I.

THNG TIN V TC GI CA GIO TRNH

- H v tn: L Th Mi - Nm sinh: 1955 - C quan cng tc: B mn Ha phn tch - Khoa Ha - Trng i hc S phm Nng - Email: lemui55@yahoo.com.vn II. PHM VI V I TNG S DNG GIO TRNH: - Gio trnh c th dng tham kho cho cc ngnh: + Chuyn ha s phm + Ha k thut + Sinh mi trng + a l - Ti nguyn mi trng - Cc trng c th s dng: Bch khoa, S phm - Yu cu kin thc trc khi hc mn ny: Ha i cng, Ha v c - Gio trnh ny cha xut bn in.

I HC NNG TRNG I HC S PHM XY ZW

L TH MI

HA HC PHN TCH
(Gio trnh dng cho sinh vin chuyn ngnh Sinh Mi trng, Ha k thut)

Nng, 2006

LI M U
Ha hc phn tch l mn khoa hc v cc phng php xc nh thnh phn nh tnh v nh lng ca cc cht v hn hp ca chng. Nh vy, ha phn tch bao gm cc phng php pht hin, nhn bit cng nh cc phng php xc nh hm lng ca cc cht trong cc mu cn phn tch. Phn tch nh tnh nhm xc nh cht phn tch gm nhng nguyn t ha hc no, nhng ion, nhng nhm nguyn t hoc cc phn t no c trong thnh phn cht phn tch. Khi nghin cu thnh phn mt cht cha bit, phn tch nh tnh phi c tin hnh trc phn tch nh lng v vic chn phng php nh lng cc hp phn ca cht phn tch ph thuc vo cc d liu nhn c khi phn tch nh tnh cht . Phn tch nh tnh da vo s chuyn cht phn tch thnh hp cht mi no c nhng tnh cht c trng nh c mu, c trng thi vt l c trng, c cu trc tinh th hay v nh hnh, ... Phn tch nh lng cho php xc nh thnh phn v lng cc hp phn ca cht cn phn tch. Ni dung ca ha hc phn tch l gii quyt nhng vn chung v l thuyt ca phn tch ha hc, hon thin nhng lun thuyt ring v cc phng php phn tch hin c v s c xy dng. Ha hc phn tch ng vai tr quan trng v c th ni ng vai tr sng cn i vi s pht trin cc mn ha hc khc cng nh cc ngnh khoa hc khc nhau, cc lnh vc ca cng ngh, sn xut v i sng x hi. Ch cn n c mt v d: Mun tng hp mt cht mi ri nghin cu cc tnh cht cng nh nhng ng dng ca n nht thit phi s dng cc phng php phn tch thch hp xc nh thnh phn nguyn t, mc tinh khit, xc nh cu trc ca n. Chnh v th, Engel tng ni: Khng c phn tch th s khng c tng hp. Do c tm quan trng nh vy nn mt lot cc chuyn ngnh ca khoa hc phn tch ra i v ngy cng pht trin mnh nh: Phn tch mi trng, Phn tch khong liu, Phn tch hp kim, kim loi, Phn tch lm sng, Phn tch dc phm, Phn tch thc phm, ... Khi phn tch mt i tng no , nh phn tch phi thc hin cc bc sau y: a. Chn phng php phn tch thch hp v cc vn cn gii quyt. Khi thc hin bc ny cn phi c bit ch n tm quan trng, ngha php l v kinh t ca cng vic phn tch, ch n ng n, lp li v tnh kh thi ca phng php phn tch. b. Chn mu i din l mu c thnh phn phn nh ng nht cho thnh phn ca i tng phn tch. T mu i din tin hnh chn v chun b mu th nghim l mu dng tin hnh phn tch cht cn xc nh. Sau thc hin vic bin mu ny thnh dung dch phn tch. c. Tch cht: phn tch cc mu c thnh phn phc tp thng phi tch hoc l cc cht l, cc cht ngn cn php xc nh cht cn phn tch hoc tch ring

4 cht cn phn tch ra khi hn hp vi cc cht khc. d. Tin hnh nh lng cht cn phn tch, tc l thc hin cc thao tc, cc php o c phn tch xc nh nng hoc hm lng cht cn phn tch trong dung dch mu chun b trong bc trn. e. Tnh ton kt qu phn tch, nh gi tin cy ca cc kt qu . Tt c cc bc trn u c tm quan trng v lin quan mt thit vi nhau khng th b qua v coi nh bc no c. Ty thuc vo bn cht ca cc phng php phn tch m ngi ta chia chng thnh cc nhm ch yu sau: 1. Cc phng php ha hc: Cc phng php ny ra i sm nht, nn n nay ngi ta thng gi nhm phng php ny l nhm cc phng php phn tch c in. phn tch nh lng mt cht no bng phng php ny, ngi ta ch dng cc thit b v dng c n gin (nh buret, pipet, cn, ...) thc hin cc phn ng ha hc. Nhm phng php ny ch dng nh lng cc cht c hm lng ln (a lng) nhng chnh xc, cho nn n nay phng php ny vn c dng nhiu trong cc phng th nghim phn tch. 2. Cc phng php phn tch vt l: l nhng phng php phn tch da trn vic o cc tn hiu vt l ca cc cht phn tch nh ph pht x, phng x, ... cc phng php ny cn dng nhng my o phc tp. 3. Cc phng php phn tch ha l: l nhng phng php kt hp vic thc hin cc phn ng ha hc sau o cc tn hiu vt l ca h phn tch, nh s thay i mu sc, c, pht quang, dn in, ... Cc phng php phn tch ha l cng nh vt l i hi phi dng nhng my o phc tp, v vy chng c tn chung l cc phng php phn tch cng c. Cc phng php phn tch cng c ra i sau cc phng php phn tch ha hc, chng cho php phn tch nhanh, c th xc nh lng nh cht phn tch kh chnh xc nn c ng dng rt rng ri. Vi s pht trin v bo ca k ngh in t, cc ngnh k thut mi v nhng yu cu ngy cng cao ca cc ngnh khoa hc v cng ngh sn xut hin i i hi v thc y cc phng php phn tch cng c ngy cng c pht trin v hon thin p ng cc nhim v ngy cng nng n ca ngnh phn tch hin i. C s l thuyt chung ca ha hc phn tch l l thuyt v cc phn ng ha hc dng trong phn tch. Trong gio trnh ny ch cp n l thuyt ca cc loi phn ng phn tch v cc phng php ha hc s dng cc loi phn ng . Chng ti xin chn thnh cm n mi c gi gp kin ph bnh v ngh v quyn sch ny. Tc gi

CHNG 1

DUNG DCH CHT IN LY CN BNG HA HC

1.1. Cht in ly mnh v yu. Cc cht in ly mnh trong dung dch thc t phn ly hon ton. a s cc mui tan, kim v axt mnh u thuc nhm ny. Trong dung dch, cc cht in ly yu phn ly khng hon ton. Cc axit yu, baz yu v phc cht l cc cht in ly yu. 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 (hng s cn bng). in ly v hng s in ly lin h vi nhau theo h thc Ostvant nh sau:
K=C 2 , trong c l nng ban u ca cht tan. 1

1.2. Cn bng ha hc v hot . 1.2.1. Nhc li mt s kin thc cn dng Trong ha hc, khi tnh ton ngi ta hay dng nng mol/l, cn phn bit cc khi nim: Nng gc C0 l nng ca cht trc khi a vo hn hp phn ng. Nng ban u C l nng ca cht trc khi tham gia phn ng. Nng ban u khc vi nng gc l do s thay i th tch khi trn cc thuc th vi
nhau: C i =
C i0 Vi0 . V

Vi0 l th tch thuc th i ly a vo hn hp phn ng. V l tng th tch ca hn hp phn ng. Khi mt phn ng t trng thi cn bng th nng cc cht tham gia phn ng ti thi im c gi l nng cn bng. Nng cn bng thng c k hiu trong ngoc vung [ ]. V d: Trong dung dch HCl: HCl = H+ + Cl- th [HCl] = 0 nn CHCl = [Cl-] Trong dung dch CH3COOH: CH3COOH CH3COO- + H+
C CH 3COOH = [CH 3 COOH] + [CH 3 COO ]

Theo nh lut bo ton nng th nng ban u ca mt cu t no bng tng nng cn bng ca cc dng tn ti ca cu t trong dung dch ti thi im cn bng. V d: Biu din nh lut bo ton nng ban u i vi ion PO43- trong dung dch Na3PO4 0,1M. Trong dung dch ta c Na3PO4 = 3Na+ + PO43- ; H2O H+ + OH+ 32PO4 + H HPO4 + 2HPO4 + H H2PO4+ H2PO4 + H H3PO4

6
C Na 3PO 4 = C PO3 = 0,1
4

2 C PO3 = 0,1 = [PO 3 4 ] + [ HPO 4 ] + [ H 2 PO 4 ] + [ H 3 PO 4 ]

4

Mt dng khc ca nh lut bo ton nng l nh lut bo ton in tch. Theo nh lut ny th m bo tnh trung ha in ca dung dch cht in ly, tng in tch m ca cc anion c mt trong dung dch phi bng tng in tch dng ca cc cation c mt trong dung dch. S in tch tuyt i tng loi ion c c bng s ion tng ng c mt trong dung dch nhn vi in tch ca n. Nh vy tng in tch q m mi loi ion c bng tch nng cn bng ca ion vi s Avgar N v in tch n ca mi ion. q = N[ ]n V d: Trong dung dch Na3PO4 trn ta c: N[Na+] + N[H+] = N[OH-] + N[H2PO4-] + N[HPO42-].2 + N[PO43-].3 V ta c: [Na+] + [H+] = [OH-] + [H2PO4-] + 2[HPO42-] + 3[PO43-].

1.2.2. Cn bng v hng s cn bng. Trong ha hc phn tch ta thng phi tnh nng cn bng ca cc cht tham gia v c to thnh trong cc phn ng phn tch, tc l nng ca cht khi phn ng t ti trng thi cn bng. tnh cc nng cn bng, ngi ta thng s dng biu thc ca hng s cn bng c thit lp bng cch dng nh lut tc dng khi lng. Gi s xt cn bng ha hc: mA + nB + ... pC + qD + ... trong A, B, C, D ... l nhng cu t tham gia cn bng m chng khng tch in. p dng nh lut tc dng khi lng, ta c:
[ C] p [ D ] q =K [A]m [B]n

(1.1)

trong [A], [B], [C], [D], ... l nng cn bng ca cc cht A, B, C, D, ... v K l hng s cn bng, l i lng ch ph thuc vo nhit . Nu A, B, C, D, ... l nhng ion th ta phi tnh n s tng tc gia chng vi nhau nn trong biu thc (1.1) ta phi thay nng bng hot . Hot a ca mt cht c xc nh bng h thc: a = fC (1.2) trong , C l nng ca ion; f l h s hot . i lng f ph thuc vo lc ion ca dung dch. Lc ion biu th tng tc tnh in gia cc ion trong dung dch. Nu Z1, Z2, ... l in tch v C1, C2, ... l nng ca cc ion trong dung dch th lc ion c xc nh bng h thc:
1 2 = ( Z1 C1 + Z 2 2 C 2 + ...) 2

(1.3a) (1.3b)

Hoc di dng tng qut:

= 1 i 2 Zi Ci 2 i =1

Nu gn bng 0 tc l dung dch rt long, tng tc tnh in gia cc ion khng ng k, th f bng 1, hot bng nng .

* Khi < 0,02 th f c tnh bng h thc: V d 1: Tnh hot ca cc ion trong dung dch hn hp KCl 10-3M, MgSO4 10 M. Tnh lc ion ca dung dch: = 0,5(1.10-3 + 1.10-3 + 22.10-3 + 22.10-3) = 5.10-3
-3

1 lg f = Z 2 2

(1.4)

= 7.10 2 = 0,07

Tnh h s hot ca cc ion: log f = lg f Cl = 0,05.1.0,07 = 0,035

f K + = f Cl = 0,92 log f Mg 2 + = log f SO 2 = 0,5.2 2.0,07 = 0,14

4

f Mg 2 + = f SO 2 = 0,72
4

Tnh hot cc ion:

a K + = a Cl = 0,92.10 3 = 9,2.10 4 mol.l 1

a Mg 2 + = a SO2 = 0,72.10 3 = 7,2.10 4 mol.l 1

4

* Khi 0,02 < <0,2 th f c tnh bng h thc:

log f = 0, 5 Z2 1+

(1.5)

V d 2: Tnh hot ca cc ion trong dung dch KCl 0,1M. Lc ion ca dung dch: = 0,5(12.0,1 + 12.0,1) = 0,1.
= 0,32

H s hot ca cc ion:
log f K + = lg f Cl = 0,5.12.0,32 = 0,121 1 + 0,32

f = 0,757 Hot ca cc ion:

a K + = a Cl = 0,757.10 1.mol.l 1

* Khi > 0,2 th h s hot f c tnh bng cng thc:

log f = 0,52 Z2 1+ + h

(1.6)

trong h l h s thay i cng vi ion. Thc nghim cho thy rng, trong dung dch long c lc ion gn ging nhau th f ca cc ion c in tch bng nhau gn ging nhau (bng 1.1)

Lc ion () 0,001 0,005 0,01 0,05 0,1

in tch 1 0,96 0,92 0,89 0,81 0,77

Bng 1.1 H s F in tch 2 in tch 3 0,73 0,86 0,51 0,72 0,39 0,63 0,15 0,44 0,08 0,33

in tch 4 0,56 0,30 0,19 0,04 0,01

Nu A, B, C, D, ... trong h thc (1.1) l nhng ion, tc l nhng phn t tch in, th biu thc hng s cn bng c dng sau:
p q aC aD = Ka m n aAaB

(1.7)

Trong trng hp ny, Ka c gi l hng s cn bng hot hay hng s cn bng nhit ng, i lng ny ch ph thuc vo nhit (khng ph thuc vo hot ). Thay a = fC vo biu thc (1.7):
Ka =
p q p q [C] p [D]q ...f C fD fC fD = K C m n m n m n [A] [B] ...f A f B fA fB

(1.8)

trong , Kc c gi l hng s cn bng nng , i lng ny ph thuc vo nhit . Cc hng s cn bng ca cc h khc nhau, v d hng s axit, hng s baz, tch s ion ca nc, tch s tan ca cc cht kh tan, hng s bn v khng bn ca cc phc cht ghi trong cc ti liu thng l cc hng s hot . Trong thc t, tnh ton c n gin, khi tnh nng cc ion trong dung dch, hng s cn bng hot thng c coi bng hng s cn bng nng , tc l ta b qua s tng tc tnh in ca cc ion trong dung dch v coi h s hot bng 1. Kt qu tnh ton, nh vy s thiu chnh xc. Nhng v ta thng dng cc dung dch long nn sai s c th nm trong gii hn c th chp nhn c. Trong cc chng sau, n gin ha vic tnh ton, h s hot thng c coi bng 1. Gi s chng ta phi xt cn bng trn m cc cht A, B, C, D, ... trong cn tham gia vo cc phn ng ph khc (nh phn ng trao i proton, phn ng to phc cht, phn ng to kt ta) th nng ca chng tham gia vo cn bng trn s gim i, ngha l cc phn ng ph nh hng n cn bng . biu th nh hng ca cc phn ng ph n cn bng , ngi ta thng dng mt dng hng s gi l hng s iu kin. Gi [A], [B], [C], [D], ... l tng nng cn bng ca cc dng ca A, B, C, D, ... trong dung dch th [A], [B], [C], [D] ch bng mt phn ca cc nng [A], [B], [C], [D], tc l: [A] = [A]A ; [B] = [B] B trong A, B l cc h s nh hn 1 l nhng i lng biu th nh hng ca cc phn ng ph ti nng ca A, B, C, D, ... t do. Thay cc nng cn bng [A], [B], ... trn vo h thc biu din hng s cn bng nng ca cn bng trn, ta c:

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p q p p q [ C] p C [ D] q q [ C] p [ D ] q C D C D [C]p [D]q ... D = = = K ' m n m m n n m n m n m n [A] [B] ... [A' ] A [B' ] B [A] [B] A B AB

Kc =

(1.9)

i lng K trong h thc (1.9) c gi l hng s cn bng iu kin, n khng nhng ph thuc vo nhit , vo lc ion ca dung dch m cn ph thuc vo c nng ca cc cht khc tc l ph thuc vo iu kin ca dung dch trong cn bng chnh (a) c thit lp. Cc v d c th s c trnh by trong cc chng sau. Trong cc phng php ha hc ni ring cng nh trong tt c cc phng php ca phn tch ni chung, ngi ta thng nghin cu s dng cc loi cn bng chnh sau y: - Cn bng axit - baz (hoc cn bng trao i proton) - Cn bng to phc. - Cn bng kt ta. - Cn bng oxy ha kh (hoc cn bng trao i electron). Trc khi i vo xt c s l thuyt ca cc loi cn bng trn v ng dng ca chng trong cc phng php ha hc cng nh ha l ca chng, chng ta hy cp n nguyn tc ca cc phng php ha hc: phng php phn tch khi lng v phn tch th tch.

TI LIU THAM KHO

1. Hong Minh Chu, T Vn Mc, T Vng Nghi. C s ha hc phn tch, NXB KH & KT, 2002. 2. L c, Ha hc phn tch. NXB H Quc Gia H Ni, 2002. 3. Nguyn Tinh Dung phn I, II, III. Ha hc phn tch. NXB Gio dc, 2000. 4. Trn T Hiu, Ha hc phn tch, NXB HQG H Ni, 2002.

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CHNG 2

I CNG V PHN TCH KHI LNG V PHN TCH TH TCH

2.1. Nguyn tc chung ca phng php phn tch khi lng Phng php phn tch khi lng l phng php phn tch nh lng c in. Tuy phng php ny ra i lu nhng n nay n vn ng vai tr c lc trong cc phng php xc nh, nht l xc nh cht c hm lng ln v trung bnh trong mu phn tch. Phng php ny c th dng xc nh hu ht cc nguyn t c chnh xc v tin cy cao. y l phng php phn tch nh lng da vo kt qu cn khi lng ca sn phm hnh thnh sau phn ng kt ta bng phng php ha hc hay phng php vt l. Do cht phn tch chim mt t l xc nh trong sn phm em cn nn da vo khi lng ca sn phm em cn d dng suy ra lng cht phn tch trong i tng phn tch. Qu trnh phn tch mt cht theo phng php khi lng: - Chn v gia cng mu. - a mu vo dung dch (ph mu) v tm cch tch cht nghin cu khi dung dch (lm phn ng kt ta hay nh phn). - X l sn phm tch ra bng cc bin php thch hp (ra, nung, sy, ...) ri em cn tnh kt qu. V d: xc nh magie, ngi ta tin hnh nh sau: Ha tan mu phn tch trong dung mi thch hp chuyn ton b lng magie vo dung dch di dng ion Mg2+. Ch ha dung dch bng cc thuc th thch hp kt ta hon ton v chn lc ion Mg2+ di dng hp cht kh tan MgNH4PO4. Lc, ra kt ta ri sy v nung 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 Mg trong mu phn tch. Trong v d ny hp cht MgNH4PO4 c kt ta tch nh lng magie nn c gi l dng kt ta cn Mg2P2O7 l hp cht c to thnh sau khi nung dng kt ta v c cn xc nh hm lng ca magie nn c gi l dng cn. Phng php phn tch khi lng magie 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. 2.2. Gii thiu v cc phng php phn tch khi lng. 2.2.1. Phng php y. Da vo vic tch thnh phn cn xc nh dng n cht ri cn. V d: Xc nh lng vng trong mt hp kim nh sau: ha tan hp kim bng nc cng toan 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, lm ngui ri cn. 2.2.2. Phng php kt ta. Trong phng php ny ta dng phn ng kt ta tch cht nghin cu ra khi

11 dung dch phn tch, thu ly kt ta, lc, ra, em nung ri cn kt qu. V d: Khi cn phn tch lng st (Fe) trong mt dung dch ta c th dng phn ng to kt ta Fe(OH)3 bng thuc th nh NH3, lc kt ta Fe(OH)3, nung v cn dng Fe2O3, t khi lng Fe2O3 thu c ta d dng tnh c lng Fe trong dung dch nghin cu. 2.2.3. Phng php in phn Ngi ta in phn tch kim loi cn xc nh trn catt bch kim. Sau khi kt thc in phn, em sy in cc ri cn v suy ra lng kim loi thot ra trn cc bch kim. Phng php ny thng c dng xc nh cc kim loi trong mi trng m pH = 7. 2.2.4. Phng php chng ct Trong phng php ny cht em phn tch c chng ct trc tip hay gin tip. Trong phng php chng ct trc tip, cht em phn tch c chuyn sang dng bay hi ri hp th n vo cht hp th thch hp. Khi lng ca cht hp ph tng ln mt lng tng ng vi cht hp th vo. V d: Khi cn phn tch CO2 trong vi ta c th phn hy lng cn mu trong mt dng c ring bng axt ri hp th ton b kh CO2 gii phng ra vo cht hp th thch hp nh hn hp CaO v NaOH hay Ba(OH)2. Cn khi lng cht hp th trc v sau khi hp th s tnh c lng CO2 trong vi. Trong phng php chng ct gin tip, ngi ta un cho bay hi ht cht cn phn tch. V d: C th xc nh hm lng nc kt tinh trong cc loi mui bng cch sy di mt nhit xc nh. Ni chung phng php chng ct khng phi l ph bin v n ch c p dng khi mu phn tch c cha cht bay hi hoc d dng chuyn sang cht bay hi. Sau y ta ch nghin cu 2 phng php chnh, l phng php kt ta v phng php in phn. 2.3. Phng php kt ta. 2.3.1. Ni dung v yu cu ca kt ta trong phng php kt ta. Phng php kt ta l phng php da vo vic cn sn phm tch ra bng phn ng kt ta. Trong phng php ny ngi ta thc hin mt lot cc thao tc nh lc, ra, sy, nung, ... Trong qu trnh nung, thnh phn ca kt ta c th thay i. V vy ngi ta phn bit 2 dng: dng kt ta v dng cn. 2.3.1.1. Yu cu ca dng kt ta. - Dng kt ta phi c tan nh th mi kt ta c hon ton cht cn xc nh. Thc t cho thy rng i vi cc kt ta loi AB, v d: BaSO4, AgCl, ... th tch s tan phi b hn 10-8 mi s dng c cn tch s tan ln hn 10-8 th khng s dng. Cht phn tch c lm kt ta mt cch nh lng, v d kt ta ti 99,99%. - Dng kt ta phi tinh khit, tinh th ht to khi lp l giy lc, gim bt hin tng cng kt v d lc, ra c th tch ra khi dung dch mt cch nhanh chng v thun li nht. Kt ta v nh hnh v c bit l li ng t nh Al(OH)3 c b mt tip xc ln nn hin tng cng kt y rt ln, kh ra v lc rt chm. Trong mt s trng hp, ngi ta c th to iu kin thch hp thu nhn c kt ta tinh th ht ln.

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- Dng kt ta phi d dng chuyn sang dng cn. 2.3.1.2. Yu cu ca dng cn - Thnh phn kt ta sau khi sy hoc nung phi ng ng cng thc nh trc. V d: Al(OH)3 c dng cn thng ngm mt s phn t nc nn mun chuyn thnh dng Al2O3, ta phi nung n nhit trn 11000C. Trong trng hp ny ta c th chn dng kt ta l cc mui baz ca nhm chuyn thnh Al2O3 ngay nhit 6400C hn dng Al(OH)3. - Kt ta thu c sau khi nung phi bn v t ht m, kh b oxy ha trong khng kh. Yu cu ny cng nhm m bo cho cht sau khi nung ng vi cng thc nh trc. V d: Kt ta CaO d dng hp ph H2O v CO2 t khng kh, thng ngi ta chuyn sang dng CaSO4 bng cch cho tc dng vi axit sunfuaric. - Hm lng ca cht cn phn tch trong dng cn cng t cng tt. Nh vy s gim c sai s h thng ca kt qu phn tch. V d: Cng mt i lng v sai s tuyt i, trong khi xc nh Cr di dng kt ta BaCrO4 v Cr2O3 th sai s v lng Cr tm c trong BaCrO4 s b gp 3,5 ln khi tm Cr2O3. V d: Khi xc nh Cr, nu mt i 1mg kt ta th i vi dng cn l Cr2O3 s mt i 0,7mg Cr cn vi dng BaCrO4 ch mt 0,2mg Cr. 2.3.2. iu kin tin hnh phn tch theo phng php kt ta. 2.3.2.1. Thuc th. Thuc th dng trong phn tch khi lng c th l thuc th hu c hay v c. Trong qu trnh to kt ta hin tng cng kt xy ra rt mnh, trong s ion b cng kt c c ion ca thuc kt ta m khi ra cng khng th sch hon ton c. V vy cn chn thuc th d bay hi hoc d phn hy trong qu trnh nung sy. V d: khi kt ta Fe3+ di dng Fe(OH)3 th dng NH4OH ch khng dng KOH hay NaOH, kt ta Ba2+ th dng H2SO4 ch khng dng Na2SO4 hay K2SO4. Ag+ th dng HCl ch khng dng NaCl. Nhng nguyn tc ny khng phi dng lc no cng c. V d: kt ta Cu(OH)2 ngi ta khng dng NH4OH bi nu tha NH4OH s to phc [Cu(NH3)4]2+ m phi dng KOH hay NaOH. Trong trng hp ny cn phi ra kt ta cn thn. Thuc th cng c chn lc cao cng tt. V nh vy s trnh c hin tng cc kt ta khc cng kt ta theo kt ta chnh. V d: khi xc nh ion Al3+ bng NH4OH v cn di dng Al2O3. Nu c mt Fe3+ th cng to Fe2O3. Do trong trng hp ny ngi ta dng Na2S2O3: 2Al3+ + 3S2O32- + 3H2O 2Al(OH)3 + 3S + 3SO2 Lc v ra kt ta (Al(OH)3 + S) ri nung th lu hunh chy ht cn Al2O3. Ion Fe3+ trong trng hp ny khng kt ta m b kh ti Fe2+. Lng thuc th cng ng vai tr rt quan trng trong phng php khi lng. Thc t cho thy rng khng tn ti kt ta no m li hon ton khng tan trong nc. Do vy tch s tan lun lun ln hn 0. T ta thy rng khng th kt ta hon ton bt k mt cht t tan no t dung dch. Trong phn tch nh tnh ngi ta thy rng qu trnh kt ta c coi l hon ton khi lng ion cn xc nh cn li trong dung dch t n mc m khng th dng phn ng no nhn ra c. Tng t nh vy trong phng php khi lng qu trnh kt ta c coi l

13 hon ton khi hm lng ion cn li trong dung dch khng vt qu 0,0002g. Thng thng th i vi cc kt ta c tan b ta ch cn lng thuc kt ta tng ng vi lng tnh theo phng trnh phn ng l thu c kt ta hon ton. Khi kt ta c tan khng nh hoc cht phn tch trong dung dch kh long, m bo kt ta hon ton ta cn tng lng thuc kt ta lm gim tan ca kt ta. C nhiu trng hp vic tng lng thuc kt ta khng nhng lm gim tnh tan m cn lm tng tnh tan theo hiu ng mui, s to phc, mui axit tan, do kt ta l lng tnh ... Thng ngi ta dng lng thuc th d gp 1,5 ln lng cn thit tnh theo phng trnh phn ng. 2.3.2.2. Nng thuc th. i vi kt ta l dng v nh hnh hay tinh th ta c yu cu v nng khc nhau. - Kt ta v nh hnh: Vi kt ta v nh hnh th tt nht l kt ta t cc dung dch c, nng. Khi lm kt ta v nh hnh ta cn ch n xu hng d to thnh dung dch keo ca chng. Mun lm ng t keo th ngi ta cho thm cht in ly no c ion khc du vi ion b hp ph: cc mui amonium hoc cc axit (nu axit khng lm tng ha tan ca kt ta). Sau khi kt ta xong d lc v gim s nhim bn do hp ph, ta pha long dung dch gp i bng nc ct nng. Lc ny cn bng hp ph s b ph v mt phn ion b hp ph s li ri b mt kt ta i vo dung dch. Kt ta thu c s chc, t b nhim bn. Sau khi lm kt ta phi lc v ra ngay ch khng nn lu, lu l bt li v trong mt s kt ta c th b c qunh li khng ra sch c. Ngoi ra khi lm kt ta v nh hnh ta thng dng cc dung dch kim cho nn kt ta s b nhim bn cc cht kh bay hi. V d SiO2 t thy tinh ln vo. - Kt ta tinh th Vi kt ta l tinh th, c kt ta ln ht ta phi lm gim qu bo ha ca dung dch bng cch kt ta t dung dch long. tng tan S ca kt ta trong qu trnh kt ta ngi ta tng nhit hay thm cht no tng tan. Sau khi kt ta xong cn lm mui kt ta bng cch ngm mt thi gian kt ta vo trong nc ci thu c kt ta c kch thc ln, ng u, d lc, d ra. Ni chung thu c kt ta tinh th phi tun theo 5 nguyn tc (xem trang 129). C ch ca qu trnh lm mui kt ta tinh th nh sau: V tinh th ln c ha tan b nn dung dch bo ha i vi tinh th ln vn cha bo ha i vi tinh th b nn tinh th b phi tan ra. Lc ny dung dch li thnh qu bo ha i vi tinh th ln v cht tan li bm ln b mt tinh th ln. By gi dung dch li thnh cha bo ha i vi tinh th b do tinh th b li tip tc tan ra. Nhit tng s lm tng tc lm mui kt ta. Sau khi lm mui ta c khng nhng mt kt ta d lc m cn tinh khit hn. i vi cc loi kt ta keo k nc th hiu qu ny khng r lm v trong vi trng hp cn cho kt qu xu. V d ngi ta xc nh c l lng cc ion Co2+, Ni2+, Zn2+ b kt ta Fe(OH)3 ko theo s tng dn theo thi gian. iu c ngha l c s hnh thnh dn nhng hp cht ha hc (cc ferit) gia hydroxyt st v cc cation k trn. gim s hao ht do tnh tan, trc khi lc ngi ta thng lm lnh lm gim tnh

14 tan ca kt ta. 2.3.2.3. Lng cht phn tch. Lng cn cht ly phn tch phi khng qu nh hoc qu ln. Lng cn ln qu s thu c qu nhiu kt ta v gy kh khn cho vic lc, ra, nung. Tri li lng cn qu nh th dung dch sau khi ph mu kh long v c th kh tch hon ton cht cn phn tch, do kt qu phn tch s kh chnh xc. Theo Tananaep lng cn phi ly th no cho lng cn kt qu phn tch vo khong 0,01ng lng gam i vi kt ta l tinh th v 0,005 ng lng gam i vi kt ta l v nh hnh. 2.3.2.4. Nhit . i vi kt ta tinh th th vic un nng c tc dng lm tng tan, lm gim qu bo ha tng i v gim c s trung tm kt tinh ban u, to c kt ta tinh th to ht. i vi kt ta v nh hnh, vic un nng gip ng t v lm to ht. i vi kt ta c tan tng khi un nng th trc khi lc phi lm ngui v phi ra bng nc ra ngui. i vi kt ta keo c tan b nh Fe(OH)3 th phi lc nng v ra bng nc ra nng trnh s pepti ha. 2.3.3. Lc, ra, lm kh v nung kt ta. 2.3.3.1. Lc kt ta. Khi lc ngi ta thng dng giy lc khng tn l giy lc c lm sch gn ht cc cht v c bng cch ra vi HCl v HF. Khi chy chng ch li mt lng tro khng ng k, lng ny c ghi v bc cc gi giy lc khng tn. Giy lc khng tn c nhiu loi dy mng khc nhau ng vi kch thc ca cc phn t kt ta cn lc. V d mun lc cc kt ta keo v nh hnh rt kh lc th ta nn dng giy lc mng nht, chy nhanh nh giy bng hay en. Mun lc a s cc kt ta khc th dng loi giy trung bnh (bng trng) v cui cng mun lc nhng kt ta rt b ht nh BaSO4 hoc CaC2O4 th nn dng loi giy dy nht (bng xanh). 2.3.3.2. Ra kt ta. Mc ch ra kt ta l ui ht cht bn, k c dung dch nc ci dnh kt ta. Thnh phn nc ra: c 4 trng hp - Ra bng dung dch thuc kt ta: Ch trong nhng trng hp him c khi ha tan ca kt ta l rt b ta mi phi b qua bin php ny. Khi ra kt ta ta cn phi cho thm vo nc ra mt ion ca kt ta, v d dng mt dung dch long ca thuc kt ta ra. V tch s hot cc ion l hng s nn khi tng nng ca mt ion trong dung dch th ha tan ca kt ta s gim n mc c th b qua c. Tt nhin l ion thm vo (hoc mt cht in gii no khc c cha ion ca kt ta) phi l mt cht d bay hi khi nung ta c th ui n ra ht khi kt ta. - Ra bng dung dch cht in ly: Mun ngn nga hin tng ha keo ta khng nn ra kt ta bng nc ct m nn dng dung dch long ca mt cht in ly no . Lc by gi cc ion b hp ph trc s b ra sch v kt ta s li hp ph cc ion ca cht in ly dng ra, y c s hp ph thay th. Cht in

15 ly phi d bay hi hay mui amnium. - Ra bng cht ngn c kt ta khi thy phn: V d kt ta MgNH4PO4 l mt cht c sn phm thy phn l NH4OH: MgNH4PO4 + H2O MgHPO4 + NH4OH nn s c ra bng mt dung dch amoniac long. - Ra bng nc: Trong nhng trng hp kt ta khng b mt do ha tan cng khng to c dung dch keo v khng b thy phn th c th dng nc ct ra kt ta. Trong a s trng hp nc ra cn phi c un nng v nh vy s lm gim c h s nht v cc dung dch nng s lc nhanh hn. K thut ra: Trc ht ra bng cch lng v ch khi gn sch ta mi ra kt ta trn giy lc. Ci li ca cch ra ny l kt ta d trn ln vi nc ra v ng thi cc phn t kt ta li khng bt l giy lc. Thng ta ra bng cch lng vi ln ri mi chuyn ton b kt ta ln giy lc. y l lc quan trng nht: Nu nh mt mt git cht lng l kt qu phn tch c th b hng. 2.3.3.3. Lm kh v nung kt ta. Sau khi ra, y phu bng mt t giy lc gi cho kt ta trnh khi b bi v trnh c chuyn ng ca khng kh, t phu vo t sy khong 20 30 pht nhit khong 90 1050C. Sau em nung trong chn s hoc chn bch kim n khi lng khng i. K thut nung: Dng a thy tinh c u nhn ko giy lc ra khi phu, gp mp giy th no kt ta tn ra xung quanh giy ri em b vo chn, cho nh nhn quay ln trn v nung cho n khi c trng lng khng i. Nu dng l in th trc ht phi t giy lc n (hoc bp in) v ch sau khi ht khi mi b vo l nung. Sau khi nung xong (khong 30 pht) cho chn vo bnh lm kh (bnh ht m) chn khi hp th hi nc trong khng kh v khi tng trng lng. Khng nn y bnh ngay m phi sau vi pht hy y v nu khng th khi chn ngui trong bnh s c khong chn khng v ta kh m np bnh.

2.4. Phng php in phn. 2.4.1. Ni dung. in phn l phng php da vo vic cn xc nh khi lng kim loi thot ra trn in cc bch kim di tc dng ca dng in. Phng php in phn thng dng xc nh mt s kim loi trong cc hp kim. Phng php ny c coi l phng php chnh xc xc nh mt s nguyn t nh Ni, Cu, Zn, Cd, v Pb trong hp kim. 2.4.2. Cc thit b. 2.4.2.1. in cc: Thng l in cc bch kim c ch to theo nhiu kiu khc nhau. Catt thng l li an bng si bch kim c hnh tr. Ant c th l li hoc dy xon bch kim. Trong mt s trng hp ngi ta cn dng in cc bch kim dng bt a bch kim. Ngoi ra cn dng cc in cc bng Ni, Ag, Au, ... (hnh 2.1)

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2.4.2.2. Ngun in: Ngun in thng dng khi in phn l cc c-qui kim hay axit c th khong 12V hay 36V. Ngi ta thng dng my pht in mt chiu hay chnh lu. 2.4.2.3. Cc thit b o: Ch yu l cc ng h o in nh vn k, ampe k.
Cc a

Cc xon

Cc li

Cc bt

Hnh 2.1: Cc loi in cc bch kim thng dng 2.4.2.4. Cc thit b khc: Bin tr con chy, my khuy in th k. Ngy nay ngi ta ch to cc my in phn chuyn dng trong phng th nghim. 2.5. ng dng ca phng php khi lng. Khi lng cht phn tch ln th phng php khi lng l phng php tin cy v chnh xc. Phng php ny cho php xc nh hu ht cc nguyn t cn gp trong thin nhin. Nhc im ca phng php l mt nhiu thi gian, nhiu khi khng p ng c nhu cu kim tra nhanh trong nghin cu v sn xut. Tuy vy v c tin cy v chnh xc cao cho nn n nay phng php ny vn c coi l phng php trng ti nh gi tnh ng n ca cc kt qu phn tch theo cc phng php khc nhau. 2.6. Phng php phn tch th tch 2.6.1. i cng Khc vi phng php khi lng, phng php phn tch th tch khng cn c vo khi lng sn phm phn ng m cn c vo th tch thuc th em dng cho phn ng suy ra lng cht cn xc nh. Thuc th y bit nng chnh xc. Gi s cn phn tch mt dung dch cht A, ta phi dng thuc th l dung dch cht B bit nng chnh xc ri cho tc dng theo phn ng: A+B=C+D Phi cho dung dch cht B vo tc dng vi cht A th no cho lng cht B tc dng vi cht A va theo phng trnh phn ng trn. Theo nh lut ng lng hoc nh lut hp thc, ta d dng tm ra nng cht A. Phng php ny nhanh hn phng php khi lng. Ngi ta ch cn o chnh xc th tch ca thuc th em dng m khng cn tch, ch ha kt ta v cn. Vn quan trng y l phi c bin php bit lc no l phn ng hon thnh. 2.6.2. Mt s nh ngha v khi nim + Nh v d nu trn, qu trnh thm t t dung dch chun cht B t burt vo

17 dung dch cht xc nh A tin hnh phn ng phn tch gi l qu trnh nh phn (s nh phn) hay s chun . + Thi im m cht B thm vo va tc dng ht vi cht A theo phng trnh phn ng gi l im tng ng. + nhn bit c im tng ng thng ngi ta dng cht ch th. Cht ch th c c tnh thay i mu ti im tng ng trong qu trnh nh phn. Thi im m mu ca ch th thay i r rt da vo ta kt thc s nh phn c gi l im kt thc s nh phn hay im cui. + Trong trng hp l tng th im kt thc nh phn trng vi im tng ng. Nhng trong thc t im kt thc nh phn thng sai lch vi im tng ng. iu ny gy ra sai s cho php nh phn. + Dung dch cht B bit nng chnh xc gi l dung dch chun (hay tiu chun). C hai phng php pha dung dch chun: * Cn trn cn phn tch (chnh xc n 0,0002g) mt lng cht no , sau ha tan vo bnh nh mc. Bit c lng cht (g), th tch dung dch thu c, ta d dng tnh chun ca n: T = g/ml. * Trong thc t pha dung dch chun ngi ta thng dng cc ng chun fixanal. l nhng ng thy tinh c hn kn 2 u, trong c cha mt lng cht kh no c cn chnh xc hoc mt th tch chnh xc ca dung dch chun cn thit pha 1 lt dung dch vi nng bit chnh xc, v d: 0,1N; 0,05N Dung dch chun bit nng chnh xc nh trong trng hp ny gi l dung dch gc v cht tng ng gi l cht gc, dung dch gc cn gi l dung dch tiu chun. Yu cu ca cht gc + Phi tinh khit v mt ha hc, tp cht khng ln hn 0,05 - 0,1%, c th kt tinh li c v sy kh mt nhit nht nh. + Thnh phn ha hc phi ng ng vi cng thc ha hc. V d cc tinh th ngm nc phi ng vi s phn t theo cng thc ha hc. + Cht gc v dung dch tiu chun phi bn trong thi gian gi gn v nng phi khng i theo thi gian. + Mol ng lng ca cht gc cng ln cng tt tng chnh xc khi xc nh nng ca dung dch. S d gi l dung dch tiu chun v n c s dng xc nh nng ca cc cht khc. Nhng trong thc t khng phi mi dung dch chun u p ng c yu cu trn. V d HCl, NaOH Do vy i vi loi cht ny ngi ta pha vi nng gn ng (dng ng ong, cn k thut). Sau ngi ta dng dung dch chun gc xc nh li nng ca dung dch trn. V d nng ca dung dch NaOH c th xc nh bng dung dch gc l axit oxalic (H2C2O4.2H2O). Dung dch chun m nng ca n ngi ta xc nh c nh dung dch gc gi l dung dch c chun ha hay dung dch chun. Trong thc t nng ca dung dch chun khng phi lc no cng c xc nh bng mt dung dch gc no . V d xc nh nng dung dch NaOH c

18 th dng dung dch chun HCl, nng ca dung dch ny li c xc nh bng dung dch gc khc. V d: dung dch gc borat natri Na2B4O7.10H2O hay Na2CO3 khan. Bng phng php ny c th tit kim c cht gc nhng li km chnh xc hn v sai s s l tng sai s ca cc php chun . C trng hp ngi ta xc nh nng bng phng php trng lng. V d xc nh nng HCl c th theo AgCl bng cch cho dung dch HCl tc dng vi dung dch AgNO3. Cui cng khi phn tch cc hp cht t nhin hay cc sn phm cng nghip ngi ta dng cc mu tiu chun xc nh nng ca dung dch chun. Mu chun l mu trong c cha nguyn t cn phn tch nhng bit nng chnh xc. V d khi xc nh Mn trong thp, ngi ta dng dung dch chun l Na3AsO3, nng ca n c xc nh bng mu thp chun c cha mt hm lng Mn chnh xc bit trc, hoc khi xc nh ng trong ng thau th xc nh nng ca dung dch chun Na2S2O3 bng mu chun ng thau bit trc hm lng ng, v.v Dng mu chun c li ch l tt c cc thao tc v cc yu t nh hng n kt qu phn tch l hon ton ging nhau khi xc nh nng dung dch chun cng nh khi thc hin phn tch mu cha bit. V vy chnh xc tng ln. 2.6.3. Cc phn ng dng trong phn tch th tch Mt c im quan trng ca phng php phn tch th tch l khng s dng d thuc th m lun theo ng phng trnh phn ng, tun theo nh lut ng lng. Nh vy r rng l khi nh phn phi xc nh c im tng ng. Trong mt s trng hp vic xc nh im tng ng rt d dng, da vo s thay i mu ca dung dch trong qu trnh chun . V d nh phn dung dch FeSO4 bng KMnO4 trong mi trng axit: 8H+ + 5Fe2+ + MnO4- 5Fe3+ + Mn2+ + 4H2O Mi ln thm 1 git KMnO4 th mu bin mt rt nhanh v ion Fe2+ kh mu tm ca MnO4- n Mn2+. Nhng khi ton b Fe2+ b oxy ha ht th mt git tha KMnO4 s lm cho dung dch chuyn sang mu hng hoc tm nht. iu ny ni ln rng im tng ng qu hay ni cch khc im kt thc nh phn xut hin. Nh vy r rng l chng ta khng kt thc nh phn ti im tng ng m hi qu mt t v do s xut hin sai s chun . V nng ca dung dch KMnO4 rt long v lng tha khng ti mt git do sai s rt nh v c th b qua. Phn ng dng v d trn gi l phn ng t ch th. Nhng trong thc t phn ln cc php nh phn phi dng ch th t ngoi vo, v d khi xc nh nng Cldng dung dch chun l AgNO3 vi ch th l K2CrO4, hoc trong phng php trung ha ngi ta dng metyl da cam, phenolphtalein. Tm li, nhng phn ng ha hc dng trong phn tch th tch phi tha mn cc yu cu sau: - Cht nh phn phi tc dng hon ton vi thuc th theo mt phng trnh phn ng xc nh, ngha l theo mt h s t lng xc nh. - Phn ng phi xy ra rt nhanh. i vi cc phn ng chm, cn lm tng tc ca chng bng cch un nng hoc dng cht xc tc thch hp. - Phn ng phi chn lc, ngha l thuc th ch tc dng vi cht nh phn

19 tch m khng phn ng vi bt k cht no khc. - Phi c cht ch th thch hp xc nh im cui vi sai s chp nhn c 2.6.4. Phn loi cc phng php phn tch th tch. - Phng php trung ha: Cc phng php ny da trn phn ng c bn l phn ng trung ha (axit - baz). - Phng php oxy ha - kh da trn phn ng oxy ha - kh. - Phng php dng cc phn ng kt hp gm cc phng php sau: phng php kt ta da vo phn ng kt ta, phng php to phc da vo phn ng to phc, thuc th dng nhiu nht l cc complexon. 2.6.5. Cc phng php chun . 2.6.5.1. Chun trc tip. Thm t t dung dch chun vo dung dch nh phn (cn xc nh) hoc ngc li. 2.6.5.2. Chun ngc. Thm mt lng d chnh xc dung dch chun vo dung dch nh phn. Sau chun lng thuc th d bng mt thuc th thch hp khc. Phng php ny c s dng khi khng c ch th thch hp hoc khi phn ng chnh xy ra chm. V d xc nh CaCO3 ngi ta cho mt lng tha dung dch chun HCl vo mt lng cn chnh xc CaCO3, sau lng tha HCl c chun bng dung dch NaOH. 2.6.5.3. Chun thay th. Cho cht cn xc nh X tc dng vi mt cht MY no : X + MY = MX + Y Sau chun cht Y bng dung dch thuc th R thch hp. Phng php ny c s dng khi kh xc nh c im tng ng hoc khi xc nh mt hp cht ha hc no khng bn. V d Cr2+ d b oxy ca khng kh oxy ha v kh chun trc tip bi mt cht oxy ha no nn ngi ta cho mt lng d Fe3+ vo dung dch cn xc nh Cr2+: Cr2+ + Fe3+ Cr3+ + Fe2+ 2+ Lng Fe c gii phng ra tng ng vi hm lng Cr2+ v ta chun Fe2+ rt d dng. 2.6.5.4. Phng php chun gin tip tc l chuyn cht cn xc nh sang mt cht khc cha t nht mt nguyn t c th xc nh trc tip c bng mt thuc th v ch th thch hp. V d xc nh ch trong qung, ngi ta ha tan qung ri lm kt ta PbCrO4, sau ha tan PbCrO4 bng dung dch hn hp HCl + NaCl thm d KI v chun lng I2 thot ra bng Na2S2O3. 2.6.5.5. Phng php chun phn on c p dng khi chun mt s cht trong cng mt dung dch bng mt hay hai dung dch chun. D cho phng php no i chng na th cng phi: - o chnh xc th tch ca 1 hay 2 dung dch phn ng. - Phi c dung dch chun. - Tnh ton kt qu. 2.6.6. Cch biu din nng trong phn tch Nng l i lng dng ch hm lng ca mt cu t (phn t, ion)

20 trong dung dch. Sau y l cc cch biu din nng trong ha phn tch: Nng th tch: Nng th tch ca mt cht lng l t s th tch ca cht lng v th tch ca dung mi (thng l nc). V d dung dch HCl 1:4 l dung dch gm 1 th tch HCl c (c khi lng ring d = 1,185g/ml) v 4 th tch nc. Nng phn trm khi lng: Nng phn trm khi lng ca mt cht trong dung dch l s gam cht tan trong 100g dung dch. Th d dung dch NaOH 25% l dung dch cha 25g NaOH trong 100g, tc l dung dch gm 25g NaOH v 75g nc. V d 1: Cn ha tan bao nhiu gam NaCl vo 100g nc c dung dch nng 10%. t a l s gam NaCl cn ha tan, ta c:
a .100 = 10; suy ra : a = 11,111g a + 100

V d 2: C bao nhiu gam H2SO4 nguyn cht trong 1 ml dung dch axit sunfuric c 98% c khi lng ring d = 1,84g/ml? t a l s gam H2SO4 cn tnh, ta c:
a .100 = 98; suy ra : a = 1,803g. 1,84

Nng mol: Nng mol ca mt cht l s mol cht tan trong 1l dung dch. Loi nng ny c k hiu bng ch M hoc mol/l hoc mol.l-1 t sau ch s ch s mol. V d: dung dch NaOH 0,1M tc l dung dch cha 0,1mol NaOH hoc 0,1x40 = 4,0g NaOH trong 1l dung dch. Nu a l s gam cht trong V lt dung dch v M l khi lng mol ca cht tan th nng mol CM c tnh theo cng thc:
CM = a M.V

Nu V biu th theo ml th:

CM = a.1000 M.V

V d: Cn ly bao nhiu gam H2C2O4.2H2O iu ch 250ml dung dch nng mol l 0,025M? t s gam tinh th ngm nc cn ly l a, ta c:
0.025 = a.1000 ; suy ra : a = 0,7880g. 126.250

tnh ton kt qu phn tch th tch, ngi ta thng da vo nh lut hp thc: "Khi phn ng t ti mc hon ton th ta cc i ca mi cht phn ng phi bng nhau". Ta cc i bng s mol ban u chia cho h s hp thc ca mi cht. Gi s ta c phn ng: aA + bB = cC + dD Trong : a, b, c, d gi l cc h s hp thc ca A, B, C, D.

nh lut hp thc:

C A VA C B VB = a b

Nng ng lng: Trc kia trong ha hc ngi ta thng dng khi

21 nim ng lng v ng lng gam nn trong ha hc phn tch, c bit trong phn tch th tch ngi ta thng dng loi nng ny, v da vo nh lut ng lng th vic tnh ton kt qu phn tch rt thun li v d dng. Nhng ngy nay trn th gii ngi ta khng dng n khi nim ng lng v mol ng lng na nn cc nc t dng khi nim nng ng lng. Nng ng lng ca mt cht l s mol ng lng () ca cht trong mt lt dung dch hoc s milimol ng lng (m) ca cht trong 1 ml dung dch v thng c k hiu bng ch N t sau ch s ch nng . V d, dung dch NaOH 0,1N l dung dch cha 0,1mol ng lng NaOH trong 1 lt dung dch ca n. Nu a l s gam cht tan trong Vl dung dch (hoc a l s mg cht tan trong V ml dung dch) v l khi lng mol ng lng (), (i lng ny trc kia c gi l ng lng gam) th c th tnh nng ng lng theo cng thc: C N =
a .V a.1000 .V

Nu a biu din theo gam cn V theo ml th: C N =

T cng thc ta suy ra, CN.V l s mol ng lng nu V tnh theo lt v l s milimol ng lng nu V tnh theo mililit. Khi lng mol ng lng ca mt s cht l s gam cht v mt ha hc tng ng vi mt nguyn t hoc mt mol ion H+ hoc OH- hoc 1 2 mol oxy (O). ng lng mol ca mt cht khng phi l mt hng s nh khi lng mol m thay i ty theo phn ng n tham gia. Mol phn t ca mt cht th khng thay i, nhng ng lng gam th thay i theo tng phn ng ha hc. Ta xt ng lng gam ca cc cht trong cc phn ng sau da trn cng thc tnh mol ng lng ca mt cht: =
M n

Trong phn ng trao i: V d 1: i vi mt axit, n l s ion H+ ca mt phn t axit tham gia vo phn ng cho: H3PO4 + NaOH = NaH2PO4 + H2O
H 3PO 4 =
H 3PO 4 = M = 98g 1

H3PO4 + 2NaOH = Na2HPO4 + 2H2O

V d 2: i vi mt baz, n l s ion OH- ca phn t tham gia vo phn ng. Ca(OH)2 + 2HCl = CaCl2 + 2H2O
Ca ( OH ) 2 = M = 37g 2

M = 49g. 2

V d 3: i vi cc phn ng trao i, to phc n l s in tch m hay dng ca mt phn t cht tham gia vo phn ng cho. K4[Fe(CN)6] + 2CuSO4 = Cu2[Fe(CN)6] + 2K2SO4
K 4 [ Fe( CN ) 6 ] = M 378 = = 94,5g 4 4

2K4[Fe(CN)6] + 3ZnCl2 = Zn3K2[Fe(CN)6]2 + 6KCl

22

M 378 = = 126g 3 3 Trong phn ng oxy ha - kh, n l s e ca 1 phn t cht oxy ha hay cht kh thu vo hay mt i trong phn ng cho. V d: 10FeSO4 + 2KMnO4 + 8H2O = 5Fe2(SO4)3 + 2MnSO4 + K2SO4 + H2O Fe2+ - e = Fe3+; MnO4- + 8H+ + 5e = Mn2+ + 4H2O
K 4 [ Fe( CN ) 6 ] =

K 4 MnO 4 =

M M v FeSO4 = 5 1

nh lut ng lng: S ng lng ca cc cht tc dng vi nhau hon ton bao gi cng bng nhau. A+BC+D V d: th mun cho 2 cht A v B tc dng vi nhau hon ton, s ng lng ca chng phi bng nhau. C cc biu thc ton hc sau: - Nu gi VA l th tch dung dch cht A, NA l nng ca ng lng ca dung dch A v VB, NB l th tch v nng ca dung dch B. Ta c: NAVA = NBVB - Nu ag cht A tc dng ht vi bg cht B th:
ag bg = A B

- Nu VA l th tch dung dch cht A (tnh bng lt) vi NA l nng ng

lng ca dung dch A tc dng ht vi bg cht B th: VANA =
bg B

chun. chun l s gam (hoc miligam - mg) cht tan trong 1 ml dung dch. Nu a l s gam cht tan trong V ml dung dch th chun T = a/V. chun theo cht nh phn. chun theo cht cn nh phn l s gam cht cn nh phn (ion, phn t hoc nguyn t) phn ng ng vi 1 ml dung dch chun v c k hiu l TR/X trong R l thuc th, X l cht cn nh phn. Cch biu din nng loi ny rt thun tin cho vic tnh ton kt qu phn tch, c bit khi phn tch hng lot mu ti cc phng th nghim nghin cu v sn xut. V d: Tnh chun ca dung dch chun KMnO4 0,02M theo st, khi chun Fe2+ theo phn ng: MnO4- + 5Fe2+ + 8H+ Mn2+ + 5Fe3+ + 4H2O Theo phng php phn ng chun trn, ta c: 1 mol MnO4- phn ng vi 5 mol Fe2+. Trong 1 ml dung dch chun KMnO4 0,02M c cha 0,02/1000 = 2.10-5 mol MnO4- v do 1ml MnO4- phn ng vi 5 x 2 x 10-5 = 10-4 mol Fe2+ hoc 10-4 x 56 = 5,6 x 10-3 g Fe. Do :
TKMnO4 0,02M/ Fe = 0,0056 g Fe.ml.

Nng (hoc hm lng) phn triu v phn t. i vi cc dung dch rt long hoc c hm lng rt nh ngi ta thng dng cc khi nim ny. Phn triu (thng c k hiu l ppm - parts per million) l s microgam

23 cht tan c trong mt gam hoc 1 microgam cht tan trong 1 gam dung dch. Mt cch tng qut ta c:
C ppm =
Khi lng cht tan (g) x10 6 (ppm) Khi lng dung dch (g)

V d: Dung dch Au3+ nng 1 ppm, tc l dung dch c cha 1g Au trong 1g hoc 1mg Au trong 1kg dung dch. i vi cc dung dch nc rt long th c th coi gn ng khi lng ring ca nc bng 1g/ml hoc 1kg/l. Do , 1ppm = 1 g/ml hoc l 1 mg/l. i vi cc dung dch long hn, ngi ta dng phn t, k hiu ppb (parts per billion)
C ppb =
Khi lng cht tan (g) x10 9 (ppb) Khi lng dung dch (g)

2.6.7. Cch tnh kt qu trong phn tch th tch. Vic tnh kt qu ph thuc vo cch biu din nng v cch phn tch. Nguyn tc chung l da vo nh ngha nng , phng trnh phn ng chun , nh lut hp thc hoc nh lut ng lng m tnh kt qu phn tch. * Trng hp chun trc tip. Cch tnh theo nh lut hp thc: Da vo th tch, nng dung dch chun v phng trnh phn ng chun tnh c lng cht cn phn tch theo s milimol hoc s mol. V d 1: Tnh nng mol ca mt dung dch NaOH bit rng khi chun 20ml dung dch th phi dng va ht 22,75 ml dung dch HCl 0,1060M. Phn ng chun : NaOH + HCl NaCl + H2O S milimol NaOH bng s milimol HCl: CNaOH x 20 = 0,1060 x 22,75 Suy ra: CNaOH = (0,1060 x 22,75) : 20 = 0,1260 M V d 2: Khi chun 0,2275g Na2CO3 tinh khit n CO2 phi dng va ht 22,35ml HCl. Tnh nng mol ca dung dch HCl . Phn ng chun : Na2CO3 + 2HCl 2NaCl + CO2 + H2O S mol Na2CO3 bng 0,5 s mol HCl. S mol HCl = (0,2275 : 106) x 2 Nng dung dch HCl = CHCl = (0,2275 : 106) x 2 : 0,02235 = 0,1920M. Cch tnh theo nh lut ng lng: Khi tnh theo nng ng lng th cn da vo nh lut v ng lng l: S mili ng lng mol ca dung dch chun bng s mili ng lng mol cht cn xc nh phn ng vi nhau. tnh c khi lng cc cht phn ng phi bit khi lng mol ng lng ca cc cht . V d 3: Tnh nng ng lng ca dung dch Na2S2O3, bit rng khi thm lng d dung dch KI tinh khit vo 20 ml dung dch K2Cr2O7 0,05N cha axit sunfuric lm mi trng th chun lng I2 thot ra bng 19,80 ml dung dch Na2S2O3 . Mili ng lng mol Na2S2O3 = 19,80 x N Na S O = s milimol ng lng K2Cr2O7 = 20 x 0,05. Do , N Na S O = (20 x 0,05) : 19,80 = 0,0506 N.
2 2 3 2 2 3

24

Cch tnh theo chun cht nh phn. V d 4: Tnh hm lng phn trm st trong qung, bit rng sau khi ha tan 0,5170 g qung, kh hon ton Fe(III) thnh Fe(II) ri chun Fe(II) bng dung dch chun KMnO4 c chun theo Fe l 5,620 mg/ml th dng va ht 57,20 ml dung dch chun . Theo nh ngha th 1 ml dung dch chun KMnO4 oxy ha c 5,620 ml Fe2+. Vy lng Fe c trong qung l 5,620 x 37,20 mg. Phn trm ca Fe l [(5,620 x 37,20) : 517] x 100 = 62,18%. * Trng hp chun ngc. V d 5: nh lng Cr trong thp, ngi ta phn hy 1,075 g mu thp thnh dung dch ri oxy ha hon ton Cr3+ thnh CrO42-. Sau thm vo 25 ml dung dch chun FeSO4 0,0410 M v lng dung dch axit sunfuric long lm mi trng. Lng Fe(II) d c chun bng 3,70 ml dung dch KMnO4 0,0400M. hy tnh hm lng theo % khi lng ca Cr trong thp. tin li ta tnh theo nh lut ng lng. Nng ng lng ca dung dch chun FeSO4 bng nng mol ca n, bng 0,0410N. Nng ng lng ca dung dch KMnO4bng 0,0400 x 5 = 0,2N. S mili ng lng mol CrO42- tc dng vi Fe2+ l: 25 x 0,0410 - 3,7 x 0,2 S ng lng mol Cr trong mu thp bng:
25.0,0415 3,7.0,2 1000

Khi lng mol ng lng ca Cr l M:3. Phn trm Cr c trong thp l:

25.0.0410 3,7.02 52 100 . . = 0,4595% 1000 3 1,075

* Trng hp chun gin tip. V d 6: nh lng ch (Pb) trong qung ngi ta phn hy 1,1050 g mu qung thnh dung dch. T dung dch thc hin quy trnh lm kt ta nh lng ch trong mu thnh PbCrO4. Sau ha tan PbCrO4 bng dung dch hn hp HCl + NaCl d. Thm vo dung dch mt lng d KI v cui cng chun lng I2 thot ra bng 24,20 ml dung dch chun Na2S2O3 0,0962N. Tnh hm lng ch trong qung theo % khi lng. Cc phn ng chnh ca qu trnh nh lng: CrO42- + Pb2+ PbCrO4 2PbCrO4 + 2H+ + 8Cl- 2PbCl42- + Cr2O72- + H2O I2 + 2S2O32- 2I- + S4O62Tnh theo nh lut hp thc: Theo cc phng trnh phn ng trn th 1 mol Pb2+ phn ng vi 3 mol S2O32-. S mol Pb2+ trong mu l: (24,2 x 0,0962) / (100 x 3). Vy hm lng % khi lng ch trong qung l:
24,2.0,0962.207,2.100 = 14,55% 1000.3.1,105

Tnh theo nh lut ng lng: Trong trng hp ny khng cn phi vit cc phng trnh phn ng thc

25 hin vic tnh kt qu v theo nh lut v ng lng, cc cht phn ng vi nhau theo nhng ng lng mol bng nhau, tc l s ng lng mol ca S2O32- bng s ng lng mol ca Pb2+. V mt ion Pb2+ to nn mt phn t PbCrO4 m CrO42- b kh thnh Cr3+ vi s nhn 3 electron, nn ng lng mol ca PbCrO4 bng 1/3 khi lng mol ca n, v vy cng thc tnh trng vi cng thc u tnh theo nng mol.

BI TP
1. xc nh hm lng ca CaCO3 trong vi ngi ta cn 0,2560g mu, ha tan thnh dung dch v kt ta ion Ca2+ di dng CaC2O4. Sau khi lc, ra v nung kt ta , cn c 0,216g CaO. Tnh hm lng CaCO3 trong mu. CaCO3 = 100, CaO = 56. 2. Khi phn tch dung dch c chit ra t mt mu t, ngi ta tm c cc kt qu sau: Hp cht CaO SO3 MgO CO2 Hm lng % 7,59 5,61 2,20 5,29 T cc s liu trn, hy tnh hm lng ca cc mui MgCO3, CaCO3, CaSO4 trong mu t. 3. Khi phn tch mt mu bari clorua ngi ta tm thy hm lng ca bari l 56,22%, ca nc kt tinh l 14,73%. Tnh thnh phn % ca bari trong bari clorua khan. 4. Phi dng bao nhiu ml dung dch (NH4)2C2O4 4% thc t kt ta ht canxi c trong 0,4154g vi c hm lng CaO l 43%. Th tch cui cng ca dung dch khi kt ta l 250ml, canxi c coi nh kt ta hon ton nu lng CaC2O4 tan trong dung dch khng qu 10-4g/l. TCaC O = 2,57.10-9, CaC2O4 = 128, CaO = 56, (NH4)2C2O4 = 124. 5. Phi thm bao nhiu ml H2SO4 c 98% (d = 1,84) vo 300 ml nc dng lng dung dch ra kt ta SrSO4 v lng kt ta mt i khng qu 10-4g TSrSO = 2,8.10-7, SrSO4 = 183,7. 6. Hy tnh mt phn t Na2CrO4 ngm bao nhiu phn t nc, nu em phn tch trng lng 0,4927g mui ngm nc th cn c 0,1095g Cr2O3. Cr2O3 = 152; Na2CrO4 = 162; H2O = 18. 7. xc nh hm lng bari trong mt mu BaCl2.2H2O, ngi ta cn 0,6531g mu, ha tan thnh 250ml dung dch, ly ra 50ml kt ta ion bari di dng BaSO4. Sau khi lc, ra, sy v nung kt ta thu c 0,1241g BaSO4. Tnh hm lng bari trong mu BaSO4 = 233, Ba = 137.
2 4
4

26

TI LIU THAM KHO

1. Hong Minh Chu, T Vn Mc, T Vng Nghi. C s ha hc phn tch, NXB KH & KT, 2002. 2. Nguyn Tinh Dung phn I, II, III. Ha hc phn tch. NXB Gio dc, 2000. 3. Trn T Hiu, Ha hc phn tch, NXB HQG H Ni, 2002. 4. Trn T Hiu, T Vng Nghi, Hong Th Tn. Bi tp Ha hc phn tch, NXB H&TH Chuyn nghip, 1984. 5. .., , , o , 1972 6. .., , , o , 1972

27

CHNG 3

CN BNG AXIT BAZ. CHUN AXIT BAZ

3.1. ngha thc t cc quan nim v axit - baz. 3.1.1. Thuyt axit - baz ca Areniut. Theo thuyt ny, axit l nhng cht trong dung dch nc phn ly cho ion hydro (H+), cn baz l nhng cht phn ly cho ion hydroxyt (OH-). nh ngha ny khng c tng qut v ch p dng c cho mt s rt hn ch v khi dung mi l nc. Nhng kt qu nghin cu v dung dch cho thy rng: s phn ly ca cc cht l do tng tc ha hc vi dung mi, trong dung dch nc ion H+ khng tn ti di dng t do, n b dung mi ha v tn ti di dng ion hydroxoni (H3O+), nhng tnh cht axit - baz cng th hin trong cc dung mi khng nc. 3.1.2. Thuyt axit - baz ca Bronsted - Lauri. 3.1.2.1. Ni dung Nm 1923 hai nh bc hc Bronsted (an Mch) v Lauri (Anh) cng ra mt nh ngha mi v axit v baz nh sau: Axit l nhng cht c kh nng cho proton v baz l nhng cht c kh nng nhn proton. Proton khng th tn ti trng thi t do, v vy mt cht ch th hin tnh axit hay baz trong dung mi c kh nng nhn hay cho proton. Mi axit sau khi cho proton i thnh mt baz lin hip vi axit . Mt cp axit - baz lin hp c th biu din bng h thc: Axit Baz + H+ (proton) Th d v cc cp axit - baz lin hp: Axit
HF CH3COOH H2 O NH4+ Al3+.H2O NH3 SHOH-

Baz F - + H+ CH3COO- + H+ OH- + H+ NH3 + H+ Al(OH)2+ + H+ NH2 + H+ S2- + H+ O2- + H+

Khi ha tan mt axit hay mt baz vo mt dung mi th s c cc phn ng: Axit + S (dung mi) Baz + SH+ Baz + S (dung mi) Axit + SV d: H3O+ + HSH2 S + H2 O NH4+ + H2O NH3 + H3O+ CH3COO + H2O CH3COOH + OHTheo thuyt ny th cc axit, baz c th l phn t, anion, cation (bng3.1)

28

Bng 3.1. Phn loi axit - baz STT Phn loi Axit Baz HCl, H2SO4, ... NH3, C6H5NH2, NaOH, ... 1 Phn t khng tch in Anion 2 HSO4 , HCO3 , ... OH-, Cl-, ... Cation 3 H3O+, NH4+, ... NH2(CH2)2NH3+, ... Ngoi ra cn c cc cht lng tnh ngha l va c kh nng nhn va c kh nng cho proton. V d: H2 O H+ + OHAxit Baz + + H 2O + H H3 O Baz Axit 3.1.2.2. Phn ng axit - baz (phn ng trung ha) Theo Bronsted, phn ng axit - baz c biu din nh sau: Axit (1) + Baz (2) Axit (2) + Baz (1) (3.1) V d: HCH3COO + NH3 NH4+ + CH3COO(3.2) HCl + NaOH H2O + NaCl Thc t cc cht phn ng vi nhau u trong mt dung mi nht nh, v d trong nc cc cn bng phi l: CH3COOH + H2O CH3COO- + H3O+ NH3 + H2O NH4+ + OHH2 O + H2 O H3O+ + OHHCH3COO + NH3 + 4H2O CH3COO- + NH4+ + 2H3O+ + 2OHThc cht khi ha tan mt axit hoc baz vo nc l ta thc hin phn ng axit - baz v bn thn nc theo quan nim ca Bronsted cng l mt cht c th l axit hoc baz. Nh vy trong phn ng axit - baz (hay phn ng trung ha) bao gi cng tn ti 2 cp axit - baz lin hp. Nh v d tng qut trn (3.1) ta c: cp axit - baz (1) v cp axit - baz (2). Trong v d (3.2) th l 2 cp: CH3COOH/CH3COO- v NH4+/NH3. Nhn ra tng cp axit - baz lin hp trong trng hp c th l rt quan trng hiu cch lp lun v tnh ton trong cc phn sau. Sau y l mt s phn ng axit - baz v cp axit - baz lin hp trong nc: (Bng 3.2) Bng 3.2. Mt s cp axt - baz lin hp
Axit (1) + Baz (2) Axit (2) + Baz (1) H2 O HS+ H 3 O+ + H2 S + + + HClO4 CH3OH CH3OH2 ClO4+ + H2 O CO32HCO3CH+ + + NH4 NH2 NH3 NH3 (Phn ng trung ha NaNH2 bi NH4Cl trong amni lng) NH4+ + OHH2 O + NH3

29

3.1.2.3. Cng ca axit v baz: hng s axit KA v hng s baz KB Mt axit cng mnh khi n c kh nng nhng proton cho dung mi cng ln. V d: Khi cho axit vo dung mi S ta c: Axit + S Baz + SH+ (3.3) Axit cng mnh ngha l cng ln, th phn ng (3.3) cng chuyn dch
mnh v pha phi, ngha l hng s cn bng K = cng ln. Trong trng hp dung mi l nc, v nng ca nc l
1000 = 55,5 18
[Baz][SH + ] ca phn ng trn [Axit ][S]

mol/lit l kh ln nn c th coi nh khng i khi dung dch long v c th vit: [Baz ][H 3O + ] (3.4) K[H 2 O] = = KA [Axit ] v KA c gi l hng s axit, n biu th cng axit. thun tin cho vic tnh ton ngi ta thng dng gi tr PKA = -lgKA thay cho KA. V d: HF c PKA = 3,2; mnh hn HCN c PKA = 9,4. i vi axit mnh trong nc phn ly hon ton khi c KA = +. Mt baz cng mnh cng c kh nng nhn proton ca dung mi. C th vit phn ng sau: Baz + S Axit + S(3.5) Baz cng mnh th phn ng (3.5) cng chuyn mnh v pha phi tc l hng [Axit][S - ] s cn bng: K = ca phn ng cng ln. [Baz ][S] [Axit][OH - ] Vi dung mi l nc, ta c: K = ; [ Baz ][H 2 O]
[Axit][OH - ] K[ H 2 O] = = KB (3.6) [ Baz ] vi KB l hng s baz, n biu th cng baz. Thng ngi ta dng PKB = -lgKB thay th cho KB. V d: NH3 c PKB = 4,75 mnh hn CH3COO- c PKB = 9,25. Vi baz mnh trong nc phn ly hon ton nn KB = . 3.1.2.4. Dung mi Theo thuyt axit - baz ca Bronsted - Lauri dung mi c mt vai tr quan trng quyt nh mnh yu ca axit hay baz tan trong . Sau y im qua mt s tnh cht ca dung mi. * Tnh axit, baz ca dung mi Da vo kh nng cho v nhn proton ca dung mi, ta chia cc dung mi thnh hai nhm: dung mi khng cha proton v dung mi c cha proton. Dung mi khng cha proton l nhng hp cht c tnh tr, phn t ca n khng c kh nng cho hay nhn proton. Phn t ca loi ion ny khng b ion ha. Cc dung mi ny khng tham d vo qu trnh tng tc proton ca cht ha tan. V d: cc loi cht nh hydrocacbua [benzen, toluen, ] v cc dn xut halogenua ca chng [tetracloruacacbon, clorofooc, ].

30

Cc dung mi c cha proton gi l dung mi protolit, l nhng hp cht ha hc c kh nng cho v nhn proton, cc dung mi ny tham gia trc tip vo qu trnh tng tc proton ca phn ng axit - baz. Dung mi protolit chia lm 3 loi: dung mi lng tnh, dung mi axit v dung mi baz. Cc dung mi protolit c kh nng t phn ly thnh ion. Dung mi lng tnh phn t ca chng va c kh nng cho va c kh nng nhn proton. V d nh dung mi nc, ru, xtn, nitril, Dung mi axit l nhng hp cht m phn t ca chng c kh nng cho proton mnh hn kh nng nhn proton. Loi dung mi ny ch th hin kh nng nhn proton i vi cc cht c kh nng cho proton mnh hn dung mi. V d: HCOOH, HCH3COO, H2SO4, Dung mi baz l nhng hp cht m phn t ca chng c kh nng nhn proton mnh hn kh nng cho proton. Chng ch th hin kh nng cho proton i vi cc cht c i lc vi proton mnh hn n. Cc cht nh amniac lng, piridin, hydrozin v nhiu loi amin thuc loi dung mi ny. phn ly ca axit, baz ph thuc vo bn cht axit, baz v ph thuc vo bn cht dung mi. Ngi ta ly dung mi khng phi l nc m l nhng cht c tnh kim yu hn nc, v d dung mi l C2H5OH th axit nitric (HNO3) tr nn hi yu i. Trong axeton hay C6H5NO2 tt c cc axit mnh trong nc tr HClO4 v H2SO4 tr nn mnh va phi. i vi nhng dung mi c i lc i vi proton khng mnh lm c ngha l d dng nhng proton, v d trong H2SO4 khan th ch c HClO4 l cn c i lc i vi proton, tc vn l axit mnh cn HNO3 th hin tnh cht ca baz bi n ly proton ca H2SO4 to nn ion nitron [NO3H2]+ nh l axit cation ging nh NH4+. Cc axit hu c, ru, te v mt s cht khc trong dung mi ny u tr thnh baz. i vi nhng dung mi c tnh cht kim mnh hn nc, v d NH3 lng th mt s axit yu trong nc tr nn axit mnh. * S phn ly ca dung mi . Hng s t phn ly: Cc dung mi protolit c kh nng t phn ly thnh ion. S phn ly ca dung mi c o bng hng s t phn ly KS. Gi s c dung mi S c th t phn ly thnh ion theo cn bng sau: 2S SH+ + SHng s phn ly KS tnh nh sau: K S = a SH .a S (a: hot ) + H3O + OH Vi dung mi nc, ta c: 2H2O do : K H O = a H O .a OH
+

Trong cc php tnh, thng thng ta thay bng: K H O = [H3O+][OH-] = 10-14 250C
2

S t phn ly nh trn ca dung mi thc cht l phn ng axit - baz, trong mt phn t dung mi ng vai tr axit, cn phn t kia ng vai tr baz. Sau y nu mt s hng s t phn ly ca mt s dung mi (bng 3.3).

31

Bng 3.3. Hng s t phn ly ca mt s dung mi Dung mi Amniac Axetonitril Hydrazin Ru izopropylic Axeton 90% Ru propylic Ru tylic Dioxan 70% Dimetyl sunfoxyt PKS 32,32 26,50 24,70 20,84 20,30 19,33 18,95 17,86 17,30 Dung mi Propylenglycol Ru metylic Etylenglycol Anhydrit axetic Nc Axit axetic Axit foocmic Monoetanol amin Axit sunfuric PKS 16,76 16,70 15,60 14,50 14,00 12,60 6,30 5,14 3,62

S dung phn: S tham gia ca cc phn t dung mi vo phn ng vi cht ha tan trong phn ng axit - baz cn gi l s dung phn. V d: khi ha tan mui CH3COONa vo nc s c phn ng sau: CH3COONa + H2O CH3COOH + Na+ + OHHoc ha tan vo ru, ta c: CH3COONa + C2H5OH CH3COOH + Na+ + C2H5OMc ha tan cng ln nu s phn ly ring ca dung mi cng mnh. V d: trong dung mi nc cc mui ca axit nitric khng c tc dng vi nc (khng b dung mi phn), nhng trong mi trng H2SO4 khan th mui ny b dung phn nh sau: 2KNO3 + H2SO4 2HNO3 + 2K+ + SO42Theo bng 3.3, ta thy a s cc dung mi hu c u c hng s t phn ly nh hn nc, do c nhiu trng hp mt cht b dung phn trong mi trng nc s khng b dung phn trong cc mi trng khng nc (khan) khc. iu ny rt quan trng trong vic ng dng dung mi khng nc nh phn bng phng php axt - baz. 3.2. Cn bng axit - baz trong mi trng nc. 3.2.1. Tch s ion ca nc, ch s hydrogen. Nc l mt cht lng tnh nn c th t ion ha theo phn ng: H2 O + H2 O H3O+ + OHc hng s cn bng: K =
[H 3 O + ][OH - ] [ H 2 O] 2

V trong dung dch long [H2O] l mt hng s nn c th vit: K[H2O]2 = [H3O+][OH-] = K H O K H O gi l tch s ion ca nc. nhit 250C: K H O = 10-14, P K H O = 14. Khi nhit tng K H O tng. V d 500C th K H O = 8.10-14, iu c th gii thch do s phn ly ca nc tng, ng thi khi nhit tng s trng hp ca cc nH2O phn t nc b ph hy: [H2O]n Trong cc dung dch nc nu [H3O+] tng ln th [OH-] phi gim xung hoc ngc li, tch s nng H3O+ v OH- phi lun bng 10-14. c thun tin biu din axit ca dung dch, ngi ta dng khi nim ch s hydrogen - k hiu l
2 2 2 2 2 2

32 pH - v ch s hydroxyl - k hiu l pOH - l tr logarit nng ion H3O+ v ion OHpH = -lg[H3O+] pOH = -lg[OH-] Ta lun c: pH + pOH = PK H O = 14 Mi trng trung tnh ng vi pH = pOH = 7 Mi trng axit khi pH < 7 v baz khi pH > 7. Thng ta dng thang pH = (0 14) ng vi dung dch n axit mnh v kim c nng 1M. Khi nng ln hn 1M th pH c gi tr m. 3.2.2. Quan h gia KA ca mt axit v KB ca mt baz lin hp vi n Nhn 2 h thc (3.4) v (3.6) vi nhau ta c:
2

KAKB =

[Baz ][H 3 O + ][OH - ][Axit ] = [H 3 O + ][OH - ] [Axit ][Baz ]

Vy KAKB = [H3O+][OH-] i vi mt cp axit - baz lin hp, nu KA cng ln, ngha l axit cng mnh, th KB cng b, ngha l baz lin hp vi n cng yu. V d: HCl l mt axit mnh (trong nc) c KA = + th baz lin hp Cl- l mt baz rt yu c KB = 0; HCN l mt axit rt yu PKA = 9,4 th baz lin hp vi n l mt baz mnh c PKB = 14 - 9,4 = 4,6. 3.2.3. Tnh gi tr pH ca mt axit, baz hoc mui trong nc. Bt k axit hoc baz no khi cho vo dung dch l nc cng tc dng vi nc sinh ra baz hoc axit lin hp nh sau: Axit + H2O Baz + H3O+ Baz + H2O Axit + OHDo tnh pH ca cc dung dch nh vy ta lp mt cng thc tng qut cho php tnh pH mt dung dch hn hp axit v baz lin hp, sau ta suy ra cc trng hp ring. 3.2.3.1. Cng thc tng qut tnh pH ca dung dch hn hp axit v baz lin hp. Nu cho vo nc mt hn hp axit yu HA v baz lin hp vi n A- (l ananion ca mui NaA chng hn) th trong dung dch s thnh lp hai cn bng: HA H+ + A(3.7) + H2 O H + OH (3.8) Nu nng ban u ca HA l CA v ca baz l CB, hng s axit ca cp axit - baz lin hp l KA th gia cc nng cn bng ca H+, OH-, HA, A- v Na+ c cc h thc sau:
[H + ] [A - ] = KA [HA] [H+][OH-] = K H 2O
-

(3.9)

(3.10) (3.11) [HA] + [A ] = CA + CB [Na+] + [H+] = [OH-] + [A-] (3.12) [Na+] = CB (3.13) Hai biu thc (3.9) v (3.10) biu din hai cn bng (3.7) v (3.8). H thc (3.11) biu din nh lut bo ton khi lng i vi A-. H thc (3.12) biu din

33 tnh trung ha in ca dung dch. H thc (3.13) th hin mui NaA l mt cht in ly mnh phn ly hon ton. T 5 phng trnh trn vi 5 n s ta suy ra:
[H + ] = K A C A - [H + ] + [OH - ] C B + [H + ] - [OH - ]

(3.14)

3.2.3.2. Tnh pH ca dung dch axit mnh. Cc axit mnh thng gp u l n axit nh: HCl, HNO3, HBr, HI, ... ch tr H2SO4 l a axit c K1 = v K2 = 10-2. Axit mnh trong nc phn ly hon ton (ngha l cho proton hon ton) nn cn bng (3.7) chuyn hon ton v pha phi: HA H+ + Ado [HA] = 0. Nhng ta li bit nng [H+] do HA phn ly ra theo (3.7) bng CA v nng [H+] do nc phn ly ra theo (3.8) bng [OH-]. Nng cn bng [H+] bng tng nng ca H+ do HA v H2O phn ly ra. Vy: [H+] = CA + [OH-] (3.15) Cng c th suy cng thc (3.15) t cng thc tng qut (3.14) vit di dng:
[H + ](C B + [H + ] - [OH - ] ) = CA - [H+] + [OH-] KA

v KA = + v [H+](CB + [H+] - [OH-]) 0 nn CB - [H+] + [OH-] = 0, do : [H+] = CA + [OH-] Thay [OH-] bng [H+]:
K H 2O [H + ] [H+]2 - CA[H+] - K H 2O = 0

vo biu thc (3.15) ta c phng trnh bc hai theo

(3.16) Phng trnh (3.16) dng tnh chnh xc pH ca dung dch axit mnh. Ta c cc trng hp sau: * Nu CA tng i ln hn 10-7 th c th b qua gi tr [OH-] trong (3.15), khi : [H+] = CA (3.17) V d:

CA = 10-6, nu cho l [H+] = CA ngha l [H+] = 10-6 v [OH-] =

( 250C). Nh vy nu b qua gi tr [OH-] trong (3.15) th sai s ch bng

10 -14 = 10 -8 -6 10

- Nu CA > 10-6 th sai s cn nh hn na nu dng cng thc 3.17. * Nu CA < 10-7, ta phi tnh pH t phng trnh (3.16). V d ly dung dch HCl c nng 10-8 M th pH khng bng 8 m bng 6,91. * Nu CA << 10-7 th c th b qua CA cnh [OH-] trong (3.15) v khi : [H+] = [OH-] = K H O (3.18)
2

10 -8.100 + = 1% ca [H ]. 10 -6

3.2.3.3. pH ca dung dch baz mnh. Lp lun nh i vi dung dch axit mnh s c h thc: [OH-] = CB + [H+].
Thay [OH-] =
K H 2O [H + ]

ta c phng trnh: [H+]2 + CB[H+] - K H O = 0 (3.19)

2

34 Phng trnh (3.19) dng tnh chnh xc pH ca dung dch baz mnh. Nu nng CB ca baz tng i ln hn 10-7 th [OH-] = CB. Do : [H+] =
K H 2O
-

[OH ]

K H 2O CB

(3.20)
K H 2O

Nu CB < 10-7 th tnh theo (3.19). Nu CB << 10-7 th: [OH-] = [H+] =

3.2.3.4. pH ca dung dch axit yu. Nu c dung dch axit yu HA th nng ban u CB ca baz lin hp A- l khng c th cng thc tnh pH s rt ra t cng thc tnh tng qut nh sau:
[H + ] = K A C A - [H + ] + [OH - ] [H + ] - [OH - ]

(3.21)

Ty tng trng hp c th ta c th n gin ha cng thc trn: * Nu [OH-] << [H+] ngha l coi nh nc khng phn ly th c th n gin ha cng thc (3.21) v cn li: [H + ] = K A
C A - [H + ] [H + ]

(3.22)

Cng thc (3.22) cng p dng c khi [OH-] << [A-] v theo phng trnh phn ly ca axit: HA H+ + A-, nu [H+] >> [OH-] ngha l nc hu nh khng phn ly th [H+] = [A-]. Cng thc (3.22) thng c p dng khi KA >> 10-7. Nu [OH-] << [H+] v [H+] << CA th ta li c:
[H + ] = K ACA [H + ] ; [H + ] = K A C A

(3.23)

Cng thc (3.23) cng c p dng khi [OH-] << [H+] v [A-] << [HA] v nu coi [H+] << CA tc l coi nh HA khng phn ly, ngha l [HA] = CA v v [OH-] << [H+] nn [A-] = [H+]. Vy iu kin [A_] << [HA] tng ng vi iu kin [H+] << CA. Cng thc (3.23) thng c p dng khi in ly ca axit HA nh hn 0,05. V theo nh lut pha long Ostvand th K = dch khng long lm c th n gin cng thc bng cch b qua gi tr in ly bn cnh s 1:
K K C < 0,05; < 0,025 hay > 400. C C K C (3.24) i vi trng hp axit yu th ta c: A > 400 KA

C 2 nu cht in ly yu l dung 1

K = C 2; =

K ; < 0,05 tc C

* Nu CA qu nh [A-] << [OH-] th [H+] trong dung dch l hu ht do nc phn ly ra. Khi [H+] = [OH-] v [H+] = K H O .
2

* Nu [OH-] << [H+] nhng [H+] - [OH-] << CA th cng thc (3.22) c th rt gn li: [H+] = K A C A + K H O . (3.25)
2

p dng ng cc cng thc trn cn phi bit c tr s tng i ca nng cn bng cc ion v cc phn t khc trong dung dch. C th dng iu kin (3.24), nhng thun li nht l dng cch gii theo logarit nng . Tuy vy trong cc php tnh gn ng ta c th dng cng thc (3.22) v (3.23).

35

V d 1: Tnh pH ca dung dch axit axtic CH3COOH 10-2M vi KA = 1,75.10-5 (PKA = 4,75).
V
CA 10 2 = KA 1,75.10
5

= 571 > 400 nn c th p dng cng thc (3.23). Ta tnh

c: [H + ] = K A C A = 1,75.10 -5.10 2 = 4,18.10-4 ; pH = 3,4. V d 2: Tnh pH ca dung dch HF 10-3M c KA = 6,75.10-4 V

CA 10 3 = KA 1,75.10
4

= 1,48 < 400 nn ta phi dng cng thc (3.22). Gii ra ta

c: [H+] = 5,5.10-4 v pH = 3,26. V d 3: Tnh pH ca dung dch HCN 10-4M c KA = 4,8.10-10. Trng hp ny phi dng cng thc (3.25) tnh [H+] = 4,8.10 10.10 4 + 10 -14 = 10-6,62 ; pH = 6,62. 3.2.3.5. pH ca dung dch baz yu. Nu cho mt baz yu vo nc th tnh pH ca dung dch ta c th p dng cng thc tng qut vi iu kin CA = 0. Cng thc by gi c dng:
[H + ] = K A [OH - ] - [H + ] C B - [OH - ] + [H + ] [OH - ] C B - [OH - ]

(3.26)

p dng cng thc ny ta c cc trng hp sau: * Nu [H+] << [OH-] th [H + ] = K A Hoc

K H 2O [OH ] = KA

[OH ] ; [OH-]2 + KB[OH-] - KBCB = 0 C B - [OH ]

KB + K2 B + 4K B C B 2

Gii ra ta c: [OH ] =

(3.27)

* Nu [OH-] << CB th: [OH-] = K B C B (3.28) Trng hp ny cng ging nh i vi dung dch axit yu, c p dng khi t s
CB > 400. KB

Ch : Cng thc tnh pH ca mt dung dch baz yu c th thu c bng cch thay cc gi tr CA, KA, [OH-]. [H+] trong cng thc tng qut (3.14). V d 1: Tnh pH ca dung dch NH3 10-2M c PKB = 4,75. Theo cng thc (3.28) ta c th tnh c: [OH-] = K B C B = 10-4,75.10-2; rt ra pH = 10,62. V d 2: Tnh pH ca dung dch axetat natri 0,05M bit KA = 2.10-5. Ta bit axetat natri l mt mui ha tan vo nc n phn ly hon ton cho 2 ion: NaCH3COO Na+ + CH3COO-

36 Anion axetat l mt baz yu: CH3COOH + OHCH3COO- + H2O tnh pH ca dung dch baz yu ny ta dng cng thc (3.28) vi ch rng:
KB = K H 2O KA 10 -14 ngha l K B = 5 . Do : [OH ] = 2.10 10 14 -6 5 0,05 = 5.10 2.10

pOH = 6 - lg5 = 5,3 ; pH = 14 - 5,3 = 8,7. 3.2.3.6. pH ca dung dch axit yu v baz lin hp vi n. Nu ta cho vo nc mt axit A v mt baz B lin hp vi n th lng ion H+ c th tng ln hoc gim i. Ty theo dung dch s tr nn axit hay baz, ta c th chia ra 2 trng hp sau: + Khi dung dch l axit: ngha l [H+] >> [OH-] th t cng thc tng qut ta rt ra:
[H + ] = K A CA CB C A [H + ] C B + [H + ]

(3.29)

Nu CA v CB kh ln hn [H+] th biu thc ny s c n gin ha nh sau:

[H + ] K A

(3.30)

+ Khi dung dch l kim (baz): ngha l [H+] << [OH-] th ta li c:

C A + [OH ] [H ] = K A C B [OH ]
+

(3.31)

V nu CA v CB kh ln hn [OH-] th ta li tm biu thc (3.30). V d 1: Tnh nng ion hydro trong dung dch cha 0,1M axit HA v 0,02M baz A- nu KA = 10-5. T biu thc (3.30) ta tm c: [H + ] = 10 -5
0,10 = 5.10 -4 0,02

0,001 = 10 -10 . y l dung dch c tnh 0,1 0,001 + 0,0001 = 1,1.10 -10 kim, th p dng cng thc (3.31) ta c: [H + ] = 10 -8 0,1 0,0001

V d 2: Tnh nng ion hydro trong dung dch cha 0,001M axit HA v 0,1M baz A- nu KA = 10-8.
T biu thc (3.30) ta c: [H + ] = 10 -8

Ta thy hai kt qu tm c khc nhau rt t, c th b qua trong cc php tnh thng thng. Mt dung dch gm axit yu v baz lin hp vi n cn c gi l dung dch m. S d nh vy v dung dch ny c kh nng thay i pH rt t khi thm mt lng axit hay baz mnh vo. Ch : Cng thc (3.30) ch p dng c khi [H+] v [OH-] khng ng k so vi CA v CB nn khng th p dng c khi dung dch kh long. Khi CA v CB < 10-3M th khng th p dng c cng thc trn. V d: Tng nng CA + CB = C t nht phi bng bao nhiu c th dng cng thc (3.30) tnh pH ca dung dch m axit axetic-axetat c CA = CB. Ta c KA = 1,75.10-5 nn [OH-] << [H+] do iu kin tnh pH theo cng

37 thc (2.30) ch cn l:
[H + ] = K A CA CA C B 100 C C [H + ] = K A A B C B 100
CA CA + CB CB 100

Nu gi thit l khi hai nng ln hn nhau 100 ln th c th b qua nng nh. Cng 2 phng trnh trn ta c: 2K A y CA = CB nn 2KA

C C . hoc K A 100 200 3.2.3.7. pH ca dung dch a axit a axit l loi axit m mt phn t hay ion ca n c th cho ln lt nhiu + [H ] v s tng ng vi cc hng s axit: K1, K2, , Kn. V d: Axit HnA HnA Hn-1A- + H+ ng vi K1 Hn-1A Hn-2A2- + H+ ng vi K2 HA(n-1) An- + H+ ng vi Kn. Thng th K1 >> K2 >> >> Kn nn t nc 2 tr i kh nng cho H+ ca a axit rt yu, do mt cch gn ng [H+] c tnh theo nc 1, v nh vy c th p dng cng thc tnh pH ca n axit. + Nu K1 > 10-4 p dng cng thc:
[H + ] = K 1 C A [H + ] [H + ]

(3.32)

V d: H3PO4 1M: H3PO4 H2PO4- + H+ , K1 = 7,6.10-3 hay pK1 = 2,12 H2PO4 HPO42- + H+ , K2 = 6,2.10-8 hay pK2 = 7,21. HPO42PO43- + H+ , K3 = 4,4.10-14 hay K1 = 7,6.10-3 > 10-4 nn c th p dng cng thc (3.32). [H+] + K1[H+] - K1CA = 0 thay vo: [H+]2 + 7,6.10-3[H+] - 7,6.10-4 = 0. Gii phng trnh bc 2 ny ta s tm c 2 gi tr ca [H+], nhng ch dng c gi tr no m [H+] > 0. + Nu K1 < 10-4 p dng cng thc: pH = (pK 1 lg C A )
1 2

(3.33)

V d: Tnh pH ca dung dch H2CO3 10-1M c K1 = 3.10-7 hay pK1 = 6,32; K2 = 4,8.10-11 hay pK2 = 10,32.
p dng cng thc (3.33) ta tnh c: pH =
1 (6,32 - lg10-1) = 3,66. 2

3.2.3.8. pH ca dung dch a baz. a baz l mt baz m mt phn t hay ion ca n c th ln lt nhn nhiu H+ . V d: Ca(OH)2, Na2CO3, Na3PO4

38

* a baz l ion-mui trung tnh ca a axit v baz mnh. V d: Dung dch Na2CO3. Trong dung dch Na2CO3: Na2CO3 CO32- + 2Na+ Na+ l mt axit rt yu, coi nh trung tnh. CO32- l a baz ca a axit tng ng H2CO3. CO32- + H+ HCO3- ng vi K 2 HCO / CO
3 23

HCO3 + H

H2CO3 ng vi K 1 H CO
2

/ HCO 3

L lun tng t nh trng hp a axit nh sau: Nh bit K1 >> K2 >> >> Kn ngha l KB1 << KB2 << << KBn. - i vi a axit K1 ln nht nn nc 1 c kh nng cho H+ ln nht, trong khi kh nng ly H+ ca baz s nh nht, ngha l KB1 b nht. L lun tng t, Kn nh nht th KBn ln nht. Vy r rng tnh kim ca a baz loi ny do dng baz c KBn hay K cui cng ca a axit tng ng quyt nh. Do ta c th dng cng thc tnh pH ca dung dch n baz trung bnh hay yu, ch khc l thay KA bng K cui cng ca a axit tng ng. - i vi a baz trung bnh: CB[H+] - K H O [H+] - Kcui cng. K H O = 0 (3.34)
2 2

- i vi a baz yu:
pH = 7 +
1 (pKcui cng + lgCB) 2

(3.35)

V d: Tnh pH ca dung dch Na2CO3 0,1M. Bit rng H2CO3 c: pK1 = 6,32; pK2 = 10,3. p dng cng thc (3.35) ta tnh c:
pH = 7 +
1 1 (pK2 + lgCB) = 7 + (10,3 + lg10-1) = 11,65. 2 2

* a baz l phn t: Cch tnh pH cng tng t nh trn. 3.2.3.9. pH ca dung dch hn hp axit hay hn hp baz Cch tnh pH ca cc hn hp axit hay hn hp baz kh phc tp. y chng ta ch nghin cu trng hp n gin: Nu nng ca axit hay baz khng chnh lch nhau nhiu lm tc l gn xp x nhau, ta c th tnh pH ca cc hn hp gn ng nh sau: Nghin cu cch tnh pH ca hn hp 2 axit A1 + A2 c hng s axit tng ng KA1, KA2 v nng CA1, CA2 (t trng hp ny s suy ra mt cch tng t cch tnh pH ca hn hp 2 baz). C 2 trng hp: * Nu KA1 > KA2: Trng hp ny gn ging nh mt a axit, ta s tnh pH ca dung dch hn hp theo A1 (v A1 mnh hn A2) bng cch p dng 1 trong 3 cng thc: - Nu A1 l axit mnh th: pH = -lgCA1 - Nu A1 l axit yu th: pH = - Nu A1 l axit trung bnh th: [H+]2 + KA1[H+] - KA1CA1 = 0
1 (pKA1 - lgCA1) 2

39

V d: Tnh pH ca dung dch 2 axit CH3COOH + NH4Cl c cng nng 0,1M. Bit pK CH COOH / CH COO = 4,8 v pK NH / NH = 9,2.
3 3 + 4

y K CH COOH > K NH v CH3COOH l axit yu, vy dung dch hn hp c

3
+ 4

pH: pH =

* Nu K1 K2 ngha l 2 axit mnh bng nhau hay gn bng nhau. Ta c th dng 1 trong 3 cng thc trn tnh pH, nhng CA l nng chung ca 2 axit. 3.2.3.10. pH ca hn hp axit yu ca cp ny v baz yu ca cp khc. Gi s trong dung dch c 1 hn hp axit yu A1 ca cp A1/B1 v baz yu B2 ca cp A2/B2. Tuy A1 v B2 u yu nhng chng vn tng tc vi nhau v tn ti cc cn bng sau: * A1 + B 2 B 1 + A2 i vi A1 ta c cn bng: * A1
B1 + H+ ng vi K1 do : pH1 = pK1 + lg
[B1 ] [ A1 ]

1 1 (p K CH3COOH - lg C CH3COOH ) = (4,8 - lg10-1) = 2,9. 2 2

i vi B2 ta c cn bng:

* B 2 + H+

A2 ng vi K2, do : pH2 = pK2 + lg

[B 2 ] [A 2 ]

Khi t n cn bng th nht tc l phng trnh tng cng ca 2 phng trnh sau, th dung dch s c pH = pH1 = pH2, do ta c th vit:

* 2pH = pK1 + pK2 + lg

[B1 ] [B 2 ] [ A1 ] [ A 2 ]

[A1], [A2], [B1], [B2]: nng ca cc axit, baz ca cp A1/B1, A2/B2 khi trng thi cn bng. Nu nng ban u ca A1 trc khi tng tc l CA1 v ca B2 l CB2 th khi t n cn bng gi s c mt lng X ca A1 phn ng vi cng mt lng X ca B2 to ra cng mt lng X ca B1 v A2. Ta c: [B1] = [A2] = X; [A1] = CA1 - X v [B2] = CB2 - X. Do : lg
C - X C B2 - X [B1 ] [B 2 ] X = lg = . B2 [ A1 ] [ A 2 ] C A1 - X X C A1 - X

V A1 v B2 u yu nn X nh v gi s CA1 v CB2 khng qu nh th khi CA1, CB2 >> X, bi vy c th b qua gi tr ca X v tnh gn ng, ta c:
C B2 - X C lg B 2 C A1 - X C A1 C 1 Vy : pH = (pK1 + pK2 + lg B 2 ) 2 C A1

lg

(3.36)

C 2 trng hp xy ra: Trng hp 1: CA1 = CB2 * Cch tnh pH:

40
C B2 = 0. C A1

Khi CA1 = CB2 th lg Vy (3.36) s l: pH =

1 (pK1 + pK2) 2

(3.36a)

* ng dng: - Tnh pH ca dung dch mui ca n axit yu v n baz yu. V d: Tnh pH ca dung dch CH3COONH4. Trong dung dch: CH3COONH4 = CH3COO- + NH4+ B2 A1 R rng CA1 = CB2, bit pK1 = 9,2; pK2 = 4,8.
Vy p dng cng thc (3.36a) tnh c: pH =

- Tnh pH ca dung dch cht lng tnh: mui axit. V d: Tnh pH ca dung dch NaHCO3 NaHCO3 = Na+ + HCO3Trong dung dch Na+ coi nh trung tnh, HCO3- l cht lng tnh v: HCO3CO32- + H+ K2 = 4,8.10-11; pK2 = 10,32 HCO3- + H+ H2CO3 K1 = 4,35.10-7; pK1 = 6,36 Do c th vit: HCO3- + HCO3CO32- + H2CO3 A1 B2 Vy r rng CA1 = C HCO = C B do ta p dng c cng thc (3.36a):
3

1 (9,2 + 4,8) = 7 2

1 1 PH = (pK1 + pK2) = (10,32 + 6,35) = 8,33 2 2 Trng hp 2: C A1 C B2

- Gi s C A = m C B thay vo (3.36):
1 2

1 1 1 pH = (pK1 + pK2 + lg ) hay pH = (pK1 + pK2 - lgm) m 2 2 - Nu m C A = C B th ta c:

1 2

(3.36b)

1 (pK1 + pK2 + lgm) (3.36c) 2 Mt cch tng qut, khi C A C B ta c cng thc tnh pH dng sau:
pH =
1 2

1 pH = (pK1 + pK2 lgm) (3.36d) 2 V d: - Thm 4 mol NH4Cl vo 1 lt dung dch CH3COONH4 1M, gi s th tch khng i, tnh pH ca dung dch hn hp ? Bit pK NH /NH = 9,2; pK CH COOH/CH COO =
+ 4
3 3 3

4,8.

Trong dung dch NH4Cl = NH4+ + ClCH3COONH4 = NH4+ + CH3COOA1 B2 Cl- coi nh trung tnh.

41 Axit NH4+ ca cp NH4+/NH3 v baz CH3COO- ca cp CH3COOH/CH3COOquyt nh pH ca dung dch. Khi thm 4 mol NH4Cl vo dung dch CH3COONH4 th nng ban u ca A1 s l C A = 5 mol/lit, ca B2: CH3COO- s l C B = 1
1 2

C 1 mol/lit. Vy ta c: B 2 = , C A1 = 5 C B2 m = 5. C A1 5 1 Thay cc gi tr vo (3.36b) ta c: pH = (9,2 + 4,8 - lg5) = 6,85. 2

- Thm 4 mol CH3COONa vo 1 lt dung dch CH3COONH4 1M, gi s th tch khng i. Tnh pH ca dung dch ? CH3COONa CH3COO- + Na+ CH3COONH4 NH4+ + CH3COOA1 B2 Theo trn ta c: C A = 1 mol/lit, C B = 5 mol/lit, m = 5.
1 2

Do :

pH =

1 (9,2 + 4,8 + lg5) = 7,15. 2

3.3. Dung dch m. 3.3.1. Khi nim v dung dch m. Dung dch m l dung dch c kh nng gi c pH ban u gn nh khng i khi ta thm mt lng nh axit mnh hay baz mnh hoc pha long. Thnh phn ca dung dch m thng l hn hp ca axit yu v baz lin hp vi n. Cng thc tnh pH ca dung dch m loi hn hp axit yu v baz lin hp:
pH = pKA - lg
CA CB

Mi mt dung dch m c mt gi tr pH xc nh. V d: - Dung dch m axetat: CH3COOH 0,1M + NaCH3COO 0,1M; pKA = 4,75 c pH = 4,75. - Dung dch m fomiat: HCOOH 0,1M + HCOONa 0,1M; pKA = 3,2 c pH = 3,2 - Dung dch m pht pht: NaH2PO4 0,1M + Na2HPO4 0,1M; H3PO4 c pK1 = 2,12; pK2 = 7,21; pK3 = 12,36. Vy: pH = pK2 + lg
CB = 7,21. CA

3.3.2. m dung Kh nng m ca dung dch m khng phi l v hn v khi thm mt lng tng i ln axit mnh hay baz mnh th pH s thay i kh nhiu. c trng cho tc dng m ca dung dch, Vanslyko a ra khi nim m dung (hay m nng), l s mol baz mnh hay axit mnh c th cho vo 1 lit dung dch m pH ca dung dch ch thay i 1 n v.
=

db da = dpH dpH

(3.37)

42 Trong : da: s mol axit mnh cn thit thm vo 1 lt dung dch m pH ca dung dch gim dpH (c du -). db: s mol baz mnh cn thit thm vo 1 lt dung dch m pH ca dung dch tng dpH (c du +). Theo cng thc bit ta tnh pH ca dung dch m:
CB C [H+] =KA A CA CB 1 ln[H+] pH = -lg[H+] pH = 2,303 1 1 dpH = d[H+] dlnx = + x 2,303[H ] db db db = 2,303 = 2,303[H + ] Do : = + dpH d[H + ] d ln[H ]

pH = pKA + lg

(3.38)

(3.39)
db . d[H + ]

tnh ta ch cn thay gi tr [H+] v tnh gi tr ca

Ta coi nng chung ca dung dch m l khng i ( cho): C = CA + CB = const (3.40) CA, CB: nng ban u ca axit A v baz B lin hp ca dung dch m. Vy: dC = dCA + dCB = 0 dCA = -dCB (3.41) T (3.38) ta ly vi phn d[H+] = d(KA Ta c: d[H+] = KAd d[H+] = -KA
CA CB CA ) theo C. CB C dC C dC = KA B A 2 A B CB

Theo (3.41) thay gi tr ca dCA ta c th vit:

dC B (C A + C B ) C2 B

(3.42)

Khi thm db ptg baz mnh vo 1 lit dung dch m th s tng 1 lng dCB ca nng baz B v lm gim cng 1 lng nh th nng axit A, do : db = dCB (3.43) T (3.42) v (3.43) ta c: hay
C +C d[H + ] d[H + ] = = K A A 2 B db dC B CB

C2 db B = + K A (C A + C B ) d[H ]
C2 B K A (C A + C B )

(3.44)

T (3.38), (3.39) v (3.44) ta c:

CA db db = = 2,303[H + ] + = 2,303K A dpH CB d[H ]

C C CACB CACB db = 2,303 = 2,303 => = 2,303 A B dpH CA + CB C C C C s t cc i khi CA = CB = v max = 2,303 = 0,576C 4 2

hay: =

(3.45) (3.46)

43

3.3.3. ng dng ca dung dch m. 3.3.3.1. Trong phn tch nh tnh. - Tch Ba2+, Pb2+ ra khi hn hp Ba2+, Pb2+, Sr2+, v Ca2+ dng Crmt. Ngi ta thy rng: pH 5, BaCrO4, PbCrO4 kt ta hon ton. pH > 5, SrCrO4 bt u kt ta. pH < 5, BaCrO4, PbCrO4 bt u tan.
Do tch Ba2+, Pb2+ dng Crmt ta dng hn hp m axetat c
CA =1 CB

th s c mi trng c pH 5. - Pht hin ion bng phn ng c trng. Tm Ni2+ bng dimetylglyoxym, phn ng ch xy ra pH 9 do ta dng dung dch m amoni. Tm Al3+ bng alizarin S to mui ni phc alizarint Al pH 9 dng hn hp m amoni.

3.3.3.2. Trong phn tch nh lng - Trong phng php it xc nh nng AsO32- da vo phn ng: I2 + AsO32- + H2O 2I- + AsO43- + 2H+ ch xy ra pH 7, ta c th dng h m cacbonat. - Trong phng php complexon: da vo phn ng to complexonat - l phn ng to mui ni phc gia comnplexon v ion kim loi cn xc nh - v da vo phn ng to mui ni phc gia thuc th hu c l cht ch th kim loi v ion kim loi cn xc nh. C 2 phn ng ny ch xy ra tt pH nht nh, do phi dng nhng hn hp m thch hp. Ngoi ra cn rt nhiu trng hp trong cc phng php nh lng khc nhau: phng php trc quang, phng php cc ph cng cn phi dng hn hp m. 3.4. Tnh nng cc thnh phn ca dung dch khi bit pH. C nhiu trng hp cn tnh nng ca cc thnh phn trong dung dch khi bit pH. V d nh tm nng tng i ca 2 dng mt cht ch th mt gi tr pH cho trc, khi tnh lc ion ca dung dch m hay xc nh nng cht to phc trong dung dch m 3.4.1. Trng hp n axit HA. Gi s axit HA c nng l CA. HA H+ + A (1) CA = [HA] + [A ]
KA =
[H + ][A ] [HA] [H + ] - = [HA] [A ] K A
1 1 [H + ] = = + KA [A ] [H ] + K A 1 + 1+ + [H ] [HA]

t 0 v 1 l phn nng ca HA v A-:

[HA] [HA] 0 = = = CA [HA] + [A ]

44 Bit 0 suy ra [HA].

1 = K [A ] 1 = = + A [HA] + [A ] [HA] + 1 [H ] + K A [A ]

Bit 1 suy ra [A-].

3.4.2. Trng hp a axit H2A:

H2 A HAH+ + HAH+ + A2K1 = K2 =

[H + ][HA ] [H 2 A] [H + ][A 2 ] [HA - ]

CA = [H2A] + [HA-] + [A2-] Ta s tnh 0 , 1 , 2 cho cc thnh phn H2A, HA-, v A2- tng ng. Thay cc gi tr tng ng rt ra t hai cn bng trn ta c: CA = [H2A] + T ta tnh c:
0 = 1 = 2 = [H 2 A] [H + ] = + 2 CA [H ] + K 1 [H + ] + K 1 K 2 K 1 [H + ] [HA - ] = + 2 CA [H ] + K 1 [H + ] + K 1 K 2 K 1K 2 [A 2 ] = + 2 CA [H ] + K 1 [H + ] + K 1 K 2 K 1[H 2 A] K 1K 2 [H 2 A] + [H + ] [H + ]2

3.4.3. Trng hp tng qut HnA. Ta vit phng trnh phn ly v tnh 0 , 1 , n . Mu s s c nhiu s hng dng sau: [H+]n + K1[H+]n-1 + K1K2[H+]n-2 + + K1K2Kn = MS
K 1 [H + ] n 1 K 1 K 2 [H + ] n [H + ] n 0 = ; 1 = ; 2 = MS MS MS
2

; n =

K 1 K 2 ...K n MS

Tng qut:
i = K 1 K 2 ...K i [H + ] n i

K K
i =0 1

K i [H + ] n i

...[H ]

+ n i

K [H
i =0 i

vi K0 = 1.

+ n i

V d: Tnh nng HPO42- trong dung dch m 0,1M vi pH = 7. Nu pK1 = 2,16; pK2 = 7,13; pK3 = 12,3. Gii: Khi pH = 7 ta c MS = 10-21 + 10-16,16 + 10-16,29 + 10-21,59 = 10-15,92
T rt ra: 2 = 0,0426 M.
10 16, 29 = 10-0.37 = 0,426. Nng HPO42- bng 0,426.0,1 = 15, 92 10

45

3.5. Chun axit - baz. 3.5.1. Bn cht ca phng php. Trong phng php ny ngi ta dng phn ng trung ho A1 + B2 B 1 + A2 (A,B l axit, baz tng ng) Nh vy v nguyn tc ta c th dng dung dch chun l mt axit xc nh mt baz v ngc li. Dng phng php ny c th xc nh mt s mui Na2CO3, Na2B4O7, xc nh cng ca nc, mui amni, nit trong cc hp cht hu c Dung dch chun trong phng php ny l cc axit nh HCl, H2SO4, hay kim nh NaOH, KOH . . . Cc cht ny khng p ng c cc yu cu ca cht gc nn khng phi dung dch chun gc. Do ngi ta ch chun b chng vi nng gn ng, sau xc nh nng chnh xc ca chng bng cc dung dch gc khc. V d cn xc nh nng ca dung dch axit ta dng borc (Na2B4O7.10H2O) hay Na2CO3 khan, cc cht ny p ng cc yu cu ca cht gc v dung dch c tnh baz. V d khi ho tan borc vo nc ta c phn ng: B4O72- + H2O 2H2BO3- + 2H3BO3 Tc l dung dch borc lng c th c xem nh l dung dch H3BO3 , ion H2BO3- trong dung dch b phn hu : H2BO3 + H2O OH- + H3BO3 hay tng qut li: Na2B4O7 + 7H2O NaOH + 4H3BO3 H3BO3 l axit yu nn dung dch borc c mi trng kim. Phn ng nh phn bng borc thc cht l: NaOH + HCl = NaCl + H2O T trn, phn ng HCl tc dng vi dung dch Na2B4O7 l : Na2B4O7 + 2HCl + 5H2O = 2NaCl + 4H3BO3
Na 2 B4O 7 = M 2

Ti im tng ng trong dung dch s tn ti hn hp NaCl v H3BO3, pH ca dung dch s l pH ca dung dch axit yu H3BO3. pH =
1 1 pKA - lgCA 2 2

Gi s nng ca borc l 0,1N v khi nh phn khng tnh n s tng th tch th pH = 5,12. Trong qu trnh nh phn axit, baz khi thm dn thuc th vo dung dch cn nh phn th khng km theo s thay i no m mt ta nhn thy c m ch mt ch s c trng ca dung dch l pH s thay i. Do xc nh im tng ng ngi ta phi thm vo dung dch mt ch th no .

3.5.2. Cht ch th trong phng php trung ha. 3.5.2.1. Khi nim. Cht ch th trong phng php trung ho l nhng cht m mu ca n thay i cng vi s thay i ca pH, dung dch mu ca cht ch th thay i trong mt khong gi tr pH hp, khong pH ny ph thuc vo tnh cht ca cht ch th ch khng ph thuc vo cc cht phn ng vi nhau. Cc yu cu i vi cht ch th: 1. Mu ca cht ch th phi khc nhau r rt trong nhng gi tr pH gn nhau. 2. S thay i mu ca cht ch th cn phi xy ra r rng trong mt khong nh pH.

46 3. Mu ca cht ch th cng m cng tt. 4. Lng kim hay axit thm vo lm thay i mu ca cht ch th cng t cng tt khi nh hng n kt qu nh phn. 5. S bin i mu phi thun nghch. Do nhng yu cu trn nn ta hn ch vic s dng cht ch th axit baz, s cht ch th s dng rng ri nht hin nay khng qu 20. Vic la chn ng cht ch th c ngha rt quan trng trong php nh phn. la chn chnh xc cht ch th phi bit r l thuyt v cht ch th. 3.5.2.2. Thuyt ion. Theo thuyt ny th cht ch th trong phng php trung ho l nhng axit hay baz hu c yu c dng phn t khc mu vi dng ion. V d qu c dng phn t mu , dng ion c mu xanh, n l mt axit yu. Gi s mi ch th axit u k hiu HInd v dng ion ca n -Ind- ta c s phn ly ca qu c biu din nh sau: HInd H+ + Ind xanh Khi ho tan qu vo trong nc th dng phn t v dng ion cng tn ti cho nn s c mu tm, nu thm dung dch axt vo th dung dch qu tm s c mu , ngc li nu thm baz vo th dung dch s c mu xanh. Loi ch th m c hai dng u c mu ngi ta gi l ch th hai mu. Metyl da cam cng l ch th hai mu: Trong mi trng axit th dung dch c mu , trong mi trng baz c mu vng, pH = 4 c mu hn hp ca c hai mu l da cam.

HInd H + + Ind vng Ngoi ra cn c cht ch th mt mu tc l ch th m mt trong cc dng c mu cn dng kia khng mu. V d phenolphtalein trong mi trng axit khng mu, trong mi trng baz c mu , l mt axit yu, dng phn t tn ti trong mi trng axit, dng ion tn ti trong mi trng baz: HInd H + + Ind khng mu mu Tng t nh vy ngi ta gii thch cho cc ch th l nhng baz hu c yu bng cc k hiu l IndOH v dng ion l Ind+. Trong dung dch chng phn ly theo phng trnh: IndOH Ind+ + OHNu thm kim vo dung dch th cn bng s chuyn sang tri v dung dch s c mu ca dng phn t IndOH. Nu thm axit vo th cn bng chuyn dch sang phi v dung dch s c mu ca dng ion. Tm li thuyt ion rt n gin v gii thch c nguyn nhn ca s thay i mu l do s thay i pH nhng cha gii thch c ton b tnh cht ca cht ch th. Do xut hin thuyt th hai - Thuyt nhm sinh mu.

47

3.5.2.3. Thuyt nhm sinh mu. Theo thuyt ny th mu ca cht ch th axit baz c quyt nh bi s c mt trong phn t ca chng mt s nhm nguyn t c bit (thng cha ni i).
Cc nhm ny thng l: nitro O = N c th bin i sang nhm HO = N ; az: N = N bin i sang = N NH , quan trng l nhm quynol c to ra t benzen chng c kh nng sinh mu gi l nhm sinh mu. Ngoi cc nhm trn cn c loi nhm th hai tuy chng khng c kh nng to mu cho ch th nhng s c mt ca chng cng vi cc nhm trn s tng cng v lm m mu hn cho ch th. l cc nhm OH, NH2, OCH3, N(CH3)2, N(C2H5)2 Theo thuyt ny th s thay i mu ca cht ch th l do s bin i cu trc bn trong ca phn t. Khi c s bin i cu trc bn trong ca phn t ch th th s xut hin hoc bin mt cc nhm trn v dn n s thay i cu trc ca ch th, s bin i ny l thun nghch. V d: i vi n-nitrophenol l ch th c cu trc n gin nht, s bin i tng h s l: O N O O N OH

OH O Mu vng Khng mu R rng l khi cho kim vo dung dch n-nitrophenol s xut hin nhm quynol v ch th s c mu vng, nu axit ho dung dch ni trn th mu vng s bin mt. Thuyt ny gii thch c nguyn nhn ca s thay i mu l do bin i cu trc trong phn t cht ch th nhng khng gii thch c s thay i cu trc phn t ph thuc vo pH ca dung dch. Do phi kt hp c hai thuyt trn .

3.5.2.4. Thuyt ion - nhm sinh mu. Da vo thuyt ny ngi ta gii thch c hu ht s thay i mu ca cc cht ch th axit - baz. Theo thuyt ny cht ch th axit - baz l nhng cht hu c, trong dung dch chng tn ti hai dng h bin (tc l nhng ng phn c th chuyn ho thun nghch ln nhau) c mu khc nhau, khi chng cho v nhn proton th cu trc ca n ng thi cng thay i theo v dn n s thay i mu. Mt trong hai dng h bin ca cht ch th c th l axit hu c yu hay mt baz hu c yu (cng c khi l mt cht lng tnh) Gi s mt trong hai dng h bin l mt axit yu trong dung dch s tn ti mt h 2 cn bng sau:

HInd0 I HInd II Ind- + H+ Cn bng (I) l cn bng h bin, cn bng (II) l cn bng axit-baz. Mu ca ch th trong dung dch do t s nng hai dng h bin quyt nh. Vy theo (1) khi pH thay i th cn bng (I) v (II) s chuyn dch sang tri hay sang phi do c th l thay i mu ca cht ch th. V d: Cht ch th phenolphtalein c dng h bin l axit yu, trong dung dch s tn ti theo 2 dng cn bng:

48

C O C O

OH (I) OH

C COO- OH

OH OH

(II) OH H+

Phn t khng mu (A) Khng mu (B) (Dng lacton) mi trng kim c pH 9 ta thy dung dch phenolphtalein c mu v khi cn bng (I) v (II) chuyn sang phi nn cht ch th cn bng nh dng (C). Ngc li trong mi trng axit th cn bng chuyn sang tri, to ra dng A khng mu. Metyl l mt cht ch th baz, metyl da cam l cht ch th lng tnh bi v phn t ca n va cha nhm axit SO3H va cha nhm baz N(CH3)2. Khi phn ly phn t metyl da cam to ion lng tnh va mang in tch dng va mang in tch m. Trong mi trng axit th c mu , trong mi trng baz c mu vng. H3C N+ N NH SO3- + OHH3C

O COOIon c mu (dng quynol) (C)

OH

N N SO3- + H2O vng T cc v d trn ta thy r l tu theo pH ca mi trng m cht ch th s tn ti dng nht nh no c mu khc nhau tu theo cu trc ca dng . 3.5.2.5. Khong i mu ca cht ch th axit - baz. * Phng trnh c bn. trn ta nghin cu mt cch nh tnh s i mu ca cht ch th theo pH ca dung dch. By gi ta xt mt cch nh lng, tc l tm mi quan h nh lng gia mu ca cht ch th tc l t s [HInd0]/ [Ind-] vi pH ca dung dch. Gi s ta c cn bng trn: I II HInd0 HInd Ind- + H+ p dng nh lut tc dng khi lng vo cn bng (I) v (II) ta c: - T (I): [HInd]/[HInd0] = Khb (hng s h bin) [HInd0] = [HInd]/ Khb. - T (II): [Ind-][H+]/[HInd] = Kpl (hng s phn ly - nu ch th l axit th l KA) [Ind-] = Kpl[HInd]/ [H+]. Vy: [HInd]/ Ind- = [H+]/ Khb.Kpl Ta t Kct = Khb.Kpl. Ta c: [H+] = Kct[HInd0]/[Ind-]

H3C N H3C

pH = PK ct lg

[HInd 0 ] [Ind ]

PKct = -lgKct gi l ch s cng ca cht ch th. y l phng trnh c bn biu din s ph thuc mu ca cht ch th vi pH ca dung dch. Thc vy khi ta thm vi git dung dch cht ch th no vo mt dung dch c pH xc nh th ng vi pH trong dung dch s c t s

49 [HInd0]/[Ind-] nht nh, do dung dch s c mu xc nh. Tri li khi dung dch cht ch th c mu xc nh no th s ng vi mt gi tr pH xc nh ca dung dch. * Khong i mu ca cht ch th. Theo phng trnh trn, khi thay i pH ca dung dch t s [HInd0]/[Ind-] cng thay i. Tuy nhin trong thc t ngi ta nhn thy rng khng phi mi s bin i gi tr pH ca dung dch u a n s i mu ca cht ch th m mt thng c th nhn thy c. S d nh vy v mt chng ta ch nhn thy cht ch th c mu ca mt dng h bin khi nng ca dng ny ln hn nng ca dng kia mt s ln nht nh (tu theo tng cht ch th). V d: i vi metyl da cam, mt chng ta ch nhn thy cht ch th c : - Mu ca dng HInd0 khi [HInd0]/[Ind-] 4,5 ng vi gii hn pH 3,1. - Mu vng khi [Ind-]/[HInd0] 4,5 ng vi gii hn pH 4,4. Khi pH 3,1 mt chng ta thy metyl da cam khng i mu m ch vn gi nguyn mu . Khi pH 4,4 ta cng thy metyl da cam vn gi nguyn mu vng. Vy r rng khi thay i dn gi tr pH trong phm vi trn 3,1 n 4,4 hay ngc li th mu ca metyl da cam s dn t sang vng hay ngc li (m mt ta nhn thy c). Khong gi tr pH t 3,1 n 4,4 hay t 4,4 n 3,1 ng vi s i mu gi l khong i mu ca cht ch th axit - baz. i vi phenolphtalein th t s [HInd0]/[Ind-] = 10 m KA 10-9 nn khong i mu s l 8 10. Trong trng hp ny khong i mu pH = pKA 1. Vy khong i mu (KM) ca cht ch th axit baz l khong gi tr pH trong cht ch th thay i mu m mt ta c th nhn thy c. * Ch s nh phn pT ca cht ch th. Trong khong i mu ngi ta nhn thy c mt gi tr pH m ti mu ca cht ch th bin i r nht. Gi tr pH gi l ch s nh phn ca cht ch th (pT). V d trong khong i mu ca metyl da cam pH: 3,1 4,4. Ngi ta nhn thy ti pH = 4 metyl da cam c mu da cam r nht. Vy metyl da cam c pT = 4. Vy ch s nh phn ca cht ch th axit baz (pT) l mt gi tr pH nm trong khong i mu, ng vi pH mu ca cht ch th bin i r nht . Khi nh phn thng nh dn dn dung dch chun vo dung dch phn tch c cha cht ch th v dng li khi dung dch i mu r nht.Vy r rng pT chnh l pH ca dung dch im kt thc nh phn cho nn pT c gi l ch s nh phn. Ch : - Khong i mu cng nh pT, gi tr ca chng hon ton khng chnh xc, thng sai lch 0,3 n v pH tu theo kh nng nhn mu ca mt i vi mi ngi v tu theo iu kin pha ch. - Mt s cht ch th l hai nc c hai khong i mu. V d thimol xanh c KM1: 1,2 - 2,8 ( - vng ) v KM2: 8 - 9,6 (vng - xanh). - Trong thc t ngi ta nhn thy pT c gi tr gn vi pKHInd v nm gia KM. - i lng pT ca cht ch th hai mu thng ph thuc vo nng , v rng s

50 bin i mu l do s bin i t ngt ca t s nng 2 dng (phn t v ion) [HInd0]/[Ind-] c mu khc nhau. Tuy nhin khi dng mt lng ln ch th mu ca dung dch s m hn nhng li kh nhn s i mu. - c bit i vi cht ch th mt mu, pT ph thuc kh nhiu vo nng . V d: Phenolphtalein chng hn. Trong dung dch n tn ti theo hai cn bng: HP0 HP H+ + P+ 0 -9 ta c KA = [P ][H ]/ [HP ] = 10 c th rt ra mt s kt lun sau: + Khi pH = 9 ngha l [H+] = 10-9 phenolphtalein chuyn mt na thnh dng . Bi vy khi nh phn thng thng ly mt lng nh (2 - 3 git) cht ch th th khi pH = 9 ta nhn thy ngay s i mu r nht. + Tuy nhin nu ly mt lng ln cht ch th, v d 510 git dung dch ru phenolphtalein 0,1% hay 23 git 1% th khi pH = 8 ch c 10% cht ch th chuyn sang dng nhng lc c th nhn c mu rt r ging nh trng hp trn. S d nh vy v trong c hai trng hp phenolphtalein u c cng nng dng [P-] nn c cng cng mu mc d pH ca n khc nhau. Nh vy trng hp ny mu xut hin pH = 8 tc pT = 8. Trong bng 3.1 l mt s cht ch th axit-baz thng dng.

Bng 3.1. Mt s cht ch th axit baz

Tn thng thng Thimol xanh Tropeolin oo Metyl da cam Metyl vng Metyl Bromfenol xanh Bromcrezon xanh Bromthimol xanh Fenol Fenolftalein Thimolftalein Tn ho hc Thimol sunfonftalein Axit 4 fennylaminoazo bezen-4-sunfonic Axit 4 - dimetyllaminoazobenzen-4-sunfonic n dimetylaminoazobenzen Axit 4 - dimetylaminobenzen-2-cacboxylic 3,3-5,5 - tetraboonfenol Sunfoftalein 3,3-5,5-tetrabrom-mcrezonsunftalein Fenolsunfoftalein Di-p-dioxyfenylftalit Dithimolftalit PKHInd 1,65 1,86 3,46 5,0 4,1 4,9 7,3 8,0 9,2 9,5 KM 1,2 - 2,8 8,0 - 9,6 3,1 - 4,4 2,9 - 4,0 4,4 - 6,2 3,0 - 4,6 4,0 - 5,6 6,2 - 7,6 Mu ca dng Axit Baz vng xanh vng vng vng vng vng vng vng xanh tm xanh xanh xanh xanh Nng (%) 0,04 0,1 0,04 0,04 0,1 0,1 0,1 0,1 0,1 0,1 0,1

vng 6,4 - 8,0 8,0 - 10,0 khng mu 9,4 - 10,6 khng mu

3.5.2.6. Cc yu t nh hng n khong i mu ca cht ch th. * Hiu ng mui ca cc cht in ly. - Chng lm thay i cng mu (do hp th nh sng) ca mt hay hai dng mu ca cht ch th. - nh hng n cn bng ca cht ch th: + Khi lc ion ln th c nh hng ln n mu sc ca ch th, i vi cc cht ch th khc nhau v cc mui khc nhau th rt khc nhau. V d hp th nh sng ca dung dch cha ion dinitrophenolat kh tng khi c cc cation ha tr 2 hoc 3 nhng n li gim khi c cc cation ho tr 1. Cc anion v ngay c cc cht khng in ly nh ur cng c nh hng n mu ca cht ch th.

51 + Khi lc ion nh n th hin nh i vi cn bng ca cht in ly thng. Trong thc t khi lc ion ln cn phi hiu chnh li gi tr pH i mu ca cht ch th. * nh hng ca nhit . Khi nhit thay i th hng s phn ly ca nc v cht ch th cng thay i. V vy nh hng ca nhit khng ging nhau i vi cc cht ch th khc nhau. Tu theo cu trc bn cht khc nhau ca cc cht ch th m mc nh hng ca nhit th hin nhiu hay t. Hin nay cha tm c quy lut no chung cho tc dng ny m ch da vo thc nghim. Cn ch mt iu l i vi cc cht ch th l axit yu th khong i mu hu nh khng thay i v t thay i KHInd. Nhng i vi ch th l baz yu th li ph thuc nhiu v khi nhit tng th K H O tng nn K H O /KIndOH tng. Ch th l baz yu (IndOH) ta c phng trnh
2 2

phn ly: IndOH

[IndOH] [OH ] K H 2O 1 = = . + + K IndOH K IndOH [H ] [Ind ]

Ind+ + OHv nh vy v [H + ] =
K IndOH [IndOH] nn . K H 2O [Ind + ]

khong i mu b h xung. * nh hng ca dung mi Khi dng dung mi khc nc, v d ru, axeton, . . . c hng s in mi nh hn nc th axit v baz s phn ly t hn, do nh hng n khong i mu ca cht ch th (thng di ra). * Th t chun : Th t chun rt quan trng v nh hng n chnh xc ca php nh phn. V d nh phn dung dch axit bng dung dch kim t burt dng metyl da cam lm ch th th phi i mu t hng sang vng, s i mu ny thng l khng chnh xc v kh xc nh do ngi ta nh phn theo th t ngc li, tc l nh phn kim bng dung dch axit t burt v s i mu t vng sang hng nhn d hn. Nhng i vi phenolphtalein l ch th mt mu th d dng nhn nn chun th no cng c. Cn ch mt iu na l thay i th t nh phn cc cht cng lm thay i gi tr pH khi kt thc nh phn. V d nh phn dung dch kim bng axit vi metyl da cam th kt thc nh phn pH = 4, cn nh phn axit bng kim th li kt thc pH = 4,4. Nu c hai gi tr pH trn u nm trong bc nhy th khng sao, nhng nu nm ngoi bc nhy th s nh hng n kt qu nh phn. Mun mu thay i r hn v c KM hp hn ngi ta dng ch th hn hp. Ngoi cc cht ch th c trnh by trong bng 3.1 cn c mt s loi ch th sau: Cht ch th hn hp: nhn bit s i mu mt cch r rt v chnh xc, ngoi cch chn cht ch th thch hp, ngi ta cn dng cht ch th hn hp. Nh dng cht ch th hn hp ngi ta c th nhn bit c khong i mu rt nh (0,2 0,5 n v pH). c bit khi chun cc axit baz yu hay chun dung dch axit baz rt long ngi ta thng dng ch th hn hp. C th lm nh sau: * C th dng mt hn hp 2 cht ch th axit - baz c mu khc nhau v c

52 khong i mu gn trng nhau. V d Crzol c khong i mu pH = 7,2 8,8 v Thimol xanh c khong i mu pH = 8,0 9,6. Nu ta trn theo t l 1:3 (nng 0,1%) th s c mt dung dch ch th hn hp i mu r hn khi pH = 8,2 ng vi mu thm v khi pH = 8,4 ng vi mu tm. * Trn mt cht ch th axit baz vi mt cht mu m mu ca n khng ph thuc vo pH ca dung dch. V d hn hp metyl da cam + metyl xanh. Metyl xanh khng i mu khi pH thay i, nhng mu xanh ca n phi hp vi mu ca metyl da cam v bin i nh sau: - pH = 4,4 hn hp c mu xanh l cy (vng + xanh). - pH = 4 s chuyn thnh mu xm nht. - pH = 3,6 c mu tm. Cht ch th tng hp: Ch th tng hp l hn hp gm mt s cht ch th. Loi ch th ny i mu nhiu ln cc gi tr pH khc nhau. V d: cht ch th tng hp gm 0,125g trinitrobenzen, 0,0355g phenolphtalein, 0,0300g cresolphtalein, 0,0085g metyl da cam v 0,0500g pentametoxy, c th dng xc nh gn ng pH trong khong pH t 1,2 n 12,7. Mu ca ch th tng hp chuyn t (pH=2) n da cam (pH = 4), vng (pH = 6), lc (pH = 7), xanh lc (pH = 8), chm (pH = 9) v chm tm (pH = 10). Ngi ta thng dng giy tm ch th tng hp. Khi dng giy tm ch th tng hp, ta cn nh mt git dung dch cn xc nh pH ln giy v i chiu mu trn giy vi thang mu ( ghi ch pH) l bit c pH ca dung dch. Cht ch th hunh quang: Loi ch th hunh quang thng dng khi chun cc dung dch c hoc dung dch bn thn c mu. Khi chiu tia t ngoi vo dung dch c ch th hunh quang th hoc hunh quang s xut hin hoc s mt hunh quang nhng gi tr pH nht nh. V d: ch th - naphtylamin s mt hunh quang (mu xanh) pH t 3,4 n 4,8. Khi dng ch th hunh quang nn tin hnh chun ch ti.

3.6. Cch xc nh im tng ng trong phng php trung ha. Khi chun mun xc nh im tng ng phi dng cht ch th. Trong trng hp l tng, khi kt thc chun cht ch th phi i mu chnh im tng ng, ngha l pT ca cht ch th phi trng vi pH ca dung dch im tng ng. Nhng thc t pT khng trng vi pH im tng ong, hoc ln hn hoc nh hn. Do ta s chun thiu hoc tha v dn n sai s. Nh vy php chun t kt qu tt nht, sai s nm trong phm vi cho php ngi ta thng dng hai phng php sau: - Phng php v ng nh phn hay l phng php th. - Phng php tnh sai s ch th Khi chun c th tin hnh trong dung mi nc hay khng nc. y ta nghin cu cc trng hp chun trong dung mi nc. Sau y ta s xt qu trnh chun axit-baz trong dung dch nc dng phng php th. 3.6.1. Khi nim ng nh phn - ng cong logarit Khi nh phn mt dung dch axit AX1 bng mt baz BaZ2 hay ngc li s

53 xy ra phn ng Axit Baz: AX1 + BaZ2 = BaZ1 + AX2 Trong qu trnh nng axit, baz ca hai cp thay i. Do pH ca dung dch cng thay i. Nu ta biu din s bin i trn mt h trc ta : trc tung biu din pH = -lg[H+], cn trc honh biu din lng thuc th thm vo: % hay ml th ta s c ng cong lin tc gi chung l ng cong logarit hay l ng nh phn. Vy ng nh phn l th biu din s bin i tnh cht no ca dung dch cht nghin cu theo lng thuc th thm vo trong qu trnh nh phn. C th ng nh phn axit baz l mt ng cong logarit biu din s thay i pH (trc tung) ca dung dch cht nghin cu (axit hay baz) theo lng (% hay Vml - trc honh) thuc th (baz hay axit) thm vo trong qu trnh nh phn. 3.6.2. Nguyn tc xy dng ng nh phn axit - baz. Gi s dung dch cht nghin cu l axit hay baz v dung dch chun l baz hay axit c cng nng xc nh, v d thng ly C = 0,1 v V = 100ml. Sau ta s tnh c cc gi tr pH ca dung dch ng vi cc thi im nh phn: - Trc khi chun : khi cha thm thuc th. - Trc thi im tng ng: giai on nh phn khi thm thuc th cha mt lng tng ng - gi s khi thm 50%, 90%, 99,9% lng cn thit. - Ti im tng ng: khi thm ng 100% lng thuc th cn thit. - Sau im tng ng: giai on thm tha thuc th: 100,1%, 101%, 110%, 200% - Ni cc gi tr pH li ta s c mt ng cong gi l ng nh phn hay l ng chun . Bng tnh ton v thc nghim u pH thy rng pH ca dung dch trong qu trnh chun gn im tng c s thay i t ngt, gi l bc nhy pH ca ng nh phn, da vo chn cht ch th. Thng ngi ta quy c bc nhy pH l on pH ng vi thi im cn 0,1% lng cht nghin cu (cht Vdd chun(ml) xc nh) cha c chun v 0,1% lng dung dch chun d so vi cht nghin cu, tc l khong pH ng vi F = 0,999 v 1,001

3.7. Cc trng hp chun . 3.7.1. Chun axit mnh bng baz mnh. Gi s chun 100 ml dung dch HCl 0,1M bng dung dch NaOH 0,1M. Phn ng chun : HCl + NaOH = NaCl + H2O 0,1 100 Vtd = = 100 ml 0,1 s milimol baz th m vo CV = gi F l phn axt c chun , tc l: F = s milimol axt ban u C 0 V0

54 Trong : - C0, V0 l nng v th tch ban u ca axt - C, V l nng v th tch ca baz thm vo Ta tnh pH ca dung dch trong qu trnh chun : - Khi cha thm NaOH, phn axit chun (F): F = 0, trong dung dch ch c: HCl pH = -lgCHCl = 1,0 - Khi thm 50 ml dung dch NaOH, trung ha c mt na lng HCl (F = 0,5):
C HCl =

- Khi thm 90 ml dung dch NaOH, trung ha c 90% HCl (F = 0,9):

50 0,1 = 3,33.10 2 pH = 1,48 100 + 50

[H]+

- Khi thm 99 ml dung dch NaOH, trung ha c 99% HCl (F=0,99) nh vy, cn 1% HCl:

10 0,1 = 5,26.10 3 pH = 2,28 100 + 90

[H]+ =

- Khi thm 99,9 ml NaOH, trung ha c 99,9% HCl (F = 0,999) nh vy cn li 0,1% HCl cha b trung ha:

1 0,1 = 5.10 4 pH = 3,3 100 + 99

[H]+

0,1 0,1 = 5.10 5 pH = 4,3 100 + 99,9

- Khi thm 100 ml NaoH, trung ha ht HCl (F = 1) trong dung dch ch c NaCl pH = 7. - Khi thm 100,1 ml NaOH, lng NaOH d 0,1 ml (F = 1,001).

[OH] =

0,1 0,1 = 10 4,3 pOH = 4,3 pH = 9,7 100 + 100,1

- Khi thm 101 ml NaOH, d 1 ml NaOH (F = 1,01)

[OH] = [OH] =

- Khi thm 110 ml NaOH, d 10 ml NaOH (F = 1,1)

1 0,1 = 10 3,3 pOH = 3,3 pH = 10,7 100 + 101 10 0,1 = 10 2,32 pOH = 2,32 pH = 11,58 100 + 110

Ghi cc kt qu trn vo bng 3.1 th hin mi quan h gia phn axit HCl c chun v pH ca dung dch. Biu din ln th ta c ng chun trn hnh 3.1.

Bng 3.1. Gi tr pH khi chun 100ml dung dch HCl 0,1M bng dung dch NaOH 0,1M
Phn axit c chun (F)
0,00 0,50 0,90 0,99 0,999

pH ca dung dch
1,0 1,48 2,28 3,30 4,30

55
1,000 1,001 1,01 1,10 7,0 9,7 10,7 11,68

Qua bng trn v ng chun , ta thy khi axit cha b chun (F = 0) cho n khi c chun 99,90% (F = 0,999) pH ca dung dch ch bin i 3,4 n v. Nhng khong chun thiu v tha 0,1% (F t 0,999 n 1,001) th pH thay i 5,4 n v, s thay i rt t ngt to nn bc nhy pH quanh im tng ng ng nh phn. Nu ta dng cht ch th c phn pT nm trong khong bc nhy trn (4,3 - 9,7) th kt thc chun khi cht ch th i mu th sai s ca php chun ch nm trong khong 0,1%

F
0, , ,

Hnh 3.1: ng cong chun dung dch HCl 0,1M bng dung dch NaOH 0,1M
Bc nhy pH trn ng chun ph thuc vo nng ca dung dch chun NaOH v nng ca dung dch axit cn chun HCl. Nng cng ln th bc nhy cng di. tin so snh, trong bng 3.2 trnh by s thay i pH khi trung ha 100 ml dung dch HCl 1M; 0,1M v 0,01M bng dung dch NaOH c cng nng , khi tnh c th k n s tng th tch dung dch khi chun .

56

Bng 3.2. Gi tr pH khi chun 100ml dung dch HCl 1M; 0,1M v 0,01M bng dung dch NaOH cng nhit Phn axit c chun (F)
0 0,05 0,9 0,99 0,999 1,000 1,001 1,01 1,1

pH ca dung dch 1M 0,1M 0,01M 0 1 2 0,5 1,5 2,5 1,3 2,3 3,3 2,3 3,3 4,3 3,3 4,3 5,3 7,0 7,0 7,0 10,7 9,7 8,7 11,7 10,7 9,7 12,7 11,7 10,7

Biu din d kin ca bng ny ln th c hnh 3.2

0,

Hnh 3.2 : nh hng nng ca dung dch axit v baz n tnh cht ca ng cong chun 1. Dung dch HCl 1M; 2. Dung dch HCl 0,1M; 3. Dung dch HCl 0,01M Sai s ch th Sai s ch th l sai s gy ra do im cui ca s chun (tc pT ca cht ch th) khng trng vi pH im tng ng. Sai s thng tnh theo sai s tng GD i: S% = 100 D G l gi tr gn ng; D l gi tr ng.

57

Th d 1: Tnh sai s ch th mc phi khi chun dung dch HCl 0,1M bng dung dch NaOH 0,1M nu dng cht ch th c pT = 5 v pT = 9. Phng trnh chun : HCl + NaOH = NaCl + H2O pHt = 7. 1. Khi dng cht ch th c pT = 5 tc l kt thc chun pH = 5, vic chun kt thc trc im tng ng.
S% = CVc C 0 V0 GD 100 = 100 D C 0 V0

Lng axit cha chun 100 Lng axit ban du Trong : - C, VC: nng v th tch ca dung dch NaOH thm vo - C0, V0: nng v th tch ca dung dch HCl (Du tr (-) v chun kt thc trc im tng ng nn lng axit chun (VCC) < lng axit ban u (V0C0)) 10 5 (V0 + VC ) S% = 100 10 1 V0 V kt thc chun gn im tng ng nn VC V0. Do : 10 5.2 V S% = 1 0 100 = 0,02% 10 .V0 2. Khi dng ch th c pT = 9, tc l kt thc chun pH = 9, vic chun kt thc sau im tng tc l d NaOH. Lng kim d S% = + 100 Lng kim cn chun (Du cng (+) v chun tha, tc l lng NaOH dng (VCC) > lng kim d cn chun V0C0). Kt thc pH = 9 [H+] = 10-9 [OH-] = 10-5 [OH ][V0 + VC ] = 10 5.2V0 100 = +0,02% S% = + C 0 V0 0,1.V0 Th d 2: Nu chun dung dch HCl 0,1M bng dung dch NaOH 0,1M th cn kt thc chun pH bng bao nhiu (hay dng cc cht ch th c pT bng bao nhiu) sai s cho php chun khng qu 0,1%. Sai s khng qu 0,1% tc l sai s trong khong t -0,1% n 0,1%. - Khi sai s -0,1% S = -0,001 hay 10-3, vic chun kt thc trc im tng ng nn: [ H + ](V0 + VC ) 3 (vi V0 VC ) 10 = C 0 V0 = 10
3

[H ].2V =
+

10 4 [H ] = 10 1.V0 2
0

58
10 4 = 4 + lg 2 = 4,3 pH = lg 2 - Khi sai s bng +0,1% S = 0,001 = 10-3, vic chun kt thc sau im tng, d NaOH nn: [OH ](V0 + VC ) (vi V V ) S= 0 C C 0 V0 10 4 2 10 1.V0 pOH = 4,3 pH = 14 4,3 = 9,7 Vy, php chun c sai s 0,1% th kt thc chun trong khong pH: 4,3 - 9,7. Tc l php chun c th dng cc cht ch th c pT nm trong khong gi tr 4,3 - 9,7. 3.7.2. Chun axt yu bng baz mnh hoc baz yu bng axit mnh. 3.7.2.1. Chun CH3COOH bng dung dch chun NaOH. Gi s chun 100ml dung dch CH3COOH 0,1M bng dung dch NaOH 0,1M. pK CH COOH = 4,75. Phn ng chun : CH3COOH + NaOH = CH3COONa + H2O - Khi cha thm NaOH, trong dung dch ch c CH3COOH 0,1M (C0) pH ca dung dch tnh theo cng thc: 10 3 =
0

[OH ].2V

[OH ] =

[H ] =
+

K A C A pH =

1 1 pK A lg C A 2 2

- Khi thm NaOH nhng cha trung ha ht, trong dung dch c CH3COOH/CH3COO-, pH ca dung dch c tnh theo cng thc:
pH = pK A lg CA CB

- Khi thm NaOH va trung ha ht CH3COOH, trong dung dch ch c CH3COO- l mt baz yu, pH ca dung dch c tnh theo cng thc:

[H ] =
+

K A K H 2O

C0 + C C0C
3

Hay tnh: pOH = K CH COO .C B ri tnh pH = 14 - pOH - Khi thm d NaOH, trong dung dch c NaOH d v CH3COO-. V CH3COOl mt baz yu bn cnh NaOH l mt baz mnh nn pH ca dung dch c tnh theo NaOH d. Tnh theo cng thc trn ta c cc gi tr pH bin i theo lng CH3COOH c chun (F) nh sau:

Phn axit chun (F)

0 0,2 0,5

PH ca dung dch
2,88 4,20 4,81

59
0,9 0,99 0,999 1,00 (im tng ng) 1,001 1,01 1,1 2,0 5,80 6,80 7,8 8,87 9,7 10,68 11,62 12,52

Biu din cc d kin ca bng trn ln th, ta c hnh 3.3 pH 14 10 8 4 0 1

HCl 0,1M
T Bc nhy pH ng tng ng

CH3COOH 0,1M

F 2

Hnh 3.3. ng nh phn 100ml dung dch CH3COOH 0,1M bng dung dch NaOH 0,1M
Nhn vo hnh 3.3 v so snh vi hnh 3.1 ta thy: 1. im tng ng khi chun axit yu bng baz mnh khng trng vi im trung ha (c pH = 7) m nm min kim (pHt = 8,87). 2. ng cong chun trong chun axit yu bng baz mnh khng i xng so vi im tng ng (khc vi hnh 3.1). 3. Bc nhy khi chun axit yu bng baz mnh (7,8 - 9,7) nh hn rt nhiu so vi bc nhy khi chun axit mnh vi cng khong sai s 0,1% (4,3 9,7). 4. Cng nh trng hp chun axit mnh bng baz mnh th bc nhy ca ng chun cng ph thuc vo nng . Nng cng ln th bc nhy cng di. V d: chun dung dch CH3COOH bng dung dch NaOH c cng nng , bc nhy t F = 0,998 n F = 1,002 c pH nh sau:

Nng CH3COOH C0 1M 0,1M 0,01M 0,001M

pH khi F = 0,998 7,45 7,45 7,44 7,37

pH khi F = 1,002 11,0 10,0 9,0 7,8

pH 3,55 2,55 1,56 0,43

Bc nhy ca ng cong nh phn cng ngn khi axit cng yu. 5. T nhn xt trn ta thy r rng bc nhy pH ca ng nh phn axit di

60 hay ngn ph thuc vo mnh hay yu ca axit m ta nh phn, ngha l ph thuc vo hng s axit KA, KA cng ln bc nhy pH cng di, KA cng nh bc nhy pH cng ngn v tt nhin KA nh n mc no th s khng c bc nhy pH. 3.7.2.2. Chun dung dch NH3 bng dung dch HCl. Gi s chun 100ml (V0ml) dung dch NH3 0,1M (C0) bng dung dch HCl 0,1M (C); cho pK NH = 4,75. Phn ng chun : NH3 + HCl = NH4Cl - Khi cha thm HCl trong dung dch ch c NH3 l mt baz yu, vy pH ca dung dch c tnh theo cng thc: [OH ] = K B C B ri tnh pH = 14 - pOH. - Khi chun , trc im tng ng trong dung dch c NH4+ + NH3, l h m nn:
3

pH = pK A lg

CA l nng ca NH4+; CB l nng ca NH3. - Ti im tng ng, trong dung dch ch c NH4Cl l mt axit yu nn: 14 [H + ] = K A C A vi : K A = 10 = 10 9, 25 K NH
3

CA vi pKa = 14 - pKB CB

Vi CA l nng ca NH4 . - Khi thm HCl d, trong dung dch c HCl d v NH4+. V NH4+ l mt axit yu bn cnh HCl l mt axit mnh, nn pH ca dung dch c tnh theo HCl d. Tnh theo cng thc trn, ta c cc gi tr pH bin i theo lng NH3 c chun (F) nh sau (vi quy c chun thiu v tha 0,2% lng baz)

Phn NH3 chun (F) 0 0,5 0,9 0,99 0,998 1,00 (im tng ng) 1,002 1,01 1,10

pH ca dung dch 11,13 9,26 8,36 7,26 6,56 5,13 3,7 3,0 2,0

Biu din cc d kin ca bng ln th ta c hnh 3.4.

61

pH 14 10 6 2 0 100 200 VHCl ( NH l) 4OH Hnh 3.4. ng nh phn dung dch 0,1M bng dung dch HCl 0,1M Ging trng hp chun axit yu bng baz mnh, ng cong chun baz yu bng axit mnh cng cho thy: 1. im tng ng khng trng vi im trung ha, m min axit (pHt = 5,13). Bc nhy pH: 6,5 - 3,7. ng cong chun khng i xng so vi im trung ha. 2. Bc nhy ca ng chun cng ph thuc vo nng v hng s phn li ca baz yu. Sai s ch th. Th d 1: Tnh sai s mc phi khi chun CH3COOH 0,1M (pKA = 4,74) bng dung dch NaOH 0,1M nu dng cht ch th metyl da cam (pT = 4), pHt = 8,87 (xem cch tnh trn). Dng ch th c pT = 4, ngha l kt thc chun pH = 4, ngng chun trc im tng, v vy trong dung dch cn CH3COOH cha c chun . Ta c: CH3COOH H+ + CH3COO[H + ][CH 3COO ] [CH 3COOH] = [H + ] KA = [CH 3COOH] [CH 3COO ] K A
T s : CH 3 COOH Lng axit cha b chun = CH 3 COO L ng axit b chun =
NaOH 0,1M NH4OH 0,1M Bc nhy pH

10 -4 = 10 0, 74 = 5,5 4 , 74 10 - Lng axit cha b chun 5,5 S% = 85% 100 = Lng axit ban du 1 + 5,5 Ngha l c 85% axit cha c chun . Th d 2: Tnh sai s mc phi khi chun dung dch NH3 0,1M (pKb = 4,74) bng dung dch HCl 0,1M nu dng ch th c pT = 9 v pT = 4; pHt = 5,13 (xem cch tnh trn). * Dng ch th c pT = 9, ngha l kt thc chun pH = 9, ngng chun trc im tng ng (v chun kim bng axit th trong qu trnh chun

62 pH gim dn), v vy, trong dung dch cn NH3 cha b chun . Ta c: NH3 + H2O NH4+ + OHKB =

[NH ][OH ] [NH ] = [OH ] [NH ] [NH ] K

+ 4

T s

[NH ]
3 + 4

[NH ] = Lng kim cha b chun

NH 3 c chun
=
10 -5 = 10 0, 26 = 0,55 4 , 74 10

3 + 4

S% =
=

- Lng NH 3 cha chun 100 Lng NH 3 ban du

[NH 3 ] 0,55 = 35% 100 = + 1 + 0,55 NH 4 + [NH 3 ]

Sai s ln, vy khng dng phenol phtalein lm ch th chun dung dch NH3 bng HCl c. * Dng cht ch th c pT = 4, vic chun kt thc sau im tng ng: Lng axit d S% = + 100 Lng axit dng chun Axit d l axit mnh HCl nn nng axit d chnh l [H+] = 10-4. Do :
S% = + S% = +

[H ].(V
+

+ Vc ) 100 10 .V0
0 1

10 4.2V0 100 = 0,2% 10 1.V0

3.7.3. Chun axit yu bng baz yu hay ngc li. nh phn 100ml dung dch CH3COOH bng dung dch NH3 cng nng C = 0,1M. 3.7.3.1. Kho st ng nh phn. * Trc khi chun : Ta c dung dch axit yu CH3COOH 0,1M, tnh pH theo cng thc (2.5):
pK CH 3COOH = 4,75 pH = 1 1 (pK A lg C A ) = (4,75 lg10 1 ) = 2,87 2 2

* Trong qu trnh chun : Khi nh dn dung dch NH3 vo dung dch CH3COOH s c phn ng xy ra:
CH3COOH + NH 3 CH 3COO - + NH+ 4 Ax1 Baz2 Baz1 Ax2 C pKA1 = 4,75 ; pKA2 = 9,25. V CH3COOH v NH3 u yu nn lun lun tn ti trong dung dch 2 cp axitbaz: CH3COOH/CH3COO- v NH4+/NH3 n gin v tnh gn ng ta p dng cng thc (2.16) tnh pH ca dung

63 dch hn hp Ax1: CH3COOH + Baz2: NH3 trong qu trnh chun :

pH =
3

C 1 pK A1 + pK A2 + lg B2 2 C A1

CB2 = C NH : Nng NH3 lc bt u trn (nng ban u). CA2 = C CH COOH : Nng ca CH3COOH lc bt u trn (nng ban u)
3

- Trc im tng ng:

99,9 ; 100

C B2 <1 C A1

V d khi thm 99,9ml NH3 ta c:

C B2 = 0,1. C B2 99,9 1 99,9 = pH = 4,73 + 9,25 + lg 6,99 C A1 100 2 100

CA2 = 0,1. - Ti im tng ng:

C B2 1 = 1 pH = (4,73 + 9,25) = 6,99 C A1 2 C B2 Sau im tng ng: >1 C A1

Gi s khi thm 100,1ml NH3 ta c:

C B2 = 0,1. 100,1 ; 100 C B2 100,1 1 100,1 = pH = 4,73 + 9,25 + lg 6,99 C A1 100 2 100

CA2 = 0,1. Vy r rng gn im tng ng khng c bc nhy pH. Da vo cch tnh pH nh trn cc thi im nh phn ta s v c ng nh phn c dng sau: (hnh 3.5) pH
1

6 7

axit d 0 kim d 10 % Hnh 3.5. ng nh phn 0,1M dung dch CH3COOH bng dung dch NH4OH 0,1M

13

10

3.7.3.2. Kt lun: Trong trng hp ny, trn ng nh phn khng c bc nhy pH nn khng chn c cht ch th axit - baz xc nh im tng ng c chnh xc, do ta khng th chun axit yu bng baz yu chnh xc c. Vy, mun nh phn chnh xc axit hay baz theo phng php trung ha khi

64 dng cht ch th axit - baz th mt trong hai cht tc dng (axit hay baz) phi l axit mnh hay baz mnh. 3.7.4. Chun a axit (hay a baz), hn hp axit (hn hp baz). 3.7.4.1. Chun a axit bng baz mnh. Cc a axt mnh nh H2SO4 c K1 = , K2 = 10-2. V vy, vic chun H2SO4 bng NaOH cng nh chun HCl. Cn cc a axt yu th khi chun s xy ra theo nhiu nc. V d nh phn 100 ml H3PO4 0,1M bng dung dch NaOH 0,1 M. Trong dung dch H3PO4 l axit 3 nc tn ti theo 3 cn bng : H3PO4 H+ + H2PO4ng vi K1 = 7,51.10-3 pK1 = 2,12. + 2H2PO4 H + HPO4 ng vi K2 = 6,23.10-8 pK2= 7,21. HPO42H+ + PO43ng vi K3 = 2,2.10-13 pK3 = 12,67. Theo 3 phn ng trn, dung dch H3PO4 c coi nh hn hp 3 axit: H3PO4 + H2PO4- + HPO42- vi cc nng C1, C2, C3 v K1 >> K2 >> K3, do khi dng dung dch NaOH chun th H3PO4 s c trung ha gn nh hon ton ln lt ht tng nc: nc 1: H3PO4 + NaOH NaH2PO4 + H2O ng vi im tng ng 1. nc 2: H2PO4- + NaOH Na2HPO4 + H2O ng vi im tng ng 2. nc 3: HPO42- + NaOH Na3PO4 + H2O ng vi im tng ng 3. * Tnh pH ca dung dch trong qu trnh chun : - Trc chun : Ta c dung dch axit: H3PO4 c th tnh theo cng thc:
pH =

- im tng ng 1: khi chun H3PO4 n H2PO4-, ta c dung dch lng tnh (mui axit NaH2PO4), c th tnh pH theo:
pH =

1 (pK1 lgC A ) = 1 2,1 lg10 1 = 1,55 2 2

- im tng ng 2: khi chun n HPO42-, ta c dung dch lng tnh (mui axit Na2HPO4), c th tnh pH theo:
pH =

1 (pK 1 + pK 2 ) = 1 (2,1 + 7,2) = 4,6 2 2

- im tng ng 3: khi chun n PO43-, ta c dung dch baz (Na3PO4), c th tnh pH theo :
pH = 7 + 1 (pK 3 + lgC B ) = 7 + 1 12,6 + lg10 1 = 12,8 2 2

1 (pK 2 + pK 3 ) = 1 (7,2 + 12,6) = 9,9 2 2

* Cch xc nh cc im tng ng: Xc nh cc im tng ng 1, 2 tc l cc im tng ng trc im tng ng cui cng: Trc ht chng ta phi tnh bc nhy pH gn cc im tng ng 1, 2 theo nguyn tc sau: - Mun nh phn t chnh xc 1% khi pK 3,6 th s kt thc nh phn trong khong pH sau: pK = 4 th pK2 - 1,8 pH pK1 + 1,8. pK 4 th pK2 2 pH pK1 + 2. - Mun nh phn t chnh xc 0,1% khi pK 5,6 th s kt thc nh

65 phn trong khong bc nhy pH sau: pK = 6 th pK2 - 2,8 pH pK1 + 2,8. pK 6 th pK2 - 3 pH pK1 + 3. Theo nguyn tc ny ta s tnh c nh sau: - im tng ng 1: ta c pK = pK2 pK1 = 7,2 - 2,1 = 5,1. Vy mun t chnh xc 1% ta c th kt thc nh phn trong khong bc nhy pH: 7,2 - 2 pH 2,1 + 2 tc 5,2 pH 4,1 - im tng ng 2: Ta c pK = 12,67 - 7,21 = 5,46 bc nhy pH s l: 12,67 - 2 pH 7,21 + 2 tc 10,67 pH 9,21 -13 - im tng ng 3: v K3 = 2,2.10 < 10-7 nn s khng c bc nhy. Nh vy im tng ng I nm gn khong i mu ca metyl da cam (3,1 4,4), nu dng metyl da cam th ta c th nh phn H3PO4 nh mt n axt, tc H3PO4 + OHH2PO4- + H2O, ng lng gam ca H3PO4 y bng chnh phn t gam ca n. Vi ch th phenolphtalein (chnh xc hn l thimolphtalein) (9,4 10,6) c th nh phn H3PO4 nh l a axt hai nc H3PO4 + 2OHHPO42- + H2O. ng lng gam ca H3PO4 pH bng mt na phn t gam. Khng th nh phn trc tip 1 - H3PO4 H3PO4 n nc 3 v khng c 2 NaH2PO4 4 bc nhy pH. ng nh phn 5 c hnh dng nh hnh v 3.6. Na2HPO4 Trong thc t ngi ta c 9 th nh phn H3PO4 n nc th Na3PO4 3 bng cch gin tip nh sau: 13 1 2 3 Cho CaCl2 tc dng vi H3PO4, S mol NaOH mt lng tng ng HCl c gii phng ra v ngi ta Hnh 3.6. ng nh phn 0,1M dung dch H3PO4 bng dung dch NaOH 0,1M nh phn lng HCl bng NaOH: 2H3PO4 + 3Ca2+ Ca3(PO4)2 + 6H+ 6H+ + 6OH- 6H2O ng lng gam ca H3PO4 trong trng hp ny bng 1/3 phn t gam ca

n. 3.7.4.2. Chun a baz bng axit mnh. Ta xt s chun dung dch Na2CO3 (hay K2CO3) bng dung dch chun HCl, CO32- l mt a baz c pKb1 = 10-4,65 K b1 =
v pKb2 = 10-7,68 K 2(H 2CO 3 )
K H 2O

K H 2O K b2 = . Cn c vo 2 gi tr pK ta thy c th chun CO32- bng HCl K 1( H 2 CO 3 )

theo 2 nc:

66

* Nc 1: CO32- + H+ = HCO3pH td1 =

1 (pK a1 + pK a 2 ) = 1 (6,62 + 10,35) = 8,34 2 2

pH ny nm trong khong chuyn mu ca phenol phtalein. V vy, c th dng n lm cht ch th chun CO32- bng HCl theo nc th nht. * Nc 2: HCO3- + H+ = CO2 + H2O pHtd2 l pH ca dung dch bo ha CO2 v khi d 1 git dung dch axit chun, pH khong bng 4 nm trong khong i mu ca metyl da cam. V vy c th dng cht ch th ny chun CO32- ti nc th hai. 3.7.4.3. Chun hn hp axt (hn hp baz). Trong thc t thng hay phi chun hn hp axt, c cc trng hp sau: nh phn hn hp axt mnh v axt yu, nh phn hn hp axt yu. Gi s ta phi nh phn hn hp axt A1, A2, A3 c nng ban u tng ng CA1, CA2, CA3 v cc hng s axit tng ng KA1, KA2, KA3 ta xt hai trng hp thng gp sau: Trng hp KA1 KA2 KA3. Trong trng hp ny ta ch xc nh c nng tng cng ca 3 axit CA1 + CA2 + CA3 v ty theo gi tr ca KA s ri vo trng hp nh phn axit mnh hay nh phn axit yu. Trng hp KA1 >> KA2 >> KA3: trng hp ny ging nh nh phn axit. Qu trnh nh phn s xy ra ln lt theo 3 phn ng sau: A1 + NaOH B1 + Na+.H2O ng vi im tng ng I A2 + NaOH B2 + Na+.H2O ng vi im tng ng II A3 + NaOH B3 + Na+.H2O ng vi im tng ng III Ch : Chun dung dch hn hp baz cng tng t nh chun dung dch hn hp axit. 3.7.5. Mt s th d v phng php chun axit - baz. 3.7.5.1. Pha ch dung dch chun HCl, NaOH. NaOH v HCl u khng phi l cht gc nn: * pha dung dch NaOH nng khong 0,1M ta cn trn cn k thut khong 4,1g NaOH loi tinh khit phn tch v pha thnh 1 lt dung dch bng nc ct mi un si ngui. Dung dch mi pha ng trong bnh polyetylen. xc nh chnh xc nng dung dch NaOH trc khi dng ta cn chun bng dung dch chun axit oxalic 0,05M vi cht ch th l phenolphtalein. Axit oxalic l cht gc c cng thc l H2C2O4.2H2O (M=126,066). Dng cn phn tch cn 6,3033 (g) tinh th H2C2O4.2H2O (tkpt), chuyn vo bnh nh mc sch 1 lt, ha tan bng nc ri nh mc ti vch mc. Dung dch ng trong bnh polyetylen hoc bnh thy tinh nt nhm. Dng pipet ly 25 ml dung dch H2C2O4 0,05M va pha cho vo bnh nn dung tch 250 ml ra sch v trng 3 ln bng nc ct. Thm vo 2 git cht ch th phenol phtalein. T buret dung tch 50ml (hay 25ml) ng dung dch NaOH cn xc nh nng , nh t t dung dch NaOH vo bnh nn, va nh va lc u cho ti khi dung dch chuyn sang mu hng nht bn trong vi giy. Tin hnh chun 3 ln ly kt qu trung bnh. Gi s th tch trung bnh NaOH ca 3 ln th nghim l VNaOH nng chnh xc ca dung dch NaOH s l:

67
25.0,05 2(mol / l ) VNaOH

C NaOH =

* pha dung dch HCl c nng khong 0,1M, ta ly khong 8,3 -8,5 ml dung dch HCl c (c nng khong 35 - 38%, D = 1,174 - 1,185 g/cm3) cho vo bnh ra sch, thm nc thnh 1 lt, lc u. ng dung dch trong bnh polyetylen hay bng bnh thy tinh c nt mi nhm. xc nh chnh xc nng dung dch va pha, ta cho n vo burt, ly 25 ml dung dch chun NaOH vo bnh nn ra, trng sch. Thm 1 - 2 git cht ch th phenolphtalein. Chun dung dch bng dung dch HCl t buret n khi dung dch chuyn t mu sang khng mu. Lm th nghim ba ln ri ly kt qu trung bnh v tnh nng dung dch HCl.
C HCl = C NaOH .VNaOH (mol / l) 25

3.7.5.2. Xc nh nng dung dch CH3COOH v dung dch NH3. * Chun dung dch CH3COOH bng dung dch chun NaOH. Cch tin hnh: Ly dung dch chun NaOH vo buret sch. Dng pipet ly 25ml dung dch CH3COOH cho vo bnh nn sch, thm vo 2 git phenolphtalein. Tin hnh chun bng dung dch NaOH n khi dung dch chuyn t khng mu sang mu hng bn trong vi giy. Lm 3 ln th nghim v ly kt qu trung bnh ri tnh kt qu. V nng dung dch CH3COOH cha bit nn trc khi chun chnh xc ta nn lm th nghim thm d, nu nng dung dch CH3COOH c qu hoc long qu th phi pha long hoc ly tng th tch ln th tch dung dch chun tiu tn ht t nht trn 20 ml. * Chun dung dch NH3 bng dung dch chun HCl. Cch tin hnh th nghim tng t nh chun CH3COOH bng NaOH. Ch khc l ly 25 ml dung dch NH3 cn chun cho vo bnh nn, cht ch th dng l metyl da cam, cn buret ng dung dch chun HCl. Vic chun kt thc khi dung dch chuyn t mu vng sang mu . Cng tin hnh chun 3 ln ly kt qu trung bnh ri tnh kt qu. 3.7.5.3. Xc nh nng dung dch H3PO4 bng dung dch NaOH. Gi s ta cn xc nh nng ca H3PO4 c. Cch tin hnh: Dng cc cn sch kh, cn trc khi lng. Dng pipet ly vo cc cn 5ml H3PO4 c cn xc nh nng . Cn trn cn phn tch. Gi s khi lng ca 5 ml axit l 8,3000 (g). Chuyn ton b lng axit va cn vo bnh nh mc 100 ml ra sch, trng ton b lng axit trong cc cn vo bnh nh mc, thm nc ct ti vch nh mc, y nt lc k. Dng pipet sch v trng nhiu ln bng dung dch H3PO4 va pha, ly 25 ml dung dch H3PO4 va pha cho vo bnh nn dung tch 250 ml ra sch. Thm vo 2 git phenol phtalein. Chun bng dung dch NaOH 1M n khi dung dch chuyn t khng mu sang mu hng bn trong vi giy. Tin hnh chun 3 ln ly kt qu trung bnh. Gi s VNaOH = 41,0 ml. Hm lng % theo khi lng ca H3PO4 l:

68
41 1 100 98 100 = 96,82% 1000 25 8,300 2
3 4

%H 3 PO 4 =

V dng ch th phenol phtalein nn chun ti nc th hai, do lg H PO = 98/2. 3.7.5.4. Xc nh Na2CO3 trong xt k thut. Xt k thut lun lun cha mt lng Na2CO3 do NaOH hp th kh CO2 trong khng kh. Cch tin hnh: Cn a (g) xt k thut, ha tan trong nc ct un si ngui cho vo bnh nh mc 100ml. Dng pipet (th d 25 ml) ly mt th tch chnh xc dung dch ny cho vo bnh nn sch, dung tch 250 ml. Thm vo 1 - 2 git phenolphtalein, dung dch s c mu . Chun bng dung dch chun HCl bit chnh xc nng n khi dung dch va mt mu hng. Khi xy ra 2 phn ng. NaOH + HCl = NaCl + H2O Na2CO3 + HCl = NaHCO3 + NaCl 1 (v pH ca dung dch lc l pH ca dung dch NaHCO3, pH = (pK 1 + pK 2 ) nm 2 trong khong i mu ca phenolphtalein). c v ghi th tch dung dch HCl tiu tn, gi s ht V1 ml dung dch HCl. Thm tip vo bnh nn 2 -3 git metyl da cam, dung dch c mu vng. Tip tc chun n khi dung dch chuyn t mu vng sang mu da cam. Ngng chun v ghi th tch V2 trn buret. Lm th nghim 3 ln v ly kt qu trung bnh (th tch V2 tnh t vch 0 ca buret). Nh vy, V2 -V1 l th tch dung dch HCl cn dng chun NaHCO3. V V1 l th tch dung dch chun HCl dng chun NaOH v nc 1 ca Na2CO3 thnh NaHCO3 nn V1 - (V2 - V1) = 2V1 - V2 l th tch dung dch HCl cn dng chun NaOH. Hm lng % ca NaOH v Na2CO3 c a (g) xt k thut l:
% NaOH =

(2V1 V2 )
1000 1000

.C HCl .

% Na 2 CO 3 =

(V2 V1 )

40 100 1 a 100 a

.C HCl M Na 2CO3

3.7.5.5. Xc nh magi (Mg2+) hoc phtpht (PO43-) Trong mi trng NH3 + NH4Cl, ion Mg2+ kt ta vi ion HPO42-. Mg2+ + NH4+ + HPO42- = MgNH4PO4 + H+ Lc v ra sch kt ta, ha tan kt ta bng mt lng d chnh xc dung dch chun HCl, sau chun lng HCl d bng dung dch chun NaOH vi ch th metyl da cam. MgNH4PO4 + 2H+ = Mg2+ + NH4+ + H2PO4H+(d) + OH- = H2O M M Theo cc phn ng trn Mg = v PO = 2 2
2+ 34

%Mg =

(VHCl. C HCl VNaOH .C NaOH )

1000

M Mg 2

100 a

69

%PO 4 =

(VHCl .C HCl VNaOH .C NaOH )

1000

M PO
2+

100 a

Cch tin hnh: Dung dch cha Mg cho vo cc 200ml, thm 4 - 6 git dung dch HCl 1M, 10 ml dung dch Na2HPO4 10% (nu xc nh PO43- th thm lng d dung dch MgCl2 5%), 2 - 3 git metyl da cam, pha long bng H2O n khong 80 ml, nu dung dch b c th thm vi git HCl n tan, sau thm tip 5 ml HCl na. un nng dung dch NH3 5% va thm va khuy, ti khi dung dch chuyn sang mu vng. Thm tip 3ml NH3 na. yn cc 2 - 3 gi. Lc kt ta bng giy lc bng xanh. Ra kt ta bng nc ti khi nc ra chy ra khng c ion Cl- (th bng dung dch AgNO3). Sau ra kt ta 3 ln bng dung dch ru etylic 50. Chuyn ton b kt ta v giy lc vo cc sch. Thm vo mt lng d chnh xc dung dch chun HCl. Khuy cho kt ta tan ht. Chun lng HCl bng dung dch chun NaOH dng cht ch th metyl da cam. Ch chung: 1. Tt c cc trng hp nh phn nghin cu trn u kho st nhit trong phng th nghim thng khong t (20 25)0C. Nu ta kho st nhit khc th cc gi tr pH tnh c trong qu trnh nh phn c khc i mt t. Tuy nhin s sai khc c thc t khng dng k, nu khi tin hnh nh phn nhit khng khc vi nhit 220C nhiu lm. 2. Cc trng hp nh phn axit - baz va nghin cu u tin hnh trong dung mi nc, ngoi ra ngi ta cn thng nh phn axit - baz trong dung mi khc khng phi l nc. Trong nhiu trng hp nh phn axit - baz trong dung mi khng nc t ra u vit hn l nh phn axit - baz trong dung mi nc v rng trong mt s trng hp axit hay baz trong nc l dung dch axit hay baz qu yu khng th nh phn chnh xc c, tri li nu chn dung mi khng nc thch hp th axit hay baz tr nn mnh iu kin nh phn chnh xc c. Bi vy ngy nay phng php nh phn axit - baz trong dung mi khng phi l nc ngy cng c p dng rng ri.

BI TP
1. Cc cht v ion sau y, cht no l axt, baz hoc lng tnh: HClO4, NH3, CO32-, HCO3-, H2CO3, S2-, NH4+, CH3COO-. 2. Hi phi thm vo dung dch c pH = 0 thuc th no sau y c mi trng axt yu: NH3, NaOH, CH3COONa, HCl, CH3COOH, NH4Cl. 3. Tnh pH ca cc dung dch sau: a. 0,1M HCl v 0,1M CH3COOH. b. Dung dch 5% HCl v 5% CH3COOH; ddd = 1,1 g/ml. c. Dung dch cha 7 g/l HCl v 7g/l CH3COOH. 4. Tnh pH ca dung dch thu c khi thm 0,102g CH3COONa vo 100ml dung dch 0,0375M CH3COOH. Bit pK CH COOH = 4,75. 5. Tnh pH ca dung dch thu c khi trn ln:
3

70 a. 50ml 0,1M KH2PO4 v 25ml 0,2M K2HPO4. Bit H3PO4 c pK1 = 2,16; pK2 = 7,13; pK3 = 12,3. b. 30ml 0,1M Na2CO3 v 15ml 0,1M NaHCO3. Bit H2CO3 c pK1 = 6,32; pK2 = 10,32. 6. Phi thm vo 100ml 0,2M HCOOH bao nhiu gam natri foocmat rn HCOONa c dung dch m vi pH = 4,3. Bit pKHCOOH = 3,77. 7. Cn bao nhiu gam CH3COONa ha tan trong 50ml dung dch CH3COOH 0,04M c pH = 5,43. 8. Tnh pH ca dung dch cha NH4Cl 0,01M v NH3 0,1M. Bit K NH = 1,75.10 5 .
3

9. Nng M v N ca dung dch H2SO4 l bao nhiu nu dung dch H2SO4 c TH SO = 0,005122 ? 10. Nng N ca dung dch Ba(OH)2 l bao nhiu nu dung dch c TBa ( OH ) / CH COOH = 0,0121 ?
2 4

11. G a. Hy tnh THCl / NH ca dung dch HCl 0,1125N ?

3

b. Hy tnh nng M, THCl, THCl/CaO ca dung dch HCl 0,1122N? 12. Cn bao nhiu ml dung dch HCl bc khi (axt c) c t trng 1,19 chun b 1.500ml dung dch HCl 0,2N. Bit rng dung dch HCl c t trng bng 1,19 th tng ng vi 38,32% (phn trm theo trng lng). 13. Hi phi pha long 1 lt dung dch HCl 0,2N n th tch l bao nhiu thu c dung dch c chun theo cht xc nh CaO l 0,005? 14. Tnh THCl/CaO ca dung dch HCl nu nh nh phn 0,104g Na2CO3 vi ch th metyl da cam (pT = 4) th tn mt 25,14ml dung dch HCl . 15. Khi nh phn 20ml dung dch HCl c chun T = 0,003512 th tn mt 21,12ml dung dch NaOH. Hy tnh TNaOH/HCl, TNaOH, TNaOH / H SO ca dung dch NaOH trn. 16. trung ha 0,5g hn hp Na2CO3 v K2CO3 ti CO2 cn 39,5ml dung dch HCl 0,2N. Xc nh % Na2CO3 trong hn hp. Bit rng trong hn hp khng cha cc cht khc na. 17. Trung ha 0,2g axt hu c th rn cn 31,7ml dung dch KOH 0,1N. Tnh ng lng gam ca axt v xc nh l cht g?
2 4

TI LIU THAM KHO

1. Hong Minh Chu, T Vn Mc, T Vng Nghi. C s ha hc phn tch, NXB KH & KT, 2002. 2. Nguyn Tinh Dung phn I, II, III. Ha hc phn tch. NXB Gio dc, 2000. 3. Trn T Hiu, Ha hc phn tch, NXB HQG H Ni, 2002. 4. Trn T Hiu, T Vng Nghi, Hong Th Tn. Bi tp Ha hc phn tch, NXB H&TH Chuyn nghip, 1984. 5. H.A. Laitinen, Phn tch ha hc. Tp 1 v 2, Nguyn Tinh Dung v Nguyn Huyn dch. NXB KH & KT, 1976.

71

CHNG 4

CN BNG OXY HA - KH. CHUN OXY HA - KH

4.1. Cn bng oxy ho - kh. 4.1.1. Phn ng phn ng oxy ho - kh v cch thnh lp cc phng trnh oxy ha - kh theo phng php ion - electron. 4.1.1.1. nh ngha phn ng oxy ha - kh. Cc phn ng oxy ho - kh l cc phn ng xy ra c km theo s trao i electron gia cc cht tham gia phn ng. Mt phn ng oxy ha - kh bao gi cng bao gm 2 qu trnh : cho v nhn electron. Cht oxy ha l cht c kh nng nhn electron . Cht kh l cht c kh nng cho electron. Mi cht oxy ha sau khi nhn electron tr thnh dng kh lin hp vi n v ngc li, khi cht kh cho electron th n s chuyn thnh dng oxy ha lin hp. Qu trnh cht kh cho electron l qu trnh oxy ha v qu trnh cht oxy ha nhn electron l qu trnh kh. Nh vy mt phn ng oxy ha - kh y bao gm hai na phn ng v ta c th biu din bng s n gin sau: OX1 + ne Kh1 Kh2 - ne OX2 OX1 + Kh2 Kh1 + OX2 (4.1) Trong thc t phn tch chng ta thng s dng cc phn ng oxy ha kh tch v nhn ra cc ion. V d v cp oxy ho - kh lin hp: Cht oxy ha Cht kh Fe3+ + e Fe2+ Zn2+ + 2e Zno Cl2 + 2e 2Cl[Fe(CN)6]3- + e [Fe(CN)6]4+ MnO 4 + 8H + 5e Mn2+ + 4H2O. Electron khng tn ti trng thi t do trong dung dch. Mt cht ch th hin tnh kh khi c cht oxy ha nhn electron ca n. Vic tnh ton trc cn bng oxy ha - kh s gip la chn d dng cc iu kin th nghim. Tuy vy cn ch rng khng phi tt c cc qu trnh oxy ha kh u l nhng qu trnh thun nghch, trong cc phn ng thun v nghch xy ra v cng nhanh t ti trng thi cn bng, m trong thc t ta gp nhiu trng hp phn ng oxy ha - kh theo tnh ton cn bng th c kh nng xy ra, nhng thc t th khng xy ra, v tc phn ng v cng b. Trong nhng trng hp nh vy cc yu t lm tng tc phn ng nh tng nhit , dng cht xc tc l cn thit. 4.1.1.2. Cch thnh lp cc phng trnh oxy ha - kh theo phng php ion electron. Phng php ion - electron da trn s cn bng khi lng v cn bng in tch cc cu t tham gia phn ng trng thi tn ti ch yu ca chng trong dung

72 dch. C th cc cht in ly mnh th vit di dng ion, cc cht in ly yu v cc cht kh th vit di dng phn t, cc cht rn th vit di dng phn t hay nguyn t. Cc bc tin hnh: + Xc nh cc cht oxy ho, kh u v cui. + Vit tng na phn ng oxy ha - kh, thot u vit di dng oxy ha v dng kh lin hp, sau cn bng khi lng, ngha l lm cho s nguyn t ca cc nguyn t hai v ca phn ng phi bng nhau. Thng thng y phi thm bt cc cht ph nh H+, OH-, H2O Khi thm bt nh vy phi ht sc ch n mi trng thc hin phn ng v khng c thay i trng thi oxy ho - kh ca cc nguyn t. V d, nu phn ng thc hin trong mi trng axit v sn phm phn ng li cha O2, m v tri khng c. Tt nhin, cn bng cn thm O2 vo v tri. y c th ly O2 dng hp cht l H2O. Trong trng hp phn ng tin hnh trong mi trng kim th phi thm ion OH- thay cho nc. + Sau khi cn bng khi lng th chuyn sang cn bng in tch, ngha l lm cho tng s in tch hai v phi bng nhau. y ta dng cch thm hoc bt electron thay i in tch. V d khi cn thm in tch m hoc bt in tch dng ta cng thm mt s electron, cn khi cn thm in tch dng hoc bt in tch m th ta phi tr mt s electron tng ng. + Sau khi vit xong cc na phn ng cn tng hp li thnh phng trnh y . Trc ht cn lm cho s electron tham gia trong cc na phn ng phi bng nhau, bng cch nhn na phn ng ny vi s electron tham gia trong na kia, sau cng chng li theo tng v. kim tra phng trnh phn ng vit ng cha, trc ht cn kim tra cn bng khi lng, bng cch cng cc nguyn t ca mi loi trong tng v xem bng nhau hay cha. Sau kim tra tng in tch mi v . V d 1: Cn bng phng trnh: CrO2- + H2O2 CrO4 2- + H2O CrO2- + 2OH- - 3e CrO42- + 2H+ H2O2 + 2e 2OHTrong phn ng th 2 cn bng khi lng ta phi thm vo v tri 2 oxy ly ion OH- (v phn ng tin hnh trong mi trng kim). Kt qu t hp cho ta: 2CrO2- + 4OH- + 3H2O2 2CrO42- + 4H+ + 6OHv 4H+ + 4OH- = 4H2O nn cui cng ta c: 2CrO2- + 2OH- + 3H2O2 = 2CrO42- + 4H2O Trong trng hp phi thit lp phng trnh di dng phn t th vn ly c s l phng trnh ion electron v thm bt cc cht ph mt cch hp l. V d 2: Vit phng trnh ha tan Ag2S trong axit nitric. Ag2S + HNO3 AgNO3 + S + NO + H2O Ag2S 2e 2Ag+ + S + NO3 + 4H + 3e NO + 2H2O 3Ag2S + 8NO3- + 8H+ = 6AgNO3 + 3S + 2NO + 4H2O 4.1.2. Cng cht oxy ho - kh. Th oxy ho - kh. Mt cht nhn electron cng d, c tnh oxy ha cng mnh, v nhng electron

73 cng d, th c tnh kh cng mnh. Trong mt cp oxy ho - kh lin hp, nu cht oxy ha mnh th cht kh yu v ngc li. Kh nng oxy ho - kh ca cc cht c nh gi bng i lng th oxy ho - kh, l i lng o cng ca cht oxy ha v cht kh ca cc cp oxy ho - kh. Th ca cp cng cao cht oxy ha ca cp cng mnh v cht kh ca cc cp oxy ho - kh lin hp cng yu. tin so snh th ca cc cp oxy ho - kh lin hp th phi o th ca chng trong iu kin ging nhau. Th ca mt cp oxy ho - kh lin hp: OX + ne Kh (thng gi l th oxy ho - kh) c xc nh bng cng thc Nec:
E Ox/Kh = E 0 Ox/Kh + RT a OX ln nF a Kh

(4.2)

Mt cch tng qut hn, nu cht oxy ha v cht kh tham gia vo cc phn ng khc nh phn ng kt ta, to phc th cng thc Nec c dng sau: V d vi trng hp : aA + bB + cC + ne mM + nN
E = Eo +
c RT a a Aa C ln m nF a M a n N

(4.3)

Hot ca cht rn B c xem bng 1, nn khng c trong cng thc. Trong E: l th oxy ho - kh R: l hng s kh R = 8,314J/mol.K T: l nhit tuyt i F: l s Faraday F = 96.500c n: l s electron trao i. aA, aC, aM, aN l hot ca cc cht tham gia v sn phm ca phn ng Nu thay R, F bng cc tr s ca chng v i logarit t nhin sang logarit thp phn, th phng trnh Nec nhit 250C c dng:
E = E0 +
c 0,059 a a A a C ... lg m n a Ma n N ...

(4.4)

E0: l mt hng s v c gi l th tiu chun. E0 ch ph thuc vo bn cht ca cp oxy ho - kh lin hp. Biu din hot qua nng ta c:
E = E0 + 0,059 [A]a [C]c ... 0,059 f A .f C ... + lg lg n n f M .f N ... [M]m [N]n ...

(4.5)

Phng trnh (3.5) cho thy th in cc khng nhng ph thuc nng cc dng oxy ha v kh trong dung dch, m cn ph thuc vo lc ion ca dung dch. Trong phn tch thng dng dung dch long nn c th chp nhn fox/fkh = 1 th ta c phng trnh n gin, trong th ch ph thuc nng :
E = E0 + 0,059 [A]a [C]c ... lg n [M] m [N] n ...

(4.6)

E0 l th thc ch dng c trong tng mi trng c th. V d, th tiu chun thc ca cp Fe3+/Fe2+ trong dung dch HCl 0,1M l 0,73V, trong dung dch HCl 0,5M l 0,72V, trong dung dch HCl 1M l 0,7V v trong dung dch H2SO4 0,1M l 0,68V,

74 Trong thc t, khng th xc nh c gi tr tuyt i th ca mt cp oxy ha - kh lin hp, m ch xc nh c gi tr tng i ca n so vi cc cp khc. c th so snh th ca cc cp oxy ho - kh lin hp vi nhau th cn phi xc nh gi tr tng i th ca cc cp y so vi th ca 1 cp oxy ha - kh lin hp quy c bng 0 khi aox = akh. Trong thc t thng so snh vi th tiu chun ca cp 2H+/H2 quy c bng 0. Sau y cho n gin hot c thay bng nng . V d, mun xc nh th tiu chun E0 ca cp Fe3+/Fe2+ th o th hiu gia cc platin nhng vo dung dch hn hp FeCl3, FeCl2 c nng bng nhau, bng 1 v cc hydrro tiu chun. Hiu th tiu chun gia cp Fe3+/ Fe2+ v cp 2H+/H2 bng 0 E0 E2 = +0,77V Fe / Fe H /H
3+ 2+ + 2

V E 2 H
0

du + ch ra rng th cp Fe3+/Fe2+ ln hn th cp 2H+/H2 v trong qu trnh Fe3+ oxy ha H2 theo phn ng: 2Fe3+ + H2 2Fe+ + 2H+ Dng electron di chuyn t cc bn cp 2H+/H2 sang cc bn cp Fe3+/Fe2+ Th tiu chun ca cp: Zn2+/Zn = - 0,76V, du ch rng th ca cp ny b hn th ca cp 2H+/H2, hay ni mt cch khc cc nhng trong cp Zn2+/Zn l cc m, v trong phn ng Zn kh H+ theo phn ng: 2H+ + Zn H2 + Zn2+ Dng electron di chuyn t cc bn cp Zn2+/Zn sang cc bn cp 2H+/H2 Trong cc sch ch ghi th tiu chun ca cc cp oxy ha - kh lin hp khi cht oxy ha v cht kh ca cp khng tham gia vo cc phn ng khc ngoi phn ng trao i electron (bng 1 - Phn ph lc). Khi biu din th in cc theo hot trong cc phn ng th phc tp hn cn ch y tt c cc cu t tham gia vo na phn ng oxy ha - kh, v y cng p dng cch ghi tng t nh khi vit theo nh lut khi lng. i vi trng hp tng qut: aOX + mH+ + ne bKh + pH2O 250C ta c: E ox/kh = E o ox/kh +
a m 0,059 a ox a H + lg b n a kh

/ H2

quy c bng 0 nn th tiu chun ca cp Fe3+/Fe2+ bng +0,77V,

V d: Vi na phn ng : PbO2(r) + 4H+ + 2e

Ta c : E PbO
2

Pb2+ + 2H2O.

/ Pb

2+

= E0 PbO

/ Pb

2+

0,059 [H + ] 4 lg 2 [Pb 2+ ]

Trong thc t cht oxy ha v cht kh ca mt cp lin hp thng tham gia vo nhng phn ng khc, nh phn ng axt - baz, phn ng to phc, phn ng kt ta... Di y ta s ln lt kho st nh hng ca cc yu t khc nhau ti in th oxy ha - kh ca mt bn phn ng. 4.1.3. Nhng yu t nh hng n th oxy ha - kh. Th oxy ha - kh iu kin. 4.1.3.1. nh hng ca pH Th tiu chun E0 ghi trong cc ti liu chuyn kho thng l th c xc

75 nh khi nng H+ bng 1M tc l khi pH = 0. T gi tr E0 c th suy ra th tiu chun cc pH khc, gi l th tiu chun iu kin E0'. Chng ta phn chia nh hng ca pH ti in th oxy ha - kh lm hai trng hp: Trng hp 1: ion H+ (hoc OH-) trc tip tham gia vo cc bn phn ng oxy ha - kh, v d i vi bn phn ng: MnO4- + 8H+ + 5e Mn2+ + 4H2O Ta c:
E MnO / Mn 2 + = E
4

0 MnO 4 / Mn 2 +

+ 8 0,059 [MnO 4 ][ H ] + lg 5 [Mn 2+ ]

R rng l khi [H+] thay i E ca h s thay i theo V d: Tnh th oxy ha - kh tiu chun iu kin ca cp MnO-4/Mn2+ trong dung dch c pH = 5, bit E 0 trong dung dch c pH = 0 l 1,51V. MnO / Mn
4

2+

Ta c: E MnO 10
-5

/ Mn

2+

= E0 + MnO / Mn 2 +
4

+ 8 0,059 [MnO 4 ][ H ] lg 5 [Mn 2+ ]

Th tiu chun iu kin E0' khi pH = 5 l th khi [MnO-4] = [Mn2+] v [H+] =

E 0' = E 0 +

0,059 lg(10 5 ) 8 = 1,04 V 5 Vy khi pH tng th th tiu chun cng gim. Cn ch l c i khi in th oxy ho - kh ca mt cp no gn gi tr pH ny th E khng ph thuc vo pH, cn khong gi tr pH khc th E li ph thuc. V d, trong mi trng axit: Zn2+ + 2e Zn. E ca h khng ph thuc pH, tri li trong mi trng kim: ZnO22- + 4H+ + 2e Zn + 2H2O. th E ca n li ph thuc pH. Trng hp 2: i vi loi ny th khi pH thay i th s lm thay i dng tn ti ca dng oxy ha hoc kh, lm nh hng n nng ca cc dng v do th ca h cng b bin i theo. lm v d, chng ta kho st nh hng ca pH n tnh cht kh ca ion S2-. S Ta bit : S2- - 2e
0 E S/S2 - = E S/S 2- +

0,059 1 0,059 lg 2 = 0,5 lg[S 2 ] 2 2 [S ]

y ta ly nhit l 250C. Trong dung dch : S2- + H+ HS- ng vi K2 phn ly + HS + H H2S ng vi K1 phn ly. Nh ta bit (xem chng 3, phn tnh nng cc thnh phn dung dch khi
[H + ] [H + ] 2 bit pH): [S ] = C H 2S 1 + K + K K 1 1 2
2
2

Trong C H S = [S2-] + [HS-] + [H2S] Thay gi tr [S2-] vo biu thc trn ta c: E = E 0 +

0,059 lg 2 1+ [H + ] [H + ]2 + K1 K1K 2 C H2S

76
0,059 [H + ] [H + ] 2 lg 1 + K + K K 2 1 1 2 0,059 2 lgC H 2S 0,059 [H + ] [H + ] 2 0 ; E0 lg x = E + 1 + K + K K 2 1 1 2

E = E0 +

E = E0 x

0,059 lgC H 2S 2

Trong : E 0 x gi l in th tiu chun iu kin, n l mt hng s mt gi tr pH khng i (v nu ti hot th phi c iu kin lc ion khng i). Tng qut ha, i vi trng hp c ion H+ (hoc OH-) ca mi trng tham gia phn ng v cc cht kh hoc oxy ha c th tn ti di dng khc nhau, in th oxy ho - kh c tnh theo cng thc sau: 0,059 [tt c cc dng OX] E = E0 + lg (4.7) n [tt c cc dng Kh] 4.1.3.2. nh hng ca s to phc in th oxy ho - kh b thay i khi t s nng ca dng oxy ha v dng kh thay i. Nu trong dung dch c cht to phc vi dng kh hoc dng oxy ha hoc c hai dng nhng vi mt mc khng ng nht th t l nng gia dng oxy ha v dng kh b thay i, kt qu l in th oxy ha ca cp oxy ho - kh b thay i. Nu nng ca dng oxy ha b gim (nng ion t do) th in th oxy ha ca h b gim, ngc li nu nng ca dng kh b gim th in th ca h tng. V d in th oxy ha - kh tiu chun ca h Fe3+/Fe2+ bng 0,77V, nu thm H3PO4 vo dung dch th H3PO4 to vi Fe3+ phc [FeHPO4+] lm cho [Fe3+] b gim xung. Cn khi ta thm KCN vo dung dch th in th ca h Fe3+/Fe2+ cng b gim xung v phc [Fe(CN)6]3- bn vng hn phc [Fe(CN)6]4-. Tri li nu thm H2P2O72- vo h V5+/V4+ th in th oxy ha - kh ca h tng v phc ion H2P2O72vi V4+ bn vng hn so vi V5+. 4.1.3.3. nh hng ca s to thnh kt ta. Khi mt trong hai dng oxy ha hoc kh l pha rn, lc in th oxy hakh ch ph thuc vo nng dng nm trong dung dch, v hot (nng ) ca cht rn trong dung dch l mt i lng khng i v c a vo in th tiu chun. V d 1: i vi h Ag+ + e Ag E = E0 + 0,059lg[Ag+] V d 2: i vi h MnO4- + 4H+ + 3e MnO2 + 2H2O
E = E0 +
+ 4 0,059 [MnO 4 ][H ] lg 3 [MnO 2 ]

Trong E0 l th tiu chun ca h. Trong dung dch lun lun bo ha MnO2, ngha l nng ca n l i lng khng i, do ta c:
E = E0' +

Trong E0 l in th tiu chun vi gi thit trong dung dch bo ha MnO2. 4.1.3.4. nh hng ca s to kh. Nu trong bn phn ng oxy ha kh c s tham gia ca kh t tan.

0,059 + 4 lg[MnO 4 ][H ] 3

77

2H2O th in th oxy ha ca h bng: 0,059 E = Eo + lg[O 2 ][H + ] 4 4 Trong E0 l th tiu chun ca h. Nu trong dung dch bo ha oxy p sut 1 atm, nhit 2980K ngha l [O2] l mt i lng khng i, lc : E = E 0 ' + 0,059 lg[H + ] trong E0 gi l th tiu chun iu kin ca h trong dung dch bo ha oxy mt p sut nht nh. 4.1.3.5. nh hng ca lc ion. Nh trn ni, v n gin cho vic lp lun, nn chng ta dng nng thay cho hot . S tht in th oxy ha - kh phi tnh theo hot . Nhng chng ta bit, khi lc ion ca dung dch thay i, hot ca cc ion cng thay i theo. S thay i hot ca dng kh v dng oxy ha lc khng ng nht, do t s hot ca chng thay i v kt qu in th ca h thay i. V d: E0 ca cp [Fe(CN)6]3-/[Fe(CN)6]4- = 0,4V; khi c mt dung dch KCl 2M th in th ca h tng ln ti 0,55V. S d th v s c mt ca KCl lm tng lc ion ca dung dch v lm gim hot ca hai ion [Fe(CN)6]3+ v [Fe(CN)6]4+, trong ion c in tch cao hn, hot b gim mnh hn. Qua y ta thy r nh hng ca lc ion, tuy nhin n gin cho tnh ton, ta vn dng nng thay cho hot . 4.1.4. Chiu ca phn ng oxy ha - kh v cc yu t nh hng. 4.1.4.1. Chiu ca phn ng oxy ha - kh Gi tr th tiu chun E0 ca cc cp oxy ho - kh cng ln th kh nng oxy ha ca cht oxy ha cng mnh, v ngc li gi tr E0 cng nh th kh nng kh ca dng kh cng ln. Trong bng 4.1 th cc cht oxy ha mnh nht nm pha trn, cn cc cht kh mnh nht nm pha di. V d: Cht oxy ha mnh nht F2 c E0 ln nht (+2,87V), sau n zn O3(+2,07V), pesulphat amni (+2,0V).Cc cht kh mnh nht l kim loi kim sau n kim loi kim th Mg, Al, Zn Nu bit c gi tr E0 ca cp oxy ha - kh ta c th on bit c chiu ca phn ng oxy ho - kh. V d: Xt phn ng sau: 2Fe3+ + Sn2+ Sn4+ + 2Fe2+ 0 E0 = +0,77 V ; E Sn = +0,15V Fe / Fe / Sn
3+ 2+ 4+ 2+

V d: O2 + 4H+ + 4e

R rng E Fe / Fe > E Sn / Sn do Fe s l cht oxy ha v Sn2+ l cht kh. Vy phn ng s xy ra theo chiu thun 2Fe3+ + Sn2+ Sn4+ + 2Fe2+ Sn phm ca bt k phn ng oxy ha - kh no cng l nhng cht kh v oxy ha mi, tuy nhin chng s yu hn nhng cht oxy ha v cht kh ban u. V d i vi phn ng trn th cht oxy ha Sn4+ v cht kh Fe2+ yu hn nhng cht ban u l Fe3+ v Sn2+. Cn ch rng mi cht oxy ha c th oxy ha c nhng cht c gi tr E0 nh hn v ngc li mi cht kh ch c th kh c nhng cht c gi tr E0 ln
0 0
3+ 2+ 4+ 2+

3+

78 hn n. Mt s v d minh ha cho quy tc trn: V d 1: T bng 5 ta thy E 0 = - 0,76V, E 0 = - 0,126V, E 0 = 0,337V Zn / Zn Pb / Pb Cu / Cu Nh vy nu cho km kim loi vo dung dch mui ca ch v ng, th s c phn ng sau: Pb2+ + Zn Pb + Zn2+ Cu2+ + Zn Cu + Zn2+ Sn phm ca hai phn ng trn l Pb v Cu, l nhng cht kh yu hn Zn v khng th kh c ion Zn2+ n km kim loi. V d 2: = + 1,359V; E 0 = +1,087. E0 Cl / 2 Cl Br / 2 Br
2+ 2+ 2+
2 2

Vy phn ng s l: Cl2 + 2Br- 2Cl- + Br2 E0 > E0 nn s c phn ng: 2Fe2+ + Br2 2Fe3+ + 2BrBr / 2 Br Fe / Fe Vy Cl2 c th oxy ha c ion Br- nhng Fe3+ khng oxy ha c BrV d 3: Trong phn tch nh tnh thng gp hn hp cht kh m cc cht ny u phn ng vi cng mt cht oxy ha khc, v d hn hp Br- v I- u tc dng vi Cl2. Xut hin cu hi y l cht no s b oxy ha trc. Nhn vo bng 5 ta thy I- s b oxy ha trc, sau mi n Br-. Tht vy gi s Br- b oxy ha bi Cl2 trc th khi xut hin phn t Br2 lp tc n oxy ha ion I n I2 v tr li Br-. Qu trnh ny tip tc cho n lc tt c ion I- b oxy ha ht. T cc v d trn ta rt ra kt lun: Trong iu kin cho ca cc qu trnh oxy ha - kh, qu trnh no c hiu s cc th in cc tiu chun ln nht th s xy ra trc tin. V d 4: Cho st kim loi tc dng vi axit nitric long. y c hai cht oxy ha l H+ v NO3-, nhng v E 0 do theo quy tc trn th NO3- s > E0 NO / NO 2H / H
3 +
2

3+

2+

tham gia vo phn ng ch khng phi H . Vn y t ra l st b oxy ha n Fe2+ hay Fe3+. Gi s Fe2+ c to thnh th theo bng 4.1 lp tc n li b oxy ha n Fe3+ di tc dng ca axit nitric tha. Do phn ng s l: Fe + 4H+ + NO3- Fe3+ + NO + 2H2O 4.1.4.2. Cc yu t nh hng n chiu ca phn ng oxy ho - kh. * nh hng ca nng . Theo phng trnh Nernst gi tr in th oxy ho - kh ca mi cp ph thuc vo t s nng ca cc dng oxy ha v dng kh, ng thi ph thuc vo mi trng. Do khi thay i t s nng v gi tr pH ca mi trng th in th s thay i v dn n thay i chiu ca phn ng oxy ho - kh. V d: Theo gi tr E ca cp Sn2+/Sn (-0,14V) v cp Pb2+/Pb (-0,13V) trong iu kin tiu chun, nng ca cc dng bng nhau v bng 1M, th s c phn ng: Pb + Sn2+ Sn + Pb2+ Hiu s cc in th tiu chun ca hai cp trn (E0 = 0,01V, do vy ch cn thay i rt t nng ca mt trong cc ion th chiu ca phn ng s thay i.

79 Nhng i vi phn ng:

0

2Ag+ + H2 2H+ + 2Ag th E = 0,8V nn mun thay i chiu ca phn ng th phi gim nng Ag+ xung mt lng ln. C th thc hin iu ny bng cch to mui kh tan ca Ag+ hoc a v phc bn. V d cho bc kim loi tc dng vi dung dch HI 1M. V tch s tan ca AgI bng 10-16 m nng ca ion I- l 1M, do nng ca ion Ag+ khng vt qu 10-16M. Trong trng hp ny in th ca cp bc l: E Ag / Ag = 0,8 + 0,05lg10-16 = -0,13V.
+

Do vy phn ng trn xy ra theo chiu ngc li, tc l phi sang tri. Tm li bc kim loi tc dng c vi HI (cng nh vi H2S) gii phng H2 mc du n ng sau hyr trong dy hot ng ha hc ca Bktp. * nh hng ca mi trng. Nu trong phn ng c s tham gia ca ion H+ th nng ca n cng nh hng nhiu n i lng in th oxy ha - kh, thay i nng ca n th chiu phn ng s thay i. V d: E ca cp H3AsO4/HAsO2 l +0,56V, cn ca cp I2/2I- l +0,536V, phn ng s l: H3AsO4 + 2I- + 2H+ HAsO2 + I2 + 2H2O Trong iu kin [H3AsO4] = [HAsO2] v [H+] = 1. Nhng nu cho vo phn ng 1 lng tha NaHCO3, dung dch ca n c pH 8 th lc ny [H+] = 10-8 M: 2 0,059 [H 3 AsO 4 ][H + ] E H AsO /HAsO = 0,56 + lg 2 [HAsO 2 ] + -8 Khi [H3AsO4] = [HAsO2] v [H ] = 10 ta c : 2 0,059 E H AsO /HAsO = 0,56 + lg(10 -8 ) = 0,068V 2 Nh vy 0,068V < 0,54V v phn ng trn s xy ra theo chiu ngc li. T v d trn y ta thy, nu trong phn ng c ion H+ tham gia th cn phi thc hin trong mi trng axit, cn nu ion H+ c to ra trong phn ng th cn phi trung ha n bng cch cho thm NaHCO3 chng hn. Khi xc nh chiu ca cc phn ng oxy ho - kh c s tham gia ca ion H+ th ngi ta thng da vo cc gi tr E0 ca cc cp oxy ho - kh tng ng trong iu kin [H+] = 1M. Nu nng ca cc ion H+ thay i th dn n cc gi tr E0 v chiu ca phn ng cng thay i theo. V d 1: Cho hai dung dch KI v KNO2 tc dng vi nhau, mc du E 0 HNO / NO =
3 4 2

0,99V v E I

0
2

/ 2 I

= 0,54V nhng phn ng vn khng xy ra. Nhng nu cho mt t

axit H2SO4 hay HCl thm ch c CH3COOH th lp tc phn ng xy ra mnh lit gii phng kh NO v kt ta mu nu en I2. 2I- + 2NO2- + 4H+ 2NO + 2H2O + I2 Tng t nh vy, trong mi trng trung tnh hay baz th cc ion H+ khng tc dng vi phn ln cc ion oxy ha nh: CrO42-, IO3-, BrO3-, ClO3-, AsO43- nhng trong mi trng axit th li xy ra phn ng. V d 2: Nu trn hai dung dch K2CrO4 v Na2S th s khng c phn ng g, nhng nu axit ha mi trng th phn ng xy ra ngay:

80 3S2- + 2CrO42- + 16H+ 3S + 2Cr3+ + 8H2O Cng ging nh trn ion CrO42- ch tc dng vi ion c tnh kh nh Cl-, Br-, I-, 2SO3 , S2O32-, SCN-, C2O42- ... trong mi trng axit. Khc vi cc ion c tnh oxy ha nh NO3-, CrO42- ion MnO4- c kh nng oxy ha khng ch trong mi trng axit, m cn c trong mi trng baz. Trong mi trng axit, ion MnO4- nhn 5 electron v b kh n ion Mn2+. Trong mi trng baz th ion MnO4- ch nhn 3e v b kh n MnO2 hay chnh xc hn n = 1,51V v E 0 = MnO(OH)2 di dng kt ta mu nu. V gi tr E 0 MnO / Mn MnO / MnO
2 4 2+
4

0,6V nn tnh oxy ha ca MnO4 trong mi trng axit v baz khc bit nhau, c th l trong mi trng axit mnh hn. 4.1.5. Hng s cn bng v vn tc ca phn ng oxy ho - kh. 4.1.5.1. Hng s cn bng ca phn ng oxy ha kh. Nh ni trn, mt phn ng oxy ho - kh bao gm hai bn phn ng: OX1 + n1e Kh1 (4.8) Kh2 + n2e OX2 (4.9) trong OX1 v Kh2 l nhng cht u, cn Kh1 v OX2 l cc sn phm to thnh, n1 v n2 l s electron nhn v cho ca mt phn t cht oxy ha 1 v cht kh 2. Ta s c c phng trnh phn ng oxy ho - kh y bng cch gp hai bn phn ng (4.8) v (4.9), v i vi mt bn phn ng phi nhn vi mt h s tng ng cho s electron cho, nhn phi bng nhau. V d i vi phng trnh (4.8) ta nhn vi p v (3.9) vi q, lc p.n1 = q.n2. p.OX1 + q.Kh2 p.Kh1 + q.OX2 (4.10) ( y cn ni thm rng c mt s trng hp h s ca OX1 v Kh2 khng bng nhau). Nh chng ta bit, da vo hng s cn bng ta c th bit c phn ng din ra chiu ny hay chiu khc. y cng vy, hng s cn bng ca phn ng oxy ho - kh cho ta kh nng on c phn ng (4.10) xy ra theo chiu no. Ni cch khc, khi ta trn hai cht OX1 v Kh2 vi nhau, phn ng c din ra hay khng. Hng s cn bng ca phn ng (4.10):
[Kh 1 ] [OX 2 ] (4.11) = p q . [OX ] 1 [Kh 2 ] 1 2 Hng s ny c th tnh theo in th oxy ho - kh ca hai cp oxy ho - kh lin hp trong phn ng :
p q p q 1 2

[Kh ] .[OX ] K= [OX ] .[Kh ]

0,059 [OX1 ] E1 = E + lg p.n 1 [Kh 1 ]

0 1 0 2

(4.12)
q

0,059 [OX 2 ] (4.13) E2 = E + lg q.n 2 [Kh 2 ] Gi s cc cht u ta ly OX1 v Kh2 nh vy trong qu trnh phn ng [OX1] gim v [Kh2] tng dn, do E1 gim dn, tri li v [Kh1] gim v [OX2] tng dn nn E2 tng dn, cui cng khi E1 = E2 h thng t ti cn bng :

81
0,059 [OX1 ] 0,059 [OX 2 ] (4.14) = E0 E + lg lg 2 + [ ] p.n 1 [Kh 1 ] q.n 2 Kh 2 t n = p.n1 = q.n2 l s electron tham gia cho nhn, th n vo phng trnh (4.14) v sau mt vi php bin i n gin ta c: q p o [ OX 2 ] .[Kh 1 ] n.(E 1 Eo 2) lg = (4.15) q p 0,059 [Kh 2 ] .[OX1 ]
p q 0 1

T (4.11) v (4.15) ta c: lg K =

Hoc: T :

0 E0 n (E 1 2) 0,059 0 lg K = 16,9.n ( E 1 E 0 2)

(4.16) (4.17) (4.18)

K = 10

0 16 , 9. n ( E1 E0 2)

Ch : Trong trng hp chung n l bi s chung nh nht ca n1 v n2. Cho nn, xc nh K cn phi xc nh n1 v n2, phi vit phng trnh cn bng ca phn ng xy ra v phi tm bi s chung nh nht ca n1 v n2 trc khi p dng biu thc (4.18). By gi ta ly vi v d lm sng t nhng iu trn V d 1: Tnh hng s cn bng ca phn ng: Fe2+ + Ce4+ Fe3+ + Ce3+ = 0,77V ; E 0 = 1,45V E0 Fe / Fe Ce / Ce Ta c n = 1; lgK = 16,9.1.(1,45 0,77) = 11,5 T : K = 1011,5 bit c th hn mc hon ton ca cc phn ng trn, ta tnh t s 3+ Fe /Fe2+ trong dung dch hn hp Fe2+ v Ce4+ pH = 0 ([H+] = 1) khi nng ng lng ban u ca cht oxy ha v cht kh bng nhau. trng thi cn bng: [Fe 3+ ]2 [Ce3+] = [Fe3+] v [Fe2+] = [Ce4+]. Vy K = = 1011, 5 [Fe 2+ ]2
3+ 2+ 4+ 3+

Do : [Fe3+]/[Fe2+] = 1011,5 = 105,75 Nh vy sau khi phn ng hon ton lng Fe2+ cn li rt t, coi nh khng ng k v phn ng xy ra n cng t tri qua phi. V d 2: Tnh hng s cn bng ca phn ng: Ag+ + Fe2+ Ag + Fe3+ = 0,80V v E 0 = 0,77V Bit E 0 Ag / Ag Fe / Fe
+

3+

2+

Ta c: lgK = 16,9.1.(0,80 0,77) = 0,507 v K = 3,21 V hng s cn bng ca phn ng khng ln nn phn ng c th din ra theo chiu ny hay chiu khc, ty theo nng ca cc dng ion trong dung dch, ngha l nu [Fe2+] ln th Fe2+ c th kh Ag+, ngc li nu d [Fe3+] th Fe c th oxy ha Ag. V d 3: Tnh hng s cn bng ca phn ng: 2+ + 2Cr2O7 + 6Fe + 14H 2Cr3+ + 6Fe3+ + 7H2O 0 = 0,77V v E Cr = 1,33V Bit E 0 Fe / Fe O / Cr
3+ 2+ 2 2 7 3+

82 Trong trng hp ny n = 6 v lgK = 56,8 K = 1056,8 (K rt ln, phn ng din ra hon ton ) V d 4: Tnh tch s ha tan ca AgCl, cho bit h: AgCl + e Ag + Cl- c E0 = 0,222V 0 Ag - e Ag+ c E 0 = 0,8V Ag / Ag
+

S dng phng trnh (4.17) ta c : LgT = 16,9 .1.(0,222 - 0,8) = -9,75 v T =1,7.10-10 = [Ag+][Cl-] T cng thc (4.16) ta thy hiu cc th tiu chun cng ln th hng s cn bng ca phn ng oxy ho - kh cng ln, phn ng cng xy ra hon ton theo chiu thun. Nu E0 nh th phi chn iu kin thch hp phn ng xy ra hon ton. V d i vi phn ng: HAsO42- + 2I- + 3H+ As02- + 2H2O + I2 c K 10 tng i b nn phn ng xy ra theo chiu thun th phi thc hin trong mi trng axit mnh v tha nng I-. Ni chung vi n = 1, khi E0 = 0,25V ta c K = 1,5.104 v K > 104: phn ng xy ra theo chiu thun. - 1 < K < 103 phn ng xy ra theo chiu thun nghch. - K < 1 phn ng khng xy ra hoc xy ra theo chiu ngc li. Cui cng cn ni thm rng, da vo in th tiu chun v hng s cn bng trong mt s trng hp cha c th kt lun c phn ng c th xy ra hay khng, m ch cho bit kh nng xy ra phn ng, cn phn ng xy ra nhanh n mc no l ty thuc vo tc ca n. 4.1.5.2. Vn tc ca phn ng oxy ha - kh. Cc phn ng oxy ha kh c mt s c im gy kh khn cho vic ng dng chng trong phn tch th tch. V d nh tnh thun nghch nh trnh by trn, trong mt s trng hp c bit khi phn tch phi khc phc tnh thun nghch . Mt c im na l vn tc ca nhiu qu trnh phn ng oxy ho - kh khng ln. Nh ta bit, nhng phn ng tin trin chm khng c li cho vic chun , v trong trng hp vic chun khng nhng phi ko di m cn khng th hon ton chnh xc. Bi th nn mun dng nhng phn ng nh th trong phn tch th tch th cn tng vn tc phn ng. Vic lm tng vn tc phn ng nhng phn ng tin trin chm c th t c bng nhiu cch, ln lt ta s nghin cu nhng cch . * Tng nhit nh hng ca nhit i vi vn tc phn ng rt ln, c tng nhit ln 0 10 C th vn tc phn ng tng 2 3 ln, iu thnh nh qui lut. Do khi tng nhit theo cp s cng, vn tc phn ng tng theo cp s nhn. V vy ngi ta gp nhiu trng hp m phn ng thc t khng xy ra nhit ca phng, nhng khi un nng li xy ra vi vn tc kh ln.Ta c th ly v d nh phn ng: 5H2C2O4 + 2KMnO4 + 3H2SO4 = 2MnSO4 + K2SO4 + 8H2O + 10CO2 xy ra khi nh phn axit oxalic bng permanganat, vic nh phn phi tin hnh nhit 700C - 800C. Tuy nhin khng phi lc no cng c th lm phn ng tin trin nhanh bng

83 cch un nng dung dch, v nu lm phn ng tin trin nhanh bng cch un nng dung dch th c th hoc lm bay hi mt trong cc cht tc dng (V d I2 khi xc nh theo phng php it) hoc cc cht b oxy ha bi oxygen khng kh (s oxy ha Fe2+ khi nh phn dung dch FeSO4 bng permanganat). * Tng nng ca cc cht tc dng v thay i [H+] V d phn ng tin trin chm: 6KI + K2Cr2O7 + 7H2SO4 = 3I2 + 4K2SO4 + Cr2(SO4)3 + 7H2O c th lm tng vn tc bng cch tng nng ion H+ hoc I- trong dung dch. Nh ta bit, theo nh lut tc dng khi lng, vn tc ca nhng phn ng trong mi trng ng th t l thun vi tch s nng ca cc cht tc dng, nng ca cc cht ny c ly tha bng cc h s tng ng. V d nh vn tc ca phn ng: 2I- + H2O2 + 2H+ = I2 + H2O Theo nh lut tc dng khi lng phi bng: v = K.[I-]2.[H2O2].[H+]2 Nu nng ca c ba cht bng nhau v bng C th ta c: v = K.C5 Tuy nhin, th nghim chng t rng trong thc t vn tc ca phn ng ny khng t l vi ly tha 5 ca nng , m t l vi bnh phng ca nng , ngha l: v = K.C2 Nhng s sai lch vi nh lut khi lng tng t nh th cn thy trong nhiu phn ng oxy ho - kh khc. Nguyn nhn ca s sai lch l do nhng tnh cht phc tp trong tin trnh ca cc phn ng oxy ho - kh y. S trao i cc in tch thng xy ra thnh mt vi giai on k tc nhau, i hi c mt thi gian lu hn.Cht oxy ha khng th nhn mt lc tt c s electron c th nhn m ch mt phn thi, chuyn v gi tr trng thi thp hn v sau li nhn tip electron tr v trng thi ha tr thp hn na V d: Ion MnO4- khng nhn mt lc 5 electron b kh v Mn2+, m nhn +3 e +e +e Mn 4 + Mn 3+ Mn 2 + qua cc giai on sau: Mn 7 + Cht kh cng c th khng cho cc electron tt c m cho tng phn. Trong mt vi trng hp cht kh lc u cho qu s electron bnh thng cn cho, v sau ly phn electron cho tha tr li. V d: S oxy ha Fe2+ bng MnO4- c th din ra nh sau: Fe2+ - 3e Fe5+ Fe5+ + 2e Fe3+ Vn tc ca ton b qu trnh ph thuc cht ch vo vn tc ca cc giai on trung gian ca n, v v th d on vn tc y da vo phng trnh tng cng ca phn ng. Thng ta khng bit c mt cch chnh xc cc giai on trung gian. Tuy nhin trong mt s trng hp c bit ngi ta cng kho st c s tin trin thc t ca qu trnh. V d: Cho phn ng: 2I- + H2O2 + 2H+ = I2 + 2H2O Theo phng trnh tng cng trn l phn ng Ng phn t. Thc nghim chng minh rng mt trong nhng giai on trung gian ca n l to thnh cc anion ca axit hypoiodit theo phng trnh: I- + H2O2 = IO- + H2O (*)

84 Sau cc ion IO- va to thnh kt hp vi cc ion H+: IO- + H+ HIO V sau ht HIO l cht oxy ha mnh oxy ha I- theo phng trnh: HIO + I- + H+ I2 + H 2 O Cng cc phng trnh trn theo tng v ta c phng trnh tng cng. Tt nhin vn tc ca cc phn ng phc tp trn xc nh bng vn tc ca giai on trung gian tin trin chm nht ca n. Giai on trung gian tin trin chm nht trong qu trnh oxy ho - kh trn l phn ng (*), v n l phn ng lng phn t nn vn tc ca ton b qu trnh phi t l vi bnh phng nng nh c xc nh bi thc nghim. Do , kt qu s sai lch i vi nh lut tc dng khi lng ta nhn thy khi nghin cu vn tc ca cc phn ng oxy ho - kh ch l s sai lch biu kin, v ngi ta gii thch bng s tn ti ca cc giai on trung gian cha bit ca qu trnh oxy ho - kh. * Cht xc tc: Cht xc tc l nhng cht lm thay i tc ca phn ng nhng khng c mt sn phm cui cng v n tham gia vo cc giai on trung gian v li c ti sinh trong nhng giai on cui. V d, mc d th tiu chun ca cp S2O82-/2SO42- = +2,0V, ln hn th tiu chun ca cp MnO4- + 8H+/Mn2+ (+1,51V) kh nhiu song nu trong dung dch ch c cc ion S2O82- v Mn2+ th phn ng gia chng rt chm, thc t gn nh khng xy ra. Nu thm vo dung dch mt lng nh mui bc lm cht xc tc th phn ng s xy ra rt nhanh. Phn ng xy ra theo cc giai on sau: S2O82- + 2H+ H2 S 2 O8 2H2S2O8 + 2H2O 4H2SO4 + 2O 2Ag+ + O + H2O Ag2O2 + 2H+ 5Ag2O2 + 2Mn2+ + 4H+ 2MnO4- + 10Ag+ + 2H2O Phn ng gia oxalat C2O42- v MnO4- trong mi trng axit thng c biu din bng phng trnh: 2MnO4- + 5C2O42- + 16H+ = Mn2+ + 10CO2 + 8H2O Nhng thc ra phng trnh ch l phng trnh tng cng nhiu phn ng ch hon ton khng ni ln c c ch ca phn ng . Nu trong dung dch ban u ch c cc ion MnO4-, C2O42- v H+ th phn ng gia chng xy ra rt chm. Nu thm vo dung dch mt lng nh mui Mn2+ (MnSO4) th phn ng xy ra rt nhanh v ion Mn2+ xc tc lm tng tc ca phn ng . Phn ng ny xy ra theo nhng giai on sau: 2MnO4- + 3Mn2+ + 16H+ 5Mn4+ + 8H2O (Phn ng nhanh) 4+ 2+ Mn + Mn 2Mn3+ (Phn ng nhanh, thun nghch) Tip theo, cc ion Mn3+ v Mn4+ phn ng vi ion C2O42- theo cc giai on sau: Mn4+ + C2O42- Mn3+ + CO2 + CO2Mn4+ + CO2- Mn3+ + CO2 (Phn ng nhanh)

85 Mn3+ + C2O42Mn(C2O4)+ (Phn ng nhanh, thun nghch) Mn3+ + C2O42- Mn2+ + CO2 + CO2Mn3+ + CO2- Mn2+ + CO2 Nu trong dung dch ban u c ion Mn2+ th ion Mn4+ c to thnh s b kh nhanh xung Mn3+, sau Mn3+ s to phc vi ion oxalat v ri phc b phn hy. Trong thc t cc cht xc tc thng c chn bng con ng thc nghim theo quy tc sau: Th tiu chun ca cht xc tc phi gia th tiu chun ca cht oxy ha v cht kh, tuy nhin cng ch l iu kin cn ch khng phi l iu kin m chng ta phi dng thc nghim nghin cu chn cht xc tc thch hp t nhng cht tha mn iu kin . * Phn ng cm ng. Phn ng cm ng l phn ng mt mnh th xy ra rt chm, nhng tc ca n c tng ln khi ng thi c mt phn ng nhanh khc xy ra. Nguyn nhn, c ch ca hin tng ny cha c gii thch mt cch thng nht. Tuy vy ngi ta thng cho rng trong qu trnh phn ng c to nn nhng cht trung gian c tnh oxy ha hoc kh mnh hn cc cht ban u. V d: Cromat CrO42- oxy ha Mn(II) rt chm, nhng nu c ng thi H3AsO3 th phn ng gia CrO42- v Mn2+ xy ra kh nhanh, v phn ng oxy ha H3AsO3 bng cromat lm tng tc phn ng gia cromat v Mn2+. Hin tng c gii thch nh sau: CrO42- + H3AsO3 H3AsO4 + CrO32(Phn ng nhanh) 2tip theo CrO3 c to thnh s oxy ha Mn(II) thnh Mn(III). CrO32- + Mn2+ + 6H+ Mn3+ + Cr3+ + 3H2O Mt trng hp rt thng gp trong thc tin phn tch l khi chun st (II) bng pemanganat MnO4-, trong mi trng axit HCl th lng pemanganat dng thng ln hn so vi lng tng ng vi lng st (II). Nguyn nhn ca sai s ny l tuy axit HCl l long v khi c mt mnh thc t n rt kh b pemanganat oxy ha, nhng nu trong dung dch ng thi c c st (II) th HCl b oxy ha bi pemanganat di dng phn ng cm ng. Nguyn nhn c l l u tin Fe(II) b pemanganat oxy ha thnh Fe(V), ri Fe(V) oxy ha Fe(II) thnh Fe(III). 2Fe2+ + Fe5+ 3Fe3+ v ng thi cng oxy ha Cl- thnh Cl2 Fe5+ 2Cl- Fe3+ + Cl2 Cl2 sinh ra li oxy ha Fe(II): Cl2 + 2Fe2+ 2Cl- + 2Fe3+ Nu tt c lng Cl2 u cn c trong dung dch th lng Fe3+ sinh ra s tng ng vi lng pemanganat tc dng vi Cl- to nn Cl2 v nh vy khng gy nn sai s. Nhng v c mt lng kh clo no bay ra khi dung dch nn phi dng d pemanganat. Kinh nghim cho thy l nu thm vo dung dch mt lng nh mui mangan (II) th s khng gy sai s v Mn(II) s d b Fe(V) oxy ha hn: Fe5+ + 2Mn2+ Fe3+ + 2Mn3+

86 Mn3+ sinh ra s oxy ha Fe2+: Fe2+ + Mn3+ Fe3+ + Mn2+ Mn3+ khng b mt i nh Cl2 do khng b mc sai s. Nhng khi nh phn H2O2 bng pemanganat hoc nh phn st (II) bng Ce(IV) th c th dng HCl lm mi trng axit m khng gy sai s nh trn. Do , cha c quy lut chc chn d on cc phn ng cm ng no s xy ra. Thng c th d on cc phn ng cm ng bng quy tc thc nghim sau: - Nu trong dung dch c hai cht kh Akh v Bkh c th oxy ha khc nhau nhiu th thng Bkh b oxy ha mt phn do hin tng cm ng. Nhng nu phn ng: Box + Akh Bkh + Aox xy ra nhanh th s cm ng khng gy sai s, v Bkh s c ti sinh li hon ton. Nu phn ng trn chm hoc mt phn Box b thot ra khi dung dch th s mc sai s. - Nu mt cht oxy ha b kh chm bi mt thuc th th tc phn ng s tng ln khi xy ra phn ng ng thi gia thuc th v mt cht khc. V d ion PO33- khng lm mt mu dung dch kali pemanganat trong mi trng axit, nhng nu c ion Fe2+ trong dung dch th PO33- s kh MnO4-. Oxy c trong khng kh c kh nng tham gia vo mt s phn ng cm ng v y l nguyn nhn gy ra sai s khi tin hnh phn tch cc cht bng phn ng oxy ha - kh. V d khi chun Sn2+ bng dung dch chun kali penmanganat hoc kali bicromat th Sn2+ b oxy ha mt phn bi oxy khng kh trong phn ng cm ng. Khi tin hnh phn ng trung ha ion HSO3- bng dung dch chun kim th n rt d b oxy ca khng kh oxy ha thnh sunfat trong phn ng cm ng.

4.2. Chun oxy ha-kh. Trong cc phng php chun oxy ha - kh ngi ta thng tin hnh phn ng chun , l phn ng trao i e gia dung dch chun cha cht oxy ha (hoc kh) vi dung dch phn tch cha cht kh (hoc cht oxy ha). nhn ra im tng ng ca phn ng chun , ngi ta cng dng cc cht ch th. 4.2.1. Ch th trong phng php oxy ha - kh. Khc vi phng php trung ha, trong phng php oxy ha-kh c th xc nh im tng ng bng cch dng cc cht ch th sau: 4.2.1.1. Khng dng cht ch th t ngoi a vo. Trong trng hp ny, thuc th l mt cht c mu ring r rt m ta s kt thc chun khi dung dch i mu. V d: Khi chun dung dch H2C2O4 bng dung dch KMnO4 trong mi trng axit theo phn ng: 5H2C2O4 + 2KMnO4 + 8H2O = K2SO4 + 2MnSO4 + 10CO2 + 8H2O khi cho tha mt git KMnO4 th dung dch phn tch s c mu hng r rt. Loi phn ng ny ngi ta gi l phn ng t ch th. 4.2.1.2. Dng cht ch th t ngoi a vo * Cht ch th c bit Loi cht ch th ny dng nhn lng thuc th tha ra mt t (1 - 2 git) trong qu trnh chun . V d: H tinh bt dng lm ch th nhn ra it khi c mt lng nh trong dung dch. Lc dung dch c mu xanh hoc dung dch s mt mu xanh khi it b tc dng ht. Chng hn khi nh phn dung dch it bng Na2S2O3 theo phn ng:

87 I2 + 2Na2S2O3 2NaI + Na2S4O6 n im tng ng va ht it th dung dch s ht mu xanh. Hoc c th dng sunfoxyanua lm ch th nhn ra Fe3+. * Cht ch th bt thun nghch. Loi cht ch th ny c c tnh l 2 dng oxy ha v kh ca n (c mu khc nhau) khng bin i thun nghch c. V d: metyl da cam hay metyl trong mi trng axit c mu , khi b oxy ha chng s chuyn thnh dng oxy ha khng mu nhng dng oxy ha ny khng th b kh tr li dng kh ban u c. Gi s ta chun dung dch Sb3+ bng dung dch KBrO3 trong mi trng axit c metyl da cam hay metyl lm ch th: 3Sb3+ + BrO3- + 6H+ 3Sb5+ + Br- + 3H2O dung dch s c mu , nu cho tha 1-2 git KBrO3 s c phn ng tip theo: BrO3- + 5 Br- + 6H+ 3Br2 + 3H2O Lc Br2 c to ra s oxy ha metyl da cam hay metyl to thnh mt hp cht khng mu, ta kt thc nh phn. * Cht ch th oxy ha-kh Cht ch th oxy ha-kh l cht ch th i mu theo in th oxy ha-kh, chng l nhng cht oxy ha hoc kh m dng oxy ha (Indox) v dng kh (Indkh) c mu khc nhau, tn ti trong dung dch theo cn bng: Indox + ne Indkh [Ind ox ] T l nng 2 dng trong dung dch quyt nh mu ca dung dch v [Ind kh ] 0,059 [ Ind ox ] lin h vi nhau theo cng thc Nec: E Ind / Ind = E 0 + . lg [ Ind kh ] n Theo biu thc trn, r rng khi in th ca dung dch thay i s lm bin i t s nng ca 2 dng v c th a n s i mu ca dung dch. Cng tng t nh s bin mu ca cht ch th axit baz: [Ind ox ] - Mt ta ch nhn c mu ca mt dng khi ln hn hay nh hn mt [Ind kh ] s ln nht nh, thng thng khong 10 ln. [Ind ox ] - Mt ch nhn thy mu ca Indox khi 10 ng vi dung dch c [Ind kh ] 0,059 E1 E 0 + n [Ind ox ] - Mt ch nhn thy mu ca Indkh khi 10 ng vi dung dch c [Ind kh ] 0,059 v mu ca cht ch th trong dung dch s bin i t mu ca E2 E0 n dng Indox sang mu ca dng Indkh (m mt ta c th nhn thy c) ng vi E 0,059 0,059 ca dung dch thay i t E 0 n E 0 + , ngha l trong gii hn: n n
ox kh

88 0,059 0,059 Edd E 0 + n n khong E gii hn gi l khong i mu ca cht ch th oxy ha-kh. Vy, khong i mu ca cht ch th oxy ha-kh l khong gi tr in th E m trong khong khi E ca dung dch thay i th mu ca cht ch th thay i (mt ta c th nhn thy c). Ch : V gi tr 0,059/n rt nh nn khong i mu dao ng thc t rt gn vi gi tr E0 ca cht ch th oxy ha-kh, cho nn thng ngi ta ch quan tm n gi tr E0 ca ch th. Mt s cht ch th thng dng c k bng 4.2 E0
Bng 4.2. Mt s cht ch th oxy ha-kh thng dng

Ch th Mu dng oxy ha Diphenyllamin Xanh tm Axit diphenylazosulphonic tm Axit phenylantranilic tm Pheroin Xanh nht Axit o,odiphenylamin dicacbonic Xanh tm

Mu dng kh E0 khi [H+] = 1 Khng mu +0,76 --+0,84 --+1,08 +1,06 Khng mu +1,26

4.2.2. ng nh phn trong phng php oxy ha-kh. Trong qu trnh chun theo phng php oxy ha-kh, nng ca cc dng oxy ha v kh ca cc cp thay i. Biu din th oxy ha-kh ca dung dch (Edd) theo lng thuc th thm vo trong qu trnh chun ln trc ta ta c ng nh phn oxy ha-kh. Xt mt trng hp c th, qua ta s suy ra cc trng hp chung ca phng php oxy ha-kh. V d ta kho st ng nh phn ca qu trnh chun V0 ml dung dch Fe2+ VC c nng C0 mol/l bng dung dch Ce4+ c nng C mol/l. Vtd = 0 0 C 4.2.2.1. Tnh th oxy ha-kh ca dung dch (Edd) trong qu trnh chun . Khi chun , phn ng s xy ra: Ce4+ + Fe2+ Ce3+ + Fe3+ = +1,45V ; E 0 = +0,77V c: E 0 Ce / Ce Fe / Fe n (E o1 E o 2 ) 1,45 0,77 lg K CB = = = 11,35 ; K CB = 1011, 35 0,059 0,059 KCB ca phn ng trn kh ln (1011,35) nn phn ng xy ra gn nh hon ton. mi mt thi im chun , phn ng s t n mt trng thi cn bng mi, do trong cng mt dung dch E Ce / ce = E Fe / Fe (v khi vn tc phn ng ca 2 chiu nh nhau) v chnh l in th ca dung dch ti thi im : Edd = E Ce / ce = E Fe / Fe
4+ 3+ 3+ 2+ 4+ 3+ 3+ 2+ 4+ 3+ 3+ 2+

c th vit:

E dd = E Ce

4+

/ Ce 3 +

E dd = E Fe

3+

/ Fe 2 +

[Ce 4+ ] [Ce 3+ ] [Fe 3+ ] = E0 + 0 , 059 lg Fe [Fe 2+ ]

= E0 Ce + 0,059 lg

89 Bi vy mun tnh in th Edd ca dung dch trong qu trnh chun ta c th tnh theo in th ca 1 trong 2 cp. Tuy nhin thun li, trc im tng ng ta thng tnh in th Edd theo E Fe / Fe v sau im tng ng tnh Edd theo E Ce / Ce (v d tnh c nng ca cc dng). Nng [ox], [kh] tnh bng n v mol/l (trong trng hp ny, nng ng lng bng nng mol/l). * in th ca dung dch trc im tng ng [Fe 3+ ] Ta tnh theo: E dd = E Fe / Fe = +0,77 + 0,059 lg [Fe 2 + ] CV Trong : [Fe 3+ ] = V0 + V C V C V CV CV = 0 0 [Fe 2+ ] = C Fe [Fe 3+ ] = 0 0 V0 + V V0 + V V0 + V CV Vy, E dd = 0,77 + 0,059 lg C 0 V0 CV * in th ca dung dch sau im tng ng. [Ce 4+ ] 0 Ta tnh theo: E dd = E Ce / Ce = 1,45 + 0,059 lg [Ce 3+ ] CV CVtd C( V Vtd ) CVtd C V Trong , [Ce 4+ ] = = 0 0 = cn [Ce 3+ ] = V0 + V V0 + V V0 + V V0 + V C(V Vtd ) Vy, E dd = 1,45 + 0,059 lg C 0 V0 * in th im tng ng Khi cho 100ml Ce4+ th ton b Fe2+ thnh Fe3+ v ton b Ce4+ s thnh Ce3+ [Fe 3+ ] [Ce 4+ ] nn ta khng d dng tnh c gi tr ca bi vy khng th tnh hay [Fe 2 + ] [Ce 3+ ] c Edd theo cc phng trnh trn. Ta c th tnh Edd theo cch sau: Khi phn ng t n cn bng, ta c th vit: [Fe 3+ ] E dd = 0,77 + 0,059 lg [Fe 2 + ] [Ce 4 + ] E dd = 1,45 + 0,059 lg [Ce 3+ ]
3+ 2+ 4+ 3+ 3+ 2+ 2+ 4+ 3+

2E dd

[Fe 3+ ] [Ce 4+ ] = 0,77 + 1,45 + 0,059 lg . T phng trnh phn ng : [Fe 2+ ] [Ce 3+ ]

Ce4+ + Fe2+ Ce3+ + Fe3+, im tng ng khi t n cn bng th: [ Fe 3+ ] = [Ce 3+ ] [Fe 3+ ] [Ce 4+ ] , do = [ Fe 2+ ] = [Ce 4 + ] [ Fe 2+ ] [Ce 3+ ]

90 [Fe 3+ ] [Ce 4 + ] 0,77 + 1,45 = = 1 bi vy: 2Edd = 0,77 + 1,45 => E dd = = 1,110V 2+ 3+ [Fe ] [Ce ] 2 p dng cc cng thc tnh ton trn, ta tnh s bin i th E ca dung dch khi chun 100ml dung dch Fe2+ 0,1M bng dung dch Ce4+ 0,1M. Cc kt qu tnh ton c trnh by trong bng 4.3.

Bng 4.3. S thay i gi tr in th E ca dung dch trong qu trnh chun

VCe thm (ml)
4+

Phn c chun (F) 0,1 0,5 0,9 0,99 0,999 1,0 1,001 1,01 1,1 2,0

[ Fe 3+ ] [Fe 2+ ]

[Ce 4+ ] [Ce 3+ ]

Th E (V) 0,71 0,77 0,83 0,89 0,95 1,11

V < Vt 10 50 90 99 99,9 V = Vt 100 V > Vt 100,1 101 110 220

10-1 1 10 102 103

10-3 10-2 10-1 1

1,27 1,33 1,39 1,45

4.2.2.2. V ng nh phn v nhn xt. T cc s liu trong bng 4.3 ta v ng nh phn (hnh 4.1) v c nhngnhn xt sau: * Tng t nh trong phng php trung ha: khi tha 0,1% Fe2+ n lc tha 0,1% Ce4+ ng nh phn c dng gn nh thng ng, ngha l Edd thay i t ngt (0,947V 1,273V) tc l y c bc nhy E trn ng nh phn ( gn im tng ng). Ngoi khong ra th Edd bin i t t (hnh 4.1) T cch tnh ton Edd u v cui bc nhy, trong trng hp chung ngi ta nhn thy rng: E0 ca 2 cp ox/kh cng ln th bc nhy E cng di. Trong mt s trng hp, ta c th ko di bc nhy E bng cch gim Edd u bc nhy hoc tng Edd cui bc nhy. V d trng hp nh phn trn, u bc nhy ta tnh c: [Fe 3+ ] E dd = 0,77 + 0,059 lg = 0,77 + 0,059 lg10 3 = 0,947V [Fe 2 + ] [Fe 3+ ] i th Edd s nh i. Gi s Nu bng cch no m gim c t s [Fe 2+ ] lc ta cho thm mt lng thch hp H3PO4 hay NaF th lm cho [Fe3+] gim i

91 [Fe 3+ ] 10 3 = 4 = 10 1 ; rt nhiu, gi s b gim i 10 ln, ngha l u bc nhy: 2+ [Fe ] 10 -1 do Edd = 0,77 + 0,059lg10 = 0,711V Vy by gi bc nhy E ca ng nh phn s l (0,711 1,273)V ngha l c ko di hn trc (bc nhy E c: 0,947 1,273 V) 0,236V.
4

E (mV)
1500 1400 1300 1200 1100 1000 900 800

ng tng ng xanh l
Bc nhy

sm
100 110

VCe (ml)
4+

Hnh 4.1. ng nh phn dung dch FeSO4 0,1N bng dung dch Ce(SO4)2 0,1N * Trong trng hp phn ng dng trong chun c pH ca dung dch khng i, h s ca 2 dng ox v kh ca 2 cp bng nhau (nh trng hp trn) th khi pha [ox ] long dung dch, nng ca 2 dng ox, kh cng gim nh nhau nhng t s [kh ] trong biu thc Nec vn khng thay i, do Edd vn khng thay i ngha l di bc nhy E khng thay i. Tri li nu h s ca 2 dng ox/kh ca 2 cp khc nhau th s pha long dung dch c nh hng n di bc nhy E. * Trong trng hp tng qut ta c phn ng: n1 (kh1) + n2 (ox2) n1 (ox1) + n2 (kh2) th ta tnh in th im tng ng nh sau: n E 0 + n 1E 0 ox E td = 2 kh n1 + n 2 2+ V d phn ng: 5Fe + MnO4 + 8H+ Fe3+ + Mn2+ + 4H2O E0 = 0.771V 0,771 + 5.1,51 Fe / Fe c: E td = = 1,387 ; 0 E MnO / Mn = 1,51V 1+ 5
3+ 2+
4

2+

4.2.2.3. Chn cht ch th xc nh im tng ng Cng tng t nh trong trng hp trung ha ta s kt thc nh phn khi cht ch th oxy ha-kh i mu trong khong bc nhy E ca ng nh phn th ch mc sai s khng qu 0,1%. Vy: xc nh im tng ng vi chnh xc cho php (thng l 0,1%) ta s chn cht ch th oxy ha-kh no c khong i mu (hay thng l E 0 Ind / Ind ) nm trong bc nhy E ca ng nh phn.
ox kh

Nh trng hp trn ta c th chn c cc cht ch th c:

92 0,95V E 0 Ind

ox

/ Ind kh

1,27V

V d c th dng axit phenylantranilic c E0 = 1,08V lm ch th hoc pheroin c E0 = 1,06V. Nu gi thit mun dng diphenylamin c E0 = 0,76V th phi ko di bc nhy th no Edd u bc nhy phi: Edd u bc nhy 0,76V Gi s ko di bc nhy bng cch thm H3PO4 hay NaF chng hn (xem cch tnh trn) 4.2.3. Mt s phng php oxy ha kh thng dng. 4.2.3.1. Phng php pemanganat. c im chung ca phng php: Phng php pemanganat da trn phn ng oxy ha ca ion MnO4-. Kh nng oxy ha ca ion MnO4- ph thuc nhiu vo axit ca mi trng phn ng. - Trong mi trng axit mnh MnO4- b kh v Mn2+: Mn2+ + 4H2O MnO4- + 5e + 8H+ 2+ + V d: MnO4 + 5Fe + 8H Mn2+ + 5Fe3+ + 4H2O - Trong mi trng axit yu, trung tnh hay kim th MnO4- ch b kh ti MnO2. MnO2 + 2H2O MnO4- + 3e + 4H+ 0 E MnO / MnO = 1,67(V)
4

MnO4- + 3e + 2H2O MnO2 + 4OHE0 = 0,57(V) MnO + H O / MnO C th gii thch kh nng oxy ha khc nhau ca MnO4- trong mi trng axit v mi trng kim bng s chuyn ha gia MnO2 v ion Mn2+ nh sau: MnO2 + 2e + 4H+ Mn2+ + 2H2O (*) Trong mi tng axit, cn bng (*) s chuyn dch v pha phi to thnh Mn2+. Nh vy, c th coi rng trong mi trng axit MnO4- trc tin b kh thnh MnO2 sau v nng ion H+ trong dung dch cao nn lp tc MnO2 b kh tip xung Mn2+. Trong mi trng trung tnh hay kim th MnO4- b kh ti MnO2 v khng b kh tip na v trong mi trng ny cn bng (*) chuyn dch sang tri, to thnh MnO2. Nh vy, kh nng oxy ha ca MnO4- trong mi trng axit ln hn rt nhiu so vi mi trng kim. Hn na trong mi trng axit, sn phm b kh l Mn2+ khng mu, nn chnh KMnO4 cng l cht ch th cho qu trnh chun , v sau im tng ng 1 git dung dch KMnO4 d cng lm cho dung dch chuyn t khng mu sang mu hng. Trong khi nu tin hnh chun trong mi trng kim hoc trung tnh hay axit yu th sn phm kh l MnO2 l cht kt ta mu nu sm, nh hng n vic xc nh im cui ca qu trnh chun . V vy, trong thc t ngi ta ch dng phng php pemanganat chun cc cht kh trong mi trng axit mnh. iu chnh mi trng axit, dng H2SO4 ch khng dng HCl (v Cl- kh c MnO4- v bin thnh Cl2) v cng khng dng HNO3 v HNO3 l cht oxy ha mnh, n s oxy ha cht kh lm kt qu chun s sai. Kali pemanganat (KMnO4) khng phi l cht gc v n thng khng tinh
4

93 khit, bao gi cng cha tp cht l sn phm kh MnO2. Ngoi ra KMnO4 l cht oxy ha mnh, d b kh bi cc cht hu c c ln trong nc, trong bi khngkh, b phn hy bi nh sng... Do dung dch KMnO4 pha xong phi ng trong l c mu nu, y kn v yn mt thi gian mi c dng, trc khi dng phi xc nh li nng bng dung dch chun l axit oxalic. Dng phng php pemanganat c th xc nh c nhiu cht v c v hu c khc nhau bng cch chun khc nhau. * Cc cht kh: cc kim loi (Fe, Bi, Ag, Cd, Zn, kim loi t him v.v...) cc phi kim (Sb, As, P v.v...) cc ion ha tr thp c kh nng cho hp cht ca nguyn t ha tr cao (Fe2+, Cr2+, Mn2+, Sn2+, Cu2+, Ti3+, V(III), V(IV), Mo(III), U(IV), W(IV); As(III) v.v...) ion phi kim nh Cl-, Br-, I-, S2- v.v... cc cht l nhng ion phc tp (SO32-, S2O32-, TeO32-, SeO32-, SCN-, CN-, NO2-, [Fe(CN)6]4-: cc axit poli v oxycacboxylic (H2C2O4, HOOC-CH2-COOH, v.v...) cc andehyt, cc axit focmit, uric, ascobic, sunfonic, ng, poliphenol, cc hp cht khng no v nhiu sn phm khc. * Cc cht oxy ha: Fe3+, Ce(IV), U(VI), Mo(VI), W(VI), Cr(VI), MnO2, PbO2, NO3-, BrO3-, ClO3-, IO3- v.v... Phng php pemanganat c cc u im sau: - Khng phi dng cht ch th. - Pemanganat c th oxy ha kh cao E 0 = 1,51(V) nn c th xc nh MnO / Mn
4

2+

c nhiu cht khi chng khng th chun c bng cc cht oxy ha yu. - Pemanganat d kim, r tin, dng KMnO4 c th chun c c nhng cht khng c tnh oxy ha kh, v d xc nh c Ca2+ bng cch kt ta vi oxalat sau chun lng cht kh d hoc ha tan kt ta s tnh c lng canxi, xc nh anhiric axetic da trn phn ng ca n vi axit oxalic sau chun lng d axit oxalic bng KMnO4 . (CH3CO)2O + nH2C2O4 2CH3COOH + CO2 + CO + (n-1)H2C2O4 anhiric axetic
4 2CO2 + 2H+ H2C2O4 (d) 4.2.3.2. Phng php dicromat c im chung ca phng php dicromat l da trn phn ng oxy ha ca ion dicromat (Cr2O72-) trong mi trng axit. 2Cr3+ + 7H2O Cr2O72- + 6e + 14H+ E0 = 1,36(V) Cr O / 2 Cr
2 2 7 3+

+ MnO-

2 / Cr 3+ cng ph thuc rt nhiu vo nng ca ion TH oxy ha ca h Cr2 O7 H+. K2Cr2O7 oxy ha yu hn KMnO4. Phng php dicromat c mt s u im sau: - K2Cr2O7 d iu ch c tinh khit, K2Cr2O7 l cht gc nn dung dch chun K2Cr2O7 d iu ch, d bo qun v bn lu. - Tin hnh chun trong mi trng axit H2SO4, H3PO4 v c HCl (v 0 ). Tuy vy khng c tin hnh chun E Cr O / 2 Cr = 1,36( V) cng bng E 0 Cl / Cl
2 2 7 3+ 2

trong mi trng HCl 2M v trong iu kin , nng Cl- rt ln nn lm gim

94 th ca cp Cl2/2Cl-, do Cr2O72- s oxy ha c mt phn Cl- thnh Cl2. Sn phm ca phn ng kh Cr2O72- l ion Cr3+ c mu xanh. im cui ca qu trnh chun khng th nhn ra c mu da cam do mt git dung dch K2Cr2O7 d, do vy xc nh im cui ca qu trnh chun ta phi dng cht ch th oxy ha kh. Cht ch th thng dng trong phng php icromat l diphenylamin (c E0 = 0,76V), mui natri (hay bari) diphenylaminsunfonat (c E0 = 0,84V), ch th ny d tan trong nc hn diphenylamin v s i mu r rt hn (t khng mu sang mu tm ). Cng c th dng axit phenylantranilic (E0 = 1,08V dng oxy ha c mu tm, cn dng kh khng mu). Kali dicromat c kh nng oxy ha c nhiu cht v c v hu c: Fe(II), Mn(III), Ti(III), SO32-, [Fe(CN)6]4-, AsO33-, I-, ru, hiroquinol, glixrin, axit ascobic, thioure v.v... Di y l mt vi phn ng oxy ha c trng ca dicromat dng trong phn tch chun . * Oxy ha hexaxianoferat (II): Cr2O72- + 6[Fe(CN)6]4- + 14H+ 2Cr3+ + 6[Fe(CN)6]3- + 7H2O * Oxy ha Fe(II): Cr2O72- + 6Fe2+ + 14H+ 2Cr3+ + 6Fe3+ + 7H2O H3PO4 * Oxy ha ru metylic: Cr2O72- + CH3OH + 8H+ 2Cr3+ + CO2 + 6H2O * Oxy ha hiroquinol: Cr2O72- + C6H4(OH)2 + 12H+ 2Cr3+ + C6H4O2 + 7H2O 4.2.3.3. Phng php iot - thiosunfat. c im chung ca phng php iot - thiosunfat. - Phng php ny da trn phn ng oxy ha ca I2 v phn ng kh ca II2 + 2e 2IE0 = 0,54 V I / 2I CN c vo gi tr E0 ta thy I2 l cht oxy ha yu hn KMnO4, K2Cr2O7 nhng I- li l cht kh mnh. Nhiu cht kh c th b I2 oxy ha, nhng cng c nhiu cht oxy ha b I- kh. Cho nn trong phn tch, ngi ta thng dng c hai tnh cht oxy ha v kh ca I2 v I- xc nh c cht kh v cht oxy ha. Trong phng php ny, ngi ta thng dng phn ng ca thiosunfat (S2O32-) vi it, v th phng php ny thng c tn gi ghp li l phng php iot - thiosunfat phn ng gia iot v thiosunfat xy ra theo phng trnh: 2S2O32- + I2 2I- + S4O62ion thiosunfat ion - tetrathionat 0 ES O2 / 2S O2 = 0,1V
4 6 2 3

H2SO4

I2 + 2e

2I- I =
2

MI

2S2O32- - 2e

S4O62-

2 S O = M S O
2 2 3 2

2 3

nhn ra im cui ca qu trnh chun ngi ta thng dng cht ch th

95 l h tinh bt. H tinh bt khng phi l cht ch th oxy ha kh m n c tnh cht hp ph I2, c mu xanh m. Khi s dng cht ch th h tinh bt, ta phi lu , nu dng dung dch I2 chun dung dch Na2S2O3 th ta c th thm cht ch th h tinh bt ngay t u, trong qu trnh chun d dung dch khng mu, sau im tng ng c d mt git dung dch I2 dung dch s c mu xanh. Nhng khi chun I2 bng dung dch Na2S2O3 th khng c cho ch th h tinh bt ngay t u, bi v nu thm h tinh bt t u n s hp ph I2, I2 b hp ph ln h tinh bt b gii hp rt chm nn khi chun lng Na2S2O3 d m mu xanh vn cha mt, do chun s qu im tng ng rt nhiu nn kt qu b sai. Bi vy, khi chun I2 bng dung dch Na2S2O3 ch c thm h tinh bt khi qu trnh chun gn kt thc ngha l khi dung dch cn li rt t I2 (dung dch lc c mu vng rt nht, nh mu ca rm nn gi l mu vng rm) , dung dch lc c mu xanh, nh t t tng git dung dch Na2S2O3 va nh va lc mnh n khi dung dch mt mu xanh th l im cui ca s chun . * Xc nh cht kh: Ta c th dng I2 xc nh nhiu cht kh bng phng php chun ngc, nguyn tc nh sau: thm mt lng d xc nh dung dch I2 bit nng vo dung dch cht kh, sau khi phn ng xy ra hon ton, ta chun lng I2 d bng dung dch chun Na2S2O3. Th d xc nh SO32-, AsO33-, H2S, Sn2+... SO32- + I2 + H2O SO42- + 2I- + 2H+ AsO43- + 2I- + 2H+ AsO33- + I2 + H2O S + 2I- + 2H+ H2 S + I 2 2+ Sn + I2 Sn4+ + 2I* Xc nh cht oxy ha: xc nh cht oxy ha bng phng php ny ta lm nh sau. Thm vo dung dch cht oxy ha mt lng d KI ri to iu kin thch hp cho phn ng gia I- v cht oxy ha xy ra hon ton. Khi o I- b oxy ha thnh I2, m I2 l cht t tan trong nc nn ta phi dng d nhiu KI I2 tch ra s kt hp vi I- to thnh I3- tan: I2 + II3Sau chun lng I2 thot ra ( dng I3-) bng dung dch chun Na2S2O3. Bng cch ny ta c th xc nh c cht oxy ha: Br2, MnO4-, Cr2O72-, ClO3, H2O2, Fe3+ v.v... Br2 + 2I- = 2Br- + I2 2MnO4- + 10I- + 16H+ = 2Mn2+ + 5I2 + 8H2O Cr2O72- + 6I- + 14H+ = 2Cr3+ + 3I2 + 7H2O ClO3- + 6I- + 6H+ = Cl- + 3I2 + 3H2O 4NO2- + 4I- + 8H+ = 4NO + 2I2 + 4H2O H2O2 + 2I- + 2H+ = I2 + 2H2O 2Fe3+ + 2I- = I2 + 2Fe2+ * Ngoi vic xc nh cc cht kh v cht oxy ha, phng php iot-thiosunfat cn c dng xc nh axit. Iodua phn ng vi iodat khi c axit theo phng trnh sau: 5I- + IO3- + 6H+ 3I2 + 3H2O

96 T phng trnh trn ta thy lng ion H+ tham gia phn ng tng ng vi lng I2 thot ra. Do , sau khi phn ng trn xy ra hon ton, ta chun lng I2 thot ra bng dung dch chun Na2S2O3. Da vo lng Na2S2O3 tiu tn ta s tnh c lng ion H+ trong dung dch. Nh vy, dng phng php iot - thiosunfat ta c th xc nh c axit. Phng php ny c tn gi l phng php iot - thiosunfat xc nh axit. Ch : * Natri thiosunfat c th kt tinh tinh khit, ng ng vi cng thc Na2S2O3.5H2O nhng n vn khng phi l cht gc bi l dung dch Na2S2O3 khng bn, nng ca n b thay i theo thi gian do tc dng ca CO2 v O2 ca khng kh. Na2S2O3 + CO2 + H2O = NaHCO3 + NaHSO3 + S Na2S2O3 + O2 = Na2SO4 + S Ngoi ra dung dch Na2S2O3 cn d b cc vi sinh vt trong khng kh phn hy. ngn cn s phn hy ny, ngi ta thm vo mt lt dung dch Na2S2O3 10mg HgI2 lm cht st trng. * Khi s dng phng php iot - thiosunfat cn ch my im sau: - Vic chun phi tin hnh trong mi trng kim yu c pH < 9. Khng c thc hin phn ng trong mi trng kim mnh bi v n c phn ng. I2 + 2OH- = IO- + I- + H2O Ion IO- to thnh c tnh oxy ha mnh, n oxy ha mt phn S2O32- thnh 2SO4 S2O32- + 4IO- + 2OH- = 4I- + 2SO42- + H2O Nng OH- trong dung dch cng ln th lng S2O32- chuyn thnh SO42cng nhiu. Do c phn ng ph ny m khng th tnh chnh xc kt qu phn tch c; ni khc i phn ng chun khng xy ra theo mt h s t lng xc nh nn khng dng c. Nu phn ng sinh ra H+ s lm pH ca dung dch gim khng m bo mi trng kim yu, th ta phi dng NaHCO3 lm cht m ly bt H+ trong dung dch i: HCO3- + H+ = CO2 + H2O Khi pH ca dung dch oc gi gn nh khng i (pH = 8), khng cn tr vic chun . - V it l cht d b thng hoa v kh nng hp th ca h tinh bt i vi I2 gim, khi nhit tng. V vy, php chun iot - thiosunfat khng c tin hnh khi un nng. - V iot t tan trong nc, nhng tan nhiu trong dung dch c d I- do c phn I 3ng: I- + I2 Nn khi xc nh cht oxy ha bng php o iot phi dng d KI. Phn ng to thnh ion I3- l phn ng thun nghch v ion I3- rt km bn nn khi chun I2 bng Na2S2O3 cn bng b ph v v chuyn dch hon ton v pha tri, ton b lng I2 thot ra c chun nh lng bng Na2S2O3. - Phn ng gia I- vi cc cht oxy ha v phn ng gia I2 vi cht kh thng xy ra chm, do sau khi thm I- hay I2 vo ta phi ch mt thi gian (khong 5 pht) cho phn ng xy ra hon ton ri mi tin hnh chun . Khi

97 yn dung dch phi y kn v t ch ti v nh sng lm tng phn ng oxy ha I- thnh I2 bi oxy khng kh. I- + 4H+ + O2 as 2I2 + H2O 4.2.3.4. Phng php bromat - bromua. Phng php ny da trn phn ng oxy ha kh, dng cht oxy ha l ion BrO3 . BrO3- + 6e + 6H+ = Br- + 3H2O M E0 = 1,44V; BrO = BrO / Br 6 + Phn ng c s tham gia ca H nn phi tin hnh chun trong mi trng axit. Mc d BrO3- l cht oxy ha mnh nhng tc phn ng oxy ha bng BrO3xy ra chm. tng tc ca phn ng cn tin hnh phn ng trong dung dch nng v mi trng axit mnh. Sau im tng ng khi d 1 git BrO3- th xy ra phn ng: BrO3- + 5Br- + 6H+ = 3Br2 + H2O Br2 t do sinh ra khng nhn ra mu. Do vy, nhn ra im cui ca qu trnh chun ngi ta thng dng cc cht mu hu c nh metyl da cam, metyl ... lm ch th. Sau im tng ng BrO3- d s phn ng vi Br- c sn trong dung dch sinh ra Br2 n s oxy ha cht mu hu c nn s mt mu. Cc cht mu hu c dng lm ch th cho php o ny khng phi l cht ch th oxy ha kh, qu trnh Br2 oxy ha chng l qu trnh bt thun nghch. Do khi chun cn lu khng c thuc th d tng vng, trong qu trnh chun , mun vy phi chun t t v phi lc u. Do tnh cht bt thun nghch ca phn ng oxy ha cht ch th bi Br2, khi chun mu c th mt trc im tng ng v th trc khi kt thc chun cn thm vi git cht ch th na. Phng php bromat - bromua c dng chun trc tip mt s cht kh, v d As (III), Sb (III), v.v... Ngoi ra phng php ny cn cho php xc nh c mt s cht hu c c kh nng b brom ha, khi ta tin hnh chun cht hu c bng dung dch chun KBrO3 khi c mt mt lng d KBr trong mi trng axit. Ngoi cc phng php trn, ngi ta dng mt s phng php khc nh phng php xri da trn phn ng oxy ha ca ion Ce4+. Ce4+ + e Ce3+
3 3

phng php vanadat da trn phn ng oxy ha VO2+: VO2+ + e + 2H+ VO2+ + 2H2O E0 = 1,0V v.v... cc php o ny t dng trong thc t v cc thuc th Ce4+ v VO2+ tng i t.
v

E0 = 1,45V Ce 4 + / Ce 3 +

98

BI TP
1. axit ca mi trng nh hng nh th no n th oxy ha ca h: a. Cr2O72-/Cr3+ b. MnO4-/Mn2+ c. SO42-/H2S d. NO3-/NO e. AsO43-/AsO332. in th oxy ha ca cp Mn2+/Mn bng bao nhiu khi cc nng Mn2+ bng: a. 2 mol/l b. 0.005 mol/l 3. in th oxy ha ca cp Sn4+/Sn2+ bng bao nhiu khi cc nng ca Sn4+ l 0,1M, ca ion Sn2+ l 0,0001M. 4. Mt pin gm c in cc tiu chun hydro ni vi cc Ni nhng trong dung dch cha Ni2+, khi nng ca ion Ni2+ bng 0,01M th pin c sc in ng l 0,172V. Tm in th ha oxy ha tiu chun ca cp Ni2+/Ni. 5. Tnh theo tr s in th oxy ha tiu chun ca cp MnO2/Mn2+ v Cl2/2Cl- th phn ng gia chng phi xy ra theo chiu nh th no? Hy gii thch hin tng l trong phng th nghim ngi ta iu ch Cl2 bng tc dng ca HCl c vi MnO2. 6. Lp cng thc tnh hng s cn bng ca cc phn ng: a. Sn2+ + I2 Sn4+ + 2Ib. MnO4- + 8H+ + 5Fe2+ Mn2+ + 5Fe3+ + 4H2O v tnh ra tr s hng s. Trong cc phn ng trn th phn ng no tin hnh hon ton hn? 7. Tnh nng N ca dung dch K2CrO4 trong phn ng oxy ha-kh, nu nh trong phn ng kt ta dung dch ny c nng N bng 0,1. 8. Tnh nng ng lng ca dung dch KMnO4 khi nh phn trong mi trng kim (kh ti MnO2) nu nh khi xc nh nng ca n ngi ta tin hnh trong mi trng axit v bit c nng ca n bng 0,1. 9. Khi chun 0,1133g Na2C2O4 sch trong mi trng axit th tn mt 20,75ml dung dch KMnO4. Tnh nng N v TKMnO / Fe ca dung dch KMnO4 trn. 10. Tnh hm lng Mn2+ trong dung dch nu khi chun dung dch ny tn mt 21,5ml dung dch KMnO4 0,02M. Khi chun Mn2+ cng nh KMnO4 u bin thnh MnO2: Mn2+ + 2MnO4- + 2H2O = 5MnO2 + 4H+. 11. Cn bao nhiu gam qung c cha gn 70% Fe2O3 sau khi ch ha ri nh phn Fe2+ to ra th tn mt 20 - 30 ml dung dch KMnO4 0,1N. 12. Lng qung (gam) cn phi ly l bao nhiu khi xc nh Fe trong th c 1ml dung dch K2Cr2O7 0,1N tng ng vi 2% Fe2O3. 13. Ha tan 0,16g vi trong HCl sau kt ta Ca2+ di dng CaC2O4 ri ha tan kt ta c ra sch trong dung dch H2SO4 long v nh phn dung dch thu c bng dung dch KMnO4 c TKMnO / CaCO = 0,006. Tnh % CaCO3 trong vi bit rng lng KMnO4 tiu tn cho nh phn l 20,75ml.
4 4 3

99 14. nh phn dung dch Fe2+ thu c t 0,2g qung Fe bng dung dch chun K2Cr2O7 0,02M. Lng K2Cr2O7 tiu tn cho nh phn l 20,5ml. M t qu trnh xc nh bng cc phn ng ha hc v tnh % Fe trong qung.

TI LIU THAM KHO

1. Hong Minh Chu, T Vn Mc, T Vng Nghi. C s ha hc phn tch, NXB KH & KT, 2002. 2. L c, Ha hc phn tch. NXB H Quc Gia H Ni, 2002. 3. Nguyn Tinh Dung phn I, II, III. Ha hc phn tch. NXB Gio dc, 2000. 4. Trn T Hiu, Ha hc phn tch, NXB HQG H Ni, 2002. 5. Trn T Hiu, T Vng Nghi, Hong Th Tn. Bi tp Ha hc phn tch, NXB H&TH Chuyn nghip, 1984. 6. H.A. Laitinen, Phn tch ha hc. Tp 1 v 2, Nguyn Tinh Dung v Nguyn Huyn dch. NXB KH & KT, 1976. 7. .., , , o , 1972 8. .., , , o , 1972

100

CHNG 5

PHC CHT V THUC TH HU C TRONG HA PHN TCH. CHUN COMPLEXON

5.1. Phc cht. 5.1.1. nh ngha. Phc cht l loi cht sinh ra do ion n (thng l ion kim loi) gi l ion trung tm kt hp vi phn t hoc ion khc gi l phi t. Trong dung dch, ion trung tm, phi t v phc cht u c kh nng tn ti ring r. Trong ha hc phn tch, nhng phc cht c nhng ng dng phong ph thng l nhng phc cht phn ly c ti mc sn phm ca s phn ly c th ha hp vi cc cht khc. V d: [Ag(NH3)2]+ Ag+ + 2NH3 Nng NH3 ln NH3 c th ha hp c vi H+. NH3 + H+ NH4+ HgCl2 HgCl+ + ClHgCl+ Hg2+ + Cl2+ Hg nhiu c th ha hp c vi S2- to thnh kt ta Hg2S mu en. y chng ta phi phn bit phc cht vi mui kp. Tri vi phc cht, mui kp khng tn ti trong dung dch m chng phn ly thnh cc ion n gin. V d: Mui Mo: (NH4)2Fe(SO4)2 = 2NH4+ + Fe2+ + 2SO42Phn nhm: KAl(SO4)2 = K+ + Al3+ + 2SO42Nhng ion nh SO42-, ClO3-, NO3- tuy c cu to ging phc cht nhng phn ly qu b nn khng gi l ion phc m thng coi nh cc ion n. 5.1.2. Phn loi cc phc cht Da vo cu to ta c th chia phc cht ra lm 2 loi: phc cht cng v ni phc. 5.1.2.1. Phc cht cng Trong dung dch chng phn ly thnh cc ion n gin v ion phc, tc l ngoi cu v ni cu c in tch ngc du nhau, ni cu thng c vit trong ngoc []. [Cu(NH3)4]Cl2 = [Cu(NH3)4]2+ + 2Cln i c u ngoi cu Trong ni cu (ion phc) ion kim loi lm nhn trung tm kt hp vi cc phi t theo lin kt phi tr khng to vng, cc phi t c th l phn t hay anion v c hoc phn t cht hu c. Phi t l phn t, thng hay gp l hydrat hay amnic.

101 NH3
V d:

H3 N

Cu NH3

NH3

; [Al(H2O)6]3+

Phi t l anion v c nh Cl-, F-, SO42-, S2O32-, CN-, V d: CN- CN-

NC

Fe

CN-

; AgCl2-, [Ca(SO4)2]2-

CN- CNPhi t l anion hoc phn t cht hu c. V d: [Fe(C2O4)3]3-. 5.1.2.2. Ni phc. Ni phc l nhng phc cht m nhn trung tm l nhng ion kim loi kt hp vi cc phi t l nhng phn t cht hu c bng lin kt phi tr hay va bng lin kt phi tr va bng lin kt ha tr to thnh mt hay nhiu vng. V d: COO OOC
H2C NH2 Cu NH2 CH2 CH2 CH2 NH2 Cu NH2 NH2 CH2 NH2 CH2

Glycocolat Cu

Etylendiamin Cu (II)

Da vo cu to v c tnh ca lin kt trong ni cu c th chia lm 3 loi ni phc: * Mui ni phc khng c ngoi cu, ch c ni cu Trong ni cu ion trung tm kt hp vi lin kt phi t va bng lin kt ha tr va bng lin kt phi tr to thnh mt hay nhiu vng. V d nh mui ni phc glycocolat Cu tan ( trn) hay dimetylglyoxim Ni t tan. Cc ni phc phn ln t tan trong nc v tan nhiu hay tan hon ton trong dung mi hu c. O ... H O H3C H3C C=N Ni C=N O N=C H ... O N=C CH3 CH3 2 vng

102
* Ni phc m ni cu l anion y l mt phc cht c ngoi cu l cation v ni cu l anion. Trong ni cu ion trung tm kt hp vi cc phi t va bng lin kt ha tr va bng lin kt phi tr to thnh mt hay nhiu vng.
- Axit ferisalixilic: H3[Fe(C6H4OCOO)3] 3H + [Fe(C6H4
+ +

COO O

)3]3 -

COO )3Cr]3 - Cromooxalat Kali: K3[(C2O4)3Cr] 3K + [( COO V d: * Ni phc m ni cu l cation y l mt phc cht c ngoi cu l anion v ni cu l cation. Trong ni cu ion trung tm kt hp vi cc phi tr ch bng lin kt phi tr to mt hay nhiu vng. V d: Clorua etylendiamino Cu (II)
CH 2 CH 2 NH 2 NH 2 CH 2 Cu Cl 2 2Cl + 2 CH 2 NH 2 NH 2
2+

Cu 2

2+

Hay , dipiridilo Fe (II):

C 5 H 4 N C 5 H 4 N

NH 4 C 5 Fe NH 4 C 5

Ni phc c mt s c tnh sau: - Phn ln t tan trong nc, tan nhiu trong dung mi hu c. - C bn ln. - C mu khc vi mu ca ion trung tm v m. 5.1.3. bn ca phc cht. 5.1.3.1. Hng s bn v hng s khng bn ca phc cht. Trong dung dch, phc cht c cn bng thun nghch: phn ly v to thnh phc cht. phn ly MnLm to thnh nM + mL Hng s cn bng i vi qu trnh phn ly phc th gi l hng s khng bn (Kkb) ca phc; trong cn bng trn th: [M ]n [L]m K kb = (5.1) [M n L m ] Hng s cn bng i vi qu trnh to thnh phc cht th gi l hng s bn () ca phc, trong cn bng trn th:

103

[M L ] [M ] [L]
n n m

(5.2)

So snh (5.1) v (5.2) ta thy hng s bn () l nghch o ca hng s khng 1 bn v ngc li: (5.3) = K Kb V d, trong cn bng sau: Cd2+ + 4NH3 [Cd(NH3)42+] 4 + [ [ Cd 2 + ][NH 3 ] Cd ( NH 3 ) 2 4 ] cn K kb = = = 2,5.10 7 4 2+ 2+ [ ] Cd ( NH ) [Cd ][NH 3 ] 3 4 2+ 2+ [Cu(NH3)4 ] Cu + 4NH3 4 + [ [ Cu ( NH 3 ) 2 Cu 2+ ][NH 3 ] 4 ] cn K kb = = = 4,6.10 14 4 2+ 2+ [ ] Cu ( NH ) [Cu ][NH 3 ] 3 4 Hng s khng bn cng nh th hng s bn cng ln tc l phc cng bn hay phc phn ly cng t. Trong hai phc trn th phc [Cu(NH3)4]2+ bn hn. Cng ging nh cc a axit, a baz, i vi phc c nhiu phi t th qu trnh hnh thnh hay phn ly ca phc cng xy ra tng nc. V d, phc [Zn(NH3)4]2+ xy ra 4 cn bng sau: [Zn(NH3)2+] Zn2+ + NH3 [Zn( NH 3 ) 2+ ] = 10 2,18 1 = [Zn 2+ ][NH 3 ] [Zn(NH3)22+] [Zn(NH3)2+] + NH3 + [ Zn ( NH 3 ) 2 2 ] 2 = = 101, 25 2+ [Zn( NH 3 ) ][NH 3 ] [Zn(NH3)32+] [Zn(NH3)22+] + NH3 [Zn( NH 3 ) 32+ ] = 10 2,31 3 = [Zn( NH 3 ) 22+ ][NH 3 ] [Zn(NH3)42+] [Zn(NH3)32+] + NH3 + [ Zn( NH 3 ) 2 4 ] 4 = = 101,96 2+ [Zn( NH 3 ) 3 ][NH 3 ] cho tin vic tnh ton, thng cn dng hng s bn tng cng ca nhiu cn bng trn. V d, cng hai cn bng u trong 4 cn bng trn ta c cn bng: [Zn(NH3)22+] Zn2+ + 2NH3 Hng s cn bng bn s l: + [ Zn ( NH 3 ) 2 2 ] 1, 2 = = 1 2 = 10 3, 43 2 2+ [Zn ][NH 3 ] Tng t ta c: 1, 4 = 1 2 3 4

[Zn( NH ) ] = 10 = [Zn ][NH ]

2+ 3 4 3 2+ 4

7,7

Da vo hng s khng bn ta c th tnh nng cn bng ca ion hoc phn t do phc cht phn ly ra tm cch tng hay gim cc nng n mc cn thit

104 cho vic phn tch. V d: Tnh nng cn bng ca cc ion trong dung dch diamino bc (II) nitrat [AgNH3)2]NO3 0,01M c KKb = 6,8.10-8 Gii: Trong dung dch, phc cht ny phn ly hon ton theo phn ng: [Ag(NH3)2]NO3 [Ag(NH3)2]+ + NO3Nng lc ban u: 0,01M 0,01M 0,01M + + Ag + 2NH3 (5.4) Nhng: [Ag(NH3)2] KKb = 6,8.10-8 [Ag + ][ NH 3 ] 2 (5.5) Vy khi cn bng ta c: = K Kb = 6,8.10 8 [Ag( NH 3 ) 2 ] + (5.6) Theo phng trnh phn ly (5.4) ta c: [NH3] = 2[Ag+] Theo nh lut bo ton khi lng ta c: (5.7) [Ag(NH3)2]+ + [Ag+] = 0,01 Gii phng trnh c 3 n s (5.5), (5.6), (5.7) ta s tnh c gi tr ca [Ag+], [NH3], [Ag(NH3)2]+. 4[Ag + ]3 = 6,8.10 8 + 0,01 [Ag ] v ion phc phn ly yu (KKb = 6,8.10-8) nn: [Ag+] << 0,01M. Do : 0,01 - [Ag+] 0,01. Vy rt ra c: [Ag+] = 5,5.10-4 [NH3] = 1,1.10-3 [Ag(NH3)2]+ = 9,45.10-3

5.1.3.2. Cc yu t nh hng n bn ca phc cht. S phn hy phc cht. Ni cu ca phc cht l nhng cht in ly yu, trong dung dch n phn ly mt phn thnh nhn trung tm (ion kim loi) v cc phi t (phn t hay ion). V d: [Ag(NH3)2]+ Ag+ + 2NH3 (5.8) Mun phc cht bn ngha l t phn ly th phi chuyn dch cn bng (5.8) t phi sang tri c th bng cch cho thm NH3, hay ni cch khc phc cht trn bn trong mi trng NH3. Ngc li nu ta gim nng ca cu t to ra ni cu nh NH3, Ag+ ca phc cht [Ag(NH3)2]+ th phc cht s km bn v c th b phn hy hon ton. Ta nghin cu mt s yu t trong mt s trng hp lm cho phc cht b phn hy. * nh hng ca pH: Ni cu do ion kim loi lm ion trung tm v cc phi t l phn t hay ion to thnh. C 2 trng hp cn xt: - Ion kim loi trung tm thng l nhng nguyn t kim loi nng, theo thuyt Bronsted chnh l nhng axit c kh nng nhng H+, ngha l c th kt hp vi OH- ca nc to thnh cc baz lin hp tng ng yu t tan, bi vy mi trng pH cao - mi trng kim - phc cht c th b phn hy. V d: Na3[Co(NO2)6] 3Na+ + [Co(NO2)6]3-

105 6NO2- + Co3+ [Co(NO2)6]3(II) Co(OH3) Co3+ + 3OHDo cn bng (II) chuyn dch t tri sang phi ko theo cn bng (I) chuyn dch t tri sang phi. - Mt khc cc phi t l phn t hay anion, theo thuyt Bronsted c th l nhng baz c kh nng nhn H+ to thnh axit lin hp tng ng yu. Bi vy trong mi trng axit phc ch t c th b phn hy. (III) V d: [Ag(NH3)2]+ (IV) Ag+ + 2NH3 2NH+ 2NH3 + 2H+ Do cn bng (IV) chuyn dch t tri sang phi ko theo chuyn dch cn bng (III) t tri sang phi. Qua s kho st trn r rng mi phc cht ch tn ti v bn trong dung dch mt khong gi tr pH xc nh. * Cu t ca ni cu kt hp vi mt cht khc to thnh mt hp cht t tan. Trong trng hp ny nu mt cht c tc dng kt hp vi ion trung tm hay vi cc phi t to thnh mt cht t tan, nu cho mt lng ln th phc cht c th b phn hy hon ton. V d: - Phc cht [Ag(NH3)2]+ s b phn hy nu cho mt lng KI ln v: (I) 2NH3 + Ag+ [Ag(NH3)2]+ (II) AgI Ag+ + I+ V I kt hp Ag to thnh AgI t tan lm cn bng (II) chuyn dch sang phi ko theo cn bng (I) chuyn dch t tri sang phi. - Phc cht [Fe(SCN6)]3- s b phn hy nu cho mt lng AgNO3 ln: [Fe(SCN6)]3- (III) Fe3+ + 6SCN6NO3- + 6Ag+ 6AgNO3 + - (IV) 6AgSCN 6Ag + 6SCN V Ag+ kt hp vi CNS- to thnh AgSCN t tan lm cho cn bng (IV) chuyn sang phi ko theo cn bng (III) chuyn dch t tri sang phi. * Cu t ca ni cu kt hp vi mt cht khc to thnh mt phc cht khc bn hn. Nu cho mt cht vi mt lng ln c th kt hp vi ion trung tm hay vi cc phi t to thnh mt phc cht khc bn hn th phc cht trc c th b phn hy. V d: Nu cho mt lng ln KCN vo dung dch [Cu(NH3)4]2+ th phc s b phn hy hon ton do to ra phc cht mi [Cu(CN)4]3- bn hn. 2[Cu(CN)4]3- + (CN)2 + 8NH3 2[Cu(NH3)4]2+ + 10CN-14 Kkb = 5.10-28 Kkb = 4,6.10 Nu cho mt lng CuSO4 ln vo dung dch phc cht [Cd(NH3)4]2+ th phc cht s b phn hy to thnh phc cht [Cu(NH3)4]2+ bn hn. [Cu(NH3)4]2+ + Cd2+ [Cd(NH3)4]2+ + Cu2+ -8 Kkb = 4,6.10-14 Kkb = 8,96.10
(I)

106

5.2. Thuc th hu c. Thuc th hu c u tin c tm ra do Ilinsky vo nm 1884 l cht nitrozonaphtol xc nh Co2+, n tc dng vi Co2+ cho ta mui ni phc c mu nu c trng. Sau vo nm 1905 Sugaep tm ra imetylglioxim lm thuc th pht hin Ni2+ m ngy nay cn ng dng xc nh nh tnh v nh lng niken. Do s pht trin ca l thuyt ha hc hu c, ngy nay ngi ta hiu c c ch nhiu phn ng c s tham gia ca cht hu c v dn dn tng hp c nhiu thuc th c nhiu c tnh qu bu, p dng c hiu qu vo ha hc phn tch. Vic s dng thuc th hu c tr thnh ph bin v khng th thiu i vi ngnh ha hc phn tch hin i. Theo nh ngha ph bin nht th: Tt c cc cht hu c ng dng trong ha phn tch nh tnh cng nh nh lng tm hay xc nh, phn chia hay lm giu cc nguyn t gi l thuc th h u c . a s cc thuc th hu c dng trong ha hc phn tch l nhng cht in ly yu v do phn ng gia chng vi cc ion kim loi cng l cc phn ng thuc loi ion. Ta thng gp cc loi phn ng sau: 5.2.1. Cc phn ng ca thuc th hu c. 5.2.1.1. Phn ng to cc hydroxyt hoc cc mui kh tan. V d cc baz hu c nh piridin C5H5N, -picolin C6H7N trong nc c phn C5H5NH+ + OHng baz: C5H5N + H2O Do khi tc dng vi mt s ion kim loi th cho kt ta hydroxyt. Cc anion ca mt s axit hu c nh oxalat C2O42-, tatrat to c mui t tan vi mt s ion CaC2O4 kim loi. V d: C2O42- cho kt ta CaC2O4: Ca2+ + C2O425.2.1.2. Cc phn ng to thnh sn phm oxy ha - kh. tm mt s ion kim loi, i khi ngi ta dng mt s thuc th hu c c kh nng tham gia phn ng oxy ha - kh vi cc ion to nn cc sn phm c mu c trng. V d nhn ra ion Fe3+ c th dng phn ng vi benzidin l mt baz hu c, n c th b ion Fe3+ oxy ha to thnh diphenylbenzidin tm. 5.2.1.3. Phn ng to phc. y l loi phn ng c nhiu ng dng quan trng nht. C th chia cc phn ng to phc gia thuc th hu c v ion kim loi thnh 2 loi: * Phn ng to phc thng. * Phn ng to thnh ni phc. y l nhm thuc th hu c ln nht v quan trng nht. V d: - Phn ng Sugaep tm Ni2+ bng dimetylglyoxim to mui ni phc dimetylglyoximat Ni: CH3 C = NO CH3 C NOH NiCl2 + 2NH3 + 2 2NH4Cl + Ni CH3 C NOH CH3 C = NOH 2 Phn

ng to cc ni phc khc:

107 CH2 CH2 NH2 + CoCl2 NH2

CH2 CH2 NH2 NH2

Co Cl2
2

etylendiamin
3C6H4 COOH + Fe3+ OH

Cloruaetylendiamino Co (II)

H3 C6H4

COO
3Fe

axit salixilic

O axit ferisalixilic

+ 3H+

5.2.2. c tnh ca thuc th hu c Khi chn thuc th hu c dng vo mc ch phn tch, ngi ta ch n cc c tnh sau: 5.2.2.1. Tnh ring bit ca thuc th C nhiu thuc th hu c khi tc dng vi cc ion v c trong iu kin nh nhau u cho phn ng gn nh nhau. V d: 8-oxy quinlin, piridin, loi nh vy gi l thuc th khng c tnh ring bit. Tri li c mt s thuc th c tnh ring bit cao, n c kh nng cho phn ng c trng vi mt hay mt s nguyn t khi c mt cc nguyn t khc. V d: tinh bt pht hin it (cho mu xanh c trng). Tuy nhin loi thuc th c tnh ring bit cao ny kh him. Ngi ta c th chn iu kin thch hp s dng thuc th hu c c tnh ring bit thp hn nhm xc nh mt s cht khi c mt mt s cht khc. Cch lm nh vy gi l s dng tnh chn lc ca thuc th hu c. 5.2.2.2. nhy nhy ca thuc th hu c th hin hiu qu phn tch ca thuc th, trong iu kin tin hnh phn ng thuc th hu c thng c nhy cao hn hn so vi cc thuc th khc. V vy mc d mt thuc th c chn lc km nhng nhy cao cng c s dng tt cho mc ch phn tch. Ngi ta thng dng khi nim nng tm c ti thiu v pha long gii hn c trng cho nhy ca thuc th hay ca phn ng. Ta gi lng ti thiu tm c l lng nh nht ca cht nghin cu (cn pht hin) c th pht hin c bng thuc th tng ng iu kin phn ng ti u v c o bng microgam (1 = 10-6gam). Cn nng pha long gii hn l t l gia khi lng ca cht ha tan trn khi lng dung mi nh nht cn c th pht hin c bng thuc th tng ng trong iu kin ti u. V d: Thuc th albrn tm brili c pha long gii hn l 4.10-7, ngha l nu pha long 1gam brili trong 107 gam nc vn cn pht hin c bng thuc ny. 5.2.3. C ch tng tc ca thuc th hu c y chng ta nghin cu ch yu c ch tng tc ca nhm thuc th hu c to cc ni phc, c bit i vi thuc th hu c to mui ni phc. Khi nghin cu ngi ta thy rng mt thuc th hu c phn ng c vi mt s ion nht nh to mui ni phc l do cu to phn t ca thuc th hu c v iu kin tin hnh phn ng.

108

5.2.3.1. Cu to ca thuc th hu c. Kt qu tng tc ca thuc th hu c vi cc ion c quyt nh bi 2 phn trong phn t ca chng: - Mt phn ca phn t quyt nh s tng tc vi ion ny hay ion khc gi l nhm chc phn tch (hay nhm nguyn t c trng). - Mt phn khc c nh hng n sn phm phn ng gi l phn gy hiu ng phn tch (nhm hot phn tch). * Nhm chc phn tch Khi gn thm vo trong phn t ca mt hp cht hu c (khng c kh nng phn ng vi ion cho) mt nhm nguyn t c bit th c th lm cho cht tr nn c kh nng phn ng. S c mt ca nhm l nhm chc phn tch. Trong nhm chc phn tch c hai nhm nguyn t nm cnh nhau. - Nhm to mui: trong nguyn t H c th cho cation kim loi thay th c to lin kt ha tr nh nhm cacboxyl -COOH, nhm oxym =NOH, nhm nol R hydrxyl -OH, nhm sunfo -SO3H. nhm amin bc 1 -NH2, bc 2 N , ... H , N
Nhm

to lin kt phi tr: Trong nguyn t N nh trong =NOH, -NH2,

R N , ... nguyn t O nh trong -OH, = CO, ... c th to lin kt phi tr v H cc nguyn t cn tha mt hay nhiu cp e- t do, lin kt ny thng c biu

din bng mi tn hoc ng chm.

V d nhm chc phn tch i vi Ni2+

C NOH v C NOH

C NH C NH

V d:

CH3 C NOH thay th + Ni 2+ + 2NH3 CH3 C N phi tr OH

CH3 C NO Ni + 2NH+ 4 CH3 C N 2 ti OH

* Nhm hot tnh phn tch: C cc nhm ch yu sau: - Hiu ng trng lng: Lm cho mui ni phc c to t tan hn. V d: + Cupferon (phenyl-nitrozo-hydroxyl amin) v nes-cupferon u to c mui ni phc t tan vi Cu2+ v Fe3+ nhng nes-cupferon lm kt ta hon ton hn v nhn naphtalen gy nn hiu ng trng lng.
N O NH4 NO ONH4 nes-cupferon
N

NO cupferon

109 + Alizarin v alizarin S u to mui ni phc t tan vi Al3+ nhng Alizarin S lm kt ta hon ton hn v n c gn thm nhm -SO3Na.

O OH OH

O OH OH SO3Na alizarin S

alizarin O O - Hiu ng tr mu: Nu a vo phn t thuc th hu c khng mu no mt nhm mang mu th phn t thuc th hu c tr thnh c mu v sn phm ca n cng mang mu. V d: nhm (CH3)2N-C6H4- lm tng hiu ng mu cho thuc th nhn piridin, quinolin. - Hiu ng chn lc: Nu gn thm vo phn nhn nhng nhm th mi c th gy ra nhng hiu ng lm thay i tnh chn lc ca thuc th. V d: Trong mi trng axit v c, axit phenylarsonic (C6H5 -AsO3H2) kt ta c vi Zr4+, Sn4+, Hf4+, Nb5+, Ta5+, Ti4+ nhng nu gn vo v tr octo mt nhm -NO2 to thnh axit Octonitro phenylarsonic th ch kt ta c vi Sn4+.
OH HO As O OH HO As O NO2

Axit phenylarsonic Axit Octonitrophenylarsonic 5.2.3.2. nh hng ca iu kin tin hnh phn ng. iu kin tin hnh phn ng c nh hng ln n tnh chn lc, quan trng nht l iu kin pH ca mi trng. C nhng thuc th hu c c kh nng tc dng c vi rt nhiu ion to thnh mui ni phc, nhng khi thay i mi trng thch hp th kh nng b hn ch. Do , c th chn mi trng thch hp lm tng tnh chn lc ca thuc th hu c. V d: Dimetylglyoxim trong mi trng amoniac th phn ng c vi niken, vanadi nhng trong HCl 2N th ch tc dng vi vanadi. 5.2.4. Mt vi loi thuc th hu c thng gp trong ha phn tch. Cc thuc th hu c l dn xut ca amoniac c tnh cht gn nh amoniac c dng iu chnh pH, lm cht che. Cc cht thng dng l piridin C5H5N, pycolin C6H7N. Cc cht ny c tnh baz yu hn amoniac nhiu. Cng nh amoniac, chng to c phc bn vi nhiu kim loi, v d: Ag+, Cd2+, Ni2+, Co2+, ... - Axit etylendiamintetraaxetic (EDTA thng c gi l complexon II) l mt axit 4 chc:

HOOC HOOC

CH2 CH 2 N CH 2 CH 2 N

CH2 CH2

COOH COOH

110 Thuc th ny c kh nng to phc bn vi hu ht cc ion kim loi theo t l 1:1. - Ditizon:

NH S C

NH

C6H5

N N C6H5 to phc vi mt s ion kim loi nh: Pb2+, Cu2+, Zn2+, ... - Dimetylglyoxim cha 2 nhm oxim:
CH3 C C CH3

HON NOH l axit yu, to kt ta kh tan vi ion Ni2+, Pb2+, to phc mu tan trong nc vi ion Fe2+. - Oxim (8 oxyquinolin) C9H6NOH:

N OH Oxim (8-oxyquinolin) C9H6NOH c tnh lng tnh, to c hp cht ni phc kh tan vi nhiu ion kim loi. Bng cch iu chnh mi trng pH thch hp, dng cht to phc ph c th dng oxim tch c nhiu kim loi khc nhau. - Thuc th to thnh sn mu: Mt s thuc th hu c b hp ph vo b mt cc hydroxit kim loi t tan v thay i mu. Bn cht ca s hp ph ny l s to phc cng cua gia thuc th v ion kim loi nm trong hydroxit. V d: Alizarin S to vi nhm sn mu do hnh thnh hp cht ni phc c cu to:
OH Al O O OH SO3Na OH

Rodamin B to phc SbCl6-HR+ mu tm vi Sb(V) chit c bi benzen:

(C2H5)2N O C C O OH N+(C2H5)2Cl
-

111

Nes-Cupferon to phc t tan vi Cu2+ v Fe3+:

N N

O ONH4

5.3. ng dng ca phc cht v thuc th hu c trong ha phn tch. 5.3.1. Pht hin v xc nh ion. V d: Khi phn tch nh tnh h thng cation nh: - Tm Al3+ bng alizarin S trong mi trng kim (pH = 9). - Tm Sb5+ bng rdamin B trong mi trng HCl m c dng mui ni phc mu tm hoa sen. - Tm Ni2+ bng dimetylglyoxim trong mi trng dung dch NH3 dng mui ni phc mu ti ... Dng iu ch dung dch m, v d hn hp m formiat biphtalat. Nhiu ion n gin khng c tnh c trng r rt, v vy t c ng dng phn tch. Tuy vy khi chuyn thnh phc thch hp th li rt c trng v c th s dng nhn ra ion . Chng hn nh ion Cu2+ c mu xanh nht v khng th nhn ra c khi c nng thp, tuy vy khi chuyn thnh phc [Cu(NH3)4]2+ th n s c mu xanh m v c th pht hin ra d dng hn. Trong phn tch nh lng dng lm cht kt ta trong phn tch khi lng. V d xc nh Ni2+ bng dimetylglyoxim, Al3+ bng 8-oxyquinolin ... Dng lm cht gc trong phn tch th tch, v d H2C2O4.2H2O c lm cht gc cho phng php trung ha v oxy ha-kh ... Dng iu ch dung dch chun nh trilon B. 5.3.2. Che du. Trong thc t rt t thuc th hon ton chn lc, ngha l ch tc dng vi mt ion nht nh m thi m thng cho phn ng ng thi vi mt s ion kim loi. Ta ni rng cc ion ny cn tr ln nhau. V vy tm mt ion no trong dung dch c cc ion cn tr khc cn phi che chng li bng mt phn ng to phc bn c trng. V d, phn ng tm Co2+ bng thuc th NH4SCN to thnh phc [Co(SCN)4]2- mu xanh trong axeton hoc te b cn tr mnh bi ion Fe3+ v ion ny to c phc mu m vi ion sunfoxyanat (Fe(SCN)3). Do nhn ra ion Co2+ cn phi che ion Fe3+, chng hn bng cch thm vo dung dch mt lng ln H3PO4 hay F- th Fe3+ s dng phc bn [Fe(HPO4)+] hay [FeF6]3- khng mu. Cht c a vo trong mi trng phn ng nhm mc ch lm trit tiu hoc km hm mt phn ng khc no c gi l cht che. Cht che em s dng phi l cht c kh nng to c vi cc ion cn tr phc c bn ln cc ion khng cn tc dng vi thuc th s dng cho ion cn xc nh, ngc li bn ca phc gia ion cn xc nh vi cht che (nu c) phi tng i b ion ny cn kh nng tham gia phn ng c trng vi thuc th s dng. Ngoi ra cng cn phi ch ti iu kin l phc to thnh gia cht che vi ion cn tr khng c gy kh khn cho vic phn ng gia ion cn xc nh vi thuc th c trng s dng. Bi ton gii quyt vn chn iu kin che ti u cho mt phn ng no

112 l kh phc tp. y phi gii quyt mt lot cc mi quan h gia cc bn ca cc phc khc nhau vi pH, vi nng ca cc cu t trong dung dch. V d: Khng th dng ion oxalat che ion Fe3+ trong phn ng tm ion Co2+ di dng phc sunfoxyanat bi v theo kt qu tnh ton th phc st (III) sunfoxyanat b ph hy gn nh hon ton khi c ion C2O42-. Khi c mt ca C2O42- th ch cn 6% phc coban sunfoxyanat tn ti trong dung dch, cn 94% lng ca n b phn hy v chuyn thnh phc oxalat. Trong thc t ngi ta thng dng NaF lm cht che v ion F- to phc kh mnh vi ion Fe3+ trong khi phc ca n vi ion Co2+ li rt t bn. 5.3.3. Thay i cng cc cht. Cn phi k n s nh hng ca s to phc ln tnh axit baz v tnh oxy ha-kh ca hp cht. Nu anion ca mt axit yu no m to phc vi cation khc th s lin kt gia n v ion H+ s yu i, v nh vy ta s c axit mnh hn axit u. V d: Tnh axit ca axit oxalic (H2C2O4) s tng ln nu c Mg2+ v ion ny to phc vi C2O42-. Axit borc s mnh ln nu c mt cc ru a chc nh glyxrin hoc manit bi axt borc to nhng axt phc vi chng l axt manitoborc HBO2[C6H8(OH)6]2 hay glyxrinoborc HBO2[C3H5(OH)3]2. Cc axt ny mnh hn axt borc nhiu. V vy trong phn tch nh lng, khi nh phn hn hp HCl v H3BO3 thng ngi ta cho vo mt t glyxrin v chun vi ch th phenolphtalein. i vi cht oxy ha v cht kh th thng thng yu i khi c s to phc bi v nng ca chng b gim i. V d ion Fe3+ mt hn kh nng oxy ha ion In I2 khi c ion F-. H2C2O4 b gim kh nng kh xung khi c tha axit molipden v MnO4- khng oxy ha c n. 5.3.4. Ha tan v tch. S to phc c th c s dng chuyn kt ta vo trong dung dch: HgI2 + 2I- = [HgI4]2Hoc s dng tch. V d tch Cu2+ v Ni2+ nhm V ra khi nhm IV trong hn hp.

Kt ta hydroxyt nhm V, IV v MnO2

+ NH4OH

Kt ta nhm IV v MnO2 Dung dch [Me(NH3)4] ca nhm V

2+

Me2+: cation ca nhm V: Cu2+, Ni2+ [Cu(NH3)4]2+ + OHTheo phn ng: Cu(OH)2 + 4NH3 5.4. Chun to phc Phng php chun phc cht l mt phng php phn tch th tch da vo phn ng to phc bn. Yu cu ca cc phn ng to phc: - Phn ng phi nhanh v hon ton. - Phn ng phi xy ra theo ng t lng nht nh. - Phi c kh nng xc nh c im tng ng. V vy ch c mt s phng php ch yu sau:

113

5.4.1. Phng php thy ngn Da vo phn ng to phc cht gia Hg2+ vi cc anion halogenua, CN-, CNSv.v... vi ch th diphenylcacbazit hay diphenylcacbazon trong mi trng pH thch hp. V d: Hg2+ + ClHgCl+ K1 = 5,5.106 HgCl2 K2 = 3,0.106 HgCl+ + ClHgCl3 K3 = 7 HgCl2 + Cl 2HgCl4 K4 = 10 HgCl3 + Cl Hai phn ng sau khng c gi tr nh lng v yu m thc t ch da vo 2 phn ng u m thi. 5.4.2. Phng php xyanua Da vo s chun dung dch xyanua bng dung dch AgNO3 to phc cht 2CN- + Ag+ [Ag(CN)2-] [Ag(CN)2-]: Nu tha Ag+ th li to ra kt ta: Ag[Ag(CN)2] c T = 10-12 Ag(CN)2- + Ag+ Nh vy ta s kt thc chun khi bt u thy dung dch vn c kt ta Ag[Ag(CN)2]. C th da vo phng php ny chun gin tip mt s ion kim loi, c bit l Ni2+, Co2+, Cu2+ v Zn2+ v chng c th to c vi CN- nhng phc cht bn hn Ag(CN)2- v phn ng xy ra theo mt quan h t lng xc nh. V d nu cho d CN- vo dung dch Ni2+ trong amoniac th ton b Ni2+ s dng phc cht [Ni(CN)4]2- bn hn Ag(CN)2- do c th chun lng tha CN- bng phng php trn. 5.4.3. Phng php complexon Da vo phn ng to mui ni phc gi l complexonat xy ra gia complexon v hu ht cc ion kim loi. Phng php ny c phm vi ng dng rng ri, c nhy v chnh xc rt cao. Hin nay n l phng php ph bin nht. 5.4.3.1. Cu to ca cc loi complexon. Complexon l nhng dn xut ca axit aminopolycacboxylic, c 3 complexon quan trng thng dng nht l: Complexon I: l axit nitriltriaxetic (NTA), k hiu H3Y cn gi l trilon A
CH2COOH N CH2COOH c M = 191,1 CH2COOH Complexon II: l axit etylendiamin tetraaxetic (EDTA) k hiu l H4Y c M = 292,1, t tan trong nc. HOOC CH 2.. .. CH2COOH N CH2 CH2 N CH2 COOH HOOC CH2

Complexon III: (vn quen quy c l EDTA) l mui dinatri ca axit H4Y, k hiu Na2H2Y, tn k thut l trilon B c M = 336,2.

114

HOOC CH2 .. N NaOOC CH2

CH2

CH 2

.. CH2 COONa
N CH2 COOH

Trong phn t ca cc complexon u c: - Nhiu nhm -COOH: C tnh axit nn cc complexon l cc a axit. Cc hng s axit KA ca chng nc u thng ln v gn nhau nn dung dch ca chng c tnh axit mnh. Cn cc KA cc nc sau nh nn trong dung dch thng c pH cao mi tn ti c cc ion cui. V d EDTA c K1 = 10-2, K2 = 10-2,76, K3 = 10-6,16, K4 = 10-10,26, pH = 2,2 tn ti dng H3Y-; pH = 4,3 tn ti dng H2Y2-; pH = 8,3 tn ti HY3-; pH = 12,4 tn ti Y4-. - Nguyn t O trong nhm COOH c kh nng to lin kt cng ha tr vi ion kim loi: Nguyn t N trong nhm amin c kh nng to lin kt phi tr i vi ion kim loi. Do complexon c kh nng to mui ni phc vi hu ht cc ion kim loi. V d vi Ca2+ complexonat Ca Na2CaY + 2H+ Na2H2Y + Ca2+ Na2H2Y c cu to: NaOOC CH2 OOC CH2 N CH2 CH2 Ca N CH2 COO CH2 COONa

5.4.3.2. S to thnh cc complexonat. V d phn ng gia complexon III v ion kim loi Men+ MeY2- + 2H+ Me2+ + H2Y2MeY- + 2H+ Me3+ + H2Y24+ 2MeY + 2H+ Me + H2Y T cc phng trnh trn, ta thy ni bt ln 2 c im: - Phn ng theo t l 1:1 tc l 1 ion kim loi (bt k ha tr my) kt hp vi 1 ion complexon to thnh 1 ion complexonat nht nh - iu ny rt c bit khc vi phn ln cc phn ng to phc cht khc. T t l 1:1 cho php ta xc nh lng ion kim loi mt cch chnh xc. - Trong cc phn ng trn, ta thy lun gii phng ra H+ nn s lm cho mi trng thnh axit mnh, nh hng n bn ca complexonat c to ra. Do ta phi duy tr phn ng trong mi trng dung dch m. Tnh cht qu gi nht ca cc complexon l kh nng to complexonat ngay c vi cc ion kim loi kim th: Mg, Ca, Ba, ... Cc kim loi ny nh ta bit rt kh hoc khng th chuyn thnh hp cht phc bng cc cch khc c. Phn ln cc complexonat kim loi thng rt bn, tc l hng s to thnh kh ln. Thng bn ca complexonat tng theo in tch ca ion kim loi: Me+ < Me2+ < Me3+ < Me4+ th hin ch complexonat Me4+ c th tn ti pH = 1, Me3+ -- pH = 12, Me2+ ch tn ti trong mi trng kim. Ni chung cc complexonat thng bn

115 trong mi trng c pH cao v xc nh, nhng vi pH cao qu th complexonat b phn hy to thnh hydroxyt t tan: Me(OH)n Me+ + nOHBi vy phi tin hnh phn ng trong mi trng m. Cc complexonat d tan trong nc hn complexon tng ng. Trong cc complexonat kim loi th Na2CaY l t tan nht. Complexonat ca ion kim loi mu th s c mu m hn, ca ion kim loi khng mu th s khng mu. 5.4.3.3. Chun bng complexon * Cht ch th trong phng php complexon xc nh im tng ng trong phng php ny ngi ta dng cc ch th nh oxy ha - kh, axit - baz, ch th kim loi nhng ph bin nht l ch th mu kim loi. l nhng cht hu c c mu c th kt hp vi ion kim loi to thnh mui ni phc kh bn, tan trong nc, c mu khc vi mu ca cht ch th kim loi dng t do. Cc cht ch th mu kim loi thng l nhng axt 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 pH ca dung dch. Cc cht ch th kim loi phi t c cc yu cu sau : - Phi nhy v kh chn lc, nng ca cht ch th em dng phi nh nht c th c. - Phc cht c to ra gia cht ch th v ion kim loi phi kh bn nhng km bn hn complexonat kim loi (t nht l 104 ln). - Phn ng to phc gia cht ch th v ion kim loi (cn xc nh) phi kh nhanh v thun nghch. - S i mu ca cht ch th phi kh r c th nhn ra c bng mt. V d: nh phn dung dch Me2+ bng Na2H2Y dng ch th kim loi Ind- (mu A). + Trc nh phn: Ta cho mt lng nh cht ch th, s c phn ng: [MeInd]+ Me2+ + Ind2+ dung dch c mu B phn ln Me trng thi t do v lng cht ch th cho vo rt nh. + Khi nh phn th Me2+ (t do) s kt hp vi thuc th Na2H2Y: MeY2- + 2H+ Me2+ (t do) + H2Y2+ Kt thc nh phn th nh mt git cui cng Na2H2Y phn hy [MeInd]+ gii phng ra Ind-, theo phn ng: [MeInd]+ + H2Y2MeY2- + 2H+ + Indmu A

* Cc cht ch th quan trng thng dng trong chun complexon. + Eriocrmen T (ET.OO): c ng dng nhiu nht, v n c th xc nh trc tip phn ln cation thng thng v mt s anion. y l cht mu az, l mui natri ca axit H3Ind:

116

OH HO3 S NO2 N N

OH (H3 Ind)

Trong dung dch n tn ti dng anion, k hiu: H2Ind-

ET.OO c tnh cht ca mt cht ch th axit - baz 3 mu, theo s sau:

H2IndInd-3 HInd-2 xanh da cam pH = 6: ch th c mu dng H2Ind pH = 7 11: ch th c mu xanh dng HInd-2 pH > 11,5: ch th c mu vng dng Ind-3 mi trng kim yu pH = 7 11, ET.OO c th kt hp vi Mg2+ v mt s cation kim loi khc to thnh ni phc c mu mn theo phn ng: MgInd- + H+ Mg2+ + HInd2Ch : - Mt s ion kim loi nh Co2+, Ni2+, Cu2+, Al3+, ... kt hp vi ET.OO to thnh phc cht bn hn complexonat tng ng nn khng nh phn trc tip c. S c mt ca chng s lm cn tr vic nh phn trc tip cc ion khc, ch c Fe3+, In3+, Se3+, Sn4+, Th4+ c chun trong mi trng axit v to phc bn vi complexon. - Mt s ion kim loi nh Pb, Hg, In, Ga, ... kt hp vi ET.OO to phc cht mu qu nht nn cng khng chun trc tip c. - Ion Fe3+ lm cn tr php chun bng complexon. - Ion Mn2+ trong mi trng kim d b oxy ha thnh Mn3+ v Mn4+ s phn hy cht ch th. Tuy nhin, c th thm cht ch th thch hp (nh axit ascobic, hydroxylamin) ngn chn s oxy ha Mn2+ v c th chun gin tip c. + Murext l mui amoni ca axit pupuric C8H5O6N5, c k hiu l H4Ind-. Trong mi trng c 0 < pH < 9 murext c mu tm dng H3Ind2-; pH > 11 murext c mu xanh dng H2Ind3-. Trong mi trng kim mnh (pH 12) murext kt hp vi Ca2+ to thnh phc mu theo s :
pK1 = 6,3 pK2 = 11,5

Ca

2+

+ murexit xanh tm

[Ca - murexit]

Ch : Murexit l ch th kim loi thng dng xc nh Ca2+ trong dung dch NaOH, xc nh Cu2+, Ni2+, Co2+ trong mi trng amoniac. Cn cc ion kim loi khc to vi murexit thnh nhng phc cht khng bn nn khng c gi tr trong phn tch . Sr2+, Ba2+, Mg2+ cng tc dng yu vi murexit do c th xc nh c Ca2+ trong dung dch hn hp Ca2+, Sr2+, Ba2+, Mg2+. * Cc cch chun . + Chun trc tip. Cho hn hp m thch hp vo dung dch phn tch, sau cho rt t cht ch

117 th tng ng (ch th thng c dng di dng dung dch hay tinh th trn ln vi NaCl hay KCl, nhng di dng dung dch khng bn nn dng di dng kh c trn ln vi t l ch th: NaCl hay KCl = 1:200 hay 1: 500. Khi chun ly khong 20 - 30 mg hn hp ny). Dung dch lc s c mu ca phc cht to thnh bi ion kim loi vi cht ch th. Sau nh phn bng dung dch chun complexon ti gn ti im tng ng cht ch th c gii phng ra dng t do. V d: Chun dung dch Mg2+ bng dung dch chun trilon B trong dung dch m NH3 + NH4Cl c pH 9 - 10 vi ch th ET.OO. Mg 2+ + ET.OO
(t do)
2+ 22-

mn ( nho)

[Mg - ET.OO] MgY

2-

Mg

+ H 2Y

+ 2H + + 2H + + ET.OO
xanh bic

[Mg - ET.OO] + H2 Y

MgY

2-

+ Chun ngc. Cho mt lng d complexon bit nng chnh xc vo dung dch phn tch iu kin pH thch hp ri chun lng complexon tha theo cch chun trc tip. Da vo lng complexon ban u v lng tha ta d dng tnh c lng ion kim loi cn xc nh. V d theo s : Men+ + Trilon B (cho d) MeYn-4 + Trilon B (tha) Trilon B tha c chun trc tip bng dung dch chun MgSO4 hay ZnSO4 vi ch th ET.OO trong mi trng m amoni. Cch chun ngc c dng khi: - Phc cht c to ra bi ion kim loi cn xc nh v cht ch th qu bn, bn hn complexont tng ng. - Khng c ch th thch hp. - Phn ng to complexonat qu chm. - Men+ cn xc nh dng kt ta. V d: Khng chun trc tip Co2+, Ni2+, Al3+. Khng chun trc tip c Tl3+ d rng TlY- rt bn nhng Tl3+ khng phn ng vi cc cht ch th thng dng. Khng chun trc tip c Pb2+ dng PbSO4 hay Mg2+ dng NH4MgPO4 hay Ca2+ dng CaC2O4. + Chun thay th. Phng php c da vo tnh cht km bn ca complexonat Mg: Na2MgY. Ngi ta cho complexonat Mg (thng l d) tc dng vi ion kim loi cn xc nh, m ion kim loi ny tc dng c vi complexonat thnh MeYn-4 bn hn MgY2kt qu ion Mg2+ b y ra ra khi Na2MgY mt lng tng ng theo phn ng: MeYn-4 + Mg2+ Men+ + MgY2sau ta ch vic chun trc tip lng Mg2+ c gii phng ra bng complexon vi ch th ET.OO trong mi trng m pH = 9 10. Phng php ny c ng dng khi khng dng c phng php chun trc tip (tng t nh chun ngc). V d: HgY2- + Hg2+ HgY2- + Mg2+.

118

BI TP
1. Vit cc cn bng xy ra trong dung dch khi ha tan K4[Fe(CN)6] trong nc. 2. Vit biu thc cc hng s khng bn tng nc v tng cng ca phc gia Bi3+ v I-, bit rng Bi3+ to phc vi I- c s phi tr cc i l 4. 3. Ion Fe3+ to phc vi ion CN- c s phi tr cc i l 6. Hy vit cc cn bng to phc khi thm dn dung dch KCN vo dung dch Fe3+. Vit cc biu thc biu din hng s bn tng nc v tng cng ca cc phc . 4. Nng ca dung dch chun trilon B (Na2H2Y) c xc nh theo dung dch c cha trong 1 lt 24g Fe(NH4)(SO4)2.12H2O. C 10ml dung dch trn th chun ht 10,3ml dung dch trilon B. Hy tnh Na H Y , Na H Y / Fe O v TNa H Y / CaO
2 2 2 2 2 3
2 2

5. Hy tnh nng Ca2+ v Mg2+ (mlg/l) trong dung dch theo cc s liu sau. xc nh tng lng Ca2+ v Mg2+ ngi ta chun 20ml c cha Ca2+ v Mg2+ vi ch th ET-OO bng Na2H2Y ht 18,15ml. xc nh ring Ca2+ ngi ta thm vo 20ml dung dch trn 19ml dung dch Na2H2Y 0,112N lng d Na2H2Y nh phn bng dung dch CaCl2 0,102N th ht 12ml. 6. Ha tan 0,114g CaCO3 nguyn cht trong HCl v pha long thnh 250ml. Chun 25ml dung dch thu c ht 40,25ml dung dch EDTA. Tnh: a. Nng mol/l ca dung dch EDTA. b. chun ca EDTA theo CaO. c. Tnh cng ca mt mu nc theo s ppm Ca2+ bit rng khi chun 100ml nc th phi dng ht 6,25ml dung dch EDTA ni trn. 7. Ha tan 0,65g mt mu hp kim ca nhm. Tch b cc nguyn t gy cn tr, thm nc n 250ml. Ly 20ml dung dch, thm complexonat magi d ri chun dung dch thu c pH = 9 dng ET-OO lm ch th ht 7,6ml dung dch ETDA 0,1M. Tnh hm lng % ca Al trong hp kim.

TI LIU THAM KHO

1. Hong Minh Chu, T Vn Mc, T Vng Nghi. C s ha hc phn tch, NXB KH & KT, 2002. 2. Nguyn Tinh Dung phn I, II, III. Ha hc phn tch. NXB Gio dc, 2000. 3. Trn T Hiu, Ha hc phn tch, NXB HQG H Ni, 2002. 4. Trn T Hiu, T Vng Nghi, Hong Th Tn. Bi tp Ha hc phn tch, NXB H&TH Chuyn nghip, 1984. 5. H.A. Laitinen, Phn tch ha hc. Tp 1 v 2, Nguyn Tinh Dung v Nguyn Huyn dch. NXB KH & KT, 1976. 6. .., , , o , 1972 7. .., , , o , 1972

119

CHNG 6

CN BNG TRONG DUNG DCH CHA HP CHT T TAN. PHNG PHP CHUN KT TA
6.1. Cn bng trong dung dch cha hp cht t tan. 6.1.1. iu kin to kt ta - Tch s tan. Khi cho dung dch NaCl tc dng vi AgNO3, ion Ag+ v Cl- kt hp vi nhau to thnh AgCl t tan tch ra khi dung dch. Cc ion NO3- v Na+ khng tham gia vo phn ng kt ta nn cn li tt c trong dung dch. AgCl s ngng kt ta khi t n cn bng. + Ag + Cl AgCl ngha l khi tc kt ta bng tc ha tan. Tc kt ta t l vi din tch b mt S ca kt ta tip xc vi dung dch v vi hot ca cc ion kt ta. Tc ha tan ch t l vi b mt S ca kt ta tip xc vi dung dch. VKT = K 1a Ag . a Cl . S
+
-

VHT = K2.S VKT v VHT l tc kt ta v tc ha tan. a Ag v a Cl l hot ca Ag+ v Cl+ -

Khi t n cn bng VKT = VHT ngha l: K 1a Ag . a Cl . S = K2.S

+
-

K2 = TAgCl : gi l tch s tan ca AgCl. K1 i vi cc cht t tan c cng thc BmAn, tch s tan ca chng l: n (6.1) TB A = a m B .a A y hot ca B phi ly tha ln m v hot ca A phi ly tha ln n v BmAn tan trong dung dch theo phng trnh: BmAn mBn+ + nAmNu ngoi ion do cht rn tan ra khng c ion no khc th lc ion ca dung dch s nh, h s hot xp x bng 1 nn c th coi hot bng nng , v tch (6.2) s tan bng: TB A = [ B] m .[A] n H thc ny l ni dung ca quy lut tch s tan. Theo quy lut ny th: * Khi TB A > [B]m .[A]n , tc l tc phn ng ha tan ln hn tc phn ng to thnh kt ta, A v B khng kt hp c vi nhau thnh kt ta. Dung dch iu kin ny gi l dung dch cha bo ha i vi BmAn v nu thm BmAn vo dung dch ny th n c th tan thm n khi t cn bng, tc l khi: TB A = [B]m .[A]n . T suy ra: a Ag .a Cl =
+
m n m n m n m n

* Khi TB A = [ B] m .[A] n , tc l tc ha tan bng tc kt ta, kt ta khng tan thm v cng khng to thm. Dung dch iu kin ny c gi l dung dch bo ha, v thm BmAn vo dung dch ny th n s khng tan thm.
m n

120 * Khi TB A < [B] m .[ A] n , tc l tc kt ta ln hn tc ha tan, A v B s kt hp vi nhau thnh BmAn lm gim nng ca A v B n khi TB A = [ B] m .[A] n th phn ng li t cn bng. Dung dch ny gi l dung dch qu bo ha. Mt kt ta c th c dng trong ha phn tch khi n t tan v tinh khit. V vy cn xt n cc yu t nh hng n tan v lm kt ta ko theo tp cht. 6.1.2. Quan h gia tan v tch s tan. Cc yu t nh hng n tan. 6.1.2.1. tan v tch s tan. tan (S) ca mt cht l nng mol/l ca cht trong dung dch bo ha nhit nht nh. Tch s tan ca cht l tch s hot ion ca n trong dung dch bo ha. Ngoi ra, tan c th c tnh bng g/lit hoc mg/lit. tan ph thuc vo nhit . Tch s tan v tan u l cc i lng c trng cho dung dch bo ha nn c th tnh tch s tan t tan hay ngc li. V d 1: Tnh tch s tan ca Mg(OH)2 200C, bit rng 100ml dung dch bo ha nhit ny cha 0,84mg Mg(OH)2. Mg2+ + 2OH (6.3) Mg(OH)2 phn ly theo phn ng: Mg(OH)2 2 2 2+ Vy: TMg ( OH ) = a Mg .a OH = [ Mg ].f Mg .[OH ] .f OH
m n m n 2 2+

2+

0,84.1000 = 1,44.10 4 mol / lit 1000.58,32.100 Theo phng trnh (6.3) mi phn t Mg(OH)2 phn ly cho ta mt ion Mg2+ v hai ion OH-. Vy: [Mg2+] = 1,44.10-4 M v [OH-] = 2.1,44.10-4 M = 2,88.10-4 M

tan ca Mg(OH)2 bng: S =

Lc ion ca dung dch bng:

2+

1 (4.1,44.10 4 + 2,88.10 4 ) = 4,32.10 4 2

Vy 1g f Mg = 0,5.4 4,32.10 4 = 0,0416

f Mg = 0,91 ; f OH = 0,98
2+

a Mg = 1,44.10 4.0,91 = 1,31.10 4

2+

a OH = 2,88.10 4.0,98 = 2,84.10 4 Tch s tan ca Mg(OH)2 l: TMg ( OH ) = 1,31.10-4.(2,84.10-4)2 = 1,1.10-11 i vi cht t tan, nng ion trong dung dch bo ha rt nh nn c th coi h s hot f = 1, tc l coi hot bng nng . Theo gi thit ny th TMg ( OH ) = 1,19.10 11 ch khc khi c k n hot l 9%. Ni chung, khi tan khng ln hn 10-4 M hoc l khi tch s tan khng ln hn 10-8 th c th coi f = 1 tnh tch s tan. V d 2: Tnh tan ca Ca3(PO4)2 trong nc 200C. Bit rng nhit th tch s tan TCa ( PO ) = 10 32,5
2 2 3 4 2

Ta c phng trnh phn ly sau: Ca3(PO4)2 3Ca2+ + 2PO43Nu gi S l tan ca Ca3(PO4)2 th: [Ca2+] = 3S; [PO43-] = 2S. Vy: TCa ( PO ) = (3S) 3 .(2S) 2 = 33.2 2.S5
3 4 2

121

S=5

V S < 10-4 M nn gi thuyt trn coi hot bng nng l ng. Trong trng hp tng qut, cht t tan c cng thc BmAn, ta c phng trnh phn ly: BmAn mBn+ + nAmT = [Bn+]m[Am-]n = (mS)m.(nS)n = mmnnS(m+n) TB A (6.4) S = (m+n ) m n m .n Cch tnh tan t tch s tan trn y ch c th p dng khi tnh tan trong nc nguyn cht ca cht rn c ion khng tc dng vi ion ca nc. Trng hp ny rt him trong thc t v thng phn ng kt ta xy ra trong dung dch cha nhiu ion khc ngoi ion ca kt ta. Nh vy s c trng hp ion ca kt ta tc dng vi cc ion khc trong dung dch v s nh hng n tan ca kt ta. Ta ln lt xt nhng yu t nh hng n tan ca mt cht t tan. 6.1.2.2. Cc yu t nh hng n tan ca mt cht t tan. * nh hng ca ion chung (ion cng tn) Ion chung l ion c trong thnh phn ca kt ta. Theo quy lut tch s tan th tch s hot ca cc ion ca kt ta trong dung dch bo ha lun lun l mt hng s nhit nht nh. Nu hot ca mt trong cc ion tng th hot ca cc ion kia phi gim. V d: Tnh tan ca BaSO4 trong 0,01M dung dch Na2SO4 v so snh vi tan ca n trong nc. Bit TBaSO = 1,1.10 10 .
m n 4

10 32,5 3 3.2 2

S = 1,3.10 -7 (mol/lit)

tan ca BaSO4 trong nc nguyn cht l: S = 1,1.10 10 = 1,05.10 5 mol/lt Trong dung dch Na2SO4 0,01M, tan S ca BaSO4 bng nng [Ba2+]. Vy nng ca ion SO42- bng tng nng ca SO42- do BaSO4 v Na2SO4 phn ly ra. [SO42-] = S + 0,01 V tan ca BaSO4 rt b, khi c Na2SO4 li cng b hn nn SO42- do BaSO4 phn ly ra khng ng k, vy c th coi [SO42-] = 0,01. Vy: TBaSO = S(S + 0,01) = 0,01S = 1,1.10 10 ; S = 1,1.10-8mol/lit. Nh vy tan ca BaSO4 trong Na2SO4 0,01M nh hn trong nc nguyn 1,05.10 = 950 ln cht: 1,1.10 8 T ta thy tan ca cht t tan b gim i khi thm vo dung dch ca n cht in ly no c ion cng tn (ion chung) vi cht t tan. V vy kt ta hon ton ion no th khi tin hnh kt ta, ngi ta thng dng d thuc th (ion chung) v khi ra kt ta ngi ta cn thm vo nc ra mt t dung dch c cha ion chung, nh vy gim sai s ca php nh lng * nh hng ca nhng ion khc ion ca kt ta (ion l) Cc ion l lm tng tan cu kt ta v s lm tng lc ion ca dung dch, ngha l lm gim h s hot f trong biu thc tch s tan, do nng ion ca kt ta s tng lm tng tan ca kt ta, nh hng ny cn gi l hiu ng mui.
4

122

V d: Tnh tan ca AgCl trong KNO3 0,1M. Bit 250C TAgCl = 1,8.10-10 Trong nc nguyn cht, lc ion qu nh, coi nh f = 1. Do , tan ca AgCl l: S = 1,8.10 10 = 1,34.10 5 M
Trong dung dch KNO3 0,1 M lc ion ln, c th l: 0,5. 0,1 lg f = = 0,88 ; f = 0,76 1 + 0,1 Nu tnh n h s hot th TAgCl = [ Ag + ]f Ag [Cl ]f Cl = S2 f 2
+

v S =

TAgCl f
2

1,8.10 -10 = 1,76.10 -5 M 0,76 2

1 (0,1 + 0,1) = 0,1 2

Vy tan ca AgCl trong nc nguyn cht l: 1,34.10-5 M v tan ca 1,76.10 5 = 1,33 ln. AgCl trong KNO3 0,1M ln hn trong nc nguyn cht: 1,34.10 5 * nh hng ca nng H+ - Nu anion A- ca kt ta MAn l gc ca mt dung dch axt yu th trong dung dch s c cn bng: MAn Mn+ + nA+ nHA nA + nH S = [Mn+] (6.5) tan S ca kt ta bng [Mn+]: + - n (6.6) v tch s tan ca MAn bng: T = [Mn ][A ] n . K . S tnh S t T ta thay trong (6.6) gi tr [Mn+] = S v [A-] = K + [H + ] C A .K v [ A ] = m CA = [HA] + [A-] = nS + K + [H ] [HA] K l hng s phn ly ca HA; K = + [H ][A ]
n.K.S K n T = S = S( nS) K + [H + ] K + [H + ]
n ( n +1)
n n

T [H + ] T [H + ] ( n +1) 1 + 1 S = n + = (6.7) Vy: S n K nn K V d 1: Tnh tan ca CaF2 trong HCl 0,01M. Bit KHF = 6.10-4, T = 4.10-11 Thay n = 2, [H+] = 10-2, K = 6.10-4 v T = 4.10-11; ta tnh c: S = 1,4.10-3 mol/lit - Nu anion l gc ca a axit th thay gi tr: nK 1 K 2 K 3 ...K m S [A m ] = + m [H ] + K 1 [H + ]m 1 + K 1 K 2 K 3 ...K m nK 1 K 2S Nu m = 2, ta c: [A 2 ] = + 2 [H ] + K 1 [H + ] + K 1 K 2

123
n

nK 1 K 2S T = S [H + ]2 + K [H + ] + K K 1 1 2
( n +1)

[H + ] [H + ] 2 (6.8) Vy: S = 1 + K + K K 1 1 2 V d 2: Tnh tan ca CaC2O4 trong dung dch c pH = 4, T = 2.10-9. Bit H2C2O4 c K1 = 6.10-2, K2 = 6.10-5. Thay cc gi tr tng ng vo biu thc (6.8) ta tnh c: S = 7,4.10-5 mol/lit. * nh hng ca cht to phc Nu M ca kt ta MA to phc vi X ln lt theo cc phng trnh sau y: (6.9) MA M+A ; [M][A] = TMA [MX] M+X MX1 ; 1 = (6.10) [M ][X] [MX 2 ] [MX 2 ] = MX + X MX2 ; 2 = (6.11) [MX][X] 1[M ][X]2 [MX n ] MXn-1 + X MXn ; n = (6.12) [MX n 1 ][X] M, A c th mang 1, 2, ... in tch, cn X c th dng phn t hay ion; 1, 2, 3, ..., n l hng s to phc (hng s bn ca phc) ca cc nc. Gi S l tan ca MA th c th vit: S = [M] + [MX] + ... + [MXn]
T nn S = [M](1 + 1[X] + 12[X] + ... + K hiu

[X]
i =1 1

i=n

(6.13)

i =1

i=n

thay cho tch 123 ... n

Ta li bit vi mt phc c dng MXn ta c cc hng s bn tng nc 1, 2, ..., n v hng s chung n = 1.2. ... n, vy nu ta thay cch tnh cc hng s tng nc bng hng s chung i (i ch phc ca mt ligan - phi t), ngha l c i nc phn ly s c: S = [M](1 + 1[X] + 2[X]2 + ... + n[X]n) = [M ] i [X]i vi 0 = 1.
i =0 i=n

Vy:

[M] =

[X]
i =0 i

i=n

Thay gi tr ca [M] trn v [A] = S vo (6.9) Ta c:

S

[X]
i =0 i

i=n

.S = T hoc S = T i [X]i
i =0

i=n

(6.14)

V d: Tnh tan ca AgCl trong dung dch m NH4Cl 0,01M, bit TAgCl = 1,8.10-10, 1 = 103,2, 2 = 103,8. AgCl Ag+ + Cl-

124 S = [Ag+] + [Ag(NH3)+] + [Ag(NH3)2+] = [Ag+](1 + 103,2.10-3 + 107.10-6) = 12,7[Ag+] S S Vy: [Ag+] = ; [Cl-] = S + 0,01; T = [Ag+][Cl-] = (S + 0,01) = 1,8.10 10 12,7 12,7 1,8.10 10.12,7 Nu coi S << 0,01 th: S = = 2,3.10 7 mol/lit 0,01 * nh hng ca nhit Tch s tan T ch l 1 hng s mt nhit nht nh. V vy nu nhit thay i th tan cng thay i. i vi cc cht khi ha tan thu nhit th tan s tng khi nhit tng, nhng i vi cc cht khi ha tan ta nhit th tan s gim khi tng nhit . V d: PbI2 tan nhiu khi un nng, tan ca AgCl 1000C ln gp 25 ln tan ca n 100C; CaSO4.2H2O c tan tng theo nhit n 600C. Trn 600C th 1 cht ny s mt bt nc thnh CaSO4. H 2 O nn tan li gim khi tng nhit . 2 Nh vy canxisunfat c tan ln nht 600C. * nh hng ca kch thc ht kt ta i vi cng 1 lng cht, kt ta ht nh tan nhiu hn kt ta ht ln, ngha l tch s tan ca kt ta ht nh ln hn tch s tan ca kt ta ht ln v trn b mt ca cc tinh th nh c nhiu gc v cnh, cc ion cc v tr gc v cnh d tan hn nhng v tr khc, v cc v tr bn trong cc ion b gi cht hn. Do trong thc t mun c kt ta tch c hon ton ra khi dung dch ngi ta tm mi cch thu c tinh th ht ln. Trong phn tch ngi ta thng phi lm kt ta hon ton mt ion no nhm tch n ra khi cc ion khc c trong dung dch hoc nh lng ion . V khng c kt ta no tuyt i khng tan nn s kt ta hon ton ch c ngha tng i. Khi tin hnh tch th mt ion no c coi l c kt ta hon ton nu lng ca n cn li trong dung dch sau khi lm kt ta khng cn gy cn tr n phn ng i vi ion khc c trong dung dch v khi tin hnh nh lng th mt ion c coi l kt ta hon ton nu lng cn li ca n trong dung dch ch nm trong gii hn chnh xc ca php cn (0,1 0,2 mg). i vi cc mc ch phn tch thng thng th php lm kt ta c coi l hon ton khi nng ion cn tch cn li trong dung dch dao ng trong khong (10-5 10-6) M. * nh hng ca dung mi Thng phn ln cc cht v c t tan trong dung mi hu c hn trong nc do phn cc ca dung mi hu c nh hn phn cc ca nc. V d: CaSO4 tan kh trong nc (S = 7,8.10-3 mol/lt) nhng hu nh khng tan trong ru etylic. V vy trong trng hp nu kt ta c to ra t dung dch nc c tan kh ln th cn thit tin hnh kt ta trong dung mi hu c thch hp. 6.1.3. Kt ta phn on 6.1.3.1. Bn cht ca kt ta phn on Gi s c 2 ion A v B trong dung dch c nng CA v CB cng kt ta c vi ion X ca thuc th tng ng cho kt ta AX v BX. Nu cho dn thuc th

125 X ta xt xem: - AX hay BX kt ta trc? - Khi no th c hai cht AX v BX cng kt ta? - Khi AX v BX cng kt ta, iu kin no dn n hp cht kt ta trc s hon ton? Ta ln lt nghin cu nhng vn . gii quyt c vn th nht, ta thy: Theo quy tc tch s tan, hp cht no s kt ta trc khi tch s nng cc ion to ra kt ta vt qu tch s tan ca hp cht . Ngha l thm dn thuc th, nu [A][X] > TAX th AX kt ta trc hay [B][X] > TBX th BX kt ta trc. Gi s AX kt ta trc, ta nghin cu xem lng thuc th cn thit cho vo bao nhiu t c kt qu . T [A][X] > TAX [X] > AX [A] T Trong khi BX cha kt ta th: [B][X] < TBX [X] < BX [B] Vy r rng lng thuc th cho dn dn vo dung dch AX kt ta trc cn BX cha kt ta phi tha mn bt ng thc: TAX T < [X] < BX (6.16) [A] [B] Theo bt ng thc ny th khi nh dn dn thuc th mun bit xem hp cht T T no kt ta trc ta ch vic so snh hai t s: AX v BX . CA CB H qu: Trong trng hp n gin nu AX v BX c cng thc tng t v CA = CB th hp cht no c tch s tan nh hn hay tan nh hn s kt ta trc. V d 1: Trong dung dch hn hp I- v Cl- c nng ban u [I-] = [Cl-] = 10-1M. Khi cho dn dung dch AgNO3 th AgI hay AgCl kt ta trc? Bit TAgI = 10-16, TAgCl = 10-10. V nng ban u [I-] = [Cl-] v TAgCl > TAgI nn khi cho dn dung dch AgNO3 vo th AgI kt ta trc. Kt lun trn hon ton ng, v rng nu so snh: TAgI 10 16 TAgCl 10 10 15 = = 10 v = 1 = 10 9 1 [ I ] 10 [Cl ] 10 R rng AgI kt ta trc. Khi no th AX v BX cng kt ta? A+X AX T [A] gim dn, do AX tng dn, mun AX tip tc kt ta cn phi thm X [A] vn tha mn bt ng thc (4.16) v qu trnh ny vn tip din n mt lc:

126
TAX TBX = [A] [B]

[X] >

[A] TAX = (6.17) [B] TBX Khi AX v BX cng kt ta, khi no th AX kt ta hon ton, BX mi kt ta Nu AX kt ta trc hon ton trong dung dch [A] cn li 10-6M, t T (6.17) ta rt ra c iu kin: [A] = AX [B] 10 6 M TBX Vy hin tng to thnh ln lt cc kt ta trong dung dch nh kho st trn tch hon ton cht A ra khi cht B c gi l kt ta phn on. V d 2: Theo v d 1, khi AgI v AgCl cng kt ta, TAgI 10 16 [Cl ] = 10 10 1 = 10 7 M [I-]cn li = TAgCl 10 R rng AgI c kt ta trc hon ton ri khi AgCl mi kt ta, ngha l c th dng AgNO3 tch I- hon ton khi Cl- trong dung dch I-, Cl- c cng nng 0,1M. 6.1.3.2. ng dng ca kt ta phn on. * Pht hin Ba2+ trong dung dch gm Ba2+, Sr2+ bng dung dch SrSO4 bo ha. V TBaSO = 1,1.10-10 < TSrSO = 2,2.10-7. * Pht hin Sr2+ trong dung dch gm Sr2+, Ca2+ bng dung dch CaSO4 bo ha v TSrSO = 2,2.10-7 < TCaSO = 2,4.10-5. * Trong phn tch nh lng c th dng dung dch AgNO3 chun lin tc dung dch hn hp I-, Cl- da vo s kt ta phn on ca I- v Cl-. * Trong phng php chun kt ta dng phng php Mo, da vo s kt ta phn on ca Cl- v CrO42- c th chun dung dch Cl- bng dung dch AgNO3 khi dng K2CrO4 lm ch th. 6.1.4. Chuyn mt hp cht kh tan ny sang mt hp cht kh tan khc 6.1.4.1. Bn cht ca vn Gi s khi cho mt dung dch thuc th B vo mt cht kh tan AX lm cho kt ta ny chuyn thnh mt cht kh tan khc. B AX dd BX Khi trong dung dch s tn ti cc cn bng: Khi c AX v BX cng kt ta. Do ta rt c:
4 4 4 4

A+X + B 2 BX V nguyn tc nu cho lng B ln, cn bng 2 chuyn dch t trn xung ko theo cn bng 1 chuyn dch t tri sang phi, v r rng s chuyn kt ta c hon ton hay khng s ph thuc vo: - TAX v TBX 1

AX

127 Lng thuc th thm vo. Trong iu kin no AX chuyn hon ton sang BX? Gi thit cn bng (1) v (2) ang chuyn dch t tri sang phi v t trn xung, ngha l AX ang tan v BX ang c to thnh, ta c th vit c: T (6.18) [B][X] > TBX [B] > BX [X] T v [A][X] = TAX [X] = A X (6.19) [A] [B] TBX Thay gi tr ca [X] vo (6.18) ta c: (6.20) > [A] TAX Vy mun kt ta AX chuyn c hon ton sang kt ta BX phi cho thuc th B mt lng nh th no lun lun tha mn bt ng thc (6.20) Vic chuyn kt ta ny c th xy ra trong 3 trng hp sau: * Trng hp 1: Nu TBX < TAX tc l chuyn t hp cht d tan sang mt hp T cht kh tan hn. Trng hp ny thc hin c d dng, v khi t s BX < 1 . TAX V d: Chuyn SrSO4 sang SrCO3 bng dung dch Na2CO3 bo ha v TSrSO = 2,8.10 7 > TSrCO = 1,6.10 9 nn ch cn mt lng nh Na2CO3 s m bo 4 3

c:

[CO ] TSrCO 1,6.10 9 > = = 5,7.10 3 . [SO ] TSrSO 2,8.10 7

2 3 2 4
3 4

* Trng hp 2: Nu TBX = TAX cng c thc hin kh d dng v khi [B] cng ch cn tha mn iu kin: > 1. [A] V d: Chuyn CaC2O4 thnh CaCO3 c TCaC O = 2,3.10 9 TCaCO = 7,1.10 9 .
2 4 3

* Trng hp 3: Nu TBX > TAX, chuyn mt cht kh tan thnh mt cht d T tan hn, thc hin kh khn hn v khi BX > 1 v trng hp nu t s ln TAX hn 1 rt nhiu th khng th thc hin c. V d: Khi chuyn BaSO4 c T = 1,1.10-10 thnh BaCO3 c T 8.10-9 bng dung dch bo ha Na2CO3. Trng hp ny thc hin c nhng kh khn hn v phi cho mt lng thuc th Na2CO3 kh ln lun lun tha mn: 2 [CO 3 ] TBaCO 8.10 9 > = 73 [SO 2 TBaSO 1,1.10 10 4 ]
3 4

Trong thc hnh ngi ta thc hin nh sau: Cho mt lng dung dch Na2CO3 bo ha ln vo kt ta BaSO4, khuy u, un nng, lng, lc kt ta qua ly tm, b dung dch i ( loi SO42-) v cho mt lng mi dung dch bo ha Na2CO3 ( tng CO32-) v c lp li qu trnh ny vi ln.

128
6.1.4.2. ng dng ca s chuyn kt ta. * Ha tan kt ta: C nhng trng hp khng th ha tan kt ta mt cch d dng nh axit chng hn, gii quyt vic ny ngi ta chuyn kt ta sang mt kt ta khc d tan hn. V d khng th ha tan BaSO4 bng ngay c axit mnh nh HCl hay HNO3, nhng nu chuyn kt ta thnh BaCO3 th c th dng axit yu CH3COOH cng c th ha tan hon ton BaCO3 c. * Tch ion: V d: Tch S2- ra khi hn hp S2-, SO32- bng cch cho mt lng thch hp bt CdCO3 vo. Do tan ca SCdS < S CdCO < S CdSO nn kt ta CdCO3 d dng chuyn sang
3 3

kt ta CdS. Kt qu trong dung dch ta c mt hn hp kt ta CdS + CdCO3 (cn tha) lc kt ta. Mun tch CdS ta ch nh vo hn hp kt ta mt t axit axtic th CdCO3 tan ht, lc, ra kt ta CdS, sau dng HCl c ha tan CdS th ta s thu c dung dch c cha S2- ( dng H2S). 6.1.5. Ha tan kt ta. Qu trnh ha tan l qu trnh lm ngc vi qu trnh to kt ta. i vi mui (hp cht) loi MmAn. MmAn mMn+ + nAmiu kin ha tan kt ta l phi thit lp iu kin tch s hot ca cc ion trong dung dch b hn tch s tan: a m .a n < TM A M A Mun vy, cn phi lm gim nng ca cc ion trong dung dch bo ha. Do nguyn tc chung v ha tan kt ta: Mun ha tan kt ta th phi gim nng ca t nht mt trong cc ion do kt ta phn ly ra trong dung dch. Trong thc t c th dng cc bin php sau: 6.1.5.1. Ha tan kt ta bng cch to vi ion ca kt ta thnh mt hp cht t phn ly. Trong trng hp ny cc hp cht t phn ly c to thnh c th l axit yu, baz yu, nc v phc cht. hiu r bn cht ca vn v rt ra c nhng kt lun cn thit, ta nghin cu mt cch tng qut trng hp n gin sau: Gi s dng thuc th cht in ly mnh XY ha tan kt ta MeA to ra mui tan MeY v cht t phn ly XA theo phn ng sau: MeA + XY MeY + XA V c th vit: MeA Me+ + A+ XY = Y- + X+
n+ m m n

XA Me + XA MeA + X Qua cc cn bng trn ta thy rng: ha tan kt ta MeA phi lun lun chuyn dch cn bng t tri sang phi v t trn xung. Vy r rng ha tan kt ta cng hon ton nu:
+ +

129 - Tng nng [X+]: lng thuc th ln. - KXA cng nh, tc l cht XA c to ra cng t phn ly th s kt hp gia Av X+ cng mnh. - TMeA khng nh qu hay kh ln, tc l MeA kh tan. Trn y l nghin cu mt cch nh tnh, by gi ta nghin cu mt cch nh lng: Tnh tan ca kt ta MeA: SMeA mol/lit C 1 mol MeA tan ra s cho 1 iong Me+ v 1 mol XA. Vy: SMeA = [Me+] = [XA] [Me + ][XA] V: = K ht [X + ] Kht: hng s ha tan ca cn bng T trn ta rt ra c: Se = ht [ + ] [X+] = Ctt: nng ca thuc th lc cn bng. By gi ta tnh Kht Ta c th vit: [Me+][A-] = TMeA [A ][X + ] V ta c: = K XA [XA] T T trn rt ra c: K ht = MeA K XA V y : TMeA .C tt K XA R rng tan S tng khi: TMeA cng ln so vi KXA cng nh. Ctt cng ln cng tt (gii hn n nng ca dung dch bo ha). S MeA =

Ch : Nu TMeA nh hn th SMeA s gim, nhng nu XA c tch ra khi mi trng phn ng (bay hi hay tan nhiu trong dung mi hu c) th SMeA s tng. V d: H2WO4 + 2OHWO42- + H2O (NaOH) Mg(OH)2 + 2NH4+ Mg2+ + 2NH4OH (NH4Cl) CaC2O4 + 2H+ Ca2+ + H2C2O4 (HCl) AgCl + 2NH3 [Ag(NH3)2]Cl 6.1.5.2. Ha tan kt ta bng phn ng oxy ha-kh Nu mt trong cc ion ca kt ta c tnh oxy ha hay tnh kh th ngi ta thng dng cc dung mi c tnh oxy ha hay tnh kh ha tan kt ta . V d: CuS khng ha tan bng axit HCl v: TCuS = 10-45 v axit H2S c to ra c K H S = 6,9.10 23 nn ngi ta thng dng HNO3 c un nng theo phn ng:
2

3CuS + 8HNO3 3Cu(NO3)2 + 3S + 4H2O + NO do tc dng oxy ha ca HNO3 nn S2- S0 lm cho S2- gim i rt nhiu.

130
6.1.5.3. Ha tan kt ta bng phng php phi hp c hai phng php trn Nu kt ta rt t tan, ngha l TMeA cc k qu nh, nu ta ch dng bin php i ha tr ion khng thi th cha gim nng ion n mc cn thit kt ta tan ra hon ton. V d: Kt ta HgS c T = 10-53, bi vy mun ha tan kt ta trong trng hp ny cn phi kt hp c 2 bin php trn. V d c th ha tan HgS bng nc cng toan: 3[HgCl4]2- + 3S + 2NO + 4H2O 3HgS + 4HCl + 2HNO3 2+ Theo phn ng ny Hg kt hp vi Cl- to thnh cht t phn ly [HgCl4]2- v S2- b oxy ha thnh S0 do nng ca c Hg2+ v S2- u b gim, nn kt ta tan c. 6.1.6. L thuyt v cu to kt ta 6.1.6.1. Kt ta tinh th v kt ta v nh hnh Kt ta tinh th l loi kt ta m cc ion to ra kt ta sp xp theo mng li tinh th theo mt chiu hng xc nh, lm cho kt ta c hnh dng nht nh. V d: PbCl2 trng, hnh kim; PbI2 vng, hnh vy ... Kt ta v nh hnh l loi kt ta khng c cu to tinh th, kt ta khng c hnh th nht nh. V d: Kt ta Al(OH)3 trng; NiS en ... Kt ta v nh hnh d bin thnh dung dch keo, b mt tng cng ln, kh lng, kh lc, kh ra v d nhim bn. 6.1.6.2. Hai giai on ca qu trnh kt ta Qu trnh to thnh kt ta l qu trnh kh phc tp. Sau y ta th xt qu trnh to kt ta BaSO4. BaSO4 Ba2+ + SO42R rng l nu ch c 2 ion n c Ba2+ v SO42- th khi gp nhau chng ch to thnh phn t BaSO4 v cha th c cu trc tinh th. to nn cu trc tinh th cn phi c nhiu ion Ba2+ v SO42- tp hp li thnh nhng tp hp nh nhng vn cha phi l kt ta. Cc tp hp ny gi l mm tinh th hay l trung tm kt tinh. Giai on ny ca qu trnh kt ta ng vi s to nn trng thi keo ca vt cht. T cc trung tm kt tinh ny cc phn t tip tc tp hp thm v ln dn ln n mc c th thnh ht kt ta trng lng xung. Vy qu trnh kt ta gm 2 giai on: - To mm tinh th - Mm tinh th ln ln Giai on sau ty thuc bn cht v iu kin kt ta m c th gy ra mt trong hai hng khc nhau to thnh kt ta tinh th hay kt ta v nh hnh. * To kt ta tinh th: Nhng trung tm kt tinh mi c to thnh s ln dn ln thnh nhng ht tinh th ln ri sau to thnh kt ta tinh th. Qu trnh ny xy ra khi qu bo ha ca dung dch nh. T dung dch ny sinh ra chm v t cc trung tm kt tinh, tc l tc kt ta nh hn tc nh hng, do to iu kin cho cc phn t c thi gian phn b ln cc trung tm kt tinh theo v tr khng gian xc nh

131 hnh thnh nn nhng tinh th ln. Do to ra kt ta tinh th c ht ln phi c gng tin hnh kt ta trong dung dch qu bo ha cng nh cng tt. * To kt ta v nh hnh: Nhng trung tm kt tinh s lin kt yu vi nhau thnh nhng tp hp nh, v cc tp hp ny li kt hp vi nhau thnh nhng tp hp ln hn v cui cng to thnh kt ta v nh hnh. Qu trnh ny c th xy ra trong 2 trng hp: - Do bn cht ca kt ta v v nh hnh: Loi kt ta ny thng thy cc cht c tan kh nh, nh cc sunfua, hydroxyt kim loi ... V tnh kh tan ca chng nn khi thm thuc th vo dung dch th dung dch tc thi t trng thi qu bo ha v qu trnh tip din nh ni trn. - Do iu kin kt ta: Nu khi tin hnh kt ta t dung dch qu bo ha ln th s sinh ng thi nhanh v nhiu trung tm kt tinh, do khng to iu kin nhng trung tm ln ln nn s to ra kt ta v nh hnh. V d: BaSO4 iu kin thng s kt ta dng tinh th nhng nu tin hnh kt ta trong hn hp nc-ru 30-60% (trong dung mi ny BaSO4 rt t tan) hay dng dung dch c v cng mt lc th s to ra dung dch keo hay kt ta v nh hnh. Qua s kho st trn ta thy rng: Nu kt ta c to ra l v nh hnh hay tinh th th phi tm nhng iu kin thun li nht tin hnh. C th i vi kt ta tinh th cn tun theo nhng iu kin sau: - Kt ta t dung dch long v thuc th long. - Thm thuc th rt chm, tng git, nht l thi gian u. - Kt ta t dung dch nng (c trng hp cn phi un nng dung dch thuc th). - Thm cc cht c tc dng lm tng tan ca kt ta. V d: khi kt ta BaSO4 th cho thm HCl, v n lm tng tan ca BaSO4 do to thnh HSO4-. - Lc kt ta sau khi lm lnh dung dch. i vi kt ta v nh hnh: - Kt ta t dung dch nng. - Thm cht in ly lm ng t keo c tt. V d: Cc loi mui amoni, cc axt. - Kt ta t dung dch c, thuc th c. - Sau khi kt ta xong phi thm mt lng ln nc un nng (khong 100ml) v khuy u lm gim qu trnh hp ph. - Khng ngm kt ta lu trong dung dch m cn phi lc ngay sau khi kt ta, c bit l khng un nng trnh hin tng kt ta chuyn sang dng khc v tng hin tng cng kt. 6.1.7. Cng kt v kt ta sau - nguyn nhn lm cho kt ta khng tinh khit. Thng kt ta khng th tch ra dng tinh khit m c km theo tp cht. Khi tp cht kt ta ng thi vi kt ta chnh th gi l cng kt, v khi tp cht kt ta sau khi kt ta chnh kt ta ht th gi l kt ta sau. Ta ln lt im qua cc

132 loi kt ta cng kt v kt ta sau. 6.1.7.1.Cng kt b mt. Cng kt loi ny l s hp ph cc tp cht trn b mt ca kt ta. Nguyn nhn ca s hp ph l nhng ion hay phn t b mt kt ta cn c kh nng ht thm nhng ion hay nhng phn t trong dung dch. V khc vi nhng ion v phn t trong kt ta, nhng ion v phn t b mt kt ta c nhng lc ha tr t do nn c th lin kt tip c vi cc tiu phn khc trong dung dch. Hp ph l mt hin tng thun nghch v nhng ion hay phn t b hp ph c th tan tr li trong dung dch hay ni mt cch khc c th b gii hp. Khi tc hp ph bng tc gii hp cn bng hp ph c thnh lp, lng tp cht b hp ph khng thay i na. C nhiu yu t nh hng n cn bng ny: * nh hng ca din tch b mt. Lng cht hp ph t l vi din tch b mt ca kt ta nn tinh th ca kt ta cng ln th lng cht b hp ph cng nh. * nh hng ca nng . Qu trnh hp ph l mt qu trnh thun nghch nn s t n mt cn bng ng. V d: Kt ta AgCl trong dung dch KCl th s hp ph ion Cl-: nAgCl.mClnAgCl + m ClTheo cn bng ny nu tng [Cl-] th s hp ph s tng. C ngha l nng cng ln th lng cht b hp ph cng nhiu, nhng sau tng chm hn nng (hnh 6.1). Ngi ta chng minh
Lng ion b hp ph trn b mt kt ta

a = KC n c rng: a: lng ion v hp ph: iong i vi 1g kt ta. C: nng ca ion b hp ph trong dung dch. Nng ion b hp ph trong dung dch K, n: h s i vi mt h cho. T h thc trn ta thy rng: Qu trnh phn Hnh 6.1 hp ph (hay gii hp) gim chm khi gim nng C. y l c s cho vic ra kt ta lm sch, nhng khng tuyt i lm sch c. * nh hng ca nhit . Qu trnh hp ph l mt qu trnh ta nhit: nAgCl.mCl- + Q nAgCl + mClnn nhit cng thp hp ph cng mnh v nhit cng cao th gii hp ph cng mnh. * nh hng ca bn cht kt ta v ion b hp ph. Cng trong mt iu kin vi cng mt kt ta, cc ion ty theo bn cht ca chng b hp ph nhiu t khc nhau. Thng ion b hp ph theo quy lut sau: ion to vi ion ca kt ta hp cht cng t tan b hp ph cng nhiu, do ion ca kt ta b hp ph nhiu hn c. V d: - AgI s b hp ph mnh I- hn Br-, hn Cl-, cn i vi NO3- th hp ph rt

133 yu v: SAgI < SAgBr < SAgCl, cn AgNO3 tan hon ton trong dung dch. - BaSO4 hp ph trc ht ion Ba2+ hoc SO42- khi d Ba2+ hay SO42- trong dung dch. BaSO4 hp ph mnh SO42- hn CO32- v S BaSO < S BaCO , nu trong dung dch c
4 3

NO3- hay Cl- th BaSO4 hp ph NO3- nhiu hn Cl- v S Ba ( NO

3 )2

< S BaCl .
2

* nh hng ca iu kin kt ta. V d vi kt ta v nh hnh nh Fe(OH)3, Al(OH)3 khi kt ta t dung dch c t hp ph hn khi kt ta t dung dch long, do lng tp cht b hp ph cng t hn. Nhng i vi kt ta tinh th th khi kt ta t dung dch long tinh th s ln hn khi kt ta t dung dch c, do cng t b hp ph tp cht hn. Khi lu kt ta trong dung dch, kt ta s ln hn v c dng tinh th hon chnh hn gi l hin tng lm mui tinh th, lng tp cht b hp ph cng gim bt. 6.1.7.2. Cng kt trong Thng xy ra i vi kt ta tinh th, da vo c im ca cng kt trong, c th chia ra lm hai loi: * Cng kt do phn ng gia kt ta v thuc th d. Khi cho Zn2+ phn ng vi K4[Fe(CN6)] th khng sinh ra kt ta Zn2[Fe(CN6)] m sinh ra kt ta K2Zn3[Fe(CN6)]2. Kh nng ion kim loi kim i vo trong phc cht ph thuc vo th tch v mc hydrat ha ca ion . Ion cng nh cng d vo mng li ca kt ta v cng t tan. Ion hydrat ha cng yu vo mng li cng d. Mc hydrat ha ca cc ion kim loi kim tng theo chiu: Cs+ < K+ < Na+ < Li+. Nh vy Cs+ d b cng kt hn c. * Cng kt ng hnh Nguyn nhn ca loi cng kt ny l kt ta v tp cht l nhng cht ng hnh, tc l nhng cht c kh nng kt tinh trong cng mt mng li tinh th. V d: phn nhm KAl(SO4)2.12H2O khng mu, ng hnh vi phn crm KCr(SO4)2.12H2O mu tm, v khi chng cng kt tinh vi nhau th s c tinh th mu tm m nht ty theo nng tng i ca chng. Thng th nhng ion kim loi c s phi tr v bn knh bng nhau th d thay th nhau trong mng li m khng lm gim bn ca mng li. V d: Ra2+ (1,52A0) c bn knh gn bng Ba2+ (1,43A0), nu trong dung dch Ba2+ c rt t Ra2+ nhng khi cho SO42- vo th RaSO4 s kt ta ng thi cng BaSO4 trong cng mt mng li. Cn Ca2+ c bn knh nh hn bn knh ca Ba2+ (1,05A0) nn Ba2+ v Ca2+ khng th cng kt tinh trong cng mt mng li. 6.1.7.3. Cng kt c hc Nhng tinh th thng c mng li khng hon ton nn c khe h hoc ch trng ng y nc ci cha tp cht. Nhng tinh th nh khi kt hp vi nhau cng c th gi tp cht gia. 6.1.7.4. Ni hp Trong qu trnh ln ln, tinh th c th mang theo tp cht trc b hp ph, th t cho cc thuc th v dung dch tc dng vi nhau rt nh hng n cht b hp ph. V d: Nu thm dn H2SO4 vo BaCl2 th tinh th BaSO4 ln dn trong mt dung dch c d Ba2+ nn hp ph nhiu Ba2+ ko theo ion Cl-. Ion SO42- s y dn

134 ion Cl- ra mt phn nhng vn cn mt t trn kt ta. Ngc li nu thm dn BaCl2 vo H2SO4 th tinh th BaSO4 ln dn trong dung dch c d ion SO42- nn hp ph ion SO42- ko theo cation khc trong dung dch. Tc thm thuc th cng nh hng n lng tp cht b hp ph. Nu thm ngay mt lc thuc th n d th kt ta s hp ph tp cht nhiu. Nu thm t t th kt ta s tinh khit hn v kt ta ln hn nn hp ph tp cht t hn v tp cht cng d b thay th bi ion ca kt ta hn. 6.1.7.5. Kt ta sau Cc loi cng kt k trn ch xy ra trong khi to thnh kt ta, nhng cng c loi cng kt ch xy ra sau khi hon thnh kt ta mt thi gian, l kt ta sau. V d: Nu lc ngay kt ta CuS khi kt ta bng H2S trong mi trng axt c ion Zn2+ th khng c ZnS trong kt ta. Nhng nu lu kt ta trong dung dch trc khi lc, trong kt ta s c c ZnS. C th gii thch hin tng ny nh sau: Kt ta CuS tip xc lu vi dung dch bo ha H2S s hp ph H2S ln b mt kt ta lm cho nng H2S tng ln r rt ZnS kt ta mc d nng axt trong dung dch kh ln. 6.1.8. Vai tr ca cng kt trong phn tch Hin tng cng kt c tc hi trc tip lm bn kt ta, do lm cn tr vic tch cc ion cn xc nh ra khi dung dch phn tch. V vy cn phi tm bin php chng cng kt nhng mt khc ngi ta cng s dng hin tng cng kt trong phn tch vi lng. 6.1.8.1. ng dng. * Tch: V d mun tch Pb2+ (vi lng) trong nc c th dng bt CaCO3, v Pb2+ b CaCO3 cng kt. * Lm giu dung dch: Gi s t dung dch Ra2+ v cng long, ta c th lm giu dung dch nh sau: C th cho bt BaSO4 vo dung dch trn, do tnh ng hnh nn BaSO4 s ko theo RaSO4. Sau tch hn hp kt ta ny, ra sch, ri chuyn sang kt ta cacbonat, cui cng dng axit ha tan thnh dung dch c th thch ty . * Pht hin ion: C th tm Mg2+ da vo hin tng Mg(OH)2 cng kt I2 to ra kt ta Mg(OH)2.I2 (trong mi trng kim) mu ta sm (nng tm c gii hn 70 mg/lit). 6.1.8.1. Cch lm gim cng kt Trng hp cng kt ngoi: Tm cch lm gim din tch b mt ca kt ta, tc l to iu kin c c th tch ln hn, hay ni cch khc phi tun theo cc quy tc thu nhn kt ta tinh th v v nh hnh trnh by trn. cho tinh th ln ln, ngi ta lm mui tinh th bng cch ngm lu tinh th trong dung dch nc ci. V d: kt ta qua mt m ri mi lc cho tinh th nh tan ra v tng s tinh th ln ln. C th thay i dng ion c kh nng cng kt lm thay i bn cht ca chng

135 v gim cng kt. V d: Kh Fe3+ xung Fe2+ t cng kt vi BaSO4 hn, hoc c th dng cht to phc che. Ra nhiu ln cng lm gim cng kt v y c qu trnh thun nghch. Trng hp cng kt trong: Khng th loi tp cht bng phng php ra. Ta c th gim bt cng kt bng cch kt tinh li nhiu ln v mi ln kt tinh li th lng tp cht s gim dn. V d: loi bt ion Mg2+ trong kt ta CaC2O4 th em ha tan CaC2O4 bng HCl, sau trung ha axit ri kt ta li CaC2O4. Ln ny nng Mg2+ nh hn ln trc nn Mg2+ s b hp ph t hn. Kt tinh li nhiu ln, Mg2+ cn li khng ng k. Tt hn ht l nn p dng mt trong cc bin php sau: - Tch ion b cng kt trc khi tin hnh kt ta bng nhiu cch nh chit chng hn. V d tch FeCl3 bng cch chit mui bng CCl4hay CHCl3 trong mi trng HCl. - Che du: C th dng thuc th thch hp tc dng vi ion b cng kt to thnh phc cht bn t hay khng b cng kt. - i ha tr: V d BaSO4 cng kt vi Fe3+ hay MnO4-, mun tch ra ch vic i ha tr Fe3+ thnh Fe2+ hay MnO4- thnh Mn2+. 6.1.9. Dung dch keo trong ha phn tch 6.1.9.1. Khi nim v dung dch keo. C nhiu trng hp mc d tch s nng ca cc ion to thnh kt ta trong dung dch vt qu gi tr tch s tan ca kt ta 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. Cc phn t khuch tn trong dung dch keo gi tt l cc ht keo. Dung dch keo khc vi dung dch thc ch n b c di nh sng phn chiu. Cc ht keo c kch thc ln hn cc phn t dung mi rt nhiu nn chng c kh nng khuych tn nh sng, tuy vy kch thc ca ht keo cng cn kh nh nn khng th nhn thy bng mt thng, cng nh bng knh hin vi, d lt qua giy lc. 6.1.9.2. Nguyn nhn bn vng ca dung dch keo Bnh thng cc phn t keo l tp hp nhiu phn t v trung ha v in, khi va chm nhau c th kt hp v vn li thnh kt ta lng xung. Tuy nhin mt tnh cht c trng ca dung dch keo l c th khng tch ra thnh kt ta trong mt thi gian rt lu do nguyn nhn sau: - Hp ph cc ion c trong dung dch nht l cc ion to ra phn t keo, do cc phn t keo tch in cng du nn y nhau v khng th kt hp vi nhau thnh kt ta c. - C th hp ph cc ion ca dung mi (i vi keo a dung mi), tc l b solvat ha to thnh mt lp v solvat ngn cch cc phn t keo khng th kt hp vi nhau c thnh kt ta, v d silic oxt. 6.1.9.3. S ng t v s pepti ha * S ng t. S chuyn mt dung dch keo (cn gi l sol) thnh kt ta (gel) gi l s ng t.

136 Mun ng t mt dung dch keo thnh kt ta, c th dng 2 bin php sau: - Trung ha in ca dung dch keo tch in bng cch thm cc cht in ly tng ng. - ung nng lm gim qu trnh hp ph v ph v v solvat. Bng 2 bin php ny s to iu kin cho cc phn t keo lin kt vi nhau thnh kt ta. * S pepti ha. Hin tng kt ta c ng t c th bin thnh dung dch keo gi l s pepti ha (tc l gel thnh sol). S pepti ha thng xy ra 2 trng hp sau: - C mt s cht keo ng t tip xc vi nc s to thnh keo, loi keo ny gi l keo thun nghch. - Kt ta c ng t tip xc vi nc c cha ion d b hp ph cng c th chuyn thnh keo. V d nh kt ta Fe(OH)3 tip xc vi nc cha FeCl3 th s thnh dung dch keo Fe(OH)3. 6.1.9.4. Trng thi keo trong ha phn tch * Cch chng trng thi keo: Trong qu trnh phn tch thng gp trng thi keo 2 khu: - Trong qu trnh to kt ta khi cho d thuc th hay d ion cn kt ta, hay trong dung dch ngui c cc ion b kt ta hp ph, kt ta s dng keo. - C th trnh trng thi keo trong trng hp ny nh sau: Ta tin hnh kt ta trong dung dch nng khng d nhiu thuc th, c thm cht in ly mnh thch hp nh axt, NH4Cl, NH4NO3, ... - Trong qu trnh ra kt ta: do lm tri mt ion trung ha in ht keo hay keo a dung mi hp ph cc phn t ca dung mi. Cch trnh: ra kt ta bng nc nng c thm mt t thuc kt ta (nu cn), mt t cht in ly thch hp. * ng dng trng thi keo trong ha phn tch: - C mt s trng hp cn thit to ra dung dch keo nhn ra ion khi c t dng kt ta c mu. V d: Nhn ra Fe3+ (lng nh) dung dch keo mu mc Fe4[Fe(CN)6]3 ( iu kin thng l kt ta). Hay c th nhn ra lng nh Cd2+ dung dch keo CdS (c th kt ta ngay trong mi trng axt). - Kt ta khng mu hay mu nht hp ph nhng cht mu v khi cht mu b hp ph s i sang mu khc. Ngi ta dng cht mu lm ch th trong phn tch nh lng m kt ta dng keo th s hp ph mnh. V d: kt ta AgCl khi b keo ha dng mAgCl.nAg+ s hp ph mnh fluortxin lm cho n i mu, t mu vng thnh hng. Trong trng hp ny cn duy tr trng thi keo, ta c th thm mt cht gi l cht bo v keo nh extrin, tinh bt, gelatin, gm aralie, ...
6.2. Phng php chun kt ta 6.2.1. c im ca phng php Phng php chun kt ta l mt phng php phn tch th tch da vo phn ng to thnh cc hp cht t tan. Cc phn ng mun dng c trong phng php ny phi tha mn cc iu kin sau:

137 - Cc kt ta to thnh phi thc t khng tan, tc l phn ng phi hon ton. - S to thnh kt ta phi kh nhanh tc l khng c hin tng qu bo ha. - Phn ng phi chn lc, ngha l nh hng ca hin tng hp ph, ca cc qu trnh cng kt kt ta khng lm sai kt qu phn tch. - Phi c kh nng xc nh c im tng ng khi dng nh phn. y l cc iu kin quan trng nht. Do ch c mt s t phn ng kt ta dng c trong phng php kt ta. - Phng php bc: Ag+ + XAgX - X c th l cc anion: Cl , Br , I , CNS-. Da vo phn ng ngi ta xy dng nn phng php bc (trong phng php ny gm nhiu phng php, chi tit nghin cu sau). - Phng php thy ngn: Hg22+ + 2XHg2X2 Dng nh phn dung dch CNS bng Hg2(NO3)2 dng Fe3+ lm ch th. - Chun ion Ba2+ bng sunfat: Ba2+ + SO42BaSO4 Dng rdizoonat natri lm ch th. Khi c mt Ba2+ th dung dch nhum mu , gn im tng ng mu s bin mt. - Chun ch bng Cromat: Pb2+ + CrO42PbCrO4 + Dng Ag lm ch th, gn im tng ng s xut hin mu gch do: Ag2CrO4 gch CrO42- + 2Ag+ - Chun Zn2+ bng feroxyanua: Da vo phn ng: 3Zn2+ + 2[Fe(CN)6]4- + 2K+ K2Zn3[Fe(CN)6]2 ch th l diphenylamin. Trong tt c cc phng php trn th quan trng v c nhiu ng dng thc tin nht l phn ng kt ta bng AgNO3. Do trong chng ny s xt c s l thuyt ca phng php chun kt ta bc. 6.2.2. ng nh phn trong phng php bc. Trong qu trnh chun dung dch cc cht to kt ta, nng ca ion to kt ta s thay i. Nu ta biu din s bin thin ch s nng ion to kt ta pIon = -lg[ion] (ion c th l cation c th l anion) trn trc tung theo lng thuc th thm vo (trn trc honh) th ta s c ng cong nh phn pIon. Ta kho st qu trnh chun dung dch NaCl bng dung dch chun AgNO3. AgCl + Na+ + NO3-; TAgCl = [Ag+][Cl-]. AgNO3 + NaCl Trong qu trnh chun , nng [Cl-] s gim. Nu ta nghin cu s bin thin ca pCl = -lg[Cl-] v pAg = -lg[Ag+] theo lng dung dch chun AgNO3 thm vo th s c ng nh phn. Gi s chun 100ml dung dch NaCl bng dung dch AgNO3 cng nng 0,1M bit TAgCl = 10-10, pAg + pCl = pTAgCl = 10. 6.2.2.1. Tnh pCl v pAg trong qu trnh chun . * Trc im tng ng: Khi cha thm AgNO3, trong dung dch ch c Cl- nn: [Cl-] = 10-1MpCl = 1. - Thm 50ml dung dch AgNO3, tc l 50% Cl- i vo kt ta. Vy: 0,1.50 = 0.033 pCl = 1,5 v pAg = 10 - 1,5 = 8,5. [Cl-] = 150 - Thm 90ml AgNO3 0,1M tc l kt ta ht 90% lng Cl- v cn 10%

138 0,1.10 = 5,3.10-3M. 190 Vy pCl = 2,3. pAg = 7,7. Tng t nh vy ta tnh cho nhng th tch dung dch chun thm vo khc nhau. * im tng ng Khi cho 100ml AgNO3 th ton b Cl- c kt ta ht thnh AgCl v [Ag+] = [Cl-] = 10-5. Vy r rng pAg = pCl = 5. * Sau im tng ng Khi cho tha AgNO3 so vi im tng ng. Gi s cho 100,1ml AgNO3 th tha ra 0,1ml AgNO3 tc tha ra 0,1% Ag+ so vi lng cn thit. Khi : Cl- cha kt ta (tnh gn ng) do [Cl-] = [Ag+] =
0,1.0,1 = 10 4 , do pAg = 4 v pCl = 6. Tng t nh vy ta tnh 100

cho cc th tch dung dch chun AgNO3 thm vo khc nhau: 101, 110. Cc s liu thu c trnh by bng sau:
Bng 6.1. Gi tr pIon khi chun dung dch NaCl bng dung dch AgNO3 0,1N

VAgNO thm vo (ml)

3

VNaCl cn li (ml)

[Cl-]

pCl

[Ag+]

pAg

0 50 90 99 99,9 100 100,1 101 110

100 50 10 1 0,1 0

10 3,3.10-2 5,3.10-3 5.10-4 5.10-5 10-5 2.10-7 2.10-8 10-8

-1

1,0 1,5 2,3 3,3 4,3 5,0 6,7 7,7 8,0

3,3.10-9 2.10-8 2.10-7 2.10-6 10-5 5.10-4 5,3.10-3 10-2

8,5 7,7 6,7 5,7 5,0 3,3 2,3 2,0

6.2.2.2. V ng nh phn v nhn xt Biu din cc kt qu tnh ton trn ln th, ta c ng nh phn hnh 6.2.
ng tng ng

pAg 8 6,7 4,3 2 90 100

VAgNO (ml)
3

BN

Hnh 6.2. ng nh phn khi chun dung dch NaCl 0,1M bng AgNO3 0,1M

139
Nhn xt: - Dng ng nh phn ging nh ng nh phn trong phng php axt baz v phng php oxy ha - kh gn im tng ng c bc nhy. - Bc nhy pIon trn ng nh phn ph thuc vo nng ca dung dch. Nu nng ca NaCl l 0,01M th bc nhy: 4,75 5,04; nu 1N th bc nhy: 3 7. Vy nng cng ln , bc nhy pIon cng di v ngc li. - Bc nhy pIon ph thuc vo tch s tan ca kt ta, tch s tan ca kt ta cng nh th bc nhy cng di v ngc li. V d: ng nh phn khi chun dung dch NaI 0,1M bng dung dch AgNO3 0,1M c TAgI = 10-16 th c bc nhy l pI = 4,3 12,7. Ngi ta thy rng ng nh phn ch c bc nhy khi T 10-10 i vi kt ta dng AB. - Khi nhit ca dung dch tng th tan ca halogenua bc tng nn chun km chnh xc, v vy trong 1 s trng hp ngi ta lm lnh dung dch trc khi chun . 6.2.3. Cch xc nh im cui. 6.2.3.1. Phng php Mohr (Mo). Dng chun dung dch Cl- bng dung dch AgNO3 vi ch th l K2CrO4 AgCl da trn hin tng kt ta phn on: Ag+ + Cl- gn hay ti im tng ng nh mt git AgNO3 cui cng kt ta gch Ag2CrO4 xut hin ta s kt thc nh phn. Ag2CrO4 gch. Do c phn ng: 2Ag+ + CrO42Mt vn t ra l lng K2CrO4 cho vo bao nhiu cho hp l. - Mun kt thc nh phn ti im tng ng ngha l khi xut hin kt ta gch Ag2CrO4, ta c: -12 [Ag+]2[CrO42-] TAg CrO = 1,1.10 12 [CrO 2 /[ Ag + ] 2 ti thi 4 ] 1,1.10
2 4

1,1.10 12 = 1,1.10 2 (M ) . Ta c im tng ng [Ag ] = [Cl ] = 10 , vy [CrO4 ] 10 10 2th tnh c nng [CrO4 ] gii hn:
+ -5 2-

+ Gi s kt thc nh phn u bc nhy pCl = 4

khi Ag2CrO4 bt u xut hin [Ag+]2[CrO42-] 1,1.10 12 1,1.10 12 [CrO 2 ] C K CrO = 1,1.10-4M. 4 (10 4 ) 2
2 4

v ta c

+ Gi s kt thc nh phn cui bc nhy pCl = 6, l lun nh trn ta c: 1,1.10 12 2 [CrO 4 ] = 1,1M . Vy r rng mun kt thc rt gn im tng ng 10 12 th phi c thm mt lng K2CrO4 th no thi im kt thc nh phn phi c 10-4M C K CrO 1M. - Thc t, v cn chu nh hng ca nhiu yu t khc trong qu trnh nh phn v nu nng ca ion CrO 2 4 ln qu th mu vng qu m lm cho kh quan st s xut hin mu gch ca kt ta Ag2CrO4 im cui. Do vy, ngi ta thng dng 10 git dung dch K2CrO4 5% trong th tch 50ml (tng ng vi
2 4

140 nng 0,001M). Nh vy, Ag2CrO4 bt u kt ta khi [Ag+] = 1,05.10-4,5 ; hay pAg = 4,5. Vic chun qu im tng ng mt t v sai s vo khong 0,1% hon ton tha mn i vi phng php phn tch th tch. iu kin chun trong phng php Mo. * Mi trng phn ng phi trung tnh, hay kim yu: pH = 6,5 10 nhng m bo chnh xc cn thit nn thc hin pH = 8 10. V rng: Nu trong mi trng axt mnh th kt ta Ag2CrO4 tan mt do K2CrO4 mt vai tr ch th. Do vy nu mi trng axt th phi trung ha bng NaHCO3 hay borac. Nu trong dung dch c ion NH4+ th phi chun pH = 6,5 7,2 v pH cao qu 7,2 c s hnh thnh r rt NH3 lm tan mt phn kt ta Ag2CrO4 v gy sai s. * Nu mi trng kim mnh th thuc th AgNO3 s tiu tn hn lng cn thit do to Ag2O. * Cn phi loi cc ion cn tr nh: - Ba2+, Pb2+, Bi3+ v chng to kt ta vi CrO42-. - S2-, SO42-, PO43-, C2O42- kt hp vi Ag+ to ra kt ta. * Dung dch chun AgNO3 bao gi cng ng buret ch khng ng bnh tam gic. * nhy ca cht ch th gim khi tng nhit do tan ca Ag2CrO4 tng, do phi chun nhit thp. Phng php Mo c th cho php chun dung dch NaCl n nng 0,001M vi chnh xc 1% nu tin hnh hiu chnh cn thn lng Ag+ d. 6.2.3.2. Phng php Volhard(Vonha). Dng chun dung dch AgNO3 bng dung dch NH4CNS chun vi ch th Fe3+ dng phn FeNH4(SO4)2.12H2O nng 1M. Khi chun thng dng 1 2 ml dung dch phn st trn 100ml hn hp chun . * Qu trnh chun nh sau: - Nh dn dn dung dch chun NH4CNS vo dung dch AgNO3 c cha ch th AgCNS Fe3+, phn ng s l: Ag+ + CNS - gn im tng ng hay ti im tng ng khi ta nh git cui cng thy dung dch nhum mu hng ta s kt thc chun v lc : Fe(CNS)3 hay dng n gin: Fe3+ + CNSFeCNS2+. Fe3+ + 3CNSBc nhy pCNS = 8 - 4 v im tng ng pCNS = pAg = 6. Qua tnh ton ngi ta thy rng nu kt thc chun trong khong bc nhy trn th phi thm FeNH4(SO4)2 mt lng nh th no vo dung dch AgNO3 nng Fe3+ ban u C0 tha mn iu kin: 3,16.10-4 C0 3,16. - ng dng quan trng ca phng php ny l c th chun ngc cc halogenua X- (I-, Br-, Cl-). Nguyn tc ca php chun ngc nh sau: cho ion halogen X- tc dng vi mt lng d dung dch chun AgNO3 ( bit chnh xc): AgX + Ag+(cn li) X- + Ag+(d) + sau chun lng Ag cn li bng dung dch chun NH4CNS theo phng php Vonha trc tip. T lng Ag+ ban u v lng Ag+ cn li ta bit c lng Ag+ tc dng vi lng X-, do tnh c lng halogenua X-. Ch : Trong s cc halogenua th chun ngc Br- v I- thun li v chnh xc hn

141 cn chun ngc Cl- kh khn hn, v tan ca kt ta AgCl (TAgCl = 10-10) ln hn tan ca AgCNS (TAgCNS = 10-12) nn khi chun lng tha Ag+ cn li ng l gn hay ti im tng ng, mt git dung dch cui cng NH4CNS nh xung th lp tc dung dch phi nhum hng ngay nhng li thy xut hin kt ta AgCNS do CNS- kt hp Ag+ ca kt ta AgCl tan phn ly ra. V vy kt qu phn tch s b sai i. AgCl Ag+ + ClAgCNS Ag+ + CNSMun chun ngc Cl- theo phng php trn t kt qu tt c th dng mt trong hai bin php sau: + Lc kt ta AgCl tch ra khi dung dch trc khi chun lng Ag+ tha cn li. + Hoc cho thm mt t dung mi hu c thch hp nh: nitro benzen lm chm qu trnh phn ly ca AgCl, ngn cn AgCl tip xc vi SCN-. * u im ca phng php - C th chun trong mi trng axt v AgCNS khng tan trong axit do c th dng phng php ny xc nh lng Ag trong hp kim khi ph mu bng axit mnh. - Ba2+, Pb2+ khng lm cn tr trong phng php ny. - Cc ion cn tr: mui ca thy ngn (I) tao kt ta vi CNS-, cc cht oxy ha s oxy ha CNS-, cht c kh nng to phc bn vi Fe3+ nh F-, PO43-. 6.2.3.3. Phng php dng ch th hp ph - phng php Fajans (Pha Gian) * Hin tng hp ph trong qu trnh chun : Trong qu trnh chun cc kt ta c xu hng ha keo, nht l cc halogenua bc. Kt ta keo hp ph chn lc, c bit hp ph mnh ion to ra kt ta c trong dung dch nn s to ra nhng ht keo tch in cng du y nhau. V d: chun dung dch KI bng dung dch AgNO3 ta thy rng: + Trc im tng ng trong dung dch c tha I- khi kt ta AgI s hp nAgI.mIph mnh I- to thnh ht keo tch in m: nAgI + mI+ Sau im tng ng: dung dch c tha Ag+, khi ta c ht keo tch in dng: pAgI + qAg+ pAgI.qAg+ + Trng thi kt ta AgI t tch in m (-) sang tch in dng (+) s c lc khng tch in, lc gi l im trung ha in (hay cn gi l im ng in). im ng in c th trng hay khng trng vi im tng ng ty theo bn cht ca kt ta. * Cht ch th hp ph Cht ch th hp ph l nhng cht mu hu c in ly yu, do trong dung dch chng phn ly yu thnh ion. Theo Fajans, cc anion ca ch th hp th khi b hp th ln b mt kt ta tch in dng s b bin dng v thay i mu. Cc cht ch th thng dng l fluoretxein v cc dn xut ca n nh eozin. Li dng tnh cht ny xc nh im tng ng. V d nh cht ch th eozin l mt axit hu c yu k hiu HE, trong dung dch tn ti theo cn bng: HE H+ + E-. E- trng thi t do c mu hng. Khi b kt ta hp ph s c mu tm hoa c. Nu dng eozin xc nh im tng ng khi chun dung dch KI bng dung dch AgNO3 ta

142 s thy: + Trc im tng ng: nAgI.mI- khng hp ph E- v cng du (-) nn dung dch c mu hng. + Sau im tng ng: pAgI.qAg+ s hp ph E- do kt ta s nhum mu tm hoa c. chnh xc ca php chun vi cht ch th hp ph ph thuc vo cc yu t sau: * Tnh hp ph chn lc ca cht ch th Trng hp l tng nht l cht ch th phi i mu ngay sau im tng ng khi in tch kt ta va i du. Nhng iu ny cn ty thuc vo quan h gia lc hp ph ca ion cht mu v ion li. S hp ph khng ch ph thuc vo tng tc tnh in m cn ph thuc vo tnh cht phn cc ca cc cht, v vy anion cht mu rt c th hp ph chy ua vi anion li. Chng hn, eozin c th y ion Cl- v chim v tr ion to th. AgCl, Cl- Na+ + flBr- AgCl, flBr- Na+ + ClDo s i mu li xy ra trc im tng ng. * nh hng ca pH: Cht mu b hp ph ch yu dng anion m nng ca n ph thuc pH, v vy khi chun phi duy tr pH thch hp sao cho nng anion mu ln bo m cn bng hp ph v s i mu r. Fluoretxein l axt rt yu (Ka = 10-7) do khng th chun pH < 7 v khi y cht ch th tn ti ch yu dng khng phn ly v kh nng hp ph b hn ch. Mt khc, cng cn lu l dng axt ca fluoretxein t tan trong nc. Diclofluoretxein l axt mnh hn (Ka = 10-4), mt khc kh nng hp ph ca anion ny mnh hn nn c th chun pH thp. Trong bng 6.2 c ghi phm vi ng dng ca mt s cht ch th thuc dy fluoretxein.
Bng 6.2. Tnh cht v phm vi ng dng ca mt s cht ch th thuc dy fluoretxein. Cht ch th Ion cn chun Cht chun pH Bin i mu Nng thp nht c th chun (mol/l)

Fluoretxein Diclofluoretxein Eozin

Cl- (Br-, I-) Cl- (Br-, I-) Br-, I-, SCN-

Ag+ Ag+ Ag+

7-10 vng lc hng 4-10 vng lc 2-10 hng thm

5.10-3 5.10-4 5.10-4

* Tnh cht b mt ca kt ta: S hp ph ph thuc nhiu vo b mt pha rn. Nu kt ta b ng t khi chun th cht ch th hp ph s km tc dng. Cn trnh s ca cc ion kim loi a ha tr (nh Al3+, Fe3+) c tc dng lm ng t mnh kt ta. trnh ng t c th cho vo hn hp chun mt cht keo bo v, v d khi chun Cl- c th cho dextrin, gelatin. Khng c chun cc dung dch c qu v s ng t s xy ra

143 d dng hn (nng chun khng c qu 0,025M). Ngoi cc cht ch th anion, ngi ta cng dng c cc cht ch th cation nh metyl tm, rozamin 6G, metyl vng... 6.2.3.4. Chun Zn2+ bng K4[Fe(CN)6] Trong phng php chun kt ta, ngoi vic chun cc halogenua bng AgNO3, ngi ta cn chun Zn2+ bng dung dch K4[Fe(CN)6]. Trong mi trng trung tnh hay axt yu ion Zn2+ tc dng vi K4[Fe(CN)6] cho mt kt ta kh tan 3ZnSO4 + 2 K4[Fe(CN)6] = K2Zn3 [Fe(CN)6]2 + 3K2SO4 xc nh im cui ca phng php ny, ngi ta dng ch th oxy ha kh l iphenylamin v trong dung dch chun c pha thm mt t K3[Fe(CN)6]. Khi Zn2+ kt ta ht vi K4[Fe(CN)6] th 1 git dung dch chun d s to nn mt cp 4 oxy ha - kh lin hp Fe(CN) 3 6 /Fe(CN) 6 trong dung dch nn xut hin mt th oxy ha v s oxy ha iphenylamin lm cho n i mu, phi ngng chun ngay.

BI TP
1. Phn bit dung dch bo ha, cha bo ha, qu bo ha. Cho v d. 2. a) Th no l tch s tan ca cht kh tan trong nc? b) Trnh by quy lut tch s tan. c) Vit biu thc tch s tan v tan ca cc cht sau: AgCl, Ag2CO3, Ca3(PO4)2, Fe(OH)3, K2Zn3[Fe(CN)6]2, MgNH4PO4. 3. Tnh tan ca CaC2O4 trong dung dch (NH4)2C2O4 5.10-2 M v so snh vi tan ca n trong nc. Cho CaC O = 2,57.10-9 250C. 4. Trong dung dch bo ha ca cht kt ta AB2X3 c cn bng: A+ + 2B+ + 3XAB2X3 Nng ca X- trong dung dch bo ha l 4.10-3M a) Tnh AB X .
2 4 2 3

b) Tnh tan ca AB2X3 trong dung dch BCl 5.10-6M. 5. Xt s kt ta phn on trong hai trng hp sau: a. Cho dn dn dung dch Na2SO4 long vo dung dch hn hp Ba2+ v Ca2+ c [Ba2+] = 10-2M, [Ca2+] = 10-1M. Bit TBaSO = 1,1.10 10 , TCaSO = 6.10 -5 250C. b. Cho dn dn dung dch AgNO3 long vo dung dch hn hp (Cl- + CrO42-) c [Cl-] = [CrO42-] = 10-2M. Bit TAgCl = 1,8.10 10 , TAg CrO = 1,1.10 12 250C. 6. Hi tan ca MgF2 v BaCO3 c bng nhau khng, bit rng tch s ha tan ca chng gn bng nhau. 7. Kt ta no s thot ra trc khi thm dn dung dch AgNO3 vo dung dch cha cc ion clorua, brmua cng nng . Bit TAgCl = 1,8.10-10 v TAgBr = 7,7.10-13 250C. 8. Tnh gi tr pH ca mi trng lc bt u kt ta v kt ta hon ton Mg2+
4 4 2 4

144 dng Mg(OH)2 nu ban u [Mg2+] = 10-2M. Bit TMg ( OH ) = 1,8.10 11 . 9. Chng minh: Khi kt ta Cd2+ v Zn2+ c cng nng ban u [Cd2+] = [Zn2+] = 0,1M bng H2S bo ha (nng 0,1M) pH = 5 th CdS kt ta hon ton m Zn2+ khng kt ta. Bit H2S c K1 = 5,7.10-8; K2 = 1,2.10-15; TCdS = 3,6.10-29; TZnS = 1,2.10-23 0 25 C. 10. Thm vo dung dch cha 0,1M Pb(NO3)2 v 0,01M Hg2(NO3)2 mt dung dch + s bt u kt ta trc v hi bao KCl, hi cation no trong 2 cation Pb2+ v Hg 2 2 nhiu phn trm ca cation cn li khi bt u kt ta cation th hai. Bit THg Cl = 1,1.10 18 v TPbCl = 2,4.10 4 25 0 C 11. Tnh pAg v pCl khi chun 25ml dung dch AgNO3 0,1M bng dung dch NaCl 0,1M ti cc im khi thm 24ml, 25ml v 26ml dung dch NaCl. Cho bit: TAgCl = 1,8.10-10 250C. 12. Tnh nng ion Br- v Ag+ trong dung dch khi chun 100ml dung dch KBr 0,1M bng dung dch AgNO3 0,1M sau khi thm 50,0; 90,0; 98,0; 99,0; 99,8; 100,0; 100,1; 100,2; 110,0ml dung dch chun. TAgBr = 4.10-13 250C. 13. Tnh pAg v pCl sau khi thm 21,0; 25,0 v 26,0ml dung dch NaCl vo 25,0ml dung dch AgNO3 0,1M. TAgCl = 1,8.10-10 250C. 14. Cc phng php xc nh im cui trong qu trnh chun cc halogenua bng bc nitrat. 15. Tnh bc nhy ca cc ng nh phn khi chun cc dung dch NaCl: NaBr: NaI c nng 0,1M bng dung dch AgNO3 0,1M (bc nhy c coi l chun tha hay thiu 0,1% AgNO3). Cho bit: TAgCl = 1,8.10-10; TAgBr = 7,7.10-13; TAgI = 1,5.10-16 250C. 16. Tnh bc nhy pAg khi nh phn dung dch K2CrO4 0,01M bng dung dch AgNO3 0,1M. Cho TAg CrO = 1,1.10-12. 17. Chun 30ml dung dch ZnSO4 0,100M th phi dng ht bao nhiu ml dung dch K4[Fe(CN)6] 0,05M. 18. Tnh hm lng ZnO c trong mu phn tch nu ly 0,380g mu ha tan thnh dung dch, thm vo 24,30ml dung dch K4[Fe(CN)6] 0,051M ri chun lng K4[Fe(CN)6] d th tn mt 8,40ml dung dch ZnSO4 0,104M. 19. Cn bao nhiu ml dung dch K4[Fe(CN)6] 0,0510M chun 25ml dung dch ZnSO4 0,100M theo phng trnh phn ng: 2 K4[Fe(CN)6] + 3Zn2+ = K2Zn3 [Fe(CN)6]2 + 6 K+ 20. Tnh nng ng lng v chun theo clo ca dung dch AgNO3, bit rng thm 0,1173g NaCl vo 30ml dung dch AgNO3 sau chun lng bc d th tn mt 3,20ml dung dch NH4SCN. Chun 10ml dung dch AgNO3 th tn mt 9,7ml dung dch NH4SCN.
2

145

TI LIU THAM KHO

1. Hong Minh Chu, T Vn Mc, T Vng Nghi. C s ha hc phn tch, NXB KH & KT, 2002. 2. L c, Ha hc phn tch. NXB H Quc Gia H Ni, 2002. 3. Nguyn Tinh Dung phn I, II, III. Ha hc phn tch. NXB Gio dc, 2000. 4. Trn T Hiu, Ha hc phn tch, NXB HQG H Ni, 2002. 5. Trn T Hiu, T Vng Nghi, Hong Th Tn. Bi tp Ha hc phn tch, NXB H&TH Chuyn nghip, 1984. 6. H.A. Laitinen, Phn tch ha hc. Tp 1 v 2, Nguyn Tinh Dung v Nguyn Huyn dch. NXB KH & KT, 1976. 7. .., , , o , 1972 8. .., , , o , 1972

146

CHNG 7

SAI S TRONG PHN TCH NH LNG HA HC

Gi tr ca mt php phn tch c nh gi ng v lp ca kt qu thu c. 7.1. Mt s khi nim. 7.1.1. ng v lp. ng phn nh s ph hp gia kt qu thc nghim thu c vi gi tr thc ca i lng o. lp phn nh s ph hp gia cc kt qu thu c trong cc th nghim lp li trong cng iu kin thc nghim quy nh ca php phn tch. Kt qu phn tch c th c c lp cao (chnh xc) nhng khng ng. V d: Khi kim tra dung dch HCl c nng chnh xc 0,1000M, hai sinh vin A v B thu c kt qu nh sau: A: 0,1002 ; 0,0999 ; 0,1004 ; 0,0996 ; 0,1003 B: 0,1014 ; 0,1017 ; 0,1016 ; 0 1015 ; 0 1014 R rng, kt qu ca sinh vin A ng hn nhng km chnh xc hn so vi kt qu ca sinh vin B. ng v lp c lin quan cht ch vi sai s phn tch. Ngi ta phn bit sai s h thng vi sai s ngu nhin. 7.1.2. Sai s h thng. Sai s h thng lm cho kt qu phn tch khng ng. Nguyn nhn ca sai s h thng l xc nh, v v nguyn tc c th bit c. Mi loi sai s h thng lm cho kt qu phn tch dch chuyn theo mt chiu nht nh (tng hoc gim). Sai s h thng c th khng i, cng c th thay i theo iu kin. V d, khi cn CaCl2 trong mt chn cn khng y np th kt qu cn s tng dn theo thi gian v CaCl2 l cht ht m mnh. Sai s ny tng theo thi gian cn v b mt tip xc vi kh quyn ... Tuy vy sai s h thng do vic pha ha cht trong bnh nh mc c chun ha sai l i lng khng i, khng ph thuc cc iu kin phn tch khc. Trong phn tch ha hc c th phn chia cc loi sai s h thng sau y: - Sai s do s dng my, ha cht v thuc th, v d s dng cn v qu cn khng ng, s dng cc dng c o th tch khng chnh xc. Sai s c th xy do cc cht l t bnh thy tinh, s v. v ... xm nhp vo dung dch hoc thuc th c ln tp cht. - Sai s thao tc do ch quan ngi phn tch gy ra, khng ph thuc my, dng c v khng lin quan vi phng php phn tch. Sai s ny c th rt nghim trng i vi nhng ngi phn tch thiu kinh nghim hoc lm vic thiu suy ngh, cn thn. Ngi mi lm phn tch th thng phm sai lm nghim trng do khng bit lm vic. Tuy vy, khi quen cng vic v nu lm vic cn thn, nghim tc th sai s thao tc thng l khng ng k.

147
- Sai s c nhn do kh nng ca ngi phn tch khng th thc hin chnh xc mt s thao tc phn tch. V d khng th nhn bit chnh xc s chuyn mu ca cht ch th ti im cui chun . Thuc loi ny cng phi k n sai s tm l, tc l khuynh hng ca ngi phn tch khi lp li th nghim mun chn gi tr ph hp vi gi tr o trc, hoc gn vi gi tr ca bn. Sai s ny kh ph bin. - Sai s phng php c lin quan vi tnh cht ha hc hoc tnh cht ha l ca h o, t lin quan vi thao tc phn tch. V d, phn ng phn tch khng xy ra hon ton hoc phn ng ph xy ra lm sai lch tnh hp thc ca phn ng chnh v.v ... Tht ra sai s phng php c lin quan cht ch vi sai s thao tc. Trong nhiu trng hp nu thao tc tt th c th lm gim sai s phng php v ngc li. Chng hn, nu ra kt ta kho sao cho th tch nc ra khng ln th s mt mt kt ta do tan s khng ng k, ngc li nu dng qu nhiu nc ra th lng cht mt i khi ra s nhiu. Hoc nu iu chnh kho nhit khi nung th c th trnh c s phn hy cht khi nung ... 7.1.3. Sai s ngu nhin. Sai s ngu nhin nh hng n lp li ca kt qu o v lm gim chnh xc phn tch. Sai s ngu nhin do nhng nguyn nhn ngu nhin, khng nhn thy trc c v lm cho kt qu phn tch dao ng theo cc chiu khc nhau (lc tng, lc gim). Sai s ngu nhin lun lun xut hin d php phn tch c thc hin ht sc cn thn v iu kin thc hin c gi c nh nghim ngt. Do c tnh ca n nh vy m vic x l v nh gi sai s ngu nhin ca mi php phn tch l rt quan trng. N cho php xc nh gi tr ca phng php phn tch, nh gi cht lng lm vic ca ngi phn tch, nh gi so snh cng vic phn tch ca cc phng th nghim khc nhau, v.v ... Do bn cht ca n m sai s ngu nhin phi c x l bng ton hc thng k.
7.2. nh gi sai s ca cc php o trc tip. Trong thc hnh phn tch ha hc phi tin hnh nhiu thao tc, trong bt buc phi c php o trc tip, tc l so snh vt o vi vt chun nh cn, o th tch. Mi php o trc tip u mc sai s ngu nhin v sai s ny cng vi cc sai s mc phi trong cc giai on phn tch khc nhau s quyt nh chnh xc ca php phn tch. Khi tin hnh th nghim chng ta thc hin mt s th nghim c lp trong cng iu kin ging nhau v t cc kt qu ring l thu c ta tin hnh x l thng k nh gi chnh xc ca php o. Cc i lng c trng thng k quan trng nht l gi tr trung bnh cng v phng sai. 7.2.1. Gi tr trung bnh cng. Gi s ta tin hnh n php o c lp i lng X vi cc kt qu X1, X2, . . ., Xn.

Gi tr trung bnh cng: X =

X
i =1

l gi tr gn vi gi tr thc ca i lng

148 cn o vi xc sut cao nht trong s cc gi tr o c. 7.2.2. Phng sai. Phng sai ca php o phn nh phn tn ca kt qu o, c nh gi bng:

k k = s bc t do. Nu ch c mt i lng cn o X th k = n - 1. Gi tr s = s 2 thng c gi l lch chun ca php o. lch chun ca i lng trung bnh cng s X c tnh theo:
sX = s2 = n

s2 =

(X
i =1

X) 2

(X

X) 2

n (n 1)

Trong thc t tin tnh ton cc i lng X, s 2 , s X , ngi ta thng chn trong dy n gi tr o c X1, . . ., Xn mt gi tr C sao cho C X . Sau tnh X v s2 theo cc cng thc sau:
X =C+

yi
i =1

y,

2 i

= y i2

( y )
i

v s =
2

x
i =1

2 i

n 1

v yi = Xi - C.

V d 1: Hy tnh gi tr trung bnh cng, lch chun, phng sai ca php xc nh niken trong thp da vo cc s liu phn tch sau y: Hm lng % ca Ni trong thp cc th nghim phn tch c lp: 0,69; 0,68; 0,70 ; 0,67 ; 0,68 ; 0,67 v 0.69.
Xi % yi.102 yi2.104

0,69 0,68 0,70 0,67 0,68 0,67 0,69

1 0 2 -1 0 -1 1 yiyi = 2.10-2

1 0 4 1 0 1 1 2 yiyi = 8.10-4

Chn C = 0,68 y i = Xi - C

tin khi tnh ton (khng phi x l cc s l) ta nhn yi vi 102 v tt nhin yi2 vi 104. 2.10 2 Ta c: X = 0,68 + = 0,683 7

149
4.10 4 x = 8.10 7 = 7,43.10 4 7,43.10 4 s2 = = 1,238.10 4 6 s = 1,238.10 4 = 1,11.10 2
2 i 4

1,238.10 4 = 1,76.10 5 7 s X = 4,21.10 3 7.2.3. chnh xc ca php o trc tip. chnh xc l gi tr tuyt i ca hiu gia gi tr trung bnh cng X v gi tr thc ca i lng phi o: = X . s2 = X

Trong thc t c nh gi ng vi mt tin cy cho, v d = 0,95 (95%) hoc = 0,99 (99%) . . . c tnh theo: = s X t ,k t , k = h s Student ng vi s bc t do k ca php o v tin cy cho trong bng. Khong tin cy ca gi tr o l khong ti c kh nng tn ti gi tr thc ca php o vi xc sut cho. X X + hay X s X t ,k X + s X t ,k
Bng 7.1. Cc gi tr h s Student t,k ng vi = 0,95 v 0,99

k 1 2 3 4 5 6 7 8 9 10 11 12 13

0,95 12,706 4,303 3,182 2,776 2,571 2,447 2,365 2,306 2,262 2,228 2,201 2,179 2,160

0,99 63,657 9,925 5,841 4,604 4,032 3,707 3,499 3,355 3,250 3,169 3,106 3,055 3,012

k 14 15 16 17 18 19 20 25 30 40 60 120

0,95 2,145 2,131 2,120 2,110 2,103 2,093 2,086 2,060 2,042 2,021 2,000 1,980

0,99 2,977 2,947 2,921 2,898 2,878 2,861 2,845 2,707 2,750 2,704 2,660 2,671

V d 2: nh gi chnh xc ca kt qu xc nh hm lng niken trong thp theo cc s liu cho trong v d 1 vi tin cy = 0,95.

150 Kt qu tnh trong v d 1 cho ta: X = 0,683 s X = 4,21.10 3 k=n-1=6 vi = 0,95; k = 6 ta c t = 2,447 (bng 7.1) =0, 95 = s X .t ,k = 4,21.10 3.2,447 = 1,03.10 2 chnh xc: 0, 95 = 0,01 Kt qu o: X 0,95 = 0,68 0,01 hay 0,67 0,69 Sai s tng i ca php xc nh: .100% X 0,01 .100 = 1,5% Trong v d trn th sai s tng i % 0,68 7.2.4. S c ngha v cch ghi kt qu phn tch. 7.2.4.1. S c ngha. Kt qu ca mt php o trc tip cng nh ca mt thao tc phn tch phi c ghi chp sao cho ngi s dng s liu hiu c mc chnh xc ca php o. V nguyn tc, s liu phi c ghi sao cho ch c s cui cng l bt nh. Chng hn, nu cn trn cn phn tch vi nhy 0,1mg th kt qu cn phi c ghi n s ch phn mi mg, v d 1,2516 gam m khng vit 1,251 gam hoc 1,25160 gam. Cc s 1, 2, 5, 1 l cc s hon ton tin cy v chng ta c c t cc qu cn, cn s 6 l bt nh v c ghi c tnh trn thang chia da theo kim ch hoc theo v tr dao ng ca vch sng. Cc s tin cy cng vi s bt nh u tin c gi l s c ngha. Trong kt qu cn trn ta c 5 s c ngha: 4 s tin cy (1, 2, 5, 1) v 1 s bt nh (6). Phng php ti u xc nh s bt nh trong kt qu o l phng php tnh cn tin cy nh thc hin trn. Trong v d 2, ta xc nh c cn tin cy l 0,95 = 0,01 . Nh vy s th hai sau du phy l bt nh v khi ghi kt qu phn tch phi lm trn n con s th hai sau du phy: X = 0,68 0,01 , y c 2 s c ngha, s 6 l tin cy, s 8 l bt nh. Trong thc t khng phi bao gi cng c y thng tin ( lch chun, s php o) tnh c cn tin cy. Do nu khng c mt thng tin b sung ngi ta thng ngm hiu rng s cui cng c bt nh 1. Chng hn, nu vit s c th tch trn buret l 23,40 ml th iu c ngha l buret c chnh xc 0,01ml, tc l vch chia trn buret n 0,1 ml, cn s c phn trm ml l bt nh (c lng). S 0 c dng thit lp im thp phn khng c tnh vo s c ngha. V d, trong s 0,0034 ch c hai s c ngha (3 v 4), nhng trong s 3,040 li c 4 s c ngha. i vi cc s dng phc tp ngi ta thng chuyn sang dng s ly tha thp phn v cc s phn nguyn c tnh vo s c ngha. V d 1064 = 1,064.103 c 4 s c ngha; 0,000520 = 5,20.10-4 c 3 s c ngha, hoc vit 5,2.10-4 c 2 s c ngha. S liu 2,4 gam c 2 s c ngha. V nu quy ra mg th phi vit

151 2,4.103 mg (2 s c ngha) m khng vit 2400 mg (4 s c ngha). i vi cc s logarit th cc s bn tri im thp phn (phn c tnh) khng c coi l s c ngha v y l cc ch s ly tha. V d lnx = 3,135 c 3 s c ngha (1, 3, 5); lgx = 2,68 c 2 s c ngha (6 v 8). 7.2.4.2. Quy tc tnh v lm trn s. Trong cc php tnh ch c php lm trn kt qu cui cng (nhm trnh vic gim chnh xc ca kt qu do vic lm trn cc giai on tnh trung gian). * Cng v tr Khi cng v tr ch gi li kt qu cui cng mt s s thp phn bng ng s thp phn ca s hng c s thp phn t nht. V d 3: Thc hin php tnh: a. Y = 6,145 + 13,24 + 34,7 Y = 54,085 Kt qu lm trn: Y = 54,1 (gi li 1 s thp phn) b. X = 1374,252 - 309,48 X = 1064,772 Kt qu lm trn: X = 1064,77 (gi li 2 s thp phn) * Nhn v chia Khi nhn v chia cn gi li kt qu cui cng mt s s c ngha bng ng s c ngha ca tha s c s c ngha t nht. V d 4: Thc hin php tnh: 3,084.0,275 a. Y = 41,256 Y = 0,020557 lm trn Y = 0,0206 (3 s c ngha) 6,125.10 5.3,7.10 8 b. X = 5,37.10 3 X = 4,220.10-6 lm trn X = 4,2.10-16 (hai s c ngha) * Logarit V d 5: Tnh logarit ca Y = 3,34.10-5 lgY = -5 + 0,5237 = -4,476 (c 3 s c ngha 4, 7, 6 tng t trong Y cng c 3 s c ngha) V d 6: pH = -lg[H+] = 6,47. Tnh [H+]. [H+] = 10-6,47 = 3,39.10-7 + lm trn: [H ] = 3,4.10-7 (hai s c ngha tng t gi tr pH c hai s c ngha). * Trong mt s trng hp khi gi li cc s c ngha cn cn nhc sao cho bt nh tng i kt qu cui cng ph hp vi bt nh tng i ca cc s liu c dng tnh ton. V d 7: 1.01 = 1,03 m khng vit 1,0 v bt nh tng i ca c hai s 1,01 v 0,98

152
0,01 0,01 0,98 u bng 1% 1% . 1,01 0,98 V d 8: 1.02 = 0,99 m khng vit 0,990 bi v bt nh tng i ca c hai s 1,02 1,03 0,001 v 1,03 cng u bng 1%. Nu vit 0,990 th bt nh s l .100 = 1% . 0,990 V d 9: lgx = lg2,114 bng 0,3251 phi vit 0,325 m khng vit 0,3251 bi v bt nh ca x l 0,001 nn nu ly lg(2,114 0,001) s c 0,3249 v 0,3253. Nh vy s bt nh l s th ba sau du phy. V d 10: lgx = -3,124 x = 10-3,124 = 7,5.10-4 m khng vit 7,52.10-4, bi v nu coi lgx = -(3,124 0,001) th x bng 7,498.10-4 v 7,533.10-4 nh vy s th hai sau du phy l bt nh! Ch : Khi lm trn s nu s l b hn 5 th c th b i, nu s ln hn 5 th c th thm 1 n v vo s trc. Nu nghi ng hoc s mt mt chnh xc th gi li mt s sau s c ngha cui nhng phi vit tt xung thnh ch s di. V d: 6,832 lm trn thnh 6,83; 7,988 lm trn thnh 7,99 ; 6,455 lm trn thnh 6,455 nu khng mun vit 6,45.

TI LIU THAM KHO

1. Hong Minh Chu, T Vn Mc, T Vng Nghi. C s ha hc phn tch, NXB KH & KT, 2002. 2. Nguyn Tinh Dung phn I, II, III. Ha hc phn tch. NXB Gio dc, 2000. 3. Trn T Hiu, Ha hc phn tch, NXB HQG H Ni, 2002. 4. Doerffl, Thng k trong ha hc phn tch. Trn Bnh v Nguyn Vn Ngc dch, NXB H&TH Chuyn nghip, H Ni, 1983.

153

PH LC
Bng 1. Gi tr in th tiu chun E0

F 2 S 2 O8 Ag2+(trong 4M HClO4) Ag2+(trong 4M HClO3) NaBiO3 + 4H+ H2O2 + 2H+ PbO2 + 4H+ Ce(SO4)322BrO3- + 12H+ MnO4- + 8H+ ClO3- + 6H+ BrO3Cl2 Cr2O72- + 14H+ MnO2 + 4H+ O2 + 4H+ 2IO3- + 12H+ Br2 (lng) NO3- + 4H+ NO3- + 3H+ Cu2+ + IHg2+ Ag+ Hg22+ NO3- + 2H+ Fe3+ H3AsO4 + 2H+ I2 [Fe(CN)6]3Cu2+ Hg2Cl2 Cu2+ Sn4+ S + 2H+ TiO2+ + 2H+ S4O622H+ Fe3+ Pb2+ Sn2+ Cd2+ 2CO2 + 2H+ V3+ Ni2+ Cd2+ Cr3+ Fe2+ As + 3H+

Dng oxy ha 1

S electron trao i 2
2 2 1 1 2 2 2 1 10 5 6 6 2 6 2 4 10 2 3 2 1 2 1 2 1 1 2 2 1 2 2 1 2 2 1 2 2 3 2 2 2 2 1 2 2 1 2 3

2F2SO42Ag+ Ag+ + BiO + Na+ + 2H2O 2H2O Pb2+ + 2H2O Ce3+ + 3SO42Br2 + 6H2O Mn2+ + 4H2O Cl- + 3H2O Br- + 3H2O 2Cl3+ 2Cr + 7H2O Mn2+ + 2H2O 2H2O I2 +6H2O 2BrNO + 2H2O HNO3 + H2O CuI Hg Ag Hg NO2 + H2O Fe2+ HAsO2 + 2H2O 2I[Fe(CN)6]4Cu 2Hg + 2ClCu+ Sn2+ H 2S Ti4+ + H2O 2S2O32H2 Fe Pb Sn Cd H 2C 2 O 4 V2+ Ni Cd Cr2+ Fe AsH3

Dng kh 3

Eo (V) 4
+2,870 +2,000 +1,970 +1,927 +1,800 +1,770 +1,455 +1,440 +1,52 +1,51 +1,45 +1,45 +1,359 +1,33 +1,29 +1,23 +1,19 +1,087 +0,96 +0,94 +0,86 +0,85 +0,7994 +0,792 +0,8 +0,771 +0,56 +0,536 +0,356 +0,337 +0,268 +0,153 +0,15 +0,14 +0,1 0,09 = 0,00 -0,036 -0,126 -0,14 -0,402 -0,49 -0,255 -0,23 -0,402 -0,41 -0,44 -0,60

154 1 2
2 2 2 2 3 2 1 1

Zn2+ FeS CdS Mn2+ Al3+ Mg2+ Na+ Li+

Zn Fe + S2Cd + SMn Al Mg Na Li

4
-0,762 -0,95 -1,17 -1,19 -1,66 -2,37 -2,713 -3,03

155
Bng 2. Hng s phn li ca mt s axit, baz thng gp Tn hp cht AXIT Axit nitro Axit xyanhydric Axit benzlic Axit lactic Axit fomic Axit axtic Axit sunfur
Cng thc Hng s phn ly K pK=-lgK

HNO3 HCN C6H5COOH CH3CHOHCOOH HCOOH CH3COOH H2SO3

Axit sunfuhydric Axit cacbonic Axit crmic Axit tactric Axit xalic Axit phtphoric Axit limnic
BAZ Amniac Anilin Mtylamin Hyrxit ch

H2S H2CO3 H2CrO4 H2C4HtO6 H2C2O4 H3PO4 C3H6H5O7

4.10-4 7,2.10-10 6,3.10-5 1,37.10-4 1,77.10-4 1,80.10-5 K1 = 1,3.10-2 K2 = 5.10-5 K1 = 5,7.10-8 K2 = 1,2.10-15 K1 = 4,31.10-7 K2 = 5,61.10-11 K1 = 1,8.10-1 K2 = 3,2.10-7 K1 = 1,04.10-3 K2 = 4,55.10-5 K1 = 5,9.10-2 K2 = 6,4.10-5 K1 = 7,51.10-3 K2 = 6,23.10-8 K3 = 2,2.10-13 K1 = 8,4.10-4 K2 = 1,8.10-5 K3 = 4.10-6

3,4 9,14 4,2 3,86 3,75 4,75 1,89 5,3 7,24 14,92 6,37 10,25 0,75 6,5 2,89 4,34 1,23 4,19 2,12 7,21 12,67 3,08 4,74 5,4

NH4OH C6H5NH2 CH3NH2 Pb(OH)2 C20H24C2N2.3H2O

Quinin

1,79.10-5 4.10-10 1,38.10-4 K1 = 9,6.10-4 K2 = 3.10-8 K1 = 2,2.10-7 K2 = 3,3.10-10

4,75 9,17 3,36 3,02 7,52 6,66 9,48

156
Bng 3. Tch s tan v tan ca mt s cht in li kh tan 18 250c

Loi cht Asenat Brmua

Hyrxit

Iua

Cacbonat

xalat

Cng thc Ag3AsO4 PbBr2 CuBr AgBr Hg2Br2 Ca(OH)2 Mg(OH)2 Cd(OH)2 Mn(OH)2 Ni(OH)2 Fe(OH)2 Co(OH)2 Zn(OH)2 Cu(OH)2 Sn(OH)2 Cr(OH)3 Al(OH)3 Fe(OH)3 Sb(OH)3 PbI2 CuI AgI Hg2I2 MgCO3 ZnCO3 BaCO3 CaCO3 SrCO3 MnCO3 FeCO3 Ag2CO3 PbCO3 CdCO3 HgCO3 MgC2O4 BaC2O4.2H2O SrC2O4.H2O CdC2O4.2H2O CaC2O4. H2O ZnC2O4.2H2O PbC2O4 Ag2C2O4

Tch s tan 4,5.10-19 7,4.10-5 5,3.10-9 7,7.10-13 5,2.10-23 3,1.10-5 5.10-12 1,2.10-14 4.10-14 4,8.10-16 6,3.10-16 2.10-16 1.10-17 5,6.10-20 5.10-26 5,4.10-31 1,9.10-33 3,8.10-18 4.10-12 8,7.10-9 5,06.10-12 1,5.10-16 1,2.10-23 1,0.10-5 2,7.10-8 8,1.10-9 4,8.10-9 1,6.10-9 8,8.10-11 2,5.10-11 6,15.10-12 1,5.10-13 2,5.10-14 9.10-17 8,57.10-5 1,2.10-7 5,61.10-8 1,53.10-8 2,57.10-9 1,35.10-9 3,2.10-11 1,1.10-11

tan (Mol/l) 1,84.10-5 2,6.10-2 7,3.10-5 8,8.10-7 2,8.10-8 2.10-2 1,1.10-4 1,4.10-5 2,1.10-5 5,4.10-5 4,9.10-6 3,7.10-6 1,4.10-6 2,4.10-7 2,3.10-9 1,2.10-8 2,9.10-9 1,9.10-9 1,9.10-11 1,3.10-3 2,35.10-6 1,2.10-8 5,2.10-8 3,2.10-8 1,6.10-5 9,0.10-5 6,93.10-5 4,0.10-5 9,4.10-6 5.10-4 1,15.10-7 3,9.10-7 1,6.10-6 2,8.10-3 9,2.10-3 3,5.10-4 2,4.10-4 1,2.10-4 5,1.10-5 3,7.10-5 5,7.10-6 1,4.10-4

tan (g/100ml) 8.5,10-4 9,54.10-1 1,05.10-3 1,65.10-5 1,57.10-6 1,48.10-3 6,42.10-4 2,04.10-4 1,87.10-4 5,01.10-5 4,50.10-5 3,44.10-5 1,40.10-5 2,34.10-6 3,51.10-8 1,24.10-7 2,26.10-8 2,03.10-8 3,28.10-10 5,99.10-2 4,38.10-5 2,82.10-7 3,41.10-6 2,70.102,01.101,78.106,94.10-1 5,91.10-4 1,08.10-4 5,79.10-5 3,17.10-3 1,04.10-5 2,76.10-6 1,29.10-4 1,03.10-4 8,55.10-3 4,26.10-3 3,05.10-3 7,45.10-4 7,01.10-4 1,68.10-4 4,25.10-8

157 Sunphat Ag2SO4 CaSO4.2H2O Hg2SO4 SrSO4 PbSO4 BaSO4 MnS FeS NiS NiS CoS CoS ZnS SnS CdS PbS CuS Cu2S Ag2S HgS Bi2S3 MgNH4PO4 Ag3PO4 Pb2(PO4)3 PbCl2 AgCl Hg2Cl2 SrCrO4 BaCrO4 Ag2CrO4 PbCrO4 7,7.10-5 6,1.10-5 6,3.10-7 2,8.10-7 2,2.10-9 1,08.10-10 1,4.10-15 3,8.10-19 3.10-21 2.10-28 7.10-23 2.10-27 1,2.10-23 1.10-28 3,6.10-29 1,1.10-29 8,5.10-45 2.10-47 1,6.10-19 4.10-53 1,6.10-72 2,5.10-13 1,8.10-18 4,5.10-32 2,4.10-4 1,8.10-10 1,1.10-18 3,5.10-5 2,41.10-10 1,1.10-12 1,8.10-14 2,7.10-3 7,8.10-3 7,9.10-4 5,3.10-4 1,5.10-4 1,0.10-5 3,7.10-8 6,1.10-19 5,5.10-11 1,4.10-14 8,4.10-12 4,5.10-14 3,5.10-12 1.10-14 6,0.10-15 3,3.10-15 9,2.10-23 1,7.10-16 3,4.10-17 6,3.10-17 2,7.10-15 6,3.10-5 1,6.10-5 1,7.10-7 3,9.10-2 1,35.10-5 1,6.10-5 5,9.10-3 1,5.10-5 1,3.10-4 1,3.10-7 8,12.10-1 1,34.10-1 3,93.10-2 9,47.10-3 4,55.10-5 2,33.10-4 3,22.10-7 5,36.10-9 4,99.10-10 1,27.10-13 7,64.10-11 1,27.10-13 3,41.10-11 1,51.10-13 8,67.10-14 7,9.10-14 8,8.10-22 2,71.10-15 8,43.10-16 1,47.10-25 1,39.10-13 8,65.10-4 4,19.10-4 1,38.10-5 1,08 1,86.10-4 7,55.10-4 1,20.10-1 3,80.10-4 4,31.10-3 4,20.10-6

Sunfua

Pht pht Clorua Crmt

158

TI LIU THAM KHO

1. Hong Minh Chu, T Vn Mc, T Vng Nghi. C s ha hc phn tch, NXB KH & KT, 2002. 2. L c, Ha hc phn tch. NXB H Quc Gia H Ni, 2002. 3. Nguyn Tinh Dung phn I, II, III. Ha hc phn tch. NXB Gio dc, 2000. 4. Trn T Hiu, Ha hc phn tch, NXB HQG H Ni, 2002. 5. Trn T Hiu, T Vng Nghi, Hong Th Tn. Bi tp Ha hc phn tch, NXB H&TH Chuyn nghip, 1984. 6. Doerffl, Thng k trong ha hc phn tch. Trn Bnh v Nguyn Vn Ngc dch, NXB H&TH Chuyn nghip, H Ni, 1983. 7. H.A. Laitinen, Phn tch ha hc. Tp 1 v 2, Nguyn Tinh Dung v Nguyn Huyn dch. NXB KH & KT, 1976. 8. .., , , o , 1972 9. .., , , o , 1972

159

M C L C
Li m u Chng 1. Dung dch cht in ly- Cn bng ha hc 1.1. Cht in ly mnh v yu. 1.2. Cn bng ha hc v hot . 1.2.1. Nhc li mt s kin thc cn dng 1.2.2. Cn bng v hng s cn bng. Ti liu tham kho Chng 2. i cng v phn tch khi lng v phn tch th tch 2.1. Nguyn tc chung ca phng php phn tch khi lng 2.2. Cc phng php phn tch khi lng 2.2.1. Phng php y 2.2.2. Phng php kt ta 2.2.3. Phng php in phn 2.2.4. Phng php chng ct 2.3. Phng php kt ta. 2.3.1. Ni dung v yu cu ca kt ta trong phng php kt ta 2.3.2. iu kin tin hnh phn tch theo phng php kt ta. 2.3.3. Lc, ra, lm kh v nung kt ta. 2.4. Phng php in phn. 2.4.1. Ni dung 2.4.2. Cc thit b 2.5. ng dng ca phng php khi lng. 2.6. Phng php phn tch th tch 2.6.1. i cng 2.6.2. Mt s nh ngha v khi nim 2.6.3. Cc phn ng dng trong phn tch th tch 2.6.4. Phn loi cc phng php phn tch th tch 2.6.5. Cc phng php chun 2.6.6. Cch biu din nng trong phn tch 2.6.7. Cch tnh kt qu trong phn tch th tch Bi tp Ti liu tham kho Chng 3. Cn bng axt - baz. Chun axt baz 3.1. ngha thc t cc quan nim v axit - baz. 3.1.1. Thuyt axit - baz ca Arnit 3.1.2. Thuyt axit - baz ca Bronsted - Lauri 3.2. Cn bng axit - baz trong mi trng nc. 3.2.1. Tch s ion ca nc, ch s hydrogen 3.2.2. Quan h gia KA ca mt axit v KB ca mt baz lin hp vi n 3.2.3. Tnh gi tr pH ca mt axit, baz hoc mui trong nc
Trang 3 5 5 5 5 6 9 10 10 10 10 10 11 11 11 11 12 14 15 15 15 16 16 16 16 18 19 19 19 23 25 26 27 27 27 27 31 31 32 32

160 3.3. Dung dch m 3.3.1. Khi nim v dung dch m 3.3.2. m dung 3.3.3. ng dng ca dung dch m. 3.4. Tnh nng cc thnh phn ca dung dch khi bit Ph 3.4.1. Trng hp n axit HA. 3.4.2. Trng hp a axit H2A. 3.4.3. Trng hp tng qut HnA 3.5. Chun axit - baz. 3.5.1. Bn cht ca phng php 3.5.2. Cht ch th trong phng php trung ha 3.6. Cch xc nh im tng ng trong phng php trung ha 3.6.1. Khi nim ng nh phn - ng cong Logarit 3.6.2. Nguyn tc xy dng ng nh phn axit - baz 3.7. Cc trng hp chun 3.7.1. Chun axit mnh bng baz mnh 3.7.2. Chun axt yu bng baz mnh hoc baz yu bng axit mnh 3.7.3. Chun axit yu bng baz yu hay ngc li 3.7.4. Chun a axit (hay a baz), hn hp axit (hn hp baz) 3.7.5. Mt s th d v phng php chun axit - baz Bi tp Ti liu tham kho Chng 4. Cn bng oxy ha - kh. Chun oxy ha - kh
4.1. Cn bng oxy ho - kh. 4.1.1. nh ngha phn ng oxy ho - kh

4.1.2. Cch thnh lp cc phng trnh oxy ha - kh theo phng php ion - electron 4.1.3. Cng cht oxy ho - kh. Th in cc 4.1.4. Chiu ca phn ng oxy ha - kh v cc yu t nh hng 4.1.5. Hng s cn bng v vn tc ca phn ng oxy ho - kh 4.2. Chun oxy ha-kh. 4.2.1. Ch th trong phng php oxy ha - kh 4.2.2. ng nh phn trong phng php oxy ha-kh 4.2.3. Mt s phng php oxi ha kh thng dng Bi tp Ti liu tham kho Chng 5. Phc cht v thuc th hu c trong ha phn tch. Chun Complexon 5.1. Phc cht. 5.1.1. nh ngha 5.1.2. Phn loi cc phc cht 5.1.3. bn ca phc cht 5.2. Thuc th hu c. 5.2.1. Cc phn ng ca thuc th hu c

41 41 41 43 43 43 44 44 45 45 45 52 52 53 53 53 58 62 64 66 69 70 71 71 71
72 74 77 80 86 86 88 92 98 99 100 100 100 100 102 106 106 107

161 5.2.2. c tnh ca thuc th hu c 5.2.3. C ch tng tc ca thuc th hu c 5.2.4. Mt vi loi thuc th hu c thng gp trong ha phn tch 5.3. ng dng ca phc cht v thuc th hu c trong ha phn tch. 5.3.1. Pht hin v xc nh ion 5.3.2. Che du 5.3.3. Thay i cng cc cht 5.3.4. Ha tan v tch 5.4. Chun to phc 5.4.1. Phng php thy ngn 5.4.2. Phng php xyanua 5.4.3. Phng php complexon Bi tp Ti liu tham kho Chng 6. Cn bng trong dung dch cha hp cht t tan. Phng php chun kt ta 6.1. Cn bng trong dung dch cha hp cht t tan. 6.1.1. iu kin to kt ta - Tch s tan. 6.1.2. Quan h gia tan v tch s tan. Cc yu t nh hng n tan. 6.1.3. Kt ta phn on. 6.1.4. Chuyn mt hp cht kh tan ny sang mt hp cht kh tan khc. 6.1.5. Ha tan kt ta. 6.1.6. L thuyt v cu to kt ta. 6.1.7. Cng kt v kt ta sau-nguyn nhn lm cho kt ta khng tinh khit 6.1.8. Vai tr ca cng kt trong phn tch. 6.1.9. Dung dch keo trong ha phn tch. 6.2. Phng php chun kt ta. 6.2.1. c im ca phng php. 6.2.2. ng nh phn trong phng php bc. 6.2.3. Cch xc nh im cui. Bi tp Ti liu tham kho Chng 7. Sai s trong phn tch nh lng ha hc 7.1. Mt s khi nim. 7.1.1. ng v lp 7.1.2. Sai s h thng 7.1.3. Sai s ngu nhin 7.2. nh gi sai s ca cc php o trc tip. 7.2.1. Gi tr trung bnh cng 7.2.2. Phng sai 7.2.3. chnh xc ca php o trc tip 7.2.4. S c ngha v cch ghi kt qu phn tch

107 109 111 111 111 112 112 112 113 113 113 118 118
119 119 119 120 124 126 128 130 131 134 135 136 136 137 139 143 145 146 146 146 146 147 147 147 148 149 150

162 Ti liu tham kho Ph lc Ti liu tham kho M c l c 152 153 158 159