You are on page 1of 217

I HC THI NGUYN KHOA KHOA HC T NHIN V X HI

GIO TRNH HA HC PHN TCH


(DNG CHO CC H KHNG CHUYN HA)

TS. Nguyn ng c

Thi Nguyn, thng 5 nm 2008

DANH MC CH VIT TT 1. AAS: 2. CBHH: 3. LTDKL: 4. HCL: 5. HSKB: 6. TTCB: Php phn tch ph hp th nguyn t Cn bng ha hc nh lut tc dng khi lng n canh rng (Holow Cathod Lamp) Hng s khng bn Trng thi cn bng

M U Ha hc Phn tch l mt mn khoa hc c lp, n l chuyn ngnh ring ca Ha hc. Trong ha hc gm c 4 chuyn ngnh: ha V c, ha Hu c, ha phn tch, Ha l th ha Phn tch ng vai tr quan trng v n l mt mn ha hc thc nghim c xy dng trn nn tng ca ha hc V c ha Hu c v Ha l, n gm c phn tch nh tnh v phn tch nh lng. Phn tch nh tnh lm nhim v pht hin thnh phn nh tnh (s c mt) ca cc cht hay hn hp cc cht, cn phn tch nh lng lm nhim v xc nh hm lng c th ca cht c trong mu phn tch (thng tnh thnh phn trm). gii quyt nhim v ca phn tch nh tnh ngi ta thng dng hai phng php phn tch ha hc nh: phng php H2S, phng php Axit - baz hoc cc phng php phn tch ha l: phn tch ph pht x nguyn t, phn tch hunh quang, phng php quang k ngn la... gii quyt nhim v ca phn tch nh lng ngi ta cng dng cc phng php phn tch ha hc: phn tch khi lng, phn tch th tch hoc cc phng php phn tch ha l: o mu, phn tch ph hp th nguyn t, cc phng php phn tch in ha, cc phng php phn tch sc k... Ha hc phn tch rt quan trng khng nhng trong cc ngnh Ha hc ni ring m cn trong cc ngnh Sinh hc ni chung: Y hc, Nng nghip, Lm nghip, Dc hc... Chnh v vy ngghen tng ni: Khng c phn tch th khng th tng hp. V quan trng nh vy nn mi sinh vin mun hc tt mn hc ny phi hc tt cc mn: Ha i cng, ha V c, ha Hu c v Ha l, v cc mn ny c s cho mn ha hc Phn tch. phn tch mt i tng no , ngi lm phn tch phi thc hn cc bc sau: 1. Xc nh cc vn cn gii quyt chn phng php phn tch thch hp. 2. Chn mu i din v chuyn mu t dng rn sang dung dch. 3. Tch cc cht, l cng vic cn thit xc nh i tng chnh trong mu c chn lc v chnh xc cao. 4. Tin hnh nh lng cc cht bng phng php phn tch chn trn. 5. Tnh ton nh gi tin cy ca n. Chng ti son gio trnh ny nhm mc ch trang b cho sinh vin cc ngnh: 3

Sinh hc, Khoa hc Mi trng, Y hc, Nng hc c kin thc c bn nht v Ha phn tch, gip cho h c vn kin thc trong qu trnh hc tp trn gh nh trng cng nh sau khi ra trng c th bt tay vo cng vic chuyn mn ca h, iu kin lm vic vi nhng cng vic lin quan n ha Phn tch. Khi bin son gio trnh ny khng th trnh khi nhng thiu st. Chng ti mong c s ng gp kin ca cc bn ng nghip v cc em sinh vin. Thng 5 nm 2008 Tc gi

PHN TH NHT C S L THUYT HA PHN TCH CHNG 1: DUNG DCH CHT IN LY - CN BNG HA HC

1.1. CHT IN LY V S IN LY 1.1.1. nh ngha v s in ly v cht in ly - S in ly l qu trnh phn t phn ly thnh ion cn cht in li l cht c kh nng phn li thnh ion khi ha tan vo nc lm cho dung dch dn c in. V d: NaCl, HCl ha tan trong nc hay trong dung mi phn cc khc. V d:

Tng qut cho mt cht in ly c cng thc AmBn th: s 1.1.2. Cht in ly mnh, cht in ly yu 1.1.2.1. Khi nim Cht in ly mnh thc t phn ly hon ton. a s cc mui tan (NaCl, KCl, NaNO3, K2SO4, Na2CO3).Cc kim mnh (KOH, NaOH) u thuc loi ny. Cc cht in ly yu trong dung dch phn ly khng hon ton (dung dch NH3,CH3COOH, HCOOH, dung dch axit ccbonic....). Trong dung dch cht in ly mnh nng ln c dn in nh, dn in tng khi pha long dung dch. Dung dch cht in ly yu c dn in nh v nng ln th dn in khc nhau khng ng k nhng khi pha long dung dch dn in tng ln mnh. 1..2.2. Cc i lng c trng cho s in li 5

c trng cho kh nng phn ly ca cc cht trong dung dch, ngi ta dng hai i lng l in ly v hng s in ly. a. in ly l t s gia phn nng in ly v phn nng ban u.

T gi tr ngi ta tm phn loi: 2%: Cht in ly yu (cc axit yu, cc baz yu). 2% 30%: Cht in ly trung bnh (HF, H SO3 nc 1). 30%: Cht in ly mnh cc axit mnh, cc baz mnh, cc mui trung tnh. b. Hng s in ly (K): Thc cht l hng s cn bng ca phn ng phn ly, l t s gia phn tch s nng ca sn phm in ly v phn tch s nng cha in ly.

Ngi ta chng minh c rng: gia v K c mi quan h vi nhau qua h thc.

Trong C l nng ban u ca cht in ly. T ta thy in ly t l nghch vi nng , nng cng cao, in ly cng gim v ngc li. 1.2. CN BNG HA HC 1.2.1. Trng thi cn bng Gi s ta c cn bng:

Khi thm 2 milimol Fe2+ vo 1 lt dng dch cha 1 milimol I3-, mu gim nhanh, ngha l phn ng xy ra theo chiu nghch.

Ngc li khi thm 2 milimol Fe3+ vo 3 milimol I- th mu tng ln, phn ng xy ra theo chiu thun. V d dn ra ch r mi quan h v nng cc cht trng thi cn bng ha hc. Mi quan h ny bin i di tc dng ca mt s yu t nhit , p sut nng (theo nguyn l chuyn dch cn bng Lsatlie). Mt trng thi cn bng c c trng bng 1 hng s cn bng. 1.2.2. Cc phng php biu din hng s cn bng. Gi s c cn bng ha hc

Gi v1 l tc ca phn ng thun v v2 l tc phn ng nghch. Theo nh lut tc dng khi lng v tc phn ng ta c:

Trong k1, k2 l hng s tc ca phn ng thun v nghch. Ti trng thi cn bng ca phn ng ta c v1 = v2 hay k1.C m .C n = k 2 .C p .C q M N P Q

Ngi ta gi K l hng s cn bng ca phn ng, k hiu l KC. phn bit nng cc cht trng thi cn bng v nng cc cht trng thi bt k, ngi ta k hiu nng cc cht trng thi cn bng qua du mc vung [ ]. Do :

Nu phn ng trn l ca cc cht kh v gi pM, pN, pP, pQ l p sut ring phn ca cc cht M, N, P, Q th ngi ta cn chng minh c hng s cn bng tnh theo p sut (Kp).

Nu phn ng M, N, P, Q thc hin trong dung dch v gi NM, NN, NP, NQ l nng phn mi ca cc cht M, N, P, Q th ta c:

Gia KC v KP v KN c mi quan h vi nhau nh sau:

Trong n = (nP+ nQ) (nM + nN) v ch p dng c khi M, N, P, Q l cc cht kh. Ngoi cc cch biu din trn y, ngi ta cn biu din hng s cn bng thng qua cc hm nhit ng. V d: vi phn ng:

Bit H0 v S0 phn ng, cho nhit phn ng l T. Gi G l th ng nhit ng p ca phn ng th:

trng thi cn bng:

1.2.3. Biu din nh lut tc dng khi lng i vi mt s dng cn bng thng gp 1.2.3.1. Cn bng axt - baz Cn bng phn ly ca Axt:

Kt gi l hng s phn ly axit (gi tt l hng s axit). Cn bng phn li ca baz:

Kb gi l hng s phn li baz (hng s baz). 1.2.3.2. Cn bng to phc

1, 2 l hng s to thnh tng nc ca cc phc cht Ag(NH3)+ v Ag(NH3)2+

1.1, 1.2 l hng s to thnh tng hp ca cc phc cht Fe(OH)2+ v Fe(OH)2+ 1.2.3.3. Cn bng to thnh hp cht tan

Ts l tch s tan ca AgCl 1.2.3.4. Cn bng phn b

KD gi l hng s phn b ca I2 1.2.3.5. Cn bng ha tan ca cht kh - nh lut Henri

Khi p sut ring phn ca kh bng 1 at th hng s Henri K chnh l tan ca kh. 1.2.4. T hp cn bng Trong cc bng tra cu v cn bng ngi ta cho gi tr hng s ca cc cn 9

bng n gin. Trong thc t chng ta thng gp cc cn bng phc tp c t hp t cc cn bng ring l. Sau y l mt s v d t hp. 1.2.4.1. Biu din cn bng theo chiu nghch Qu trnh thun:

Qu trnh nghch:

Nh vy hng s cn bng ca qu trnh nghch bng gi tr nghch o hng s ca cn bng ca qu trnh thun. V d:

Nh vy, 1 c gi l hng s bn ca phc v K, c gi l hng s khng bn ca phc. 1.2.4.2. Cng cn bng Cho:

Tnh hng s cn bng ca M + 2A

MA2

1.2

(c)

Cn bng (c) thu c khi ta cng v theo v ca cc cn bng (a), (b), ng thi loi b s hng MA cng c mt hai v.

10

Hng s cn bng t hp thu c khi cng cc cn bng vi nhau bng tch cc hng s cn bng ring l.

1.2.5. Tnh gn ng khi h ch c mt cn bng ch yu Trong trng hp n gin thng gp ch c mt cn bng duy nht th c th t hp nh lut bo ton nng vi nh lut tc dng khi lng (LTDKL) tnh nng cn bng cc cu t. V d l: Trong dung dch MX c nng C mol/1 ch c cn bng.

Theo nh lut bo ton nng i vi MX, ta c:

Theo biu thc LTDKL p dng cho (a) ta c:

Thay (c) v (e) vo (d) ta c:

Gii phng trnh (g) cho php nh gi X v t (c), (e) ta tnh c nng cn bng cc cu t trong dung dch. 11

cho tin ta ghi s tnh ton nh sau: Cn bng: Nng ban u (mol/1) MX C Mn+ + XnO +x O +x x (K)

Nng phn li: (C) (mol/l) - x Nng ln: ([ ]) (mol/l) Theo LTDKL:

c-x x

Nu x << C (khi K rt nh).

Trong trng hp K ln, ngha l phn ng xy ra mnh theo chiu thun th nn t nng cn bng ca cu t c nng b nht v tri ca phng trnh phn ng lm n s. V d 2: Tnh nng cn bng ca cc cu t trong dung dch HCN 0,01M . Trong dung dch c cn bng:

Bi v Ka rt b (10-9,35) nn s phn li ca HCN xy ra khng ng k. Ta chn n s v phi ca phng trnh: [H+] = [CN-]= x. i lng ny cng chnh l nng phn ng. Ta c s : HCN H+ + CN-

Nng ban u C (mol/l) 0,1 C (mol/l) [ ] (mol/1) -x 0,0 1 - x x x x x

Vy ta chp nhn: 12

1.3. HOT Theo thuyt v cht in li mnh ca bai - Huken, vi nhng dung dch long v rt long khong cch gia cc con cch xa nhau, lc tng tc gia cc ion l khng ng k, c tnh bng cng thc:

Trong F l lc ht gia cc con, ql v q2 l din tch hai ion, r l khong cch gia cc ion, E l hng s in mi ca dung mi. Cn vi dung dch m c hn, xung quanh mt cation cn c nhiu anion v ngc li hin tng bao bc ny to thnh lp "kh quyn" ion:

Do lc tng tc F gia cc ion b gim hn v c hiu ng chn gia cc con vi nhau v nng th hin hot tnh ha hc ca chng b gim xung v nng c hot tnh ha hc thc s ny c gi l nng hot ng, gi tt l hot v k hiu l a(active concentration). Nh vy a = f.c, trong f c gi l h s hot , v a < c nn f < 1. Da trn l thuyt ng hc phn t, nh lut phn b Bolztman, cc ng thit lp phng trnh tnh f:

Trong Zi l in tch ln th i, l lc ion. Lc ion t c tnh theo cng thc.

Trong : i l ion th i; n l tng s ion c mt trong dung dch. 13

Nu 0,01 0,2. Ta tnh lgf theo (1.12). V d: Tnh hot ca ion Ca2+ trong dung dch bao gm CaCl2 0,01M v NaNO3 0,01M. Gii:

Tnh h s hot f:

1.4. CC LOI PHN NG S DNG TRONG PHN TCH TH TCH 1.4.1. Phn ng trung ha - Axit mnh v baz mnh:

- Axt yu v baz mnh:

- Axt mnh v baz yu:

- Baz mnh v axit a chc:

14

1.4.2. Phn ng oxy ha kh

1.4.3. Phn ng kt ta

1.4.4. Phn ng to phc

1.5. NNG DUNG DCH. 1.5.1. Cc loi nng dng trong phn tch th tch Nng dung dch l: lng cht tan trong mt n v th tch hay mt n v khi lng. 1.5.1.1. Nng % khi lng (C%) ch ra c bao nhiu gam cht tan trong lng dung dch. V d dung dch NaOH 40% tc l trong lng dung dch NaOH c 40g NaOH nguyn cht.

Trong a l s gam cht tan v b l s gam dung mi. 1.5.1.2. Nng mol /l (gi l nng mol, k hiu l M) ch ra c bao nhiu mt cht tan trong 1 lt dung dch. V d dung dch H2SO4 0,5M ngha l trong 1 lt dung dch H2SO4 c 0,5mol axt:

Trong a l s gam cht tan, p l khi lng v V l s lt dung dch. 15

1.5.1.3. Nng ng lng gam/ lt, cn gi l nng ng lng, k hiu l N ch ra c bao nhiu ng lng gam cht tan trong mt lt dung dch. V d dung dch KMnO4 0,1N ngha l trong 1 lt dung dch c 0,1 ng lng KMnO4.

Trong a l s gam cht tan, D l ng lng gam v V l s lt dung dch. 1.5.1.4. chun T l s gam (hay miligam) cht tan trong 1mililt dung dch. 1.5.1.5. chun (A) theo cht c xc nh (cht nh phn). TNB ch ra c bao nhiu gam cht nh phn B tc dng vi lu dung dch chun A. V d, TAgNO /Cl =
3

0,004 (g/ml) ngha l 0,004g cht nh phn Cl- tc dng va vi lu dung dch chun AgNO3. 1.5.1.6. Mi lin h gia cc loi nng : Nu gi nng % ca dung dch l C%, khi lng ring ca dung dch l d, P l phn t gam cht tan, D l ng lng gam cht tan, ta c:

1.5.2. Cc bi ton v nng dung dch 1.5.2.1. Pha ch dung dch t lng mui rn tinh th V d: Hy pha 2 lt dung dch Axt oxalic 0,1N t Axt tinh khit H2C2O4.2H2O. p dng cng thc:

Ta tnh ra lng gam axt cn thit pha dung dch l: a = 0,1.63.2 = 12,6g Vy, ta cn chnh xc 12,6g axit tinh khit, ha tan hon ton vo nc ri chuyn ton b lng dung dch ny sang bnh nh mc 2 lt, nh trng cc ha tan axt ba ln, mi ln 10ml H2O, ht vo bnh 2 lt. Cui cng thm nc n vch mc, o u. 1.5.2.2. Pha ch dung dch t dung dch gc (quy tc ng cho) a. Vi nng phn trm: Gi s phi trn dung dch 1 c nng % l C1, th tch V1, khi lng ring l d1 vi dung dch 2 c nng % l C2, th tch V2, 16

khi lng ring l d2 c dung dch c nng %C2. Ngi ta chng minh c:

Cc v d: 1. Trn 500ml dung dch HNO3 30% vi 500ml dung dch HNO3 10% thu c dung dch HNO3 bao nhiu % (cho d1 = 1,2g/ml, d2 = l,05g/ml). p dng (1.19) ta c:

2. Cn bao nhiu ml dung dch HNO3 25% (d = 1,19) trn vi dung dch HNO3 5 %(d = 1,04) c 1 lt dung dch HNO3 10% p dng (1.19):

Hy pha 2 lt dung dch HCl 0% t axt c 36% (d = 1,19 g/ml). y l trng hp pha long dung dch trong dung dch th 2 l H2O c nng % bng khng v khi lng ring l 1 g/ml. p dng (1.19) ta c:

Vy ta ong 448ml axt c, chuyn ton b sang bnh 2 lt, trng bnh bng 17

nc ct v thm nc ct n vch mc, ri y kn np bnh, o i o li trn u dung dch. b. Vi nng M, N. Gi s phi trn V1 ml dung dch th nht c nng mi l M1 (hoc nng ng lng N1) vi V2 ml dung dch th hai c nng mi l M2 (hoc nng N2) c dung dch c nng l M (hoc N) th tch l V = V1 + V2 (ml). Khi ta c:

Cc V d: 1. Pha 2 lt dung dch H2SO4 0,5 M vi 1 lt dung dch H2SO4 0,1 M c dung dch bao nhiu M. p dng cng thc (1.20) thay s vo ta c:

2. Cn bao nhiu mililt dung dch NaOH 0,5N trn vi 1 lt dung dch NaOH 0, l c 2 lt dung dch NaOH 0,2N. p dng (1.20) ta c:

V1 = 600ml 3. Pha 2 lt dung dch HCl 0,1N t axt HCl 0,5M. y cng l s pha long dung dch trong nc l dung dch th hai c nng bng khng. Do p dng (1.20) ta c:

Vy cn ong chnh xc 0,4 lt dung dch HCl 0,5M, chuyn ton b sang bnh nh mc 2 lt trng bnh chuyn ht HCl sang bnh nh mc thm nc n vch mc, o u bng cch y np kn vo o ln o xung.

18

CU HI - BI TP CHNG 1

1.1. Vit phng trnh phn ng dng ion thu gn xy ra (nu c) trong cc dung dch nc sau:

1.2. Trn 20,00 ml dung dch Ba(OH)2 0,0211M vi 40ml dung dch Na2SO4 0,0153M. Hy Cho bit nng gc, nng ban u v nng cn bng ca cc ion trong dung dch (coi phn ng xy ra hon ton). 1.3. Vit biu thc nh lut tc dng khi lng i vi cc cn bng sau:

1.4. Cho bit nng cn li ca dung dch H2SO4. 1.5. Hy pha 2 lt dung dch H2SO4 0,1N t axt c 98% (d= 1,84g/ml). 1.6. Tnh lc ion ca dung dch gm NaNO3 0,01M, NaOH 0,02M v BaCl2 0,005M. 1.7. Tnh h s hot ca ion OH- trong dung dch NaOH 0,001 M v NaCl 0,009M. 1.8. Tnh in li ca dung dch HCN 0,10-4M, cho Ka = 10-9.35. 1.9. Tnh nng cn bng ca cc ion trong dung dch gm Fe3+ 0,1 M, 1,00M v I- 0,100M. Bit rng cn bng ch yu xy ra:
H+

1.10. Tnh nng cn bng trong dung dch gm CH3COOH 0,10M v CH3COONa 1,00M. Bit cn bng ch yu xy ra trong dung dch:

19

CHNG 2: PHN NG AXIT - BAZ

2.1. AXT BAZ 2.1.1. Quan im axit v baz ca Bronsted - Laury Axit l cht cho proton, baz l cht nhn proton. Axt:

Baz:

Trung tnh:

Lng tnh:

Ngi ta chng minh c [H+][OH-] = [H3O+][OH-] = 10-14 250C theo qui c quc t: pH = - lg(H+) v POH = lg(OH-) (2.1) 2.1.2. nh ngha phn ng axit - baz. Phn ng axit - baz l phn ng gia mt axit v mt baz l nhng phn ng trung ha nghin cu trn y, to ra sn phm l mt mui axit hoc trung tnh v nc. mnh axit c c trng bng hng s phn li. Khi mnh baz c 20

c trng bng hng s phn li Kb.

Trong dung dch nc bao gi cng tn ti mt cp axt baz lin hp,

Cp: V: Cp: c gi l cc cp axt - baz lin hp. Vi 1 cp axt baz lin hp nu axt cng mnh th baz cng yu v ngc li. Mi quan h gia Ka v Kb cng c biu din bng h thc sau:

2.2. PHNG TRNH BO TON PROTON Phng trnh bo ton proton ca mt dung dch axit - baz l phng trnh biu din s trao i proton ca cc axit baz c trong dung dch qua cc nng cn bng ca cc cu t trong dung dch: s mol proton cc axit cho lun bng s mol proton cc baz nhn. Sau y l mt s th d: V d l: Phng trnh bo ton proton ca nc nguyn cht. Trong nc nguyn cht ch c mt cn bng trao i proton: H3O v H+.

S mol proton nc nhn l [H3O+] bng s mol proton [OH-] cho v 1 phn t H2O khi cho i 1 proton th bin thnh ion OH- nn phng trnh bo ton proton l [H3O+] = [OH-] V d 2: Xt dung dch HCl nng C mol/l. Trong dung dch c hai axit l HCl v H2O v 1 baz l H2O. Trong xy ra cc qu trnh sau: 21

S mol proton H2O nhn bng s mol proton HCl cho v H2O cho:

V d 3: Xt dung dch hn hp HCl C1M + CH3COOH C2M. Trong dung dch c axit mnh HCl, axt yu CH3COOH v baz yu H2O, axit yu H2O nn xy ra cc qu trnh sau:

S mol proton nc nhn bng s mol proton 3 axit cho nn:

V d 4: Xt dung dch NH3 l dung dch ca 2 baz (H2O, NH3) v mt axit (H2O):

S proton cc baz nhn bng s proton cc axit cho:

V d 5: Xt dung dch hn hp CH3COO- v CN-. Trong dung dch c 3 baz v 1 axit, nn xy ra cc cn bng

Tng s mol proton m cc baz nhn bng s mol proton nc cho nn phng trnh bo ton proton l:

V d 6: Xt dung dch H3PO4 Dung dch gm hai axit: a axit (H3PO4), n axit v n baz (H2O) nn trong dung dch c cc cn bng sau:

22

Phng trnh bo ton proton ca dung dch ny:

V d 7: Xt dung dch a baz CO32- (Na2CO3) cc Cn bng trong dung dch ny:

Phng trnh bo ton proton ca dung dch:

V d 8: Xt dung dch NH4CH3COO. Trong dung dch ny c cc cn bng sau:

Phng trnh bo ton proton ca dung dch l:

2.3. TNH pH TRONG CC DUNG DCH NC Gi s c h gm: mt axt yu HA c hng s Ka v nng Ca mt baz yu NaA (mui ca axit yu v baz mnh) c nng Cb.

Ngoi cc phng trnh (1, 2, 3) ta cn c: Phng trnh trung ha in: [H+] + [Na] = [CH3COO-] + [OH-] Phng trnh bo ton nng : [HA] + [A-] = Ca + Cb Bng cc php bin i ton hc, t 5 phng trnh trn, ngi ta chng 23 (4)

minh c:

y l phng trnh tng qut tnh [H+] trong dung dch, n l phng trnh bc 3 ca [H+]. Do tnh pH trong cc dung dch nc, ta phi dng cch gii gn ng. 2.3.1. Dung dch axt mnh c nng Ca.

2.3.2. Dung dch baz mnh c nng Cb.

2.3.3. Dung dch axit yu c Ka, Ca. V l mt Axt yu nn [OH-] << Ka v Cb = 0, do t (2.5) ta c:

2.3.4. Dung dch ca mt baz yu c Kb v Cb. V l mt baz nn

T (2.5) ta c:

24

2.3.5. Dung dch gm 1 axit yu v 1 baz yu (dung dch m) 2.3.5.1. nh ngha: Dung dch m l dung dch c gi tr pH khng thay i hoc thay i rt t khi thm mt lng nh axit mnh hoc mt lng nh baz mnh vo dung dch , k c khi pha long dung dch. V d h m axtat 1 M:

Thm 10ml HCl 0,1M vo pH = 4,7 Thm 10ml NaOH 0,1 M vo pH = 4,9 2.3.5.2. Cc loi dung dch m - m axtt: CH3COOH / CH3COONa - m cacbonat: NaHCO3/ Na2CO3 - m Amoni: NH4Cl / NH4OH - m pht pht: Na2HPO4 / Na3PO4 (hoc NaH2PO4 / Na2HPO4; H3PO4 / NaH2PO4). Nhng h m ch c mt cp axt baz lin hp c gi l m n, cn h c 2 cp axt baz lin hp c gi l m a. 2.3.5.3. Cng thc tnh pH ca dung dch m V dung dch c mt axt yu v mt baz yu nn t (2.5) ta c:

25

2.3.6. Dung dch axit a chc: H3PO4, H2SO3, H2CO3. Loi axit a chc ny phn li theo nhiu nc ?

Nu nc (1) cch xa nhiu nc (2) hng vn ln th khi tnh ton vi axt 2 nc ngi ta khng tnh n nc 2, coi nh nh mt n axt yu m pK1= pKa ca n axt yu:

Vi axit ba nc ngi ta tnh pH nc 1 NaH2PO4 theo cng thc sau:

Cn nc th 3 c tnh (Na3PO4):

2.4.CC V D TNH pH CA DUNG DCH: V d l: Tnh pH ca dung dch HCOOH 0,1M. Cho Ka= 10-4. Ta p dng (2.8).

V d 2: Tnh pH ca dung dch NH3 0,1 M. Cho KNH3 = 10-4,8. p dng (2.9) ta c:

V d 3: Tnh pH ca dung dch thu c khi thm 15ml HCl 0,1M vo 20ml dung dch NH3 0,1M. Cho KNH3 = 10-4,8 Phn ng xy ra: HCl + NH3 = NH4Cl Nng hai cht u bng nhau v u l 0,1 M nn th tch tiu tn phi tng ng nhau. Do th tch HCL trung ha NH3 l 15ml, lng NH3 cn l 26

5ml, y l mt baz yu, dung dch cn c NH4Cl to thnh l 15ml v l mt axt yu. Dung dch thu c l mt h m. p dng (2.10):

Thay pKa = 14 - pKb v

vo ta c:

V d 4: Tnh pH ca dung dch thu c khi thm 20ml KOH 0,1 M vo 25ml dung dch HCOOH 0,1 M. Cho Ka = 10-4 Phn ng xy ra:

Cng tng t bi trn, ta thy dung dch sau phn ng cn d HCOOH l 5ml, lng mui HCOOK to thnh l mt baz yu c nng tng ng nng KOH thm vo. Do dung dch thu c l h m. p dng (2.10), ta c:

2.5. CN BNG AXIT - BAZ TRONG DUNG MI KHNG NC 2.5.1. Phn loi cc dung mi V nguyn tc, mi cht lng u c th dng lm dung mi. C cc dung mi phn t trong tn ti ch yu cc phn t khng mang in (v d nc, ru, amoniac lng, cc axit cc boxylc, cc amin...) c cc dung mi ion, trong ch tn ti cc cation v anion v loi dung mi kim loi l kim loi nng chy ( nhit cao). Cc dung mi phn t ng vai tr quan trng, trong cc dung mi lng tnh l quan trng hn c. 2.5.2. Phn ng Axt - baz trong dung mi lng tnh Trong cc dung mi lng tnh c qu trnh t phn proton ca cc phn t dung mi. Chng hn vi dung mi HS. 27

Tch s ion ca dung mi.

Phn ng t phn proton ca mt s dung mi lng tnh. Nc:

Ru etylic:

Axit focmic:

Cng nh trong nc, trong dung mi lng tnh HS, ta c:

V pKi = pH + pS Trong dung mi nguyn cht pH = pS =1/2 pKi Dung dch s c phn ng axt khi [H2S+] > [S-] hoc pH < pS, s c phn ng baz khi [H2S+] < [S-] hoc pH > pS Ni chung trong dung mi ny pH c xc nh trong phm vi pH = 0 cho n pH = PK(HS). Trong bng (2.1) c cho c tnh axit - baz ca mt s dung mi lng tnh. Bng 2.1. c im axit - baz ca mt s dung mi lng tnh. Dung mi (HS) H2SO4 HCOOH CH3OH C2H5OH Ionlioni H3SO4+ HCOOH+ CH3OH+ C2H5OH2+ Ionliat HSO4HCOOCH3OC2H5OKi 10-3,8 10-6 10-16,7 10-19 Thang pH 0 - 3,8 0 - 6,0 0 - 16,7 pH trung bnh 1,9 3,0 8,35

28

Trong nc HCL l mt axt mnh, nhng trong dung mi axt axtc bng c tnh baz rt yu nn HCl li l mt axit yu.

i vi cc dung mi c hng s in mi th thng xy ra s lin hp gia cc ion tch in ngc du. Chng hn, trong dung dch axt HA, cn xy ra s lin hp gia cc ion H2S+ v A- to ra cc cp ion H2S+A- (hay H+A-) khc vi phn t HA. Do trong cc dung mi ny lc axt ca nhiu cht gim i. trong H2O ( = 78,5) axit axetic c pKa = 4,76; cn trong ru (etanol = 24,2) th pKa ca axt axetic bng 10,3, ngha l lc axit gim i nhiu. Hng s phn li ca axt Ka ph thuc vo hng s in mi ca dung mi, ph thuc vo in tch v kch thc cc ion v nng cc ion. Bng 2.2. cho ch s hng s axt v ch s hng s baz ca mt s cp axit baz trong etanol v trong axit axetic bng. Bng 2.2. Ch s hng s axit v baz Cp Axit Baz HNO3/ NO3HCOOH/HCOOCH3COOH /CH3COOHClO4/ClO4HCl/ClHNO3/NO3Dung mi C2H5OH C2H5OH C2H5OH CH3COOH bng CH3COOH bng CH3COOH bng pKa 3,6 9,2 10,3 2,9 5,0 9,4 pKb 15,4 9,5 8,7 11,5 9,4 5,0

Vic nh gi pH trong cc dung dch khng nc cng tng t nh trong dung dch nc.

29

CU HI V BI TP CHNG 2
2.1. Tnh [OH-], pH, pOH i vi dung dch axt c nng [H+] = 0,0010M, coi h s hot cc cu t bng 1. 2.2. Thm 300ml H2O Vo 200ml dung dch HCl c nng ln H+ 0,10M. Tnh pH ca dung dch sau khi pha long. 2.3. Tnh pH, pOH v [H+], [OH-] ca dung dch HCl 1,0.10-3M. 2.4. Trn 200ml dung dch HCl c pH = 2,0 vi 300ml d HNO3 c pH = 3,0. Tnh pH ca dung dch thu c. 2.5. Nh 1 git HCl 3,4.10-3 M vo 300,00 ml nc. Tnh pH ca dung dch, bit th tch 1 git l 0,03ml. 2.6. Tnh [H+], [OH-], pH ca dung dch thu c khi thm 20,0 ml dung dch NaOH l,00.10-3M vo 80,00 ml dung dch HCl 2,5.10-4 M. 2.7. Tnh pH ca dung dch HCOOH 0,1M.

2.8. Tnh nng ca dung dch CH3COO- phi c trong dung dch sao cho pH = 3,0. pH= 3,0 << 7,0. Vy s phn li ca nc l khng ng k.

2.9. Tnh pH ca dung dch NaCN 0,010M, Kb = 10-4,65 2.10. Trn 20,00ml HCl 0,02M vi 30,00 ml dung dch CH3COOH 0,15M. Tnh pH ca hn hp thu c, cho Ka. 10-4,76. 2.11. Tnh pH ca dung dch CH3COOH Cl= 0,01 M v NH4Cl C2= 0,100M, Ka = 10-4,76, Kb= 10-4,76. 2.12. Tnh pH trong hn hp HCOOH 1,00.10-3 M v KCN 0,100M, Ka = 10-9,75. 2.13. Tnh pH ca hn hp HCN 1,00.10-3M v KCN 0,100M, Ka = 10-9,36. 2.14. Tnh pH v nng S2- trong dung dch H2S 0,10M: K1 = 10-7,03, K2= 10-12,92 30

CHNG 3: PHN NG TO PHC

3.1. KHI NIM V PHC CHT 3.1.1. nh ngha - phn loi Phc cht l nhng hp cht c thnh phn phc tp, bn trong dung dch nc, ngha l kh nng phn li km. V d: Cho 1mmol (NH4)2SO4. Fe2(SO4)3.12H2O ha tan vo th tch xc nh nc v cho vo lng KCNS d, dung dch nhn c c mu mu. Cho 2mmol K3[Fe(CN)6] ha tan vo th tch nc nh trn v cho vo lng KCNS d dung dch nhn c s c mu hng. iu chng minh K3[Fe(CN)6] bn hn (NH4)2SO4 Fe2(SO4)3. 12H2O. Kh nng phn li ra Fe3+ t do ca [Fe(CN)6]3- l rt yu v n l phc cht, cn (NH4)2SO4.Fe2(SO4)3.12H2O l mui kp. Phc cht c hai loi, l phc cht v c v phc cht hu c. - Phc cht v c: K3[Fe(CN)6], K4[Fe(CN)6], NH4+ [Ag(NH3)2]Cl, CdCl3-, CdCl42-... - Phc cht hu c: +Me2+ to vi mui 2 ln th Na ca EDTA (Etylen Diamin Tetra Axetic axit):

Pb2+ to vi Dietyl Dithio Cacbamat Natri:

Phc [DDC]Pb/2 c cng thc nh sau:

31

3.1.2. Cch gi tn phc cht: S ch s phi t + tn phi t + tn ion trung tm + tn ion cu ngoi. - [Cu(NH3)4]SO4: Tetramino ng (II) sun pht. - K3[Fe(CN)6]: Kali hexa xyanua st (III) Tn ca phi t: X-halogien nua; OH - hyroxo; NO3- nitrato; H2O - aqu; NH2(NH3- NH) amino; CO - cacbonyl. 3.1.3. Hng s bn v khng bn ca phc cht:

Trong :

c gi l hng s khng bn nc 1 th:

l HSKB nu 6, cn c gi l hng s khng bn tng hp. Ngc li: th c gi l hng s bn nc 1 (3.4)

cn:

32

c gi l hng s bn nc 2

(3.5)

v c gi l hng s bn nc 6 (3.6)

Cn phn ng: c gi l hng s bn tng hp (3.7)

i vi phc nhiu nhn th hng s to thnh tng hp c th thm ch s cho bit s lng ln trung tm, ch s ny sau ch s phi t. V d:

3.2. TNH NNG CN BNG CA CU T TRONG DUNG DCH PHC CHT Gi s c cc phn ng to phc xy ra theo s :

Nng cc dng ng:

Nh vy khi bit c dng tn ti ch yu ca phc cht, ta c th tnh c nng cn bng theo nh lut tc dng khi lng hoc theo nh lut bo ton 33

nng i vi ion kim loi v i vi phi t. 3.2.1. Phi t rt d so vi ion trung tm. t c iu phi tnh ton bng nhng phng php gn ng thch hp. Khi phc to thnh s c th c s phi tr cao nht (v CL >> CM). Ta c nng cn bng phi t bng nng ban u ([L] CL) V d 1: Tnh nng cn bng cc cu t trong dung dch AgNO3 0,01M, NH3 1,00 v NH4NO3 1,00M. Cc qu trnh xy ra trong dung dch:

Xt cc iu kin gn ng. Tnh gn ng pH ca dung dch. T cn bng (3) ta c:

gi tr pH ny: [NH3] = 1 = CNH3 Nh vy c th b qua s proton ha ca NH3. T (4) ta c:

Nh vy s to phc hiroxo cng xy ra khng ng k. T (1), (2) ta c:

Vic so snh (5) v (6) vi [NH3] CNH3 = 1 cho thy.

34

Vy phc tn ti trong dung dch ch yu l Ag(NH3) T lp lun trn ta c th tnh gn ng nh sau: - Xc nh thnh phn gii hn:

Tnh CB theo s Kamar:

Vi x << 0,01 ta tnh ra:

Nh vy cc gi thit gn ng trn u hon ton tha mn. V d 2: Tnh nng cn bng trong dng dch Cd(NO3)2 0,01M v HCl 1,00M.

Xt cc iu kin gn ng. - Mi trng axt, c th b qua s to thnh phc Hiroxo ca ion Cd2+.
- C Cl >> C Cd , cc gi tr lg khng qu ln v khng chnh lch nhau nhiu.
2+

Do c th coi [Cl-] C Cl nhng khng th coi 1 dng phc no l chim u th

(1 2 3 4). 35

Khi tnh gn ng, phi k s c mt ca tt c cc dng phc cloro ca Cd2+ p dng nh lut bo ton nng ban u i vi ion Cd2+ ta c:

p dng nh lut TDKL cho cc cn bng (1) (4) v thay cc gi tr tnh c ca cc dng phc vo (5) ta c:

Sau khi t hp ta rt ra:

Chp nhn [Cl-] C Cl = 1. Gii (7) ra ta c:

Vic kim tra bng cch thay cc kt qu tnh c vo phng trnh (5) cho thy:
C Cd 2 + = 9,975.10 M so vi gi tr ban u ( C Cd 2+ = 0,010) th sai s l khng
-3

ng k (-0,25%). Nu thay cc kt qu tnh c vo phng trnh nh lut bo ton nng i vi ion Cl- th:

Suy ra: Sai s: C th chp nhn c, nu ch rng sai s ca cc hng s cn bng c th dao ng trong khong 1 - 10%. Cc kt qu tnh ton cng cho thy trong h Cd2+(010M) + Cl-(1,0M) cc dng phc tn ti mc ngang nhau, trong nng CdCl2 hi ln hn, c nng CdCl42- li b nht. 3.2.2. Ion trung tm rt d so vi phi t (CM>> CL) Trng hp ny thng gp khi pht hin nh tnh cc ion. 36

V d: Thm 1 git (0,03 ml) dung dch NH4CNS 0,10M vo 1,00ml dung dch FeCl3 0,100M khi c mt HCl 1 M (coi th tch thay i khng ng k khi thm thuc th). Tnh nng cn bng cc cu t trong dung dch.

Xt cc iu kin gn ng. V nng ln H+ ln nn c th b qua s phn li ca ion NH4+ v s to phc hidroxo ca Fe3+. V C 3+ >> CSCN- nn c th coi phn ng to thnh phc FeSCN2+ l ch Fe yu:

Thnh phn cc ion:

Ngoi phc FeSCN2+ trong dung dch cn cc qu trnh:

37

Vic kim tra cho thy:

u rt b so vi [FeSCN2+]. Vy cch tnh gn ng trn l hon ton ph hp. 3.3. NH HNG CA pH V CA CC CHT TO PHC PH N NNG CN BNG CA PHC. HNG S KHNG BN V HNG S BN IU KIN Trn y chng ta nghin cu cn bng to phc trong iu kin ln trung tm v phi t ch tham gia vo mt phn ng duy nht l phn ng to phc gia chng vi nhau. Trong thc t cc trng hp rt t gp m ta thng gp cc trng hp trong ion trung tm hoc phi t hoc c hai thng tham gia vo nhng phn ng ph khc. V d: cation Cu2+ v anion etylen - iamintetraaxetat (vit tt l EDTA) v c k hiu l Y4- khng nhng ch phn ng vi nhau to thnh phc CUY2- m Cu2+ cn c th to phc vi cc phi t khc nh OH-, NH3, v Y4- cn c th tham gia phn ng vi ion H+. V vy, nhng ion v phn t ny (OH-, H+, NH3) l nhng yu t lm thay i s to phc ca Cu+ v EDTA. Trong trng hp ny ngi ta thng dng hng s bn hoc khng bn iu kin phn nh nhng iu kin c th trong phn ng to phc c nghin cu xy ra ng thi n gin ha vic tnh ton cc nng cn bng. Hng s bn iu kin. Gi s ion kim loi Mn+, ngoi vic tham gia phn ng to phc chnh vi anion EDTA Y4-:

cn tham gia phn ng ph vi phi t L to nn cc phc ML, ML2 MLm v anion Y4- cn tham gia phn ng vi cc ion H+ to thnh HY3-, H2Y2-, H3Y-, H4Y. Trong iu kin ny hng s bn iu kin MY ca phc MYn-4 c nh ngha nh sau:

Trong : [M] l tng nng cn bng cc dng tn ti ca Mn+, tr phc MYn-4, tc l:

38

[Y,] l tng cc nng cn bng ca cc dng tn ti ca Y4-, tr phc MYn-4, tc l:

Nu k hiu hng s bn tng nc ca cc phc ML, ML2 ln lt l 1, 2, m v cc hng s axit tng nc ca H4Y ln lt l K1, K2, K3, K4 th ta c:

Thay (3.12, 3.13) vo (3.11) ta c:

Do hng s bn iu kin ch l hng s trong nhng iu kin xc nh. Ti nhng iu kin xc nh, gi tr hng s bn iu kin ca mt phc cng ln th phc cng bn tc l trong iu kin phc to thnh cng hon ton. Hng s khng bn iu kin K'MY l nghch o ca hng s bn iu kin.

V d 1: Tnh hng s bn iu kin ca phc MgY2- trong dung dch c pH = 11,0. Bit hng s ca phc l MgY = 108,7. Hng s bn ca phc MgOH+: MgOH + = 102,58, H4Y c pK1 = 2,0; pK2 = 2,67; pK3 = 6,27; pK4 = 10,95; t l hng s bn iu kin ca phc MgY2- ti pH = 11, ta c:

39

Trong Hy tnh Mg(OH) v (H)

Hng s bn iu kin ca phc MgY2- trong dung dch c pH = 11 l

Tc l c nh hn cht t v gi tr ny kh ln chng t trong dung dch c pH = 11 v khng cn cht no khc to phc vi ion Mg2+ th ion Mg2+ to vi EDTA thnh phc kh hon ton. V d 2: Tnh nng cn bng pH = 11 ca cc cu t trong dung dch Mg c nng ban u 0,01M v EDTA c nng ban u l 0,02M. Trong th d trn, ta tnh c hng s bn iu kin ca phc MgY2- trong dung dch c pH = 11 l = 108,28.
2+

Phng trnh bo ton khi lng ca Mg2+:

v ca EDTA l:

T hai phng trnh trn suy ra: Thay [MgY2-] = 0,01 - [Mg] v [Y] = 0,01 + [Mg] vo biu thc ca hng s bn iu kin:

40

Gi s [Mg'] << 0,01 th:

Nh vy, gi thit trn l ng v [Mg'] ch bng mt phn triu ca 0,01. Ta bit: [Mg'] = [Mg2+]Mg(OH). Trong v d trc ta tnh c Mg (OH ) = 1,38; do
+

Nh vy ti pH = 11 ton b Mg2+ to phc vi Y4-. V d 3: Tnh hng s bn iu kin ca phc NiY2- trong dung dch m NH3 1M + NH4Cl l,78M. Bit rng trong iu kin nng ban u ca ion Ni2+ khng ng k so vi nng NH3. Phc ca Ni2+ vi EDTA c hng s bn = 1018,62. Phc ca Ni2+ vi NH3 c cc hng s bn tng cng ln lt l 102,67; 104,80; 106,46; 107,50 v 10+. pk ca H4Y cho trong cc phn trn. Theo nh ngha:

V nng [Ni2+] kh nh khng ng k so vi nng NH3, nn ta coi pH ca dung dch l pH ca hn hp m NH3 1M + NH4Cl 1,78M.

Tnh (H). Ta tnh (H) tng t nh v d 1. Khi [H+] = 10-9, ta tnh c (H) = 101,28. Ta tnh c Ni ( NH ) = 1 + 1.1 [NH3] + + 1.5 [NH3] thay cc gi tr , [NH3]
3

Tnh Ni ( NH ) = 108,2. Do ta tnh c NiY


3

41

Nh vy trong dung dch m NH3 + NH4Cl c nng NH3 kh ln, c pH = 9, ion Ni2+ va to phc vi EDTA va to phc vi NH3 nhng khi tnh MY ta thy gi tr hng s rt ln chng t Ni2+ to phc nh lng vi EDTA. 3.4. PHC CHT CA CC ETILENDIAMINTETRAAXETIC. ION KIM LOI VI AXIT

Trong s cc cht to phc vng cng (Chelate) vi cc ion kim loi th nhm thuc th hu c c tn chung l complexon c ng dng rt rng ri trong ha phn tch, cc complexon l nhng dn xut ca cc axit aminopolycacboxilic. V d: Nitrylotriaxetic hay complexon I.

Axit etylendiamintetraaxetic (EDTA) hay complexon II.

c vit tt l H4Y. V EDTA tng i kh tan trong nc nn trong thc t ngi ta thng dng mui inatri ca n tan nhiu trong nc. Mui Na2H2Y c gi l complexon III hay Trilon B. Cc complexon to c phc bn vi hng chc ion kim loi. Cc phc ny tha mn cc iu kin ca nhng phn ng dng trong phn tch th tch, v vy ngy ny ngi ta s dng rt rng ri phng php chun to phc dng cc complexon c gi l phng php chun complexon. Trong phn ny chng ta s bn ti bn ca cc phc complexon c gi l cc complexonnat. Complexon III to phc vi hu ht cc ion kim loi. Bng sau y ghi li hng s bn ca cc phc v gi tr l ca cc hng s

42

Bng 3.1. Hng s to thnh ca cc complexonat kim loi Cation KL Ag+ Mg2+ Ca2+ Sr2+ Ba2+ Mn2+ Fe2+ Co2+ Ni2+ Cu2+ Zn2+ Cd2+ Hg2+ Pb2+ Al3+ Fe3+ V3+ Th4+ Phc conplexonat AgY3MgY2CaY2SrY2BaY2MnY2FeY2CoY2NiY2CuY2ZnY2CdY2HgY2PbY2AlYFeYVYThY 2,1.107 4,9.108 5,0.1010 4,3.108 5,8.107 6,2.1013 2,1.1014 2,0.1016 4,2.1018 6,3.1018 3,2.1015 2,9.1016 6,3.10211 1,1018 1,3.1016 1,3.1025 7,9.1025 1,6.1023 lg 7,32 8,69 10,70 8,63 7,76 13,79 14,33 16,31 18,62 18,80 16,50 16,46 21,80 18,04 16,13 25,10 15,90 13,20

EDTA l axit 4 ln axit, cc hng s axit tng nc ca n l:

V phn to phc vi ion kim loi y l anion Y4- nn s to phc ca ion kim loi ph thuc vo bn cht ca ion kim loi (th hin cc gi tr hng s bn nhit ng trong bng 3. 1) v vo pH ca dung dch. i vi mi ion kim loi ta c th tnh c pH kim loi to phc mt 43

cch nh lng vi EDTA. Ta hy tnh pH ca dung dch phi bng bao nhiu khi trn hai th tch bng nhau ca dung dch ton kim loi Mn+ v dung dch EDTA c nng bng nhau Co th 99,9% lng ion kim loi to phc complexonat l MYn-4. Khi trn hai th tch bng nhau ca dung dch EDTA v ca dung dch Mn+ th nng ca chng gim i mt na, bng th:
C0 . Theo nh lut bo ton khi lng 2

trong : [Y'] l tng nng cc dng tn tn ti ca EDTA tr phc MeYn-4. T (a) v (b) suy ra: [Mn+] = [Y'] Khi 99,9% lng in kim loi to phc MYn-4, tc l: (c)

Thay cc gi tr ca [MYn-4], [Mn+], [Y'] vo biu thc ca hng s bn iu kin ', ta c:

Nh vy, mun cho 99,9% lng ion kim loi to phc complexonat th hng s bn iu kin ca phc phi bng Ta bit, theo nh ngha:
2.106 . Ta hy tnh pH ' bng gi tr . C

Gi s ta tm iu kin to phc hon ton khi nng ban u v EDTA u bng nhau v bng 2.10-2M (nng thng gp trong thc tin). Trong trng hp ny:

Vi mi phc, ta s tm c mt gi tr (H) ' = 108. 44

Phng trnh biu din i lng (H) l phng trnh bc 4 i vi [H+]:

Nn khi bit (H) ta phi gii phng trnh bc 4 tm pH l vic cc k kh khn. Do , ta nn v th biu din s ph thuc ca (H) vo pH ca dung dch. Mun vy ta thay cc gi tr [H+] ln lt bng 10-1, 10-2... v 10-12 vo phng trnh (d) trn ri tnh cc gi tr (H) tng ng. Cc kt qu tnh c tp hp trong bng 3.2 sau y. Bng 3.2. Cc gi tr (H) cc pH khc nhau pH (H) pH (H) 1 2 17,13 10 1013,43 7 103,32 8 102,27 3 1010,6 9 101,28 4 108,44 10 100,45 5 106,45 11 100,07 6 104,66 12 1

Bng 3.1 ghi gi tr ca cc phc complexonnat cc kim loi khc nhau. T cc gi tr , ta tm c gi tr (H) cho ' = 108. Dng th trn ta c th tnh c pH ng vi gi tr . l pH ti thiu khi trn hai th tch bng nhau ca dung dch in kim loi 2.10-2M vi dung dch EDTA 10-2M th 99,9% lng ln kim loi i vo phc vi EDTA. Bng 3.3 l cc gi tr (H) ca cc phc kim loi = 108 tc l cc gi tr (H) cn thit cc phc c to hon ton. Bng 3.3. Cc gi tr (H) cc phc complexonat kim loi c ' = 108. Phc complexonat AgY3MgY2CaY2SrY2BaY2MnY2FeY2CoY2(H) 10-0,68 190,69 102,70 100,63 10-0,24 105,8 106,33 108,31 45

NiY2CuY2ZnY2CdY2Hg2PbY2AlYFeYVYThY-

1010,62 1010,8 108,5 108,46 1013,8 1010,04 108,13 1017,1 1017,9 1015,2

Hnh 3.1. Gin s ph thuc ca (H) vo pH ca dung dch v trn ng cong biu din s ph thuc c cc chm biu th gi tr phc kim loi c ' = 108. T im ta tm c gi tr pa tng ng trn trc honh l gi tr pH ti thiu 99,9% lng ion kim loi to phc complexonat. T th ta thy cc ion Fe (III), In (III), Th (IV), Se (III) v Hg (I) to bn phc trong khong pH = 1 - 2. Cc ion Ni (II), Cu (II), Pb (II), Zn (II) v l (III), Cd (II), Co (II) to phc hon ton trong khong pH = 2 - 5. Cc kim loi kim th to phc hon ton trong khong pH = 8 - 10.

Hnh 3. 1. Gin s ph thuc ca (H) vo pH. pH ti thiu 99.9% lng ion kim loi to phc complexonat t dung dch ion kim loi nng 2.10-2M. 46

3.5. NG DNG PHN NG TO PHC TRONG HA HC PHN TCH 3.5.1. Phn tch nh tnh cc cht Cc phn ng mu c trng thng c s dng pht hin cc ion. a. Cc phc ca ion kim loi vi amoniac. V d Cu(NH3)42+ mu xanh m dng pht hin ion Cu2+, phc Co2+ vi NH3 c mu vng CO(NH3)62+ b oxi ha bi khng kh hoc H2O2 to thnh phc CO(NH3)63+ c mu hng c trng. Phc thioxyant kim loi, v d Fe(SCN)n(3-n) (n = 1 -5) c mu mu c trng c dng pht hin Fe3+. Phc Co(SCN)42- c mu xanh t bn trong nc nhng bn vi dung mi hu c (axeton, cc ancol, ete etylic) v vy phn ng gia Co2+ vi SCN- khi c mt dung mi hu c c dng pht hin Co2+. b. Cc thuc th hu c c dng pht hin ion kim loi kh phong ph: Pht hin Ni2+ bng imetyl glyoxim, Al3+ bng Alizarin hoc Aluminon, Fe2+ bng O - phenantrolin hoc , ' dipiridin.... 3.5.2. Xc nh nh lng cc ion kim loi. a. EDTA l thuc th quan trng c dng xc nh nh lng nhiu ion kim loi. b. Phn ng mu gia nhiu thuc th hu c vi cc ion kim loi c dng nh lng trc quang hoc chit trc quang cc ion kim loi. V d nh lng Ni2+ bng imetylglyoxim, Fe3+ bng SCN-, Al3+ bng Aliuminon, Pb2+ bng ithizon v Cu2+ bng ietyl ithiocacbamat... Cd2+ bng Amoni Pirolidin ithio cacbamt (APDC). 3.5.3. Ha tan cc kt ta kh tan, tch cc ion. Nhiu thuc th to phc c s dng ha tan cc kt ta. V d AgCl tan trong NH3 do to phc Ag(NH3)2+; Cu(OH)2 tan trong NH4Cl do to phc Cu(NH3)42+; - cng o c tnh ny m ngi ta c th s dng cc thuc th to phc tch cc ion, v d dung NH3 d tch hn hp Fe3+, Al3+ v Cu+ do Fe3+, Al-3+ c chuyn vo kt ta Hydroxit Fe(OH)3, Al(OH)3, cn Cu2+ c gi li trong dung dch di dng phc Cu(NH3)42+. 3.5.4. Che cc ion cn tr Mt trong cc ng dng quan trng ca phc cht trong phn tch ha hc l che cc ion cn tr. Khi mt thuc th c kh nng phn ng vi ion B cng c mt trong dung dch cha ion phn tch A th ta ni n ion B cn tr phn ng ca A vi thuc th. loi tr nh hng ca B ta phi kt ta B vi mt thuc th thch hp. 47

Mt bin php tch cc l "che" ion B, ngha l khng cn tch B m chuyn n sang to phc vi mt thuc th khc n khng cn tr phn ng chnh. Cht c a vo lm trit tiu hoc km hm phn ng cn tr c gi l cht che. V d: ion Fe3+ cn tr n phn ng gia Co2+ v SCN- ta che n bng cch cho Fe3+ to phc vi F- v phc FeF63- bn hn nhiu phc Fe(CNS)nn-3 trn. Cht che phi c kh nng to phc bn vi ion cn tr n khng cn tc dng vi thuc th chnh dng nh lng, ion cn xc nh, mt khc bn ca phc gia cht che v ion cn nh lng phi rt b khng gy cn tr cho phn ng chnh. Chng hn, vic tm ion Cd2+ trong dung dch cha ion Cu2+, Co2+, Ni2+ bng Na2S khng thc hin c v cc ion ny cho kt ta sunfua mu en khng cho php nhn ra kt ta CdS mu vng. che cc ion ny ngi ta dng KCN, v cht che ny to ra cc phc bn Cu(CN)42-, Co(CN)42-; Ni(CN)42- khng phn ng vi Na2S, trong khi phc Cd(CN)42- km bn, Cd2+ phn ng vi Na2S.

48

CU HI - BI TP CHNG 3

3.1. M t cc qu trnh xy ra trong dung dch nc ca cc cht sau y: [Ag(NH3)2]Cl, [Cu(NH3)4]SO4, K2[HgI4], FeF3. 3.2. Nh rt chm dung dch NH3 vo dung dch CuSO4 th mi u c kt ta xanh lam xut hin, sau kt ta tan v dung dch to thnh c mu xanh da tri. Nu thm tip tng git HCl long vo dung dch th mu xanh da tri bin mt, dung dch hi c ri trong sut v c mu xanh nht, gii thch hin tng. Vit cc phng trnh phn ng ion. 3.3. Nh HCl vo dung dch AgNO3 c kt ta trng, thm dn NH3 vo hn hp th kt ta tan. Thm chm tng git HNO3 vo hn hp thu c th li c kt ta trng xut hin. Gii thch hin tng, vit cc phng trnh phn ng ion. 3.4. Tnh nng cn bng trong dung dch Pb2+ 0,1 M v CH3COO- lm pH = 2,0, + = 0,56.
PbCH COO 3

3.5. Tnh nng CH+ lm gim nng Ag(NH3)2+ 0,1M xung cn 1,0 10-6 M, Ag(NH3)+ = 103,32. 3.6. Thm 1ml dung dch NH4SCN 0,10M vo 1ml dung dch Fe3+ 0,01M v F1,00M. C mu ca phc xut hin hay khng ? Bit rng mu ch xut hin khi CFeCN2+ > 7.10-6M v dung dch c axit ha va s to phc Hiroxo ca Fe(III) khng xy ra. Cho CFe3+ (= 0,0 1) < CF (= 1). 3.1. Hng s bn tng cng ca cc phc to bi ion Hg2+ v ion 1- ln lt l: 1.1 = 109,05, 1.2 = 1017,33, 1.3 = 1019,74 v 1.4 = 1021,0. Tnh cc hng s bn v khng bn tng nc ca cc phc . 3.8. Tnh nng cn bng ca cc ion v phn t trong dung dch Cd(ClO4)2 10 M v KI 1 M. Trong dung dch c HClO4 Cd2+ khng to phc c vi OH- m ch to phc vi I-; cc phc c hng s bn tng cng ln lt l 102,88, 103,92, 105,00, 106,11.
-3

3.9. Tnh nng cn bng ca cc ion trong dung dch gm bc nitrat 10-3M v amoniac c nng cn bng l: a) 10-3M v b) 10-2M Cc phc ca Ag+ v NH3 c logarit hng s bn tng nc l 3,32 v 3,92. 3.10. Tnh nng cn bng ca ion v phn t trong dung dch HgCl2 10-2M. 49

Phc ca Hg2+ v Cl- c logart hng s bn tng cng l 6,74 v 13,22. 3. 11. Tnh nng cn bng ca ion Fe3+ v FeY- trong dung dch hn hp Fe3+ 10-2M v Na2H2Y 10-2M c pH = 2,0, FeY = 1025,1. 3.12. Cn phi thm NH3 vo dung dch AgNO3 10-2M n nng cn bng no gim nng Ag+ t do xung 10-8M. Phc ca Ag+ v NH3 c logant hng s bn tng cng ln lt l 3,32 v 7,24.

50

CHNG 4 PHN NG KT TA

4.1. IU KIN TO THNH CHT KT TA Phn ng kt ta l phn ng ha hc xy ra khi mt trong cc sn phm to thnh l cht rn t tan. Cht rn t tan c gi l cht kt ta. 4.1.1. Tch s tan (T) Khi thm dung dch NaCl vo dung dch AgNO3, s c cn bng sau:

Qu trnh dng li khi c s cn bng gia qu trnh ha tan v qu trnh kt ta:

Theo nh lut TDK th:

Vi dung dch bo ha K = const v c gi l tch s ha tan, k hiu l T. Vy T = [Ag+] [Cl-] Theo hot , ta c:

Tng qut cho qu trnh:

Hoc coi hot ng bng nng th: Nu: (dung dch bo ha) (dung dch qu bo ha) (dung dch cha bo ha).

51

4.1.2. tan (S) ca kt ta, quan h gia S v T. tan (S) ca cht tan l nng mol/l ca cht trong dung dch bo ha. Gia S v T c mi quan h:.

V d: Tnh TMg(OH)2 200C, bit trong 100ml dung dch bo ha nhit ny c cha 0,84mg Mg(OH)2.

4.2. CC YU T NH HNG N TAN 4.2.1. nh hng ca ion chung Ion chung l ion c trong thnh phn ca kt ta. Nu thm ion chung vo dung dch bo ha, tch s nng ion s tng ln, dung dch tr nn qu bo ha v s xut hin kt ta, tc l tan gim i. V d l: Tnh SPbSO4 trong nc nguyn cht v trong dung dch Na2SO4 10 M, cho TPbSO4 = l,6.10-8.
-2

Gi tan ca PbSO4 trong nc nguyn cht l S.

Theo cng thc tnh tan ta c:

tan ca PbSO4 trong dung dch Na2SO4 10-2M.

52

S = 16.10-6 mol/l kt qu ny cho thy gi thit trn l ng. Vy tan ca PbSO4 trong dung dch Na2SO4 l 1,6.10-6 v thy rng tan ca n nh hn trong H2O rt nhiu, c th ti V d 2: Tch s tan ca CaC2O4 200C bng 2.10-9. Hy so snh tan ca n trong H2O v trong dung dch (NH4)2 C2O4 0,1 M. Gi tan ca CaC2O4 trong nc nguyn cht l S, theo cn bng. Ta c:

Theo cng thc:

- tan ca CaC2O4 trong dung dch (NH4)2 C2O4 0,1 M

Gi tan ca CaC2O4 trong dung dch (NH4)2 C2O4 0,1M l S th:

Gi s: S << 0,1 th

Vy tan ca n so vi trong nc nguyn cht nh hn:

4.2.2. nh hng ca ion H+(pH) v cht to phc n tan ca kt ta, tch s tan iu kin tan ca kt ta s tng ln nu cc ion kt ta c tham gia phn ng ph vi cc cht l c mt trong dung dch. phn nh c cc nh hng ca cc phn ng ph, ngi ta dng tch s tan iu kin. 53

Chng hn kt ta AmBn trong dung dch c ion H+ c kh nng phn ng vi B v c cht to phc L c kh nng to phc vi A, trong dung dch c cc ion bng:

A to phc vi L:

- B phn ng ph vi H+

K1, K2 l hng s khng bn ca phc HB, H2B cng l hng s phn li ca axit HB v H2B. - Nu gi S l tan ca kt ta th:

T cc hng s K 1, K2 ta tnh c [HB], [H2B].... theo [B] v [H+] Ta c:

54

V d: Tnh tan ca CaF2 trong dung dch HCl 10-2M cho KHF = 6.10-4 v TCaF2 (trong nc) = 4.10-11. Trong nc:

V Ca2+ khng tham gia phn ng ph vi F nn [Ca2+] = S. Cn F- tham gia phn ng ph: H+ + F- = HF

4.2.3. nh hng ca cht to phc ph Cc cht to phc ph c mt trong dung dch c th lm hn ch hoc ngn cn qu trnh kt ta do s to phc vi kim loi: Tnh cht ny c dng che cc ion cn tr. V d Khi lm kt ta Cd2+ bng H2S c mt ca ion Cu2+ th ion Cu2+ s cn tr qu trnh kt ta CdS do s to thnh kt ta CuS mu en. "che" ion Cu2+ ngi ta cho KCN d vo dung dch. y xy ra cc qu trnh sau:

Phc Cu(CN)43- bn hn rt nhiu so vi phc Cd(CN)42- nn khi cho H2S li qua dung dch th ch c kt ta CdS c to thnh.

55

K1 kh ln, phn ng (4) xy ra d dng. Trong khi phn ng kt ta Cu2S xy ra kh khn:

Qua v d trn ta thy qu trnh kt ta ph thuc vo nhiu yu t: hng s bn ca phc to thnh gia ion kim loi v cht to phc, tch s tan ca kt ta, tnh cht axit - baz ca thuc th lm kt ta v ca cht to phc. Khi tnh ton gn ng c th p dng nh lut tc dng khi lng cho cn bng ch yu hoc tnh theo hng s iu kin. V d 2: Trn 1,00ml hn hp m (A) gm NH3 2,0M + NH4NO3 2,0M vi 100ml dung dch B gm FeCl3 2,0.10-3M + NaF 0,20M. C kt ta Fe(OH)3 hay khng? Cho Sau khi trn ta c:

Cc qu trnh xy ra: Trong dung dch B, Fe3+ tn ti ch yu di dng phc Floro (CF- >> CFe3+).

Trong dung dch A:

T cn bng (4) ta c:

56

Gi s Ta c: Vy vn c kt ta Fe(OH)3 4.2.4. nh hng ca nhit . V qu trnh ha tan thu hoc ta nhit, n nh hng khng c qui lut nn khng c nhng biu thc nh lng chung. S thay i tan mt cht theo nhit c lin quan ti hiu ng nhit khi ha tan. i vi nhng cht thu nhit khi ha tan th tan s tng theo nhit , th d PbI2 tan nhiu khi un nng. tan ca AgCl 1000C ln gp 25 ln tan ca n 100C. i vi nhng cht ta nhit th ngc li, tan gim khi nhit tng. Th d CaSO4.0,5H2O 600C c tan ln gp 3 ln tan ca n 1000C. 4.2.5. nh hng ca kch thc ht kt ta. i vi cng mt lng cht kt ta c dng ht nh tan nhiu hn kt ta c dng ht ln v b mt ca cc tinh th nh c cc gc, cnh, cc ion v tr gc, cnh d tan hn nhng v tr khc v cc ion v tr bn trong b gi cht hn. Ngoi cc yu t k trn, cn c yu t khc nh qu trnh sp xp tinh th t dng ny sang dng khc bn hn. 4.3. KT TA PHN ON. Nu trong dung dch c cha hai hay nhiu con c kh nng to c kt ta cng vi mt con khc, nhng cc kt ta hnh thnh c tan khc nhau th khi thm cht lm kt ta vo dung dch cc kt ta ln lt c to thnh. l s kt ta phn on. n gin cho vic tnh ton, cc v d sau ta b qua s l thp phn ca cc i lng tch s tan. V d 1: Cc ion Cl-, I- u c kh nng to kt ta vi ion Ag+, nhng c tch s tan khc nhau. Ta c: 57

Khi thm AgNO3 vo dung dch hn hp gm Cl- v I-, v TAgI << TAgCl nn u tin AgI kt ta v khi AgCl bt u kt ta, hai phn ng xy ra trong cng mt dung dch nn t hai biu thc (a) v (b) ta c: khi trong dung dch xut hin c hai kt ta AgI v AgCl th [I-] = 10-6 [Cl-]. Nu mi c AgI kt ta cn AgCl cha kt ta th:

Khi t s

c ngha l [I-] < 10-6 [Cl-] th AgO cha kt ta.

Gi s nng ban u ca Cl-(CCl-) gp 100 ln nng ban u ca I-(CI-) v AgCl bt u kt ta khi [I-] = 10-6[Cl-] lc % [I-] cn li trong dung dch l:

([I-] l nng cn li khi Cl- bt u kt ta v Cr l nng ban u ca n).

Nh vy, trong iu kin ny khi AgCl bt u kt ta th c th coi I- i vo kt ta ht (ch cn 0,01%). R rng c th kt ta ln lt cc ion I- v O- bng Ag+. V d 2: Tnh nng ln Cl- cn li trong dung dch khi thm AgNO3 vo dung dch hn hp gm 10-2 mol/1 Cl-v 10-2 mol/l Cr42-, cho TagCl = 10-10, TAg2CrO4 = 10-12.

Khi thm AgNO3 vo dung dch hn hp, Ag2CrO4 bt u kt ta th:

58

Tc l t khi nng Cl- trong dung dch nh hn hng vn ln nng Cr)42Theo cc d liu ca bi ton khi Ag2CrO4 bt u kt ta th:

V % Cl- cn li trong dung dch l:

Cng c th coi khi Ag2CrO4 bt u kt ta th Cl- i ht vo kt ta AgCl. 4.4. KT TA KEO C nhiu trng hp tch s con vt qu tch s tan nhng kt ta to thnh vn khng tch ra c m ch hnh thnh nhng ht rt nh l lng trong dung mi, dung dch gi l dung dch keo. Nguyn nhn c kt ta trong trng thi keo l do cc ht kt ta hp ph cc ht mang in nn n mang in tch. Chng hn, thm Na vo dung dch AgNO3, khi trong dung dch hnh thnh keo AgCl. Lc s c hai kh nng hp ph xy ra ty thuc vo lng d Ag+ hay Cl AgCl Khi d Ag+ th v d Cl-

lm ng t keo ny ta phi thm vo dung dch cht in li mnh khc c nng cao v c in tch ln. Nhng loi keo a nc nh silic oxit (SIO2) thng c khuynh hng to nn dung dch keo rt bn v cc ht keo c bao bc bi lp dung mi. Mun cho keo ng t trong trng hp ny phi ph b c lp v dung mi th cht in li mi xm nhp c trung ha in tch cc ht keo. ph keo silic ta phi axt ha bng dung dch axit clohydric v phi un cn kh, i khi phi t nng ti nhit trn 1000C th lp nc bc ht keo mi b ph v. 59

Khi lc cc kt ta keo gp rt nhiu kh khn v cc ht keo thng nh nn phi dng loi giy lc mn, rt kh chy. Khi ra kt ta keo, cht in li dng lm ng t keo b loi bt mt phn, kt ta c th tr li trng thi keo hin tng ny gi l s ti keo hay pptin ha. V vy khi ra kt ta keo phi chn cht in li thch hp trnh s ti keo. 4.5. S HA TAN CC KT TA KH TAN TRONG NC. Qu trnh ha tan xy ra ngc vi qu trnh to kt ta, mun c qu trnh ha tan xy ra cn lm gim tch s con ca cht t tan xung i lng b hn tch s tan ca hp cht bng cc bin php sau: - Ha tan kt ta trong axt hoc kim. - Chuyn kt ta sang phc cht bn t phn li. - Chuyn ion ca cht t tan sang dng oxi ha kh. - Chuyn hp cht t tan ny sang hp cht t tan khc c kh nng tan d trong thuc th thch hp. 4.5.1. Ha tan kt ta trong axt v kim 4.5.1.1. Ha tan cc hyroxit a. Cc hyroxit kim loi tan trong cc axit to thnh mui tan v nc t phn li. tan ph thuc tch s tan ca hyrxit v hng s phn li ca axit. V d 1: Mg(OH)2 (pTS = 10,9) tan d trong c cc axt rt yu (NH4+ c DKa = 9.24).

Nhng Fe(OH)3 (TS= 10-37) ch tan trong t mnh, khng tan trong cc axt yu nh NH4+.

b. Cc hyroxit lng lnh (Al(OH)3; Cr(OH)3; Zn(OH)2; Pb(OH)2) tan trong axt v trong kim d.

4.5.1.2. Ha tan cc mui Cc mui ca cc axt yu tan trong axt mnh hn to thnh axt t phn li. a. Cc mui cacbonat tan trong axit (k c axit axetic, H2CO3). 60

V d 2: nh gi tan ca CaCO3 trong axt axetic.

Khi nng CO2 vt qu tan th CO2 bay ra khi dung dch. Lc :

Hng s cn bng ca cc qu trnh (1) v (2) tng i ln KI = 0,072; KII = 2,19 cho php d on kh nng tan d ca CaCO3 trong axt axetic nht l khi un nng (ui CO2). Mt khc CaCO3 cng d tan trong dung dch bo ha kh CO2. V d 3: nh gi tan ca CaCO3 trong dung dch c bo ha lin tc bng kh CO2 P = 1 at.

Coi cn bng (5) l ch yu, ngha l nng Ca2+ to ra t cn bng (5) ln hn rt nhiu nng Ca2+ do qu trnh (1) sinh ra. V nng HCO3- cng ln hn nng HC O3- sinh ra do (3). T c th tnh tan theo (5).

Nh vy c th coi nng [Ca2+] ch yu do (5) to ra. Cng vy, t (2) v (3). 61

[H+] << [HCO3-] do c th coi nng ln HCO3- sinh ra do (5) l ch yu. Vy c th chp nhn cch tnh gn ng trn. tan ca CaCO3 trong dung dch bo ha CO2 l 7,3.10-3, trong khi tan CaCO3 trong nc l 7.10-5 M. b. Cc oxalat c kh nng tan trong cc axt mnh, nhng kh tan trong axt yu. Chng hn CaC2O4 kh tan trong axt axetic yu hn nhiu so vi axt oxalic (pK1 = 1,25; pK2 = 4,27). V d 4: tan ca CaC2O4 trong HAC 1M vo khong 8,3.10-4 M (HAc l CH3COOH). c. Cc Cromat cng tng t cc oxalat, tan c trong axt mnh, nhng kh tan trong axt axetic (Ka(HAc) ~ Ka(HCrO4-)) V d 3:

d. Cc sunfua c tch s tan khc nhau nn tan trong cc axit cng rt khc nhau:

Bng sau cho gi tr hng s K ca phn ng ha tan mt s sunfua trong axit. Sunfua MnS FeS NiS CoS pTs 9,6 17,2 18,5 20,4 lgK 10,32 2,72 1,42 -0,48 Kh nng tan trong axt Tan d trong axt, k c HAc Tan d trong HCl Tan d trong HCl Tan d trong HCl 62

CdS CuS HgS

26, 1 35,2 51,8

9, 18 -15,28 -31,88

Tan d trong HCl > 1 M Kh tan trong HCl Kh tan trong HCl

Li dng tnh tan khc nhau trong cc axt m ta c th thit lp cc iu kin tch cc mui sunfua. V d 5: Thit lp nng HCl tch CdS v CuS. Phn ng ha tan CdS trong HCl.

ho tan hon ton v d 0,10 mal CdS cn thit lp nng HCl bng bao nhiu?

Gii ra ta c C = 0,73M Trong iu kin ny CuS khng tan. V d trong HCl 2M th:

Tng t trn ta c:

Nh vy tch CdS khi CuS ch cn thit lp nng axit HCl khong 1 2M 4.5.2. Ho tan kt ta trong cc thuc th to phc Trong trng hp ion ca kt ta to c phc bn vi mt thuc th, th c th dng thuc th ny ho tan kt ta ca ion . tan ph thuc tch s tan ca kt ta, hng s bn ca phc to thnh, pH ca dung dch, nng thuc 63

th... V d, mt s ion to c phc bn vi NH3 do c th dng NH3 ho tan kt ta hyroxit ca nhiu ion kim loi: Cu(OH)2, Zn(OH)2, Ag2O, Cd(OH)2. Mt s mui ca cc kim loi ny cng tan c trong NH3, v d AgCl tan d dng trong NH3:

Tuy vy AgI, Ag2S, CuS, Zns, CdS c tch s tan qu b nn khng th tan trong NH3:

Cng vy, HgS khng tan trong HCl bi v tch s tan ca HgS qu b, mc du Hg2+ to phc bn vi ion Cl-:

Vic nh gi gn ng theo cn bng trn cho thy tan ca HgS trong HCl 1 M vo c S 3,3.10-9M. tan ny rt b mc du ln gp nhiu ln so vi tan ca HgS trong nc (= 10-26M). 4.5.3. Ho tan kt ta trong thuc th oxi ho - kh Nu ion ca kt ta c tnh oxy ho th c th s dng phn ng oxy ho kh ho tan kt ta bng mt thuc th thch hp. tan ph thuc tch s tan ca kt ta v bng hng s cn bng ca phn ng oxy ho kh. V d cc kt ta sunfua kim loi c kh nng tan trong HNO3:

64

Thay cc i lng ny vo biu thc tnh K ta c:

i vi CuS, Ts = 10-35,2; lgK = 37,4 HgS, Ts = 10-51,8; lgK = - 12,4 Do ta thy CuS tan d dng trong HNO3 Cn HgS tan rt kh trong HNO3 Ngoi HNO3 c th dng H2O2 (mi trng axit) (NH4)2S2O8, PbO2. ho tan cc kt ta c tnh kh. V d: Ho tan kt ta trong HCl + H2O2

Ho tan kt ta MnO(OH)2 trong PbO2 + HNO3:

C th dng mt s thuc th c tnh kh ho tan cc kt ta c tnh oxy ho: ho tan MnO(OH)2; CO(OH)3 trong HCld, trong H2O2 (mi trng axit)

Trong mt s trng hp s ho tan kt ta l kt qu phn ng o xi ho kh v s to phc. V d: c th ho tan HgS trong hn hp HNO3 + HCl, ion S2- b oxi ho bi HNO3 ng thi vi s to phc ca Hg2+ vi Cl-: 65

Phn ng xy ra rt nhanh v k rt ln. 4.5.4. Ho tan cc kt ta kh tan bng cch chuyn chng sang hp cht khc d tan trong thuc th thch hp Mt s kt ta kh tan trong cc thuc th thng thng, V d: BaSO4, CaSO4, SrSO4 rt kh tan trong cc axit. C th chuyn chng sang mui Cacbont tng ng tan d trong axit. Nu tch s tan ca mui to thnh b hn tch s tan ca hp cht cn chuyn ho th qu trnh chuyn ho xy ra d dng. Cn nu ngc li s chuyn ho xy ra kh khn hn. V d 6: Tnh nng Na2CO3 phi ly 1 lt dung dch ny c th chuyn ho hon ton cc mui sau: a) 0.010 mol CaSO4 b 0,0 10 mol BaSO4 chuyn ho mui sunft thnh cabonnat ngi ta cho kt ta sunfat tc dng vi mui cacbonat tan, V d: Na2CO3

66

trng hp (1) ch cn nng Na2CO3 0,010M l . Cn trng hp (2) th cn nng Na2CO3 ln gp 50 ln. Thc t chuyn ho c th phi dng Na2CO3 bo ho v chuyn nhiu ln, mi ln u phi un nng dung dch.

67

CU HI V BI TP CHNG

4.4. Trong dung dch bo ho ca mui AB2X3 c cn bng:

Nng ln X- trong dung dch bng 4,0.10-3 M 1. Tnh tch s tan ca kt ta AB2X3 2. Tnh tan ca AB2X3 trong dung dch BCl 5,0.10-6M 3. Tnh tan ca AB2X3 trong dung dch ACl 1,0.10-4M 4.2. Hy cho bit nh hng ca cc cht n tan S ca kt ta trong cc trng hp sau: 1. NH4Cl n SMgNH4PO4 2. NH3 trn SMg(OH)2 3. H+ n SAg2CrO4 Gii thch ti sao? 4.3. Trn 1,0ml K2CrO4 0,120M vi 2,0ml Ba(OH)2 0,009M, c kt ta BaCrO4 xut hin hay khng, 4.4. Cho H2S li qua trung dch CuCl2 0,010M, FeCl3 0,010M v MnCl2 0,010M cho n bo ho bng 0,10M. C hin tng g xy ra? Cho pTs ca cc cht: CuS(35,2), FeS (17,2); MnS (9,6); pKa ca (H2S): 7,02; 12,9 4.5. Trn 1,0 ml HCl 0,30M vi 1,0ml Pb(NO3)2 0,01M . C kt ta PbCl2 tch ra khng? Cho T = 1,6. 10-5. 4.6. Tnh tan ca AgI trong: a) Dung dch KNO3 10-2M b) Dung dch Ba(NO3)2M c) Dung dch Al(NO3)3 10-2M tan ca AgI trong cc dung dch tng bao nhiu ln so vi tan ca n trong nc tinh khit. Tch s tan ca AgI 20oC l 8,3.10-17. 4.7. Tnh tan ca CaC2O4 trong dung dch (NH4)2C2O4 5.10-2M v so snh vi tan ca n trong nc. Tch s tan ca kt ta ny l 1,38.10-9M 68 4. NaOH n SPbSO4 5. NH3 n SAg2CrO4

4.8. Ngi ta dng 20ml dung dch NH4NO3 ra kt ta MgNH4PO4. Hy tnh nng dung dch NH4NO3 theo phn trm khi lng khi ra khng mt qu 0,01mgMgO. 4.9. Tnh nng ion H+ t nht cn phi c trong dung dch CaCl2 0,02M v K2C2O4 0,1 M CaC2O4 khng kt ta. Nu dung dch gm CaCl2 2.10-2M, HCl 10-2M v K2C2O4 10-2M th CaC2O4 c kt ta c khng?

4.10. Tnh tan ca cc sunphua sau: Ag2S, Cu2S, PbS v HgS trong nc, c k n tng tc ca ion ca kt ta vi cc ion ca H2O.

4.11. Mg(OH)2 c kt ta c khng khi thm 1ml dung dch MgO2 1 M vo 100ml dung dch NH3 + NH4Cl (1 M); Mg(OH)2 c T = 10-9,22 v NH3 c pKb = 4,75. 4.12. Nng cn bng ca NH3 trong 100ml dung dch cha 10-2M kt ta AgO phi l bao nhiu ho tan hon ton lng kt ta , TAgCl = 1,1.10-10, cc phc Ag(NH3)+, Ag(NH3)2+ c 1.1 = 103,32, 1.2 = 107,24. 4.13. Thm dung dch Ag+ 0,1 M vo dung dch hn hp Cl- 0,1 M, Br- 0,1 M th ion no kt ta trc v khi ion th hai bt u kt ta th con th nht c nng cn bng l bao nhiu ? AgCl v AgBr c tch s tan ln lt l 109,75 v 10-42,29. 4.14. Thm dung dch Ag+ vo dung dch hn hp Cl-(10-1m)v Cr42- (10-2M) Tnh nng cn bng ca ion Cl- khi kt ta nu Ag2CrO4 bt u xut hin. TAgCl= 10-9,75, TAg2CrO4 = 10-11,95.

69

CHNG 5 PHN NG OXY HO - KH

5.1. KHI NIM V PHN NG OXY HO KH 5.1.1. nh ngha 5.1.1.1. Phn ng oxy ho kh l phn ng trong c s thay i mc oxi ho, cht oxi ho nhn electron v mc oxi ho gim, cht kh nhng electron v mc oxi ho tng. C th nh ngha theo nhiu cch khc. 5.1.1.2. Cht kh l cht cho electron s oxi ha tng, ho tr tng, cn cht oxi ho l cht nhn electron v s oxy ha gim. 5.1.1.3. Qu trnh kh l s nhn eletrn qu trnh oxi ho l s nhng electron. V d: 2Fe + 3O2 = 2 FeCl3 - Cht kh: Fe - Cht oxi ho: Cl2 - S kh Fe: - S oxi ho Cl-: Cl0 + 1 e = ClFe - 3e = Fe3+

5.1.2. Cn bng phn ng oxi ho kh (Theo phng php thng bng e). 5.1.2.1. Nguyn tc: Tng electron m cht kh nhng i bng tng electron m cht oxi ho thu vo. 5.1.2.2. Cc bc: a. Xc nh cht oxi ho, cht kh. b. Thnh lp phng trnh electron c. Cn bng phng trnh electron (Tm BSCNN ca tng thu v tng nhng ri tm h scn bng). d. Hon thin phng trnh phn ng. V d:

70

Bc 1: Cht kh l As2S3; Cht oxy ha l HNO3 Bc 2 v 3: thnh lp phng trnh electron v cn bng:

Bc 4: hon thin phng trnh phn ng:

5.2. TH OXI HO KH - CHIU CA PHN NG OXI HO KH 5.2.1. Th oxi ho kh - Phng trnh Nernst n gin ta xt cp oxi ho kh lin hp.

Theo nguyn l II nhit ng hc, nu G < 0 th phn ng xy ra theo chiu thun, G > 0 phn ng xy ra theo chiu nghch v G = 0, phn ng t trng thi cn bng. Nu G cng m, phn ng cng xy ra theo chiu thun v kh nng oxy ho ca cht oxi ha cng ln khi th kh ca cp cng ln. Th ng nhit ng p ca phn ng c tnh theo cng thc:

(K l hng s cn bng ca phn ng (5.1)) trng thi cn bng, G = 0, ngha l: G = G0 + RTlnK = 0 Mt khc: G0 = -A' (A' l cng hu ch chuyn n moi electron trong in trng c hiu s in th E, m A' = -nFE v n gin ta t E = E. V mt nhit ng hc E c trng cho TTCB ca phn ng kh Ox + ne = Kh nn n c gi l th kh. V mt ho hc c trng cho mnh yu ca cp Oxh/kh nn gi l th oxi ho kh. Cn v in ha hc n ch ra th in cc ca cp in cc to nn nguyn t ganvanic nn c gi l th in cc.

Chia c 2 v cho - nF, ta c:

71

iu kin tiu chun, T = 25oC + 273 = 298o, F: 96.500C. ng thi chuyn lnK = 2,3.lgK; R = 8,314 J/mol.K

l phng trnh Nernst tnh th oxi ho ca cp oxi ho kh lin hp. Eo c gi l th oxi ho kh tiu chun ca cp oxi ho kh lin hp c o iu kin chun v nng dng oxi ho bng nng dng kh = 1mol/l p dng (5.5) cho 3 trng hp sau:

5.2.2. Chiu ca phn ng oxi ho kh xt chiu ca phn ng oxi ho kh, ta da vo th tiu chun Eo ca cc cp. Cp no c Eo ln th dng oxi ho ca cp s oxi ho dng kh ca cp c th tiu chun nh hn.

C nhiu yu t nh hng n th oxi ho kh v chiu ca phn ng oxi ho kh.

72

5.2.2.1. nh hng ca nng Xt chiu phn ng a) Khi b) Khi Cho T (1) ta c 2 bn phn ng:

a) Khi Ta c:

Nh vy Hg22+ oxy ho Ag0 Ag+, phn ng xy ra theo chiu nghch. b) Khi

Lc ny Ag+ oxi ho Hg22+ Hg0, phn ng xy ra theo chiu thun.

5.2.2.2. nh hng ca s kt ta Xt chiu phn ng:

T (2) ta cng c hai bn phn ng: 73

Do c kt ta CuI to thnh m TCuI = 10-12 rt b nn nng Cu+ trong dung dch gim mnh, lm th E, tng ln:

y chnh l th tiu chun iu kin khi (Eo) khi c s kt ta CuI. Th ny ln hn th nn Cu2+ oxi ho c I- thnh I2 theo chiu thun. 5.2.2.3. nh hng ca pH Xt phn ng Xt chiu phn ng pH = 0 v pH =8 cho T phn ng (3) ta cng tch ra c hai bn phn ng:

Do c nh hng ca [H+] nn lm nh hng n th E1 * Ti pH = 0, [H+] = 1mol/1

V E1 > E2 nn AsO43- oxy ha c I- thnh I2 theo chiu thun. * Ti pH = 8, [H+] 10-8 mol/l

V E1 < 0,54V nn I2 oxi ha AsO33- thnh AsO43- (theo chiu nghch). 74

5.2.2.4. nh hng ca cht to phc Tnh th oxi ho kh tiu chun iu kin ca cp Co3+/ Co2+ khi c mt NH3. Cho hng s bn tng cng ca phc Co(NH3)63+ l tng cng ca phc CO(NH3)62+ l Trong dung dch c cn bng: hng s bn

Phn ng oxi ho kh khi c mt NH3

Khi khng c mt NH3:

Khi c mt NH3 th:

Ta c cc biu thc tnh bng s bn

T (2) ta c:

75

Vy E

'o Co 3 + / Co 2 +

=E

o Co 3 + / Co 2 +

1II6 . + 0,0591 lg II 1 .6

'o ECo3+ / Co2+ = 1,84 + 0,0591 lg

10 4,39 'o = 0,05V ( ECo3+ / Co2+ l th tiu chun iu kin) 1035, 21

Nh vy hot tnh oxi ha cu Co3+ gim, hot tnh kh ca Co2+ tng ln. 5.3. HNG S CN BNG CA PHN NG OXI HO KH. Xt hai bn phn ng sau:

Gi s OX1 l cht oxi ho mnh v Kh2 l cht kh mnh th:

trng thi cn bng G = 0, tc l

Nh vy lc cn bng ta c:

Nhn c t v mu ca v tri vi n1, a vo biu thc logant, nhn c t v mu v phi vi n2 a vo biu thc logarit, bin i ta c:

76

Thay cc gi tr: F = 96.500C, lnK = 2,3lgK, R = 8,314J/mol.K,T = 298K Ta c:

Khi n1 = n2 = n th:

V d: Ngi ta thm d thu ngn lng vo dung dch Fe3+.10-3M. Lc cn bng ch cn 4,6% Fe dng Fe3+ ( 298K). Bit th kh tiu chun ca cp Fe3+/Fe2+ = 077V Tnh th kh ca cp Hg22+ /Hg nu phn ng xy ra duy nht trong h l:

Bi gii:

HSCB ca phn ng trn l K:

Theo (5.7):

77

CU HI - BI TP CHNG 5

5.1. Thit lp s ph thuc th - pH i vi cc h oxi ho - kh sau:

5.2. nh gi kh nng oxi ho ca Fe3+ i vi I khi c mt ca F-. Gi s Fe3+ ch to phc vi F-:

v cc qu trnh trao i electron:

5.3. nh gi kh nng oxi ho I- bi Fe(CN)63- cho bit hng s khng bn tng hp ca FeF63- l 10-42 v ca FeF64- l 10-35 v cc hng s CB ca cc sn phn ng: K1, K2 tng ng c 5.4. nh gi kh nng oxi ho - kh ca cp Ag+/Ag khi c mt ca ion

5.5. Tnh th oxy ho kh tiu chun iu kin ca cp Fe(III)/Fe(H) trong 0 dung dch c d F- to phc FeF63+c 1.6 = 106,1, bit E Fe Fe =0,77V.
3+ 2+

5.6. Th oxi ho kh tiu chun ca cp Cu2+/Cu l 0,337V. Th oxi ho kh tiu chun iu kin khi c d NH3 to phc Cu(NH3)42+ l - 0,07V. Tnh hng s bn tng cng ca phc . 5.7. Th oxy ho kh tiu chun ca cp Cu2+/cu+ l E0 = + 0,153V. Tnh th oxi ho kh tiu chun iu kin ca cp khi c thiocyanat SCN- to kt ta CuSCN c tnh s tan ca TCuSCN = 10-14.32. 5.8. Gii thch ti sao bc kim loi khng tc dng vi HCl m tc dng vi HI 0 gii phng ra Hidro (H2) cho E Ag Ag = 0,80V, TAgCl= 10-10, TAgI= 10-16
+ 0

5.9. Tnh hng s cn bng cc phn ng oxi ho kh: 78

trong dung dch nng ln H+ l 1M.

Cho

0 ECe4+ / Ce3+ = 1,55V ,

0 ECr O2 / 2Cr 3+ = 1,36V


2 7

0 E MnO / Mn2+ = 1,51V ,


4

0 E Fe3+ / Fe2+ = 0,77V

E I02

= 0,54V ,
2l

5.10. Tnh HSCB ca phn ng gia ASO33- v I2 a) Trong mi trng axit c pH = 2 b Trong mi trng NaHCO3 0,1 M c pH = 8.

79

PHN TH HAI CC PHNG PHP PHN TCH HA HC

Nh nu trn ho hc phn tch gm phn tch nh tnh v phn tch nh lng. Phn tch nh lng gm cc phng php phn tch ho hc v cc phng php phn tch ho l. Cc phng php phn tch ho hc gm c phn tch khi lng v phn tch th tch. Cc phng php ho l gm phn tch o mu, phn tch sc k, phn tch in ho.

CHNG 1 PHN TCH KHI LNG

1.1. NGUYN TC CHUNG CA PHNG PHP PHN TCH KHI LNG Phn tch khi lng l phng php nh lng ha hc trong ngi ta o chnh xc bng cch cn khi lng ca cht cn xc nh hoc nhng hp phn ca n c tch ra trng thi tinh khit ha hc hoc l di dng hp cht c thnh phn bit trc. Th d, nh lng vng trong hp kim, ngi ta ly mt mu i din cho hp kim em ha tan mu ny trong mt lng thch hp nc cng toan 3HCl + 1HNO3 c chuyn hon ton mu thnh dung dch. em ch ha dung dch bng nhng thuc th thch hp, ri kh chn lc v nh lng vng (III) thnh vng kim loi (Au). em lc, ra kt ta Au ri sy v nung n khi lng khng i. Cui cng cn lng Au trn cn phn tch xc nh khi lng ca n. T khi lng ny, xc nh hm lng vng trong mu hp kim. xc nh Mg, ngi ta tin hnh nh sau: ha tan mu phn tch trong dung mi thch hp chuyn ton b lng Mg vo dung dch di dng in Mg2+. Ch ha dung dch bng cc thuc th thch hp kt ta hon ton v chn lc in Mg2+ di dng hp cht kh tan MgNH4PO4. Lc, ra kt ta v sy n nhit thch hp chuyn hon ton thnh hp cht Mg2P2O7. Cui cng cn xc nh khi lng ca n. Da vo cng thc ca kt ta v khi lng va cn c s tnh c hm lng ca Mg trong mu phn tch. Trong th d ny hp cht MgNH4PO4 c kt ta tch nh lng Mg c gi l dng kt ta, cn 80

Mg2P2O7 hp cht c to thnh sau khi nung dng kt ta v em cn xc nh hm lng ca Mg c gi l dng cn. Phng php phn tch khi lng Mg nh trn c gi l phng php kt ta. Phng php kt ta l phng php c s dng ph bin nht trong phn tch khi lng. xc nh CO2 trong qung ccbnt ngi ta phn hy lng mu CaCO3 bng axit trong mt dng c ring:

Ton b lng kh CO2 gii phng ra c hp th ht vo hn hn Cao + NaOH ng trong mt bnh ring. Lng CO2 c xc nh theo tng khi lng ca bnh ng hn hp hp th, phng php xc nh hm lng CO2 nh trn gi l phng php ct. xc nh SO42- ngi ta kt ta n di dng BaSO4 (dng kt ta), lc ra, sy, nung, cn kt ta (dng cn), ta tnh ra c hm lng SO42- trong dung dch no . 1.2. YU CU CA DNG KT TA V DNG CN phng php phn tch khi lng t c chnh xc cao, dng kt ta phi tha mn nhng yu cu sau: - Kt ta cn phi thc t khng tan. Mun vy khi tin hnh kt ta ngi ta phi chn nhng iu kin thch hp nh pa ti u, nng thuc th, nhit thch hp kt ta hnh thnh thc t khng tan, hoc nh ngi ta ni cht phn tch c kt ta mt cch nh lng, th d kt ta ti 99,99%. - Kt ta thu c cn phi tinh khit, khng hp ph cng kt v ni hp cc tp cht. Ch c nh vy th dng cn mi c thnh phn xc nh ng ng vi cng thc ha hc ca n. - Kt ta cn thu c di dng d lc ra c th tch ra khi dung dch mt cch nhanh chng v thun li nht. Yu cu quan trng nht ca phn tch khi lng l cht rn thu c cui cng phi c cng thc xc nh t khi lng ca n tnh ra c chnh xc hm lng nguyn t hoc tn cn nh phn. i vi nhng kt ta loi BaSO4 c cng thc xc nh, bn vng nhit cao, nn sau khi ra sch v sy kh th t khi lng ca n s c th tnh c lng ln Ba2+ hoc SO42- c trong dung dch phn tch. Nh vy, trong trng hp ny ang kt ta v dng cn l mt hp cht. Nhng khng t kt ta, chng hn Fe(OH)3 v Al(OH)3 thng khng c cng thc xc nh nn khng th chn l dng cn m phi nung chng nhit 81

cao ti khi c khi lng khng i chuyn chng thnh Fe2O3 hoc Al2O3 l nhng dng cn phi tha mn nhng yu cu sau: - Phi c cng thc xc nh, c thnh phn khng i t khi sy hoc nung xong n khi cn n trn cn phn tch. Th d, dng cn khng c ht m, khng hp th kh CO2 c trong khng kh, khng b phn hy bi nh sng... tha mn yu cu ny cn phi tin hnh phn tch theo nhng k thut nht nh. H s chuyn (cn gi l h s phn tch) cng nh th cng tt. Th d, c th xc nh Cr3+ di dng cn l BaCrO4 hoc Cr2O3. Gi s, sai s tuyt i khi cn BaCrO4 v Cr2O3 u l 1 mg, nhng khi cn dng Cr2O3 th sai s l 52 x 2/152 = 0,7mg Cr, cn khi cn dng BaCrO4 th sai s l 52x1/253,3 = 0, 20mg Cr, nh hn trng hp trc 0,7/0,2=3,5 ln. 1.3. CCH TNH KT QU TRONG PHN TCH KHI LUNG a/ H s chuyn cn gi l h s phn tch Thng thng dng cn khng phi l dng cn xc nh hm lng, v vy, t khi lng ca dng cn tnh khi lng ca dng cn xc nh hm lng. Do , tin cho vic tnh kt qu phn tch, ngi ta a ra khi nim h s chuyn. l i lng m ta cn phi nhn khi lng ca dng cn vi n c khi lng ca dng cn xc nh, thng thng h s chuyn l t s ca khi lng ca mt, hai hoc nhiu nguyn t hoc phn t hoc tn ca dng cn xc nh v khi lng phn t ca dng cn. Ni cch khc h s chuyn ch ra c bao nhiu gam nguyn t (cht) cn nh phn trong 1 gam dng cn. Trong trng hp cn xc nh Si th h s chuyn t SiO2 (dng cn) thnh Si dng cn xc nh l:

Th d khc: nu dng cn l Mg2P2O4 v dng cn xc nh hm lng l Mg; MgO hay MgCO3 th h s chuyn ln lt l

b) Cch tnh kt qu phn tch Thng thng ngi ta tnh kt qu theo % khi lng ca cht cn nh phn trong mu. 82

Gi s lng cn mu l p (g). Khi lng dng cn l q (g). K l h s chuyn. Hm lng tnh theo % khi lng x.

Nu p (g) mu cha trong v (ml) dung dch m ly ra v (ml) phn tch th:

Trong trng hp phn tch kh v hi th cch tnh kh n gin. V d, xc nh m ca mu, ta ly p (g) mu, Sau khi sy kh th cn li p (g). Vy m ca mu l:

83

CHNG 2 PHN TCH TH TCH

2.1. NHNG KHI NIM C BN CA PHN TCH TH TCH 2.1.1. Nguyn tc ca phng php 2.1.1.1. nh ngha: Phng php phn tch th tch l phng php phn tch da trn vic o chnh xc th tch dung dch thuc th (l dung dch chun) phn ng va vi dung dch phn tch. T th tch v nng ca dung dch chun chng ta tnh ra hm lng cht cn phn tch. o th tch chnh xc ca dung dch chun ta dng dng c l Bu rt (cn gi l ng chun ) cn bnh ng dung dch phn tch gi l bnh nn. Bu rt c chia n 0,1ml, thng dng l 25, 50, 100ml. Cn bnh nn thng dng c dung tch 50,100, 250ml. Qu trnh thm t t dung dch thuc th B t trn Buret xung cht nh phn A gi l s chun . im m A phn ng va vi B gi l im tng ng. xc nh im tng ng ngi ta cho ch th vo bnh nn. Ti im tng ng ch th b mt mu hoc xut hin mu hoc i mu do bn thn n phn ng vi lng d ca thuc th (ch cn 1,2 git) l xut hin hay i mu. V d: Khi chun HCl bng NaOH

Ta cho phenolphtalein vo bnh nn cha HCl, dung dch khng mu. Nhng khi lng HCl ht th 1 git NaOH d xung s lm dung dch chuyn sang mu hng do phenolphtalein tc dng vi OH-. 2.1.1.2. Cc yu cu ca phn ng dng trong phn tch th tch Do qu trnh chun din ra nhanh li i hi nhn bit i mu tc khc kt thc chun ng lc nn phn ng trong phn tch i hi cc yu cu sau: a) Phn ng phi hon ton: C ngha l phn cht cn li sau khi kt thc nh phn nh hn sai s cho php. V d: Sai s 0,1% l cho php c. iu c ngha l tc phn ng phi ln, qua tnh ton v qua thc t tc phn ng phi ln hn 106. Nu phn ng din ra khng hon ton th phi c bin php thc y phn ng 84

bng cch to phc hoc kt ta vi sn phm, v d:

phn ng hon ton phi cho thm KCNS vo va to phc bn Cu2(CNS)2 va trnh kt ta c, va d nhn bit s chuyn mu. b) Phn ng phi chn lc: Ngha l ch cho mt loi sn phm duy nht khng km theo phn ng ph to ra cc sn phm ph va kh xc nh im tng ng va gy sai s ln v thuc th (dung dch chun) hoc cht nh phn tiu tn mt lng no vi cht l m ta khng tnh c loi tr. khc phc tnh trng ny ta phi dng cht cht bng cch thm cht to phc vo n s ngn cn ion l khng phn ng vi thuc th hoc cht nh phn cng c trng hp ch cn iu chnh pa ca mi trng s ngn cn c phn ng ph. v d khi chun Cl- bng AgNO3, ta phi thc hin trong mi trng trung tnh hoc kim yu v nu mi trng kim mnh th:

hoc axit mnh s phn ng vi CrO42- (cht ch th) theo phn ng:

lm mt tc dng cht ch th: c) Tc phn ng phi ln: Trong phn tch th tch im tng ng c xc nh bng s i mu ca ch th, nu chm s d rt nhiu dung dch chun nu phn ng chm th phi thm vo h phn ng cht xc tc no . d) Phi xc nh c im tng ng bng ch th: Trong phng php trung ho ta dng ch th pH, trong phng php oxy ho kh v trong phng php kt ta v to phc dng ch th l cc cht v c hoc hu c c kh nng to vi thuc th d mt sn phm c mu c trng. e) ng lng gam ca thuc th cng ln cng tt: khi pha dung dch tiu chun sai s cn l nh nht. 2.1.2. Phn loi cc phng php chun . 2.1.2.1. Phn loi theo bn cht v c ch phn ng: Theo cch ny c bn cch chun : a) Chun trung ho (cn gi l phng php trung ho): l php xc nh nng mt axit hay kim bng dung dch chun kim hay axit, ch th ca php chun ny l ch th pH, khong pH i mu ca ch 85

th nm trong bc nhy pH ca php chun , v d Phenolphtalein, metyldacam. b) Chun oxy ho kh (cn gi l phng php oxy ho kh): Phng php ny c da trn vic xc nh nng cc cht oxy ho (hoc cht kh) bng cc cht kh (hoc oxy ho) ch th ca php chun l cht ch th oxy ho kh c khong th i mu nm gn hoc gn gn trong bc nhy th. V d chun Fe2+ bng dung dch chun Cr2O7.

Sau khi lng Fe2+ (di bnh nn) ht th Cr2O72- d s phn ng vi iphenyl quan, lm cho n bin i t khng mu sang mu tm xanh. Khi ta kt thc nh phn. c) Chun kt ta (phng php kt ta): Sn phm to thnh l kt ta, song vn nhn bit c s i mu ch th no . V d vic xc nh Cl- bng AgNO3, khi d AgNO3 n s phn ng vi K2CrO4 (l Cht ch th di bnh nn):

Mu ca dung dch chuyn t c trng (mu ca AgCl) sang hng nht bo hiu s kt thc chun . d) Chun to phc (phng php to phc): Sn phm to thnh phi l nhng phc cht bn v tan trong nc. Dung dch chun cng l nhng cht to phc, chng to vi ion kim loi thnh phc bn hn phc ca ch th vi ion kim loi. Sau tng ng cng c s i mu r rt ca ch th:

2.1.2.2. Phn loi theo trnh t v thao tc th nghim. a) Chun trc tip: Cho dung dch chun tc dng trc tip vi dung dch nh phn.

86

b) Chun gin tip: l vic xc nh nng cht nh phn thng qua sn phm to thnh gia A (dung dch nh phn) v B (dung dch chun). V d:

Thc t l vic xc nh A khng thng qua B m phi c C (sn phm ca A v B) tc dng vi E ri t E suy ngc li gin tip tnh ra A. c) Chun ngc: l vic xc nh A..phi qua hai dung dch chun (B v C) B d + A = E + D B cn + C = G + H Tnh A theo cng thc sau: 2.1.3. Tnh ton trong phn tch th tch. tnh ton ngi ta phi da vo loi nng c bn l nng ng lng v chun theo cht c xc nh v phi dng nh lut ng lng. 2.1.3.1. Nng ng lng. a) Nng ng lng (cn gi l nng chun hay l nguyn chun). l s ng lng gam cht tan c trong mt lt dung dch.

Trong : a l s gam cht tan, D l ng lng gam cht tan, V l s lt dung dch. xc nh ng lng gam (D) ta da vo biu thc:

(P l phn t gam ca cht tan n l i lng c trng cho tng loi phn ng). - Trong phn ng trung ho, n: S mol H + (hoc OH-) ca axit(hay baz) trao i. 87

- Trong phn ng oxy ho kh, n = s electron m cht oxy ho (hoc cht kh) trao i.

- Trong phn ng kt ta, n = s in tch trao i,

b) chun theo cht c xc nh (TA/B) chun ca mt thuc th (A) theo cht cn xc nh (B) l s gam cht cn xc nh (B) tc dng va vi 1 ml dung dch chun A. tc l 1 ml do AgNO3 tc dng va vi 0,00355g Cl-. chun Trong a l l s gam cht A, DA' DB l ng lng gam ca A, B. 2.1.3.2. nh lut ng lng: Cc cht phn ng vi nhau theo nhng ng lng bng nhau:

Gi VA, NA l th tch v nng ca cht nh phn A. Gi VB, NB l th tch v nng ca dung dch chun B. Theo nh lut ng lng ta c:

y l dng c bn ca nh lut ng lng tnh ton trong phn tch th tch. 88

V d 1: C bao nhiu gam Ba(OH)2 ho tan trong 250ml dung dch nu chun 20ml dung dch ny ht 22,4ml dung dch HCl 0,09884N? Ta c phn ng chun :

p dng nh lut ng lng ta c:

V d 2: Tnh % H2C2O4 trong mu, nu cn 0,200g mu v ho tan vo 50ml dung dch, chun dung dch ny trong mi trng axit ht 30,5ml KMnO4 o,lon. Gii: Ta c phn ng chun .

Dng cng thc: Ta c: Suy ra

2.2. CC PHNG PHP PHN TCH TH TCH 2.2.1. Phng php chun axit - baz (phng php trung ha) Phng php chun axit - baz da trn phn ng trao i proion gia dung dch chun v dung dch nh phn xc nh nng ca cc axit v baz. Cc phn ng dng trong phng php ny u tha mn cc yu cu ca phn ng dng trong phn tch th tch. Cc dung dch chun dng trong phng php ny thng l cc dung dch axit mnh hoc baz mnh. Trong qu trnh chun nng ca cc in H+ v OH- thay i, tc l pH ca dung dch ny thay i. V vy, xc nh im tng ng ngi ta thng dng nhng cht m mu sc 89

ca chng thay i theo pH ca dung dch. Nhng cht ny c gi l cht ch th axit - baz hoc cht ch th pH. ng biu din s ph thuc ca pH trong qu trnh chun vo th tch dung dch chun thm vo hoc lng cht nh phn c chun c gi l ng nh phn. Ngi ta thng da vo ng nh phn chn cht ch th thch hp nht. 2.2.1.1. Cht ch th axit-baz. Cc cht ch th axit - baz phn ln l cc phm nhum hu c. Chng l cc axit hoc baz hu c yu trong dng axit v baz lin hp c mu khc nhau. v vy mu ca chng ph thuc vo pa ca dung dch. Ta k hiu cht ch th l axit HInd v baz l IndOH. y rong nc cc cht ch th phn ly nh sau:

Trong cc dng lin hp tng ng ca mi cht c mu khc nhau. S thay i mu ca cht ch th ph thuc vo pH ca dung dch c gii thch bng thuyt ion - mang mu. Khi pH thay i th cc cn bng (a) hoc (b) s chuyn dch v pha phi hoc pha tri, cht ch th s tn ti ch yu di mt trong hai dng lin hp, nn c mu ca dng no tn ti ch yu trong dung dch. V d: nu cht ch th l HInd th khi thm axit vo dung dch ca n th cn bng (a) s chuyn v pha tri nn dung dch c mu ca dng axit HInd. Ngc li nu gim axit ca dung dch (chng hn thm kim vo) th cn bng (a) s chuyn sang pha phi nn dung dch c mu ca dng Ind- (dng baz). Khi pH ca dung dch cha cht ch th thay i th cu trc ca phn t trong c nhng nhm mang mu thay i dn n s thay i mu ca cht ch th. V d: Phenolphtalein c th tn ti trong dung dch cc dng cu trc phn t sau y:

90

V vy trong mi trng axit v trung tnh phenolphtalein tn ti ch yu di dng lacion khng mu, trong mi trng baz tn ti ch yu di qui non mu hng, nhng trong mi trng kim mnh li tn ti dng khng mu. Metyl da cam c th tn ti trong dung dch di cc dng sau:

Mi cht ch th axit - baz thng c mt khong pH i mu. Ta hy xt cht ch th l axit hu c yu HInd. Trong dung dch nc cha lng nh ca cht ch th :

T s

quyt nh mu ca dung dch. trong khong

Mt ta thng ch phn bit c s i mu khi t l

1/10 - 10. Ni cch khc khi nng ca dng axit chnh lch vi nng dng baz khong 10 ln th ta ch thy c mu ca dng c nng ln. Thay i t s nng : vo biu thc (2.7), ta c:

91

Nh vy, khong i mu m mt ta nhn thy c l 2 n v pH. Tuy nhin i vi mt s cht ch th mt ta c th nhn c s i mu nh hn 2 n v, ngha l khi t s nng ca cc dng nh hn 10 ln. i vi cht ch th loi IndOH, ta cng lp lun tng t xc nh khong pH i mu. Trong bng sau y l mt s cht ch th axit - baz quan trng nht. Bng 2. Mt s cht ch th axt-baz quan trng Tn thng dng Thimol xanh Metyl vng Metyl da cam Bromcresol xanh Metyl Bromcresol ta Bromthimol xanh Phenol Cresol ta Phenolphtalein Thimolphtalein Alizann vng GG Khong i mu 1,2 - 2,8 2,9 - 4,0 3,1 - 4,4 3,8 - 5,4 4,2 - 6,3 5,2 - 6,8 6,2 - 7,6 6,8 - 8,4 7,6 - 9,2 8,3 - 10 9,3 - 10,5 10 - 12 1,65 3,55 3,46 4,66 5,00 6,12 7,10 7,81 8,40 9,15 9,90 11,00 pKa Mu ca dng axit-baz vng - vng da cam Vng - xanh - vng Vng - ta Vng - xanh Vng - Vng - ta K0 - hng K0 - xanh K0 - vng

i vi loi cht th th c mu tc l ch mt trong hai dng axit - baz lin hp c mu, chng hn cht ch th loi HInd m dng HInd khng mu th mu ca dung dch s do nng dng c mu Ind- quyt nh. Nu C l gi tr m nng Ind- cn t ti ta nhn ra mu ca n v Co l nng ban u ca cht ch th th pH ca dung dch ti mu ca Ind bt u xut hin l:

Nh vy, pH lm i mu ph thuc vo nng cht ch th. V d, trong dung dch phenolphtalein bo ha, mu hng xut hin khi pH = 8 cn trong dung dch long hn 10 ln th pH = 9 mi xut hin mu. Ngoi khong i mu ca cht ch th, ngi ta cn dng khi nim ch s pT ca cht ch th axit - baz ch pa m ti cht ch th i mu r nht. Ta thng thy gi tr pT trng vi gi tr pKaHInd ca cht ch th. 92

2.2.1.2. ng nh phn ng nh phn trong chun axit - baz l ng biu din s lin h gia nng cn bng ca ion H+ v lng axit hoc baz chun . Thit lp c phng trnh nh phn ta c th v c ng thy c s bin thin pH ca dung dch trong qu trnh chun , chn cht ch th thch hp cho vic chun v khi c phng trnh ng phn nh ta d dng tnh sai s ch th. a. ng nh phn khi chun axit mnh bng baz mnh: Gi s chun V0 ml axit mnh HA nng Co (mol/l) bng dung dch chun baz mnh NaOH hoc KOH nng C (mol/1). Phng trnh phn ng chun l:

Hoc vit di dng ion:

Gi F l phn axit c chun , tc l:

Phng trnh bo ton proton ca dung dch trong qu trnh chun :

a F vo phng trnh (2.12) bng cch nhn 2 v ca phng trnh vi

Phng trnh (2.14) l phng trnh tng qut ca ng nh phn, n cho ta bit mi lin h gia pH ca dung dch v phn axit c chun . Nu bit c gi tr ca V, ta bit c F v da vo phng trnh trn ta tnh c [H+], tc l pH ca dung dch. Khi mi chun cn tng i xa im tng ng, trong dung dch cn nhiu [H+], nn [H+] >> [OH-] nn t (2.14) suy ra:

93

Phng trnh trn cho ta thy nng [H+] bng nng axit cha c chun b pha long bng V ml dung dch chun NaOH c thm vo. Tuy nhin, iu ny ch ng khi tng i xa im tng ng. Cng gn n im tng ng ta phi k n s phn ly ca nc. Ti im tng ng khi F = 1, t (2.14) ta c:

Sau v xa im tng ng v d tng i nhiu NaOH nn [OH-] >> [H+] v t phng trnh (2.14) suy ra:

St trc v sau im tng ng [H+] [OH-] nn phi gii phng trnh (2.14) tnh pH. Cn ch rng, c th coi CV = CoVo, tc l:

V d 1: v ng nh phn khi chun 100ml dung dch HCl 0,1M bng dung dch NaOH 0,1M. p dng cng thc (2.15), (2.16) kt hp vi (2.17) ta tnh c pH khi cho nhng th tch NaOH khc nhau vo dung dch HCl chun HCl. Cc kt qu c tp hp trong bng sau: V(ml) F pH 0 0 1 10 0,1 1,1 50 0,5 1,48 90 0,9 2,28 99 99,9 100 1 7,0 100,1 101 110 1,1

0,99 0,999 3,30 4,30

1,001 1,01 9,70

10,7 11,68

Nhn xt v ng nh phn axit mnh bng baz mnh: - Trc v sau im tng ng khi F nh hn 0,99 v ln hn 1,01 th pH ca dung dch bin i rt t. Tri li vng gn im tng ng pH thay i rt nhiu to nn bc nhy pH st im tng ng. - on pH ng vi thi im cn 0,1 % lng axit cha c chun v 0,1 % lng kim d so vi axit, tc l khong pH ng vi F = 0,999 v 1,001 thng 94

c quy c l bc nhy ca ng nh phn. Trong trng hp ny bc nhy ca ng nh phn l 5,4 n v pH (9,70 - 4,30) - Da vo bc nhy ca ng nh phn ta c th d dng chn cht ch th. Trong trng hp ny ta chn bt k cht ch th pa no c pT nm trong bc nhy. Tc l trong khong pH t 4,3 - 9,7 ta u nhn ra im tng ng vi sai s khng vt qu 0,1 %.

Hnh 2. ng nh phn chun HCl 0,1M bng NaOH 0,1M

- Nng axit cng ln th bc nhy cng di. Ta hy Tnh pH ca bc nhy. Khi chun thiu 0,1 % tc l:

Gi s C v Co gn im tng ng nn V gn Vo, ngoi ra c th b qua OH- cnh H+, nn phng trnh trn c n gin thnh:

Khi chun tha 0,1 % tc l:

V sau im tng ng nn ta b qua H+ cnh OH- v c th coi V = Vo nn 95

phng trnh trn c n gin ha thnh:

Bc nhy bng hiu s 2 gi tr pH trn pH

V d 2: Tnh pH ca bc nhy trong cc trng hp sau: Chun dung dch HCl c nng bng: a) 1 M; b) 0,1 M; c) 0,01 M v d) 0,005M bng dung dch NaOH cng nng . Sau khi p dng cng thc (c) trn v tp hp cc kt qu trong mt bng ta c: Nng Bc nhy 1 0,1 0,01 3,4 v pH 0,005 2,8 v pH 0,001 1,4 v pH

7, 4 v pH 5,4 v pH

Ta thy ngay rng, bc nhy pa ti im tng ng khi chun axit mnh bng baz mnh cng nng cng ln khi nng cng ln. Sai s ch th: Trong phn tch th tch ni chung v phng php chun axit - baz ni ring, ngoi sai s th tch do s dng dng c (buret, pipet, bnh nh mc...) gy nn, cn hai loi sai s quan trng khc l sai s do pa ca cht ch th khng trng vi pH im tng ng gi tt l sai s ch th v sai s do xc nh sai pT ca cht ch th, tc l xc nh pH im cui c gi l sai s im cui. Sai s ch th l sai s do im cui c nhn ra bng cht ch th khng trng vi im tng ng. Ta hy thit lp phng trnh tnh sai s di dng sai s tng i S. Theo nh ngha:

hoc di dng phn trm: S% = (F 1).100 Khi F nh hn 1 th S l phn axit cha c chun v c du m. Khi F ln hn 1, S l phn axit tng ng vi lng baz d v c du dng. Da vo phng trnh ng nh phn, ta lp c phng trnh sai s ch th theo pH 96

im cui tc l theo pT ca cht ch th. i vi trng hp chun axit mnh bng baz mnh t phng trnh (2.14) ta c:

Trong : c l ch vit tt ca ch cui. Nu kt thc chun gn im tng ng th:

Trc im tng ng, nu [H+] >> [OH-] th:

Sau im tng ng, nu [OH-] >> [H+], th:

Nu st im tng ng th dng phng trnh (2.19). Th d 1: Tnh sai s chun dung dch HCl 0,1M bng dung dch NaOH 0,1M nu kt thc chun a) pH = 5,0 v b) pH = 10,0. Trng hp a, ta p dng (2. 14):

Trng hp b, ta p dng (2.21):

Th d 2: Nu chun dung dch HCl 0,1M bng dung dch NaOH 0,1 M th cn kt thc trong khong pH no sai s ch th khng qu 0,1 %. i vi sai s - 0,1 % tc l S = - 0,001: ngha l lng NaOH thm vo cha . p dng cng thc (2.20), ta c:

i vi sai s + 0,01%; tc l S = +0,001; ngha l lng NaOH thm vo d: Ta dng (2.2 1):

97

Nh vy, mun sai s ch th khng vt qu 0,1 % ta phi kt thc chun trong khong pH t 4,3 v 9,7 hay ni cc khc l dng cc cht ch th c pH nm trong khong 4,3 - 9,7. b. Chun n t yu bng baz mnh Phn ng chun :

Phng trnh bo ton proton

Ta cng t F = v a F vo phng trnh trn, ta c:

Phng trnh trn l phng trnh bc 3 theo [H+] nhng trong cc giai on ca qu trnh chun n c n gin ha. Khi cha chun F = 0, V = 0 trong dung dch Axt nng C, ta b qua nng ln OH-, phng trnh (2.22) c bin i thnh:

V nu [H+] >> Ka th [H+]2 = Ka.Ca

(2.24)

Ta c cng thc quen thuc tnh pH ca dung dch axit yu v t cng thc (2.25) d dng suy ra: pH = 0,5pKa - 0,5lgCo - Sau khi thm v ml NaOH vo nhng cn xa im tng ng, th [H+] v [OH-] thng nh hn [Na+] v [A-] nhiu nn c th b qua s hng do phng trnh (2.20) tr thnh:

T (2.26) suy ra c: 98

Trong phng trnh (2.27), 1 - F ng vi phn axt HA cn li cha c chun , cn F ng vi phn axit c chun sinh ra baz A- lin hp vi n. v vy, phng trnh chnh l phng trnh tnh pH ca dung dch m gm axit HA v baz lin hp A-. Ti im tng ng F = 1, ta c dung dch A-, nn [OH-] >> [H+] v phng trnh (2.22) tr thnh:

Nu axit khng qu yu th Ka >> [H+], nn ta c th b qua [H+] cnh Ka v phng trnh trn ch n gin thnh:

y chnh l cng thc tnh pH ca dung dch A- c th k n s pha long. Sau v tng i xa im tng ng F > 1 ta c dung dch bm yu A- v baz mnh NaOH d, nn [OH-] >> [H+] v nu:

tc l [HA] << [OH-] th phng trnh (2.22) ch cn l:

vng st im tng ng ng vi 0,999 < F < 1,001 ch b qua c [H+] cnh [OH-] v Ka thng khng b qua c s hng no trong 2 s hng

ta phi gii phng trnh: 99

V(ml) F pH

0 0

20 0,2

50

90

99

99,9 100 100,1 101

110 1,1

150 1,5

0,5 0,9 0,99 0,999 1,0 1,001 1,01 7,8 8,74 9,7 10,7

2,88 3,4 4,75 5,8 6,8

11,6 12,5

Hnh 2. ng nh phn CH3COOH 0,1M bng NaOH 0,1M Nhn xt v ng cong chun trong trng hp chun axit yu bng baz mnh: - Cng ging nh chun n axt mnh bng baz mnh, trc v sau im tng ng khi chun n axit yu bng baz mnh pH t bin i theo F nhng st im tng ng pH tng t ngt theo F to nn bc nhy ca ng nh phn. Nu cng qui c bc nhy l pa ng vi s chun tha v thiu 0,1 % lng axit th trong trng hp ny bc nhy ngn hn trng hp chun axit mnh bng baz mnh (1,9 n v pH so vi 5,4 n v pH). - Khc vi trng hp chun axit mnh khi chun axit yu pH ti im tng ng khng bng 7,0 m ln hn 7 v sn phm ca pa phn ng chun l baz yu CH3COONa. - Bc nhy ca ng nh phn ph thuc vo cng axit. Axit cng yu th bc nhy pH vng im tng ng cng ngn. Ta hy gi s chun cc dung dch axit HA nng 0,1 M bng dung dch chun NaOH 01M. Cc axit c pha ln lt l 3, 4, 5, 7 v 9. Trong trng hp ny ta s tnh pH ti im tng ng v bc nhy l gi tr pH khi chun thiu v tha 0,2%. Ta c bng sau:

100

Cng axit (pKa) 3,0 4,0 5,0 7,0 9,0

pH tng ng 7,85 8,35 8,70 9,85 10,85

Bc nhy pH 5,7 10,0 6,7 10,0 7,7 10,0 9,7 10,3 10,84 10,9 1

pH 4,3 v 3,3 v 2,3 v 0,43 v 0,06 v

Qua cc kt qu trn ta thy, cc dung dch axt cng nng nhng c pKa khc nhau th vi axit cng yu, tc c pKa cng ln th pH ti im tng ng cng ln hn 7 nhiu v bc nhy pa ti im ng ng cng ngn. Khi pKa bng 9 th thc t khng c bc nhy. i vi axit c pKa bng 7 bc nhy pH cha t c 0,5 n v pH; nn kh chn c cht ch th c th phn bit c s i mu bng mt thng. i vi axit c pKa bng 8 hoc 9 th khng th chun c v khng th chn c cht ch th. - Bc nhy ca ng nh phn cn ph thuc vo nng ca axit cn chun v nng ca dung dch chun baz mnh. Ta hy tnh nc nhy ng nh phn khi chun cc dung dch CH3COOH pKa = 4,75 c cc nng l 1,0; 0,1; 0,01; 0,001M bng cc dung dch chun NaOH cng nng . Trong trng hp ny gi s bc nhy ng vi F - 1 = 0,002; tc l chun thiu v tha 0,2% lng axit cn chun . Sau khi gii phng trnh (a), ta c cc kt qu sau: Nng CH3COOH v NaOH 100 M 0,10 M 0,01 M 0,001 M pH bc nhy 7,45 - 11,0 7,45 - 10,0 7,44 - 9,0 7,37 - 7,8 pH 3,55 v pH 2,55 v pH 1,50 v pH 0,43 v pH

Qua cc v d trn ta thy bc nhy cng ngn nu nng axit cng nh. Cc dung dch nng nh hn 0,001M gn nh khng c bc nhy, nn nu chun s mc sai s ch th rt ln hoc khng th chn c cht ch th. Phng trnh tnh sai s ch th khi chun axt yu bng baz mnh: T phng trnh ng nh phn ta rt ra phng trnh tnh sai s cht ch th: 101

Nn im cui gn im tng ng th:

Ty theo pT ca cht ch th, ta c th n gin ha c cc phng trnh trn hn na. V d 1: Tnh sai s ch th, khi chun dung dch CH3COOH 0,1 M bng dung dch NaOH 0,1M dng cc cht ch th c pT bng a) 4,0; b) 8,0; c) 9,0. Trc ht tnh pH ti im tng ng theo (2.28)

a) Trng hp pH = 4: V [H+] = 10-4 v [OH-] = 10-10 nn c th b qua s hng th hai trong phng trnh (2-31) tnh sai s:

Ngha l mc sai s m rt ln: 85% lng axit cha c chun . b) Trng hp pH = 8: Ta kt thc chun trc im tng ng nn vn b qua s hng th 2 trong phng trnh (2.31) tnh sai s:

hoc -0,056%. Sai s kh nh v ch cn 0,056% lng axit chua b chun . c) Trng hp pH = 9: Ta kt thc chun sau im tng ng khi d lng nh kim ca dung dch chun. Trong trng hp ny ta b qua s hng th nht trong phng trnh (2.31) tnh S:

102

Sai s rt nh v ch ch chun tha 0,02% lng axit. V d 2: tnh sai s chun dung dch CH3COOH 10-3M bng dung dch NaOH cng nng v kt thc chun khi pH = 7,5. p dng phng trnh (2.28) tnh pH im tng ng:

Khi kt thc chun pH = 7,5 tc l st trc im tng ng, ta tnh sai s theo phng trnh (2.32).

Tc l -0,26%. Sai s ny chp nhn c. c) Phng trnh ng nh phn baz yu bng axit mnh: Tt c cc lp lun i vi trng hp chun axit yu bng baz mnh cng dng cho trng hp chun n baz yu bng axit mnh. V vy, ch cn hon v H+ cho OH- v thay Ka bng Kb trong phng trnh (2.22) ta s c phng trnh ng nh phn dung dch n baz yu bng dung dch n axt mnh.

Phng trnh c biu th F - 1 theo [H+] v [OH-] v Kb. Nhng ta cng c th thit lp phng trnh ng chun theo cch tng t v biu th F -1 theo [H+], [OH-] v Ka l hng s axit ca axit yu lin hp vi baz. Phng trnh nh sau:

v ng nh phn hoc tnh sai s ch th ta c th dng phng trnh (2.33) hoc (2.34) u a n cng mt kt qu. Cng tng t nh ng nh phn n axit yu bng n baz mnh, ng nh phn n baz yu bng n axit mnh, th d: chun dung dch NH3 bng dung dch chun HCl c nhng tnh cht tng t nhau. i vi trng hp ny, pH im tng ng khng phi l 7,0 m nh hn 7 v ph thuc vo nng dung dch baz cn nh phn v dung dch im tng ng l dung dch n axt lin hp vi baz cn nh phn. ng nh phn cng c bc nhy pH vng im tng ng v bc nhy ny ngn hn bc nhy ca ng nh 103

phn n axt mnh. Bc nhy di hay ngn cn ph thuc vo cng baz v nng ca n, baz cng yu th bc nhy cng ngn, nng baz cn nh phn cng nh bc nhy cng cng ngn. Ta hy dng phng trnh (2.34) tnh pH ti im tng ng v pH bc nhy (vi qui c chun thiu v tha 0,2% lng baz) khi chun dung dch NH3 c nng khc nhau 1 M; 0,1 M; 0,001 M bng dung dch HCl cng nng . Ti im tng ng tc l khi F = 1, phng trnh (2.34) c n gin ha khi b qua [OH-] cnh [H+], Ka= KNH4+ = 10-9,25 cnh [H+] v C0 = C nn khi tr thnh v ta c:

Khi gii phng trnh (2.34) vi F -1 = + 0,002; tc l u bc nhy ta c th b qua [OH-] cnh [ H+] v KNH4 + cnh [H+] ng thi thay - Khi gii phng trnh (2.34) vi F 1 = + 0,002 tc l cui bc nhy khi d 0,2% lng axit cn trung ha NH3 ta b qua s hng th 2 trong phng trnh v ng thi b qua [OH-] cnh [H+] s hng th nht. Vi s n gin , sau khi gii ta c cc kt qu sau: Nng dung dch NH3 (mol/l) pHt (F = 1) pH bc nhy (F - 1 = 0,002) 1,00 0,10 0,01 0,001 4,78 5,28 5,78 6,28 6,55 - 3,00 6,55 - 4,00 6,56 - 5,00 7,16 - 5,97

tnh sai s ch th trc ht ta cng tnh pH ti im tc dng n gin ha vic gii phng trnh:

V d: Tnh sai s khi chun dung dch NH3 0,1 M bng dung dch HCl 0,1M dng cht ch th c pT bng a) 5; b) 4,0. 104

a) Trng hp kt thc chun khi pH = 5. Ta tnh pH ti im tng ng pHt = 4,78 - 0,5lg0,1 = 5,28 Khi pH = 5,0 tc l [H+] = 10-5 nn c th b qua [OH-] cnh [H+] v b qua KNH4+ cnh [H+]. V pH ny gn pH ti im tng ng v v C = Co nn thay

b) Trng hp kt thc chun khi pH = 4,0. pH ny tng i xa pH im tng ng, nn ta b qua s hng th 2 trong phng trnh tnh sai s, b qua [OH-] cnh [H+] trong s hng th nht.

d. ng nh phn chun a axit bng baz mnh: Ta hy thit lp ng inh phn chun dung dch a axit H2A nng mi l Co bng dung dch chun ba mnh NaOH nng C. S chun ny c tin hnh theo 2 nc:

Trong trng hp ny ta cng biu th mc chun bng i lng F vi nh ngha:

Tc l phn axit c chun . Khi chun theo cc nc th nht, tc l tin hnh chun theo phn ng (a) th ti im tng ng th nht, ta c F = 1. Khi chun theo nc th 2, tc l tip theo phn ng (b), ti im tng ng th 2, ta c F = 2. Trong trng hp chun a axit ny cng c F - 1 l sai s khi chun theo nc th 1 v F - 2 l sai s ch th theo nc th 2. Ta hy thit lp phng trnh ng nh phn theo nc th nht. Ta vit phng trnh bo ton proton xut pht t sn phm phn ng (a), tc l t HA- & H2O khi c mt H2A v thm vo V ml NaOH. 105

Nhn 2 v ca phng trnh trn vi

ta c:

Phng trnh trn l phng trnh bc cao theo [H+] nhng c th c n gin ha trong tng giai on ca qu trnh chun . Khi cha chun V = 0, F = 0. Ta b qua c [OH-] v [A2-] cnh [H2A] nn (2.35) c n gin ha thnh:

Khi mi chun cn xa im tng ng th nht. [H+]; [OH-] v [A2] khng ng k so vi H2A v HA-, phng trnh (2.35) c n gin ha thnh:

Nh vy, khi K1 >> K2 v thng nh vy nn ta c th coi H2A nh n axit yu nng Co v c K4 = K1 v ta c phng trnh tnh pH ca dung dch m ca h H2A v HA. St im tng ng th nht (bc nhy pH th nht ca ng nh phn) ta thng b qua c [OH-] v hai s hng [H+]2 (tng ng vi phn H2A rt nh cha c chun ) v K1K2 (tng ng vi lng A2- cng rt nh do HAphn ly ra) trong v phi ca (2.35) nn phng trnh c n gin ha thnh:

Ti im tng ng th nht, khi F - 1 = 0, C.V = Co.Vo, phng trnh (2.38) tr thnh :

106

Bin i, chuyn v ta tnh ra H+:

Nu

ln hn nhiu K, th c th b qua K, trong mu s biu thc

trong cn ca (2.39) v (2.39) tr thnh:

lp phng trnh ng nh phn cho nc th hai, ta vit phng trnh bo ton proion ca dung dch xut pht t cc sn phm ca phng trnh chun nc l A2- v H2O

Nhn 2 v ca phng trnh trn vi

ta c:

Phng trnh (2.40) trn cng l phng trnh bc 3 theo [H+] nhng trong giai on ca qu trnh chun n c th n gin ha. Khi ang chun nc th hai, cn xa im tng ng th 2 ta c th b qua c [H+], [OH-], [A2-] v [H2A] nn (2.40) c n gin ha thnh:

v suy ra

107

Phng trnh (2.41) chnh l phng trnh tnh pH ca dung dch h m HA v A2- trong biu thc (2.41), 2- F1 ng vi nng HA- cn li cha b trung ha. Cn 1-F ng vi nng phn HA- b trung ha thnh A2-. st im tng ng th 2 ta c th b qua c [OH-], [H2A], [HA-] nn phng trnh ng nh phn cn l:

Ti im tng ng th 2,

Ty theo gi tr ca K2 so vi nng ion H+ im tng ng (gi tr H+ thng ln hn 10-7) m phng trnh trn cn n gin ha hn na. Sau im tng ng ngoi bc nhy khi d OH-, ta b qua s thy phn ca A2-, tc l b qua s hng th hai v phi phng trnh (2.35) nn phng trnh ch con:

V d: v ng nh phn chun dung dch H2C2O4 0,1M bng dung dch NaOH 0,1M, H2C2O4 c pK1 = 1,25 v pK2 = 4,27. v ng phn nh hy tnh pH khi F = 0,5; 0,9; 1,00; 1,1; 1,5; 1996; 2,00 v 2,004; 2,5. p dng cng thc trn y, tnh pH ti cc im ca ng nh phn ta c cc kt qu sau y: F pH 0,5 1,15 0,9 2,2 1,00 2,76 1,10 1,50 3,32 3,27 1,996 6,67 2,00 2,004 8,35 2,5

9,97 12,16

Nhn xt: axit oxalic c pK1 kh nh tc l K1 kh ln, K1 v K2 khng ln hn nhau nhiu nn khi chun bc nhy im tng ng th nht hu nh khng c, ch c bc nhy im tng ng th hai nh khi chun axit axetic cng nng . V vy, khi chun axit oxalic ta ch chun theo nc th 2 v c th dng cc cht ch th c pT nm trong khong pH t 7,0 n khong gn 10.

108

Hnh2.3. ng nh phn dung dch H2C2O4 0,1M bng dung dch chun NaOH 0,1M. e. nh phn a baz bng n axit mnh: Chng ta xt trng hp c th: nh phn dung dch CO32- mt tia baz rt thng gp trong thc t. V d: phi chun dung dch (Vo ml) Na2CO3 nng Co bng dung dch chun HCl nng mi C. Phng trnh ng nh phn: Chun CO32- theo nc th nht:

thit lp phng trnh ng nh phn v phng trnh sai s ch th ta cng vit phng trnh bo ton proton xut pht t sn phm phn ng l HCO3 v H2O. Ta cng t

Nhn 2 v ca phng trnh trn vi

Phng trnh trn l phng trnh tng qut, n cng c n gin ha trong tng giai on ca qu trnh chun . - Khi cha chun F = 0, ta b qua c [H+] cnh [OH-], [H2CO3] cnh [CO32-] nn (2.45) c n gin ha thnh: 109

T phng trnh trn suy ra:

Ti vng gn im tng ng, cc gi tr [H+] v [OH-] khng ng k so vi [HCO3-] v [CO32-] nn phng trnh (2.45) c n gin ha thnh:

Ti im tng ng th nht, F - 1 = 0, phng trnh (2.47) tr thnh:

Khi chun tip tc theo nc th hai:

thit lp phng trnh ng nh phn ta cng c th vit phng trnh bo ton proion ca dung dch xut pht t sn phm ca phn ng l CO2 + H2O hoc ly phng trnh F - 1 - 1, phng trnh cui cng thu c:

Ti vng st im tng ng th 2 phng trnh (2.49) c gin ha thnh:

V d 1: Tnh sai s ch th khi chun dung dch Na2CO3 0,1M bng dung dch HCl 0,1 M. Theo nc th nht khi dng cht ch th c pT = 9. p dng phng trnh (2.47) tnh F - 1 ti im pH = 9 ta c S = - 0 0477 tc l sai s bng -4,77%. V d 2: Tnh sai s ch th khi dng cht ch th c pT = 4 nhn ra im tng ng khi chun dung dch Na2CO3 0,1M bng dung dch chun HCl 0,1M. Gi thit l ton b CO2 cn li trong dung dch. tnh sai s ta dng phng trnh (2.50) tnh F - 2. Khi thay [H+] = 10-4, C = Co = 0,1 vo ta tnh c: 110

F - 2 = - 0,00146 = -0,0015. tc l sai s thiu 0,075%. V d 3: Cn thm bao nhiu ml dung dch HCl 0,05M vo 20 ml dung dch Na2CO3 0,1M pH ca dung dch thu c bng a) 9,0 v b) 5,0. (Gi s khi pH bng 5,0 ton b kh CO2 cn li trong dung dch.) c) khi pH = 5,0 em un si dung dch lng CO2 trong dung dch khng ng k th pH ca dung dch bng bao nhiu v khi thm tip HCl 0,1M th cn thm tip bao nhiu ml HCl vo pH ca dung dch = 4,0. Gi s lc ny nng CO2 cng khng ng k. a) Gi th tch dung dch HCl cn thm vo pH ca dung dch thu c bng 9,0 l V. tnh V ta dng phng trnh (2.47):

Thay Co = 0,1; [H+] = 10-9; K1 = 10-6,35, K2 = 10-10,32, C = 0,05 vo phng trnh trn, gii ra c V = 38,09 ml. b) Cng s dng phng trnh trn v thay cc i lng vo nhng vi [H+] = 10 ri gii th ta c V = 78,48 ml.
-5

c) Nu khi thm HCl vo n pH = 5, ta un si dung dch loi CO2 khi dung dch th pH ca dung dch l pH ca HCO3- cn li cha c chun ht theo nc th hai. pH ca dung dch gn bng 0,5 (pK1 + pK2) = 8,35, tc l pH li tng ln. Sau khi un si dung dch pH bng 5 nu ta tip tc chun v gi s CO2 vn khng ng k, v d do ta lc mnh dung dch khi tip tc chun th c th xem nh chun baz mnh v ta dng phng trnh:

Thay

vo, ta gii c: V = 80,20 ml.

Vy sau khi thm HCl vo n pH = 5, loi CO2, ta cn thm tip vo 80,20 ml -78,48 = 1,72 ml HCI 0,05 M th pH = ca dung dch bng 4,0. g. nh phn hn hp axit v hn hp baz. Trong thc tin ta thng gp nhiu trng hp phi xc nh nng tng axit hoc tng baz trong cc hn hp ca chng. C rt nhiu hn hp axit hoc baz nhng khng c nhiu trng hp c th chun ln lt tng axit bng dung dch chun baz mnh hoc chun ln lt tng baz bng th Fluorexein 111

vo dung dch Clorua cn chun th trc im tng ng AgCl do hp ph ion Cl- tch in m nn cc ht kt ta khng hp ph mun FInd- ca cht ch th. Nhng ngay sau im tng ng cc ht kt ta AgCl do hp ph cation Ag+ tch in dng s hp ph mun ca cht ch th n bin dng v i mu lc sang mu hng. Cht ch th ny l mt axit hu c yu c pKa = 8 nn pH ca dung dch phn tch phi ln hn hay bng 6,5. FInd- phn ly ra lm cht ch th i mu r rt nhng pH ca dung dch phn tch khng c vt qu 10 v kt ta Ag2O mu en hnh thnh s ngn cn vic nhn ra im cui. Nu thay Fluorexein bng eoxin (Tetrapromo - Fluorexein) l axit mnh hn Fluorexein th c th dng cht ch th ny chun brommua, iodua v thioxianat ti nhng pH thp hn (pH = 2-4). Tuy vy, ta khng th dng eoxin lm cht ch th chun clorua v mun ca cht ch th ny c th y Cl- b hp th yu hn ra khi kt ta ngay khi cn nhiu clorua trong dung dch. Khi dng cc cht ch th hp ph nng cc halogenua phi nm trong khong 0,005 - 0,25M v nu dung dch phn tch long qu th s chuyn mu ca cht ch th khng r rng nu dung dch khc c th kt ta bc halogenua d vn cc gn im tng ng lm gim hiu ng hp ph gy kh khn cho s chuyn mu ca cht ch th. c) Phng php Volhard Nh ha hc ngi c Jacob Volhard ngh dng dung dch cha ion Fe (III) lm cht ch th chun ln Ag+ bng dung dch thioxianat SCN-. Khi chun ht bc, ngay sau im tng ng lng d rt nh ion SCN- ca dung dch chun to vi ion Fe3+ mt phc mu mu Fe(SCN)2+ lm trung dch c mu hng da cam trn kt ta trng AgSCN. u im ca phng php l tin hnh chun c trong dung mi axit mnh. Cn mi trng axit chng s thy phn ca ion Fe3+. Phng php ny c p dng chun ngc mun Cl- v Br-. xc nh Cl- ngi ta thm vo dung dch phn tch lng d dung dch chun AgNO3 bit trc nng . Lc b kt ta AgCl ri chun lng Ag+ cn li bng dung dch chun thioxianat vi ch th l phn st ha tr III. nh phn b sau khi thm lng d dung dch chun AgNO3 khng cn lc b kt ta AgBr v tan ca AgBr nh hn tan ca AgSCN m kt ta ngay trong dung dch phn tch ri chun lng ln Ag+ bng dung dch chun SCN- vi cht ch th st ha tr III. 2.2.4. Phng php chun oxi ha - kh Trong cc phng php chun oxi ha - kh ngi ta thng tin hnh phn ng chun l phn ng trao i electron gia dung dch chun cha cht oxi ha (hoc kh) vi dung dch phn tch cha cht kh (hoc cht oxi ha). nhn ra 112

im tng ng ca phn ng chun ngi ta cng dng cc cht ch th.

tnh sai s ch th khi chun hn hp cc axit a baz nh trng hp ny, cch tt nht, t b nhm ln khi tnh ton l da vo th tch dung dch chun ng vi im cui v im tng ng. Nu gi Vo v Vt l th tch dung dch chun ng vi im cui v im tng ng th sai s (tng i) ch th l:

V d 1: Cn phi thm bao nhiu ml dung dch chun NaOH 0,05M vo 20 ml dung dch hn hp HCl 0,05M + H3PO4 0,1M tnh pH ca dung dch hn hp thu c bng a) 4,0 v b) 9,0. T tnh sai s ch th i vi mi cht HCl v H3PO4 khi chun hn hp ca chng bng dung dch NaOH 0,05M dng cht ch th c pT = 4, pT = 9 v tnh nng mi axit nh trn trnh by. t Vo l th tch dung dch hn hp hai axit (20ml), V1 v V2 l th tch dung dch thm vo ln lt c pH =4; pH =9. Co l nng mi ca dung dch HCl (0,05M), Co l nng mi ca H3PO4 (0,1M) v C l nng dung dch chun NaOH (0,05M). a) Tnh th tch V1 ca dung dch NaOH cn thm vo pH = 4, phng trnh bo ton proton xut pht t H2O v H2PO4-:

Ti pH = 4 ta b qua c [OH-], [HPO42-], [PO43-] trong phng trnh trn, sau khi n gin ha phng trnh, thay cc nng cn bng ca chng bng cc biu thc theo K v [H+] n gin ha bng cch b cc s hng b bn cnh cc s hng ln, thay cc gi tr bng s ca cc i lng , gii phng trnh ta tm c V1 = 59,43 ml. b) Tnh th tch V2 cn thm vo pH ca hn hp bng 9,0: Phng trnh bo ton proton xut pht t H2O v HPO42-:

Khi pH = 9, ta c th b qua cc gi tr nng [H+], [H3PO4], [PO43-] trong 113

phng trnh trn. Gii phng trnh , sau khi c n gin ha cc i lng nh bn cnh cc i lng ln ta c V2 = 99,37 ml. Nh vy nu chun H3PO4 theo mt nc da vo s i mu ca cc cht ch th c pT = 4, pT = 9 th th tch theo thc nghim l Vo = 99,37 - 59,43 = 39,94 ml. Theo u bi, v nng ca H3PO4 = 2 ln nng NaOH nn th tch NaOH ng vi im tng ng khi chun theo mt nc l 20x2 = 40,00ml. Do sai s i vi H3PO4 l:

Th tch ng vi im cui khi chun HCl l: 59,43 - 39,94 = 19,49(ml). V nng ca HCl v NaOH bng nhau nn th tch NaOH chun HCl ng vi im tng ng l 20,00ml. Sai s i vi nng HCl l:

Trong phn trn (2.48) chng ta bit rng c th chun a baz Na2CO3 bng dung dch chun HCl dng 2 cht ch th l phenolphtalein (vi im tng ng th nht) v metyl da cam (vi im tng ng th hai). V vy, ta cng c th chun dung dch hn hp NaOH v Na2CO3 bng dung dch chun HCl, hai cht ch th tng t nh chun dung dch hn hp HCl + H3PO4 bng dung dch chun NaOH trnh by trong phn trn. Khi phenolphtanein i mu ta chun NaOH v nc th nht ca Na2CO3.

Khi metyl da cam i mu, ta chun Na2CO3, theo nc th 2:

t th tch dung dch hn hp hai baz trn l Vo, nng dung dch chun HCl l C, th tch dung dch HCl khi phenolphtalein i mu l V1, khi metyl da cam i mu l V2, th tch dung dch HCl dng chun mt nc ca Na2CO3 l V2 V1 (Cc th tch c tnh t im 0 ca buret). Th tch HCl chun NaOH l V1 - (V2 V1) = 2V1 - V2. Do biu thc tnh nng tng cht l:

V d 2: Cn thm bao nhiu ml dung dch cho 0,05M vo 100ml dung dch hn hp NaOH 0,1M + NaHCO3 0,02M pH ca dung dch hn hp thu c 114

bng a) 9,0 v b) 4,0. bit H2CO3 c pK1 = 6,35; pK2 = 10,3. t th tch dung dch hai baz l Vo, nng HCl l C, th tch dung dch chun HCl thm vo pH t c 9,0 l V1, t c pH = 4 l V2 (V1, V2 tiu c tnh t im ca buret). Nng ca NaOH trong hn hp l Co, ca Na2CO3 l Co. a) Tnh th tch HCl cn thm vo pH = 9,0. Phng trnh bo ton proton xut pht t H2O v HCO3-:

Khi [H+] = 10-9, ta b qua c [H+], [H2CO3], [OH-] dng phng trnh trn, nn n ch cn:

Thay gi tr ca cc i lng vo cc phng trnh (a) gii ra ta tnh c V1 = 238,1 ml. b) Tnh th tch V2 bng bao nhiu ml pH ca dung dch bng 4,0. Phng trnh bo ton proion xut pht t H2O v H2CO3:

dung dch [H+] = 10-4, th phng trnh (b) c n gin ha khi b qua [OH-], [CO32-] thnh:

Sau khi thay cc gi tr bit vo phng trnh trn (b), gii ra ta c V2=279,64 ml. Nh vy th tch HCl dng chun 1 nc ca Na2CO3 l: 279,64 - 238,1 = 41,54 ml. Nng ca dung dch Na2CO3 l Sai s l: 115

Th tch dung dch chun HCl dng chun NaOH l 238,1 - 41,5 = 196,56. Nng ca dung dch NaOH l sai s l: Bng phng php tng t, chng ta c th chun dung dch hn hp NaOH + Na3PO4 bng dung dch chun HCl dng hai cht ch th l phenolphtalein (khi chun ton b NaOH v Na3PO4 thnh Na2HPO4) v metyl da cam (khi chun Na2HPO4 thnh NaH2PO4). 2.2.2. Phng php chun to phc Cc phng php chun to phc da trn phn ng to phc ca cc cht. Trong phn tch th tch, ngi ta thng dng cc phng php chun to phc sau y: Phng php thy ngn II. Phng php ny da trn phn ng to phc bn gia con Hg2+ vi cc anion clorua, bromua, iodua v xianua. Th d:

Phng php bc: Phng php ny da trn phn ng to phc ca ion Ag+ v ion xianua.

Phng php complexon: Phng php ny da trn phn ng to phc ca cc ion kim loi vi nhm thuc th hu c c tn chung l complexon nh ni trong chng 3 trn. Complexon l nhng dn xut ca axit aminopolycacboxilic. Trong s cc thuc th th complexon III (mui inatri ca axit etyleniamin - tetraaxetic) l hp cht c s dng ph bin nht. Cc complexon ni chung v complexon m ni ring to phc bn vi hng chc ion kim loi. Cc phn ng to phc ny tha mn cc iu kin ca cc phn ng dng trong phn tch, do , ngy nay phng php complexon l phng php c s dng rng ri nht trong phn tch th tch. Trong chng ny chng ta cp ch yu n phng php chun ny. phn ny chng ta xt phng php chun dng dung dch complexon III lm dung dch chun. 116

2.2.2.1. Cht ch th trong phng php complexon xc nh im tng ng ca phng php chun complexon, ngi ta dng mt s loi cht ch th, loi cht ch th c s dng nhiu nht (c ti hng chc cht khc nhau) c gi l cht ch th mu kim loi. y chng ta ch xt loi cht ny. Cc cht ch th mu kim loi l nhng cht mu hu c c kh nng to vi cc ion kim loi phc cng cua c mu v trong nhng iu kin xc nh mu ca phc khc vi mu ca cht ch th t do. Cc cht ch th mu kim loi thng l nhng axit hu c yu hoc baz yu, phn t ca chng cha nhng nhm mang mu v tr mu nn cng l nhng cht ch th pH. Do c im k trn mu ca cht ch th loi ny bin i theo pM (pM = - lg[Mn+]) v theo pH ca dung dch. Khi chn cht ch th cho s chun mt ion kim loi no bng phng php complexon, ngi ta phi chn pH thch hp (bng cch dng cc dung dch m thch hp) phn ng to complexonnat kim loi xy ra hon ton, cht ch th t do v phc ca cht ch th vi ion kim loi phi c mu khc nhau, d phn bit v s i mu ca cht ch th phi xy ra rt gn im tng ng, bn ca phc gia kim loi vi Complexon bn hn vi ch th. Khong i mu ca cht ch th mu kim loi l khong tm trong c th xy ra s bin i mu ca cht ch th. Gi s Ind l dng ca cht ch th to vi ion kim loi phc mu. Da vo cn bng:

ta c th tnh c khong i mu ca cht ch th ( y n gin ha trong cn bng trn ta khng vit in tch ca cc ion). Th d, xt trng hp ca ion Mg2+ v cht ch th Eriocrom en T (thng c vit tt ET - 00). ET - 00 l a axit yu, ta k hiu H3Ind, anion Ind3- c mu da cam, to ion Mg2+ phc cht c mu :

Hng s khng bn ca phc :

117

Ion Ind3- cn phn ng vi ion H+ to thnh nhng dng axit c mu khc nhau:

t Ind3- l nng ca cc dng ca cht ch th khng lin kt vi ion kim loi dung dch, tc l:

Hng s khng bn iu kin ca phc gia Mg2+ v ET- 00 l:

T biu thc cc hng s cn bng (b) v (c), ta suy ra:

T (2.53) v (2.54), suy ra:

Nh vy ng vi mi gi tr ca tng, ti pH xc nh, t s [MgInd-]/[Ind3-] c gi tr xc nh. Mu sc ca dung dch ph thuc vo t s . Ta phn bit mu ca mt trong hai dng khi nng ca n ln hn dng kia mt s ln (thng thng khong 10 ln). V trong trng hp ny khong i mu ca cht ch th l pK 1, khi pM pK + 1 dung dch c mu ca cht ch th t do khi pM pK-1 dung dch c mu ca phc MgInd. Mu sc ca cht ch th t do cn ph thuc 118

vo pH ca dung dch, khi pH < pK2 cht ch tn ti trong dung dch ch yu di dng H2Ind mu . Khi pK2<PH<pK3 cht ch th tn ti ch yu trong dung dch di dng HInd2- mu xanh v khi pH > pK3 cht ch th trong dung dch tn ti ch yu di dng Ind3- mu da cam. Da vo phng trnh (2.56) ta c th v c gin s ph thuc ca khong i mu ca cht ch th vo pH ca dung dch. Trn hnh 2.4 l gin i vi trng hp ET - 00 - Mg2+. Cng nh trong phng php trung ha chn cht ch th thch hp cho s chun mt ion kim loi no , trong phng php complexon ngi ta cng da vo ng nh phn hoc vic tnh sai s ch th. Trn hnh 2.4 l gin biu din s ph thuc khong i mu ca ET - 00 i vi ion Mg2+ v pH ca dung dch. Da vo th ny v ng nh phn khi chun magi ta thy c vic chn iu kin nh th no (chn pH dung dch nh th no) khong i mu nm trong bc nhy ca ng nh phn.

Hnh 2.4. Khong i mu ca ET-00 ph thuc vo pH dung dch 2.2.2.2. ng nh phn trong phng php complexon Gi s chun Vo ml dung dch mui kim loi c nng mi l Co bng dung dch complexon III c nng mi l C. ng nh phn l ng biu din s bin thin ca phi theo phn chun F, pM = f (F) trong cng nh cc chng trc, pM = -lg[M] v F = CV/CoVo l mc lng ion kim loi c chun hay l phn ln kim loi to phc vi complexon. Ta hy thit lp phng trnh ca ng nh phn. Trong qu trnh chun trong dung dch c cc cn bng sau: - Cn bng to phc gia Y4- v ion Mn+ ( n gin ta khng vit in tch ca cc ion): 119

- Cc cn bng ca 4 nc phn ly ca axit H4Y:

- Cc cn bng to phc ph ca Mn+ vi cc ion khc c trong dung dch nh vi ion OH- hoc l mt thnh phn ca dung dch m (NH3).

Gi [M'] v [Y'] l tng cc nng cn bng ca cc dng ca ion kim loi M v ca EDTA tr phc MY gia M v Y. tnh [M'] theo F ta dng cc phng trnh sau:

vo (d) bng cch nhn 2 v ca (d) vi

Phng trnh (2.57) l phng trnh ng nh phn khi chun ln kim loi M bng dung dch chun EDTA. Bng phng trnh ta c th tnh chnh xc M theo F t suy ra theo cng thc:

ri t cc gi tr ca F v [M] tng ng ta v ng nh phn. Phng trnh l 120

phng trnh bc 2, nhng n c th c n gin ha trong tng giai on ca qu trnh chun : - Trc v tng i xa im tng ng, nu kh ln. [Y'] s khng ng k cnh [M'], phng trnh (2.57) c n gin ha thnh:

- Ti im tng ng F = 1, vy: [Y'] = [M] hoc:

[M] rt nh so vi

nn c th b qua, vy:

- Sau v tng i xa im tng ng [M'] khng ng k so vi [Y] v khi c d complexon trong dung dch, nn:

V M rt nh so vi nn

phng trnh trn c n gin ha thnh

Ngay st trc v sau im tng ng khi 0,999 F 1,001; th [M'] v [Y'] xp x nhau, nn phi dng phng trnh y (2.57). Trong trng hp ny c th khng k [M'] so vi nn ta c:

Cch tnh ' xin xem cc chng trc. Th d: v ng nh phn khi chun 100 ml dung dch mui Mg2+ 0,01M c m bng hn hp m NH3 + NH4Cl gi pH = 10 bng dung dch EDTA 121

0,01M. Phc Mg2+ vi EDTA c = 108,7. Trong dung dch ny c ion Mg2+ thc t ch to phc vi EDTA do hng s bn iu kin ca phc l:

trong : MgY = 108,7 v

Thay [H+] = 10-10 vo biu thc trn ta c (H)= 100,45. T tnh c = 108,25. p dng cc cng thc t (2.58) n (2.61) tnh pha ta c cc kt qu sau: Th tch EDTA (ml) 25,00 50,00 75,00 90,00 99,00 99,90 100,00 F 0,25 0,50 0,75 0,90 0,99 0,999 1,00 Mg2+ 10-2,2 10-2,48 102,85 103,28 10-4,30 10-4,95 10-5,00 pMg 2,2 2,48 2,85 3,28 4,30 4,94 5,00 V (ml) 100,10 101,00 110,00 125,00 150,00 F 1,001 1,01 1,10 1,25 1,50 Mg2+ pMg 10-5,10 10-5,7 10-6,7 107,10 10-7,40 5,10 5,70 6,70 7,10 7,40

Hnh 2.5. l ng nh phn v theo cc s liu ca bng trn. Qua ng nh phn chng ta thy rng trc v sau im tng ng pMg tng chm nhng vng im tng ng tung tng nhanh to nn bc nhy im tng ng trn ng nh phn. khi F tng t 0,99 1,00 v t 1,00-1,01, tc l 1 % th pMg 0,7 n v. Bc nhy ca ng nh phn ph thuc vo nng dung dch chun EDTA v hng s bn iu kin ca phc gia EDTA v ion kim loi. Khi cc i lng cng ln th bc nhy ca ng nh phn cng di.

122

Hnh 2.5. ng nh phn khi chun dung dch Mg2+ 0,01M Th d: Nu quy c bc nhy l hiu pMg khi F tng t 0,99 - 1,01 th bc nhy khi chun Mg2+ 0,01M pH bng 10 bng dung dch EDTA cng nng l 1,4 n v pMg, bc nhy khi chun dung dch 0,1M cng pH bng dung dch EDTA cng nng l 2,4 n v pMg. Hng s bn iu kin ph thuc vo pH ca dung dch. Th d i vi ion Mg2+ khi tng pH nu hng s bn iu kin cng ln th bc nhy cng di. Da vo ng nh phn v gin i mu ca cht ch th cho vic chun mt tn kim loi bng EDTA. Th d theo gin 24 ti pH bng 10 cht ch th ET - 00 i mu trong khong tng t 4,3 - 5,7; khong nm trong bc nhy ca ng nh phn ca cc dung dch Mg (II) 0,1 M v 0,01 M bng dung dch chun EDTA cng nng . 2.2.2.3. Mt s cht ch th quan trng dng trong cc phng php chun complexon Ngy nay ngi ta tng hp c hng chc thuc th hu c lm cht ch th mu kim loi trong chun complexon. Sau y l mt s cht ch th quan trng nht c s dng rng ri trong cc phng th nghim phn tch v s lng cc cht ch th rt nhiu, nn tnh ph bin ca cc phng php chun complexon ngy cng c m rng v ngi ta ni cc phng php chun complexon l ht nhn ca phn tch th tch hin i. Eriocrom en T (ET- 00) l mui natri ca axit (1-oxi -2 -naphtylazo)-6-nitro-2-naphtol-4- sunfonic. Cng thc cu to ca cht ch th l:

123

ET - 00 l cht mu, cht ch th t do c mu khc nhau ph thuc pH ca dung dch ha tan n. Cht ch th l a axit H3Ind. Khi pH = 6 cht ch th c mu nho, trong dung dch c pH nm trong khong 7 - 11 n c mu xanh bic, khi pH = 11,5 n c mu da cam. V H3Ind c pK1 = 6,3; pK2 = 11,5 5. ET - 00 to phc hoc hng vi cc ion kim loi Mg2+, Zn2+, Cd2+ thng c dng chun trc tip cc ion trong mi trng c pH = 10 dng hn hp m NH3 - NH4+. Ngoi ra n cn c dng nh phn gin tip cc ion kim loi khc nh nh phn Ni2+, Pb2+ bng phng php chun ngc vi mui Zn2+ (pH = 10), chun Ca2+ pH = 10 bng cch thm phc MgY2- vo. Murexit Murexit l mui amoni ca axit pupuric C8H5O6N5. Trong mi trng axit mnh anion H4Ind- c cng thc cu to nh sau:

Anion H4Ind- ca Murexit trong dung dch axit mnh, axit pupuric l a axit c pK1 = 0, pK2 = 9,2, v pK3 = 10,9. Nn mu ca cc dng ca cht ch th ph thuc vo pH ca dung dch. Trong dung dch nc c pH < pK2 cht ch th c mu tm, trong khong pH t pK2 - pK3 c mu tm hoa c v khi pH = pK3 cht ch th c mu xanh tm. Murexit to phc vi cc ion kim loi sau: vi Ca2+ khi pH = 12 phc mu ; vi Co2+, Cu2+ v Ni2+ khi pH trong khong 7 - 9 (dung dch m amoniac) phc c mu da cam; vi ion Ag+ trong dung dch m NH3 pH = 10 - 11,5 phc c mu . Murexit l cht ch th tt cho vic chun trc tip cc ion Ca2+, Cu2+, Ni2+ v Ag+. 124

2.2.2.4. Phng php bc. Chun xianua Trong phng php to phc ny ngi ta chun dung dch xianua bng dung dch chun bc thut. Trong qu trnh chun , trc im tng ng, trong dung dch c d cc ion CN- nn xy ra cc phn ng to phc:

Hng s bn tng cng ca phc 1,2 = 1020,9 Sau Ag+ kt ta vi ion phc Ag(CN)2-:

Kt ta trn c tch s tan T = 10-14,2. phc,gia Ag+ v OH- km bn so vi phc gia Ag+ v O-. S thy phn ca CN- c th b qua, nn trong qu trnh chun trong dung dch ch yu ch xy ra 2 phn ng (a) v (b). S xut hin kt ta Ag[Ag(CN)2] lm gc dung dch c th dng lm du hiu ch th kt thc chun ln CN- bng dung dch chun Ag+ theo phn ng (a). Chng ta c th tnh sai s khi kt thc chun ti thi im kt ta Ag[Ag(CN)2] mi xut hin da vo cc cn bng (a), (b) v cc hng s tng ng. 2.2.2.5. Phng php thy ngn, chun cc halogenua Ion Cl- to phc kh bn vi ion Hg2+(1= 5,5.106, 2 = 3.106). Do nu chun dung dch clorua bng dung dch Hg2+ (dng thut) thy phn II) th trong qu trnh chun xy ra phn ng:

nhn bit im tng ng ngi ta dng cht ch th l iphenyl cacbazol. Cht to vi Hg2+ phc c mu xanh tm. Ngay sau im tng ng ion Hg2+ ca trung dch chun s to phc mu vi cht ch th . Khi dng iphenylcacbazol th pH ca dung dch phi trong khong 1,5 - 2,0. Ngi ta c th dng cht ch th khc iphenylcacbazon, trong trng hp ny pH ca dung dch phi trong khong 2,0 - 3,5 v ch nhng pH ion Hg2+ ca dung dch mi to phc mu vi cht ch th, phng php thy ngn cn dng chun cc halogenua khc nh bromua, iodua v c xianua v thioxianat. Tuy nhin phng php ny khng c nhiu u im nh phng php kt ta dng dung dch chun bc nitrat nn y chng ta khng xt ti. 2.2.3.Chun kt ta 2.2.3.1. Nguyn tc chung ca phng php 125

Phng php chun kt ta da trn vic s dng cc phn ng to thnh cc hp cht kh tan (kt ta). Cc phn ng kt ta c s dng phi tha mn cc yu cu sau: - Kt ta c to thnh trong phn ng chun phi thc t khng tan, tc l phn ng phi hon ton v theo mt t lng xc nh. - Tc to thnh kt ta phi ln, tc l khng to thnh dung dch qu bo ha. - Phn ng phi chn lc, ngha l nh hng ca cc qu trnh cng kt, hp ph, kt ta theo phi khng ng k. - Phi c cht ch th thch hp xc nh c im tng ng. Tuy s lng cc phn ng kt ta rt nhiu nhng thng khng tha mn cc yu cu trn nn a s cc phn ng ch c p dng trong phn tch nh tnh cn rt t c p dng trong phn tch nh lng. Trong thc t phn tch, ngi ta thng ch dng cc phng php chun kt ta sau: - Phng php bc, trong dng dung dch chun AgNO3 chun cc ion halogenua Cl-, Br-, I- v thioxianat SCN-

Ngoi ra cn dng phng php kt ta to thnh cc mui t tan ca Hg (I) nh Hg2Cl2, Hg2I2 v phn ng to thnh kt ta K2Zn3[Fe(CN)6]. Nhng y chng ta ch xt n phng php bc l phng php chun kt ta c nhiu ng dng thc tin. 2.2.3.2. Phng trnh ng chun cc halogenua Gi s chun Vo ml dung dch cha anion halogenua X- nng Co (mol/lit) bng dung dch chun AgNO3 nng C (mol/lit). Phng trnh phn ng chun :

Khi thm vo dung dch phn tch V ml dung dch chun (1) xy ra th cc ion Ag+ v X- c nng cn bng lin h vi nhau bng cc h thc sau:

126

Trong , U l s mol kt ta ng vi 1 lt dung dch. t tc l phn lng anion X- c chun ri ly (3) tr i ta c:

(2) v nhn 2 v ca phng trnh nhn c vi

Cc phng trnh (2.62) v (2.63) trn dng v ng nh phn tc l ng biu din s ph thuc ca pAg (tc l -lg [Ag+] hoc pX tc l - lg[X-] theo V hoc theo F). Cc phng trnh l phng trnh bc 2 ca [Ag+] hoc [X-] nhng chng s c n gin ha trong tng giai on ca qu trnh chun . Trc v xa im tng ng [Ag+] rt nh so vi [X-] c th coi nh khng ng k. Nn (2.62) c n gin ha thnh:

Ti im tc dng, tc l khi CV = CoVo, F - 1, ta c:

Sau v tng i xa im tng ng khi d Ag+, X- rt nh coi nh khng ng k, nn ta c:

Rt st im tng ng ta khng b qua c [Ag+] hoc [X-] nn phi gii phng trnh (2.62) hoc (2.63). V d: v ng nh phn chun 100 ml dung dch NaCl 0,1M bng dung 127

dch chun AgNO3 0,1M. F Cl- 0,1M pCl 0,50 0,90 0,99 0,999 1,000 1,01 1,10 1,50 1,48 2,28 3,30 4,30 5,00 6,70 7,70 7,97 pAg 8,52 7,72 6,70 5,70 5,00 3,30 2,30 0,03 Cl- 10 M pCl 0,48 1,28 2,30 3,30 5,00 7,70 8,70 7,67 pAg 9,52 8,72 7,70 6,70 5,00 2,30 1,30 0,33 I- 0,1 M pI 1,48 2,28 3,30 4,30 8,00 12,70 13,70 15,67 pAg 14,52 13,72 12,70 11,70 8,00 3,30 2,30 0,33

v ng nh phn trong v d ny ta tnh ph hoc pH theo F khi F = 0,999 ta p dng cng thc (2.63) tnh ph v t ph tnh pH. Khi F = 1,01 ta dng cng thc (2.65) rt st im tng ng nu mun tnh ta dng cc cng thc (2.62) v (2.63). Trn bng (2.62) l cc gi tr tnh c ca ph, pH v tri khi chun cc dung dch cc dung dch Cl-, I- bng cc dung dch AgNO3 cng nng . 2.2.3.3.ng nh phn Ta thy cc ng nh phn cc dung dch Cl- v I- bng dung dch chun AgNO3 cng nng l cc ng c bc nhy theo ph ti vng st im tng ng v ng nh phn i xng qua im tng ng. Ti im tng ng nng ca cc ion to nn kt ta bng nhau. Nng dung dch cng ln, tch s tan ca kt ta cng b th bc nhy pAg ti im tng ng cng ln (hnh 2.6).

128

Hnh 2.6. ng nh phn cc dung dch Cl- v Ibng cc dung dch chun AgNO3 cng nng . 2.2.3.4. Sai s chun Cng nh trong phng php trung ha tnh sai s ch th ta s dng phng trnh nh phn l tin li nht. Phng trnh tng qut tnh sai s ch th l:

Phng trnh c th c n gin ha. Nu dng cht ch th kt thc chun trc im tng ng th:

Nu kt thc chun sau im tng ng th:

Nu kt thc chun st im tng ng th:

V d 1: Tnh sai s khi chun dung dch Cl- 0,1M bng dung dch chun Ag+ cng nng nu kt ta chun khi pAg = 4,3. Ly tch s tan ca AgCl- l 10-10. Kt thc chun pAg = 4,3 tc l khi [Ag+] = 5.10-5. p dng phng trnh 129

(2.69) ta c

V d 2: Chun dung dch NaCl 0,1 M bng dung dch chun AgNO3 0,1 M. Mun sai s chun khng vt qu 0,2% th phi kt thc chun trong khong ph no? Cho TAgCl = 10-10. Ta phi tnh ph khi F - 1 = 0,002. Khi F - 1 = -0,002.

Gii ra, ta c [Ag+]c = 10.10-6, tc l pAg = 6,0. Khi F 1= +0,002.

Gii ra ta c [Ag+]c = 10.10-4, tc l pAg = 4,0. Vy phi kt thc chun trong khong pAg t 4,0 n 6,0 th sai s khng vt qu 0,2%. 2.2.3.5. Chun hn hp Trong mt s trng hp khi mt con, v d Ag+ to c kt ta vi hai hoc ba ln khc m cc hp cht kh tan c to thnh c tch s tan khc nhau nhiu th cc kt ta s kt ta ln lt hoc l kt ta phn on v ta c th tin hnh chun phn on, v d chun hn hp Cl- + Br hoc Cl- + Br- + I- bng dung dch chun AgNO3. 2.2.3.6. Cc cht ch th dng trong phng php bc Phng php bc l phng php chun kt ta c s dng rng ri nht trong cc phng php kt ta. Trong phng php ny ngi ta dng dung dch AgNO3 lm dung dch chun nh phn cc anion Cl-, Br-, I-, SCN-. Trong phng php bc c th dng mt s cch xc nh im cui. a. Phng php Morh Nh ha hc Morh ngh s dng dung dch CrO42- lm cht ch th xc 130

nh cc anion Br-, Cl- bng dung dch chun Nitrat bc v ion Ag+ to vi anion CrO42- mt kt ta mu nu. Kt ta ny c tan ln hn tan ca AgCl v AgBr. Nu thm vo dung dch phn tch mt t dung dch cha ion CrO42- th AgCl hoc AgBr s kt ta trc v n khi Ag2CrO4 mu nu (b gch) bt u kt ta th lng Br v Cl- kt ta hon ton. Ta hy tnh nng ln CrO42trong dung dch phi bng bao nhiu Ag2CrO4 bt u kt ta ti im tng ng khi chun Cl- bng dung dch chun Ag+, v TAgCl = 10-10, nn ti im tng ng [Ag+] = 10-5. Nng CrO42- phi bng:

Nhng vi nng ny mu ca cromt qu m. V vy thng dng nng Cromt l 0,005M s xut hin mu gch c r rng. Phng php Morh c dng nh phn Cl- hoc Br- ch khng dng nh phn I- v SCN- v vi cc anion ny s hp th sy ra kh mnh. Phng php Morh c dng chun nhng pH trong khong 6,5 - 8,5 v nhng pH thp hn nng ln cromat s gim do to thnh ion HCrO4- theo phn ng:

cn nhng pH cao th s kt ta Ag2O kh tan mu en b. Phng php FaJans Phng php ny c gi l phng php cht ch th hp ph do nh ha hc ngi Ba Lan ngh nm 1926. Theo Fajans mt s cht mu hu c nh Fluorexein hoc eosin khi b hp ph dng anion trn b mt kt ta tch in dng s b bin dng v thay i mu. Nu thm mt lng nh cht ch dung dch axit mnh tng t nh chun ln lt cc nc ca a axit nh H3PO4 hoc a baz nh Na2CO3 vi cc cht ch th thch hp vi chnh xc chp nhn c nh ta thy trong cc phn trn. Gi s chng ta c hn hp hai n axit HCl v CH3COOH nng khng khc nhau nhiu. Thot u ta c th tng rng c th chun ln lt chng bng dung dch chun NaOH v mt axit l axit mnh (HCl c K v cung ln) v axit cn li l axit yu (CH3COOH c K =10-4,75). Nhng khng phi nh vy v khi thm t t dung dch chun NaOH vo hn hp hai axit , ng nhin u tin HCl b trung ha v n l axit mnh, nhng axit CH3COOH cng b chun ng thi vi HCl khi lng HCl cn kh nhiu v trong thc t nu dng my o pH theo di s bin thin pH trong qu trnh chun hn hp ny th ta thy 131

trn ng nh phn ch c mt bc nhy pH ng vi s chun tng s c hai axit ch hu nh khng c bc nhy pH im tng ng th nht i vi s chun mt mnh HCl. vng gn im tng ng th nht th CH3COOH bt u s chun sinh ra CH3COO- to thnh mt h m (CH3COOH + CH3COO-) nn pH bin thin rt t t lm ng nh phn khng c bc nhy pH im tng ng th nht . Trong phn trn chng ta bit, i vi dung dch H3PO4 l a axit c pK1 << pK2 << pK3 v pK2 = 7,21 khng qu nh nn ta c th chun c tng nc ca dung dch axit vi hai cht ch th l metyl (cho nc th nht) v phenolphtalein (cho nc th hai). V vy, trong trng hp ny ta c th chun c hn hp hai axit HCl v H3PO4 dng hai cht ch th . Khi thm dn dung dch NaOH vo dung dch hn hp 2 axit , u tin HCl b chun :

sau n H3PO4 c chun theo nc th nht:

Khi metyl hoc metyl da cam i mu tr ton b HCl v nc th nht ca H3PO4 c chun . V vy khi tip tc chun th lc ny ch mt mnh nc th 2 ca H3PO4 b chun thi:

Nu t Co l nng HCl, c Co' l nng ca H3PO4 trong hn hp ca chng. C l nng ca NaOH, V1 l th tch ca NaOH c thm vo n khi metyl da cam i mu v V2 l th tch ca NaOH c thm vo n khi phenolphtalein i mu (V1 v V2 u c tnh t im khng ca buret) th V1 l th tch dung dch NaOH dng chun ton b HCl v nc th nht ca H3PO4. V2 V1 l th tch dung dch NaOH tiu tn chun mt nc ca H3PO4.

2.2.4.1. Cht ch th oxi ha - kh i vi chun oxi ha - kh trong mt s trng hp c th nhn ra im cui bng s thay i mu ca dung dch khi d mt git dung dch chun. V d, khi chun dung dch cc cht kh khng mu bng dung dch chun pemanganat, th mt git dung dch chun d ra cng lm dung dch c mu hng. Mt trng hp khc na l mt trong hai dng oxi ha hoc kh to cht 132

mu vi mt cht khc chng hn tt to mu xanh vi h tinh bt th cng dng cht (h tinh bt) lm cht ch th cho phn ng chun tt hoc dung dch cht kh bng dung dch chun tt. Trng hp ny h tinh bt khng tham gia phn ng oxi ha - kh. Trong i a s cc trng hp cht ch th trong phng php oxi ha - kh l nhng cht oxi ha - kh m dng oxi ha v dng kh ca n c mu khc nhau. V vy, mu ca cht ch th ph thuc vo th oxi ha - kh ca dung dch. Mi cht ch th oxi ha - kh cng c mt khong i mu. Ta hy xt mt cht ch th oxi ha - kh. Gia dng oxi ha v dng kh ca n c cn bng trao i electron.

Phng trnh Nernst i vi h ny l:

Gi s rng ta phn bit c mu ca mt dng khi nng cn bng ca n ln hn dng kia khong 10 ln. Do khong th i mu ca cht ch th oxi ha - kh t:

Sau y l mt s cht ch th oxi ha - kh thng c s dng. Diphenylamin: C6H5 - NH - C6H5. c s dng di dng dung dch 1 % trong axit sunfuric c. Cht ny c th tiu chun Eo = +760mV (+0,76V). Dng oxi ha c mu tn dng kh khng mu. iphenylbenziin: Cht ch th c cng thc cu to:

N c s dng di dng dung dch 1 % trong axit sunfuric c. Cht ch th c th tiu chun = +0,76V. Dng oxi ha c mu tm dng kh khng mu. Phc ca Fe2+ vi 2.2' - ipiridin: Cng thc cu to l:

133

c s dng di dng dung dch HCl long. Cht ch th ny c th oxi ha kh tiu chun l +O,97V. Dng oxi ha mu xanh nht, dng kh c mu . Feroin: Phc ca Fe2+ vi 1,10 - phenaltrolin: Cht ch th ny c cng thc cu to l:

Dung dch cht ch th c chun b bng cch ha tan 1,26 g phenal - trong clohydrat v 0,695 g FeSO4 trong 100 mi nc. Cht ch th ny c Eo l + 1,06V. Dng oxi ha mu xanh nht, dng kh mu . Axit fenylantranilic Cht ch th ny c cng thc cu to l:

N thng c s dng di dng dung dch 0,2% trong nc hoc 0,1% trong dung dch Na2CO3 0,2%. Th tiu chun Eo l +1,08V. Dng oxi ha c mu tm dng kh khng mu. chn cht ch th cho mt php chun ngi ta thng dng phng php v ng nh phn v phng php tnh sai s ch th tng t nh cc phng php chn cht ch th trong chun trung ha, chun complexon. 2.2.4.2. ng nh phn a. Chun Fe2+ bng Ce4+ Thit lp phng trnh ng nh phn khi chun Vo ml dung dch Fe2+, nng ng lng No bng dung dch chun Ce4+ nng ng lng N. Cho bit cc th tiu chun ca cc h l:

134

Phn ng trao i electron ca tng cht trong cp ca n:

Do nng ng lng ca cc dung dch Ce4+ v Fe2+ u bng nng mi ca chng. Phn ng chun l:

Phng trnh bo ton electron ca dung dch xut pht t sn phm phn ng (Ce3+, Fe3+), khi thm V ml dung dch Ce4+ vo Vo ml dung dch Fe2+:

Gi F l phn Fe2+ b chun , tc l nhn 2 v ca (2') vi ta c;

a F vo (2') bng cch

Cc nng cn bng trong phn t A l nng mi s tnh t cc phng trnh bo ton khi lng ca Fe2+ v Ce4+. T (3) ta tnh c cc t s nng ca Fe3+/Fe2+ v Ce4+/Ce3+ theo F v thit lp c phng trnh chun l phng trnh biu din s ph thuc ca th oxi ha - kh ca dung dch vo F. * Trc im tng ng tc l khi F < 1, trong dung dch cn d Fe2+, ngoi ra v phn ng xy ra kh hon ton (K = 1012,8), nn [Ce4+] khi rt nh, khng ng k so vi [Fe2+], nn phng trnh (3) tr thnh:

Ta bit rng: nn suy ra:

Nn (4) tr thnh: 135

Chia t v mu s ca v phi phng trnh (4') vi Fe2+, ta c:

T suy ra:

Phng trnh ng nh phn l:

* Ti im tng ng, khi lng dung dch Ce4+ thm vo tng ng vi lng Fe2+, 2 cht tc dng va vi nhau, tc l F = 1 v F - 1 = 0, ta c:

Ngoi ra, ta lun c: Do , ta suy ra:

T 2 phng trnh Nernst ca 2 h:

Ta suy ra E ti im tng ng:

* Sau im tng ng, tc l khi F > 1, ta thm vo nhng lng dung dch chun Ce4+, nn ta b qua c [Fe2+] trong (3) v phng trnh tr thnh: 136

vo (5), ri b qua [Fe2+] v

qu nh ta c:

Do phng trnh nh phn l:

Nh vy, trc im tng ng ta tnh th oxi ha - kh ca dung dch bng phng trnh Nerst ca cp lin hp cha cht kh (cp Fe3+/Fe2+) sau im tng ng ta tnh th cn bng phng trnh Nernst ca cp cha cht oxi ha (Ce4+/Ce3+). Ti im tng ng th ca dung dch c xc nh bng phng trnh Nemst ca c hai cp v th l hng s ch ph thuc vo Eo ca hai cp. Bng sau cho ta thy cc d kin tnh theo cc phng trnh trn v ng nh phn khi chun dung dch Fe2+ 0,1M bng Ce4+ 0,1M. Th oxi ha - kh E trong qu trnh chun dung dch Fe2+ 0,1M bng dung dch Ce4+ cng nng . F E (v) 0,1 0,62 0,5 0,68 0,9 0,74 0,99 0,78 0,999 1,000 1,001 0,86 1,04 1,26 1,01 1,32 1,10 1,35 1,50 1,42

T cng thc trn v v d v ng nh phn ta c nhng nhn xt sau: Dng ca ng nh phn khng ph thuc vo nng ca dung dch chun cng nh cht cn xc nh. Khi mi bt u chun v c bit im tng ng dc ca ng cong rt cao v ti im tng ng c bc nhy th. Ti vng xung quanh F = 0,5. Th bin thin rt t ta c th dng dung dch m th. - Dng ca ng nh phn khng ph thuc vo pH, tuy nhin axit lm thay i dng ca cc cht (Fe (III) v Ce (IV)) do lm mt s thy phn hoc s to phc lm thay i th tiu chun ca cc h.

137

Hnh 2.7. ng nh phn dung dch Fe2+ 0,1M bng dung dch Ce4+ 0,1M. Cn ch l i vi c hai h va xt h s ca cht oxi ha v cht kh lin hp trong phng trnh trao i electron l bng nhau nn cc phng trnh thit lp tnh th khng ph thuc vo nng ca cc cht. Tuy nhin i vi trng hp cc h s.bt i xng th cc kt qu s khc i. Ta hy tnh th trong qu trnh chun dung dch Fe2+ bng dung dch chun Cr2O72- trong mi trng axit. b. Chun Fe2+ bng Cr2O72- Gi s ta cn v ng nh phn khi chun dung dch Fe2+ 0,1M bng dung dch chun K2Cr2O70,03M trong mi trng axit c [H+] = 1M. Bit cc th tiu chun

Phng trnh chun

Phng trnh bo ton electron c vit xut pht t cc sn phm phn ng l Cr3+ v Fe3+ khi thm V ml dung dch chun Cr2O72- vo Vo ml dung dch Fe2+:

Gi F l phn Fe2+ b chun tc l c 2 v ca (2) vi bin i ra ta c:

a F vo (2') bng cch nhn

138

Phn ng gia Fe2+ v Cr2O72- xy ra rt hon ton v th tiu chun ca hai cp khc nhau nhiu (K = 1066,1). Do , trc im tng ng ta b qua c [Cr2O72-] bn cnh [Fe2+] trong phng trnh (2.75), phng trnh cn:

Kt hp vi phng trnh

Ta i n phng trnh ng nh phn

Ti im tng ng, khi NoVo = NV, ta c:

Sau im tng ng. Khi F> 1, ta b qua nng [Fe2+] trong phng trnh (2.77) v tnh th theo phng trnh Nernst ca h Cr2O72-/Cr3+:

Trong

p dng cc phng trnh trn ta c cc gi tr th trong qu trnh chun Fe 0,1M bng Cr2O72- 0,1M v v c ng nh phn ca php chun ny.
2+

Nu qui c bc nhy ti im tng ng l hiu th hiu ng vi F 1 = 0,002 th ta tnh c hiu th l 0,552V. Nh vy, trong trng hp khi c ion H+ tham gia vo phn ng chun v khi h s ca cc cht oxi ha - kh lin hp trong phng trnh phn ng chun khng bng nhau th th oxi ha - kh kh ca dung dch ti im tng ng v sau im tng ng ph thuc vo axit cng nh vo nng ca cht oxi ha hoc cht kh.

139

Hnh 2.8. ng nh phn dung dch Fe2+ 0,1N bng dung dch Cr2O72- 0,2M 2.3. NI DUNG V NG DNG CA CC PHNG PHP PHN TCH TH TCH 2.3.1.Phng php trung ho 2.3.1.1. Bn cht v ni dung Phng php trung ho c da trn phn ng trung ho. H+ + OH- = H2O Do c th dng axit xc nh nng cc baz (gi l php o axit) hoc dng cc baz xc nh nng cc axit (php o baz) a) Php o axit: y ta phi dng cc axit c nng chnh xc, l cc axit gc (H2C2O4.2H2O, ax Tactrics, (... C4H6O6) cht gc ca phn tch th tch l cht phi m bo ba yu cu: - D iu ch, d kt tinh dng tinh khit ho hc. - Bn khi ngoi khng kh (khng b phn hu bi nh sng, oxy, khng kh, khng ht nc, khng hp th CO2). - C nng n nh sau khi pha dung dch. Nh vy ta phi pha dung dch chun gc l H2C2O4.2H2O ri t xc nh nng NaOH, t NaOH li xc nh nng cc axit nh HCl, HNO3, H2SO4, CH3COOH. b) Php o baz. Ta dng cht gc l Na2CO3.10H2O; Na2B4O7.10H2O xc nh nng cc axit HCl, HNO3, H2SO4 140

2.3.1.2. ng dng v tnh ton Phng php trung ho c dng xc nh nng cc baz t axit gc hoc ngc li. V d, dng H2C2O4 tiu chun xc nh nng NaOH vi ch th l phenolphtalein, sau li dng NaOH xc nh nng HCl, CH3COOH vi ch th phenolphtalein, ri t HCl ta li xc nh nng NH4OH vi ch th metyl da cam. xc nh nng ca chng ngi ta tin hnh chun trc tip H2C2O4, HCl, CH3COOH bng NaOH v chun trc tip NH4OH bng HCl v tnh ton trc tip theo cng thc ca nh lut ng lng.

Chng ta ch xt chi tit ba trng hp sau y: a) Xc nh nng hn hp baz v hn hp axit: * Xc nh nng hn hp baz (NaOH + Na2CO3) bng HCl. Vic chun hn hp baz xy ra theo hai bc: - Bc 1: ng vi vic trung ho ton b NaOH v nc th nht ca Na2CO3, v im tng ng ca chun NaOH bng HCl c pH = 7 v im tng ng ca chun nc 1 ca Na2CO3 chnh l pH ca dung dch HCO3- c tnh theo cng thc:

C hai gi tr pH ny u nm trong khong i mu ca phenolphtaelin, nn nu dng phenolphtalein lm ch th th khi phenolphtalein i mu, ton b NaOH v nc th nht ca Na2CO3 c trung ho. c th tch HCl tiu tn, ta c V1. Bc 2: Tip tc chun dung dch cn li bng HCl, khi HCO3- H2CO3, pH ca dung dch ny c tnh theo cng thc ca mt n axit yu:

Nu coi:

Gi tr pH ny nm trong khong chuyn mu ca metyl da cam. Do c th thm tip metyl da cam vo dung dch va chun (nc 1) v chun bng HCl n khi metyl da cam i mu t vng da cam sang nht da cam th dng chun , ghi th tch V2. 141

V th tch HCl tiu tn cho nc 1 v nc 2 bng nhau nn 2V2 l th tch HCl tiu tn cho chun ton b Na2CO3. Cn th tch HCl tiu tn cho vic chun ring NaOH: V1 + V2 - 2V2 = V1 - V2 (ml) Do :

Nu xc nh nng chung ca hn hp NaOH v Na2CO3 ta ch vic chun trc tip hn hp bng HCl vi ch th l metyl da cam v:

b. Xc nh nng hn hp HCl v H3PO4 bng NaOH: Nu ch chun ring H3PO4 bng NaOH, khi nc 1 ca H3PO4 mc trung ho (H3PO4 H2PO4-) (pH1 = 4,6) ng vi s chuyn mu ca metyl da cam. Khi nc 2 ca H3PO4 c trung ho (H2PO4- HPO4- v pH2 = 9,6) ng vi s chuyn mu ca phenolphtalein) Khi thm dn dung dch NaOH vo dung dch hn hp HCl v H3PO4 c cng nng , u tin HCl b chun :

Sau n H3PO4 mc chun theo nc th nht:

Do nu cho ch th l metyl hoc metyl da cam vo hn hp v chun bng HCl, khi ch th i mu th nc 1 ca H3PO4 v ton b HCl c trung ho. Ghi ly th tch V1(HCl) tiu tn. Cho phenolphtalein vo v tip tc chun dung dch th nc 2 ca H3PO4 l H2PO4- c trung ho.

V nc 2 ca H3PO4 c trung ho bi lng NaOH cng bng nc 3 ca n, nn th tch NaOH chun cho nc 2 v nc 3 nh nhau cng bng th tch NaOH chun cho nc 1 ca H3PO4 do th tch NaOH chun cho ring H3PO4 l 3 V2, cn th tch NaOH chun ring cho NaOH l V1- V2.

142

Cn nng chung ca hn hp HCl v H3PO4:

b) Xc nh cng ca nc: * cng tm thi ca nc c tnh bng s mt ng lng gam mui cacbonat axit magi v canxi trong mt lt nc xc nh KTT ngi ta chun trc tip nc cng bng dung dch chun H vi ch th metyl da cam, phn ng chun xy ra:

Khi metyl da cam i mu th dng chun v ghi th tch HCl tiu tn (V1). Do :

Sau un si dung dch chun ui ht CO2. ngui dung dch v xc nh cng tng cng ca nc. * cng tng cng (KTC) c tnh bng tng s mt ng lng gam mui Me (Ca2+, Mg2+) trong mt lt nc. xc nh n, ngi ta dng phng php chun ngc.
2+

u tin, kt ta ton b Me2+ bng hn hp NaOH, Na2CO3 bit nng trn, khi th tch hn hp l Vh2

Sau chun lng hn hp cn li bng HCl vi ch th l metyl da cam:

Khi metyl da cam i mu, ghi th tch HCl tiu tn (V2): Do : 143

* cng vnh cu (KVC) ca nc l tng mt ng lng gam mui Me2+ t do, c sn trong mt lt nc. Do :

2.3.2. Phng php oxi ho kh 2.3.2.1. Php o Pemanganat a) Bn cht v iu kin p dng ca php o: Ngi ta dng dung dch chun gc H2C2O4 xc nh nng KMnO4 v bn thn KMnO4 khng phi l cht gc:

Do phi chun trc tip bng. Khi H2C2O4 phn ng ht th dung dch KMnO4 d s nhum dung dch thnh mu hng nht, lc khng tan th dng chun . Ta tnh nng KMnO4 theo cng thc.

T KMnO4 ngi ta c th xc nh Fe2+, HI, H2O2 theo c ch tng t.


0 V EMnO
4

/ Mn2 +

= 1,51 V c gi tr kh ln, nn MnO4 l cht oxi ho mnh, do

khng c chun trong mi trng HCl m phi chun trong mi trng H2SO4. Mt khc, phn ng chun xy ra nhanh ta phi un nng dung dch trc khi chun ln ti 60 700C. b) ng dng: ng dng quan trng ca php o l vic xc nh nng Ca2+ trong dung dch (thm ch c Pb2+). u tin kt ta Ca2+ bng lng C2O42- d:

Sau em lc ra v ho tan kt ta bng H2SO4 nng:

Cui cng chun lng H2C2O4 gii phng ra bng KMnO4 theo phn ng trn: 144

Theo cc phng trnh phn ng trn th:

2.3.2.2. Php o Bicromat. y ngi ta dng dung dch chun gc l K2Cr2O7 xc nh trc tip Fe vi ch th l iphenylamin:
2+

Ngi ta cho vo bnh nn dung dch Fe2+, xc nh (VFe2+) axit H2SO4 v H3PO4, iphenylamin chun Fe2+ bng K2Cr2O7 t trn buret xung. Khi lng Fe2+ phn ng ht th Cr2O72- d s phn ng vi iph (dng kh) chuyn thnh iph (dng oxy ho) c mu tn xanh. Nh ni trn, trong php chun ny ta phi cho thm H3PO4 vo PO43- lin kt vi Fe3+ thnh phc [Fe(PO4)2]3- bn, lm cho th ca h u bc nhy gim v khong th i mu ca iphenylamin nm gn trong bc nhy th. Khong th i mu ca iphenyllanin l E = 0,73-0,79 (V). Ta tnh trc tip nng ca Fe2+ theo biu thc:

2.3.2.3. Php o Iod a. Ngi ta xc nh cc cht oxi ho (hoc kh) nh cch gin tip. - Cht oxi ho + KId I2 + lot sn phm khc. - Sau chun I2 gii phng ra nh Na2S2O3 vi ch th l h tinh bt.

Khi mu xanh m bin mt (mu ca phc ca h tinh bt vi I2) th dng chun . b. Trong phng php ny cn lu mt s im sau: - Khng c tin hnh chun t dung dch nng v I2 d bay hi. 145

- Phi cho KI d I2 sinh ra c ho tan do to phc KI3 (Poliiodua), ng thi cht oxi ho phn ng ht. Khng c tin hnh chun trong mi trng axit mnh v gy ra phn ng ph:

- Khng c tin hnh chun trong mi trng kim mnh v khi sinh phn ng ph:

Chnh IO- li tc dng vi Na2S2O3. - Phi cho h tinh bt vo lc dung dch c mu vng rm v I2 phn ng nhy vi h tinh bt, nn ch cn lng nh cng c mu c trng v I2 t l trng tinh bt "chui" ra phn ng. b. ng dng: - Thng dng php o I2 xc nh Cu2+ nh phn ng.

- Na2S2O3 phi c xc nh li nng sau khi pha nh php o Iod: + Cho dung dch chun K2Cr2O7 tc dng vi KI d.

+ Chun lng I2 gii phng ra bng Na2S2O3:

2.3.3. Php chun kt ta: 2.3.3.1.Phng php Mor. 146

Chun trc tip Cl- nh dung dch chun AgNO3 vi ch th K2CrO4:

Khi dung dch chuyn t c trng sang hng nht lc khng tan th dng chun . Phng php Mor ch c chun trong mi trng trung tnh hoc kim yu v nu trong mi trng axit mnh th vai tr ch th ca CrO42- b bin mt do c phn ng.

Cn trong mi trng kim mnh th Ag+ s phn ng ph:

Dung dch phi vng mt Ba2+, Bi3+, Pb2+ v chng cng to kt ta gch vi CrO42-. Ngoi ra dung dch phi vng mt mui amoni, v n s ho tan AgCl do to phc vi AgCl. 2.3.3.2. Phng php Vothard Xc nh Cl- bng cch chun ngc bng AgNO3. - u tin cho Cl- kt ta bi Agno3d

Sau chun AgNO3 cn bng dung dch chun KCNS vi ch th Fe3+

Phng php Volhard ch c dng trong mi trng axit mnh v nu trong mi trng trung tnh hoc kim yu th Fe3+ b thu phn - y khng cn vng mt Ba2+, Pb2+ nhng li khng c c mt mui amoni v khi s to phc gia AgCl v NH3

147

Vic tnh ton nng Cl- theo phng php ny c phc tp hn.

2.3.4. Php chun phc cht 2.3.4.1. Php chun Komplexon Php chun komphexon da trn s to phc bn v tan trong nc ca komplexon vi cc ion kim loi. Trong tiu biu nht l Trilonb, n chnh l mui hai ln th ca axit etylen iamin tetraaxetic.

Vit tt l Na2H2Y Ch th ca phng php l Eriocrom en T (vit tt l ET_OO) hay Murexit. V phc ca ch th vi kim loi km bn hn phc ca Trilonb vi kim loi nn khi cho dung dch trilonb xung dung dch cha phc kim loi vi ch th (Meind), th phc ny b ph hu v ion kim loi s to phc vi Trilonb. Ton b qu trnh chun c m t bng s sau: - Cho ch th (Eriocrom en T) vo dung dch cha ion kim loi th ion kim loi phn ng vi ch th:

Sau chun dung dch cha ion kim loi bng Trilonh th ion kim loi t do s phn ng vi Trilonb.

Sau khi ht ion kim loi t do th:

Khi dung dch chuyn t nho sang xanh da tri th ng chun vi phng php ny cn lu my im sau: - V Trilonb phn ng vi cc ion kim loi c ho tr khc nhau u gii phng ra 2H+: 148

- Mi phn ng chun u sinh ra H+ nn ta phi thm hn hp m amoni vo n nh pH ca dung dch, hn hp m amoni c pH = 8 -10, nh vy mu ca phc bn. - Php chun thng hay dng xc nh cng ca nc v trong nc c rt nhiu Ca2+, Mg2+. - Tnh ton theo phng php chun trc tip:

C ch to phc gia Me2+ v Trilonb c biu din bng s sau:

Nh vy ion kim loi lin kt vi Trilonb nh hai lin kt chnh vi hai nhm a x tt v hai lin kt phi tr vi 2 nguyn t N nn phc ny bn khng mu v tan trong nc. 2.3.4.2. Phng php thu ngn chun cc halogennua Ion Cl- to phc kh bn vi Hg2+ (1 = 5,5.106, 2 = 3.106).Do nu chun dung dch clonla bng Hg2+ th trong qu trnh chun xy ra phn ng :

nhn ht im tng ng ngi ta dng ch th l iphenylcacbazol, n to vi Hg2+ thnh phc c mu xanh tm. Ngay sau im tng ng Hg2+ s to ngay vi ch th lm dung dch c mu xanh tm nht. Khi dng iphenylcacbazol th pH phi khong 1- 2. Ngi ta c th dng ch th khc l iphenylcacbazid, khi pH to phc l 2,0 - 3,5. Phng php thu ngn cn dng chun cc Halogennua khc nh Br-, CNS-, I-. Tuy nhin n khng c nhiu u im nh phng php chun Cl- bng AgNO3. 149

CU HI V BI TP CHNG 2

2.1. Phn tch th tch v s chun l g? Tnh ton ca phn tch th tch da trn c s no? Cho v d. 2.2. Bn cht v phm vi ng dng ca phng php trung ho, cch pha ch dung dch chun ca phng php trung ho. 2.3. Cht ch th ca phng php trung ha, oxi ho kh kt ta v to phc. 2.4. Nhn xt v cc dng ng cong chun ca phng php trung ho. 2.5. ng dng ca phng php trung ho. 2.6. Nhn xt v bc nhy ca ng cong chun pH, oxi ho kh v quy tc chn ch th. 2.7. Bn cht ca phng php oxi ho kh. Nng dng oxi ho v dng kh nh hng th no n bc nhy th. 2.8. Hy trnh by cch xc nh im tng ng trong phng php oxi ho kh. 2.9. So snh v ng cong chun trung ho v chun oxi ho kh. 2.10. So snh s ging v khc nhau v php o Pemanfanat v php o Bicromat. 2.11. Ch th mu ca oxi ho kh l g? H tinh bt c phi l cht ch th ny khng? 2.12. Bn cht v c im v ng dng ca php o Iod. 2.13. Bn cht c im v ng dng ca php chun kt ta. 2.14. Bn cht c im v ng dng ca php chun Komplexon. 2.15. pha dung dch chun Na2CO3 ngi ta cn chnh xc mt lng l,325g mui Na2CO3 tinh khit sau em ho tan trong bnh nh mc 250ml v thm nc n vch mc. Tnh chun v nguyn chun ca dung dch thu c. 2.16. Pha long 2,9ml H2SO4 iu kin 96%(d= 1,84 g/ml) trong bnh nh mc 1 lt s thu c dung dch c nguyn chun bng bao nhiu? 2.17. Khi chun dung dch Na2CO3 bng HCl 0,12N th ht 22ml axit. Tnh s gam Na2CO3 trong dung dch v t suy ra chun ca HCl theo Na2CO3. 2.18. Tnh (khng k s thay i th tch) bc nhy pH khi chun 20ml dung 150

dch NH4OH 0,2N bng dung dch HCl 0,2N cho KNH3 = 10-4,75 2.19. Tnh (khng k s thay i th tch) bc nhy th v th ti im tng ng khi chun 100ml dung dch FeSO4 0,1N bng dung dch chun KMnO4 0,1N trong mi trng axit c nng ln H+ l 1 mol/l, cho
0 0 EMnO / Mn2+ = 1,51V , E Fe3+ / Fe2+ = 0,77V
4

2.20. Hi c bao nhiu gam canxi trong 250 ml dung dch CaCl2, bit rng nu cho 40 ml dung dch (NH4)2C2O4 vo 25ml dung dch CaCl2 th sau khi tch kt ta phi dng ht 15ml dung dch KMnO4 0,02N chun lng (NH4)2C2O4 khng tham gia phn ng, cho Ca= 40. 2.21. Chun hn hp NaOH, Na2CO3 bng dung dch H2SO4 0,1N, chia lm hai phn bng nhau: a) Phn th nht chun bng Phenolphtalein ht 20ml axit H2SO4 b) Phn th hai chun bng metyl da cam ht 25 ml. Tnh thnh phn % ca hn hp, cho H = 1, C = 12, O = 16, Na = 23. 2.22. Tnh p Ag v p Cl khi chun 25 ml dung dch AgNO3 0,1 M bng dung dch chun NaCl 0,1M ti cc im khi thm 24,0; 25,0; 26,0ml NaCl cho AgCl = 10-10. 2.23. Tnh sai s mc phi khi chun 50 ml dung dch AgNO3 0,1 M bng AgNO3 0,1M nu kt thc khi pAg = 4,9 v bng 5,25. 2.24. Thm 20 ml H2C2O4 0,25M vo mt mu cn 1,2340g PbO2 kh PbO2 Pb2+ v ho tan PbO. Trung ho dung dch bng NH3 ton b Pb2+ kt ta ht dng mui oxalat. Nc lc em chun bng dung dch KMnO4 0,04M ht 10ml. Kt ta lc c em ho tan trong axit v chun bng KMnO4 ht 30ml. Tnh thnh phn% khi lng ca PbO v PbO2 cho PbO = 223,2 v PbO2 = 239,2. 2.25. Tnh sai s mc phi khi chun dung dch HCl 0,1M bng dung dch NaOH 0,1M nu kt thc chun pH = 3,0 v pH = 11. 2.26. Tnh sai s mc phi khi chun dung dch CH3COOH 0,1 M bng dung dch NaOH 0,1 M nu kt thc chun pH = 6,0 v pH = 11. V d 2: Tnh nng cn bng pH = 11 ca cc cu t trong dung dch Mg c nng ban u 0,01M v EDTA c nng ban u l 0,02M. Trong th d trn, ta tnh c hng s bn iu kin ca phc MgY2- trong dung dch c pH = 11 l = 108,28.
2+

Phng trnh bo ton khi lng ca Mg2+: 151

v ca EDTA l:

T hai phng trnh trn suy ra:

vo biu thc ca hng s bn iu kin:

Nh vy, gi thit trn l ng v [Mg'] ch bng mt phn triu ca 0,01. Ta bit: [Mg'] = [Mg2+]Mg(OH). Trong v d trc ta tnh c MgOH+ = 1,38; do :

Nh vy ti pH = 11 ton b Mg2+ to phc vi Y4-. V d 3: Tnh hng s bn iu kin ca phc NIY2- trong dung dch m NH3 1M + NH4Cl 1,78M. Bit rng trong iu kin nng ban u ca ion Ni2+ khng ng k so vi nng NH3. Phc ca Ni2+ vi EDTA c hng s bn = 1018,62. Phc ca Ni2+ vi NH3 c cc hng s bn tng cng ln lt l 102,67; 104,80; 106,46; 107,50 v 108,10. pk ca H4Y cho trong cc phn trn. Theo nh ngha:

V nng [Ni2+] kh nh khng ng k so vi nng NH3, nn ta coi pH ca dung dch l pH ca hn hp m NH3 1M + NH4Cl 1,78M. 152

C: L nng cht tan (mol/l) l: L chiu dy lp dung dch, tnh bng cm. : L h s hp th phn t l h s tt ca dung dch khi nng C l 1 mol/1 v chiu dy dung dch = 1cm. l mt i lng khng i c trng cho mi cht mu v ph thuc vo bc sng ca nh sng chiu vo, bn cht ca cht tan, nhit dung dch v tng ng vi mt quang ca dung dch c nng mol/l ca cht nghin cu. Thc nghim xc nh vi nhiu hp cht mu thy thng khng vt qu 2.105.

1.1.2.2. Cc i lng trc quang v ngha ca n. a. truyn qua l t s cng dng sng sau khi i qua dung dch It vi cng dng sng di vo dung dch Io. K hiu l

i lng T ng vi chiu dy lp dung dch bng 1 cm c gi l h s truyn qua. b. Mt quang: (hay tt: Extinxim) ca dung dch l logarit thp phn ca i lng nghch o vi truyn qua, gi l mt quang (hay tt), k hiu bng ch A (hay E) v bng:

T nh ngha ny ta suy ra: Mt quang t l thun vi nng cht tan trong dung dch v chiu dy ca dung dch. Ni mt cch khc: Khi chiu dy ca dung dch ca cht cho l nh nhau, mt quang ca dung dch s cng ln, khi lng ca cht mu trong dung dch cng ln. Hoc ngc li, khi nng ca cht tan(cht mu) cho bng 1, mt quang ca dung dch ch ph thuc vo chiu dy ca n. T y, c th i n kt lun: Nu hai dung dch ca cng mt cht mu c 153

nng khc nhau, cng mu ca cc dung dch s t c nh nhau, khi chiu dy ca chng t l nghch vi nng dung dch.

Kt lun ny rt quan trng bi v n l c s ca mt s phng php phn tch o mu. Nu biu din bng th s ph thuc mt quang (A) vo nng (C) trn trc honh biu din nng , trc tung biu din mt quang, ta s thu c mt ng thng i t gc ta . dc ca ng thng ny s ph thuc vo i lng h s tt phn t.

Nu dung dch tun theo nh lut c bn Bug - Lm be - Bia, th s l ng thng. Nu dung dch khng tun th theo Bia, th biu din s tuyn tnh (A v C) s ph hy ti mt khong no hoc trn ton b trng biu din. l iu rt hay thng gp trong thc t. vi cng mt cht th trong khong nng ln c s sai lch ng k (ph hy quan h tuyn tnh). Nh vy, nh lut Bia p dng c mt khong nng nht nh. nh lut Bia cn khng ap dng vi cc dung dch huyn ph v hunh quang v cc dung dch c s khuch tn nh sng rt ln v nh sng sau khi i qua li c ln hn, vic o cng nh sng hp th khng chnh xc. nh lut Bia cn b sai lch do nh hng ca cc qu trnh pha long. 1.1.2.3. Nhng yu cu i vi hp cht mu (dung dch mu) v qui tc lm vic. a. Phc phi c bn ln: tc l hng s khng bn nh, h s hp th phn t ca phc phi ln. 154

- Nu Kkb nh th ion Men+ to phc nhiu, dng t do t, lm cho chnh xc ca phng php tng thm, nhy tng, v ch cn nng Men+ rt long to phc mu. V d: Me + nR = MeRn

- Phc bn th cc ion l nh hng n vic to phc cng t. - H s hp th phn t ca hp cht mu ln th nhy ca phng php tng ln. V d phc [Cu(NH3)42+] trong H2O c = 500, phc ithizol ca Cu2+ trong H2O c = 5000. V vy m nhy ca phc ithizol hn phc amiact l 10 ln. - Mu ca phc nghin cu phi chn lc. Mi cht mu tng t hoc lm gim cng mu ca cht nghin cu phi tch ra hoc lin kt vo nhng phc khng mu. b. Phc phi c thnh phn khng i. Ngha l phi ng ng vi mt cng thc ha hc nht nh, c nh vy mt quang dung dch mi t l.vi nng phc ti cng mt bc sng hp th. Mun vy, phi chn cc iu kin thch hp nh: - Thuc th ch to nn mt loi phc mu. - Mi trng pH nh hng ti thnh phn phc phi n nh mu ca phc khng i, ngha l phi to phc pH ti u no . - Thi gian to phc mu bn nht phi ln, t thch hp trong mu phc mnh nht v bn nht, ng thi phi o mu trong khong ny. Nhn chung cc phc mu khng bn theo thi gian do c hin tng thy phn, oxy ha - kh, do tc ng ca mi trng... Trong thc t ngi ta thng phi chn cc phc bn mu trong khong 10 n 30 pht kp o. - C th thm vo phc mu nhng cht lm bn mu nh gilatin. Trong mt s trng hp phi to dy mu gi. Dy mu gi l dy dung dch c mu sc v cng ging dung dch phc mu kho st, nhng mu bn hn, nn thng dng c lu, thng c th pha ch t hp cht v c. V d dng K2Cr2O7 to dng dch mu da cam. c. Mu khng c thay i theo nhit : nu c s thay i cn o mu ti nhit xc nh 155

d. Cng mu phi t l vi nng ca cht nghin cu (tun theo nh lut Bia): nng ca cc dung dch em o mu khng c qu thp hoc qu cao, v mt ta kh phn bit s thay i cng mu ca nhng dung dch nh th. 1.1.3. Cc phng php phn tch o mu: Trong o mu c chia lm 2 phng php chnh: - Phng php ch quan (cng sng c o bng mt). - Phng php khch quan hay phng php quang in (tc l cng sng c o bng t bo quang in)... 1.1.3.1. Phng php o mu bng mt. a. Phng php dy tiu chun: - So snh cng mu ca dung dch nghin cu vi cng mu ca cc dung dch tiu chun bit nng (d nhin chiu dy ca dung dch nghin cu v dung dch tiu chun nh nhau). Nng ca dung dch nghin cu bng nng ca dung dch tiu chun no c mu trng vi n hoc bng nng trung bnh cng ca hai dung dch chun k nhau, trong mt dung dch c mu m hn cn mt dung dch kia c mu nht hn. - Cch pha long dung dch mu tiu chun: Ly 5-6 bnh nh mc ng nht cho vo dy dung dch tiu chun ca ion cn xc nh vi lng tng dn. Sau thm dung dch thuc th v cc cht cn thit n th tch bng nhau. Ta c dy tiu chun c cng mu tng dn. - Pha dung dch nghin cu: Cho mt lng dung dch kho st vo bnh nh mc khc (ging bnh tiu chun) v cng cho thuc th cng cc cht cn thit nh cc ng tiu chun. Sau ly cc ng nghim ng nht nh s v th t cc dung dch mu tng ng ri em so snh theo nguyn tc trn. - Trong mt s trng hp thu c nhng kt qu chnh xc hn, ngi ta phi to ra mt dy dung dch tiu chun trung gian. i vi nhng dung dch c mu khng bn, ta dng dung dch tiu chun trung gian gi (ch t cc cht c mu bn vng nh FeCl3 - vng, CoCl2 - hng, CuSO4 -lam, K2Cr2O7- da cam). Gn y, ngi ta c dng cc b knh thy tinh mu gi. u im hn ch ca phng php. - Phng php dy tiu chun c u im l dung dch khng cn tun theo 156

nh lut Bia, n c th tin hnh nhanh, khng cn dng c phc tp. Song phng php c hn ch ch l ch bit c gn ng nng ca dung dch kho st nm trong khong hai dung dch tiu chun k nhau. Nhng dung dch mu tiu chun thng khng..bn, cn nu thay bng dung dch gi hoc knh thy tinh mu gi th gp kh khn trong vic tuyn la ng mu sc ca chng. b. Phng php chun o mu (kp i). - Ni dung v nguyn tc: y l phng php phn tch gin tip, ngi ta so snh mu ca hai dung dch tnh trng lun lun c th tch bng nhau. Mt bn l dung dch mu nghin cu cha bit nng , c th tch ban u xc nh cn mt bn l nc v thuc th to mu c th tch ban u tng ng. Sau tin hnh chun : thm vo bn nc v thuc th dung dch tiu chun bit nng t buret xung. Ngi ta thm vo bn dung dch mu nghin cu mt th tch H2O tng ng th tch dung dch chun cho xung cng nh mt buret th 2.

Cch tnh nng cht cn xc nh. C hai trng hp tnh nng nghin cu nh sau: Gi s th tch ban u ca dung dch nghin cu l V, th tch ca dung dch tiu chun cho thm lc mu bng nhau l W, chun ca dung dch tiu chun l T, nng Cx ca dung dch nghin cu c tnh theo cng thc:

- u nhc im ca phng php: Khi chun o mu, dung dch mu khng cn tun theo nh lut c bn Bug - Lm be - Bia. Vic tin hnh c th nhanh chng. Song khng phi mi 157

phn ng to mu bit u dng c, m ch c mt s phn ng to mu m bo c iu kin nh: sinh mu tc thi v s to mu khng gn lin vi nhng qu trnh ha hc ph thuc khc. V d: phn ng to phc mu sau:

l dng c; cn phc ca silc di dng amni mlp t th khng dng c, v phn ng gn lin vi s kh hoc nhng qu trnh ho hc khc. c. Phng php cn bng dng t sc k Duy bt. C s v nguyn tc: C s ca phng php l da vo quan h gia chiu dy ca lp dung dch vi nng ca chng. Trong phng php ny ngi ta iu chnh b dy ca dung dch kho st v tiu chun n cng mu ca hai ng bng nhau (thy c trn th knh ca my). Tc l khi hai dung dch hp th cng mt t l nh nhau ca dng sng ri vo, ngha l mt quang bng nhau: Atc = Aks hay chnh l Ctc.ltc = Cks.lks (v l nh nhau vi cng mt cht mu). T y ta suy ra:

S quang hc ca t sc k uybt (hnh 1.3) v nguyn tc hot ng ca t sc k.

158

- Tia sng t ngun sng qua thu knh to thnh 2 tia. + Mt tia i qua cu vt bn phi ng dung dch mu kho st qua trc thy tinh lng knh, knh lc ri tp trung vo na tri ca th trng. + Tia kia qua cu vt tri ng dung dch mu tiu chun, ri tr thy tinh (2 tr thy tinh lun nhng trong dung dch), tip n lng knh, knh lc v tp trung vo na phi ca th trng. Ngi ta iu chnh tr thy tinh ln xung sao cho khi quan st th knh thy mu ( sng) ca hai na th trng bng nhau. nhng ca tr thy tinh vo dung dch su, nng l b dy ca dung dch kho st v tiu chun c phn nh trn thang ca my. - u nhc im ca phng php. Phng php cn bng l phng php o mu bng mt chnh xc nht. Song phng php ny ch c th p dng phn bit nhng dung dch mu tun theo nh lut c bn ca php o mu, phng php i hi dng c c bit t sc k Duy bt. e. ng dng ca phng php o mu bng mt. ng dng quan trng nht l xc nh pH dung dch, da trn nguyn tc dy tiu chun. Mun xc nh pH ca dung dch m cng nh dung dch nghin cu, ta dng mt b cht ch th c khong pH i mu khc nhau. Bng cch th ln lt tng cht ch th, ta xc nh c gn ng pH ca dung dch nghin cu Sau xc nh chnh xc pH. Chn mt dy tng ng cc dung dch m cng nh dung dch nghin cu. Nhng dung dch no c mu bng nhau l c tr s pH bng nhau. chnh xc phng php o mu ch quan ph thuc vo nhy ca mt ngi quan st. Cc phng php ny lm mt mi mt nu phn tch nhiu. Cho nn thun li hn vi vic t ng ha cn dng phng php o mu quang in. 1.1.3.2. Phng php o mu quang in. a. Nguyn tc chung: Cc phng php o mu quang in u da trn s nguyn tc chung sau y:

159

Dng sng i qua cu vt (hoc ng th) ng y dung dch mu kho st. nh sng qua dung dch b tip thu bi t bo quang in, trong nng lng nh sng bin thnh nng lng in. Dng in c pht sinh khi c o bng ganvanmt c nhy cao. T bo quang in l dng c trong quang nng c bin thnh in nng. Stltp ch ra: Cng dng in c pht sinh di tc dng ca nng lng nh sng ln t bo quang in t l thun vi cng nh sng. b. Cc phng php o mu quang in * o ph trc tip: o hp th A ca dung dch, tnh nng C ca dung dch da vo gi tr E11 bit trc (tra cu).

Vi phng php ny phi kim tra my o v bc sng v mt quang A. * Phng php so snh:

* Phng php thm: o hp th Ax ca dung dch cn tm nng Cx. Thm mt lng cht tan bit vo dung dch, o hp th Ax ca dung dch to thnh.

160

- Phng php ng chun: Chun b mt thang tiu chun vi nng tng dn C1, C2, C3 o MQ ca cc dung dch ny A1, A2, A3 o mt quang Ax ca dung dch c Cx. Dng ng chun A = f(c), t php ni suy th ta tnh Cx.

Vy tan ca n so vi trong nc nguyn cht nh hn:

4.2.2. nh hng ca ion H+ (pH) v cht to phc n tan ca kt ta, tch s tan iu kin tan ca kt ta s tng ln nu cc ion kt ta c tham gia phn ng ph vi cc cht l c mt trong dung dch. phn nh c cc nh hng ca cc phn ng ph, ngi ta dng tch s tan iu kin. Chng hn kt ta AmBn trong dung dch c ion H+ c kh nng phn ng vi B v c cht to phc L c kh nng to phc vi A, trong dung dch c cc cn bng:

A to phc vi L:

- B phn ng ph vi H+

K1, K2 l hng s khng bn ca phc HB,. H2B cng l hng s phn li ca axit HB v H2B. 161

- Nu gi S l tan ca kt ta th:

T cc hng s K1, K2 ta tnh c [HB], [H2B].... theo [B] v [H+] Ta c:

Cch xc nh Cx: Cch 1: Ko di th v bn tri, ct trc honh ti u, l Cx. Cch 2: T O k 1 ng ph song song vi th. T Ao k 1 ng thng song song trc honh, ct ng ph ti M. T M k vung gc trc honh ti Cx. Tuy nhin trong thc t phn tch c rt nhiu yu t nh hng n kt qu o mt quang nh lng d thuc th, pH mi trng, cc cation l... Tm li: thc hin mt php o quang hon chnh cho mi php xc nh hm lng cc nguyn t, tc l tm ra qui trnh phn tch thch hp cho cc nguyn t, nh ha hc phn tch phi thc hin tt cc bc sau y: Gi s mun xc nh Cr3+ trong mu nh php o quang, chng ta cn thc tu cc bc nghin cu sau y: 1. Nghin cu s to phc ca ion kim loi vi thuc th, v d Cr6+ vi 1,5 iphenylcabcbazide ( max = 542 nm). * Kho st ph hp th ca phc mu tm gia Cr6+ v 1,5 Difphenuycacbazide, gm: * Xc nh pH ti u Qua kho st, pH = 1,5 2,5 (pH = 2,0). * Kho st nh hng ca lng d thuc th n s to phc (V = 2ml). * nh hng ca thi gian (t = 10 - 15') n bn ca phc. * Kho st s tun theo nh lut Bia ca phc Cr(6+) vi 1,5D phenylcacbaz (C = 0 - 4 mg/l). * Kho st nh hng cc ion l: Pb2+, Zn2+, Fe2+, Fe3+, Mn2+... Ch Fe2+, Fe3+ v Cu2+ nh hng (nh hng hn c l Fe3+), loi tr cc ion a lng Ca2+, Al3+, Ba2+, Mg2+ khng nh hng. 162

T ta tm cch loi tr cc yu t nh hng: Fe3+ dng phng php che bng cch cho to phc bn vi PO43- (trong mt s trng hp khc che bng CN, F-...); cn loi tr nh hng ca Cu2+ bng cch cho kt ta trc n bng thuc th thch hp (cufferon). 2. Xy dng ng chun da trn cc d kin a kho st trn. 3. Pha cc mu gi ri xc nh nguyn t cn phn tch, t kt qu tnh sai s (x l kt qu thng k ng chun theo phng php bnh phng ti thiu). Xc nh chnh xc ca php phn tch v kt lun dng c hay khng dng c qui trnh chn. 4. Xc nh hm lng cc nguyn t trong mu thc. 1.2. PHNG PHP PH HP TH NGUYN T(AAS) 1.2.1. Nhng vn chung v ph hp th nguyn t 1.2.1.1. S xut hin ph hp th nguyn t (cha tha ng cn ni r hn) Khi nguyn t trng thi c bn, nng lng ca n l ngho nn nht. Nhng khi trng thi kch thch (th kh, hi) nguyn t t do hp th c nng lng v sinh ra ph gi l ph hp th nguyn t Nu gi nng lng tia sng b nguyn t hp th l E th chng ta c:

Nh vy ng vi mi gi tr nng lng Ei m nguyn t hp th ta s c mt vch ph hp th vi di sng i c trng. Qu trnh hp th ch xy ra i vi cc vch ph nhy, cc vch ph c trung v cc vch cui cng ca cc nguyn t. 1.2.1.2. Cng ca vch ph hp th. Nghin cu s ph thuc ca cng mt vch ph hp th ca mt nguyn t vo nng C ca nguyn t trong mu phn tch, mi quan h gia cng vch ph hp th v nng N ca nguyn t trong m hi cng tun theo nh lut Lambe - Bia. Ngha l nu chiu 1 chm sng cng ban u l I0 qua m hi nguyn t t do ca nguyn t phn tch nng N v b dy l L cm, chng ta c:

Trong : KV l h s hp th nguyn t ca vch ph tn s v0 v KV l c trng cho tng vch ph ca mi nguyn t. 163

Nu gi D l cng ca vch ph hp th nguyn t, t cng thc: I = I0.e-(KVN.L) chng ta c:

y, D chnh l tt nguyn t ca chm tia sng cng I0 sau khi qua mi trng hp th. D ph thuc vo nng nguyn t N trong mi trng hp th, ph thuc vo c b dy ca L ca lp hp th. Nhng trong my o th L = const, nn:

Gia N v C c mi quan h qua biu thc:

y l cng thc tng qut tnh gi tr N trong ngn la nguyn t ho mu theo Wine Fordner v Vicker. Trong : - F l tc dn mu vo h thng nguyn t ho (ml/pht). - W l hiu sut aerosol ho mu. - S l hiu sut nguyn t ho. - NR0 l s phn t kh nhit ban u. T0(0K). - nT l s phn t kh nhit T (0K). - Q l tc ca dng kh. - C l nng nguyn t phn tch c trong dung dch mu. Phng trnh trn l rt phc tp, ph thuc vo nhiu yu t. Nhng nhiu kt qu thc nghim ch ra trong mt gii hn nht nh ca nng C th

(Ka l hng s thc nghim, b l hng s bn cht) Tm li ta c: D = a.Cb (1.16) y l phng trnh c bn ca php o phn tch ph hp th nguyn t (AAS) 164

1.2.2. Nguyn tc trang b ca php o AAS. Da trn chc nng ca b phn thit b AAS nguyn tc trang b cho php o gm: Phn 1: Ngun pht tia bc x cng hng chiu vo mi trng hp th cha cc nguyn t t do ca nguyn t. l cc n HCL (Holow Cathod Lamp), cc n phng in khng in cc EDL (Electrodeless Discharge Lamp) hay ngun pht bc x lin tc c bin iu. Phn 2: H thng nguyn t ha mu phn tch. l k thut nguyn t ha bng ngn la F-AAS (Flame Atomic Absorption Spectrophotometry) v k thut nguyn t ha khng ngn la ETA-AAS (Electro Thermal Atomization Atomic Absorption Spectrophotometry) gm 2 b phn l b phn dn mu vo bung aerosol ha v b phn thc hin qu trnh Aeroxol. Phn 3: My quang ph lm nhim v thu, phn li v chn tia sng cn c hng vo nhn quang in pht hin tn hiu AAS ca vch ph.

Phn 4: L h thng ch th tn hiu hp th ca vch ph. H thng ny c th c cc trang b: in k ch nng lng hp th E ca vch ph, my t ghi vo pc ca vch ph, b bin s, b my in. 1.2.3. Php phn tch ph hp th nguyn t (AAS). 1.2.3.1. C s l thuyt. a. Phng trnh c bn ca php o. Nu chiu chm tia sng n sc cng lo i qua mt chm mi trng cha mt loi nguyn t t do nng N v c b dy l L cm, th mi quan h 165

gia I0 v phn cng sng I i qua mi trng c tnh theo cng thc:

y i lng log (I0 / I) chnh l nng lng ca tia sng b mt i do s hp th ca cc nguyn t t do trong mi trng . Nh vy n chnh l cng ca vch ph hp th v chng ta c:

V N l nng trng thi kh, do ta phi tm mi quan h gia C v N, c xc nh theo cng thc:

Trong K l hng s thc nghim, n ph thuc vo tt c cc iu kin ha hi nguyn t ha mu, b l hng s bn cht. Nu: Nh vy D = f(K, L, C), trong K-, L u khng i theo mi php o (F AAS v ETA - AAS) do D ch cn ph thuc vo nng C ca nguyn t cn xc nh trang mu phn tch. Do vy mt cch tng qut chng ta c D = a.cb y chnh l phng trnh c bn ca php o AAS. b. Mu u dng ng chun. * Cc mu u phi c trng thi vt l v ha hc nh mu phn tch, ngha l mu phn tch phi tn ti trng thi, mi trng v dng lin kt no th mu u cng phi c tnh cht ging nh th. C nh th mi loi tr c nh hng ca thnh phn ca mu n kt qu phn tch. Mu u v mu phn tch phi c ch luyn trong cng iu kin nh nhau. * Cc mu u phi bn vng theo thi gian ngha l khng b thay i thnh phn sau khi ch luyn v bo qun s dng lu di. * Nng cc nguyn t cn phn tch trong cc mu u rt chnh xc theo yu cu ca php phn tch. c. Cc loi nng trong php o AAS. Nng microgam / ml hay mg/l c s dng ph bin trong phn tch lng vt v thng c biu th theo hai cch: 166 (1.20)

+ mg/l hay g/ml. + mg/ kg hay g/g - Nng ppm v c s ca n: Nng ppm (part per milion), nng phn triu cng c biu th theo hai cch. + Vi mu rn nu trong 1g cha 10-6 g cht phn tch th gi tr ny (10-6g) c gi l 1ppm. Uc s ca ppm l ppb - nng phn t. + Vi mu lng trong 1 lt c cha 10-6g mu phn tch th cng tng ng 1 ppm hay 1 mg/l (hay 1 g/ml). d. Khi nim v nhy: - nhy tuyt i l lng gam (khi lng) nh nht ca nguyn t phn tch c trong mi trng hp thu cn thu c cng ca vch ph hp thu chn chim 1% ton bng hp th, hay bng 3 ln dao ng ca tn hiu nn. Mi nguyn t v mi vch ph s c nhy khc nhau. - nhy tng i cn gi l nhy nng n l nng nh nht c trong mu c th pht hin c tn hiu hp th ca n theo mt vch ph nht nh chn v tn hiu ny phi bng 1% ca bng hp th ton phn, hay bng 3 ln dao ng ca gi tr nn. e. Gii hn pht hin: - Gii hn pht hin tng i ca mt nguyn t theo mt vch ph nht nh c xem l nng nh nht ca nguyn t trong mu phn tch cn c th pht hin c tn hiu hp th ca n theo vch ph trong mt iu kin chn. - Gii hn pht hin tuyt i ca mt nguyn t l khi lng ti thiu ca nguyn t trong mi trng hp th ca n cng trong mt iu kin nht nh chn pht hn c tn hiu hp th ca n. e. Khong xc nh: - Trong AAS, vic nh lng mt nguyn t l da vo phng trnh c bn. D = a.Cb (1.21) Trong mi quan h ny, D ch ph thuc tuyn tnh vo C khi b = 1, ngha l khi nhit C l rt nh, khi chng ta c th vit.

Nh vy, mi quan h gia D v C l tuyn tnh. 167

Khong nng C ca nguyn t phn tch ng ng vi phng trnh (1.20) c gi l khong xc nh ca nguyn t theo phng php nu. Trong khong nng ny th quan h gia D v C c dng y = ax. 1.2.3.2. Cc phng php phn tch AAS. a. Phng php ng chun Chun b 5 mu u c nng tng dn C1 C2 C3 C4 C5 Chn cc iu kin ph hp ngun n (HCL) bc sng (nm) o ca n, rng khe o (nm) cng bng n (mA), nhit nguyn t ha mu, hn hp kh t, tc dn mu (l/pht). Tin hnh o ta c cc gi tr A1, A2, A3, A4, A5. Tnh Cx nh php ni duy t th b. Phng php thm chun: Nguyn tc ca phng php ny l ngi ta dng ngay mu phn tch lm nn chun b mt dy mu u bng cch ly mt lng mu phn tch nht nh v cho thm vo nhng lng nht nh ca nguyn t cn xc nh theo tng bc nng (theo cp s cng). V d lng thm vo l C1, C2, C3 Ta c dy mu u l:

168

Cng chn cc iu kin th nghim nh trn ri tin hnh o cc dung dch trn ta c A0, A1, A2, A3, A4 tng ng v xy dng th A C. Cch xc nh nng : + Cch 1: Ko di ng chun, ct trc honh ti C0 th OC0 l nng Cx. + Cch 2: T O k ng song song ng chun. T A0 k ng song song vi trc honh ct ng chun ti M. T M k vung gc vi trc honh, ct M ti X ta c Cx phi tm.

169

CHNG 2 I CNG V SC K

2.1. MT S KHI NIM C BN 2.1.1. Sc k l g ? Sc k l mt nhm cc phng php ha l dng tch hn hp thnh cc thnh phn ca mt hn hp . S tch sc k c da trn s phn chia khc nhau ca cc cht khc nhau vo hai pha khng trn ln vo nhau v lun tip xc vi nhau: mt pha tnh v mt pha ng. Qu trnh sc k gm 4 giai on: - Np cht hp th vo ct. - a hn hp ln pha tnh (v d a cc sc t ln u ct cacbont). - Cho pha ng chy qua pha tnh (v d, dung mi ete, du ha qua ct). Qu trnh tch s din ra trn ct. - Pht hin cc cht: Sau khi tch c cc sc trn bng cch hng vo cc bnh khc nhau ta d dng pht hin chng, thm ch xc nh nh lng ng. 2.1.2. Phn loi: 2.1.2.1. Theo bn cht vt l cc pha (theo trng thi tng hp). - Sc k lng - lng. - Sc k lng - rn. - Sc k kh - lng - Sc k kh - rn. 2.1.2.2. Theo bn cht hin tng - Sc k hp ph: pha tnh l cht rn c kh nng hp ph (L - R v K - R). - Sc k phn b: pha tnh l cht lng khng ha ln vi pha ng, cht lng c bao trn b mt cht rn, gi l gi hoc cht mang (tr khng tham gia vo sc k) trn ct v trn giy. - Sc k trao i ln: pha tnh l nha trao i, pha ng l dung dch cha cht tan di qua ct. - Sc k theo loi c.

170

2.1.2.3. Theo k thut v phng tin sc k - Sc k trn ct. - Sc k lp mng. - Sc k trn giy. 2.1.3. S tch sc k v sc Xt qu trnh tch hai cht A, B trn ct (hnh 2.1).

Ti t1 hai cht A, B cn trong hn hp di A v B cn xen ph nhau mt phn. Ti t2 chng tch khi nhau: A pha di ct, B trn ct. Ti T3, A c tch di ct, cn B vn trn ct. Ti T4 th B c tch nt (bt u xung bnh). Vy nu ct c di cn thit, ta c th tch ring- cc cht trn vy theo thi gian, trong qu trnh di chuyn cc di b m rng lm nh hng n vic tch hai di cnh nhau.

171

2.2. C S L THUYT CA SC K. hai cht c tch hon ton khi nhau ta thy: - Hai pic phi cch xa nhau ngha l hai cht phi c tc di chuyn khc nhau r rt (hay b lu gi mnh yu khc nhau r rt trn ct): sc (b) (hnh 2.3) - Hai pic phi gn (hp v cn i) ngha l khng c s dong pic (hay s m di) (sc (c)) (hnh 2.3).

2.2.1. Tc di chuyn ca cc cht, c c trng bi h s phn b ca n gia hai pha, bi cc i lng v s lu gi ca cht trn cc pha tnh (thi gian lu, th tch lu). a) Thi gian lu. (tR) l thi gian cn thit mt cht di chuyn t ni tim 172

mu qua ct sc k ti detector v cho pic trn sc (tnh t lc tim n khi xut hin nh ca pic). Thi gian cht (tM) l thi gian cn mt cht khng b gi li trn ct. tR cng ln, cht tan b lu gi cng mnh v tc di chuyn qua n cng nh. b) H s phn b K

y CS v CM l nng cht tan trong pha tnh v pha ng c. H s dung lng K l mt i lng quan trng c dng rng ri m t tc di chuyn ca mt cht.

QS, QM l lng cht tan phn b trn pha tnh v pha ng Do trong VS, VM l th tch pha tnh, pha ng

V t ta c: tR = tM (l + K) Khc vi K, K khng nhng ph thuc vo bn cht cc pha, bn cht ca cht tan, vo nhit m cn ph thuc vo c im ca ct (t l VS/VM ca ct). Nu K cng ln tc di chuyn cng thp. tch mt hn hp cc cht, ngi ta thng chn ct, pha ng, cc iu kin phn tch khc sao cho K cc cht nm trong khong t 1 - 8. Nu K > 8 th thi gian phn tch qu di. Nu K < 1 pic s xut hin qu sm d ln vi pic khc. Tc di chuyn t i ca hai cht: c c trng bi tha s chn lc hay h s chn lc .

Theo qui c, B b lu gi li mnh hn A v vy lun ln hn 1, cn c gi l lu gi t i (relative retetion). 2.2.2. S dong pic v hnh dng pic Khi quan st cc pic trn sc k hay biu nng cht trn ct, ta thy 173

chng c dng tng t nh ng cong phn b chun Gauss thu c khi ta v ng cong ph thuc gia gi tr ca kt qu cc th nghim lp v tn s xut hin cc kt qu (hnh 2.4).

Hnh dng l tng ca pic l lc i xng. Trn thc t pc sc k ch gn i xng. nh gi tnh bt i ca cc lc ngi ta dng h s bt i.

b = 1/2 chiu rng pha sau ca lc, a = 1/2 chiu rng pha trc.

Chiu rng ca pic c o 1/10 chiu cao ca pic. Mt ct c nhi tt s c gi tr AF trong khong 0,9 - 1,1. 174

S dong pic hay s m rng di l hin tng c bit quan trng trong sc k v c nghin cu qua thuyt v a v thuyt ng hc. S dong pic l kt qu ca s di chuyn nhanh chm khc nhau ca cc phn t ca cng mt cht khi i qua ct st k. Cc lc ra mun bao gi cng t hn. Mt ct sc k tt s cho cc lc nhn. 2.2.3. phn gii v cc yu t nh hng. phn gii l i lng o mc tch hai cht trn mt ct sc k. Xt trng hp tch hai cht A v B (hnh 2.6).

tng RS:

- Tng chiu di ct tng N. - Thay i thnh phn pha ng tng KB - Tng (bng cch thay ct tc l thay i pha tnh hoc thay i thnh phn pha ng).

175

2.2.4. Thi gian phn tch l yu t quan trng nht. t c phn gii RS xc nh th cn thi gian phn tch l bao nhiu. Mun vy ta dng cng thc.

tR,B l thi gian lu ca pic cui cng u l tc thng ca dung mi. H l hiu lc ct. 2.3. CC PHNG PHP TC SC K 2.3.1. Sc k lng hiu nng cao. 2.3.1.1. My sc k lng hiu nng cao

Cc thnh phn chnh ca my sc k lng cao p. a. Bnh cha dung mi v h thng s l dung mi, bng thy tinh hoc thp khng r. b. H thng bm phi c p sut cao (3000 - 6000psi hoc 250 - 500at, lu lng bm khong 0,1- 10ml/ph, khng b n mn bi nhiu loi dung mi). c. H tim mu: ph bin l dng 1 van tim c vng cha mu vi dung tch xc nh v chnh xc 5 - 500 l. d. Ct sc k (di 10 - 30cm), bng thy tinh hoc thp khng g. e. Detector: pht hin cc cht v cho cc tn hiu c ghi trn sc (t ngoi (UV) dng n Dteri hay n Vonfram). 2.3.1.2. Cc phng php sc k. 176

a. Sc k phn b hiu nng cao: Gm hai loi: sc k lng - lng v sc k pha lin kt. * Sc k lng - lng: Pha tnh l cht lng c hp ph (bo ha - bao) trn b mt cht mang (support), pha ng l dung dch cha cht tan (cn tch qua ct), pha tnh thng b dung mi ha tan dn. * Sc k pha lin kt: Pha tnh c gn ha hc (lin kt vi cht mang) to nn HC c siloxan

- Nu R l nhm dung mi t phn cc nh octyl (C8) octadecyl (C18)hay phenyl (C6H5) v dung mi phn cc nh methanol, acetonitril th c sc k pha o. - Nu R l nhm kh phn cc nh ankyl amin-(CH2)n-NH2 hay ankylnitril ta c sc k pha thun. * ng dng ca sc k phn b hiu nng cao tch cc cht thuc nhiu lnh vc: thuc khng sinh, thuc an thn, thuc gim au. b. Sc k hp th hiu nng cao: cht tan b gi li trn b mt pha tnh tc l cht hp ph v b dung mi y ra (phn ng hp ph). - Pha tnh l nhng bt mn silicagel v Al2O3 - pha ng l cc dung mi hu c: hexen, heptan. - ng dng: tch cc cht t phn cc, cc cht hu c khng tan trong nc. c. Sc k trao i ion hiu nng cao. * Nha trao i ln l hp cht cao phn t c cha nhm chc c kh nng trao i. Phn thnh hai loi: cationt vo anionit: cationit axt mnh (HSO3-) v c dng rng ri, cationit axt yu - COOH. Anionit baz mnh c nhm quan bc 4 N(CH3)3+, OH- v aniont baz yu c nhm amin bc 2 hoc bc 3.

177

* Hng s trao i ion:

KA/B > 1, < 1 v = 1 biu th i lc ca B+ vi RA mnh, yu hoc thun nghch. - Vi cationt:

- Vi anionit.

* Dung lng trao i c trng cho kh nng trao i ca ion cht tan vi 1g iont. N ph thuc vo bn cht cht hp ph, dung mi v nhit . * ng dng: tch cc cht hu c v v c. 2.3.2. Sc k lng trn mt phng Qu trnh sc k c tin hnh trn mt t giy hay mt lp bt vi v c gi trn mt mt tm knh, cht do hay kim loi. Bn thn lp mng c th l pha tnh hay ch l cht mang gi pha tnh trn . Ph bin nht l sc k lp mng. 2.3.2.1. Sc k lp mng. Dng th tinh khit ca sn phm, c dng trong cc th nghim lm sng, trong nghin cu sinh hc, ha sinh. N c tin hnh trn mt bn thy tinh c ri mt lp mng dnh chc ca cc ht bt mn. a. Trang b. * Cht hp ph: silicagel (0,07 - 0,1 mm), Al2O3, thch cao, celuloza, bt poli axt... * Bn mng: - Bn mng dnh chc (cht hp ph trn thm cht kt dnh (thch cao, tinh bt), n l knh c cc c khc nhau). - Bn mng khng dnh chc, ri bt c hot ng thch hp ln tm knh v ri bng mt a thp. * Dung mi phi tinh khit: hexan, heptan, xyclohexan, cacbon tetra clorua. * Bnh sc k: C th dng cc bnh chuyn dng hoc cc l rng ming, bnh hnh tr thng thng. 178

b. Qu trnh chun b v k thut sc k. * Chun b: - Bn mng v bnh sc k thch hp. - Chm dung dch ln lp mng. - t bn sc k vo bnh. - Hin hnh sc ph. 2.3.2.2. Sc k giy. a. Trang b: * Giy sc k: c lm bng mt loi gy c bit. Bt giy c ch ha bng hn hp axt v c HCl + HF cc si xenluloz phi thng v dung mi di chuyn chm trn giy ny. * Dung mi: - Pha tnh l nc c pha axt, kim, cc dung dch m hay cc dung mi phn cc. - Pha ng thng t phn cc hn pha tnh: butanol, ancolbenzilc, benzen, axeion. b. Qu trnh tch v k thut sc k. * Bnh sc k: lm bng b can thy tinh hay l ming rng. * Chun b bn mng v bnh sc k thch hp. Cho dung mi vo bnh, quanh thnh bnh lt giy lc bo ha dung mi c nhanh hn. Nu tin hnh sc k phn b th chun b dung mi v bnh tng t nh sc k giy. Vi lp mng dnh chc c th nh du ng xut pht mp di khong 1cm. Dng micropipt hay ng mao qun chm ln nhng im cch nhau t nht 1 cm. Vt chm phi gn. * Xc nh h s chm: Rf

Trong :

Lx l vt di chuyn ca di Lm l vt di chuyn ca dung mi, c tnh t im xut pht n vch cui cng ca n. H s chm Rf khng ph thuc vo 179

nng m ch ph thuc nhit iu kin tin hnh, pH mi trng vo bn cht ca cht phn tch.

(1. bn mng sc k; 2. hi dung mi; 3. Dung mi; 4. ming knh ; 5 vch xut pht).

180

CHNG 3 CC PHNG PHP PHN TCH IN HO


Trong phn tch in ho ngi ta chia ra nhiu phng php sau: Phng php do th, phng php cc ph, phng php in phn, phng php in trng lng, phng php in dn.... Tuy nhin chng ta ch nghin cu hai phng php o th v phng php cc ph. 3.1. PHNG PHP O TH 3.1.1. Th in cc Trong trng hp tng qut, xt phn ng:

Cho ta mt th gi l th oxy ha kh (hay th in cc).

Thay gi tr ca R = 8,314J/mol. K; T = 298 K; ln = 2,303lg; F = 96.500 Culong vo (3.1) ta c:

3.1.1.1. Cch xc nh th in cc xc nh th in cc ca bn phn ng: M2+ + 2e = M0(s) y M0 l kim loi to ra 1 in cc dng mch o th hnh 3.1.

Hnh 3.1. Mch o th in cc. - in cc kim loi M (1) - Cu mui (2) - in cc hyr tiu chun (3) 181

C k hiu: Pt, H2 (p at) // H+(x M) Nu kim loi M l Cd nhng vo dung dch c nng ln Cd2+ l 1mol/l, th vn k ca mch s ch l 0,403V. Lc Cd ng vai tr 1 anot, cc electron i t kim loi ny qua mch ngoi n in cc Hyro tiu chun, phn ng trn 2 in cc l:

Phn ng in ha ton phn l:

Nu thay Cd bng Cu c tnh kh km hn H2 ta c phn ng.

V Cu ng vai tr canh, cn H2 l anot. Nh vy khi ghp vi H2 th, Cd anot. Cu - catot. Theo qui c Jupac (Stockhom 1953) du ca th c xc nh chnh bng du ca in cc ny khi ghp vi in cc H2 chun ca mch galvanc in cc Zn, Cd l nhng nht cho cc electoron qua mch ngoi i n in cc H2. Nh vy cc kim loi ny l du m ca mch, gi tr th ca n mang du m.

Cn Cu khi ni vi in cc H2 chun s l cc dng ca mch.

p dng phng trnh Nernst cho cc phn ng oxy ha kh:

- C H+ tham gia:

- C kim loi hnh thnh:

182

- C OH- tham gia

3.1.1.2. Mch in ha * Mch in ha phn ra 2 loi: mch ganvanc, mch in phn. * Mch in ha gm c 2 dy dn gi l hai in cc nhng vo hai dung dch cht in ly, mt in cc gi l catot, in cc kia gi l anot, y xy ra qu trnh oxi ha. * Cch k hiu: M/M2+(ymol) // H+ (x mol) / Pt, H2 (p at). 3.1.2. Cc loi in cc 3.1.2.1. in cc so snh L loi in cc tr m th thay i t khng ng k. Thng dng l in cc calomen v in cc bc clourua. a. in cc calomel // Hg2Cl2bh, KCl (x M) / Hg, Pt (X l nng mi ca KCl trong dung dch). Phn ng in ha trn 2 in cc. Th in cc ph thuc vo nng Cl- v nhit . Sau y l cc s liu lin quan n in cc calomel: Tn in cc bo ho Nng KCl Bo ha 1N 0,1N 1M 0,1M Th in cc nhit t0C + 0,241 - 6.6.10-4(t-25) + 0,280 - 2,8.10-4(t-25) + 0,334 - 8,8.10-5(t-25)

b. in cc bc clorua (in cc bc). Tng t nh in cc calomel, si dy bc nhng vo dung dch KCl bo ha mui AgCl. // AgCl bo ha, KCl (xM) / Ag Phn ng in cc: 183

in cc ny thng c ch to vi dung dch KCl bo ha, th 250C (o vi in cc Hydro chun) l 0,197V. C hai in cc ny lun sn c trn th trng. 3.1.2.2. in cc ch th Chia lm hai nhm: - in cc ch th kim loi. - in cc mng chn lc ion. a. in cc ch th kim loi. * in cc loi 1, cho cation: in cc ny dng xc nh nng trong dung dch. N gm 1 dy dn kim loi nhng vo dung dch mui ha tan ca kim loi . V d:

* in cc loi 2, cho anion: in cc kim loi c th ch th gin tip cho anion to ta t tan hoc to phc bn vi kim loi . V d: - Th in cc bc phn nh nng ln I- trong dung dch: - in cc Hg khi c mt ca phc EDTA (Y4-) vi Hg2+ Phn ng in cc:

* in cc cho h oxi ha kh. - Mt s kim loi nh Pt, Au, Pd, Cd thng lm in cc cho h oxi ha kh. V d 1 si dy Pt nhng vo dung dch ha tan ca mui Ce+3 v Ce+4 c th E:

in cc ny c th lm ch th khi chun vi dung dch chun Ce4+. b. in cc mng. * in cc thy tinh o pH. - Cu to. + Bn thy tinh mng mng c b dy khong 0,03 0,1nm. 184

+ Mt in cc AgCl nm trong bn thy tinh mng. Mng thy tinh ny to ra th in cc ph thuc vo pH ca dung dch. - Mch o pH. - Khi ni in cc thy tinh vi in cc calomel bo ha (Electrod Calomel Saturation (SCE)) ta c mch in ha o pH dung dch SCE // H3O+ = a1/mng thy tinh / H3O+ = a2, Cl-, AgCl bo ha / Ag. in cc thy tinh. E = L + 0,059 lg aH+ (L l mt hng s a = 1). Tnh cht ca in cc thy tinh nhy vi pH c nghin cu u tin (1906) bi nh ha hc. M.Cremer. * in cc mng chn lc ion: Mng rn l 1 mng dn in ion, c th l: + n tinh th LaF3 chn lc ion F-. + a tinh th Ag2s. + Tinh th hn hp cha cc mui khc nhau ca ion Ag+ hay S2phn tn trong nn Ag2S - Mng lng to nn in cc phc tp hn. N gm hai ng ng tm. ng trong ng dung dch in cc Ag/AgCl. Gia 2 thnh ng c cht trao i ln lng v c. Phn di ng l cht do gi cht lng trao i ln.

(a) in cc thy tinh: in cc Ag/ AgCl(1) nhng vo dung dch ng trong mng thy tinh (2). (b) in cc mng rn: in cc Ag/AgCl nhng vo dung dch c cc ion Na , Cl- v F-. Mng (2) phn di chn lc con c th l mng n tinh th a tinh th hay tinh th hn hp.
+

(c) in cc mng lng: in cc Ag/AgCl nhng vo dung dch c cha ion 185

chn lc. V d Ca2+ (nhng vo mui CaCl2: mng cht do (2) gi cht trao i ln ng gia hai ng ng tm (3)). y l mt cht lng hu c khng bay hi, khng ha tan trong H2O. Phn ng chn lc vi ion Ca2+, in cc mng lng chn lc ion Ca2+ hin c vi cht trao i ln l dieste ca axit phosphoric ha tan trong mt dung mi phn cc. Cn bng qua mng l:

3.1.2.3. Cc phng php o th. a. Phng php o th trc tip * C s l thuyt Phng php o th trc tip da vo gi tr chnh lch th gia catot v anot E = E C Ea (3.5)

Sc in ng E ca mch ganvanic ny dc dng nh lng khi ngi ta dng in cc so snh lm catot v in cc ch th lm nut. Khi 2 dung dch in li c thnh phn khc nhau, tip xc vi nhau to ra 1 th b mt tip xc. Th pht trin b mt gi l th tip xc lng (Ej). Th ny bt ngun t tc dch chuyn khc nhau ca cc ion (cation v anion) gia 2 dung dch. Nu thnh phn dung dch n gin ngi ta c th tnh c th tip xc lng t linh cc ion. Trong thc t ca phng php o th trc tip. Thnh phn dung dch thng phc to nn kh tnh ton c gi tr Ej. Mt s yu t thc nghim lm gim ng k Ej l cu mui ni hai dung dch. Nng cht in li tng ng k l linh cation v anion gn nhau b mt phn cch l hiu qu do cu mui mang li trong thc hnh thng dng dung dch bo ha KCl (nng khong 4M). p ng c hai mt. - Nng cht in li cao. - Linh ca K+v Cl- ch khc nhau khong 4% vi vic s dng cu mui trong nhiu trng hp tr s Ej khong v mV. Tr s ny c th b qua. Mch o trc tip: in cc ch th / Dung dch cn phn tch X (ax) // in cc so snh C tr s: E = ER - EC + Ej (3.6) ER v EC l th in cc so snh v in cc ch th tng ng. Th ca EC: 186

em gi tr ny vo (3.6)

Q = (ER + Ej L) ch c th nh gi bng thc nghim vi dung dch chun c nng bit. * Cc cch xc nh nng . - Lp ng chun vi n dung dch chun. - Phng php so snh: Tnh gi tr Q t phng trnh (3.7) khi o E ca dung ch bit nng . - Phng php thm: Dung dch phn tch c nhit Cx cha bit th tch Vx. Thm VS ca dung dch bit nng CS. Gi tr th o c trc khi thm l E1, sau khi thm l E2. T (3.7). Ta c:

* o pH vi in cc thy tinh: Khi in cc so snh l in cc calomel v in cc ch th l in cc thy tinh. Th ca in cc thy tinh.

b. Chun o th. u im: - nhy cao - Dng c vi dung dch mu c - Khng c sai s ch quan. Yu cu: Ging chun th tch thng thng. 187

* Chun o th khng dng. y l phng php c in: Trong qu trnh chun ngi ta o sc in ng ca mch galvanc khng c dng i qua (i = 0). Chun ny c th thc hin vi cc phn ng c bn cht ha hc khc nhau * Chun axt baz: dng in cc ch th cho s thay i pH ca dung dch thng dng l in cc thy tinh. * Chun kt ta: chun halogen bng ion Ag+ ngi ta dng in cc bc lm in cc ch th. - Phn ng chun :

- Phn ng in ha trc im tng ng.

- Phn ng in ha sau im tng ng:

Do in cc bc thun nghch vi ion Ag+ nn cng nng vi ion Ag+ hai phng trnh (a) v (b) c gi tr ngang nhau: E1 = E2 v nh vy:

Nh vy s khc nhau th trc v sau im tng ng vi bc nhy th l:

Nu TS cng b th bc nhy th cng ln. * Chun bng complexon III: Cht ny khng c phn ng in cc, nhng khi s dng in cc thch hp s c phn ng in ha trn b mt to ra th n nh. V d: Complexon III (H2Y2-) to ra phc bn vi nhiu kim loi:

188

Vi in cc kim loi M0 khi c mt H2Y2- phn ng in ha sau d dng xy ra:

Sau khi phn ng (e) kt thc, ion M2+ c d (c thm vo) cho phn ng in cc mi:

Ly gi tr [M2+] t phng trnh (e) thay vo phng trnh (i) ta c:

Do E1 = E2 nn t (k) v (e) ta c:

Ngha l K cng ln bc nhy th cng di. * Cch xc nh im kt thc khi chun o th. C 2 cch v th biu din E = f(v) (hnh 3.3a) hoc v th biu din (hnh 3.3b)

* Chun o th dng khng i (i 0) Bng ngun ngoi ngi ta cho qua in cc ch th mt dng in cng 189

vi microampe - tc l lm phn cc in cc, nh lm tng nhanh qu trnh cho nhn electron trn in cc - lm qu trnh nhanh t n cn bng, v vy th n nh nhanh, lp li tt. Gi tr th ph thuc vo tr s dng phn cc. - C th phn cc nut hay phn cc catot. - C th dng 2 in cc ging nhau trong cng mt dung dch nhng phi lm phn cc c 2 in cc. 3.2. PHNGPHP CC PH V CHUN AMPE 3.2.1. Phng php cc ph 3.2.1.1. C s ca phng php cc ph Nu t mt hiu th vo hai cc nhng vo dung dch cht in li v tng dn th hiu , ban u dng in chy qua dung dch hu nh khng i. Khi hiu in th tng n mt gi tr phn hu cht in li th cng dng s tng ln mt cch t ngt. Gi tr th hiu gi l th phn hu. Nu dng mt trong hai cc c b mt nh (thng dng catt git thu ngn) cn cc kia c b mt ln, th khi cho dng mt chiu qua dung dch, cc c b mt nh xy ra s bin thin nng (do cht in li phn hu); v b mt in cc qu nh nn mt dng in cc ln. Cng vi s tng th hiu gia hai cc, cng dng chy qua dung dch v mt dng trn cc nh tng ln, th con b kh vng st vi b mt cc nh tng ln nn lm gim nng ca ion b kh xung. Tip tc tng th hiu gia hai cc ln th s tng mt dng trn in cc nh dn ti kt qu l n mt lc tt c cc ion c chuyn n canh u b phng in. S b sung cc ion t dung dch cho lp in cc xy ra chm hn qu trnh phng in trn b mt in cc. Khi s tng tip hiu in th gia hai cc s khng gy ra c s tng ng k cng dng in chy qua dung dch. 3.2.1.2. Dng khuch tn trn in cc git Hg. Cc ph l qu trnh in phn dung dch nghin cu trong nhng iu kin c trng, l: a. in cc: Dng in cc git thy ngn lm ch th. l in cc c din tch b mt nh nn mt dng kh ln (A/cm2). Nh khi in phn, khu vc gn in cc nng ln tham gia phn ng gim nhanh, t n cn bng, to ra dng gii hn. in cc so snh c b mt kh ln, ln hn nhiu in cc ch th. V vy mt dng b. gn in cc s thay i nng ion rt nh, khng nh hng n 190

ng cong dng th. Nh vy trong cc ph, in cc git thy ngn b phn cc to ra sng cc ph, cn in cc so snh khng b phn cc. Git Hg c to ra t mt mao qun di (5-10cm) ng knh trong l 0,05mm. Nu bu thy ngn cao 50cm, dng chy to ra cc git Hg ging nhau c ng knh 0,5 1mm. Phn ng in ha xy ra trn git ny. S thnh cng ca cc ph ph thuc trc ht vo lp li ca git Hg. b. Cht in li nn: vic chuyn cc ion tham gia phn ng in ha trn in cc do nhiu yu t tc ng nh: Lc ht tnh in, khuy trn c hc, s khuch tn do gradient nng . Trong iu kin cc ph phn cc catot git Hg, ngi ta thm mt cht in ly tr vo dung dch lm nn cc ph. l cht in ly to ra 1 cation khc tham gia phn ng kh canh hn ion cn xc nh, nng li cao hn nhiu (gp 100 1.000 ln ion tham gia phn ng in cc). l cht in li nn nh KCl, KNO3, R4 NX. Cc cation ca nn di chuyn n in cc nhng khng tham gia phn ng in cc ( th cho). Chng trn b mt in cc, to nn lp in kp. Do trng in canh b chn bi cation nn cho nn cation kh cc ch c th tip cn in cc nh qu trnh khuch tn. V vy dng to ra gi l dng khuch tn... Ngoi ra cn cc dng khc nh dng xc tc, dng ng hc. c. Trong iu kin cc ph nh trn, th t ln 2 in cc c thay i lin tc t 0-2V, dng khuch tn i qua dung dch khong 1 - 100 A. Tr s dng ny trong cng iu kin ph thuc vo th phn cc: th hin qua s chnh lch nng trong lng dung dch C v nng trn b mt in cc C*. Khi tt c cc ion trn b mt in cc b kh ht tc l C = 0, dng khuch tn in cc c gi l dng khuch tn gii hn. Gi tr trung bnh ca dng ny ( i a) c m t bi phng trnh Ilcovic:

- i d dng khuch tn gii hn. - D - h s khuch tn (cm2/ s). - m: Tc nh git (g/s). - t: thi gian nh git (s) - C nng cht kh cc (mol/l) Tr s m2/3. t1/6 c gi l hng s mao qun. Vi mao qun v cht kh cc 191

xc nh th i d tuyn tnh vi nng .

V y l c s cho phng php cc ph. d. Th bn sng: l th im gia ca sng cc ph. N ph thuc vo bn cht ca cation kh cc c lp vi nng C c k hiu E1/2. Gi tr ny thay i theo cht nn l mt thng s s dng trong nh tnh bng cc ph. Trn hnh 3.4 l cc ph ca dung dch CdCl2 0,001M.

1. Dng d 3. Th phn hy ca Cd2+ 5. Dng gii hn i ca Cd2+

2. Kh nn K+ 4. Dng khuch tn ca Cd2+

Phng trnh lin quan gia th E v dng khuch tn i mt im bt k trn cc ph .

Da vo phng trnh ny c th tnh gi tr E1/2 theo cc s liu ca cc ph . Tnh gi tr i / ( i d - i) = R. V th ca lgR E im th lg R = 0 (tc i = i d/2) ng vi E1/2 trn trc E (hnh 3.5). 192

e. nh hng ca cc yu t n sng cc ph. - nh hng ca cht nn: - nh hng ca s to phc: Khi c mt ca cht to phc sng cc ph s chuyn v pha m hn. - nh hng ca c tnh thun nghch. 3.2.1.3. Dng khuch tn trn in cc rn. Khi cn lm vic th dng trn + 0,3V - tc l dng phn ng oxi ha anot trn in cc ch th - ngi ta dng vi in cc rn - trong nhng iu kin nht nh c th ghi c dng khuch tn. Thng dng nht l in cc Pt. Qu th hydro trn in cc Pt b. Ion H+ b kh th - 0,1V. Nhng qu th oxi kh ln, v vy c th kho st sng oxy ha nut n +1,3V. in cc rn c th ng yn (in cc tnh) hay quay. a. Trn in cc rn tnh: Dng i qua vi in cc rn ph thuc vo nhiu yu t:

C - nng cht kh cc trong dung dch, C* - nng trn b mt in cc; b dy lp khuch tn. Dng khuch tn gii hn i d t l vt nng dung dch:

i d t l vi C b dy phi khng i. Thc t trn in cc tnh dng gii hn id cn nhiu thi gian t n gi tr cn bng khng i. iu hn ch 193

phm vi ng dng. khc phc nhc im ny ngi ta dng in cc quay. b. in cc rn quay: Cht lng xung quanh in cc quay c khuy trn lin tc. V vy nng cht kh cc gn in cc lun c nng cao, s thay i ny ch b hp vng gn in cc, khng phi trong ton b dung dch. Trn in cc a quay mt dng i c tnh t phng trnh Levich.

W - Tc quay ca a, - nht ca dung dch. Nhc im ca in cc quay: Thit b phc tp, lp li km. u im: Nghin cu phn ng oxy ha anot n + 1,3v v khng ng c nh in cc git Hg. 3.2.1.4. Thit b cho in cc git Hg. * My cc ph.

1. Ngun in 1 chiu 4 6V 2. Bin tr: 3. Vn k 4. Ganva nomt 5. in cc git Hg 6. Anot Hg. Th t ln in cc thay i t 0 3V c do nh vn k (3). Dng i qua in cc git Hg (5) c o bng Ganvanomt 4 (4). * in cc so snh: calomel, in cc HgSO4, in cc AgCl... 194

3.2.1.5. ng cc ph ng cc ph l ng biu din s ph thuc ca gi tr cng dng chy qua dung dch (biu din trn trc honh) c dng nh trn hnh 3.7 v 3.8.

Trn ng cc ph t O n A, s in phn khng xy ra. Tng ng vi iu cng vi s tng th, s bin i ca cng dng chy trong mch thc t cng khng xy ra. Cng dng chy trong mch rt nh. Dng trong khong th c sinh ra do s tch in git thu ngn v s kh tp cht. Trn phn ng th phn hu vi cht phn tch cha t ti gi tr ti a. Trn phn t A n B, mt s tng khng ng k ca hiu in th cng gy ra mt s tng ng k cng dng chy qua dung dch. Phn ng cong ny c trng cho s in phn xy ra bnh thng km theo s lm ngho rt nhanh lp ion cht phn tch st b mt cc. Phn t B n C c trng cho qu trnh khi tt c cc ion ca cht phn tch c lp b mt cc u b phng in. Tc khuch tn cc ion cht phn tch t dung dch n b mt cc nh hn tc khuch tn cc ion cht phn tch t dung dch n b mt cc nh hn tc kh ion. Phn ng cong ny c trng cho s khng bin i dng trong mch khi tng dn th hiu gia hai cc. ng biu din s ph thuc cng dng chy qua dung dch vo in th hai cc c gi l ng von ampe hay sng cc ph. Sng cc ph ph thuc vo bn cht ca ion cn phn tch v c trng mt cch nh lng cho cht phn tch. Chiu cao sng H (hnh 3.8) c trng cho dng gii hn v v vy cho ta kh nng xc nh nng ln cn phn tch. Nu chia i khong cch t im A n im B t im nhn c ng vi 195

gi tr th trn trc honh c gi l th na sng E1/2, n c trng cho th cn thit t c na dng gii hn. Th na sng khng ph thuc vo nng ca cht tan v ch ph thuc vo bn cht ca ion b kh. Do th na sng c s dng phn tch nh tnh cc ion c mt trong dung dch. 3.2.1.6. Catt git thu ngn 1. ng ng thu ngn v dy platin lm tip xc; 2. Bu cha thu ngn ni vi canh git thu ngn; 3. ng dn bng cao su ni bu cha thu ngn vi mao qun bng thu tinh; 4. Mao qun thu tinh qua git thu ngn (catt thu ngn) chy ra; 5. Bnh in phn; 6. Lp thu ngn c ni vi dy tip xc bng platin (nut thu ngn); 7. ng nhnh dn kh hidro hoc nh vo loi oxi Hnh 3.6. S catot git thu ngn n gin nht Trong thc t khi b mt ca cc nh (vi in cc) c dng lm catt thng b cc sn phm kh ph ln, lm thnh phn ho hc ca n b thay i v kt qu thu c khng lp li. Kt qu ch lp li khi kch thc v bn cht ca catt c gi khng i; l trng hp l tng. Qua nghin cu ngi ta thy ch c catt git thu ngn mi p ng c nhiu nht nhng yu cu i vi vi in cc dng trong cc ph. in cc git thy ngn c trnh by trn hnh 3.9, thu ngn c chy ra t mt mao qun thnh tng git vi mt tc xc nh. Catt cu to nh vy nn b mt ca catt git thu ngn nh v thc t khng i v kch thc v thnh phn v thu ngn chy lin tc nn lun lun c i mi. Do th kh ca mi con c gi mc xc nh. S to thnh hn hng khi cc cation kim loi b kh trn b mt canh git thu ngn ri xung y bnh in phn v s i mi b nt in cc do s chy ca thu ngn v c thay th bng git khc lm cho iu kin tin hnh phn tch trn cc git gn vi cc iu kin l tng. 3.2.1.7. Nn cc ph trn ta xt, trong qu trnh phn tch cc ph, cc ion kim loi trong lp st in cc c b sung nh s khuch tn. Nu trong dung dch phn tch ch c ion ca mui cn phn tch th s chuyn 196

dng t cc ny n cc kia c thc hin bng cc ion ca mui tan . Nhng tn di tc dng ca dng in, cation chuyn ti nut. Tc chuyn ng ca cc ion di tc dng ca dng in ph thuc vo nhiu yu t nh: hiu th gia hai cc, bn knh v in tch ca ion phn tch, nng ca n trong dung dch... Do s vn chuyn ca cc ion di tc dng ca dng in s lm sai lch qu trnh xc nh cc ph v gy tr ngi ln cho qu trnh phn tch. lm gim s chuyn vn , ngi ta thm vo dung dch phn tch mt mui khc m s phn hu n ch bt u hiu th ln hn so vi hiu th cn thit i vi cht cn xc nh, th cc cation ca nn cng chuyn ng ti canh, nhng chng khng b phng in ti th c t vo. V vy phn ln ca cht tham gia vo s chuyn ng b gim i. Nu nng mui thm vo ln hn so vi nng cht phn tch, th thc t tt c dng u c vn chuyn bi ion ca mui c thm vo. Trong trng hp ny, tc chuyn ng ca cc ion cht phn tch di tc dng dng in gn nh bng khng v c th b qua. Mui tr c thm vo loi tr s vn chuyn ca ion cht phn tch di tc dng ca dng in gi l nn cc ph. cho dng in mt chiu chy qua dung dch khng gy ra s vn chuyn ng k ca cc ion cht phn tch th nng ca nn phi ln hn t 100 - 1000 ln nng mui cn cn xc nh. Do phng php cc ph c ng dng rng ri phn tch cc tp cht c hm lng khng ng k trong dung dch. 3.2.1.8. Phm vi ng dng ca phng php phn tch cc ph. Dng phng php phn tch cc ph c th xc nh c cc cht v c cng nh hu c, nu chng c th b kh hay b oxi ho trn b mt cc cc khi c dng in mt chiu i qua. Do phn tch cc ph c ng dng rng ri trong cc phng th nghim ho phn tch ca cc c s nghin cu khoa hc v ca cc nh my. Trong thi gian gn y, phng php cc ph s dng cc vi in cc rn quay c s dng ngy cng nhiu. Ti nay c nhiu phng php phn tch cc ph hin i xc nh c nhng lng nh ti 10-9 - 10-10 nh cc ph sng vung, cc ph xung vi phn, cc ph von ampe ho tan, cc ph xc tc... 3.2.1.9. Quy trnh ca phng php phn tch cc ph phn tch mt cht no bng phng php cc ph, trc ht cn chuyn n vo dung dch. Sau to nn mi trng cn thit v tch cc cht ngn cn s xc nh cc ph. iu bt tin nht i vi phn tch cc ph l trong dung dch phn tch c cc 197

cht c th kh gn vi th kh ca nguyn t cn xc nh hoc c th thp hn oxi ho tan trong dung dch, chng s cn tr php xc nh. tch cc cht ngn cn, ngi ta s dng cc phn ng kt ta, to phc, oxi ho kh, tch bng sc k... tch oxi ho tan l cht cng b kh trn canh, ngi ta cho kh hidro hay nh qua dung dch ui oxi. i vi cc dung dch kim ngi ta dng cht kh l Na2SO3. Vic chn ng cht lm nn cho cc ph c ngha ln. Vic ny thng c gii quyt bng thc nghim. Dung dch chun b phn tch, tch cc cht cn tr c cho vo bnh in phn. ng mch dng mt chiu v tng th gia 2 cc ln mt cch t t v ghi s bin i dng ph thuc vo in th. Da vo cc d kin thu c ta v ng cc ph. 3.2.1.10. Cc phng php phn tch cc ph phn tch nh lng bng phng php cc ph, ngi ta dng phng php ng chun, phng php mu chun v phng php thm. Khi s dng phng php ng chun, ngi ta ghi cc cc ph ca mu dung dch chun. Da vo chiu cao sng cc ph ca mu phn tch (ghi trong iu kin cng vi iu kin khi ghi cc ph cc mu chun) ri xc nh nng ca n theo mu chun. Trong phng php mu chun, ngi ta ch ghi cc ph ca mt dung dch chun (Cch) ri xc nh chiu cao ca sng cc ph mu chun (hch) sau ghi cc ph mu phn tch (trong cng iu kin nh ghi mu chun) c nng Cx v xc nh chiu cao hx ca sng cc ph . Tnh nng ca dung dch phn tch bng cng thc:

phn tch bng phng php thm, ngi ta rt vo bnh in phn mt th tch xc nh dung dch cht cn phn tch (Cx) v ghi sng cc ph ca cht cn xc nh chiu cao sng cc ph hx. Sau thm vo dung dch 1 - 3 ml dung dch chun cn phn tch v ghi ph ln na, ta nhn c sng tng s c chiu cao hts. Nng cht phn tch c tnh theo cng thc:

Trong : Cth - nng cht chun thm vo bnh in phn. 198

3.2.2. Chun ampe. Chun Ampe thc hin trong hai iu kin: - Mt trong cc phn ng, c kh trn catot Hg hoc oxi ha trn in cc rn. - Tr s dng khuch tn gii hn t l vi nng i d = K.C C th s dng cc loi phn ng: Kt ta to phc v oxy ha kh cho chun ny vi 2 phng php k thut - chun vi in cc ch th v chun vi 2 in cc ch th. 3.2.2.1. Chun ampe vi mt in cc ch th. Bnh chun (1) ni vi in cc so snh (2) qua cu mui (3). in cc ch th (4) c phn cc nh ngun (5). Dng qua mch c o bng galvanomet (6) trong qu trnh chun bng dung dch t buret (7).

* ng cong chun : im mu cht l chn th lm phn cc in cc ch th. vic chn tr s th ty thuc vo hp cht no: Dung dch chun, cht cn nh lng (hoc c hai) cho phn ng in cc. V ng cong chun : S ph thuc ca dng in vo th tch dung dch chun. ng cong chun gm hai on thng ct nhau. im ct nhau ng vi im kt thc ca phn ng chun . Hnh 3.11 cho ta cc dng ng cong chun .

199

a) Cht cn nh lng cho dng kh catt. b Cht chun cho phn ng trn catt. c) C cht khun l cht cn nh lng cho phn ng trn in cc. d) Trn th chn, cht cn nh lng cho dng oxy ha cn lng d cht chun cho dng kh (id,c). . e) Cht cn nh lng cho dng kh id,c cn dung dch chuyn cho dng oxi ha id,a. c dng khuch tn gii hn id th lm phn cc in cc ch th phi ri vo khong th to dng id ca thnh phn cho phn ng in cc, thng m hn 0,1 - 0,3V so vi tr s E1/2. Hnh 3.12. Trnh by cch xy dng ng cong chun ampe t ng cong I-V cho trng hp (a).

200

E l tr s in th lm phn cc in cc trc honh l % cht c chun . 3.2.2.2. Phng php ampe kp Trong chun ampe kp, c 2 in cc ch th c nhng trc tip vo dung dch phn tch. Hai in cc ging nhau. Gia hai in cc c s chnh lch th trn in cc xy ra cc phn ng in ha, t c dng in qua mch th phn cc khng ln: 0,01 0,1V. Dng ng cong chun ph thuc vo tnh cht thun nghch ca cc h (cht cn chun v cht chun) cng nh tr s th lm phn cc hai in cc. * V d: Kho st chun ln Fe(II) bng Ce4+

- Khi cha thm Ce4+ trn anot xy ra qu trnh oxy ha Fe(CN)4-, cn trn catt Fe(CN)63- b kh. Khi thm Ce4+ vo ion [Fe(CN)6]3- tng ln nn dng qua mch tng ln. T s dng t cc i khi nng hai ion bng nhau, tc l chun c 50% ion Fe(CN)64-. Sau nng cht kh gim ko theo gim dng qua mch. - im tng ng dng i 0 bi nng cht kh [Fe(CN)6]4 rt b. - Sau im tng ng Ce4+ c d trong dung dch nn trn anot oxy ha Ce3+ cn trn catt kh Ce4+. Dng qua mch li tng ln (hnh 3.13a). y ta c hai h thun nghch:

Nu cht cn chun thun nghch, cn dung dch chun khng thun nghch th sau im tng ng dng khng tng. V d chun iod bng thiosunfat (Hnh 3.13.b). 201

Nu h khng thun nghch c chun bng mt h thun nghch, dng qua mch khng ng k cho n im tng ng. Ch sau im ny dng tng ln (hnh 3.13c). V d chun Na2S2O3 bng dung dch Iod.

202

PHN TH T SAI S TRONG PHN TCH X L S LIU THC NGHIM

I. CC NH NGHA V SAI S Trong phn tch vic nh gi cc kt qu l mt trong nhng bc khng th thiu c ca cc qu trnh phn tch. Trong bc ny vic tnh sai s l quan trng nht v n cho ta bit kt qu phn tch thu c ng v chnh xc ti mc no. C th ni rng khng bao gi chng ta c th tin hnh mt php phn tch m kt qu thu c li hon ton khng mc sai s. iu c ngha l chng ta khng th bit c gi tr thc ca mt i lng cn xc nh. Chng ta ch c th c gng thc hin phn tch sao cho sai s nh nht, kt qu thu c cho ta mt gi tr chp nhn c tt nht bng phng php thng k hc ta c th xc nh c gii hn trong cha gi tr thc ca i lng cn xc nh vi mt mc xc sut cho trc. Gi s chng ta tin hnh xc nh mt i lng no n ln bng mt quy trnh phn tch duy nht (ta ni php xc nh c lp li n ln), cho ta cc kt qu tng ng x1, x2, x3 xn. Gi tr trung bnh s hc x , thng khc vi gi tr thc ca i lng cn xc nh:

Hiu s gia gi tr trung bnh x v gi tr thc (hoc gi tr c chp nhn ng tin cy nht). K hiu l :

Sai s tuyt i khng cho ta thy mc gn nhau ca gi tr xc nh c v gi tr thc tc l khng cho ta thy c ng ca php phn tch. bit c ng ca php xc nh ngi ta thng dng sai s tng i. Sai s tng i S: L t s gia sai s tuyt i v gi tri thc hoc gi tr trung bnh x

Thng thng sai s tng i c biu th theo %:

203

Th d khi lng ca cht A cha trong mt mu l 45,2 mg, ca cht B cha trong mt mu tng t l 215,4 mg. Gi tr xc nh c theo cng mt phng php ca A l 45,8 mg v B l 216,0 mg. Nh vy sai s tuyt i khi xc nh A v B u nh nhau bng +0,6 nhng ta thy ngay l php xc nh B ng hn v xc nh 216 mg mi ch sai 0,6 mg trong khi khi xc nh A th ch vi 45,8 mg sai s 0,6 mg. Sai s tng i s ch ra vic xc nh B chnh xc hn xc nh A: Vi A, S% = (+0,6/45,2).100 = 1,3% Vi B, S% = (0,6/216,4).100 = 0,3% Ty thuc vo nguyn nhn gy ra sai s, ngi ta dng khi nim sai s h thng v sai s ngu nhin. Sai s h thng hoc sai s xc nh l nhng sai s do nhng nguyn nhn c nh gy, v vy n lun c du + hoc -. Sai s h thng c th do chnh phng php khng ng (do cc dng c o lng nh cn, dng c o th tch nh buret, pipet hoc bnh nh mc khng ng th tch trn vch chia; do ha cht khng tinh khit; do xc nh nng dung dch chun sai; do ngi tin hnh phn tch khng c k nng ngh nghip thiu kinh nghim phn tch). Sai s ngu nhin l nhng sai s gy nn bi nhng nguyn nhn khng c nh, khng bit trc, thay i khng theo quy lut, khi dng, khi m, th d do ngi phn tch mt lc no thiu tp trung hoc tin hnh thao tc i khi thiu cn thn, s thay i v nhit , p sut kh quyn ni lm phn tch. Ta c th tn c sai s h thng, t loi tr c nguyn nhn gy ra sai s bng nhng bin php thch hp nh sa cha hiu chnh dng c my mc, pha li v kim tra li cc dng c, dung dch chun v iu ch li ha cht dng lm thuc th v..v. i vi cc sai s ngu nhin ta khng th bit trc loi tr cc nguyn nhn gy ra n m ch c gng gim sai s ti mc ti thiu bng cch phn tch tht cn thn v tng s ln phn tch ri cui cng s l cc s liu bng phng php thng k ton hc. Sai s h thng phn nh, ng ca phng php phn tch, sai s ngu nhin phn nh phn tn ca cc kt ta phn tch tc l lch gia cc gi tr ring l v gi tr trung bnh tc l phn nh lp li. 204

Hnh 1. ng v lp li ca phng php phn tch a. lp li v ng u thp; b. ng cao, nhng lp li thp; c. lp li cao nhng ng thp; d. ng cao v lp li cng cao.

Sau y chng ta nu ra nhng khi nim ton hc c lin quan trc tip n vic x l cc d kin thc nghim theo phng php thng k ton hc. II. CC I LNG TRUNG BNH Trung bnh s hc. Gi s tin hnh n ln phn tch c cc gi tr ca i lng no (c th dng, m) x1, x2, x3 xn. Gi tr trung bnh s hc x c xc nh bng h thc:

Trung bnh bnh phng. Gi s tin hnh n ln phn tch lp c cc gi tr x1, x2, x3 xn. Trung bnh bnh phng l cn bc hai tng bnh phng cc gi tr chia cho n ln. Tc l:

Trung bnh nhn. Gi s sau n ln phn tch ta c cc gi tr x1, x2, x3 xn. Trung bnh nhn l gi tr dng cn bc n ca tch s cc gi tr , tc l:

Thng thng trung bnh nhn c biu th di dng logarit thp phn, tin cho vic tnh ton:

205

III. CC I LNG C TRNG CHO PHN TN. Khi tin hnh nhiu php phn tch tc l tin hnh lp li th nghim ta thu c mt dy cc d kin thc nghim. Cc khi nim sau y c trng cho phn tn cc d kin . lch trung bnh

Phng sai: Phng sai l trung bnh cng ca cc bnh phng nhng hiu gia cc gi tr ring l v gi tr trung bnh tc l:

Trong n l s ln th nghim v n c gi tr nh, nh hn 20, n -1 c gi l bc t do, nu n> 10 th c th b qua mt cnh n v (10) tr thnh.

Cc i lng S2 v 2 u c gi l phng sai l nhng i lng rt quan trng c trng cho phn tn dng tnh sai s ngu nhin. lch chun hay sai s bnh phng trung bnh lch tiu chun hay sai s bnh phng trung bnh bng cn bc hai ca phng sai

y l i lng c trng cho phn tn v c dng ch mc sai s ngu nhin. i lng (xi - x )2 trong cc cng thc (10) v (12) thng c tnh theo cc biu thc ton hc tng ng sau y:

206

lch chun gi tr trung bnh Phng sai ca gi tr trung bnh bng phng sai chia cho s th nghim

Do lch ca gi tr trung bnh

H s bin ng Gi s tin hnh phn tch lp li n ln ta c cc gi tr kt qu x1, x2, x3 xn. T cc biu thc ton hc c trnh by trn ta tnh c x v S. H s bin ng V ca phng php phn tch c xc nh bng h thc:

Nh vy chng ta c th tnh h s bin ng theo lch chun v ngc li. IV. CC LOI PHN B. Phn b thc nghim Gi s kim tra th tch ca pipet dung tch 10 ml ta tin hnh cn th tch ca pipt. Chng ta tin hnh 50 ln cn. Ghi cc kt qu vo mt bng thy c quy lut phn b cc kt qu thc nghim ta dng phng php th. Trn trc honh ta biu th gi tr th tch pipet (bng cch chia cc gi tr khi lng nc cn c cho khi lng ring ca nc), cn trn trc tung ghi tn s tc l s % xut hin tng kt qu so vi tng s ln xc nh th tch, ta s c th biu th s phn b thc nghim. Trn bng 1 ghi tn xut phn b cc kt qu tnh c t cc kt qu thu c ca 50 ln xc nh dung tch pipet. Hnh 2 l ng phn b thc nghim.

207

Bng 1. Tn xut phn b cc kt qu thc nghim Khong th tch, ml 9,969 ti 9,971 9,962 ti 9,974 9,975 ti 9,977 9,978 ti 9,980 9,981 ti 9,983 9,984 ti 9,986 9,987 ti 9,989 9,990 ti 9,992 9,993 ti 9,995 S ln xut hin 3 1 7 9 13 7 5 4 1 % xut hin 6 2 14 18 26 14 10 8 2

Hnh 2. ng phn b thc nghim A v ng phn b chun Gaus (B) Phn b chun hay phn b Gau x (Gauss) Thng thng nu sai s cha php phn tch l sai s ngu nhin th th biu din s phn b cc kt qu thc c nh th d trn y s c dng i xng theo l thuyt ton hc: V xc xut thng k th cc loi phn b quan trng v ph bin nht l phn b chun hay phn b Gau x. Cc i lng ngu nhin trong ha phn tch thng tun theo phn b ny. Cng theo l thuyt ton hc n s ln thc nghim v cng ln, tc l n tin ti v cng th hm phn b chun s c dng nh sau:

Trong l gi tr thc, x l gi tr thc nghim, l lch chun. y v l 208

nhng s thc, c gi l tham s phn b, y lm hm s ca x chnh l tn s ca gi tr x hoc xc xut ca x. Hm phn b c cc i x = v c im un x1 = v x2 = +

Theo phng trnh (17) gi tr cc i ca

gi tr cng ln nu

lch chun cng nh. Hnh (4) hay ni cch khc lp li cng cao ngha l s cc gi tr thu c gn gi tr thc cng nhiu. Din tch ca hnh to bi ng cong phn b v trc honh bng 1 gm cc gi tr x t - n + . Din tch gii hn trong khong 2 l 0,9546; trong khong 3. V vy ngi ta thng dng quy tc 3 phn bit i lng ngu nhin (sai s ngu nhin) vi cc i lng h thng (sai s h thng) hoc pht hin sai s th.

Hnh 4. Dng ca ng phn b chun ph thuc vo lch chun V. BIN GII TIN CY. Nu sai s ngu nhin tun theo phn b chun th c th xc nh c bin gii tin cy tc l khong trong cha gi tr thc

209

Tuy nhin trong thc tin phn tch, s th nghim thng nh lch chun tnh theo cng thc (11.12) nn phi dng cc chun khc. l chun studentt tm bin gii tin cy

Gi tr t ph thuc vo s bc t do k = n - 1 v vo xc xut tin cy P. S th nghim cng nh, xc xut P cng ln th gi tr t cng ln, (xem ph lc 11.1) Bng 1. Gi tr ng vi tin cy P v s bc t do K = n -1. K 1 2 3 4 5 6 7 8 9 10 15 20 T biu thc (18), ta c: 0,90 6,31 2,92 2,35 2,13 2,01 1,94 1,89 1,86 1,83 1,81 1,75 1,73 P 0,95 12,7 4,3 3,18 2,78 2,57 2,45 2,36 2,31 2,26 2,23 2,13 2,06 0,99 63,7 9,92 5,84 4,60 4,03 3,71 3,50 3,36 3,25 3,17 2,95 2,79

l bin gii tin cy. 210

nh vy, gi tr thc nm trong khong x - < < x + . Vi xc sut tin cy no c biu th theo n v tuyt i nh x . nu biu th theo n v tng i (%) th ta c:

v (20) c dng:

VI. KIM TRA THNG K CC D LIU THC NGHIM Cng vic ny thng gm nhng cng vic sau: Dng chun Q hoc chun i sn kim tra cc gi kin nghi ng loi b cc gi tr mc sai s th khi s th nghim n nh hn 10. Chun Q c tnh theo cng thc:

Trong x l gi tr ghi ng. xn + 1 l gi tr ln cn gi tr xn v xmin, xmax tng ng vi gi tri nh nht v ln nht. Bng 2. Gi tr Q ng vi tin cy P v s ln o n n 3 4 5 6 7 8 0,9 0,89 0,68 0,56 0,48 0,43 0,40 0,95 9,94 0,77 0,64 0,56 0,51 0,48 0,99 0,99 0,89 0,76 0,70 0,64 0,58

Trc ht tnh gi tr Q thc nghim (Qm) sau so snh vi gi tr Qlt (bng 2). Nu Qm ln hn Qlt cn la b gi tr xn v ngc li sau khi kim.tra cc gi tr ln nht v b nht cn kim tra tip cc gi tr tip theo. Th d: Nhng kt qu xc nh hm lng % Fe2O3 trong mt loi mu l: 211

2,25; 2,11; 3,21; 2,38; 2,32. C nn loi b gi tr no khng. Trc ht sp xp cc gi tr tng dn, ta thy gi tr b nht l 2,11 v gi tr ln nht ln 3,2 1. Kim tra gi tr 3,2 1.

Tra bng 2 thy ng vi n = 6 v P = 0,95 th Qm = 0,56 v Qm ln hn Qlt nn cn b gi tr 3,11. Sau kim tra cc gi tr 2,11 v 2,38 ta thy cc Qm u nh hn Qlt nn chng u l cc gi tr ng tin cy. V b i mt gi tr 2,11 hoc 2,38 th n = 5 v xmax = 2,38. Chun F (chun Fis) Chun ny dng so snh lp li ca hai dy th nghim bng cch so snh t s ca hai phng sai.

Trong S12 l phng sai ln hn ng vi s bc t do K1 = n1 - 1, S22 l phng sai ln hn ng vi bc t do K2 = n2 - 1. Do , F lun b hn 1. Trong bng 3 l cc gi tr F l thuyt ng vi xc sut tin cy P = 95%. V d theo kt qu ca 6 ln phn tch hm lng CaCO3 bng phng php A tnh c lch chun ca phng php ny 4,3 mg. Theo 5 ln phn tch theo phng php B ta tnh c lch chun l 2,1 mg. Hi lp li ca cc phng php c ng nht hay khng?

Theo bng 3 ng vi K1 = 5, K2 = 4 th Ftn = 6,26. Vi lp li ca hai phng php l ng nht. Bng 3: Gi tr F ng vi tin cy P = 0,95 v cc s bc t do. 1 1 2 3 4 5 161 10,13 7,71 6,61 2 200 9,55 6,94 5,79 3 216 9,28 6,59 5,41 4 225 9,12 6,39 5,19 5 230 9,01 6,26 5,05 6 234 8,94 6,16 4,95 8 239 8,84 6,04 8,22 10 242 8,73 5,96 4,74 12 244 8,74 5,91 4,68 212

18,51 19,00 19,16 19,25 19,30 19,33 19,37 19,29 19,1 ]

6 7 8 9 10 11 12 15 20

5,99 5,59 5,32 5,12 4,96 5,84 4,75 4,54 4,35

5,14 4,74 4,46 4,26 4,10 3,98 2,88 3,08 3,49

4,76 4,35 4,07 3,36 3,71 3,59 3,49 3,29 3,10

4,53 4,12 3,84 3,63 3,48 3,36 3,26 3,06 2,87

4,39 3,97 3,69 3,48 3,23 3,20 3,11 2,90 2,71

4,28 3,87 3,58 3,37 3,22 3,09 3,00 2,79 2,60

4,15 3,73 3,44 3,23 3,07 2,95 2,85 2,64 2,45

4,06 3,63 3,34 3,13 2,97 3,86 2,76 2,55 2,35

4,00 3,57 3,23 3,07 2,3 1 2,79 2,69 4,48 2,28

Tnh sai s h thng: tm sai s h thng trc ht ta tm gi tr thc nghim sau so snh vi gi tr tt (bng 1) ng vi sc xut 0,85. Nu tnt tc l x v khc nhau kh nhiu v l sai s h thng gy ra. Th d nhng kt qu phn tch khi lng ca nguyn t X l 53,2; 53,6; 54,9; 52,3; 53,6; 53,1 mg. Hi phng php phn tch c mc sai s h thng khng? Nu gi tr thc ca X c coi l 56,5 mg. Trc ht ta kim tra theo chun Q ta thy khng cn b i gi tr no, sau t tnh: 1 - Gi tr trung bnh s hc 2- lch chun

Theo bng P = 0,95, K = 5 th t = 2,57. Vi phng php ny mc sai s h thng. VII. NH GI KT QU PHN TCH THEO THNG K C hai trng hp: a) Trng hp cha bit h s bin ng hoc lch chun ca hai phng php. Theo 5 ln phn tch hm lng Al2O3 ta thu c cc kt qu phn trm Al2O3: 2,25; 2,19; 2,11; 2,38; 2,32. vi hm lng thc ca Al2O3 nm trong gii hn no vi xc xut 0,95 ? 213

Ta thc hin cc bc sau: 1. Kim tra theo chun Q: khng b i gi tr no 2- Tnh x 3- Tnh S:
x = 2,25

4- Tra tlt ng vi P = 0,95 v n = 5 th tlt = 2,78 5 - Tm bin gii tin cy: 6- Kt lun: Hm lng % Al2O3 nm trong khong: 2,25 0,14 tc nm trong khong 2,11 2,39 %. b) Trng hp bit h s bin ng hoc lch chun. V d: Kt qu phn tch 4 ln hm lng Mn theo mt phng php l 0,33; 0,32; 0,33; 0,34%. bin ng ca phng php l 5%. Xc nh hm lng Mn vi tin cy 0,95 ? 1. Kim tra theo chun Q: khng b i gi tr no. 2- Tnh lch chun 3- Tnh bin gii tin cy 4- Hm lng thc ca Mn:

214

TI LIU THAM KHO

1. Nguyn Tinh Dung (2001), Ha hc phn tch, Cn bng ion trong dung dch, Nxb Gio dc, H Ni. 2. Trn T Hiu (1984), Bi tp ha phn tch, Nxb i hc v Trung hc chuyn nghip. 3. Trn T Hiu (1999), Phn tch trc quang, Khoa Ha - Trng i hc Khoa hc T nhin - i hc Quc gia H Ni. 4. Phm Gia Hu - Trn T An (2002), Ha hc phn tch, tp 1 + 2, Trng i hc Dc H Ni. 5. Nguyn Vit Huyn (1999), C s cc phng php phn tch in Ha, Khoa Ha, Trng i hc khoa hc t nhin - i hc Quc gia, H Ni. 6. Phm Lun (2006), Phng php phn tch ph nguyn t, Nxb i hc Quc gia H Ni, 7. T Vng Nghi (2001), Ha hc phn tch phn I, Nxb i hc Quc gia, H Ni. 8. Trnh Xun Sen (2006), in ha hc, Nxb i hc Quc gia, H Ni

215

MC LC
PHN TH NHT C S L THUYT HA PHN TCH..................................................... 5 CHNG 1: DUNG DCH CHT IN LY - CN BNG HA HC .................................... 5 1.1. CHT IN LY V S IN LY ........................................................................................ 5 1.1.2. Cht in ly mnh, cht in ly yu ...................................................................................... 5 1.2. CN BNG HA HC .......................................................................................................... 6 1.3. HOT .............................................................................................................................. 13 1.4. CC LOI PHN NG S DNG TRONG PHN TCH TH TCH ............................ 14 1.5. NNG DUNG DCH. ..................................................................................................... 15 CU HI - BI TP CHNG 1 .............................................................................................. 19 CHNG 2: PHN NG AXIT - BAZ.................................................................................. 20 2.1. AXT BAZ .......................................................................................................................... 20 2.2. PHNG TRNH BO TON PROTON ........................................................................... 21 2.3. TNH pH TRONG CC DUNG DCH NC..................................................................... 23 2.4.CC V D TNH pH CA DUNG DCH: .......................................................................... 26 2.5. CN BNG AXIT - BAZ TRONG DUNG MI KHNG NC .................................. 27 CU HI V BI TP CHNG 2.......................................................................................... 30 CHNG 3: PHN NG TO PHC...................................................................................... 31 3.1. KHI NIM V PHC CHT............................................................................................. 31 3.2. TNH NNG CN BNG CA CU T TRONG DUNG DCH PHC CHT...... 33 3.3. NH HNG CA pH V CA CC CHT TO PHC PH N NNG CN BNG CA PHC. HNG S KHNG BN V HNG S BN IU KIN................... 38 3.4. PHC CHT CA CC ION KIM LOI VI AXIT ETILENDIAMINTETRAAXETIC. ....................................................................................................................................................... 42 3.5. NG DNG PHN NG TO PHC TRONG HA HC PHN TCH ....................... 47 CU HI - BI TP CHNG 3 .............................................................................................. 49 CHNG 4 PHN NG KT TA........................................................................................... 51 4.1. IU KIN TO THNH CHT KT TA...................................................................... 51 4.2. CC YU T NH HNG N TAN...................................................................... 52 4.3. KT TA PHN ON. ..................................................................................................... 57 4.4. KT TA KEO...................................................................................................................... 59 4.5. S HA TAN CC KT TA KH TAN TRONG NC. ............................................. 60 CU HI V BI TP CHNG............................................................................................. 68 CHNG 5 PHN NG OXY HO - KH ............................................................................. 70 5.1. KHI NIM V PHN NG OXY HO KH ................................................................. 70 5.2. TH OXI HO KH - CHIU CA PHN NG OXI HO KH .................................. 71

216

5.3. HNG S CN BNG CA PHN NG OXI HO KH.............................................. 76 CU HI - BI TP CHNG 5 .............................................................................................. 78 PHN TH HAI CC PHNG PHP PHN TCH HA HC........................................... 80 CHNG 1 PHN TCH KHI LNG .................................................................................. 80 1.1. NGUYN TC CHUNG CA PHNG PHP PHN TCH KHI LNG................ 80 1.2. YU CU CA DNG KT TA V DNG CN ......................................................... 81 1.3. CCH TNH KT QU TRONG PHN TCH KHI LUNG......................................... 82 CHNG 2 PHN TCH TH TCH ......................................................................................... 84 2.1. NHNG KHI NIM C BN CA PHN TCH TH TCH ........................................ 84 2.2. CC PHNG PHP PHN TCH TH TCH ................................................................. 89 2.3. NI DUNG V NG DNG CA CC PHNG PHP PHN TCH TH TCH.... 140 CU HI V BI TP CHNG 2........................................................................................ 150 1.2. PHNG PHP PH HP TH NGUYN T(AAS) ................................................... 163 CHNG 2 I CNG V SC K ................................................................................... 170 2.1. MT S KHI NIM C BN......................................................................................... 170 2.2. C S L THUYT CA SC K.................................................................................. 172 2.3. CC PHNG PHP TC SC K ................................................................................ 176 CHNG 3 CC PHNG PHP PHN TCH IN HO................................................ 181 3.1. PHNG PHP O TH .................................................................................................. 181 3.2. PHNGPHP CC PH V CHUN AMPE ....................................................... 190 PHN TH T SAI S TRONG PHN TCH X L S LIU THC NGHIM............ 203 I. CC NH NGHA V SAI S............................................................................................. 203 II. CC I LNG TRUNG BNH ....................................................................................... 205 III. CC I LNG C TRNG CHO PHN TN.................................................. 206 IV. CC LOI PHN B. ........................................................................................................ 207 V. BIN GII TIN CY. ........................................................................................................... 209 VI. KIM TRA THNG K CC D LI U THC NGHIM........................................... 211 VII. NH GI KT QU PHN TCH THEO THNG K ................................................ 213 TI LIU THAM KHO........................................................................................................... 215

217

You might also like