2Cr3+ + 6Fe3+ + 7H2O 4.2.2. iu kin xc nh iu kin ph mu: Tng t iu kin ph mu ca phng php iod. iu kin oxi ha Cr3+ Cr2O72- v VO2+ VO3-: Trang 21
Phn tch kim loi
Do E0 MnO 4 2 _ ,H+ / Mn2+ =1.51V v E0 VO 3 _ / VO 2+ =1.0V nn phn ng oxi ha VO2+ VO3- c th dng KMnO4 oxi ha d dng, nh lng, trong iu kin ny th Cr3+ hon ton khng b oxi ha, v vy qu trnh oxi ha VO2+ bng KMnO4 l qu trnh oxi ha chn lc. Vi qu trnh oxi ha Cr3+ Cr2O72-: Dng (NH4)2S2O8/xc tc AgNO3 l hp l. Do: E
0 S2 O 8
2_
/ SO 4
2_
= 2.02V cn E
Cr2 O 7 2 _ / 2Cr 3+
= 1.36V
qu trnh oxi ha Cr3+Cr2O72- bng S2O82- c kh nng oxi ha Mn2+ MnO4c mu tm l mt du hiu cho bit qu trnh oxi ha Cr3+ Cr2O72- kt thc. Do Cr3+ b oxi ha trc ri mi n ion Mn2+. Lng KMnO4 sinh ra c loi bng HCl (hoc loi bng H2C2O4) theo phn ng: 2KMnO4 + 16HCl 2MnCl2 + 2KCl + 8H2O + 5Cl2 . iu kin chun vi h kh Fe2+ Mi trng chun l H2SO4 6N Dung dch chun Fe2+ cn c hiu chnh bng dung dch chun gc K2Cr2O7 vi ch th ferroin. Nn dng ch th Ferroin thay cho ch th diphenylamin hay ch th acid phenyl antranilic v mu tm nht sau im tng ng d b che lp bi mu xanh ca ion Cr3+. 4.2.3. Qui trnh xc nh a. Xc nh Vanai Cn chnh xc (0,20,5) 0,0002g mu, chuyn lng cn vo bnh nn chu nhit 250ml, t phu thy tinh ln ming bnh nn v rt t t qua phu 3040ml hn hp acid (160ml H2SO4 m c + 120ml H3PO4 m c + H2O = 1 lt), un trn bp in c li aming, thm 23ml HNO3 m c vo (khi mu tan gn ht), em c mu n khi c khi trng bay ra. ngui dung dch, thm tng git KMnO4 4% cho ti khi dung dch c mu tm nht, thm nc ct sao cho tng th tch khong 100ml, lc u, un nng ri thm tng git H2C2O4 4% n khi mt mu tm, thm d 3 git H2C2O4 4% na, thm 3 git ch th ferroin ri chun bng dung dch chun Fe2+ 0,02N ti khi xut hin mu nu . Ghi th tch Fe2+ 0,02 N tiu tn cho Vanai l V1. b. Xc nh Crm Dung dch sau khi xc nh Vanadi c chuyn vo bnh nn 250ml, thm 10ml AgNO3 loi 15g/l, 10ml (NH4)2S2O8 10%. un si k dung dch, sau thm 12ml NaCl loi tr KMnO4. Lm ngui dung dch sau thm nc ct sao cho tng th tch trong bnh nn khong 100ml, thm 10ml H2SO4 6N, 3 git ch th ferroin ri chun bng dung dch Fe2+ 0,02N ti khi xut hin mu nu , ghi th tch tiu tn ca Fe2+ 0,02N cho Crm l V2. Khoa CNHH Chuyn ngnh Ha phn tch Trang 22
Phn tch kim loi 4.2.4. Tnh ton %V =
m V ( NV1 ) Fe 2 + 100 mm
V f vi m =
1 51 eVO -%Cr = do VO2+ 3 1000
mCr ( N V 2 )Fe2+ 100 mm

4.3. Phng php so mu 4.3.1. Nguyn tc
f vi m Cr =
52,01 . 3000
Mu c ph bng hn hp HCl, HNO3 v H2SO4 chuyn Cr Cr3+. Sau oxi ha Cr3+ CrO42- v loi tr ion gy nh hng bng KMnO4 trong mi trng kim. Dch chuyn cn bng CrO42- Cr2O72- bng acid H2SO4 ri to phc Cr2O72v thuc th diphenyl carbazid. o hp thu ca phc to thnh bc sng 536nm. Dng phng php ng chun xc nh hm lng Crm c trong mu. 4.3.2. Ha cht v dng c Dung dch HCl m c, HNO3 m c, H2SO4 1:1 v H2SO4 1:4 Dung dch KMnO4 1% Dung dch Na2CO3 20%, ethanol nguyn cht
- Dung dch thuc th diphenylcarbazid 1%: 1g diphenylcarbazid pha trong 100ml aceton pA, ch pha trc khi dng. Dung dch chun gc 0,0001g Cr/1ml: 0,2819g K2Cr2O7 pA/1 lt. Dung dch chun lm vic: pha long 10 ln dung dch chun gc Cc dng c thy tinh cn thit
- My so mu o c t 3001100nm 4.3.3. Qui trnh xc nh - i vi mu: Cn 0,2000 0,0001g mu cho vo bnh nn 100ml, chn bng 1 phu thy tinh nh, rt qua phu 10ml HCl m c, un nng t t ha tan mu. Thm tng git HNO3 n khi ngng si bt, cho d 23ml HNO3, sau un n ht kh NO (ht NO2). Lm ngui dung dch, sau thm 5ml H2SO4 1:1, un n khi bc khi trng. Lm ngui dung dch, thm 30ml nc ct, un nng ha tan mui, thm vo lc dung dch ang nng khong 23ml dung dch KMnO4 1% (dung dch ny c un nng sn), tip tc un nng lng, mui MnO2. Thm tip vo 50ml nc ct, thm tng git Na2CO3 20% (khong 30ml), lm ngui ri chuyn ton b vo bnh nh mc 250ml, nh mc ti vch bng nc ct, lc u v lc qua giy lc bng , b 10ml dung dch u qua lc. Ly 25ml dung dch lc tip theo (nu hm lng Crm t 0,010,06%) hoc 5ml (khi hm lng Crm t 0.060.3%) cho vo bnh nh mc 100ml, thm 3ml H2SO4 1:4, ngui, thm tip 5ml dung dch diphenylcarbazid 1%, nh mc ti vch bng nc ct, trn u, sau 5 pht em o
Trang 23
Phn tch kim loi
=536nm. Kt hp vi ng chun tnh hm lng Crm c trong mu qui v hm lng phn trm Crm (%Cr). - i vi chun: Cho vo 6 bnh nh mc nh s ln lt 2, 4, 6, 8, 10, 12ml dung dch lm vic, dng nc ct nh mc ti vch. T cc bnh ny rt ra 25ml cho vo 5 bnh nh mc 100ml tng ng, khi hm lng Crm tng ng l 0.01 ; 0.02 ; 0.03 ; 0.04 ; 0.05 ; 0.06%. Thm vo mi bnh 3ml H2SO4 1:4 + 5ml dung dch thuc th diphenylcarbazid 1%, ri nh mc ti vch, lc u, sau 5 pht em o cng vi mu =356nm. 5. Xc nh Carbon bng phng php o th tch kh Carbon trong gang thp tn ti di 2 dng: - Carbon t do dng than ch: khi ha tan kim loi bng hn hp acid v c c s tch ra di dng bt mu en. - Carbon ti dng dung dch rn: khi ha tan kim loi trong acid v c c, nng th bay hi ra di dng carbur hydro. Carbon dng kt hp ch yu tn ti dng carbur kim loi nh Fe3C, FeC, Mn3C, Cr3C2 Dng ny l dng tn ti ch yu trong thp, cn trong gang th tn ti dng t do. Lng carbon cao hay thp c nh hng ln n tnh cht ca kim loi, hm lng carbon tng th nng chy ca kim loi gim lm kh khun, gia cng, khi %C > 2% th tng bn v rn nhng gim tnh do. Trong thp %C = 0.50,8%, trong gang th %C =1,56,6%. Khi phn tch thng xc nh carbon ton phn bng phng php o th tch kh. 5.1. Nguyn tc t mu kim loi c cha carbon nhit 120012500C c oxi sch tham gia chuyn ton b C CO2. o th tch hn hp kh trc v sau khi hp thu suy ra th tch kh CO2 iu kin thc nghim, t tnh ra %C iu kin tiu chun. Cc phn ng: C + O2 CO2 (dng t do) 4Fe3C + 13O2 4CO2 + 6Fe2O3 (dng kt hp) Mn3C + 3O2 CO2 + Mn3O4 (dng kt hp) 4Cr3C2 + 17O2 8CO2 + 6Cr2O3 (dng kt hp) CH4 + 2O2 CO2 + 2H2O (dng carbur hydro) 5.2. iu kin xc nh iu kin t mu: V nhit : phi m bo cao hn nhit nng chy ca kim loi, v vy nhit s dng y l 120012500C l ph hp. V ngun kh cung cp phi l kh O2 sch, kh trnh gy sai s khi o th tch: do phng php s dng l phng php o th tch kh Khoa CNHH Chuyn ngnh Ha phn tch Trang 24
Phn tch kim loi
Vn tc cung cp kh phi ph hp sao cho lng kh d thc hin qu trnh t chy mu nhng khng c qu d. Vn tc ca dng kh oxi cung cp c theo di qua bt kh, khong 45 bt/s l ph hp. iu kin ny, ton b C chuyn thnh CO2, cn Fe chuyn thnh Fe2O3 v Fe3O4 (x). ng thi S c trong gang thp cng chuyn thnh SO2, SO3 theo phn ng: 4FeS + 7O2 2Fe2O3 + 4SO2 2SO2 + O2 2SO3 Lng kh ny phi loi b trc khi hp th bng cch cho hn hp kh i qua lp oxit CrO3 hoc dung dch PbCrO4: 3SO2 + 2CrO3 3SO3 + Cr2O3 SO3 + H2O H2SO4 3SO2 + 2PbCrO4 2PbO + Cr2O3 +3SO3 SO3 + PbO PbSO4 Khi lng C trong mu > 3%, khi , nu t theo iu kin trn th s chuyn ha C CO2 khng trit v c phn ng: C +
1 O2 CO. V vy phi chuyn 2
lng CO ny v CO2 bng cch lt vo phn cui ca ng t 1 lp CuO. Khi c phn ng: CO + CuO CO2 + Cu Cu +
1 O2 (d) CuO 2
lng CuO sinh ra li tip tc phn ng trn. Ngoi ra s phn hy C trong mu c nhanh, ngi ta trn vo lng cn mu 1 lng Sn hoc Pb nguyn cht (c th Cu). C th coi cc cht ny nh l cc cht xc tc. V trong iu kin t mu trn th nhng kim loi ny kt hp v lung oxi d lm nhit ca thuyn s tng nhanh lm qu trnh t mu c y nhanh hn v mt thi gian. Ngoi ra qu trnh nhng O2 t cc oxid Sn v oxid ch cho carbon l ng pha rn nn qu trnh xy ra d v trit hn so vi lung kh Oxi (pha kh) i qua b mt mu cha carbon (pha rn). p sut ca lung O2 i vo ng l t mu tt nht 510 kg/cm2. Lng cn mu phi ph hp, nu %C>1,5% th ly 0,5g, %C <1,5% th ly 0,2g. iu kin hp th v o kh CO2: Vic o th tch kh trc hp th v lng kh O2 d sau khi hp th i hi phi chnh xc. Qu trnh hp th kh CO2 vo dung dch KOH phi c tin hnh nhiu ln cho n khi kh c hp th hon ton, nhn bit bng cch theo di n khi th tch Khoa CNHH Chuyn ngnh Ha phn tch Trang 25
Phn tch kim loi
kh cn li sau hp th phi c nh, khng gim. S d khng dng hoc trnh dng NaOH hp th CO2 v d sinh vng Na2CO3 lm c hoc tt kha ca ng o. Qu trnh hp th v o kh phi tun theo nguyn tc v o kh (xem gio trnh phn tch mi trng II). Trong cn ch cch s dng cc b kha ca my o, phi thao tc chnh xc, thun thc, khi y v ht kh sang bnh o phi t t, nh nhng v quan st cht ch mc bin thin ca dung dch i ln. Cc b phn trong my o phi hon chnh, kn. Khi c kt qu lun lun phi c c t0, p iu kin thc nghim. iu kin v thit b: My o C v S thng c 3 b phn chnh. B phn cung cp v lm sch oxy: Gm 3 b phn l bnh thp ng oxy ni vi h thng bnh cha, p k oxy gm c 2 p k, p k th o p sut trong bnh cha thng dao ng t 3035kg/cm2 v p k mn dng o p sut oxy vo l t thng dao ng t 510kg/cm2. Cui cng l h thng lm kh v sch oxy gm 2 bnh ng KMnO4 4% pha trong KOH 30% lm sch O2, bnh cha CaCl2 khan hoc H2SO4 m c lm kh kh O2. B phn l t: Gm cc b phn l nung c bin tr, ng t bng s hay thch anh, thuyn s cha mu, cc vt liu s khng c trng men, ng s =1822mm, L=600mm, 2 u nt bng cao su mm, thuyn s di 7090mm, rng 1012mm, su 810mm. Thuyn s trc khi dng phi nung 120013500C trong 1 gi, ngui n 80900C ri cho vo bnh ht m, ri ly ra dng dn (nhiu thuyn s). B phn bin th in, b phn o nhit. B phn hp th kh CO2: Gm b phn lc bi (ch yu l bi oxit st), b phn hp th kh SO2 cha dung dch acid cromic/H2SO4, b phn lm lnh (ng sinh hn), b kha 3 nhnh, ng o kh V=450500ml 0,01ml, thc o CO2 hoc %C sai s 0,005%, bnh thng bng cha NaCl c th tch 750ml dng ht v y kh, cui cng l bnh hp th KOH. iu kin v lng cn v cht tr dung: Ty theo lng C c trong mu m lng cn c ly theo bng sau: (cht tr dung c th l Cu tinh khit hoc Sn).
THI T B
PHN TCH CACBON TRONG KIM LO I

c
13
14
18
15
Khoa CNHH Chuyn ngnh Ha phn tch 8
4 a
12 http://www.ebook.edu.vn b 7
Trang 26 d
Phn tch kim loi
Loi mu
%C
Lng (g) mu
Lng (g) cht tr dung
Thp carbon Thp hp kim thp Thp hp kim trung bnh Thp hp kim cao (Cr, Ni, Mn)
0,10,4 0,41,0 >1 0,11 >1 0,10,5 >0,5
1 1 0,5 1 0,5 1 0,5
1 1 1 1 1 1 2
1: Bnh Oxi 2,4: Ap k th v mn 3: Bnh cha KMnO4 4% 5: Bnh cha KOH 30% 6: ng o bt kh
c: Van 3 nhnh
12: Bnh cha DD Cr hp d: Van x kh bnh th SO2 13: ng sinh hn lm lnh thng bng 7: ng s hoc ng kh ra khi l 14: Nhit k thch anh 15: ng o kh 16: Thc o kh 17: Bnh thng bng
8: L in a: Van iu chnh O2 t bnh 9: Bng iu khin cha va l b: Van iu chnh hn hp kh 10: Thuyn s ra khi l
11: B phn lc bi 18: Bnh KOH hp th ca hn hp kh ra l CO2
5.3. Qui trnh xc nh Chun b thit b: Trc khi tin hnh t mu phn tch, phi kim tra li kn ca thit b nh sau: nng bnh 17 ln, dung dch NaCl s trn qua y ng o kh 15 ln ti st kha 3 nhnh c, lc kha c ang v tr m thng vi bn ngoi. Khi dung dch y ng 15 th kha c li, ng kha d. M kha b, mc nc trong ng 15 s tt xung 1 t m khng tt xung na th my kn, nu mc dung dch trong ng 15 m c tt dn th my cha kn c th ng s b nt hoc nt cao su 2 u ng s b h. Khoa CNHH Chuyn ngnh Ha phn tch Trang 27
Phn tch kim loi
Khi my kn, th dng mu tiu chun c %C=0,51 kim tra chnh xc ca my. Thng thng 1 tun kim tra 1 ln. Trc khi kim tra mu th phi t l 10001000C bng oxy sch trong vng 2 pht loi ht tp cht cn li trong ng l. Trc khi y thuyn s mu vo l th ng o kh 15 v bnh hp th nhnh tri phi y dung dch, cc kha, van ca thit b tuyt i kn. Tin hnh phn tch: Cn mu vo thuyn s, dng mc y thuyn s vo gia l. y nhanh bng nt cao su ni vi bnh oxy, sau 1 pht, t t m kha a cho oxy i vo ng l sao cho p k mn ch 510kg/cm2 hoc m bt kh 6 sao cho 45 bt kh/s, sau 30s, m kha b v m kha 3 nhnh c cho thng vi ng o kh. Khi dung dch trong ng 15 h n cch vch 0 khong 2cm, ng van a, tt l in, m nt cao su u vo, ly thuyn s ra ngui. Sau 30s, chuyn kha 3 nhnh c v v tr ban u (kha li). Sau cn bng mc dung dch sao cho mc dung dch trong ng o kh 15 v bnh 17 bng nhau. c s o trn thc o %CO2 l V. Quay kha c thng bnh hp th KOH vi ng o kh. Nng bnh thng bng 17 ln cao qu bnh hp th18 y kh trong ng 15 sang bnh hp th 18, h bnh thng bng 17 xung v lp li qu trnh thm 3 ln na. Sau chuyn ton b kh trong bnh 18 v ng o 15 bng cch h bnh 17 xung, sau kha c v v tr ban u (v tr ng kn ban u). Cn bng mc dung dch ng o 15 v bnh thng bng 17. Ghi li s o thc o 16 l V. Ghi p sut v nhit trn nhit k 14. 5.4. Tnh kt qu Theo phng trnh trng thi: Trong : P1, T1, V1 l iu kin thc nghim; P2, T2, V2 l iu kin ch to thc o CO2. Theo qui tc th thc o CO2 trong iu kin p = 760mmHg; T2=273+16 (nghi l 160C) cn V2 gi l VCO2 . P1=P-b vi P l p sut kh quyn (mmHg), b l p sut hi nc bo ha trong ng o kh tra bng t t0 c c nhit k 14. Rp cc thng s vo phng trnh ( ) Ta c: VCO 2 =
16
P1V1 P2V2 ( ) = T2 T1
16
(P b).V1 (272 + 16)(P b) V1 = 0,38 760(273 + t) 273 + t

2 2 2 2
Mt khc:
16 16 m16 = VCO .d16 = 0,001867 .VCO CO CO
16 ( d CO2 = 0,001876 )
Trang 28
Phn tch kim loi
16 M: c 44g CO2 12g C mCO2 th c
12 m16 gC16 CO 44
2
Vy:
%C16
12 m16 100 CO m 100 44 (P b).V1 100 12 0,001867 0,38. = = = mm 273 + t 44 mm mm

16 C
2
%C 0, 0194- h s rt gn
16
0,0194(P b) V1 mm (273 + t)
P- p sut kh quyn (mmHg) (tra bng) b - p sut hi nc bo ha (mmHg) (tra bng) t - nhit c p k 14
V1 = V V' l th tch CO2 (ml)
mm: khi lng mu (g) 6. Xc nh lu hunh (phng php t trong l in) Hm lng S trong gang thp u thp v l thnh phn c hi. Tiu chun cho php phi < 0,05%. Thng tn ti dng sulphur. Thng c xc nh bng phng php t trong l in v chun bng dung dch iod. 6.1. Nguyn tc t mu gang thp 115012500C bng O2 d trong l in. Ton b S dng sulphur s oxi ha chuyn thnh SO2. Kh SO2 c hp th vo H2O. Chun H2SO3 bng dung dch chun I2 vi ch th h tinh bt. Nu kh SO2 c hp th vo dung dch H2O2 sinh ra H2SO4 th chun bng dung dch NaOH vi ch th Tashiro. Cc phn ng: 3FeS + 5O2 Fe3O4 + 3SO2 3MnS + 5O2 Mn3O4 + 3SO2 SO2 + H2O H2SO3 H2SO3 + H2O + I2 2HI + H2SO4 H2SO3 + H2O2 H2SO4 + H2O 6.2. iu kin xc nh iu kin ph mu: Trang 29 H2SO4 +2NaOH Na2SO4 + 2H2O
Phn tch kim loi
Ngun kh O2 cung cp phi trit chng m, k c dng c phn tch. V iu kin t nng, nu trn ng i ca SO2 c hi H2O hoc O2 m th S+4 S+6 do khng tc dng vi I2 gy ra sai s. V lng cn: ty theo hm lng S m ly lng cn ph hp theo bng sau: %S < 0, 01 0, 01 0, 07 0, 07 0, 15 Lng cn mu 1 0, 5 0, 2
Cn c thm cht tr dung Sn + Al2O3 hoc Pb + Al2O3. Nhit : nhit 120013000C l hp l. - Khi lm kh kh O2 bng H2SO4 m c th phi thn trng khi m kha bnh O2, khng c m qu mnh lm tro acid vo cc ng cao su lm ng cao su b chy sinh ra SO2 gy ra sai s v nguy him. Nu lm kh bng CaCl2 khan v vi ti xt th gia 2 lp CaCl2 (nm di) v vi ti xt (lp trn) c ngn cch nhau bng mt lp bng thy tinh. - Thit b o S tng t nh thit b o S trong pyrit gm 3 b phn chnh: B phn cung cp v lm sch oxy, b phn t mu, b phn hp th v chun . b phn cung cp v lm sch oxy gm c: Bnh cha oxy, ng h v van iu chnh tc dng oxy, bnh cha dung dch KMnO4 4% pha trong dung dch NaOH 40%, thp lm kh oxy cha H2SO4 m c hoc hn hp CaCl2 khan + vi ti xt, kha thy tinh 2 hoc 3 nhnh iu chnh dng oxy sch vo l. b phn t mu gm c: Bin tr iu chnh nhit trong l, l in, ng s khng trng men, ng knh trong 1820mm, chiu di sao cho phn l ra 2 u thn l khng ngn hn 180200mm, 2 u c bt kn bng cao su mm c bit chu nhit. Thuyn s khng trng men L=70130mm, rng 742mm, cao 510mm, trc khi s dng thuyn s phi c nung 120013500C, bo qun trong bnh ht m s dng dn. b phn hp th v chun phi c ng lc bi cha bng thy tinh sch, bnh hp th c l cm ng chun v ng hp th kh SO2, u ng dn kh SO2 vo bnh hp th c mng bn thm. - Cn phi loi b trit lng Fe2O3 bm trong ng s v bng thy tinh b phn lc bi v iu kin ny th c nguy c Fe 3+ tc dng SO2 gy ra sai s: 2Fe3+ + SO2 + 2H2O 2Fe2+ + 4H+ + SO42- Dng dung dch hp th H2O c 45 mu phn tch th nn thay dung dch trong bnh hp th.
Trang 30
Phn tch kim loi
- Pha ch th h tinh bt 0,04% 0,1%: 0.5g h tinh bt + 20ml H2O ct khuy u, ri thm 500ml nc si, un 13 pht, lm ngui, thm 3g KI + 3git HCl m c + H2O thnh 1 lt. 6.3. Qui trnh xc nh
a. Qui trnh xc nh theo phng php iod
1 15
THI T B
PHN TCH L U HU NH
3 6
9 7 8 1
12 14 1
17
13
1: Bnh Oxi 8: Thuyn s khng trng 17: C t 18 1 5 4 2,3: ng h v van iu men 18: My khuy t chnh dng O2 9: L in 19: Van x dung dch sau khi 4: Bnh KMnO4 4%/ 10: u bt ng l cao su kt thc th nghim NaOH 40% 11: Bng iu khin 13: Mng bn thm 12: B phn lc bi cha 14: Bnh chun 7: ng s khng trng men bng thy tinh 15: Phu b sung nc 16: Buret Chun b thit b v dng c cho th nghim: Np dung dch hp th vo bnh 14 + 100ml nc ct + 1ml h tinh bt 0,04%, chun b 1 bnh ngoi so snh mu: 100ml nc ct + 1ml HTB 0,04% + 1 git I2 0,05N, dung dch c mu xanh l, mu ny dng lm mu i chng. Khoa CNHH Chuyn ngnh Ha phn tch Trang 31 6: ng o bt kh
Phn tch kim loi Kim tra kn ca thit b.
Gia nhit l t t 120012500C. - Tin hnh xc nh: Cn chnh xc (0,51) 0,0002g mu kim loi trong thuyn s, di y l lt sn 1 lp bt Al2O3 + 1g thic (hoc Pb hay Cu). Khi nhit ca l ln n 12000C dng kp y nhanh thuyn s 8 cha mu vo gia ng l 7. Sau 1 pht m kha 3 cho dng kh O2 vo ng l, dng kha 2 d iu chnh tc oxy vo ng l vi tc 2,5l/pht (45 bt kh/s xem trn ng o bt kh 6). SO2 sinh ra s hp th vo bnh 14. Dng I2 0,05N chun u n tng git t buret 16 cho n khi mu xanh ca bnh chun bng mu xanh ca bnh i chng. Th nghim xong, kha 2 v 3, ngt l in, ly thuyn s ra, lp cc b phn vo nh c, t th tch I2 0,05N tiu tn tnh %S c trong mu.
b. Qui trnh xc nh theo phng php acid-baz
Cc bc chun b tng t nh phng php Iod, nhng np vo bnh 14 khong 100ml dung dch H2O2 trung tnh + 3 git ch th Tashiro. Cn mu vo thuyn s, thm 0,250,5g Sn hoc Cu. Dng kp y thuyn s vo gia ng l sau khi nhit l t n 12000 C. Sau 1 pht, m kha 3 v 2, dng kha 2 iu chnh tc v ca dng oxy l 2,5l/pht. SO2 sinh ra c hp thu vo dung dch H2O2 bnh 14. Chun u n dung dch NaOH tng git cho n khi dung dch t mu tm chuyn sang xanh lc n nh. 6.4. Tnh ton %S = Vi m = chnh.
S
m S ( NV ) I 2 100 mm
2
m S ( NV ) NaOH 100 = mm
32 , NI v NNaOH l nng ca cc dung dch sau khi hiu 2000
7. Xc nh Ni trong thp hp kim Cng nh Cr, Ni tn ti trong hp kim di dng Ferro-Niken. Hp kim Ni c nhiu c tnh qu nh tnh chu mi mn, tnh n hi, chng r tt. Trong phn tch, ty thuc lng Ni cao hay thp m c th s dng mt trong cc phng php sau: Phng php khi lng khi %Ni > 0, 5%. Phng php so mu Phng php in phn
7.1. Phng php khi lng dioximat 7.1.1. Nguyn tc
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Phn tch kim loi
Mu c ph bng hn hp acid HCl + HNO3 un nng. Ni kim loi s chuyn thnh ion Ni2+. Loi b ion gy tr ngi v kt ta ion Ni2+ di dng kt ta nikendioximat bng thuc th dimethylglyoxim trong mi trng kim amonic. em lc, ra kt ta, sy kh 1200C hoc nung 8500C chuyn thnh NiO. Cc phn ng: Ni2+ + 2HCl NiCl2 + H2
OH CH3 2 CH3 C C N N OH OH CH3 CH3 C C N Ni N O N OH C O N C CH3 CH3
Ni
2+
+ 2H
2Ni2+ + 4C4H8O2N2 + 2NH4OH 2Ni(C4H7O2N2)2 + 2H2O + 4NH4Cl 7.1.2. iu kin xc nh - iu kin ph mu: Dng HCl c c thm HNO3 un nng ph mu. HNO3 oxi ha Fe2+ Fe3+ lm mu tan nhanh. Vi hn hp acid ny, ngoi Fe, Ni tan cn c cc hp cht carbur ca Cr, Vanadi, W, Mo cng tan trong dung dch. - iu kin loi b ion tr ngi: Trong iu kin kt ta Ni2+ mi trng kim NH4OH th cc ion kim loi nh Fe, Cr, V, W...cng kt ta hydroxyt, tuy nhin v hm lng thp nn cng c th p dng bin php che vi cht che l citrate hay tartrate.
CH2 OH C CH2 COO COO COO Me hay HOOC HOOC CH CH O O Me
phc citrat
phc tartrat
- iu kin kt ta: Kt ta Ni2+ vi thuc th dimethylglyoxim l kt ta dng tinh th, ht mn, c tnh kim, d tan trong acid, d nt vn, khi un nng th vn cc v c tan tng khi thuc th d nhiu. V vy cn phi kt ta trong mi trng NH4OH, dung dch nng, long, trnh khuy trn nhiu, khi cho thuc th vo th cn un nng nh kt ta vn chc, lc trn giy lc dy. Lng thuc th phi cho thch hp. C 0,1g Ni th cn 10ml thuc th dimethylglyoxim 1% pha trong C2H5OH 500. - iu kin x l kt ta: C th lc kt ta bng phu lc xp thy tinh s 4 vi bm ht chn khng hoc lc qua giy lc bng vng, gim tan ca kt ta nn ra s b kt ta bng dung dch NH3 1%, sau ra bng cn 500. Lng cn mu phi ly ph hp, ty theo hm lng ca Ni m ly lng cn theo bng sau: Khoa CNHH Chuyn ngnh Ha phn tch Trang 33
Phn tch kim loi %Ni Lng cn mu (g) 7.1.3. Qui trnh xc nh 0,5 2
Chng 1: Phn tch kim loi en 0,51 1 15 0,5 59 0,2
Cn 0,2 0,0002g mu trong bnh nn 250ml chu nhit, thm 30ml HCl 1:1, un nh trn bp in c li aming, khi mu tan gn ht, thm tng git HNO3 1:1 cho ti khi mu tan hon ton, un tip n khi ht khi nu bay ra. Nu mu c W, Si th lng HNO3 m c t 35ml, un si tch H2WO4, sau thm 10ml HCl m c, c n kh, ri thm 10ml HCl 1:1 vo, thm nc ct si, lc b H2WO4 v H2SiO3, dng HCl 1/20 ra b trn lc cho n ht ion Fe3+. Dung dch qua lc v nc ra tp trung vo cc thy tinh 250ml, thm 20ml acid citric loi 250g/l, dng NH3 1215% trung ha n pH=67. Nu c Ni2+ th dung dch c mu xanh nn chui. Thm 510ml dung dch thuc th dimetylglyoxim trong cn 500, thm 12ml NH3 12,5% na, khuy nh ri un nng dung dch ln khong 70800C, lng kt ta 20 pht, em lc qua giy lc nh lng bng vng bit trc khi lng giy, dng nc ct nng (60700C) ra 3 ln, ra bng C2H5OH 500 1 ln, em sy 1200C trong 6090pht, trong bnh ht m 30 pht ri em cn. Hoc sau khi ra xong, chuyn kt ta vo chn nung bit trc khi lng, nung 8500C khong 5060 pht, ly ra ngui bnh ht m 30 pht ri cn. 7.1.4. Tnh ton %Ni = f =0,2032 (phng php sy) Hoc f = 0,7853 (phng php nung). 7.2. Phng php so mu 7.2.1. Nguyn tc Phng php da trn vic to phc ca Ni2+ vi thuc th dimetylglioxim hp thu =530nm trong mi trng NH4OH. Da vo ng chun xc nh hm lng ca Ni. 7.2.2. Qui trnh xc nh - Mu: Ha tan lng cn mu (% Ni=0,1 th cn 0,5g, %Ni>0,15 th lng cn l 0,25g) trong becher 250ml bng 30ml H2SO4 1/5, un n tan ht, thm tip 45 git HNO3 m c, un 3 pht, nu mu cha tan ht, thm tip 10ml HCl 1:4 + 20ml HNO3 m c + 30ml H2SO4 1:5, c n khi xut hin khi trng. ngui, chuyn sang bnh nh mc 250ml, thm nc ti vch nh mc, lc u, lc b 2025ml dung dch u. Dng pipet ly 25ml dung dch qua lc cho vo bnh nh mc 100ml, thm 20ml dung dch acid citric 100g/l, 5ml HCl 1:5 + 5ml hn hp dung dch KBrKBrO3 (39g KBr + 10g KBrO3 + H2O = 1 lt) + 25ml NH3 15%, lc u, dng nc ct nh mc ti vch. Dng pipet rt ra 1 th tch chnh xc 50ml cho vo 2 bnh, 1 Khoa CNHH Chuyn ngnh Ha phn tch Trang 34
m 100 f m
Phn tch kim loi
bnh thm vo 1ml thuc th dimethylglyoxim, cn bnh kia lm mu trng, lc u, sau 5 pht em o 530nm. Khng c qu 25 pht sau khi cho thuc th vo. - Chun: c tin hnh t dung dch Ni tiu chun c pha t 0,1g Ni ha tan v nh mc thnh 250ml. S im chun khng k mu trng l 5 im. Ht vo cc bnh 250ml l 2, 4, 6, 8, 10ml dung dch Ni tiu chun, sau tin hnh tng t nh mu xc nh. 8. Xc nh Wonfram (W) bng phng php chun acid-baz 8.1. Nguyn tc Mu c ph bng acid HCl c HNO3, W tch ra khi mu di dng kt ta H2WO4, lc, ra kt ta cho sch ht acid. Ha tan kt ta bng lng kim NaOH tiu chun d chnh xc, chun lng d NaOH bng dung dch chun HCl vi ch th pp cho n khi dung dch t mu hng sang khng mu. Cc phn ng: W + 2HNO3 H2WO4 + 2NO H2WO4 + 2NaOH Na2WO4 + 2H2O NaOH d + HCl NaCl + H2O PP 8.2. iu kin xc nh - iu kin ph mu: HCl ng vai tr ha tan mu, HNO3 dng ha tan cc kim loi ng sau H2, oxi ha Fe2+ Fe3+ lm mu tan nhanh v trit . c bit HNO3 lm tc nhn kt ta W. Khi cho acid th HCl phi cho vo trc, n khi mu tan gn ht mi thm HNO3 vo, trnh tnh trng HNO3 vo trc s ta H2WO4 lm cn tr qu trnh ha tan mu v tiu tn lng HNO3 khng cn thit. Khi c kh mu, nu dng HCl th c kh nnh hnh thnh keo H2SiO3. Lng kt ta keo ny s cng kt vi kt ta H2WO4 lm cho qu trnh kt ta H2WO4 nhanh v kt ta H2WO4 d mui v hnh thnh cu trc nhanh hn. C th xem keo H2SiO3 nh l cc mm kt tinh ban u, xc tc cho s hnh thnh kt ta H2WO4. - iu kin kt ta: kt ta H2WO4 chc, to ht cn phi c kh trc khi lc, lng HNO3 cho vo sau cn c tc dng ha tan cc kim loi khng tan trong HCl, trnh cc kim loi ny ln trong kt ta cn tr qu trnh lc, ra v ha tan kt ta sau ny. - iu kin ra, lc v ha tan kt ta: Do c kh nng kt ta H2WO4 c ln kt ta keo H2SiO3 c nht ln, nn khi lc kt ta th cn thm nc ct nng vo gim nht ca keo H2SiO3 lm cho qu trnh lc nhanh hn. Ngoi ra khi c cn th cc kim loi hnh thnh cc mui kt tinh, v vy vic thm nc ct nng vo sau khi c kh lc kt ta H2WO4 l cn thit. Do cn gi kt ta trn lc, v vy phi lc bng giy lc bng xanh, trnh kt ta lt qua giy lc. Khi ra kt ta phi chc chn ra ht acid. V kt ta H2WO4 c tnh acid, v vy cn phi dng kim mnh qu trnh ha tan xy ra d dng, trit , sau khi ha tan xong, phi dng nc ra ht lng kim do phng php xc nh theo k thut chun ngc lng kim d ny.
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Phn tch kim loi
- trnh tnh trng giy lc nt do ngm lu trong dung dch, gy ra hin tng hp ph ch th, lm ko di im cui chun , v vy cn phi ha tan kt ta trn giy lc. - Ti im tng ng, tn ti mui Na2WO4 l mui baz mnh, acid yu nn pH tng ng ri vo vng kim, v vy dng ch th PP l hp l. 8.3. Qui trnh xc nh Cn 1 0,0002g mu thp hp kim dng phoi nh c cha W vo bnh nn. Rt qua phu vo bnh nn 30ml HCl 1:1, un si mu trn bp cch ct hoc bp in c li aming. Thm 45ml HNO3 m c, c gn kh, thm tip 23ml HNO3 m c. C kh mu v ngui. Thm 100ml nc ct nng (80900C), khuy u, lc qua giy lc bng xanh. Ra kt ta bng dung dch HCl 1% nng 1 ln, sau dng nc ct nng ra cho n ht acid (dng giy qu tm th), thay bnh nn mi c 3 git PP 1%. Ha tan kt ta trn giy lc bng dung dch NaOH 0,1N n khi dung dch qua lc c mu hng, thm d 5ml dung dch NaOH 0,1N na, ra giy lc n khi ht NaOH bng nc. Sau o em i chun bng dung dch HCl 0,05N n khi dung dch mt mu hng. 8.4. Tnh ton kt qu
%W =
m W [( NV ) OH _ _( NV ) H + ] m mau
Vi mW =
100
184 2000
9. Xc nh ng trong thp bng phng php chit trc quang 9.1. Nguyn tc Mu thp c ha tan bng acid H2SO4 v HNO3 chuyn Cu kim loi trong hp kim thnh Cu2+. Loi tr cc ion gy nh hng bng acid tartric (hoc acid citric) v KCN vi k thut che, nng pH v chit Cu2+ ra khi mu di dng phc diethyldithiocarbamat ng bng dung mi CHCl3 c cha thuc th ch diethyldithiocarbamat. em o v so snh mt quang ca mu vi chun bng k thut so snh 1 chun vi mu trng l dung mi CHCl3. 9.2. iu kin xc nh iu kin ph mu Vi h s pha long 10 ln th lng cn mu l 0,250,5g ha tan v nh mc thnh 100ml l ph hp. H2SO4 ng vai tr l dung mi, tuy nhin nng ca n khng qu long, vi loi H2SO4 1:4 l ph hp, HNO3 c thm vo ha tan nt phn kim loi khng tan trong H2SO4, ng thi oxi ha Fe2+ Fe3+. Cn phi loi b trit NO ra khi dung dch, v NO ha tan trong nc c th ng vai tr l 1 ligand to phc nitroso.
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Phn tch kim loi
- Loi b ion gy tr ngi: Do qu trnh to phc ca Cu2+ vi diethyldithiocarbamat thc hin trong mi trng kim, y l mi trng kt ta nhiu ion kim loi ha tr II, III. c bit l Fe3+, Mn2+, Ni2+, Cr3+ v vy cn phi loi tr. Bin php n gin l dng cht che ph hp, vi kim loi ha tr III th dng acid tartric, vi kim loi ha tr II th dng KCN. Qu trnh che cn thc hin trc khi nng pH ln mi hiu qu, v vy thm acid tartric trc khi nng pH ln 89 bng NH3. iu kin thuc th v dung dch chun Do phc ca Cu2+ v diethyldithiocarbamat l hp cht t phn cc, kch thc phn t ln nn n u tin phn b vo cc dung mi khng phn cc hoc phn cc km. qu trnh chit tin hnh n gin, nn chn dung mi c t trng ln hn nc. V vy vic chn dung mi CHCl3 hay CCl4 l ph hp. Do thuc th diethyldithiocarbamat tan trong nc, km bn, d h. thuc th bn th pha n trong dung mi dng chit l CHCl3. Nhng v diethyldithiocarbamat l hp cht phn cc nn khng tan c trong CHCl3. tan c trong CHCl3 th phi to phc vi 1 ion kim loi sao cho phc ca n vi diethyldithiocarbamat bn nhng li km bn vi Cu2+. Ion kim loi l Pb2+. Cch iu ch dung dch ch diethyldithiocarbamat nh sau: chun b 2 phu chit 125ml, thm vo 1 phu chit 4ml dung dch acetat ch 1% (pha trong CH3COOH 1:3) + 2ml KNO3 10% + 2ml dung dch KCN 5% + 4ml natridiethyl dithiocarbamat 1% pha trong nc, lc u, khi s c kt ta trng ch diethyl dithiocarbamat, thm vo phu chit ny 100ml dung dch CHCl3 lc ha tan kt ta, sau ch tch lp, chuyn pha hu c qua phu chit khc. Ra 23 ln bng nc, sau lc lp dung mi qua phu c lt giy lc kh v c 1 t Na2SO4 khan, dch qua lc thu vo bnh thy tinh mu nu c nt nhm. Dung dch chun: c pha t Cu kim loi nguyn cht trong HNO3 c c dung dch 500ppm (0,5g Cu/1lt). Hoc c pha t Cu(NO3)2 pA vi nng tng t, ch khi pha t mui th phi tm t lng cn Cu(NO3)2 bng HNO3 m c trnh qu trnh thy phn. Dung dch lm vic pha long t dung dch chun 10 ln v ch pha trc khi dng (50 ppm). iu kin chit Mi trng chit pH = 89 c iu chnh bng dung dch NH3 1:1 v 25% vi Cresol 0,1%/C2H5OH lm ch th ( tm). Thi gian lc l 1,5 pht, thi gian tch lp l 0,5pht, s ln chit l 2 ln, mi ln l 10ml ch diethyl dithiocarbamat/CHCl3, trnh to nh, bt kh trong qu trnh lc chit. Khi ly pha hu c ( c phc ng diethyldithiocarbamat) vo bnh nh mc o khng c php c ln nc (c), cn x hi trnh p sut cao trong phu chit. iu kin o: Phi o ngay sau khi chit bng cuvet thy tinh 1cm, phi c np y trnh hi dung mi CHCl3 bay ra lm h my v mt quang khng n nh. Bc sng o l 430436nm. 9.3. Qui trnh xc nh Khoa CNHH Chuyn ngnh Ha phn tch Trang 37
Phn tch kim loi
- Cn 0,20,5g mu (ty theo hm lng) cho vo bnh nn 100ml, rt qua phu thy tinh 15ml H2SO4 1:4, un nng nh ha tan mu, sau thm tng git HNO3 m c n khi ngng si bt kh, un tip n khi ht kh NO (ht khi nu NO2), ngui. Chuyn dung dch vo bnh nh mc 100ml, nh mc ti vch bng nc ct, lc trn u. - Dng pipet ly chnh xc 1020ml dung dch trn (cha khng hn 0,5mg Cu), cho vo phu chit loi 125ml, thm vo 10ml dung dch acid tartric 10% (C4H4O6), lc trn u, thm 3 git ch th Cresol , dng NH3 25% trung ha n mu tm, thm d 10ml NH3 10%, thm 10ml dung dch ch diethyldithiocarbamat/CHCl3, lc chit 1,5pht, yn 0,5 pht, chit lp hu c vo bnh nh mc kh 25ml, lp li qu trnh chit thm 1 ln na, dng CHCl3 nh mc ti vch. em o = 430nm hoc 436nm. - Vi chun lm tng t, ch thay dung dch mu bng 10ml dung dch Cu2+ 50ppm. 9.4. Tnh ton kt qu
Am Ac A 100 = C m = m Cc %Cu = Cm f Cm Cc Ac mm
( C m s gam Cu c trong VX)
IV. CU HI N TP V BI TP
1. Trnh by ngha ca vic ly mu khi phn tch cc ch tiu ha l trong kim loi en. 2. So snh v gii thch cc k thut ly mu kim loi tng ng vi cc dng mu khc nhau: Tm, thanh, thi, l nung? 3. Trnh by nguyn tc, phn ng, iu kin xc nh khi phn tch ch tiu Silic bng phng php trng lng? 4. Trnh by nguyn tc, phn ng, iu kin xc nh khi phn tch ch tiu Silic bng phng php so mu? 5. Trnh by nguyn tc, phn ng, iu kin xc nh khi phn tch ch tiu Photpho bng phng php th tch molybdate? 6. Trnh by nguyn tc, phn ng, iu kin xc nh khi phn tch ch tiu Photpho bng phng php so mu? 7. Trnh by nguyn tc, phn ng, iu kin xc nh khi phn tch ch tiu Mn bng phng php Persulfat bc? Khoa CNHH Chuyn ngnh Ha phn tch Trang 38
Phn tch kim loi
8. Gii thch nhng im khc bit khi phn tch Mn trong gang v thp vi ba trng hp: c loi crom; khng loi crm v trong li thp bng phng php persulfat bc? 9. Trnh by nguyn tc, phn ng, iu kin xc nh khi phn tch ch tiu Mn trong thp bng phng php so mu? 10. Trnh by nguyn tc, phn ng, iu kin xc nh khi phn tch ch tiu Crm trong thp bng phng php iod? 11. Trnh by nguyn tc, phn ng, iu kin xc nh khi phn tch ch tiu Crm bng phng php persulfat bc? 12. Trnh by nguyn tc, phn ng, iu kin xc nh khi phn tch ch tiu Crm bng phng php so mu? So snh u v nhc ca 3 phng php phn tch crm. Phm vi p dng cho tng phng php? 13. Trnh by nguyn tc, phn ng, iu kin xc nh khi phn tch ch tiu Carbon bng phng php o th tch kh? 14. Trnh by nguyn tc, phn ng, iu kin xc nh khi phn tch ch tiu S bng phng php Iod v phng php trung ha? u v nhc ca mi phng php? 15. Trnh by nguyn tc, phn ng, iu kin xc nh khi phn tch ch tiu Niken bng phng php trng lng? 16. Cho bit khi h s pha long f = 1, hm lng ca Si dao ng t 0.5 3% th chnh lch chn cn l bao nhiu. Bit rng lng cn mu dao ng t 0.2 3 gam? 17. Cho bit trong 0.5469g kt ta keo SiO2 c ln 6,8% Fe2O3. Cn phi dng bao nhiu ml HF 30% x l ht lng SiO2 ? cho php HF d 10%? Sau khi x l xong, chnh lch trong lng ca chn trc v sau khi x l HF l bao nhiu? Nn dng cn my s l? V sao? 18. Cho bit %Si trong mt mu thp l 0.1 0.2%. Lng cn mu l 0.2 gam ha tan v nh mc 100ml, rt ra 10ml xc nh. Cn bao nhiu ml dung dch Amonimolybdate 5% to phc Silicomolybdate cho php thuc th ny d 10% v bao nhiu ml dung dch mui morh 4% kh ht phc silicomolybdo ln phc silicomolybden? Nu d 20% th th tch mui morh l bao nhiu? Khoa CNHH Chuyn ngnh Ha phn tch Trang 39
Phn tch kim loi
19. nh lng Silic trong mt mu thp bng phng php so snh. Bit mu cha khong 0,4% SiO2, ha tan thnh 100ml dung dch mu, dng 5ml mu to phc thnh 50ml dung dch o vi cuvet 1cm. Tnh lng cn mu khi o thi mt quang Am ( 0.2 0.6). Bit rng khi o mt dung dch chun Si c hm lng Si trong bnh o l 0.2mg vi cng th tch, cng cuvet th A= 0.45? Tnh h s ca phc to thnh? Nu dng phng php thm chun th Am+ C l bao nhiu? 20. nh lng P trong mt mu gang bng phng php th tch molybdate: - Dung dch mu: Ha tan 2.0000 gam mu gang, sau khi chuyn ha qua cc cng on tin hnh kt ta P di dng vng molybdat, lc , ra v ho tan kt ta bng 12.5ml NaOH 0.1N. Chun lng d ca NaOH th tiu tn ht 6,2ml HCl 0.05N. Tnh hm lng %P c trong mu thp? Vi lng P c trong mu gang, hy tnh th tch (NH4)2MoO4 15% kt ta ht P c trong mu, bit rng thuc th dng d 5% so vi l thuyt ca phn ng. - cng on chuyn ha photphor ln photphoric cn phi dng bao nhiu git KMnO4 4%? Bit ch cho php d 5% so vi lng cn thit, 1ml KMnO4 4% xp x 20 git. - Gii thch s khc nhau trong qui trnh xc nh P bng phng php th tch molybdate ca mu gang v mu thp? 21. nh lng P c trong mu thp bng phng php so mu: Cn 1.0457 gam mu thp tin hnh cc bc ph mu, loi tr cc yu t nh hng, ln mu v kh ln xanh molybden v nh mc thnh 100ml dung dch o bc sng 680nm c Am = 0.548. Dung dch chun c chun b t 0.1g mu thp tiu chun 0.02% v tin hnh tng t nh mu xc nh ri o c Ac = 0.487. Tnh %P c trong mu thp. Trng hp dng phng php thm chun th cn bao nhiu ml dung dch chun c T = 0.1mgP/ml hm lng ca P tng ng vi hm lng ca 0.1g mu thp tiu chun 0.02%?. Nu trong 1 gam mu thp c tng hm lng Al + Fe l 98.9% th can bao nhiu gam NaF che ht hai ion ny?
22. Tin hnh phn tch Mn trong mu gang bng phng php Persulfat bc. Bit hm lng ca Mn c trong mt mu gang dao ng t 1 2%. Tnh lng mu Khoa CNHH Chuyn ngnh Ha phn tch Trang 40
Phn tch kim loi
cn cn sau khi ha tan to thnh dung dch em chun bng dung dch Fe2+ th th tch dung dch chun tiu tn t 5 8 ml. 23. nh lng Mn trong mu thp bng phng php so mu vi k thut thm chun: Cn 0.5 gam mt mu thp ha tan v nh mc thnh 50ml ( DD I). Dung dch mu 1: 20ml dung dch 1, tin hnh oxi ha Mn2+ ln MnO4- bng 0.05 gam KIO4 trong mi trng H2SO4 6N, nh mc thnh 25ml dung dch o bc sng 550nm c Am = 0.452. Dung dch mu 2: 20ml dung dch I + 2ml dung dch chun Mn2+ 0.001M, tin hnh oxi ha bng KIO4 tng t nh mu dung dch 1, nh mc thnh 25 ml dung dch em o c Am+c = 0.628. Tnh %Mn c trong mu hp kim Theo phn ng l thuyt ca qu trnh oxi ha th KIO4 thc t s dng d bao nhiu % mi bnh dung dch 1 v dung dch 2? 24. nh lng crm c trong mt mu thp bng phng php so mu: Oxi ha Cr3+ ln Cr2O72- bng mt lng d S2O82- trong mi trng acid Vit phng trnh phn ng? Bit Cr2O72- hp thu bc sng 455nm, c h s = 1800 cm-1.mol-1.lt. Cho bit Fe3+ c nh hng n kt qu nh lng khng? Bit phc Fe Oxalate khng mu, c th dng oxalate loi tr nh hng ca Fe3+ c khng? Nu c tnh nng ti thiu tng qut ban u ca oxalate cn thm vo dung dch o loi tr nh hng ca Fe3+. Trong thc t phn tch Crm trong thp, c th dng k thut che loi tr nh hng ca Fe3+ khng? V sao. Nu mt bin php bit loi tr nh hng ca Fe3+ ? Nu hm lng ca Crm l 5%, tnh lng cn mu cn cn sau khi ph mu, nh mc thnh 100ml, dng 10ml oxi ha ri nh mc thnh 100ml dung dch o. Bit my ch lm vic vi Ao 3, cuvet c l = 1cm. Nu dng phng php so mu vi thuc th Diphenylcarbazid vi k thut thm chun, khi lng cn mu l 0.2 gam ha tan, x l thch hp v nh mc thnh 250ml. T dung dch ny ly 25ml cho to phc vi thuc th ri nh mc thnh 50ml o bc sng 356nm thu c Am = 0.255 (DD mu). Tin hnh trong iu kin tng t nh DD mu, nhng c thm vo 3ml dung dch chun Cr 0.01mg/ml em o thu c Am+c = 0.362 ( DD mu + chun). Tnh hm lng %Cr c trong mu thp? Trang 41
Phn tch kim loi
25. a/ Cn m gam mt mu thp hp kim, ha tan v x l thch hp tin hnh phn tch Ni theo phng php trong lng thu c 100ml dung dch. Ly 20 ml dung dch i kt ta Ni bng dung dch Dimetylglyoxim. Tnh m mu m [ 0.2 0.3] gam. Bit hm lng Ni c trong mu thp khong 5% v kt ta thu c x l theo phng php nung? Cho bit hm lng st c trong mu thp l 90%, hy tnh th tch ca acid citric 250g/l che ht st c trong 20ml dung dch em kt ta? b/ Do hm lng Fe c trong mt mu thp khng loi tr trit bng phng php che v hm lng Ni nh nn mt k thut vin xc nh bng phng php chit trc quang nh sau: Cn 0.2 gam mu ha tan bng acid v nh mc thnh 100ml, to phc vi Dimetylglyoxim v c chit qua dung mi CHCl3 pH = 8 vi th tch dung dch o l 50ml , bc sng o l 375nm, = 3500 cm1 .mol-1.lit. truyn quang Tm = 42%. Tin hnh chit lng niken chun t 2ml dung dch Ni2+ 0.001M vi iu kin nh mu thu c Tc = 45,5%. Tnh hm lng ca Ni c trong mu thp bit MNi = 58.7 v A = 2 LgT. 26. Mt k thut vin tin hnh phn tch hm lng S trong gang bng phng php trng lng thay th cho phng php th tch iod v phng php acidbaz. Cn 4.6728 gam mu. Ha tan bng HCl 1:1 trong h thng kn. H2S sinh ra c dn vo bnh hp th Cd2+ d sinh ra mt kt ta CdS tng ng. Chuyn ha kt ta CdS bng dung dch CuSO4 d trong iu kin thch hp thu c CuS. Nung CuS iu kin nhit v thi gian xc nh thu c 0.05849 gam CuO. Tnh %S c trong mu gang. Nu cng vi mu gang trn, nhng lng cn gim 5 ln th tiu tn ht bao nhiu ml I2 0.05N? 27. nh lng Cu trong mt mu thp bng phng php chit trc quang vi thuc th Dithiocarbamatnatri, cn 0.5 gam mu, ha tan v x l mu thch hp ri nh mc thnh 100ml. T dung dch ny rt ra 20ml em chit bng CHCl3 vi th tch dung dch o l 25ml. Dung dch chun c chun b tng t nh mu, cha 10g Cu2+ trong th tch dung dch o l 20ml. o hp thu ca chun v ca mu bc sng 436nm vi l = 1cm. Kt qu Ac = 0.420 v Am = 0.356. Tnh hm lng ca Cu (ppm) trong mu?
Trang 42
Phn tch kim loi
CHNG 2 PHN TCH KIM LOI MU

Trn 80 nguyn t kim loi tm ra th ch c Fe, Cr, Mn l kim loi en, s cn li thuc nhm kim loi mu. Tuy s kim loi mu nhiu nhng tr lng li thp. Cc m kim loi mu khng tp trung m phn b ri rc, tr lng thp. Kim loi mu c mt v tr quan trng trong nhiu ngnh cng nghip nn c nh hng n nn kinh t quc phng. Kim loi mu c mt s tnh cht quan trng sau: nng chy khng cao nh Ag:960oC, Au:1063oC, Cu:1085oC, Sn:232oC C tnh do tt. Cc c tnh nh bn nhit, un do, n hi, kh nng chng mi mn tt. c bit l tnh dn in v dn nhit cao, c t tnh cao nh Ni, Co. Mt s c tnh phng x nh uranium, thorium. Mt s c tnh bn v tr ha hc, kh b oxi ha, rt qu, khng b r st, oxi ha nh Au, Pt
Trong cng nghip, kim loi mu s dng rng ri v vi lng ln l cc hp kim ng, hp kim nhm v hp kim km. V vy, ni dung chnh ca chng ny s cp n ni dung phn tch ca 3 hp kim ny.
I. PHN TCH HP KIM NG

Trong hp kim ng, ch yu l ng thau c cc thnh phn sau: Kim loi H.lng % Cu 84-85 Sn 3-4 Zn 6-7 Pb 4-5 Ni 0.5-1.0 Fe 0.5-1.8
Ni dung phn tch hp kim ng ch yu l phn tch Pb, Sn, Zn. Cn Ni th xc nh tng t nh trong thp. 1.1. Xc nh Pb trong hp kim ng bng phng php cromat xc nh ch trong hp kim ng, thng s dng phng php in phn v phng php th tch cromat. Vi phng php in phn c th xc nh ng Pb v Cu; nhng c nhc im l chm v cn c thit b in phn. Nu ch xc nh ring l Pb m khng yu cu xc nh hm lng Cu th thng dng phng php th tch cromat. 1.1.1. Nguyn tc Mu hp kim ng c ha tan bng hn hp acid HCl v HNO3. Pb kim loi s chuyn thnh ion khi mu ha tan. Tch ch ion ra khi mu di dng kt ta PbCrO4 bng lng d thuc th K2CrO4 pH=5-6. Lc, ra kt ta v ha tan kt ta bng HCl d trong iu kin ny sinh ra lng CrO42- tng ng. iu chnh mi trng thu c Cr2O72- tng ng, sau dng phng php I2 hay phng php Fe2+ xc nh. Khoa CNHH Chuyn ngnh Ha phn tch Trang 43
Phn tch kim loi Cc phn ng:
3Pb + 8 HNO3 3Pb(NO3)2 + 2NO + 4H2O Pb2+ + CrO42pH =56
PbCrO4
PbCrO4 + 4HCl PbCl4- + CrO42- + 4H+ 2CrO42- + 2H+ Cr2O72- + H2O Phng php Iod vi k thut chun th: Cr2O72- + 6I-d +14H+ 2Cr3+ + 3I2 + 7H2O
I2 + I- I 3
2 I3- + 2S2O 3
HTB
Ferroin
S4O62- + 3I2Cr3+ + 6Fe3+ + 7H2O
Phng php Fe2+ vi k thut chun trc tip: Cr2O72- + 6Fe2+ + 14H+ 1.1.2. iu kin xc nh iu kin ph mu:
2+
Do E0Pb / Pb = 0.126V ; E0 NO 0,744V >> 0,3V

E0 Cu / Cu = 0.345V , 0,615V >> 0,3V
2+
,H+ / NO
= 0.96V E = 0,96 - 0,126 =
E0NO
,H+ / NO
= 0.96V
E = 0,96 0,345 =
Hp kim ng c cha ch tan rt tt trong mi trng acid HNO3. Tuy nhin, trong hp kim ng cn c Sn, tan trong HNO3 to Sn4+, ion Sn4+ d b thy phn, c bit l iu kin kt ta PbCrO4 gy cn tr cho qu trnh lc ra v ha tan kt ta PbCrO4. V vy cn thit phi tch Sn ra khi dung dch cha Pb2+ v Cu2+ trc khi tin hnh kt ta PbCrO4. Bin php tt nht l tch Sn ra bng cch thm HCl vo trong qu trnh ph mu, khi Sn tan v to mui phc thic clorua, mui ny d b thy phn khi c kh to kt ta keo Sn(OH)4 tch ra khi dung dch d dng. 3Sn + 4HNO3 + 18HCl 3H2[SnCl6] + 4NO + 8H2O H2[SnCl6] + 4H2O Sn(OH)4 + 6HCl - iu kin v lng cn: Lng cn c tnh ton trn c s l lng kt ta PbCrO4 thu c khng qu t s mc sai s trong qu trnh lc ra v ha tan kt ta, nhng nu lng kt ta qu nhiu s ko di thi gian phn tch khu lc, ra kt ta v chun , c bit l c nguy c mc sai s d do ra kt ta khng sch ht ion CrO42- thuc th. Mt khc lng cn cng phi c tnh ton sao cho th tch tiu tn cho qu trnh chun tt nht l 5-10ml (xem phn phn tch nh lng). Hy lm mt s php tnh ton s b nh sau: Khoa CNHH Chuyn ngnh Ha phn tch Trang 44
Phn tch kim loi
Gi s dung dch chun Na2S2O3 0,05 N (hoc dung dch chun Fe2+ 0,05 N), %Pbmu = 5% Theo cng thc:
m Pb ( NV ) R 100 6,91( NV ) R %Pb = = mm mm

mm =
6,91( NV ) R = 0,0691VR 5
Vi VR = 5-10ml mmu = 0,3455g - 0,691g. Vy lng cn ly thch hp l t 0,35g-0,5g. iu kin loi b ion gy tr ngi Do iu kin kt ta PbCrO4 PH=5-6, y l iu kin kt ta Fe(OH)3 do phn ng thy phn l kt ta v nh hnh, thnh phn kt ta ny khng ch c Fe(OH)3 m cn c Fe(OH)2+ Hay FeOH2+. Cc dng ny mang in tch dng l cc ht keo rt d hp th ion mang in tch m, c bit l ion CrO42-. Mt khc, do c tnh b mt ca dng kt ta v nh hnh Fe(OH)3 rt d hp th ion l, nht ln. y l nhng nguyn nhn chnh ca cn tr qu trnh kt ta PbCrO4, lm kt ta PbCrO4 nhim bn v c bit l ra kt ta rt kh khn trong vic loi tr ion CrO42- d, ko di thi gian ra. c bit Fe(OH)3 cng kt ta vi PbCrO4 s cng ha tan trong HCl to ion Fe3+. y l ion c tnh oxi ha, trong iu kin thch hp s phn ng I- gy sai s nu nh s dng phng php Iod xc nh. V vy, cn thit phi loi tr Fe3+. loi tr Fe3+, ngi ta dng k thut che bng cch to phc citrat st bng axid citric. Ch , cn phi che st trc khi nng pH ln kt ta PbCrO4. Mt khc Cu2+ cng gy nh hng do: 2Cu2+ + 4I- 2CuI + I2 Phn ng ny sinh ra mt lng I2 khng mong mun, v vy khi ra kt ta cn thit phi ra sch lng Cu2+. iu kin kt ta PbCrO4. Phi tin hnh che Fe3+ bng acid citric trc khi tin hnh kt ta. Do kt ta PbCrO4 l kt ta tinh th gn trung tnh, kt ta khng chc ht, d =1,3.10-7 20oC).V vy cn phi tin hnh kt ta trong mi tan ( tan SPbCrO trng pH=5-6 trnh tan kt ta, iu kin nng, thuc th K2CrO4 long. Ngoi ra, pH=5-6 th mi trnh cn bng:
4
2CrO42- + 2H+ Cr2O72- + H2O Lm mt tc dng ca thuc th K2CrO4.V kt ta PbCrO4 l kt ta tinh th, nn khi cho thuc th K2CrO4 vo dung dch th phi cho t t, khuy k v lng yn lu t 2-4 gi kt ta mui, chc, trnh b tan ra trong qu trnh ra kt ta. iu kin lc, ra kt ta Trang 45
Phn tch kim loi
Cn phi lc gn qua giy lc bng xanh, khi ra kt ta th ra lng gn, lc u cn ra bng dung dch K2CrO4 1%, sau ra lng gn nhiu ln bng nc ct ngui cho n khi ht ion CrO42-, ion Cu2+ (th bng dung dch acetat ch 5% pha trong m acetat pH=6) hoc bng dung dch AgNO3 0,1N pha trong CH3COOH 5%. iu kin ha tan kt ta trnh mt kt ta do chuyn kt ta ra khi giy lc th nn ha tan kt ta ngay trn giy lc. Dng HCl ha tan kt ta PbCrO4 trong iu kin nng l tt nht. iu ny cng d hiu bi qu trnh ha tan da trn c s phn ng acid mnh y acid yu ra khi mui, mt khc PbCl2 s kt ta nu dung dch ngui. c bit nu dng phng php iod xc nh th nn ha tan bng hn hp NaCl + HCl. Vic dng NaCl trong hn hp vi mc ch cung cp ion Cl-. V trong mi trng acid c d ion Clth PbCl2 +2Cl- PbCl42Nh phn ng ny m Pb2+ tn ti di dng phc PbCl42- trnh c phn ng: PbCl2 + 2I- PbI2 + 2Cl (do TPbI < TPbCl )
2 2
Vn c t ra l v sao khng dng HCl m c ha tan (nhiu ion Cl-) m phi thm NaCl, y cn phi tnh n giai on nng pH ln trc khi cho I- vo thc hin phn ng sinh ra I2, nu dng HCl nng cao th phi trung ha nhiu NH3. Kt ta PbI2 sinh ra lm cn tr vic nhn mu ti im tng ng. Nu dng phng php Fe2+ th khng cn dng thm NaCl. Ch cn dng HCl 2N, nng 7080oC l ha tan kt ta PbCrO4. Ch rng, khi ha tan kt ta xong, cn phi ra sch giy lc cho n ht ion Cr2O72- (v lc ha tan PbCrO4 bng acid th xy ra phn ng: 2CrO4- + 2H + Cr2O72iu kin chun : i vi phng php I2 th phi tun th theo cc iu kin ca phng php chun iod (xem phn tch nh lng) i vi phng php Fe2+ th ch iu kin chun l mi trng acid H2S04 6N, iu kin s dng ch th, do ti im tng ng hnh thnh ion Cr3+ c mu xanh en (xanh ti), v vy nu dng ch th diphenylamin hay acid phenylantranilic th vic nhn mu s kh khn do mu chuyn t mu xanh tm sang khng mu. Nhng thc t l mu chuyn t mu xanh xanh Cr3+. khc phc nn s dng ch th ferroin (ch th phc cht). im tng ng xy ra khi xut hin mu nu trn nn xanh Cr3+ rt d nhn mu. Mu nu l mu ca phc hnh thnh gia Fe2+ vi 1.10 phenantrolin c trong ch th ferroin. 1.1.3. Qui trnh xc nh Cn chnh xc khong 0,35-0,5g 0,0002g mu hp kim ng trong bnh nn chu nhit loi 100ml, rt t t qua phu thy tinh 20ml HCl 1:1 (t ng ong), un bnh nn t t trn bp in c li aming, thm 3-5ml HNO3 m c (d=1,4g/ml), Khoa CNHH Chuyn ngnh Ha phn tch Trang 46
Phn tch kim loi
un cho n khi mu tan hon ton, tip tc un cho n ht khi nu bay ra, thm tip 5ml HCl 1:1 em c kh mu, thm 20ml H2O ct nng, khuy u, lc nng loi Sn(OH)4, ra kt ta bng H2O nng, tp trung dch lc v nc ra, ngui, thm 10-15ml H2O ct, thm tip 2ml acid citric 10%. Sau dng NH3 10% trung ha ti khi xut hin mu xanh l ca phc [Cu(NH3)4]2+. Sau iu chnh v pH=5-6 bng CH3COOH 20% ti khi xut hin mu xanh ca Cu2+ (pH=5-6) thm 2g CH3COONa to mi trng m acctat (nu cn, dng giy pH kim tra pH). Thm t t va thm va khuy nh 10-15ml K2CrO4 10%, kt ta lng 4-5h (tt nht l qua m). em lc kt ta qua giy lc bng xanh. Dng dung dch K2CrO4 1% ra kt ta 2 ln, sau dng H2O ct ngui ra n khi ht ion CrO42(th bng Pb(CH3COO)2 hoc AgNO3). Ha tan kt ta trn giy lc bng 25ml hn hp acid nng (20ml HCl m c + 5g NaCl + H2O = 100ml) dng H2O ct nng ra giy lc n khi ht acid, thm vo dung dch qua lc 10ml dung dch KI 10%. Cho vo ti, 5 pht sau ly ra chun nhanh n mu vng nht bng dung dch Na2S2O3 0,05N, thm 5 git HTB 1%, tip tc chun n khi dung dch mt mu. Nu dng phng php Fe2+ th ha tan kt ta PbCrO4 trn lc bng 25ml HCl nng 1:1 ra giy lc n sch acid, thm tip 3ml H3PO4 6N + 5ml H2SO4 6N (H3PO4 che Fe3+) + 3 git ch th ferroin 0,1%. Ri chun bng dung dch Fe2+ 0.05N n khi xut hin mu nu . 1.1.4. Cng thc tnh ton
m Pb ( NV ) R 100 %Pb = mm
Vi: m
Pb 2 +
207 = 0,0691 3000
(NV)R: S mili ng lng dung dch chun s dng. mm : Khi lng mu cn (g) 1.2. Xc nh ng thi Pb, Cu, Zn, Fe cng mt lng cn bng phng php kt hp in phn phc cht 1.2.1. Nguyn tc Mu hp kim ng c ha tan bng hn hp HNO3 + HCl. Cc kim loi c chuyn thnh ion tan vo dung dch. Tch Pb2+ v Cu2+ ra khi Zn2+ v Fe3+ bng k thut in phn, Cu c xc nh catod, Pb c xc nh anod, Sn c loi bng bng bin php c kh mu v lc. Dung dch sau in phn cha Zn2+ v Fe3+ c xc nh bng phng php chun phc cht vi k thut song song ch th. Ghi ch: mt s loi hp kim Cu khng c Fe th ch xc nh Pb, Zn, Cu theo phng php ny. Cc phn ng: Khoa CNHH Chuyn ngnh Ha phn tch Trang 47
Phn tch kim loi
Chng 1: Phn tch kim loi en 3Cu + 8HNO3 3Cu(NO3)2 + 2NO + 4H2O 3Pb + HNO3 3Pb(NO3)2 + 2NO + 4H2O
3Sn +18HCl + 4HNO3 3H2[SnCl6] +4NO +8H2O Fe +4HNO3 Fe(NO3)3 + NO +H2O H2[SnCl6]+4H2O Sn (OH)4 + 6HCl Cu2+ (catod) -2e- Cu (catod) Pb2+(anod) +2e- Pb4+ Pb4+ +2H2O PbO2 + 4H+ Fe3+ +H3S
pH = + + -12 [FeH2Sal]2+ + H+
[FeH2Sal]2+ + Y4- FeY- + H3Sal Zn2+ +Ind6- ZnInd4ZnInd4- + Y41.2.2. iu kin xc nh

pH=56 ZnY2- + Ind4
Tng t nh iu kin ph mu ca chi tiu xc nh Pb bng phng php cromat, ch rng cn phi loi tr trit Sn di dng Sn(OH)4. V nu cn Sn4+, di iu kin in phn th Sn4+ thy phn bm ln in cc s gy ra sai s ln. iu kin in phn: thc hin ng thi xc inh Pb v Cu th iu kin in phn phi ph hp v gi tr th ngoi t vo v cng dng in. Th ngoi t vo 2 in cc ca thit b in phn phi tnh n th in phn, qu th v th chun iu kin in phn sao cho thc hin ng thi qu trnh in phn Cu Catod v Pb Anod. Th ngoi p vo ph hp l 2,0-2,5V. Cng dng in cng phi ph hp sao cho mt dng ln, nu cng dng khng ph hp th hoc ko di thi gian phn tch (mt dng nh) hoc Cu bm ln catod khng chc, d bong trc gy ra sai s (mt dng ln ). Do , cng ph hp l 2,5-3A Khi lp rp s in phn th in cc dy xon anod nm ti tm ca in cc li catod, tuyt i khng 2 in cc chm vo nhau, phi kim tra chc chn trc khi ng mch in (kha K). Cc in cc trc khi in phn phi c sy kh v cn trc bit khi lng. Khi nhng cc in cc vo dung dch phn tch th in cc ch nhng ngp 1/2-2/3 in cc m thi, phn tip xc vi khng kh chnh l phn gip cho qu trnh kim tra xc nh thi im kt thc phn ng. Sau khi ng kha K th iu chnh th ngoi p vo 2 in cc n gi tr th in phn bng cch di chuyn bin tr con chy R v theo di s ch vn k, sau iu chnh ampe k c cng dng ph hp. Cng c th thay i tc in phn bng cch iu chnh s ch ampe k. Khoa CNHH Chuyn ngnh Ha phn tch Trang 48
Phn tch kim loi
kim tra thi im kt thc in phn c th dng 2 cch, cch th nht l nng cc cha dung dch in phn cao hn so vi v tr c 1,5cm hoc thm H2O vo sao cho mc dung dch tng ln 1,5cm. Do trong dung dch, hm lng Cu2+ cao hn rt nhiu so vi Pb2+, v th nu kim tra ht Cu th Pb chc chn s ht. Vic kim tra bng cch tip tc in phn 5-10pht v quan st phn mi ngp vo dung dch ca catod, nu khng thy Cu kt ta ln catod (khng c mu ) th kt thc, ngc li th tip tc in phn. Trong qu trnh in phn, cn khuy trn dung dch bng my khuy t, vic khuy trn nh vy nhm trnh hin tng phn cc nng v c th trnh c qu trnh in phn b dng (A=0) do tc di chuyn cc ion trong lng dung dch n b mt in cc chm hn tc in phn (tc phng in ca cc ion lp dung dch st b mt in cc). Sau khi dng in phn, ngt mch in v ra sch in cc bng H2O ct, nc ra nhp vo dung dch trong cc cha dung dch in phn. iu kin sy in cc catod v anod l 105oC trong 1 gi. Nu quan st thy c kt ta PbO2 rt ra khi anod (lng nh) th phi lc qua giy lc bng vng sy 105oC trong 1 gi v bit trc khi lng, lng PbO2 trn giy lc cng vi lng PbO2 bm ln catod chnh l lng Pb c trong mu. iu kin xc nh Fe3+ v Zn2+ Nng pH ln 1-2 bng dung dch NH3 10%, thm 2 git ch th acid sulfosalycilic 10% (H3Sal) nu c mu tm tc c Fe3+ th chun bng dung dch EDTA 0,05N n mu vng chanh. Nu khng c mu tm sau khi thm ch th H3Sal th khng c Fe3+ Tip tc nng pH=5-6 to mi trng chun Zn2+. Cn phi n nh pH =5-6 bng dung dch m acetat PH=5 Chun Zn2+ bng dung dch chun EDTA 0,05N n khi mu t hng chuyn sang vng chanh vi ch th xylenon da cam.
1: Kha K ng v ngt dng in 2: Ngun in 1 chiu 3: Vn k 4: Ampe k A 5: Bin tr con chy R 6: Cc cha DD xc nh 7: Catod li Pt 8: Anod dy Pt 9: C t v my khuy t Khoa CNHH Chuyn ngnh Ha phn tch
THI T B
I N
H
3 8
K
4 7
Trang 49
Phn tch kim loi
1.2.3. Qui trnh xc nh - Cn khong 0,5000g 0,0002g mu hp kim ng vo bnh nn, tin hnh ha tan mu v loi tr Sn4+ tng t nh xc nh Pb bng phng php th tch Cromat. Dung dch sau khi tch Sn c nhp chung vi nc ra dng phn tch Pb, Cu, Zn, Fe sao cho tng th tch 100ml. - Ra sy kh cc in cc, sau b bnh ht m cn bng nhit ri cn bit khi lng moC, moA, mogiy. - Lp rp thit b in phn, kim tra chc chn catod v anod khng chm vo nhau. Rt dung dch in phn vo cc 250ml, cho c t vo. - ng kha K, iu chnh n s ch volk 2-2,5V, iu chnh ampe k n s ch 2,5-3A. - Tin hnh in phn, sau 1h, thm H2O sao cho hn mc c l 1,5cm, sau 510pht, nu ht Cu kt ta ln catod th dng in phn, nu cn th tip tc cho n khi Cu2+ in phn ht. - Tho cc in cc catod v anod, dng bnh tia ra sch cc in cc, nc ra nhp chung vo cc. em cc in cc sy kh cng iu kin ban u, em cn c khi lng m1C, moA. Nu dung dch c kt ta PbO2, th lc qua giy lc bng vng c chun b phn trn, ly giy lc + kt ta (sau khi ra sch) sy cng iu kin ban u ri cn c khi lng m1 giy. Nu khng thy kt ta trong y cc th b qua giai on ny. Dung dch + nc ra c chuyn vo bnh 250ml. Dng NH3 10% chnh n pH = 1-2, thm 3 git ch th axid sufosalicylic 10%, nu c mu tm th em i chun bng dung dch EDTA 0,05N n mu vng chanh ghi V1EDTA tiu tn. Nu dung dch khng c mu tm th tip tc thm NH3 10% n pH = 5-6 (th bng giy pH), thm tip 10ml dung dch m acetat PH = 5+3 git ch th xylenon da cam 0,1% pha trong HCl 1N. Chun bng EDTA 0,05N n khi dung dch t mu tm mn sang mu vng chanh, ghi V2EDTA. 1.2.4. Tnh ton kt qu
-
%Cu =
A (m1
c (m1
mc ) 100 0 mmau
%Pb=
A A gia A m0 ) 100 [(m1 + m1 y ) (m0 + mgiay ) 0 f 100 hoc %Pb = mm mm
Trang 50
Phn tch kim loi
Vi f=
MPb 207 = MPbO 239

2
m Fe ( NV 1 ) EDTA 100 56 Fe vi m = % Fe = mm 2000

m Zn ( NV 2 ) EDTA 100 % Zn = mm
1.3.1. Nguyn tc Mu c ph bng hn hp acid HNO3 + HCl trong iu kin nng chuyn Sn vo dung dch dng mui phc thit, bng phng php c kh thy phn mui phc thic, lc, ra v ho tan kt ta hydroxyt thic bng HCl, ri kh Sn4+ thnh Sn2+ bng bt kim loi Zn(Al) trong mi trng acid, chun lng Sn2+ sinh ra bng dung dch chun I2 trong mi trng kh tr vi ch th tinh bt. Cc phn ng: 3Sn + 4HNO3 + 18HCl 3H2[SnCl6] + 4NO + 8H2O H2[SnCl6] + 4H2O Sn(OH)4 + 6HCl Sn(OH)4 + 4HCl + Zn SnCl2 + 2ZnCl2 + 4H2O SnCl2 + 2HCl + I2 1.3.2. iu kin xc nh
HTB 2HI + SnCl4
vi m
Zn
65 2000
1.3. Xc nh Sn trong hp kim ng bng phng php Iod
- iu kin ph mu: HNO3 dng ha tan hp kim ng l tt nht, iu kin un nng thc y nhanh tc ha tan kim loi v ui kh NO lm qu trnh ha tan trit hn. Vic dng HCl c vai tr chuyn Sn thnh dng mui phc thic IV Clorua. Nu thiu HCl th Sn s chuyn thnh keo Sn(OH)4 bao ph cc phoi kim loi mu cn tr s tip xc gia acid vi mu lm qu trnh ha tan chm li, gy si cc b. iu kin ng t keo Sn(OH)4: Khi mu ha tan, cn phi c kh ui HCl, khi s xy ra qu trnh thy phn gip cho qu trnh Sn(OH)4 xy ra hon ton, cc ht keo Sn(OH)4 to, chc hn nh qu trnh c kh s gip cho qu trnh lc d dng v trnh mt kt ta. Phn ng thy phn ca H2[SnCl6] l 1 phn ng thun nghch, mun phn ng xy ra theo chiu thun, cn phi un nng ui HCl, ng thi trung ha dung dch bng NH3 ti khi dung dch c mi trng kim, trong iu kin ny Cu2+ s chuyn thnh phc tan [Cu(NH3)4]2+. Nu dng NaOH trung ha th s to Cu(OH)2 gy nh hng ln n qu trnh lc, ra, ha tan kt ta Sn(OH)4 v qu trnh Sn4+ Sn2+ sau ny cng nh nh hng n qu trnh chun Iod do Cu2+ tc dng c vi I-. Khoa CNHH Chuyn ngnh Ha phn tch Trang 51
Phn tch kim loi
Khi trung ha dung dch bng NH3 nng pH nhm thc hin qu trnh keo t Sn(OH)4 th s sinh ra mt lng Fe(OH)3, kt ta Fe(OH)3 l mt kt ta v nh hnh d hp th ln cc ht keo Sn(OH)4, iu ny lm cho qu trnh ng t keo s xy ra nhanh hn, lm gim nht nn kt ta nhanh, d lc. V vy, nu trong hp kim ng c hm lng Fe thp th khi ng t keo Sn(OH)4 cn thm mt lng FeCl3 thch hp. iu kin ha tan kt ta v kh Sn4+ Sn2+ Do kt ta l hydroxyt nn vic ha tan kt ta d nhin l acid, tuy nhin do giai on k tip l giai on kh, v vy acid phi m bo khng c tnh oxi ha v khng c kh nng to ta vi Sn2+ hoc Sn4+. Acid HCl c chn lm acid ha tan. iu cn quan tm y l trong mi trng acid HCl nng kh cao th qu trnh ha tan kt ta to ra Sn4+ v FeCl4-. Nh vy, v mt l thuyt vi th chun E0 Sn / Sn = 0.15V ; E0 Zn / Zn = _ 0.76V ; E0Fe / Fe = 0.77V th nu dng Zn kh Fe3+ s b kh trc ri n Sn4+ b kh sau, nhng do trong iu kin d ion Cl- (HCl 1:1), Fe3+ to phc vi ion Cl4+ 2+ 2+ 3+ 2+
Nn: E0 FeCl4-/Fe2+ =E0 Fe3+/Fe2+ +

3+
1 0,059g lg FeCl 1
-
Hng s bn to phc Fe vi ion Cl ph thuc vo nng ion Cl-; nu nng HCl l 1:1 (khong 6-7N) th FeCl 1012
4
E0 FeCl4-/Fe2+=0,77-0,059x 12 0,1V< E0 Sn / Sn = 0.15V Sn4+ s b kh trc ri mi n Fe3+.Do Fe3+ tn ti dangFeCl-4 c mu vng nn c th da vo mu vng ny kt thc qu trnh kh.
4+ 2+
Khi ha tan kt ta th HCl c un nng qu trnh ha tan xy ra nhanh chng theo phn ng: Sn(OH)4 +4HCl SnCl4 +4H2O Fe(OH)3 + 3HCl FeCl3 + 3H2O. H kh c th dng bt Zn hay bt Al trong mi trng HCl, dung dch nng, trong thit b ct th Jones. Bn cht ca qu trnh kh l bt Zn(Al) tan trong HCl sinh ra [H] c tnh kh mnh: Zn + 2HCl ZnCl2 + 2HCl. SnCl4 + 2[H] SnCl2 + 2HCl. FeCl-4 + 2[H] FeCl2 + 2HCl. Thi im kt thc qu trnh kh l da vo s bin mt mu vng ca FeCl . 4 4+ Khi chc chn l Sn c kh ht. Trong qu trnh kh, do[H] cng nh Sn2+ u c tnh kh mnh d dng tc dng vi O2 trong khng kh v O2 ha tan. khc phc cn phi kh trong thit b kh trnh s xm nhp oxi c kh tr (N2 l kh c s dng do r tin) v bu kh
Khoa CNHH Chuyn ngnh Ha phn tch Trang 52
Phn tch kim loi
quyn CO2, iu kin un nng. to ra bu kh quyn CO2 trong qu trnh kh, cn thm 1 lng nh Na2CO3 vo: Na2CO3 + 2HCl 2NaCl + H2O + CO2 Trc khi np dung dch vo thit b kh, phi to ra mi trng kh tr, v vy phi cho dng kh N2 nng chy qua thit b trong vng 5 pht, khi np liu (dung dch, bt Zn) cn phi trnh s xm nhp ca khng kh vo thit b. iu ch hn hp Zn-Hg: Cn 300g Zn ht (d=0,8mm) tinh khit trong mt bnh nn, thm vo 300ml dung dch HgCl2 hay Hg(NO3)2 (nng dung dch mui Hg2+ sao cho trong 300ml dung dch cha khong 80-100g Hg) thm tip 1-2ml HNO3 m c. Lc u 5-10 pht, lng ri gn phn dung dch ra. Sau ra lng gn n khi ht acid, hn hp thu c phi c mu sng ng nh. Qu trnh kh: Np hn hp iu ch vo ct kh, ra bng 500ml H2O ct. Sau np y H2O, ct lun lun phi y nc trnh O2 khng kh tip xc vi hn hng. Di qua ct 20-50ml HCl 0,5-2N. Sau di dung dch cn kh qua ct, bnh nn di hng dung dch qua ct kh, tc c th iu chnh bng kha b. Sao cho c 100ml dung dch qua ct trong 1 pht, sau li di qua ct 25 50ml HCl 0.52N v cui cng l nc ct.
CT KH JONES
+ Thit b kh (ct Jones): Hnh v trnh by mt thit b kh n gin, d thc hin theo hng to bu kh quyn tr (oxh-kh) CO2. ly ht khng kh trong ng kh th ng kha a, m kha b, gn vi c vo my ht chn khng, cho bm ht trong vng 2-5 pht, sau tt ng thi bm v kha b li. Trc khi ht, cn np vo bnh nn bt Zn hay km ht trc. + Ch l c th iu ch ct kh Jones s dng nhiu ln v tng hiu qu kh bng cch thay Zn bng hn hng Zn-Hg. Cch iu ch v tin hnh nh sau:
N P
Khi kh theo cch ban u, th sau khi cho Zn ht vo, rt qua phu ct kh khong 1-2ml Na2CO3 5%, sau mi rt dung dch cn kh vo thit b qua phu. - iu kin chun : Mi trng chun l mi trng acid HCl nhm trnh s thy phn ca cc ion kim loi, cn thc hin nhanh v trong mi trng kh tr trnh O2 phn ng vi Sn2+ v I2 b nh hng bi nh sng, nn s dng buret nu. Trong iu kin ny, Fe2+ khng phn ng vi I2 m ch c kh nng Fe3+ phn ng vi I-, iu ny khng nh hng n qu trnh chun . 1.3.3. Qui trnh xc nh - Cn chnh xc khong 1,0000 0,0002g mu hp kim ng trong bnh nn 250ml chu nhit, rt t ng ong 20ml hn hp acid (HCl m c theo t l 1:1) qua phu
Phn tch kim loi
vo bnh nn, un si nh, t t trn bp in cch ct hay c li aming. Khi mu tan hon ton, c kh mu, tm bng 5ml HCl 1:1 + 25ml FeCl3(12g/l) thm H2O ct nng ti khong 100ml, un nng dung dch n khong 70oC. Dng NH3 1:1 (12,5%) trung ha ti mu xanh ca phc [Cu(NH3)4]2+. un nng dung dch n gn si, em lc kt ta qua giy lc bng vng. Dng NH3 1% ra kt ta n khi ht mu xanh ca [Cu(NH3)4]2+. Chuyn kt ta + giy lc qua 1 bnh khc, sch ri ha tan kt ta Sn(OH)4 trn lc bng 40ml HCl 1:1 (nng khong 70oC). Dng H2O ct ra giy lc (khong 50ml). Gp dch lc vo nc ra c c dung dch cn kh. - Cho vo bnh nn 4-5 ht km, 1-2 ht ch (hoc Al), lp thit b nh hnh v. ng kha a, m kha b v gn vi c vo bm ht chn khng, cho bm chy 1-2 pht tt bm ng thi kha b li. t dung dch cn kh qua phu, m kha a cho dung dch chy xung gn ht, kha a li, thm H2O ct vo 3 ln, mi ln 5ml ly ht phn dung dch vo ct. Sau ng kha a, m kha b cho dung dch chy xung ht, nhanh chng kha b li. Sau khi trng ct bng 1 t H2O ct v thm tip khong 2ml Na2CO3 bo ha. un si dung dch n khi mt mu vng, ngui, thm 5ml KI 10%, ( khi chun I2 xung, I2 d tan vo dung dch hn d dung dch I2 c pha trong KI) + 5 git HTB 1% em chun nhanh bng dung dch I2 0,05N n khi dung dch xut hin mu xanh l. 1.3.4. Tnh ton kt qu
%Sn =
m Sn ( NV ) I 2 mm
100
Sn Vi m =
118,7 2000
1.4. Xc nh km trong hp kim ng bng phng php Ferocyanur
Hp kim ng c 3% Zn tr ln gi l ng thau, trong ng thau, Zn tn ti di dng Cu5Zn8 v CuZn3. C nhiu phng php xc nh Zn trong hp kim ng nh phng php phc cht, phng php cc ph, phng php in phn tch Pb v Cu. Trong phn ny, s trnh by thm mt phng php xc nh Zn l phng php ferocyanur l phng php chun kt ta. 1.4.1. Nguyn tc Mu hp kim ng c ha tan bi HCl v HNO3 trong iu kin nng. Zn chuyn vo dung dch, loi b ion tr ngi ri em chun Zn2+ bng dung dch chun kaliferocyanur K4[Fe(CN)6] vi ch th diphenylamin trong mi trng acid pH=5-6. im tng ng nhn c khi dung dch chuyn t mu xanh tm sang khng mu (tht ra l mu vng lc). Cc phn ng: 3Zn + 8HNO3 3Zn(NO3)2 + 2NO + 4H2O 3Zn(NO3)2 + 2K4[Fe(CN)6] K2Zn3[Fe(CN)6]2 + 6KNO3 1.4.2. iu kin xc nh
H+
Phn tch kim loi
iu kin ph mu: Tng t nh cc ch tiu trn iu kin loi b ion gy tr ngi Do s dng phng php chun kt ta pH=5-6 nn ion Fe3+, Cu2+ gy nh hng v to kt ta hydroxyt pH ny. S to thnh kt ta gy c dung dch v mu xanh ca Cu2+ hoc [Cu(NH3)4]2+ lm cn tr vic nhn mu ti im tng ng. Loi b Fe3+ di dng Fe(OH)3; loi b Cu2+, Pb2+ bng H2S hoc Na2S 15%, Cu2+ v Pb2+ tch ra khi dung dch di dng CuS, PbS pH=0-1 v pH=3-4 th Zn2+ s kt ta ZnS. Cc kt ta PbS, CuS c lc b, phi loi b lng H2S d bng cch un si trong t ht. H2S cn d s gy nh hng giai on chun . nhn bit thi im kt thc sc H2S vo dung dch c th da vo vic ngng xut hin kt ta CuS v PbS (mu en) ng thi dung dch ht mu xanh ca Cu2+. Phng php ny c do kh H2 S nn khi tin hnh phi thc hin trong t ht, ch pH phi m bo l mi trng tht acid (pH=01) nhm trnh mt ZnS, khi ra kt ta cng nn dng dung dch Na2S 1% ra nhm trnh kt ta tan.
- iu kin chun : V y l phng php chun kt ta nn cn c cht tr lng s dng hiu ng in li l Na2SO4. Cn kim sot pH cht ch theo ch th MR v iu chnh mi trng bng NH3 1:1 v H2SO4 6N. V phn ng xy ra chm nn khi chun cn lc mnh v chun chm tng git. - iu kin chuyn mu ca ch th: Ch th diphenylamin l ch th oxi ha kh, trong mi trng acid, trc im tng ng n tn ti dng oxi ho c mu xanh tm (dng diphenyl benzidin). Cht chun ferocyanur va l tc nhn to mui kp va l cht kh. Tuy nhin lc cn ion Zn2+ (trc im tng ng) th ferocyanur phn ng vi Zn2+, khi d 1 git dung dch chun K4[(Fe(CN)6] ng vi thi im ht Zn2+ th fero (dng kh ) s phn ng vi ch th (dng oxi ho: diphenyl benzidin) chuyn ch th sang dng dng kh (diphenylamin) khng mu, iu ny lm thay i [ I nd ] oxh S chuyn mu t l [ I nd ] kh Ch : C th dng k thut chun thay th vi dung dch chun Na2S2O3 bng cch thm vo dung dch 1 lng d KI v fericyanur. Khi s c phn ng: 2KI + 3Zn2+ +2K3[Fe(CN)6] K2Zn3 [Fe(CN)6] 2 +I2 + 6K+ (*) Lng I2 sinh ra tng ng vi lng Zn2+ c chun bng Na2S2O3 vi ch th HTB. Phn ng (*) thc ra l do 2 phn ng: 2[Fe(CN)6] 3- +2I - I2 + [Fe(CN)6] 4feri fero 3Zn 2+ + 2K4[Fe(CN)6] K2Zn3 [Fe(CN)6] 2 + 6K+
Trang 55
Phn tch kim loi
Dung dch chun fero c hiu chnh bng chun gc pha t ZnSO4.7H2O pA hoc theo KMnO4 dung dch pha trong 0,1g Na2CO3/1lit dung dch chun v cha trong chai mu nu. 1.4.3. Qui trnh xc nh Cn chnh xc khong 1,5000 0,0002g mu hp kim ng vo bnh nn chu nhit loi 100ml rt t ng ong vo bnh nn 10ml HNO3 1:1 qua phu (hoc hn hp acid). un si nh mu n khi mu tan hon ton, un si k ui ht kh NO, thm 15ml NH4NO3 10% un si k ( lm ng t keo H2SnO3 v tch Cu2+, Zn2+ b hp ph ra khi kt ta). lng 10 pht em loc nng v ra kt ta bng dung dch NH4NO3 1% ( c acid ha bng HNO3). Ra kt ta bng nc ct cho u ht mu xanh ca Cu2+. Dch qua lc cng vi nc ra c gp chung v em c n kh, thm 50ml H2O ct nng, dng HCl 1:1 iu chnh n pH=01, sau sc kh H2 S vo dung dch n khi thy ngng xut hin kt ta v dung dch ht mu xanh Cu2+, lc kt ta v ra kt ta bng nc ct c pha 0,1% Na2S, dng NH3 1:1 (12,5%) trung ha dung dch ti mu vng theo ch th MR 0,1%, thm d 23ml NH3 1:1. un nng dung dch, em lc nng loi Fe(OH)3, ra kt ta bng NH3 1%, dch qua lc v nc ra tp trung li, dng H2SO4 6N chnh tng git n khi dung dch c mu hng (pH=46), thm 2g Na2SO4 tr lng + 20ml H2SO4 6N + 2 got feri 0,2% v thm tng git ch th diphenylamin (1% pha trong H2SO4) n khi dung dch c mu xanh tm. Sau 10 pht em chun bng chun dung dch chun fero 0,01 M n khi dung dch t mu xanh tm sang mu vng lc. 1.4.4.Tnh ton kt qu Do c 3Zn2+ 2fero mgZn = 3 65.37 = 0.0981 2 1000
m Zn ( NV ) Fero %Zn = 100 mm
II. PHN TCH HP KIM NHM

Al l 1 kim loi nh, nhit nng chy thp, do, c dn in v dn nhit cao. Hp kim nhm thng pha thm Cu, Fe, Na, NiLm cho hp kim Al c nhiu c tnh qu nh nh, bn, cng bng, chu c s ma st, chng r tt. Trong hp kim Al ngoi Al l thnh phn chnh cn c %Cu=38, %Na=0,10,8, %Ni=1845, %Fe=0,11,8Hp kim d tan trong dung dch kim nng v khi xc nh cht lng thng phn tch 2 ch tiu trn l Cu v Fe.
1. Xc nh ng trong hp kim nhm bng phng php iod
Phng php ny nhanh, c th xc nh ng c hm lng Cu 0,1%. 1.1.Nguyn tc Mu hp kim Al c ph bng NaOH c nng, cc kim loi lng tnh c trong hp kim nhm l Zn, Pb, Sn v c Al tan vo trong dung dch. Phn cn khng tan
Phn tch kim loi
gm c (Fe, Cu, Mg.) c lc ra v ha tan bng HNO3, loi b cc thnh phn tr ngi ri xc nh Cu2+ bng phng php iod vi k chun th trong mi trng CH3COOH ngui. Cc phn ng: Zn + 2NaOH Na2ZnO2 + H2 Al + NaOH + H2O NaAlO2 +
3 H2 2
Sn + 2NaOH Na2SnO2 + H2 3Cu + 8HNO3 3Cu(NO3)2 + 2NO + 4H2O Fe + 4HNO3 Fe(NO3)3 + NO + 2H2O Cu2+ + 4I- 2CuI + I2 (1) I2 + I- I-3
1.2. iu kin xc nh
a. iu kin ph mu
I-3 + 2S2O32- S4O62- + 3I-
V hp kim Al cha nhiu kim loi lng tnh nn tch Cu ra khi hp kim phi dng kim c, nng, mnh d ha tan. Nu khng tch Cu ra th trong iu kin chun Cu2+ bng phng php iod, Al3+ s kt ta gy c dung dch, kh nhn im tng ng. Trong iu kin kim c, nng c th Cu tan 1 lng nh di dng Cu2+. khc phc thm 1-2 git Na2S 15% ta Cu2+ di dng CuS. Lc kt ta v c ha tan cng cn Cu bng HNO3 nng. -
Ha tan cn Cu, Fe, Mg... bng HNO3 nng
iu kin loi b cc thnh phn tr ngi: Do xc nh Cu2+ bng phng php iod nn Fe3+ l ion gy tr ngi chnh do hnh thnh Fe(OH)3 hoc Fe3+ tc dng c vi I- gy cn tr. V vy cn phi loi b giai on trung ha di dng Fe(OH)3. Tuy nhin cn phi dng NH3 trung ho trnh Cu2+ kt ta di dng Cu(OH)2. Fe3+ + 3NH4OH Fe(OH)3 + 3NH4+ Cu2+ + 4NH4OH [Cu(NH3)4](OH)2 + 2H2O + 2H+
b. iu kin chun
Mi trng chun l mi trng acid acetic c pH=45 vi lng d KI, iu kin ngui. [Cu(NH3)4](OH)2 + 6CH3COOH Cu(CH3COO)2 + 4NH4CH3COO + 2H2O 2Cu(CH3COO)2 + 4KI 2CH3COOK + I2 + 2CuI Mc d E0 cu 2+ /Cu+ = 0,17V < E0 I /2I = 0,54V, nhng do Cu+ kt ta vi I- di dng CuI co T CuI = 10- 12
2 --
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Phn tch kim loi E0 cu 2+ /Cu I = E0 cu 2+ /Cu +

0,059 1 = 0,17 + 0,72 = 0,89V lg 1 TCuI
phn ng xy ra gia Cu 2+ vi I -:
2Cu2+ + 4I- 2CuI + I2 phn ng (1) xy ra trit v s chuyn mu xy ra t ngt, d nhn cn thm vo 1 lng SCN-, khi s xy ra phn ng: CuI + NH4SCN NH4I + CuSCN Phn ng trn xy ra do TCuSCN < TCuI. Nh phn ng ny m I2 khng hp th ln b mt CuI c theo phn ng hp ph: CuI + I2 CuI:I2. Nh vy m im tng ng xy ra dt im khng ko di. - Cc iu kin cn li th theo iu kin ca phng php chun iod. 1.3. Qui trnh xc nh - Cn chnh xc 0,5000 0,0002g mu hp kim nhm vo trong bnh nn chu nhit loi 250ml, rt qua phu 20ml dung dch NaOH 20% sau 510 pht ngm mu, un nh cho n khi mu ha tan (ch : phn ng sinh ra [H] sau mi kt hp thnh H2 v vy phi un mu trong t ht). - Thm vo 100ml H2O ct, 12 git Na2S 15%, un si dung dch 35 pht, lc dung dch qua giy lc bng xanh vi k thut lc gn, dng nc ct nng ra lng gn kt ta (khng chuyn kt ta ln giy lc). - Dng 10ml HNO3 11 ha tan cn trong bnh nn, dng HNO3 1:1 ha tan phn cn t trn giy lc (nu c). Tp trung dch ha tan li, c ti khi ht kh NO (NO2), c tip cho n gn kh, thm nhanh 15ml NH4OH 11, khuy u, lc qua giy lc bng vng, dng NH3 1% ra kt ta trn giy lc n khi giy lc ht mu xanh ca phc Cu2+, tp trung dich lc + dch ra vo bnh nn 250ml c nt mi. - Dng CH3COOH 15% trung ha ti khi phc [Cu(NH3)2](OH)2 ph v chuyn sang mu xanh Cu2+, thm 50ml hn hp KI + NH4SCN (2,5g KI + 10g NH4SCN + H2O = 100ml, cha trong chai mu nu) lc trn u v cho vo ti 5 pht, ly ra chun bng dung dch Na2S2O3 0,05 N theo ch th h tinh bt. 1.4. Tnh ton kt qu
%Cu =
2.1. Nguyn tc
m Cu ( NV )S O 2
2 3
100 vi m Cu =
63,54 1000
2. Xc nh Fe bng phng php KMnO4
Mu hp kim Al c ha tan bng HCl nng, Al v Fe c chuyn thnh Al3+, Fe2+. Chun trc tip Fe2+ bng dung dch chun KMnO4 trong mi trng kh tr im tng ng c xc nh khi dung dch c mu tm nht. Cc phn ng:
Phn tch kim loi
2Al + 6HCl 2 AlCl3 + 3H2 Fe +2HCl FeCl2 + H2 5Fe2+ + MnO4 + 8H+ 5Fe3+ + Mn2+ + 4H2O 2.2. iu kin xc nh
a. iu kin ph mu
Dng HCl lm 1 acid mnh, c tnh kh ha tan mu nhm trnh Fe Fe3+. trnh Fe2+ Fe3+ do oxi trong khng kh khi ha tan cn un nng, v cho mt t Na2CO3 to bu kh quyn CO2.
b. iu kin chun
Do hm lng Fe trong hp kim nhm khng cao nn dng dung dch KMnO4 long, chun ngui trnh phn ng phn hy KMnO4, mi trng H2SO4 6N, trc khi chun thm mt t Na2CO3 to bu kh quyn CO2 v hn hp bo v Zymerman (xem PTL). 2.3. Qui trnh xc nh Cn 1,000 0,0002g mu hp kim nhm vo bnh nn loi 100ml, rt qua phu 3040ml HCl 1:1 un nh n khi mu tan ht, ra nhanh v thm 100ml hn hp Zymerman, 0,1g Na2CO3 em chun bng KMnO4 0,01N n khi xut hin mu tm nht bn vng 3040 giy. 2.4. Tnh kt qu
%Fe =
m Fe ( NV ) MnO mm
100 vi m Fe =
56 1000
III. XC NH KM OXIT CNG NGHIP

Km l mt kim loi mu, trong cng nghip sn xut pin kh,c s dng lm cc m. Trong cng ngh m, km c s dng m to lp bo v, chng n mn. ZnO c sn xut t qung ZnCO3, ZnO c dng bt mu trng, hm lng ca n trong bt ZnO cng nghip 90%. Hm lng PbO c trong bt ZnO cng nghip khong 8 10%. Ngoi ra cn c Fe 1%; m 1%. iu ch ZnO cng nghip t qung ZnCO3 bng k thut nhit luyn nhit 12000C. ZnCO3 (t0) = Zn0 + O2+ CO2 Zn0 + O2 = ZnO Song song vi qu trnh ny c qu trnh to ocid ch theo phn ng: Pb0 + O2 = PbO Ngoi ra trong qu trnh thng hoa hi km v hi ca Pb cn c ln mt lng nh Fe bay hi theo. ZnO tinh khit cn c s dng trong dc phm. ZnO c dng lm nguyn liu u sn xut cc loi mui km c nhiu ng dng nh ZnSO4.7H2O, ZnCl2.H2O; ZnSiF6
Phn tch kim loi
1. Xc nh ZnO trong ZnO cng nghip ( Phng php chun kt ta) 1.1. Nguyn tc
Mu ZnO cng nghip c x l bng HCl chuyn v trng thi dung dch ri chun trc tip bng dung dch chun kaliferocyanua vi hn hp ch th fericyanua + diphenylamin. im tng ng nhn c khi dung dch t mu xanh tm sang khng mu. 1.2. iu kin xc nh - iu kin ph mu: Mu d tan trong acid v c mnh, thngchn acid HCl 1:1 ph mu theo cc phn ng: 2HCl + ZnO = ZnCl2 + H2O 2HCl + PbO = PbCl2 + H2O - Mi trng chun c pH = 2 3 nhm trnh kt ta hydroxyt. C ch chuyn mu xem ch tiu xc nh km trong hp kim ng. phn ng xy ra nh lng cn thm cht tr lng nh Na2SO4 hoc (NH4)2SO4. Trc khi chun cn phi trung ha dung dch xc nh ti pH = 2 3 bng dung dch NaOH 10%. Khi gn ti im tng ng cn lc mnh. - Phn ng chun : ( xem ch tiu xc nh Zn/ hp kim ng). 1.3. Qui trnh xc nh Cn 1,0000 gam mu ZnO cng nghip vo mt becher sch kh, ha tan bng 10ml dung dch HCl 1:1, sau khi tan ht, chuyn vo bnh nh mc 250ml, dng nc ct ra, trng v nh mc ti vch ( DD I). Ly chnh xc 10ml DD I cho vo bnh nn loi 250ml, dng NaOH 10% chnh tng git ti pH = 1 2 ( dng giy pH th). Thm khong 1 gam (NH4)2SO4 lm cht tr lng, lc cho tan, thm 5 6 git ch th Diphenylamin ri chun bng dung dch chun K4[Fe(CN)6] 0.1N n khi dung dch chuyn t mu xanh tm sang khng mu. 1.4. Tnh kt qu
m ZnO ( NV ) fero %ZnO = 100 f mm

Vi : m ZnO =
3 * 81.4 2.10 3
2. Xc nh PbO trong ZnO cng nghip ( Phng php th tch cromat) 2.1. Nguyn tc
Ha tan mu ZnO bng acid HCl, tin hnh kt ta Pb2+ di dng PbCrO4 bng thuc th K2Cr2O7 trong mi trng pH = 5 6. Lc ra v ha tan kt ta sinh ra mt lng ion cromat tng ng. Xc nh lng cromat sinh ra bng phng php iod t tnh c hm lng PbO c trong mu qui v %PbO. Cc phn ng:
Phn tch kim loi
2HCl + ZnO = ZnCl2 + H2O 2HCl + PbO = PbCl2 + H2O 2 Pb2+ + CrO42pH =56
PbCrO4
PbCrO4 + 4HCl PbCl4-2 + CrO42- + 4H+ 2CrO42- +2H+ Cr2O72- + H2O
Phng php Iod vi k thut chun th: Cr2O72- + 6I-d +14H+ 2Cr3+ + 3I2 + 7H2O
I2 + I- I 3
2 I3- + 2S2O 3
HTB
S4O62- + 3I-
2.2 iu kin xc nh
- Ph mu bng acid HCl l hp l, c th un si tng vn tc phn ng. Nu mu c Fe th cn thm HNO3 oxi ha Fe2+ v Fe3+. loi tr Fe trit cn phi s dng cht che amonicitrate trc khi kt ta PbCrO4 bng K2Cr2O7 pH = 5 6. V Ph ny Fe3+ s kt ta hydroxyt v c gi li trn lc cng vi kt ta PbCrO4. iu ny s gy sai s do khi ha tan kt ta th trong dung dch s c Fe3+, ion Fe3+ s tc dng vi I- sinh ra mt lng I3- gy ra sai s d. - iu kin kt ta: PbCrO4 l mt kt ta tinh th mn ht, d tan trong mi trng acid mnh v cng c kh nng trong mi trng kim mnh do ion ch lng tnh. V vy cn kt ta pH = 5 6 l hp l. Khi cho thuc th th phi cho t t, va cho va khuy, nng thuc th phi long. Thi gian lng kt ta t nht 2 gi. Cn phi iu chnh Ph dung dch v pH = 5 6 bng NaOH 10% trc khi cho thuc th K2Cr2O7 vo. - iu kin lc, ra kt ta: Lc kt ta qua giy lc bng xanh vi k thut lc gn, ra kt ta 2 ln bng dung dch K2Cr2O7 1% sau ra bng nc ct cho n khi ht ion cromat th bng dung dch Ag+ hoc Ba2+ - iu kin ha tan kt ta v chun : Dng hn hp dung dch HCl + NaCl ha tan kt ta trn lc trong iu kin nng. HCl lm dung mi ha tan, cn NaCl c tc dng chuyn kt ta PbCl2 v mui phc Na2PbCl4 trnh phn ng: PbCl2 + 2KI = PbI2 vng + 2KCl . Kt ta PbI2 gy cn tr cho phn ng chun . - Khi chun cn phi acid ha chuyn ion CrO42- v Cr2O72- bng H2SO4 6N. Dung dch chun l dung dch Fe2+ c tnh kh nn cn chun trong mi trng ngui trnh Fe2+ b oxi ha v Fe3+ bi oxi. Nn s dng ch th Feroin nhn im tng ng r rt. 2.3. Qui trnh xc nh Ly chnh xc 50ml DD I cho vo becher loi 250ml, thm nc ct ti khong 100ml, thm 10ml amonicitrate 10%, khuy u, dng NaOH 10% cho tng git va cho va khuy n khi xut hin kt ta trng ( kt ta ca Zn(OH)2). Thm 20ml CH3COOH 10% ri un nng. Thm t t 20ml K2Cr2O7 10%, khuy k, lng 2
Phn tch kim loi
gi. Sau lc v ra kt ta n khi ht CrO42- (th bng DD Ba2+ 5%). Ha tan kt ta trn lc bng 20ml HCl + NaCl nng. Ra giy lc bng nc ct nng n khi ht ion CrO42-. Tp trung dch lc + nc ra vo bnh nn (tng th tch khng qu 100ml) thm 5ml H2SO4 6N, thm nhanh 10ml KI 10%, trong ti 5 pht. Ly ra chun bng dung dch Na2S2O3 0.1N vi 5 git ch th HTB 5% n khi mt mu xanh. 2.4. Tnh kt qu:
%PbO =
m PbO ( NV ) Na2S 2O3 mm
100 f Vi m PbO =
223 3.10 3
3. Xc nh ng thi ZnO v PbO ( phng php EDTA) 3.1. Nguyn tc
Ha tan mu bng acid HCl, sau tch ch ra di dng kt ta PbSO4 bng H2SO4. Lc thu kt ta, dung dch qua lc dng xc nh Zn2+ bng phng php EDTA pH = 5 6 vi ch th xylenon da cam. Kt ta PbSO4 c ha tan bng amon acetat ri cng xc nh bng EDTA nh xc nh km trong cng iu kin v pH v ch th. Cc phn ng: 2HCl + ZnO = ZnCl2 + H2O 2HCl + PbO = PbCl2 + H2O PbCl2 + H2SO4 = PbSO4 + 2HCl Zn2+ + H2Y2- = ZnY2- + 2H+ PbSO4 + 2CH3COONH4 = (CH3COO)2Pb + (NH4)2SO4
3.2. iu kin xc nh
Pb2+ + H2Y2- = PbY2- + 2H+
- iu kin tch ch v km: Do Pb2+ v Zn2+ cng to phc bn vi EDTA cng khong Ph nn cn phi tch chng ra khi nhau. tch Pb2+ di dng PbSO4 cn phi c cn n khi bc khi trng ca H2SO4 nhm lm chc v kt ta hon ton PbSO4. Khi kt ta phi ch 2 gi mi c lc qua giy lc bng vng. Khi ha tan kt ta cn ha tan trong iu kin nng do kt ta PbSO4 d tan trong iu kin nng. - iu kin chun : V mi trng chun c pH = 5 6 nn trc khi chun cn phi iu chnh Ph v n nh Ph bng dung dch m acetatnatri c pH = 5. Dung dch EDTA c nng 0.05N 0.1N l ph hp. Ch th s dng l xylenon da cam ph hp cho vic xc nh c hai ion Pb2+ v Zn2+. 3.3. Qui trnh xc nh - Ph mu: Cn 1.0000 gam mu ZnO cng nghip trong mt becher loi 250ml, thm 10ml HCl 1:1 un cho n khi mu tan ht, thm 7 8 git HNO3 1:1 un n khi ht kh mu nu bay ra, thm tip 10ml H2SO4 1:3, un cho n khi bc khi trng, ngui, khuy u v lng 2 gi ri lc qua giy lc bng vng, ra kt ta trn
Phn tch kim loi
lc bng nc ct n khi ht ion Cl-, dung dch + nc ra tp trung v c nh mc ti 250ml (DD I). - Xc nh Zn2+: Ly chnh xc 10ml dung dch I cho vo bnh nn, trung ha n pH = 5 6 bng tng git NaOH 10% , thm 10ml dung dch m CH3COONa pH = 5, 2ml amonicitrat 10% + 3 git ch th xylenon da cam ri chun bng dung dch EDTA 0.1N n khi dung dch chuyn t mu hng sang mu vng. - Xc nh Pb2+: Ha tan kt ta trn giy lc bng 20ml dung dch CH3COONH4 10%, ra giy lc bng nc ct nng + 10ml dung dch m CH3COONa pH = 5 + 3 git ch th xylenon da cam ri chun bng dung dch EDTA 0,05N n khi dung dch chuyn t mu hng sang mu vng. 3.4. Tnh ton kt qu
m ZnO ( NV ) EDTA %ZnO = 100 f m mau

Vi m ZnO =
81.4 2.10 3
m PbO ( NV ) EDTA %PbO = 100 f mm

Vi m PbO =
223 2.10 3
IV. CU HI N TP V BI TP
1. Trnh by nguyn tc, phn ng, iu kin xc nh, qui trnh xc nh v cng thc tnh khi phn tch ch tiu Pb trong hp kim ng bng phng php cromat?. 2. Trnh by nguyn tc, phn ng, iu kin xc nh, qui trnh xc nh v cng thc tnh khi phn tch ng thi ch tiu Pb, Cu, Fe trong hp kim ng? 3. Trnh by nguyn tc, phn ng, iu kin xc nh, qui trnh xc nh v cng thc tnh khi phn tch ch tiu Pb trong hp kim ng? 4. Trnh by nguyn tc, phn ng, iu kin xc nh, qui trnh xc nh v cng thc tnh khi phn tch ch tiu Sn trong hp kim ng bng phng php iod? 5. Trnh by nguyn tc, phn ng, iu kin xc nh, qui trnh xc nh v cng thc tnh khi phn tch ch tiu Zn trong hp kim ng bng phng php Ferocyanur? 6. Trnh by nguyn tc, phn ng, iu kin xc nh, qui trnh xc nh v cng thc tnh khi phn tch ch tiu Cu trong hp kim nhm bng phng php iod? 7. Trnh by nguyn tc, phn ng, iu kin xc nh, qui trnh xc nh v cng thc tnh khi phn tch ch tiu Fe trong hp kim nhm bng phng php KMnO4?
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Phn tch kim loi
8. Trnh by nguyn tc, phn ng, iu kin xc nh, qui trnh xc nh v cng thc tnh khi phn tch ch tiu ZnO trong Km ocid cng nghip? 9. Trnh by nguyn tc, phn ng, iu kin xc nh, qui trnh xc nh v cng thc tnh khi phn tch ch tiu PbO trong Km ocid cng nghip bng phng php cromat? 10. Trnh by nguyn tc, phn ng, iu kin xc nh, qui trnh xc nh v cng thc tnh khi phn tch ng thi ch tiu ZnO + PbO trong Km ocid cng nghip bng phng php phc cht?
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CHNG 1 PHN TCH KIM LOI EN

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II. PHNG PHP LY MU

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III. NI DUNG PHN TCH

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FeSi + HCl + nH2O t SiO2. nH2O + FeCl2 + H2

1000 C SiO2. nH2O 950 1.1.2. iu kin xc nh

b. iu kin c kh mu v ng t keo SiO2

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Si4+ + Fe3+ + H2O + NO2

Mo2O 5 (Mo2O 7)5

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31 do 2(NH4)3H4[P(Mo2O7)6] 2P 46NaOH 1P 23.10 3

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Hoc Fe(NO3)3 + Na2SO3 + H2O Na2SO4 + Fe(NO3)2 + HNO3

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% P: l hm lng phn trm ca P c trong mu xc nh

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AgNO3 + NaCl AgCl + NaCl

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Khoa CNHH Chuyn ngnh Ha phn tch

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E0 CrO 4 2 _ ,OH_ / Cr3+ = _ 0.13V ; E0MnO 4 2 _ ,OH_ / MnO 2 = 0.6V

E0 CrO 4 2 _ / Cr 3+ =1.36V ; E0 MnO 4 2 _ ,H+ / Mn2+ =1.51V

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mm - khi lng mu, (g)