Giao Trinh Hoa Phan Tich 8431

B gio dc v o to Trng i hc nng nghip H Ni --------------------------
Pgs.ts. NGUYN TRNG SN (Ch bin) Nguyn Th Hng Linh, Bi Th Vnh
Gio trnh
HO PHN TCH
Nm 2007
Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch1
Li ni u
Gio trnh Ho phn tch ny c bin son trn c s cng mn hc chnh thc dng cho khi ngnh Nng- Lm- Ng nghip c Trng i hc Nng nghip I duyt (Quyt nh Q 25/2004/Q-H1 ngy 14. 1. 2004). Gio trnh nhm cung cp cho sinh vin nhng kin thc c bn v Ho phn tch v dnh cho sinh vin khi Nng Lm Ng nghip. tip thu c nhng ni dung trnh by trong gio trnh, yu cu sinh vin phi c kin thc v ton hc cao cp, ton xc sut thng k, vt l hc, ho hc i cng, ho hc v c v ho hc hu c. D rt c gng cho gio trnh c nhiu thng tin, d c v d tip thu, song, khng th trnh khi nhng khim khuyt, chng ti rt mong nhn c nhng kin ng gp ca bn c v ng nghip khi ti bn gio trnh c hon thin hn. H Ni, 2006 Cc tc gi
Bng k hiu
K hiu A C D E E% e e% I Ind K K L l l M M M N p ppb ppm Q q T T% TKHH TKPT TK w Ting Vit hp th quang nng mt quang ng lng gam th in cc, hiu in th phn trm chit electron sai s phn trm cng nh sng ch th hng s cn bng hng s cn bng biu kin, hng s cn bng thc nghim phi t, ligand chiu di lt bc sng nh sng nng mol/lt (nng phn t gam) kim loi M khi lng mol phn t (phn t gam), khi lng mol ion (iongam), nng ng lng gam -lg mt phn t mt phn triu h s phn b t s phn b tch s tan truyn quang tinh khit ho hc tinh khit phn tch tinh khit khi lng
Mc lc
Li ni u Bng k hiu Chng I: Cc khi nim c bn ca Ho phn tch 1. Ho phn tch v vai tr ca n 2. Phn loi phng php phn tch 2.1. Phn loi theo bn cht ca phng php phn tch 2.2. Phn loi theo khi lng v lng cha ca cht phn tch trong mu 2.3. Chn la phng php phn tch 3. Cc bc c bn trong Ho phn tch 4. Ly mu v x l mu phn tch 4.1. Ly mu 4.2. Lp h s mu 4.3. Khong ho mu 5. Ho phn tch nh tnh 5.1. Phn tch nh tnh cc hp cht v c bng phng php ho hc 5.2. Phn tch nh tnh cc hp cht hu c bng phng php ho hc 5.3. Phn tch nh tnh cc hp cht bng phng php cng c 6. Ho phn tch nh lng 7. Dng c, thit b o v ho cht 7.1. Dng c thu tinh 7.2. Thit b o 7.3. Ho cht sch, nc ct 8. Mt s loi nng dung dch thng dng trong Ho phn tch Cu hi n tp, bi tp Chng II: Phn tch khi lng 1. Cc khi nim c bn trong phn tch khi lng 1.1. Phng php tch 1.2. Phng php chng ct hoc t chy 1.3. Phng php nhit phn 1.4. Phng php kt ta (Phng php phn tch khi lng kt ta) 2. Phng php phn tch khi lng kt ta 2.1. Yu cu ca dng kt ta 2.2. Yu cu ca dng cn 2.3. S gy bn kt ta 2.3. Mt s k thut trong phng php phn tch khi lng kt ta 2.4. Mt s ng dng c th 2.5. u nhc im ca phng php phn tch khi lng kt ta Cu hi n tp, bi tp Chng III: Phn tch th tch 1. Nhng khi nim c bn v phn tch th tch 2. Yu cu ca phn ng chun 3. Phn loi phng php chun 3.1. Phn loi phng php chun theo loi phn ng
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1 2 6 6 6 6 8 8 8 9 9 10 10 11 11 16 17 18 18 18 19 21 21 23 24 24 24 24 25 26 26 30 31 32 35 37 38 39 39 40 41 41
Trang 3.2. Phn loi phng php theo cch tin hnh chun 43 4. Cch pha dung dch tiu chun 45 5. Cch tnh kt qu phn tch 47 6. ng chun 48 6.1. nh ngha 48 6.2. ng chun trung ho 48 6.3. ng chun oxi ho kh 63 6.4. ng chun kt ta 67 6.5. ng chun to phc 70 6.6. Nhn xt chung v ng chun . ng dng ca ng chun 73 7. Ch th 74 7.1. Phn loi ch th 75 7.2. Khong i mu ca ch th 75 7.3. Nguyn tc chn ch th 77 8. Cc php chun thng dng 78 8.1. Chun trung ho 78 8.2. Chun oxi ho kh 79 8.3. Chun kt ta 83 8.4. Chun complexon 85 9. u nhc im ca phng php phn tch th tch 88 Cu hi n tp, bi tp 89 Chng IV: Phn tch cng c 91 1. Phn loi phng php 91 1.1. Nhm cc phng php quang hc 91 1.2. Nhm cc phng php in t 92 1.3. Nhm cc phng php tch 92 1.4. Nhm cc phng php nhit 92 2. Phng php quang ph hp th phn t vng t ngoi v nh sng nhn thy 92 2.1. C s l thuyt ca phng php so mu 93 2.2. Yu cu i vi phc cht mu 95 2.3. Ph hp th v chn bc sng o 97 2.4. o so mu 99 3. Phng php o in th 101 3.1. t vn 101 3.2. in cc 101 3.3. o in th 103 3.4. ng dng phng php o in th trong phn tch 104 4. Phng php chit 105 4.1. Khi nim 105 4.2. Chit cht rn bng cht lng 105 4.3. Chit cht lng bng cht lng 105 Cu hi n tp, bi tp 106 Chng V: Sai s trong Ho phn tch 108 1. Sai s 108 1.1. Phn loi sai s 108
1.2. Biu din kt qu phn tch v sai s 2. L thuyt v sai s 3. ng, chnh xc v tin cy ca kt qu phn tch 3.1. ng 3.2. chnh xc 3.3. tin cy 4. Tnh ton sai s h thng 4.1. Sai s h thng do s cn bng ca phn ng ho hc gy nn 4.2. Sai s h thng do ch th gy nn Cu hi n tp, bi tp Ti liu tham kho Cc bng ph lc
103 111 112 112 112 112 113 113 114 116 117 118
CHNG I CC KHI NIM C BN CA HO PHN TCH

1. HO PHN TCH V VAI TR CA N Ho phn tch l mn khoa hc ng dng s dng cc kin thc ca Ho v c, Ho hu c, Ho l, Ho sinh, Vt l... nhm tr li cu hi vt cht nghin cu c cu to t cc thnh phn no v hm lng ca tng thnh phn l bao nhiu. Ho phn tch c s dng t rt lu trong Ho hc ni chung. Song, phi t th k 17, vi nhng c s bt u t cc cng trnh ca R. Boyl v sau l ca M. V. Lomonosov, A. L. Lavoisier v R. Fresen, Ha phn tch mi tr thnh mt ngnh khoa hc ring bit. Trong nhng th k tip theo, cc nh khoa hc khng ngng pht trin ngnh hc ny theo hng phn tch nhanh hn, chnh xc hn, t ng ho hn v gi thnh r hn. Chnh v th, ngoi cc phng php phn tch ho hc thng thng, cc phng php phn tch bng cng c pht trin mnh m v tr thnh b phn khng th thiu ca phn tch hin i nh cc phng php: quang ph, sc k, cc ph Trong thc t, Ho phn tch thm nhp vo nhiu lnh vc khoa hc v l cng c nghin cu ca chng; ngoi ra, n cng chim mt v tr quan trng trong sn xut. Ho phn tch thng c chia thnh hai phn Ho phn tch nh tnh v Ho phn tch nh lng. Nhim v ca Ho phn tch nh tnh l xc nh vt cht nghin cu c cu to t cc thnh phn no, cn ca Ho phn tch nh lng l xc nh hm lng ca cc thnh phn cu to nn vt cht nghin cu. 2. PHN LOI PHNG PHP PHN TCH C nhiu phng php phn tch, tin cho s chn la, trong Ho phn tch, thng chia cc phng php phn tch theo hai cch: da trn bn cht ca phng php phn tch v hm lng cht cn phn tch cha trong mu.
2.1. Phn loi theo bn cht ca phng php phn tch

Khi phn tch, thng s dng cc tnh cht ho hc, tnh cht vt l v cc cng c o khc nhau tin hnh phn tch. Do , c cc phng php: phn tch ho hc, phn tch ho l, phn tch vt l, phn tch sinh ho Cc phng php ny c chia thnh 3 nhm chnh: - Phng php phn tch ho hc. - Phng php phn tch bng cng c. - Phng php phn tch sinh ho. Trong cc phng php phn tch ho hc v phn tch bng cng c l thng dng nht. a. Phng php phn tch ho hc Thng c gi ngn gn l phn tch ho hc, y, s dng cc phn ng ho hc thch hp phn tch cht cn xc nh. V d, khi xc nh Cl- dng phn ng: Cl- + AgNO3 = AgCl + NO3-, (trong mi trng axit HNO3) trng
S xut hin kt ta trng cho bit trong mu c ion clorua, cn khi lng kt ta cho bit hm lng ca ion clorua trong mu. Phn ng trn c gi l phn ng phn tch, dung dch AgNO3 c gi l dung dch thuc th. Phng php phn tch ho hc c u im: c chnh xc cao, dng c phn tch n gin. Tuy nhin, trong phn tch dng mt quan st cc hin tng xy ra, nn phng php c nhy khng cao, ch c th phn tch c cc cht khi hm lng ca n trong mu ln hn 10-2 % (bng B. I.1), ngoi ra khng th t ng ho c qu trnh phn tch. Trong nhm cc phng php ho hc c cc phng php: phng php phn tch khi lng (chng II) v phng php phn tch th tch (chng III). b. Phng php phn tch bng cng c Cn c gi ngn gn l phn tch cng c (chng IV). Gm cc phng php phn tch ho l v phn tch vt l. *Phng php ho l y, dng cc cng c o cc i lng vt l c lin quan n phn ng ho hc xy ra. V d: dng in cc bc o in th dung dch ca phn ng gia ion Cl- v AgNO3 ni trn, gip theo di c din bin ca phn ng Phng php ho l c nhy kh cao, cho php xc nh c cc mu vi hm lng ca cht phn tch nh ti 10-6 % (bng B.1.1). V d: phng php so mu, phng php cc ph * Phng php vt l y, s dng cc cng c o cc i lng vt l c lin quan n thnh phn cn phn tch. Phng php c nhy rt cao, cho php phn tch cc thnh phn rt nh trong mu, ch chim khong 10-8 - 10-9% (bng B.1.1). Bng B. 1.1: Gii hn xc nh ca mt s phng php phn tch Phng php
12
Hm lng cht cn phn tch (%) _____________________________________ 102 100 10-3 10-6 10-9 10------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Khi lng, chun Cc ph Quang ph pht x Quang ph ngn la Quang ph hp ph Quang ph hp ph nguyn t Quang ph hunh quang Quang ph khi Phn tch phng x
Vi phng php vt l c th ng thi xc nh nh tnh v nh lng nhiu cht (phng php cc ph, phng php quang ph rn ghen, quang ph pht x, quang ph hp th nguyn t, cc phng php sc k.) v i khi khng cn phi ph hu mu (phng php quang ph rn ghen, quang ph pht x). Phng php phn tch cng c c u im:
- C nhy cao nn c th dng phn tch mu vi khi lng nh hoc mu c cha lng nh thnh phn cn phn tch. - C kh nng t ng ha cao. Song, nhc im ca nhm phng php ny l my o rt t tin v chi ph vn hnh my o ln, hn ch phn no s ph cp ca chng.
2.2. Phn loi theo khi lng v lng cha ca cht phn tch trong mu
Da vo khi lng mu ly phn tch v lng cha ca cht phn tch trong mu, xy dng cc phng php ghi trong bng B.2.1. Bng B.2.1: Phn loi cc phng php phn tch theo lng mu phn tch Tn phng php Lng mu (g) Mi Gram Xentigram Miligram Microgram C Thng lng Bn vi lung Vi lng Siu vi lng 10-1 10-2 - 10-1 10-4 - 10-2 10-4 Lng cha cht phn tch (g) Thnh phn th lung Chnh Ph (1-100%) (0,01-1%) 10-3 10-5 -3 -1 10 - 10 10-5 - 10-3 10-6 - 10-2 10-8 - 10-4 10-4 10-6 Thnh phn vi lng 0,01% 10-5 10-5 10-5 10-5
2.3. Chn la phng php phn tch

Khi phn tch, tu theo yu cu v chnh xc, iu kin phng phn tch cng nh hm lng thnh phn cn phn tch c trong mu vt, khi lng mu vt cng nh ngng xc nh ca phng php m chn phng php thch hp. Nguyn tc chung: lng mu nhiu, hm lng ln dng phng php km nhy v ngc li lng mu t, hm lng b dng phng php c nhy cao. V d: phng php quang ph thch hp cho xc nh 10-6 - 10-8 gam cht cn phn tch, song, phng php chun thch hp cho vic xc nh cc hm lng c gam, xentigam cht. Vi cc mu cha cht cn phn tch vi lng qu nh i khi vn phi lm giu mu trc khi phn tch. 3. CC BC C BN TRONG HO PHN TCH Qu trnh phn tch bao gm 4 bc: 1 - Ly mu 2 - a phn cn phn tch v dng m qua c th tin hnh phn tch nh tnh hoc phn tch nh lng thng qua theo di mt s tnh cht vt l, ho hc thch hp. 3 - o xc nh 4 - Tnh ton kt qu.
Bc 1: Ly mu l vic lm rt quan trng, lm sao ly c mu i din cho vt cn phn tch (mc 4 chng I, trang 10), kt qu phn tch phn nh ng tnh cht ca mu. Bc 2: Bao gm cc cng on nh nh chuyn mu thnh dung dch (mc 4 chng I, trang 12), tch cc thnh phn gy nhiu, chuyn thnh phn cn xc nh sang dng m c th phn tch nh tnh hoc xc nh nh lng n. V d: xc nh ion Cu2+ di ng trong t, chit ion Cu2+ t t bng axit HNO3 1M ri tch ion Cu2+ di dng phc cht tan [Cu(NH3)4]2+, sau chuyn phc cht amo ng sang dng phc cht Cu dithizon (mu ) trong mi trng axit o xc nh bng phng php so mu. Bc 3: Chnh l o cc i lng vt l nh khi lng, th tch, cng mu, dn in (cc chng II, III, IV) c lin quan n tnh cht v hm lng ca thnh phn cn xc nh. V d: o cng mu ca phc mu Cu - dithizon ni trn. Bc 4: T cc gi tr o c ca i lng vt l cn theo di suy ra kt qu v nh tnh cng nh nh lng ca thnh phn cn phn tch. 4. LY MU V X L MU PHN TCH Mt nhim v quan trng khi tin hnh phn tch l ly mu v x l mu phn tch, nhng cng vic ny thng gy ra sai s, i khi sai s ny cn ln hn nhiu so vi sai s do phng php phn tch gy nn. Do , vic ly mu v x l mu cn tun th ng qui trnh v ng yu cu phn tch.
4.1. Ly mu
Trong phn tch, rt t khi c th phn tch ton b vt th cn nghin cu. V d: khi nghin cu tnh cht nng ho ca mt tha rung, thnh phn dinh dng ca mt kho thc n gia sc khng th mang phn tch ton b t ca tha rung hoc c kho thc n Do vy, kt qu phn tch c ngha thc tin cn tin hnh trn mu i din (mu trung bnh). Mu i din l mu cha thnh phn v t l hm lng ging nh vt th cn phn tch. Tuy nhin, kh c th ly c mu i din p ng yu cu trn m ch c th ly c mu c tnh cht gn ng vi yu cu m thi. Mu phn tch rt a dng v nhiu mt nh v trng thi tn ti, v ng nht, cng nh khi lng ca mu. V th, ly c mu i din cn tun th mt s nguyn tc ly mu cho tng loi i tng. * Vt th phn tch c khi lng nh: Vi vt th c khi lng nh, c th phn tch ton b, th mu ly l ton b vt th. V d: Vt mu, mu bnh phm nh nc di ca vt nui * Vt th ng tnh: L cc vt th m mi im thnh phn v hm lng ca cht cn phn tch l nh nhau. V d: vt th cn phn tch l ho cht sch, mu vt l dung dch Trong trng hp ny, c th ly mu bt c im no ca vt th. V d: khi phn tch hm lng axit HCl trong dung dch, c th dng pipet ht dung dch bt c v tr no trong bnh cha. * Vt th khng ng tnh: Khi vt th cn phn tch c khi lng ln v khng ng tnh, th vic ly mu da trn nguyn tc ly mu nhiu im ri trn li vi nhau c mu i din. Tuy nhin, vic ly nhiu hay t im ph thuc vo trng thi ca vt cn phn tch.
i vi cht kh, do tnh linh ng ln ca cc phn t cht kh, khi kh d ng nht ho trn ton b khng gian, nn c th ch cn ly mu mt im bt k. Trong trng hp ring bit, khng m bo tnh ng nht ca khi kh th ly mu nhiu im ri trn li, v d, khi ly mu nghin cu nh hng ca cht kh thi t ng khi l cao. i vi cht lng, do tnh linh ng ca cc phn t cht lng cng kh ln, nn khi ly mu ch cn ly mt s lng im mu va phi theo tng v theo khu vc ri trn li c mu i din. i vi cht rn, v nguyn tc chung phi ly mu nhiu im ri trn li, sao cho khi lng mu t yu cu. Mi im ly mt lng t nht phi bng 3 ln khi lng ca ht to nht v lng mu ly ch chim khong 1% khi lng ca ton b cc im trn li. Nu khi lng mu t cc im vt qu khi lng cn ly th dng k thut chia t gim bt. K thut chia t l: p hoc thi mu thnh cc ht nh, mnh nh, ri vun ng thnh khi hnh tr. Chia khi tr thnh 4 phn bng nhau, b i hai phn i din v trn u 2 phn cn li vi nhau. Nu phn cn li vn qu ln, tip tc s dng k thut chia t gim bt tip lng mu n khi c khi lng cn thit. Khi ly mu cn s dng ng cc dng c qui nh cho tng i tng mu. Mu phn tch sau khi ly xong cn c bo qun cn thn trong cc dng c ng mu trnh b nhim bi mi trng xung quanh. i khi phi phi, sy kh trc khi bo qun (v d: i vi mu sinh vt ti) hoc x l s b bng cc ho cht bo qun thch hp trnh s chuyn ho ca thnh phn cn phn tch (v d: khi phn tch ion Fe2+ trong t th mu phi bo qun trong axit HCl long ion Fe2+ khng b chuyn thnh ion Fe3+ di s tc ng ca oxi trong khng kh).
4.2. Lp h s mu
Sau khi ly xong, mu phn tch c chia t nht thnh hai phn: mt phn gi i phn tch, cc phn cn li c lu gi phng khi mu b hng, b tht lc trn ng vn chuyn hoc khi cn phn tch thm ch tiu hoc khi cn phn tch kim chng. Trn c hai phn ca mu cn lm h s y v nh nhau. Trn h s phi ghi r: tn mu, ngy ly mu, ngi ly mu, a im ly mu, cch ly mu, cch s ch mu (nu c) v mc ch ca vic ly mu ( phn tch ch tiu no). Vic lp h s cn chnh xc khng b nhm ln mu cng nh nhm ln kt qu phn tch. Cng vic ny cng quan trng i vi cc vt th cn phn tch theo thi gian. V d: khi nh gi cht lng ca mt ngun nc, phi phn tch nc theo ch thu vn v theo di trong nhiu nm, do vic c nh thi im, v tr v cch thc ly mu l rt quan trng trong vic so snh kt qu sau ny.
4.3. Khong ho mu
Khi phn tch, nht l vi cc mu rn, thng chuyn mu phn tch thnh dung dch. Cng vic ny c gi l khong ho mu hay cn gi l cng ph mu. Trong khong ho mu thng dng cc ho cht c tnh cht ho hc i khng vi tnh cht ho hc ca mu cn khong ho. Mu cha thnh phn ch yu l cc cht c tnh baz th dng cc axit mnh cng ph, v d, khong ho mu t dng axit H2SO4 c phi hp vi cc axit HClO4 v HF; mu c tnh kh nh mu thc vt dng cc cht c tnh oxi ho hay hn hp cc cht oxi ho nh H2SO4 + K2Cr2O7, H2SO4 + HNO3 hay NaOH + NaNO3
Trong khong ho mu cn c gng s dng cng t ho cht cng tt, ho cht cng n gin cng tt trnh lm bn mu do ho cht dng cng ph, gim s tn hi ca dng c cng nh trnh c hi cho ngi phn tch v cho mi trung. Do , khi khong ho thng chn cc ho cht theo tun t: H2O (ngui, nng), axit long, baz long, axit c hoc kim c, hn hp axit c vi cht oxi ho, hn hp kim c vi cht oxi ho Khi khong ho cn lu n ch tiu phn tch s dng ho cht khong ho v cch khong ho thch hp nhm khong ho mt phn hay hon ton cht cn phn tch. Trong phn tch cc i tng nng nghip, mc khong ho ph thuc vo ch tiu cn phn tch nh phn tch thnh phn d tiu hay tng sV d: xc nh mui tan trong t, dng nc ct chit mui ho tan; phn tch kali d tiu trong t dng dung dch amoni axetat 1M lm dung mi chit, nhng, phn tch kali tng s phi khong ho mu t bng cch un n vi hn hp 3 axit c H2SO4, HClO4 v HF. Thng dng hai phng php khong ho: khong ho t v khong ho kh. Khong ho t l cho dung dch ho cht tc ng ln mu nhit thng hoc un nng. Phng php ny c u im: ch dng cc dng c n gin, tc phn ng nhanh. Tuy vy, trong mt s trng hp, khong ho t khng thnh cng, v d, khong ho mu thc vt cha nhiu xenlulo. Khong ho kh l nung mu vi ho cht nhit xc nh ph hp vi tnh cht ca mu vt v ho cht khong ho. Phng php c s dng khi phng php khong ho t khng thnh cng, v d, khong ho mu thc vt cha nhiu xenlulo nh ni trn. Phng php ny c u im: trong mt lc cng ph c nhiu mu, nhng, tc phn ng chm v phi dng cc dng c chuyn dng iu chnh nhit khong ho. i khi phi phi hp c hai phng php khong ho chuyn ton b mu phn tch vo dung dch. Cng nh vic ly mu, vic khong ho mu c vai tr quyt nh n cht lng phn tch sau ny, nn khi khong ho cn phi tin hnh ng qui trnh dng cho tng i tng, tng ch tiu phn tch c th. 5. HO PHN TCH NH TNH Nhim v ca Ho phn tch nh tnh l xc nh cc thnh phn cht c trong mu phn tch nh: nguyn t, ion, nhm nguyn t hoc hp cht to nn vt cht hoc mu vt nghin cu. Ho phn tch nh tnh cn c gi l phn tch nh tnh. Phn tch c th c tin hnh bng s dng phng php ho hc hoc bng phng php cng c.
5.1. Phn tch nh tnh cc hp cht v c bng phng php ho hc

Trong phn tch nh tnh cc hp cht v c bng phng php ho hc, n nay, tn ti rt nhiu phng php, l phn tch theo h thng v phn tch ring. Phn tch theo h thng l chia cc ion cn phn tch thnh cc nhm bng cc thuc th c th c gi l thuc th nhm, ri dng cc ho cht c th c gi l thuc th chn lc tm tng ion trong mt nhm phn lp. Thuc th nhm l ho cht m trong iu kin xc nh ch c mt nhm cc ion phn ng. Thuc th chn lc l ho cht m trong iu kin c th ch c mt ion tham gia phn ng. V d: tch cc ion to kt ta clorua (gm cc cation Ag+, Pb2+, Hg22+) ra khi hn hp cc ion bng
thuc th nhm HCl 2M. Li tm ly kt ta, ri nh vo thuc th chn lc SnCl2 5%, nu kt ta chuyn sang mu en hoc xm, iu chng t c ion Hg22+ trong mu: = AgCl , Ag+ + Cltrng Pb2+ + 2Cl= PbCl2 , trng 2+ = Hg2Cl2 , Hg2 + 2Cl trng Hg2Cl2 + SnCl2 = 2Hg + SnCl4 en Trong phn tch cc cation, thng s dng hai h thng phn tch: h thng hidrosunphua (H2S), h thng axit-baz. im chung ca cc phng php phn tch theo h thng l phn tch c trin khai ln lt tng bc tch cc ion theo tng nhm bng cc thuc th nhm, t nhm u tin n nhm cui cng. Trong gio trnh ny, ch trnh by nguyn tc ca hai h thng phn tch: h thng hidrosunphua v h thng axit-baz. * H thng phn tch hidrosunphua Da trn tan ca cc mui sunphua, clorua, cacbonat v cc hydroxit, thuc th nhm l kh H2S hoc dung dch H2S bo ho v cc dung dch HCl, (NH4)2S v (NH4)2CO3. Cc cation kim loi c chia thnh 5 nhm: 1- Gm cc cation to kt ta sunphua trong mi trng axit vi thuc th nhm l dung dch H2S bo ho, song, cc kt ta ny khng tan trong amoni polysunphua (NH4)2Sx. Cc cation ny li c chia thnh 2 nhm nh: 1a- Gm cc cation: Ag(I), Pb(II), Hg2(II), Tl(I), to kt ta clorua. 1b- Gm cc cation: Hg(II), Cu(II), Cd (II), Bi(III), khng to kt ta clorua. 2- Nhm cc cation to kt ta sunphua trong mi trng axit vi thuc th nhm l dung dch H2S bo ho, song, cc kt ta ny tan trong (NH4)2Sx, to thnh cc phc cht tan, gm cc cation: As(III, V), Sb(III, V), Sn (II, IV), Mo(VI), V(V), Se(VI). 3- Gm cc cation khng to kt ta sunphua trong mi trng axit vi thuc th nhm l dung dch H2S bo ho cng nh kt ta clorua, ch to kt ta vi (NH4)2S hoc vi H2S trong mi trng kim. Cc kt ta ny gm hai loi: 3a- Kt ta sunphua ca cc cation: Fe(II, III), Ni(II), Co(II), Zn(II), Mn(II). 3b- Kt ta hidroxit ca cc cation: Al(III), Cr(III), Be(II). 4- Gm cc cation to kt ta cacbonat trong mi trng cha NH4Cl, (NH4)2CO3 nhng khng to kt ta vi cc thuc th nu trn, l cc ion Ca(II), Ba(II), Sr(II). 5- Gm cc cation khng to kt ta vi tt c cc thuc th nu trn, l cc ion Mg(II), Na(I), K(I), Rb(I), Cs(I) v NH4+. Phng php hidrosunphua c u im l kh n gin, tch v chng minh c nhiu cation vi chnh xc cao, song, c nhc im l s dng kh H2S c tnh c i vi ngi phn tch v mi trng. * H thng phn tch axit-baz Da trn tan ca cc mui clorua, sunphat v ca cc hidroxit trong mi trng d cht kim hoc d NH3, thuc th nhm l cc dung dch: HCl , H2SO4, NaOH v NH4OH. Cc cation kim loi c chia thnh 6 nhm: 1- Gm cc cation to kt ta clorua vi thuc th nhm l dung dch HCl, l cc ion: Ag(I), Pb(II), Hg2(II), Tl(I).
2- Gm cc cation to kt ta sunphat vi thuc th nhm l dung dch H2SO4, l cc ion: Ca(II), Ba(II), Sr(II). 3- Gm cc cation to kt ta hidroxit tan trong NaOH hoc KOH d, l cc cation lng tnh nh Be(II), Zn(II), Al(III), Sn(II, IV), Cr(III). 4- Gm cc cation to kt ta hidroxit khng tan trong NaOH hoc KOH d v NH4OH d, l cc ion Mg(II), Sc(III), Bi(III), Mn(II), Fe(II, III). 5- Gm cc cation to kt ta hidroxit tan trong NH4OH d, l cc ion Cu(II), Cd (II), Hg(II), Co(II), Ni(II). 6- Gm cc cation khng thuc cc nhm trn, l cc ion Li(I), Na(I), K(I), Rb(I), Cs(I) v NH4+. Phng php axit-baz c u im l kh n gin v t c, nhng, phng php ny km nhy hn phng php hidrosunphua. Trong phn tch cc anion cng tn ti nhiu h thng phn tch, nh h thng s dng mui tan ca cc ion Ba2+ v Ag+ lm thuc th nhm. Theo h thng ny cc anion c chia thnh 3 nhm: 1- Cc ion to kt ta vi ion Ba2+: SO42-, SO32-, SiO32-, PO43-, CO32- , F-, CrO42-, 3BO3 . 2- Cc ion to kt ta vi ion Ag+: Cl-, Br-. I-, CNS-, S2-, CN-, [Fe(CN)6]4-, [Fe(CN)6]3-. 3- Cc ion khng phn ng vi cc ion Ba2+ v Ag+: NO2-, NO3-, ClO4-, ClO3-, MnO4-. Tuy vy, trong phn tch cc i tng nng nghip thng ch gp cc ion SO42-, Cl-, NO3-, SiO32-, PO43-, CO32-, l cc ion d dng c chng minh bng phng php phn tch ring. Ngy nay, cc phng php phn tch cation v anion theo h thng ch cn c ngha s phm, t c s dng, m thay vo s dng phng php phn tch nh tnh ring. * Phng php phn tch nh tnh ring Phn tch cc cation theo h thng nu trn c u im l cc ho cht dng trong phn tch u n gin, ph bin. Song, vic phn tch tn nhiu thi gian, lng dung dch thuc th dng nhiu nn d gy s nhim bn mu phn tch bng tp cht trong ho cht dng lm thuc th, dn n cht lng phn tch c th khng m bo. Ngoi ra, phn tch theo h thng phi qua nhiu bc nn dung dch tm cc cation cc nhm cui b pha long qu nhiu gy kh khn cho phn tch nht l khi s dng cc phn ng c nhy khng cao. Ngy nay, vi s hiu bit v tnh cht ho hc ca cc nguyn t, cc hp cht v c cng vi s lng thuc th ngy cng nhiu v c chn lc cao v kt hp vi thc th rng khi phn tch mt s ion khng nht thit phi p dng hon ton qui trnh tch theo h thng, xy dng phng php phn tch t do hn, l s dng ti thiu cc phn ng tch ri dng thuc th chn lc tm thng ion trong mu, thuc th dng c th tu chn. Cch phn tch nh vy gi l phn tch nh tnh ring (gi ngn gn: phn tch ring), v vic phn tch tng ion l c lp vi nhau. Phng php phn tch ring cho tc phn tch cao v kt qu chnh xc, nht l khi phn tch cc dung dch long. Di y trnh by phng php phn tch ring thng dng trong phn tch mt s ion thng gp khi nghin cu cc i tng nng nghip.
+ Tm ion NH4+: Cho vo dung dch phn tch dung dch NaOH d, s xy ra phn ng: NH4+ + OH- = NH4OH Khi un nng dung dch NH4OH b phn hu: to NH4OH = NH3 + H2O Amoniac bay ln gp giy qu tm t s lm cho mu ca giy qu chuyn thnh mu xanh. C th tm ion NH4+ bng thuc th Nestler (K2HgI4). Hi NH3 bay ln tc dng vi thuc th cho kt ta nu: NH3 + 2K2HgI4 + 3KOH = [Hg2ONH2]I + 7I- + 2H2O nu + Tm ion K+: Chnh pH dung dch phn tch v gi tr 5 7. Cho vo dung dch thuc th natri cobantinitrit Na3[Co(NO2)6], nu c ion K+ trong dung dch xut hin kt ta mu vng: 2K+ + Na3[Co(NO2)6] = NaK2[Co(NO2)6] + 2Na+ vng + Khi c mt ion NH4 trong dung dch phn tch, phi ui hon ton n i trc khi phn tch ion K+ bng cch cho vo dung dch phn tch NaOH d v un nng. + Tm ion Na+: Trung ho dung dch phn tch v mi trng trung tnh ri cho vo dung dch vi git thuc th km uranylaxetat (Zn(UO2)3(CH3COO)8), nu c ion Na+ s hnh thnh kt ta mu vng: Na+ + Zn(UO2)3(CH3COO)8 + CH3COO- = Na Zn(UO2)3(CH3COO)9 vng C th nhn bit ion K+, Na+ bng cch quan st mu ngn la ca chng. Nhng mt dy Pt sch vo dung dch phn tch ri t n trn ngn la khng mu, nu c ion K+ s thy ngn la pht mu tm, cn nu c ion Na+ s thy ngn la mu vng. Nu cng c c hai ion Na+ v K+, th mu vng s che lp mu tm v nn nhn thy mu tm cn nhn n qua knh mu chm. + Tm ion Mg2+: Cho vo dung dch phn tch cc dung dch (NH4)2CO3 v (NH4)2S kt ta tt c cc ion kim loi tr cc ion kim loi kim, NH4+ v Mg2+. Tm ion Mg2+ trong dung dch lc bng thuc th Na2HPO4 trong mi trng c NH4Cl v NH4OH: Mg2+ + Na2HPO4 + NH4OH = MgNH4PO4 + 2Na+ + H2O trng 3Nu mu cha ion PO4 th phi tch b n bng cch cho vo dung dch phn tch mui Al(NO3)3 trc khi lm kt ta mu bng (NH4)2CO3 v (NH4)2S. + Tm ion Ca2+: Cho vo dung dch phn tch dung dch K2SO4 6% kt ta cc ion Ba2+, Sr2+ (ion Ca2+ trong iu kin ny hu nh cha b kt ta). Lc tch kt ta, iu chnh pH dung dch v pH = 4 bng dung dch m axetat v cho vo mt th tch tng ng ca dinatri etylendiamintetraaxetat (Na2EDTA) 10% che cc ion gy nhiu. Sau ,
cho vo dung dch Al(CH3COO)3 d che Na2EDTA v tm ion Ca2+ trong dung dch bng (NH4)2C2O4: Ca2+ + (NH4)2C2O4 = CaC2O4 + 2NH4+ trng + Tm ion Ba2+: Cho vo dung dch trung tnh cn phn tch tun t cc dung dch Na2EDTA 10% (ly d, che cc ion kim loi nng) v Mg(CH3COO)2 (ly d, che Na2EDTA d). Sau , cho vo dung dch thuc th K2Cr2O7 v dung dch CH3COONa, nu c ion Ba2+ s xut hin kt ta mu vng BaCrO4: K2Cr2O7 + 2OH- = 2CrO42- + 2K+ + H2O Ba2+ + K2CrO4 = BaCrO4 + 2K+ vng + Tm ion Mn2+: Cho vo dung dch phn tch dung dch K2S2O8, axit HNO3 v xc tc AgNO3. un nng dung dch, nu dung dch chuyn sang mu tm, th trong mu c ion Mn2+: 2Mn2+ + 5S2O82- + 8H2O = 2MnO4- + 10SO42- + 16H+ tm S gy nhiu ca ion Cl- c kh bng cch cho thm vo dung dch phn tch dung dch AgNO3. S gy nhiu ca ion Fe3+ nng cao (mu vng ca ion Fe3+) c kh bng s to phc cht khng mu [Fe(PO4)2 ]3- vi vic cho H3PO4 vo mu phn tch. + Tm ion Fe3+: Cho vo dung dch phn tch dung dch NaOH v NH4OH d. Tch kt ta hnh thnh v ho tan n bng dung dch HCl, ri tm ion Fe3+ bng cc phn ng vi thuc th KCNS hay K4[Fe(CN)6]: Fe3+ + 6KCNS = [Fe(CNS)6]3- + 6K+ mu 3+ 4Fe + 3K4[Fe(CN)6] = Fe4[Fe(CN)6]3 + 12K+ xanh Berlin 2+ + Tm ion Cu : Cho vo dung dch phn tch NH4OH c d v un n si. Dung dch thu c c trung ho bng axit CH3COOH n khi mt mu hng ca phenoltalein, ri cho vo thuc th K4[Fe(CN)6]. Nu xut hin kt ta mu nu chng t dung dch cha ion Cu2+ (vi hm lng Cu2+ nh ch nhn thy dung dch mu hng): 2Cu2+ + K4[Fe(CN)6] = Cu2[Fe(CN)6] + 4K+ nu + Tm ion Hg2+: Cho vo dung dch phn tch axit HCl kt ta cc ion Hg22+, Ag+ v Pb2+. Dng CH3COONa chnh pH dung dch v pH = 5 v cho vo dung dch SnCl2. Nu c ion Hg2+, s xut hin kt ta en: = Hg + Sn4+ Hg2+ + Sn2+ en + Tm ion SO42-: Axit ho dung dch phn tch bng HNO3 long (nu c kt ta th lc b), thm t t vo vi git Ba(NO3)2. Dung dch cha ion SO42- s cho kt ta trng: Ba2+ + SO42- = BaSO4
trng + Tm ion Cl : Axit ha dung dch phn tch bng axit HNO3 (nu xut hin kt ta th lc b), cho tip vi git dung dch AgNO3. Nu c kt ta hnh thnh chng t mu c th cha cc ion Cl-, Br-, I- (X-): AgNO3 + X- = AgX + NO3Li tm ly kt ta v cho vo hn hp gm 4 phn (NH4)2CO3 bo ho + 1 phn NH4OH (6M), th AgCl s tan ra: AgCl + 2NH4OH = [Ag(NH3)2]+ + 2H2O + ClTch dung dch ra khi kt ta v cho vo HNO3, nu xut hin kt ta chng t c ion Ag+ : [Ag(NH3)2]Cl + 2HNO3 = AgCl + 2NH4NO3 trng gin tip chng minh s tn ti ca ion Cl-. + Tm ion NO3-: Cho vo dung dch phn tch dung dch FeSO4 d ri thm t t tng git H2SO4 c theo thnh ng nghim. Nu c ion NO3- th b mt tip xc gia hai lp dung dch v H2SO4 c s c mt vnh mu nu: 2HNO3 + 8FeSO4 + 3H2SO4 = 3Fe2(SO4)3 + 2FeNOSO4 + 4H2O nu 3+ Tm ion PO4 : Cho vo dung dch phn tch axit HNO3 d lm mi trng, ri thm vo thuc th amoni molypdat, nu c ion PO43- s xut hin kt ta mu vng (khi lng ion PO43- t, ch nhn c dung dch mu vng): PO43- + 3NH4+ + 12MoO42- + 24H+ = (NH4)3[P(Mo3O10)4] + 12H2O vng 2+ Tm ion CO3 : Cho vo dung dch phn tch mui Hg(II) v KMnO4 loi b cc gc mui ca cc axit d bay hi khc. Sau , axit ho dung dch bng axit H2SO4 (1: 4) v dn kh CO2 thot ra vo dung dch Ba(OH)2 , nu c CO2 s to thnh kt ta mu trng BaCO3 : CO32- + H2SO4 = CO2 + H2O + SO42CO2 + Ba(OH)2 = BaCO3 + H2O trng
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5.2. Phn tch nh tnh cc hp cht hu c bng phng php ho hc

Nhim v ca phn tch nh tnh cc hp cht hu c l xc nh s tn ti ca mt cht c th do cn phn tch nh tnh cc nguyn t, cc nhm chc cu to nn hp cht hu c hoc phn tch xc nh c cng thc cu to phn t ca hp cht hu c. C 3 phng php trong phn tch nh tnh cc hp cht hu c: phn tch nguyn t, phn tch cu to v phn tch phn t. a. Phn tch nh tnh cc nguyn t trong hp cht hu c * Phn tch C v H Nung hn hp cht phn tch vi CuO trong ng nghim thu tinh chu nhit. Trong trng hp ny, C b t chy thnh kh CO2, dn kh ny sang bnh ng Ba(OH)2, nu c CO2 bnh s b vn c; H b t chy thnh nc, hi nc bay ln to
thnh cc git sng bm ln thnh ng nghim. khng nh chc chn l nc, c th rc ln cc git sng bt CuSO4 khan, nu l nc, mu trng ca CuSO4 khan chuyn thnh mu xanh ca CuSO4.5H2O. * Phn tch N, S v halogen Nung chy cht cn phn tch vi kim loi Na hoc K, ri ho tan vo nc. Trong trng hp ny N chuyn thnh ion CN-, S thnh ion S2-, halogen thnh cc ion halogenua. - Chng minh ion CN-: Cho vo dung dch phn tch dung dch FeSO4, sau cho thm vi git dung dch ion Fe3+. Nu c ion CN-, trong dung dch xut hin kt ta mu xanh: 6CN- + Fe2+ = [Fe(CN)6]4Fe3+ + 3 K4[Fe(CN)6] = KFe[Fe(CN)6] xanh Berlin - Chng minh ion S2-: Cho vo dung dch phn tch dung dch Pb(NO3)2, nu c ion S2-, trong dung dch xut hin kt ta en hoc nu en: S2- + Pb(NO3)2 = PbS + 2NO3en
- Chng minh ion Cl-: Tin hnh tm ion Cl- nh mc 5.1 chng I trnh by trn. * Phn tch P Mu phn tch c khong ho bng hn hp axit H2SO4 c v K2Cr2O7. Axit H3PO4 hnh thnh c chng minh nh trnh by mc 5.1 chng I. b. Phn tch cu to cc hp cht hu c Cu to ca cc hp cht hu c quyt nh tnh cht ca chng, do c th s dng cc tnh cht ny xc nh cu to ca cc hp cht hu c. Thng s dng tnh tan ca cc hp cht hu c trong cc dung mi khc nhau, phn ng ca cc nhm chc v phn ng ca cc mch cacbon. * S dng tnh tan: Cu to khc nhau ca cc cht hu c dn n s tan khc nhau ca chng trong cc dung mi khc nhau. Cc dung mi c s dng l: nc, ete, dung dch NaOH long, dung dch NaHCO3, dung dch HCl long, H2SO4 c ngui. Bng vic s dng tnh tan ny c th chia cc hp cht hu c thnh 8 nhm. * S dng phn ng ca nhm chc: y, cng tn ti phn ng nhm vi thuc th nhm v phn ng chn lc (hay cn gi l phn ng phn loi) vi thuc th chn lc (hay cn gi l thuc th phn loi). V d: Thuc th phenylhidrazin to cc hp cht phenylhidrazon vi cc hp cht c nhm chc cacbonyl >C=O, do , phenylhidrazin l thuc th nhm cho cc hp cht cha nhm cacbonyl. Cc hp cht ru, phenol u phn ng vi kim loi Na, nn c th ni Na l thuc th nhm ca cc cht ny. Song, phenol c th tham gia cc phn ng th, v d, vi axit nitric to thnh cc sn phm nitro c mu vng, do , trong trng hp ny c th ni axit nitric l thuc th chn lc ca cc hp cht nhm phenol.
c. Phn tch phn t cc hp cht hu c Phng php phn tch ny da trn tnh cht vt l ca cht cn phn tch. Mi mt cht hu c u c c trng bi cc hng s vt l nh: im tan, im si, khi lng ring, h s chit quang, quay quang Theo di cc i lng ny cho php khng nh s tn ti ca mt c th no hoc xc nh sch ca chng.
5.3. Phn tch nh tnh cc hp cht bng phng php cng c

Bng cc cng c o, l cc my o hin i, c th cng mt lc pht hin nhiu ion, hp cht da trn vic theo di cc hin tng vt l gn vi cht cn phn tch nh: s pht x, s hp th nh sng ca ion, hp cht cn phn tch (quang ph pht x, quang ph hp th), s kh hoc oxi ho ca ion cn tm trn in cc (phng php cc ph, phng php von - ampe) V d: - Tm ion Na+, c th dng phng php quang k ngn la (thuc nhm phng php quang ph pht x), nh sng mu vng do nguyn t Na pht ra trong ngn la c bc sng 589nm (5890Ao), nu my o quang k ngn la c tn hiu bc sng ny chng t c ion Na+. - Tm cc hp cht hu c c th s dng quang ph hng ngoi vng tn s 700 1400cm-1, , mi cht hu c c ph c trng ca mnh cho php khng nh l cht no. Trong khun kh gio trnh ny, khng th trnh by nhiu v nhm phng php cng c. c gi c quan tm su hn, xin c cc gio trnh hoc sch vit ring v lnh vc ny. 6. HO PHN TCH NH LNG Nhim v ca Ho phn tch nh lng l xc nh hm lng ca cc thnh phn to nn mu phn tch. y l phn chnh ca gio trnh ny v c trnh by trong cc chng II, III v IV. Vic phn chia Ho phn tch thnh hai phn Ho phn tch nh tnh v Ho phn tch nh lng ch mang tnh cht kinh in v tnh s phm, v chng c quan h mt thit vi nhau. lm tt phn tch nh lng mu vt cn phi bit thnh phn nh tnh ca n th mi chn c phng php phn tch ti u. V d: khi phn tch nh lng ion Cl- c th dng phng php chun trc tip theo Mo, song, khi c mt ca cc ion CO32-, PO43- phi dng phng php chun gin tip theo Fonha (mc 8.3 chng III). Cn kt qu ca phn tch nh lng li khng nh kt qu ca phn tch nh tnh hoc thnh phn nh tnh. V d: khi ni trong mu c cha 16,2% Al2O3 tc bao hm c yu t nh tnh l mu cha Al2O3. Tuy vy, ngy nay, vi trang thit b phn tch ngy cng hon thin cho php phn tch ng thi c nh tnh v nh lng mt mu nghin cu, cng vi phng php phn tch ngy cng hon chnh, phn tch nh tnh trong nhiu trng hp tr nn khng cn thit. V d: th nghim phn tch Na nu trn (mc 5.3 chng I), khi s dng phng php quang ph pht x, bc sng nh sng pht x 589nm cho bit l nguyn t Na (yu t nh tnh), cn cng ca sng ny cho bit hm lng ca n
(yu t nh lng); nh vy khi phn tch ch cn chnh bc sng ca my o v gi tr 589nm th cng nh sng o c s phn nh hm lng Na trong mu. 7. DNG C, THIT B O V HO CHT Trong phn tch thng s dng kh nhiu cc loi dng c, cng c khc nhau dng cha dung dch, o th tch dung dch, cn khi lng ho cht, o cc i lng vt l ca h phn tch Di y l mt s dng c, cng c c bn thng c dng trong Ho phn tch.
7.1. Dng c thu tinh

Cc dng c thu tinh dng trong phn tch phi lm t thu tinh chu nhit v chu ho cht hoc tt nht t thu tinh thch anh (tuy nhin thu tinh thch anh rt t tin). Ngy nay, mt s dng c thu tinh c th c thay bng nha tng hp chu nhit v khng b ho cht n mn nh l nha teflon. Ngoi dng c lm t thu tinh cn c cc dng c lm t kim loi chu n mn nh Pt, Ni hoc lm t gm. Nu dng dng c bng gm cn lm mu trng kim tra kh nng s dng ca n. Nhng dng c nh bnh nh mc, buret, pipet dng o chnh xc th tch dung dch. Nhng dng c khc nh ng ong, cc chia ch dng o gn ng th tch. * Bnh nh mc: Bnh nh mc l bnh c th tch xc nh chnh xc, c dng pha dung dch tiu chun. Bnh nh mc c dng hnh cu, y bng, c nh, c nt mi, s o th tch c ghi trn thn bnh (hnh H.1.1). Khi s dng cn kim tra th tch ca bnh, nhit xc nh th tch v vch xc nh th tch (trn c bnh). Khng c un nng bnh nh mc, nu cn ho tan bng nc nng th phi un ring v sau khi pha cn ch cho dung dch ngui n nhit phng ri mi rt vo bnh v nh mc n vch. * Buret Buret l dng c o chnh xc th tch dung dch tiu tn trong qu trnh chun . Buret c dng ng hnh tr c chia vch xc nh th tch, phn cui c van kho (hnh H.2.1). Buret thng thng c cc loi vi th tch 10, 25, 50ml c chia vch n 0,1ml, th tch ca mt git khong 0,02 - 0,03ml. Microburet c th tch t 1 - 5 ml, c chia vch n 0,02 hoc 0,01ml. Th tch ca mt git ph thuc vo tit din u mao qun ca buret, tit din cng nh th tch git cng nh. Buret c dng trong chun hoc c dng ly chnh xc mt th tch dung dch. Khi c kt qu trn buret phi tm mt ngang vi mt thong ca dung dch, trnh nhn t trn xung di hoc t di ln. Thng thng, vi dung dch khng c mu, c vch xc nh th tch l vch trng vi y mt thong ca dung dch trong buret; vi dung dch mu, nn c vch xc nh th tch l vch trng vi bin trn ca mt thong dung dch trong buret. Sau khi kt thc chun , ch khong 30 giy mi c kt qu trnh sai s do phn dung dch bm trn thnh buret to nn. * Pipet Pipet l dng c ly th tch chnh xc dung dch. Pipet thng thng c 2 loi: - Loi hnh ng c chia vch (hnh H.3a.1), loi ny cho php ly mt th tch dung dch tu .
- Loi hnh bu (hnh H.3b.1), loi ny ch cho ly chnh xc th tch dung dch theo nh dung tch ghi trn pipet khi ly trn c bu. Trong phn tch th tch thng dng pipet bu ly trn mt th tch dung dch ch khng dng pipet thng v pipet bu c tit din phn vch c nh hn nn sai s c nh hn. Pipet cn c thnh 3 loi A, B, C theo chnh xc ca vch chia , trong k hiu A c chnh xc cao nht, k hiu C c chnh xc thp nht. Trong Ho phn tch, ch dng pipet c k hiu A. Khi s dng pipet cn lu : - V sai s khi ly trn th tch ca cc loi pipet l nh nhau nn ly pipet tng ng ht lng dung dch cn thit. V d: cn ly 3 - 5ml dung dch dng pipet 5ml, ly 6 - 10ml dung dch dng pipet 10ml. Trnh ht nhiu ln, sai s ly dung dch l nh nht. - Bao gi cng ly dung dch t vch xut pht. * ng ong v cc chia Sai s ca cc dng c ny l rt ln vt qu sai s phn tch cho php nn khng dng chng ly th tch chnh xc dung dch, ch dng ly th tch gn ng.
7.2. Thit b o
a. Cn Trong Ho phn tch, s dng cc loi cn c chnh xc khc nhau, v d: cn k thut vi sai s cn 0,01g, 0,001g, cn phn tch vi sai s cn 0,0001g (dng cho phn tch thng thng), 0,00001g (dng cho phn tch bn vi lng), 0,000001g (dng cho phn tch vi lng) v vi cc gii hn khi lng c cn khc nhau. Tu theo mc ch m s dng cn thch hp. Nguyn tc chung l: - c k hng dn s dng cn v gii hn ti a ca khi lng c cn, m bo sai s cn v an ton ca cn. - Khi cn cn xc nh lng ti thiu cn cn m bo sai s cn khng ln hn sai s phn tch cho php. V d: vi sai s phn tch 0,1%, cn phi cn bao nhiu mg mu trn cn phn tch 0,0001g, sai s cn khng vt qu sai s cho php? Gii: Khi cn phi cn hai ln: cn b v cn b cng vi khi lng phi cn a, nn mc hai ln sai s cn. Theo nguyn tc tnh sai s (mc 2 chng V), sai s tng i e% = [(2. sai s cn)/a ].100, suy ra: a = 2.0,1. 100: 0,1 = 200mg. Vy phi cn t nht 200mg mu.
Hnh H.1.1 Bnh nh mc
Hnh H.2.1 Buret
Hnh H.3a.1 Pipet thng
Hnh H.3b.1 Pipet bu
Hnh H.4.1 ng ong
- Khi cn cn chnh xc nhng ho cht nh l cht gc pha dung dch tiu chun hoc ho cht l dng cn trong phn tch khi lng, dng cn phn tch. V d: khi cn H2C2O4.2H2O tinh khit phn tch l cht gc pha dung dch tiu chun gc, BaSO4 l dng cn trong phn tch xc nh ion SO42- - Khi khng cn cn chnh xc, nh khi cn nhng ho cht d bay hi, d ht m, d phn hu, dng cn k thut. V d: khi cn NaOH b. Cc my o Nh my o so mu, my o pH, cn thao tc ng theo ti liu hng dn s dng my.
7.3. Ho cht tinh khit, nc ct

a. Ho cht tinh khit Trong cng nghip ho cht, tu theo mc ch s dng, ho cht sn xut ra c cc mc tinh khit khc nhau. C 4 mc tinh khit: tinh khit ho hc (TKHH) ( tinh khit 99,9%, tinh khit phn tch (TKPT) ( tinh khit = 99,9%), tinh khit (TK) ( tinh khit = 95%) v k thut (KT) ( tinh khit 80 85%). Trong phn tch thng lng dng ho cht c tinh khit TKPT, trong phn tch vi lng v siu vi lng dng ho cht c tinh khit TKHH. Nhiu khi ngi phn tch phi t tinh ch ly ho cht bng cch kt tinh li ho cht hoc chng ct li ho cht t ho cht tinh khit. Mt nguyn tc cn lu l: nu cn tinh khit TKPT phi i t ho cht tinh khit, dng nc ct v cc ho cht ph c tinh khit TKPT, nu cn tinh khit TKHH phi i t ho cht c tinh khit TKPT, nc ct phi l nc ct hai ln, cc ho cht ph phi c tinh khit TKHH, cc dng c phi lm t thu tinh thch anh hoc cc kim loi tr nh Pt, Au. b. Nc tinh khit v ct nc * Nc tinh khit:
Gm hai loi nc sch khong v nc ct. Nc sch khong c tinh ch t nc sch dn dng bng phng php trao i ion. Nc ct l nc tinh khit c tinh ch bng vic ct nc sch dn dng. Nc tinh khit cng c cc mc tinh khit tng t nh ho cht. Trong Ho phn tch ch dng nc c tinh khit TKPT hoc TKHH. Khi phn tch thng lng, dng nc c tinh khit TKPT. Nc ny c th t c bng cch ct 1 ln nc thng (nc dn dng) hoc dng phng php trao i ion lm sch nc thng. Khi phn tch vi lng, dng nc c tinh khit TKHH. Nc ny c th t c bng cch ct li nc ct 1 ln hoc nc sch khong, v th nc thu c cn gi l nc ct 2 ln, nc ny c tinh khit TKHH. * Ct nc: - Nc ct 1 ln: Dng b ct lm t thu tinh thng, trc khi ct cho thm 0,025g KMnO4 v 2 ml H2SO4 c 95% cho 1 lt nc. Khi ct b 20 ml nc ban u cho 1 lt nc em ct. - Nc ct 2 ln: Dng b ct lm bng thu tinh thch anh, hoc b ct lm t bc, platin. Nc ct l nc ct 1 ln hoc nc qua trao i ion. (Lu , nc ct hai ln khng phi l nc thu c khi ct hai ln trn b ct bng thu tinh thng, v trong thu tinh thng c nhiu cc hp cht ho hc khc nhau tan c trong nc nng). 8. MT S LOI NNG DUNG DCH THNG DNG TRONG HO PHN TCH Trong Ho phn tch thng dng cc nng mol/lt, nng ng lng gam, nng phn trm, nng phn triu, nng phn t v cc dung dch vi cc chun khc nhau. * Nng mol/lt: L s mol cht tan c trong mt lt dung dch. Nng ny cn c gi l nng phn t gam v c k hiu l M. Nng mol/lt c tnh theo biu thc I-1: M = w/(M.V) (I-1) Trong : w- khi lng cht tan (g), M- khi lng mol phn t (phn t gam) cht tan (g/mol), V- th tch dung dch (l). Nng mol/lt c dng biu din kt qu phn tch. Ngoi ra, n cn c s dng trong tnh ton cc hng s cn bng hoc cc i lng c lin quan n hng s cn bng phn ng. Nng mol/lt cng c dng th hin nng ca cc dung dch lm mi trng trong cc phn ng ho hc. * Nng ng lng gam: L s ng lng gam cht tan c trong mt lt dung dch v c k hiu l N. Nng ng lng gam c tnh theo biu thc I- 2: N = w/(.V) (I- 2) Trong : w- khi lng cht tan (g), - ng lng gam cht tan (g/mol ), V- th tch dung dch (l). Nng ng lng gam c dng biu din kt qu phn tch trong phn tch th tch.
Trong mt phn ng ho hc c th, mi quan h gia hai nng mol/lt v nng ng lng gam c th hin bng biu thc I- 3: N = n.M (I- 3) y, n l tr s (ch s) ng lng, n cho bit mt phn t cht tham gia phn ng tng ng vi bao nhiu ng lng cht . V d: vi phn ng: H2SO4 + 2NaOH = Na2SO4 + 2H2O , n ca H2SO4 bng 2, cn ca NaOH bng 1. * Nng phn trm: L s phn khi lng cht tan c trong 100 phn khi lng dung dch. Nng ny c k hiu l % v c tnh theo biu thc I- 4: (I% = [wcht tan/( wcht tan + wdung mi)].100 4) Trong : wcht tan - khi lng cht tan (g), wdung mi - khi lng ca dung mi (g). Nng phn trm c dng biu din kt qu phn tch. Ngoi ra, n cn c dng th hin nng ca cc dung dch lm mi trng trong cc phn ng ho hc. * Nng phn triu (ppm part per million) v nng phn t (ppb part per bimillion): Tng t nh nng phn trm, nng phn triu l s phn khi lng cht tan c trong mt triu phn khi lng dung dch v nng phn t l s phn khi lng cht tan trong mt t phn khi lng dung dch. Cc nng ny c tnh nh sau: ppm = [wcht tan/(wcht tan + wdung mi)].106 ppb = [wcht tan/(wcht tan + wdung mi)].109 Trong : wcht tan - khi lng cht tan (g), wdung mi - khi lng ca dung mi (g). Song, do phn cht tan qu b so vi phn dung mi, nn c th tnh gn ng: ppm = [wcht tan/wdung mi].106 (I5) (Ippb = [wcht tan/wdung mi].109 6) Trong : wcht tan - khi lng cht tan (g), wdung mi - khi lng ca dung mi (g). Nng ppm v ppb thng c dng biu din nng ca cc dung dch chun cng nh kt qu phn tch i vi cc lng cha rt nh mc vi lng hoc siu vi lng. * chun: C nhiu loi chun khc nhau nh mg/ml, g/ml l cc nng c biu din bng s mg hoc s g cht tan c trong mt ml dung dch. Cc loi nng ny c dng biu din nng ca cc dung dch chun cng nh kt qu phn tch.
Cu hi n tp
1. Nhim v ca Ho phn tch? Ho phn tch nh tnh v nh lng l g? Quan h ca hai lnh vc ny.
2. Mu i din l g? Nguyn tc ly mu i din? 3. Ni dung v ngha ca vic lp h s mu? 4. Nguyn tc ca vic khong ho mu? 5. Cc phng php khong ho mu? 7. Phng php hidrosunphua v phng php axit baz trong phn tch nh tnh cc cation l g? 8. Cch phn tch nh tnh cc anion theo nhm? 9. Phn tch nh tnh ring l g? So snh phng php ny vi cc phng php phn tch theo h thng? 10. Phn tch nh tnh ring ca mt s cation? anion? 11. Phn loi ho cht, nc theo tinh khit? 12. Cch s dng cc dng c, thit b thng gp trong Ho phn tch! 13. Cc loi nng thng dng trong Ho phn tch v cch pha chng?
Bi tp
1. Ly chnh xc 100ml dung dch 0,2M H2SO4 cho vo bnh nh mc 250ml v in nc ct ti vch. Hy tnh nng ng lng gam ca dung dch mi nhn c v s gam H2SO4 c trong 100ml dung dch ny! (p s: 0,16N; 0,7846g). 2. Dung dch NH3 m c c nng 26% (d = 0,904). Dung dch ny c nng mol/lt l bao nhiu? Nu ly 100 ml dung dch ny pha thnh dung dch NH3 1N th th tch dung dch sau khi pha long l bao nhiu ml? (p s:13,8M; 1380ml). 3. Trn 500ml HCl 0,1N vi 250ml HCl 0,2N. Dung dch thu c c nng ng lng gam l bao nhiu? (p s: 0,133N). 4. Trn 500ml HCl c pH = 1 vi 250ml HCl c pH = 2. Dung dch thu c c nng mol/lt l bao nhiu? (p s: 0,07M). 5. Cn cn bao nhiu mg CuSO4.5H2O pha 100 ml dung dch 1000ppm Cu? (p s: 390,6 mg). 6. Ha tan 100mg CaCO3 bng axit HCl thnh 100ml dung dch. Nng ppm ca ion Ca2+ l bao nhiu? (p s: 400ppm). 7. Cn ly bao nhiu ml dung dch Cd2+ 5ppm pha thnh 100ml dung dch Cd2+ 500ppb? (p s: 10ml).
Chng II PHN TCH KHI LNG

1. CC KHI NIM C BN TRONG PHN TCH KHI LNG y l phng php c lch s lu i nht trong cc phng php phn tch nh lng. Phng php ny da trn khi lng cn chnh xc ca sn phm sch, c cng thc ho hc xc nh cha nguyn t, ion, hoc thnh phn cn phn tch c tch ra sau khi chuyn ho chng bng cc phn ng thch hp, t tnh ra lng cht cn phn tch c trong mu. V d: khi phn tch ion Fe3+ trong dung dch, lm kt ta n di dng Fe(OH)3 bng dung dch NH4OH. Lc ly kt ta v ra sch. Nung kt ta nhit 1000oC n khi lng khng i, nhm chuyn kt ta thnh Fe2O3. ngui mu nung n nhit phng, ri cn khi lng ca n bng cn phn tch. T khi lng cn tnh ra khi lng ion Fe3+. Da trn cch tin hnh khc nhau, c th chia cc phng php phn tch khi lng thnh 4 nhm phng php chnh sau: + Phng php tch + Phng php chng ct hoc t chy + Phng php nhit phn + Phng php kt ta
1.1. Phng php tch

Trong phng php ny, thnh phn cn xc nh c tch ra trng thi t do, ra sch, lm kh v cn bng cn phn tch. V d: xc nh Au trong cc hp kim Au Cu, ho tan mt lng hp kim trong nc cng thu (HNO3 c + HCl c). Dung dch thu c cho tc dng vi hidropeoxit, ion Au3+ s b kh n trng thi Au t do v tch ra khi dung dch, cn ion Cu2+ khng phn ng: 2Au3+ + 3H2O2 = = 2Au + 6H+ + 3O2 Sau khi ra sch, lm kh, lng Au c cn bng cn phn tch v t lng cn suy ra hm lng Au c trong hp kim. Phng php tch thng c dng trong cc ngnh sn xut cng nghip, trong phn tch i tng nng nghip n t c dng.
1.2. Phng php chng ct hoc t chy

Trong phng php ny, thnh phn cn xc nh c tch ra th kh bng nhng phn ng ho hc thch hp (phn ng phn hu, phn ng t chy), sau cc cht kh thot ra c ct v c hp ph vo bnh hp ph. T s tng khi lng ca bnh hp ph suy ra hm lng cht cn phn tch. V d 1: Xc nh CO2 trong vi. Da vo phn ng phn hu CaCO3 bng axit: CaCO3 + 2H+ = Ca2+ + H2O + CO2 Kh CO2 thot ra c dn vo bnh hp ph cha hn hp NaOH + Ca(OH)2. y, xy ra phn ng: 2NaOH + CO2 = Na2CO3 + H2O
Na2CO3 + Ca(OH)2 = 2NaOH + CaCO3 do , khi lng bnh hp ph tng ln v t s tng khi lng ny suy ra lng CO2 cng nh CaCO3 trong mu. V d 2: Xc nh hm lng C v H trong cht hu c. Da vo phn ng chy ca cht hu c trong oxi vi s c mt ca cht xc tc AgMnO4 hoc hn hp oxit coban (II) v (III) nhit 5500C chuyn C thnh CO2 v H thnh H2O. Dn cc kh CO2 v H2O ln lt qua bnh hp ph cha cht hp ph H2O nh P2O5 , Mg(ClO4)2 khan ri qua bnh hp ph cha cht hp ph CO2 nh KOH, hoc hn hp NaOH vi Ca(OH)2 phn tn trn si aming (azbest) v t s tng khi lng cc bnh hp ph suy ra hm lng C v H trong mu. Phng php t chy thng c dng trong phn tch cc cht hu c. Trong phn tch cc hp cht hu c, ngoi phn tch C v H, i khi cn phi phn tch N. Nit trong cc hp cht hu c khi b t chy cho cc sn phm nit phn t v cc oxit ca n, cc oxit ny c kh thnh nit phn t bng bt ng nhit 5500C. o th tch kh nit v t tnh ton hm lng cha nit trong mu. Ngy nay, sn xut ra my phn tch t ng C, H, N trong cc hp cht hu c. Thi gian phn tch cho mt mu mt khong 15 pht. Cht hu c c t bng oxi sch trong bu kh quyn heli vi s c mt ca cht xc tc.
1.3. Phng php nhit phn

Trong phng php ny, hm lng cht cn xc nh c suy ra t s gim khi lng cn ca mu phn tch sau khi sy hoc nung mu. Phng php nhit phn thng c dng xc nh m, thnh phn nc kt tinh hay cc hp cht d b phn hu khi nung nhit cao. V d 1: Xc nh nc kt tinh ca mui bari clorua. Cn trc mt mu mui, ri mang sy nhit 1050C n khi lng khng i, ngui v cn phn sn phm thu c: to BaCl2.xH2O = BaCl2 + xH2O Trc khi nung Sau khi nung Da vo s chnh lch v lng cn trc v sau khi nung suy ra hm lng nc kt tinh trong mu. V d 2: Xc nh hm lng NaHCO3 trong hn hp vi Na2CO3 bng cch nung mu. Khi nung, NaHCO3 b phn hu: to 2NaHCO3 = Na2CO3 + H2O + CO2 Nh vy, bng s chnh lch khi lng cn trc v sau khi nung s tnh c lng NaHCO3 trong mu.
1.4. Phng php kt ta (Phng php phn tch khi lng kt ta)
Trong phng php ny, thnh phn cn xc nh c kt ta di dng hp cht kh tan. Kt ta c lc, ra sch, sy hoc nung chuyn sang dng c cng thc ho hc xc nh v em cn. Da vo lng cn tnh ra hm lng thnh phn cn xc nh. V d: xc nh ion Al3+ trong mu. Kt ta ion Al3+ di dng Al(OH)3 bng NH4OH: Al3+ + 3NH4OH = Al(OH)3 + 3NH4+
Sau khi lc, ra sch, kt ta c nung nhit 1000oC chuyn sang dng Al2O3: 1000oC Al2O3 + 3H2O 2Al(OH)3 = c thnh phn ho hc xc nh v cn. T lng cn Al2O3 tnh ra hm lng ion Al3+ trong mu. Trong 4 phng php k trn, phng php kt ta thng c dng nhiu nh lng cc cht nht l cc hp cht v c, v qu trnh chuyn thnh phn cn xc nh vo mt hp cht kh tan d dng hn nhiu so vi qu trnh tch n di dng t do, thm na, cng v cc phn ng to kt ta c th s dng trong phn tch c nhiu hn nhiu so vi cc loi phn ng khc. Ngoi ra, phng php kt ta cn l mt trong nhng phng php tch cht cn phn tch hay cht gy nhiu rt hiu qu. Phng php kt ta thng c s dng trong phn tch nng nghip, do vy, di y s tp trung trnh by v phng php ny. 2. PHNG PHP PHN TCH KHI LNG KT TA Tin trnh ca phng php kt ta bao gm ln lt cc cng on sau: Cn mu Dung dch Kt ta Lc, ra Sy hoc nung Cn Tnh ton. Tt c cc cng on u c nh hng trc tip n chnh xc ca kt qu phn tch. Song, cng on lm kt ta c nh hng ln nht n kt qu cng nh n tc phn tch, v chnh xc ca php phn tch ph thuc rt nhiu vo vic chn cht kt ta, vo lng kt ta, vo iu kin thc hin kt ta S dng phng php kt ta ph hp s trnh c hoc lm gim cc nh hng xu nh: s tan ca kt ta, s bn kt ta, cng nh gip cho qu trnh lc ra d dng v vic chuyn dng kt ta sang dng cn c thun li.
2.1. Yu cu ca dng kt ta
Dng kt ta l hp cht t tan thu c khi cho thuc th thch hp tc dng vi thnh phn cn xc nh trong dung dch. V d: nh lng ion SO42-, c th dng thuc th Ba(NO3)2,v phn ng xy ra nh sau: Ba2+ + SO42- = BaSO4 Sn phm kt ta BaSO4 thu c, c gi l dng kt ta. Trong ho hc, mt nguyn t hoc ion c th c chuyn vo nhiu dng kt ta khc nhau. V d: ion SO42- c chuyn vo cc dng kt ta BaSO4, PbSO4, hoc SrSO4; ion Fe3+ c th chuyn sang cc dng kt ta Fe(OH)3, FePO4, Fe(cuferon)3, FeS Nhng, ch c dng kt ta p ng cc yu cu di y mi c dng trong phn tch kt ta: a. Dng kt ta phi t tan Khi phn ng to kt ta MaXb t cc ion Mm+ v Xn- hon thnh, kt ta v cc ion to ra n nm trong trng thi cn bng theo II- a: aMm+ + bXn(II- a) MaXb Do c trng thi cn bng m trong dung dch vn tn ti mt lng cht cn theo di dng ho tan gy ra mt kt ta, hin tng ny c gi l s khng hon ton ca phn ng. Lng kt ta b mt do cht cn phn tch khng i vo kt ta c tnh theo biu thc II- 1: w = M.C.V (II- 1)
Trong : w - khi lng kt ta b mt (g), M - khi lng ca mt mol phn t cht kt ta (phn t gam) (g/mol), C nng mol/lt ca ion cn phn tch cn li trong dung dch (mol/l), V - th tch dung dch khi ngng lm kt ta (l). y chnh l ngun gy sai s phn tch. Nng ca ion cn phn tch (v d ion Mm+) cn li trong dung dch, sau khi phn ng to kt ta MaXb xy ra c tnh nh sau: Nu trong 1 lt dung dch c s mol phn t kt ta MaXb tan ra theo II- a (s cn c gi l tan ca kt ta), th s c as mol ion Mm+ v bs mol ion Xn- hnh thnh: aMm+ + bXnMaXb s as bs Nh vy, CMm+ = as. T cho thy, s khng hon ton ca phn ng to kt ta ph thuc vo s tan ca kt ta tc ph thuc vo tan ca kt ta. C rt nhiu yu t nh hng n tan ca kt ta, y, ch trnh by mt s yu t chnh, t tm cch lm kt ta thch hp. *nh hng ca tch s tan n tan ca kt ta T cn bng II- a, tch s tan ca kt ta MaXb l: TMaXb = [ Mm+ ]a [ Xn- ]b (II2) v nh trn trnh by, s c [ M m+]a = as v [ Xn- ]b = bs. Do , TMaXb c vit l: TMaXb = (as)a . (bs)b = aa.bb sa+b (II3) Trong iu kin va xt, tr s ca s cng c th coi l trng vi tan ca kt ta MaXb, do tan s s l: s = (TMaXb /aa.bb)1/(a+b) (II4) Nh vy, tan t l thun vi tch s tan ca kt ta, do , mun phn ng phn tch l cng hon ton th phi chn loi phn ng cho kt ta c tch s tan cng b cng tt. Trong trng hp phn tch w gam ion Mm+ c khi lng mt mol ion k hiu l MMm+, vi sai s % (e %) cho trc v th tch khi dng kt ta l V lt, th TMaXb phi t gi tr: (IITMaXb (10-2.e.w/V.MMm+)a+b.aa.bb 5) Thng thng, trong phn tch khi lng kt ta, khi lng cht phn tch khong 0,1g, th tch dung dch l 0,1lt, khi lng mt mol ion cht cn phn tch l khong 100g, sai s phn tch l 0,1%, th vi m = n = 1, tch s tan ca kt ta MX cn t l: TMX 10-10, hay s 10-5M, khi lng thuc th l va . * nh hng ca ion chung n tan ca kt ta Ion chung l ion c trong thnh phn kt ta, nh vy, vic b sung ion chung vo dung dch bo ho ca kt ta s lm cho phn ng II- a chuyn dch v pha to kt ta v lm gim tan ca kt ta (nguyn l Le Chatelire) V d: tnh tan ca PbSO4 trong nc v trong dung dch Na2SO4 10-2M, cho TPbSO4 = 1,6 . 10-8 - Trong nc: Kt ta PbSO4 phn li: PbSO4 Pb2+ + SO42-
Vy, tan ca n theo biu thc II- 3 l: T PbSO4 = s.s = s2 s = (1,6.10-8)1/2 1,3.10-4M. - Trong dung dch Na2SO4 10-2M: C: [ Pb2+ ] = s, [ SO42- ] = s + 10-2, nn TPbSO4 = s(s + 10-2). Gi thit s 10-2 th TPbSO4 = 10.s, suy ra: s = 1,6.10-6M 10-2M. Nh vy, tan ca PbSO4 trong dung dch Na2SO4 10-2M nh hn tan ca PbSO4 trong nc khong 100 ln. Qua v d trn cho thy: mun cho kt ta xy ra hon ton v nht l i vi cc kt ta c tch s tan ln th cn dng d thuc th, tuy nhin, s d cn va , nu khng s dn n: - Tn km, - Tng s hp ph thuc th ca kt ta gy kh khn cho vic ra kt ta, - To phc cht tan trong iu kin thuc th d, gy s tan kt ta, lm mt mu. V d: khi lm kt ta ion Al3+ di dng Al(OH)3 (TAl(OH)3 = 1.10-32), nh vy, theo biu thc II- 5 kt ta s hon ton vi nng ca [OH-] = 10-9M, tc pH = 5. Nu lm kt ta pH 6 s lm cho mt phn kt ta Al(OH)3 tan ra di dng phc cht tan [Al(OH)4] -, gy ra sai s phn tch. * nh hng ca phn ng ph Thng hay gp l cc phn ng thu phn v phn ng to phc cht. + nh hng ca phn ng thu phn: Trong mi trng nc cc cation Mm+ cng nh cc anion Xn- c th b thu phn m s thu phn li ph thuc vo pH mi trng. Khi pH tng ln cc cation b thu phn mnh hn v ngc li khi pH gim i th cc anion b thu phn mnh hn. S thu phn s lm cho nng t do ca cc ion to kt ta gim i dn n kt ta s tan ra, hay tan ca kt ta tng. V d: Khi lm kt ta ion Ca2+ di dng kt ta CaC2O4: Ca2+ + C2O42- = CaC2O4
2
nu tin hnh phn ng ti pH 5, s dn n cc phn ng: C2O42- + H+ = HC2O4HC2O4- + H+ = H2C2O4 lm gim nng ion C2O42-, dn n kt ta CaC2O4 s tan ra. + nh hng ca phn ng to phc: Trong s c mt ca cht to phc, cation Mm+ cn c th to phc cht tan vi cc phi t Ln-: Mm+ + xLn- = [MLx]m-xn lm cho nng t do ca cc ion to kt ta gim i dn n kt ta s tan ra, hay tan ca kt ta tng ln. V d: khi lm kt ta ion Fe3+ di dng kt ta Fe(OH)3 ti pH = 4 5, trong mi trng c ion CN-, kt ta s khng hnh thnh, v ion Fe3+ to phc cht tan [Fe(CN)6]3- lm cho nng t do ca ion Fe3+ qu b khng kt ta Fe(OH)3. Cc phng trnh phn ng trn cho thy s thu phn, s to phc cht u dn n s gim nng cc ion to kt ta ([Mm+], [Xn-]), do lm tng s ho tan ca kt ta theo phng trnh II- a (nguyn l Le Chatelier).
* nh hng ca cc yu t khc n tan kt ta Cc yu t khc c nh hng n tan ca kt ta l: nhit , kch thc ht kt ta, s gi ha ca kt ta, tnh cht ca dung mi + nh hng ca nhit n tan kt ta: i b phn cc kt ta c tan tng khi tng nhit ca mi trung to kt ta. + nh hng ca kch thc ht n tan kt ta: Nng lng b mt ca ht to nh hn nng lng b mt ca ht nh, do khi tng kch thc ht th tan ca kt ta gim. + nh hng ca s gi kt ta n tan ca n: Khi lu kt ta trong mi trung kt ta (lm gi kt ta, lm chn kt ta, lm mui kt ta) s dn n cc hin tng: - Cc ht nh s tan ra v cc ht ln s ln ln, dn n tan kt ta gim. - Cc ht kt ta cha nc kt tinh c th s mt nc v dn n tan gim. V d: kt ta CaC2O4.2H2O chuyn thnh CaC2O4.H2O. - S polime ho cc ht kt ta, nht l i vi cc kt ta sunphua, hidroxit dn n tan ca kt ta gim. V d: cc kt ta CuS, ZnS d to thnh mch: -M-S-Mgy ra s chuyn dng tinh th v tan gim. + nh hng ca dung mi n tan kt ta: i b phn cc kt ta trong mi trng nc (dung mi c tnh phn cc ln nht) u c tan ln hn trong dung mi hu c. Do , khi tin hnh kt ta trong dung mi hu c thch hp s lm cho kt ta hon ton hn so vi khi lm kt ta trong mi trng nc. V d: kt ta AgCl, trong H2O, c tan 0,00191g/lt, song, trong mi trng etanol, c tan 0,000015g/lt, hoc kt ta CaSO4 (TCaSO4 = 9,1.10-6) tan nhiu trong nc, song, trong mi trng c b sung etanol hoc axeton th tan gim i nhiu ln. Nghin cu v tan ca kt ta cho thy c yu t lm gim tan nhng li c yu t lm tng tan. Do , khi s dng loi kt ta no trong phn tch cn xc nh iu kin lm kt ta thch hp, qu trnh phn tch n gin m vn m bo chnh xc cng nh to iu kin thun li cho cc cng on phn tch tip theo. b. Kt ta phi chn lc Thng thng, i cng vi ion cn xc nh cn c cc ion khc c th tham gia phn ng vi thuc th dn n sai s phn tch, do chn phn ng sao cho ch ion cn phn tch tham gia l ht sc quan trng m bo kt ta thu c sch, ni cch khc l tng chn lc ca phn ng phn tch. S kt ta chn lc c th t c bng nhiu cch nh: * Chn dng kt ta thch hp: Khi khng c ion gy nhiu, chn kt ta c tan nh nht s kt ta l hon ton hn. Trong trng hp c mt cc ion gy nhiu, chn kt ta c chn lc cao, mc d c tan ln v lm gim tan ca kt ta bng cc bin php thch hp nh dng thuc th d V d: khi lm kt ta Pb2+ trong s c mt cc ion Cu2+, Zn2+, chn kt ta PbSO4 (TPbSO4 =1,6.10-8) ch khng chn cc kt ta PbCO3 (TPbCO3 = 7,49.10-14), PbCrO4 (TPbCrO4 = 1,8.10-14), PbS (TPbS = 2,5.10-27), bi v cc ion Cu2+, Zn2+ cng to kt ta vi cc ion CO32-, CrO42- v S2-. Trong iu kin ny, s khng hon ton ca kt ta PbSO4 c khc phc bng vic s dng d ion SO42-.
* Chn iu kin kt ta thch hp: Chn iu kin sao cho ch c ion phn tch phn ng, nh thay i pH mi trng... V d: phn tch ion SO42- trong mu cha cc ion PO43-, CO32- di dng kt ta BaSO4, cn tin hnh lm kt ta mi trng HNO3 hay HCl pH = 4, cc ion PO43-, CO32- khng to cc kt ta Ba3(PO4)2, BaCO3 gy nh hng n kt qu phn tch. * Che ion gy nhiu: y l bin php chuyn ion gy nhiu vo phc cht bn v khng phn ng vi thuc th, nh vy, ch c ion cn phn tch tham gia phn ng vi thuc th. V d: khi phn tch ion Mg2+ trong s c mt ca cc ion Fe3+, Al3+ di dng kt ta MgNH4PO4.6H2O, cho vo mi trng kt ta ion xitrat, nh vy cc ion Fe3+, Al3+ s to phc cht bn vi xitrat v khng tham gia phn ng to kt ta photphat. Nu cc gii php nu trn khng th tin hnh c, th phi tch cc ion gy nhiu hay ion phn tch trc khi lm kt ta. c. Dng kt ta phi d lc, d ra sch Mun vy, nn chn dng kt ta tinh th, c b mt tip xc nh, t hp ph cht bn v khng bt kn l giy lc, d ra sch v lc nhanh hn. Cc dng kt ta v nh hnh v nht l cc loi kt ta keo, nh cc kt ta hidroxit, u c b mt tip xc ln, d hp ph nhiu cht bn, nn kh lc v kh ra sch. V d: khi chn la 2 kt ta c tan tng ng nhau kt ta v nh hnh Al(OH)3 (TAl(OH)3 = 1.10-32) v kt ta tinh th AlPO4 ( TAlPO4 = 5,7.10-19), nu c th, u tin kt ta AlPO4. d. Dng kt ta phi d dng chuyn hon ton sang dng cn y l yu t c bn lm cn c cho s tnh ton thnh phn cn xc nh. Do , cn chn dng kt ta sao cho khi sy hoc nung s ch thu c mt sn phm duy nht, n nh (dng cn). V d: khi phn tch Pb2+ thng kt ta n di dng PbSO4 l dng d dng chuyn sang dng cn PbSO4 ch khng dng dng PbS (mc d c tan nh hn), v khi sy, nung, dng PbS khng n nh d b oxi trong khng kh oxi ha: to 2PbS + 3O2 = 2PbO + 2SO2 dn n sn phm thu c sau khi sy, nung l hn hp PbO v PbS khng c cng thc ho hc xc nh, khng th lm dng cn.
2.2. Yu cu ca dng cn
Dng cn l dng kt ta sau khi em sy hoc nung n khi lng khng i. Tu theo bn cht ca kt ta, dng kt ta v dng cn c th c cng hoc khng cng cng thc ho hc. V d: kt ta BaSO4 cho dng kt ta v dng cn nh nhau, u l BaSO4. Vic sy hoc nung, trong trng hp ny, ch lm mt i nc hp ph. Nhng, i vi dng kt ta Fe(OH)3, khi nung s thu c dng cn l Fe2O3: 10000C 2Fe(OH)3 = Fe2O3 + 3H2O c th t khi lng dng cn tnh ton c hm lng ca thnh phn cn phn tch, th dng cn cn phi m bo cc yu cu sau: a. Dng cn phi c cng thc ho hc xc nh c th tnh c kt qu phn tch bt buc dng cn phi c cng thc ho hc xc nh, k c phn nc kt tinh.
V d: cc kt ta hidroxit hay cc kt ta mui baz khng th dng lm dng cn c v thnh phn ca chng khng n nh v ph thuc vo iu kin kt ta. Cn phi nung chuyn cc kt ta ny sang dng n nh v cng thc ho hc nh cc dng oxit, dng mui V d: kt ta Fe(OH)3 chuyn thnh Fe2O3 nh nu trn. b. Dng cn phi bn v phng din ho hc Nh khng c hp th hi nc hay CO2, khng tham gia phn ng oxi ho kh vi oxi trong khng kh. V d: khi phn tch ion Ca2+ di dng kt ta CaC2O4.H2O, c th c cc dng cn: CaC2O4.H2O, CaCO3, CaO, song, khng nn dng dng CaO v n ht m rt mnh, khi cn s mc sai s. c. Hm lng ca thnh phn cn tm trong dng cn cng b cng tt Khi cn s mc sai s cn, do hn ch c nh hng ca sai s ny th hm lng ca thnh phn cn tm trong dng cn cng b cng tt. V d: khi xc nh ion Al3+ di dng oxit nhm Al2O3 (M = 101,96) s gp sai s 2,4 ln ln hn so vi khi xc nh di dng AlPO4 (M = 121,95) nu cng cn sai mt lng nh nhau. Nhng yu cu nu trn i vi dng kt ta v dng cn cho thy vic chn dng kt ta, dng cn l rt quan trng trong phng php kt ta, v n quyt nh chnh xc cng nh tc ca php phn tch.
2.3. S gy bn kt ta
Kt ta thu c trong mi trng kt ta s tng tc vi cc ion c trong mi trng v to nn s bn kt ta. C 2 nhm nguyn nhn chnh gy bn kt ta l s cng kt v s kt ta theo. a. S cng kt Kt ta c hnh thnh trong qu trnh phn tch thng ko vo cu trc ca mnh cc tp cht (cc ion l). Khi cc tp cht cng kt ta ng thi vi kt ta chnh mc d nng ca chng cha t ti trng thi bo ho, th hin tng ny c gi l s cng kt mt yu t gy nn sai s phn tch. Cc nguyn nhn gy nn s cng kt l: s hp ph b mt, s kt vn, s to tinh th hn hp. *S cng kt do hp ph: Xy ra khi kt ta chnh dng keo trong s d tha thuc th. Cc ht keo hp ph ion hot ng ca thuc th s dn n s hp ph cc ion tri du. V d: kt ta BaSO4 trong iu kin d ion SO42- s hp ph cc ion dng. Trong trng hp ny, thc t cho thy ion gy nhiu no to mui vi thuc th c tan nh hn, s b hp ph nhiu hn; vi kt ta BaSO4 ni trn, th s hp ph i vi cc cation nh sau: Na+ < K+ < Ca2+ < Pb2+. Nhm khc phc s hp ph, nn tin hnh kt ta vi dung dch long thuc th long, kt ta nng v khng nn kt ta qu lu trong dung dch. *S cng kt do hin tng kt vn: Gy bn c hc kt ta, bi khi tin hnh kt ta mt phn cht gy nhiu b kt ta bao bc. Hin tng ny thng gp khi kt ta vi dung dch c, kt ta nhanh v khuy khng tt. loi tr s cng kt ny, cn tin hnh kt ta vi dung dch long nng, kt ta chm v khuy tt hoc lm kt ta ng tnh. Nu khng thnh cng, th phi s dng bin php kt ta li. *S cng kt do hin tng to tinh th hn hp: Xy ra khi bn knh ion ca ion trong kt ta chnh v ion gy nhiu khng khc nhau nhiu ( sai khc nh hn 10 15%). Lc ny cc ion gy nhiu c th thay th
cho ion to kt ta chnh trong mng tinh th. V d: ion MnO4- c th thay th ion SO42-, nn khi kt ta BaSO4 vi s c mt ca ion MnO4- s thu c tinh th kt ta c cha ion MnO4-. S cng kt ny khng th loi b c bng cch ra hoc kt ta li m ch c th loi b c bng cch che, kh cc ion gy nhiu i. Chng hn, v d trn, c th loi nh hng ca ion MnO4- bng cch kh n v ion Mn2+ khi cho axit oxalic vo dung dch phn tch trc khi lm kt ta. Trong phn tch, s cng kt khng phi lc no cng gy hi m i khi li c li. Khi phn tch hm lng nh cc cht, thng s dng s cng kt gom cc cht cn phn tch. V d: khi xc nh ion Pb2+ t dung dch long, nng ca n nh n mc m kt ta PbS, l kt ta t tan nht ca ion Pb2+, cng khng hnh thnh. Cho vo dung dch phn tch ion Ca2+ v kt ta ion Ca2+ di dng CaCO3, trong iu kin ny ion Pb2+ b cng kt theo. Sau , ho tan kt ta cacbonat vo axit axetic v phn tch ion Pb2+ bng cc phng php thng thng. Mt v d khc, l s gom lng nh cc ion kim loi ho tr 2 nh Cu2+, Cd2+, Mn2+, Zn2+ trn kt ta Fe(OH)3 hoc Al(OH)3.. Bng s cng kt c th lm tng nng cc cht cn phn tch ln hng ngn, hng vn ln. b. S kt ta theo Ngoi s cng kt, trong thc t cn gp hin tng kt ta theo lm cho kt ta chnh b bn. Hin tng ny xy ra khi kt ta chnh kt ta xong v khng c tch kp thi ra khi dung dch, th sau mt thi gian s hnh thnh trn kt ta chnh kt ta ca cc cht bn mc d trong iu kin bnh thng n khng kt ta. V d: MgC2O4 l cht tan, khng cng kt ta vi CaC2O4, nhng sau khi CaC2O4 kt ta ht v lu trong dung dch (khong 2 gi), th MgC2O4 b kt ta theo. khc phc s kt ta theo cn tch kp thi kt ta chnh trc khi kt ta theo xut hin.
2.4. Mt s k thut trong phng php phn tch khi lng kt ta

Sau khi chn c phn ng to kt ta thch hp, cc bc tip theo bao gm: chn dng thuc th, lm kt ta, lc ra kt ta, sy v nung kt ta chuyn sang dng cn, cn sn phm v tnh ton. a. Chn thuc th lm kt ta Khi c phn ng phn tch, vic chn dng kt ta rt quan trng m bo vic phn tch nhanh v chnh xc. V d: khi phn tch ion Fe3+ di dng kt ta Fe(OH)3, chn ho cht no trong s ho cht: NaOH, NH4OH, Na2CO3, ure, lm thuc th? Vic chn la dng thuc th phi theo cc nguyn tc sau: + Chn loi thuc th khng bn vi nhit, nh vy, khi sy nung kt ta n d dng b phn hu v bay i khng gy nn sai s phn tch. V d: trong trng hp phn tch ion Fe3+ ni trn s dng NH4OH hoc ure. + Chn loi thuc th c tan ln, khi ra kt ta th phn d ca thuc th b hp ph bi kt ta d b loi i. V d: lm kt ta ion Ba2+ bng axit H2SO4 ch khng dng Na2SO4, v H2SO4 c tan ln hn nn d b ui ra khi kt ta hn khi ra. + Chn loi thuc th cho php tin hnh kt ta ng tnh, chnh l gii php iu ch thuc th ngay trong dung dch, nh vy, thuc th s xut hin mi ch v phn ng to kt ta s xy ra mi ni cng mt lc. V d: trong trng hp phn tch ion Fe3+ ni trn s dng ure. Khi cho ure vo dung dch, n ho tan nhanh v phn b u trong ton b khng gian. un nng dung dch, ure b thu phn nhanh to ra NH4OH:
to CO(NH2) 2 + 3H2O = 2NH4OH + CO2 v phn ng to kt ta Fe(OH)3 xy ra ti mi im cng mt lc. S kt ta ny gi l kt ta ng tnh. + Dng mt lng thuc th d so vi l thuyt (thng dng d gp i), v tan ca kt ta s gim i nhiu, khi trong dung dch c ion chung. Tuy nhin, cn lu , mt s kt ta c th tan trong thuc th d. V d: cc kt ta AgCl, HgI2 tan c trong thuc th d (Cl- , I-) do s to thnh cc phc cht tan [AgCl2]- , [HgI4]2-, cc trng hp ny, phi tnh ton lng thuc th sao cho va kt ta hon ton v trnh c s ho tan ca kt ta do s to phc cht tan. b. Lm kt ta Lm kt ta trong cc chu nhit. Khi lng kt ta cn nm trong khong 200mg, th tch khi kt thc lm kt ta khong 100 - 200ml. Tu theo bn cht ca kt ta (dng tinh th, dng keo hay dng v nh hnh) m chn cch lm kt ta thch hp. * Lm kt ta tinh th S to thnh kt ta bao gm hai qa trnh: s pht sinh cc mm kt tinh l trung tm ca s kt ta v cc mm tinh th ln dn ln. + S pht sinh cc mm kt tinh l trung tm ca s kt ta. Cc mm kt tinh c th t hnh thnh trong qu trnh lm kt ta, cng c trng hp to nn bng cc thao tc thch hp nh dng a thu tinh c vo thnh bnh to mm tinh th (trng hp kt ta MgNH4PO4) + Cc mm tinh th ln dn ln. tng cng qu trnh ny, thng yn kt ta trong vi gi hoc lu hn (lm mui kt ta, kt ta). giai on ny, cc tinh th nh s tan ra, cn cc tinh th ln s ln ln, v trong cng iu kin, dung dch s bo ho i vi tinh th ln nhng c th cha bo ho i vi tinh th nh. Nh vy, khi lm kt ta tinh th, c kt ta tinh th ht ln, phi hn ch qu trnh to mm tinh th v phi c thi gian lm mui kt ta. hn ch s mm tinh th cn lm kt ta chm bng cch kt ta vi dung dch long, thuc th long hoc lm tng tan ca kt ta nh kt ta vi dung dch nng, thuc th nng hoc pH thch hp Sau , s kt ta hon ton c m bo bng vic dng thuc th d hay bng iu chnh pH hoc thnh phn dung mi V d: kt ta ion Ca2+ di dng CaC2O4. u tin un nng dung dch phn tch vi axit oxalic ( s mm tinh th c to thnh t do c t ion C2O42-), sau trung ho mi trng bng NH4OH n pH 5 (tng lng ion C2O42-). yn kt ta khong 1 gi (lm mui), ri lc ly kt ta. * Lm kt ta v nh hnh: Ngc li vi vic lm kt ta tinh th, khi lm kt ta v nh hnh cn phi tin hnh nhanh trong dung dch nng vi thuc th d v khuy tt, c thm cht in li h thng keo nhanh b ng t v chng c s pepti ho. Nh vy, kt ta s dy c, vng chc hn, b mt tip xc s b hn. Sau khi lm kt ta xong phi lc ngay, v lu kt ta qunh li gy kh ra. Nu c th c, nn lm kt ta ng tnh. T nhng phn tch trn c th thy nhng thao tc trong phn tch khng th tin hnh mt cch tu m phi theo mt qui nh nghim ngt m bo cho vic phn tch t kt qa chnh xc. Nng thuc th c, long, cho d nhiu hay t hoc lm kt ta nhanh hay chm l nhng qui nh m mi ngi lm phn tch phi tun theo.
c. Lc kt ta lc kt ta thng dng 3 loi dng c lc: phu lc, cc lc bng gm v cc lc bng thu tinh. * Phu thu tinh: c thi t thu tinh chu ho cht vi cc tiu chun: gc to bi hai ng sinh bng 90o v chiu cao ca phu t 9 12cm. i vi phu lc phi dng giy lc khng tn, tc loi giy khi t chy hon ton cho lng tro khng ng k (< 0,0001g, sai s ca cn phn tch). Giy lc c chia lm 3 loi ty theo kch thc l ca giy: - Loi l nh (giy lc bng xanh) dng lc gi cc kt ta c ht nh. - Loi l trung bnh (giy lc bng vng, bng trng) dng lc gi c ht va. - Loi l to (giy lc bng ) dng lc gi cc loi ht th. Vic chn giy lc cho ph hp vi c ht l rt quan trng nhm loi tr vic kt ta chui qua giy v to cho vic lc, ra c nhanh. B lc ny c u im l rt ph bin trong phng th nghim. Tuy nhin, khi chuyn sang dng cn nht thit phi nung kt ta v phi t chy giy lc. Ngoi ra, khng th s dng k thut ht chn khng vi b lc ny, v vic ht chn khng s lm thng giy lc, gy mt mu. * Cc lc bng gm: L loi cc lm bng gm c y l mng gm xp vi cc kch c ca cc l hng khc nhau. K hiu cho tng loi cc ca cc nc c khc nhau, v d: A1, A2, A3 (c), trong A1 c kch thc l to nht, A3 c kch thc l b nht. u im ca loi cc lc ny l cho php dng k thut lc chn khng v c th sy hoc nung chuyn dng kt ta sang dng cn. * Cc lc bng thu tinh: L loi cc lm bng thu tinh c y l mng thu tinh xp vi cc kch c ca cc l hng khc nhau. K hiu cho tng loi cc ca cc nc c khc nhau, v d: S1, S2, S3, S4, (Sc), G1, G2, G3, G4 (c), trong S4, G4 c l hng ln nht v S1, G1 c l hng b nht, thng dng loi S2, S3 hay G2, G3. u im ca loi cc lc ny l cho php dng k thut lc chn khng, song, ch c th sy chuyn dng kt ta sang dng cn. Khi lc thng kt hp gn ra v lc mau t c kt ta sch. Trc tin, cht phn nc trong ln h thng lc, cho tip dung mi vo kt ta v khuy u ri sa lng. Cht tip phn nc trong ln h thng lc. Qu trnh ny c lp li khong 3 ln, sau mi chuyn ton b kt ta ln h thng lc v tin hnh ra kt ta. d. Ra kt ta Mc ch ca s ra kt ta l loi cc tp cht hp ph trn kt ta. Trong khi ra, cc kt ta thng tan ra cho nn cn chn dung dch ra, dung mi ra v cch ra thch hp. Thng chn dung dch ra nh sau: - Dung dch ra c cha thuc th, nu thuc th l cht d bay hi hoc d b phn hu khi sy v nung kt ta. Ra bng cch ny s hn ch c s tan ca kt ta. V d: ra kt ta AgCl bng dung dch cha HCl long. - Dung dch ra c cha cht in gii d b bay hi khi nung. Ra bng dung dch ny s hn ch c hin tng keo tn (pepti ho) ca cc kt ta keo. V d: ra kt ta Fe(OH)3, Al(OH)3 bng dung dch NH4Cl, NH4NO3.
- Dung dch ra c cht ngn cn s thu phn ca kt ta. V d: ra kt ta MgNH4PO4 bng dung dch cha NH4OH hn ch s thu phn ca MgNH4PO4 . - Nu kt ta l cht t tan, khng b thu phn, khng b pepti ho th ch cn dung dch ra l nc ct. Khi ra cn lu rng: vi cng mt lng dung dch ra, nu chia ra ra lm nhiu ln v trong mi ln ra cn chy ht nc ra mi nc ra mi, th kt ta mau sch hn v t b tan hn. iu ny d dng nhn thy qua biu thc II- 6: Cn = Co [R/(V + R)]n (II- 6) trong : n s ln ra V th tch dung dch ra R th tch dung mi b kt ta hp ph C0 nng cht b hp ph khi bt u ra Cn nng cht b hp ph sau ln ra th n. Qu trnh ra kt thc khi khng pht hin phn ng ca thuc th hoc ion ch th trong nc lc. V d: khi ra kt ta CaC2O4 hnh thnh t phn ng gia ion Ca2+ v thuc th (NH4)2C2O4. V kt ta hnh thnh hp ph ion C2O42- nn khi ra ion ny s c gii phng vo dch lc. Thu ly dch lc v nh vo dung dch ion Ca2+, nu dch lc khng c phn ng to kt ta CaC2O4, chng t vic ra hon tt. e. Sy v nung kt ta Sy v nung nhm chuyn kt ta sang dng cn. i vi kt ta c cng thc ho hc ging vi dng cn th ch cn sy loi b nc nhit 950 1050C. Cn i vi kt ta c cng thc khng trng vi cng thc dng cn hoc khi cn phi t chy giy lc, th sau khi sy kh, kt ta c nung mt nhit xc nh. Sau thi gian sy, nung khong 2 3 gi, mu ly ra c trong bnh ht m n khi ngui v nhit ca phng cn th mang cn trn cn phn tch. Sau , mang sy hoc nung mu thm 30 pht, ri ngui v cn. Nu khi lng cn c khng sai khc so vi khi lng cn ln trc (vi sai s cn cho php), th vic sy nung kt thc. Nu khi lng gim i, th cn nhc li qu trnh sy, nung n khi khi lng khng i. Nhit nung phi chnh xc, chuyn hon ton dng kt ta sang dng cn, nhng khng lm dng cn tip tc bin i. V d: chuyn Fe(OH)3 sang Fe2O3 phi nung nhit 1000 oC, nu nung nhit 1200 oC, st ba oxit s b phn hu thnh st hai oxit, kt qu s thu c hn hp 2 oxit vi cng thc ho hc khng xc nh: 1000oC 2Fe(OH)3 = Fe2O3 + 3H2O 1200 oC 2Fe2O3 = 4 FeO + O2, f. Cch tnh ton kt qu Hm lng ca thnh phn cn xc nh trong mu c tnh ton t khi lng ca dng cn thng qua h s chuyn F. V d: xc nh Al3+ trong mu phn tch cn a(g) mu v ho tan vo dung dch. Kt ta nhm di dng Al(OH)3 bng NH4OH. Sau khi nung chuyn Al(OH)3 thnh Al2O3 th cn c b(g). Hy tnh thnh phn phn trm nhm trong mu? Cch gii: Cc phn ng phn tch xy ra: Al3+ + 3NH4OH = Al(OH)3 + 3NH4+ 2Al(OH)3 = Al2O3 + 3H2O
C 101,96 g Al2O3 c 53,96g Al, vy trong b(g) Al2O3 c x g Al x = (53,96/101,96). b (g) Thnh phn phn trm y% ca Al trong mu l: y% = 100.(53,96/ 101,96). b/a Trong cng thc trn, t s 53,96/101,96 c xc nh bng nh lut thnh phn khng i ca cc cht tham gia phn ng, l mt hng s v c gi l h s chuyn F. Vy h s chuyn F l t s gia khi lng ca thnh phn cn xc nh c trong mt mol phn t ca dng cn vi khi lng ca mt mol phn t ca dng cn. Do , cng thc tng qut tnh thnh phn phn trm cc thnh phn cn xc nh l: y% = 100F. b/a (II- 7) F - h s chuyn. b - khi lng ca dng cn (g). a - khi lng ca mu ly vo cn phn tch (g). Cc php phn tch khc nhau c h s chuyn khc nhau. V d: xc nh Ba2+ qua kt ta BaSO4 c F =137,34/233,40, cn xc nh Fe qua Fe2O3 c F = 111,69/159,69
2.5. Mt s ng dng c th
ng dng ca phng php kt ta rt a dng v cho php phn tch hng lot cc ion, cc hp cht (bng B.1.2). Di y, ch trnh by nguyn tc cc phng php thng dng trong phn tch mt s ion thng gp nng nghip: * Xc nh ion SO42-: Dng kt ta v dng cn u l BaSO4. Mu phn tch c axit ho n pH = 4 bng axit HNO3 v lm kt ta ion SO42bng dung dch thuc th Ba(NO3)2 ly d. Trong iu kin ny, cc ion CO32-, PO43khng gy nh hng n kt qa phn tch. Kt ta BaSO4 sau khi c ra sch bng nc ct, th em nung nhit 700oC n khi lng khng i v cn. H s chuyn FSO42- = 0,4116. Bng B.1.2: Mt s phng php phn tch khi lng kt ta Nguyn t c xc nh Ag Al Ba Ca Dng kt ta AgCl AgBr AgI Al(OH)3 AlPO4 BaCO3 BaCrO4 BaSO4 CaC2O4.H2O CaC2O4.H2O CaC2O4.H2O CaSO4.H2O Tch s tan (T) 1,78.10-10 5,3.10-13 8,3.10-17 1.10-32 5,75.10-19 5,1.10-9 1,2.10-10 1,1.10-10 2,3.10-9 9,1.10-6 Nhit sy, nung (oC) 130 130 130 1000 1000 600 550 700 900 500 105 600 Dng cn AgCl AgBr AgI Al2O3 AlPO4 BaCO3 BaCrO4 BaSO4 CaO CaCO3 CaC2O4.H2O CaSO4 H s chuyn (F) 0,7526 0,5744 0,4594 0,5292 0,2212 0,6959 0,5421 0,5884 0,7147 0,4004 0,2743 0,2944
AgCl 1,78.10-10 900 AgCl 0,8141 CoNH4PO4.H2O 1100 Co2P2O7 0,4039 BaCrO4 500 BaCrO4 1,2.10-10 0,2052 1000 Cr(OH)3 6,3.10-31 Cr2O3 0,6842 Cu CuCNS 4,8.10-15 110 CuCNS 0,5225 F CaF2 4,0.10-11 500 CaF2 0,4866 -38 Fe Fe(OH)3 3,2.10 1000 Fe2O3 0,6994 I AgI 8,3.10-17 130 AgI 0,5405 Mg MgNH4PO4.6H2O 2,5.10-13 1100 Mg2P2O7 0,2184 Mn MgNH4PO4.H2O 1.10-12 1100 Mn2P2O7 0,3871 Ni NiNH4PO4.6H2O 1100 Ni2P2O7 0,4030 -13 P MgNH4PO4.6H2O 2,5.10 1100 Mg2P2O7 0,2790 Pb PbCrO4 140 PbCrO4 1,8.10-14 0,6411 550 PbSO4 1,6.10-8 PbSO4 0,6832 S BaSO4 1,1.10-10 700 BaSO4 0,1374 Si SiO2.xH2O 1000 SiO2 0,4674 Zn ZnNH4PO4.6H2O 1100 Zn2P2O7 0,4291 * Xc nh ion Cl : Dng kt ta v dng cn u l AgCl. Mu phn tch c axit ho bng axit HNO3 n pH 1 v lm kt ta ion Clbng dung dch thuc th AgNO3. Kt ta AgCl sau khi c ra sch th sy nhit 130oC v cn. H s chuyn FCl- = 0,2474. Trong phng php ny, cc ion CO32-, PO43khng gy nh hng n kt qu phn tch. * Xc nh ion PO43-: Dng kt ta MgNH4PO4.6H20, dng cn Mg2P2O7. Cho vo dung dch phn tch c axit ho bng axit HCl thuc th MgCl2 + NH4Cl v sau dng NH4OH chnh pH mi trng n khi kt ta hon ton ion PO43di dng MgNH4PO4.6H2O. kt ta hon ton cn dng d NH4OH (khong 1/5 th tch dung dch NH4OH 20%). Kt ta c ra bng dung dch NH4OH 5% v sau khi sy kh th c nung nhit 1100oC chuyn hon ton sang dng cn Mg2P2O7. H s chuyn FPO43- = 0,8535. Trong trng hp c cc ion Al3+, Fe3+ trong mu, cn lm kt ta MgNH4PO4 trong mi trng cha ion xitrat ngn nga s to kt ta FePO4 hay AlPO4. * Xc nh ion SiO32-: Dng kt ta H4SiO4 (hay SiO2. 2H2O), dng cn SiO2. Ion SiO32- c kt ta trong mi trng cha 20% axit HCl v 5% gelatin hay agar. Mang nung kt ta thu c nhit 1000oC c khi lng a (g). Thng trong kt ta c ln mt s tp cht, nn sau khi nung cho tip vo phn cht rn cn li axit HF v axit H2SO4 c v nung tip ui ton b SiF4. Khi lng cht rn cn li l b (g). T lng hao ht (a b) cho bit lng SiO2 cha trong mu. H s chuyn FSiO2 = 1,000, FSiO32- = 1,5333. * Xc nh ion Fe3+: Dng kt ta Fe(OH)3, dng cn Fe2O3. Cho vo mu phn tch mui NH4Cl hay NH4NO3 ( lm cht in gii) v kt ta ion Fe3+ t dung dch nng bng lng d dung dch thuc th NH3 long (1:3). Kt ta Fe(OH)3 c lc v ra bng dung dch nng NH4NO3 hay NH4Cl 1% v sau Cl Co Cr
mang nung nhit 1000oC chuyn ton b Fe(OH)3 sang dng cn Fe2O3. H s chuyn FFe = 0,6994. * Xc nh ion Al3+: Dng kt ta Al(OH)3, dng cn Al2O3. Cho vo mu phn tch mui NH4Cl hay NH4NO3 ( lm cht in gii) ri kt ta ion Al3+ t dung dch nng bng dung dch thuc th NH3 long (1:3). pH khi dng kt ta: 5 6. Kt ta Al(OH)3 c lc v ra bng dung dch nng NH4Cl hay NH4NO3 1% v sau mang nung nhit 1000oC chuyn hon ton Al(OH)3 sang dng cn Al2O3. H s chuyn FAl = 0,5293.
2.6. u nhc im ca phng php phn tch khi lng kt ta
Phng php phn tch khi lng kt ta c nhng u nhc im chnh sau: * u im: - Trang thit b dng trong phn tch n gin v khng t tin nn c kh nng ph cp cao. - chnh xc rt cao, v khi phn tch tch c phn cn xc nh ra khi hn hp, nn c dng lm phng php chun kim tra cc phng php khc v kim tra cc dung dch m (l dung dch c nng 10-2M, khi s dng th pha long thnh cc dung dch vi nng nh hn). - C th dng phn tch hu ht cc ion v c. - Phng php kt ta cn c s dng tch cc ion ra khi nhau. * Nhc im: - Tc phn tch chm. - nhy thp nn khng th dng phn tch lng nh cht cn phn tch nu khng lm giu mu trc khi phn tch. - Khng th t ng ho c qu trnh phn tch. Do , ngy nay, trong phn tch ng dng t s dng phng php ny.
Cu hi n tp
1. Trong cc cng on ca phng php phn tch khi lng kt ta, cng on no l quan trng nht? Ti sao? 2. Dng kt ta cn phi tho mn nhng iu kin g? Ti sao? 3. Dng cn cn phi tho mn nhng iu kin g? Ti sao? 4. Cc yu t nh hng n tan ca kt ta? 5. S cng kt l g? Cch khc phc? v s dng hin tng ny? 6. Nguyn tc chon thuc th trong phng php phn tch khi lng kt ta 7. Hy nu cch lm kt ta. 8. Hy nu cch lc v ra kt ta. 9. Cch tnh ton kt qu phn tch. 10. ng dng phng php phn tch khi lng kt ta trong phn tch mt s i tng nng nghip.
Bi tp
1. Cn 0,400g mu cha SO42- ri ho tan thnh 200 ml dung dch. Ly 100ml dung dch ny v lm kt ta bng Ba(NO3)2 ly d trong mi trng axit HNO3. Lc ly kt ta, ra sch v sy kh c 0,1165g. Hy tnh thnh phn % SO42- trong mu. (p s: 24%). 2. Cn 0,500g mu cha Cu2+, Pb2+ v tp cht khng tham gia phn ng ri ho tan thnh 250ml dung dch. Ly 100ml dung dch ny cho tc dng vi axit H2SO4 0,5M ly d th thu c 0,151g kt ta. Mt khc, khi ly 100ml dung dch trn cho tc dng vi H2S d th thu c 0,1675g kt ta. Hy tnh thnh phn % Cu2+ v Pb2+ trong mu. (p s: 16,0%Cu2+, 51,6Pb2+). 3. Cn 0,500g mu cha CO32- v SO42- ri ho tan thnh 200ml dung dch. Ly100ml dung dch ny lm kt ta vi Ba(NO3)2 ly d trong mi trng kim yu th thu c 0,414g kt ta. Mt khc, khi lm kt ta dung dch trn pH = 4 vi Ba(NO3)2 ly d th thu c 0,233g kt ta. Hy tnh thnh phn % ca hai ion trn trong mu. (p s: 38,6%CO32-, 38,4%SO42-). 4. lng kt ta MXn mt do phn ng khng hon ton khng ln hn 0,1mg (sai s cn), th TMXn l bao nhiu, nu th tch khi ngng lm kt ta l V lt? (p s: TMXn = [10-4/(MMXn.V)]n+1.nn]). 5. Tnh khong pH kt ta hon ton ion Fe3+ (khi [Fe3+] <10-6M) trong hn hp vi ion Mg2+. Gi thit nng ion Mg2+ khi dng kt ta ion Fe3+ l 0,01M. Cho TFe(OH)3 = 3,2.10-38, TMg(OH)2 = 6,0.10-10. (p s: 3,5 < pH <10,4). 6. Tnh nng AgNO3 d cn thit, khi kt ta ion Cl- th s mt Cl- do kt ta khng hon ton khng vt qu sai s cn (0,1mg). Bit th tch khi dng kt ta l 0,2 lt, TAgCl = 1,78.10-10. (p s: [AgNO3] = 1,27.10-5). 7. Tnh lng CaC2O4 mt i khi ra n bng 100ml nc ct (gi thit b qua s thu phn). Cho TCaC2O4 = 2,3.10-9. (p s: 0,0004g). 8. Cho dung dch NH3 d vo 25 ml dung dch FeCl3. Thu ly kt ta, ra sch, nung n khi lng khng i c 0,1952 gam cht rn. Tnh nng mol/l ca FeCl3 trong dung dch phn tch. (p s: 0,0976M). 9. Tnh lng AgCl b mt khi ra n bng: a- 200ml nc ct; b- 200ml HCl 0,01M. Cho TAgCl = 1,78.10-10. (p s: a) 3,8.10-4g; b) 5,1.10-7g).
CHNG II PHN TCH TH TCH

1. NHNG KHI NIM C BN V PHN TCH TH TCH Phng php phn tch th tch (phng php chun ) l phng php phn tch nh lng da trn vic o chnh xc th tch dung dch thuc th c nng chnh xc phn ng va vi dung dch phn tch. T lng thuc th tiu tn tnh ra hm lng cht cn phn tch c trong mu phn tch. Dung dch thuc th c nng chnh xc gi l dung dch tiu chun. Tnh ton kt qu ca phng php ny l da vo nh lut ng lng: Cc cht tham gia phn ng theo s ng lng gam bng nhau: Vx.Nx = Vtc.Ntc (III- 1) (trong x l cht cn xc nh, tc l cht tiu chun). Nh vy, nu bit th tch ca dung dch phn tch Vx ly, th tch dung dch tiu chun Vtc c nng Ntc tiu tn, s d dng tnh c nng ca dung dch cn xc nh Nx. o chnh xc th tch dung dch tiu chun tham gia phn ng, s dng dng c o chnh xc, l buret. Qu trnh a t t dung dch tiu chun t buret vo dung dch phn tch gi l qu trnh chun hay qu trnh nh phn. Tuy vy, trong thc t chun , nhiu khi cht cn phn tch trn buret. im m ti dung dch tiu chun tc dng va vi dung dch phn tch gi l im tng ng. Trong nhiu phn ng khng th dng mt xc nh im tng ng. V d: vi phn ng HCl + NaOH = NaCl + H2O, cc ho cht tham gia u khng c mu, nn khng th dng mt xc nh khi no t n im tng ng. xc nh im tng ng, cn dng ch th cho vo bnh phn ng. Ch th l ho cht hoc cng c o, n thay i tnh cht ca mnh nh mu sc hoc tn hiu o ngay ti im tng ng, bo hiu s dng chun (kt thc chun ). Song, trong thc t nhiu trng hp, ch th khng phn ng ng im tng ng dn n sai s chun v c gi l sai s ch th. Sai s ch th mang tnh cht sai s h thng do phng php (chng V). V d: chun xc nh HCl bng NaOH vi vic NaOH trn buret, ti im tng ng c pH = 7, nu dng ch th l qu tm (c pKa = 7) th phn ng ch th xy ra ng im tng ng v chun c sai s bng 0, nu dng ch th l metyl (c pKa = 5) th phn ng ch th xy ra trc im tng ng, nh vy khi kt thc chun trong dung dch cn mt lng d axit HCl, dn n sai s ch th (sai s m), cn khi s dng ch th phenophtalein (c pKa = 9) th phn ng ch th xy ra sau im tng ng, nh vy khi kt thc chun trong dung dch cn mt lng d baz NaOH, dn n sai s ch th (sai s dng). Sai s ch th phn trm (ss%, e%) c tnh theo biu thc III- 2: e% = [(Vkt - Vt)/Vt].100, (III- 2) trong , Vt l th tch dung dch tiu chun cn t im tng ng, Vkt l th tch dung dch tiu chun dng khi kt thc chun .
T s (Vkt/Vt).100 cn c gi l phn trm chun (% chun ), do sai s ch th % s l: e% = % chun - 100. 2. YU CU CA PHN NG CHUN Khc vi phng php phn tch khi lng, trong phng php phn tch th tch, thi gian chun ngn v khng c php cho d thuc th, nn phn ng chun c s dng phi tho mn cc iu kin sau: a. Phn ng phi hon ton C ngha l phn cht cn phn tch cha tham gia phn ng phi nh hn sai s cho php, hay sai s ca php cn Trong Ho phn tch sai s cho php thng l 0,1% ( mt s trng hp c th c th cho php sai s ln hn nh 1%, 2%, 5% ). Mun vy phn ng phi c hng s cn bng ln. Da vo sai s cho php c th tnh ln cn thit ca hng s cn bng. V d: vi phn ng chun : A + B = A + B (III- a) hng s cn bng K ca n c xc nh bng biu thc III- 3: [B]-1 K = [A] [B] [A]-1 (III- 3) Theo phng trnh III- a, nng ton phn ca cc A v B l: CA = [A] + [A] CB = [B] + [B] Nu sai s cho php l - 0,1% th: [A] = (0,1/100). CA = (1/999). [A] [B] = ( 0,1/100). CB = (1/999). [B] Nh vy: K 999. 999 106 Khi phn ng xy ra khng hon ton, phi c bin php thc y phn ng xy ra hon ton, chng hn dng phn ng ph V d: - Trong chun complexon III (mc 8.4 chng III) xc nh ion kim loi Mm+: Mm+ + Na2H2Y = MYm-4 + 2Na+ + 2H+, pH ca dung dch lun gim, nn phi dng h m pH duy tr pH dung dch gi tr bo m cho phn ng xy ra hon ton. - Vi phn ng thun nghch: 2Cu2+ + 4I- Cu2I2 + I2 khi cho thm KCNS, sn phm Cu2I2 c thay bng kt ta Cu2(CNS)2 v gii phng KI, lm tng lng KI v gim lng Cu2I2, gip cho cn bng xy ra theo chiu thun: Cu2I2 + 2KCNS = Cu2(CNS)2 + 2KI b. Phn ng ch cho mt loi sn phm duy nht, hay ch c mt phn ng xy ra C nh vy mi xc nh c ng lng gam hoc lng tiu tn thc ca cc cht tham gia phn ng. Nu phn ng c th xy ra theo nhiu hng khc nhau, th phi gii hn iu kin ch mt phn ng nh lng xy ra. V d: chn pH mi trng, ion MnO4- ch tham gia 1 trong tham gia 3 phn ng: pH = 1 MnO4- + 8H+ + 5e = Mn2+ + 4H2O
pH = 7 = MnO(OH)2 + 4OH MnO4 + 3H2O + 3e pH > 10 MnO4- + e = MnO42Hay khi chun chun ion Cl- bng AgNO3. phi duy tr mi trng trung tnh hoc axit yu, v trong mi trng kim xy ra phn ng: 2Ag+ + 2OH- = Ag2O + H2O lm mt mt lng thuc th, gy nn sai s. c. Phn ng phi chn lc trnh nh hng ca ion gy nhiu Nu c cc ion gy nhiu th cn gii hn iu kin phn ng xy ra l chn lc hoc phi tch, che ion gy nhiu. V d: - Chun complexon III xc nh ion Fe3+ trong iu kin c cc ion Al3+, 2+ Mg , Ca2+ cn chun ti pH = 2, lc ny ch c ion Fe3+ tham gia phn ng chun , cc ion khc khng tham gia nn khng gy nn sai s chun . - Chun complexon III xc nh ion Ca2+ trong iu kin c ion Mg2+, cn chun ti pH = 12, lc ny ch c ion Ca2+ tham gia phn ng chun ; cn ion Mg2+ b kt ta di dng Mg(OH)2 khng tham gia nn khng gy nn sai s chun . - Chun complexon III xc nh ion Mg2+ trong iu kin c ion gy nhiu Fe3+, Cu2+, c th che cc ion Fe3+, Cu2+ bng ion CN- di dng cc ion phc cht tan [Fe(CN)6]3-, [Cu(CN)4]2-, lc ny ch c ion Mg2+ tham gia phn ng vi complexon III. - Chun complexon III xc nh ion Mg2+ trong iu kin c ion gy nhiu 3+ Fe , Al3+, c th tch cc ion gy nhiu Fe3+, Al3+ di dng cc kt ta hydroxit Fe(OH)3, Al(OH)3 ti pH = 5 - 6, lc b kt ta s thu c dung dch ch c ion Mg2+, sau mi tin hnh chun . d. Tc phn ng phi ln phn ng tc thi t cn bng Nh vy, s trnh c s d thuc th do trng thi qu bo ho ca n ti im tng ng, nguyn nhn gy nn sai s. Nu tc phn ng chm phi dng xc tc tng tc hay chn cch chun ngc (mc 3.2 chung III). V d 1: Dng xc tc tng tc ca phn ng chun xc nh H2C2O4 bng KMnO4 trong mi trng axit bng cch un nng dung dch n nhit 60 - 800C hoc cho vo dung dch chun ion Mn2+. V d 2: Chn cch chun ngc chun complexon III xc nh ion Al3+. e. Phi c ch th xc nh im tng ng Nu khng c th d phn ng tho mn cc iu kin trn cng khng s dng c. V d: phn ng Ca2+ + C2O42- = CaC2O4 tho mn tt c cc iu kin t a n d, song, khng dng c, v khng c ch th mu thch hp xc nh im tng ng.
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3. PHN LOI PHNG PHP CHUN Cc phng php chun thng c phn loi theo hai cch: - Da theo loi phn ng ho hc xy trong chun . - Da theo cch tin hnh chun .
3.1. Phn loi phng php chun theo loi phn ng

Trong dung dch, cc ion tham gia phn ng theo hai nhm phn ng chnh: - Phn ng trao i gm cc phn ng: trung ho, kt ta v to phc. - Phn ng oxi ho kh. Do , cc phng php chun c chia thnh 4 nhm: - Chun trung ho. - Chun oxi ho kh. - Chun kt ta. - Chun to phc. a. Chun trung ho L phng php chun da trn phn ng trung ho ca Bronsted: axit1 + baz2 = baz1 + axit2, (III- b) Trong mi trng nc, c th vit n gin ho theo Arrhenius: H+ + OH- = H2O Nh vy, y dung dch tiu chun l cc dung dch axit hoc baz v dng xc nh cc cht c tnh baz hoc axit. V d: xc nh NaOH, Na2CO3 bng dung dch tiu chun HCl. Trong php chun ny, ng lng gam () ca cht tham gia phn ng c xc nh bng biu thc III- 4: = M/n (III- 4) Trong n l ch s (tr s) ng lng. y, n l s nhm OH- hoc H+ m mt phn t cht tham gia phn ng cho hay nhn. V d: trong phn ng: H2SO4 + 2NaOH = Na2SO4 + 2H2O H2SO4 = MH2SO4/2 NaOH = MNaOH, cn trong phn ng H3PO4 + NaOH = NaH2PO4 + H2O H3PO4 = MH3PO4, mc d axit H3PO4 c cha 3 proton; cn vi phn ng: Na2CO3 + 2HCl = 2NaCl + H2O + CO2 Na2CO3 = MNa2CO3/2 b. Chun oxi ho kh L phng php chun da trn phn ng oxi ho kh aox1 + bkh2 = akh1 + box2 (III- c) c ngha l y xy ra hai qu trnh : aox1 + ame = akh1 (III- c1) box2 + bne = bkh2 (III- c2) v tho mn iu kin am = bn (m, n l s electron m mt phn t ox1 hay ox2 nhn). Trong phng php chun ny, dung dch tiu chun l nhng cht oxi ho hoc cht kh c dng xc nh cc cht mang tnh kh hoc c tnh oxi ho. V d: chun ion Fe2+ bng dung dch tiu chun KMnO4. ng lng gam ca cc cht tham gia phn ng cng c xc nh bng biu thc III- 4 vi n l s electron m mt phn t cht tham gia phn ng nhn hoc nhng. V d: trong phn ng chun
6Fe2+ + K2Cr2O7 + 14H+ = 6Fe3+ + 2Cr3+ + 7H2O + 2K+ Fe2+ = MFe2+/1, v t Fe2+ sang Fe3+ ch nhng mt e, cn K2Cr2O7 = MK2Cr2O7/6, v phn t K2Cr2O7 c 2 Cr(VI), m mi Cr(VI) nhn 3e thnh Cr(III), do c phn t nhn 6e. c. Chun kt ta L phng php chun da trn phn ng to kt ta: (III- d) M + nX = MXn ( n gin, y b qua in tch ca cc ion M v X). Mc d phn ng to kt ta c nhiu, song, trong thc t cc phn ng c dng trong chun rt t v khng tm c ch th thch hp. Trong phn tch cc i tng nng nghip, thng ch dng nhm phn ng ca AgNO3 vi cc ion Cl-, Br-, I-, CNS- (k hiu chung l X-): AgNO3 + X- = AgX + NO3 xc nh cc ion ny. y, qui nh ng lng gam ca AgNO3 bng chnh khi lng mol phn t ca n: AgNO3 = MAgNO3. * Do X- = MX-. d. Chun to phc L phng php chun da trn phn ng to phc: Mm+ + tXn- = [MXt]m-nt (III- e) Cc phn ng to phc c nhiu, nhng thng dng cc phn ng ca Hg(NO3)2, Hg(ClO4)2, vi cc ion Cl-, Br-, CN-, CNS- (cc ion X-) da trn s to hp cht phc [HgX2] t phn li hoc ca AgNO3 vi ion CN- tao hp cht phc [Ag(CN)2]v c bit l cc phn ng ca nhm phi t cc cht hu c cha nhm CH2 COOH aminocarboxylic axit (N ) (nhm hp cht complexon) vi CH2 COOH cc ion kim loi. Trong quan trng nht l nht l hp cht dinatri etylendiamintetraaxetat (complexon III, Na2EDTA, Na2H2Y,), cht ny tham gia phn ng vi cc ion kim loi Mm+ to cc phc cht bn: Mm+ + Na2H2Y = MYm-4 + 2Na+ + 2H+ Trong cc phn ng chun ny, qui nh Na2EDTA = MNa2EDTA/2. Do , ng lng gam ca cc cht tham gia phn ng tnh theo qui nh ny m khng da vo in tch ca ion tham gia phn ng, tc Mm+ = MMm+/2. V d: vi phn ng Fe3+ + Na2H2Y = FeY- + 2Na+ + 2H+ th: Fe3+ = M Fe3+/2.
3.2. Phn loi phng php theo cch tin hnh chun
Da theo thao tc tin hnh phn ng gia cht cn xc nh v thuc th c th chia cc phng php chun thnh 2 nhm: - Chun trc tip. - Chun gin tip. a. Chun trc tip L chun ch da vo mt phn ng duy nht gia cht cn xc nh v dung dch thuc th. Chnh v th, nn cc phn ng v cc thao tc trung gian gim i, do
kt qu chun trc tip thng chnh xc hn chun gin tip. V d: chun xc nh NaOH bng dung dch HCl, hay chun xc nh ion Cl- bng AgNO3 vi ch th K2CrO4 (phng php Mo) (mc 8.3, chng III). -----------------------------------------------------------------------------------------------------------* V trong phn tch th tch, dung dch AgNO3 cn l dung dch tiu chun cho chun to phc xc nh ion CN -: AgNO3 + 2CN- = [Ag(CN)2] - + NO3AgNO3 = MAgNO3, nn CN- = 2MCN-. Chun trc tip ch thc hin c khi: - Phn ng phn tch c tc ln (trnh hin tng qu bo ho cht tham gia phn ng im tng ng). - Ch c mt phn ng duy nht gia cht cn xc nh v thuc th. - C ch th thch hp xc nh im tng ng. Trong chun ny, s ng lng gam ca cht cn xc nh lun bng s ng lng gam thuc th cn dng cho chun , tc l Vx . Nx = Vtc . Ntc. ng lng gam ca cc cht tham gia phn ng c xc nh theo loi phn ng chun xy ra (mc 3.1 chng III). b. Chun gin tip c dng khi cht cn phn tch khng phn ng trc tip c vi dung dch tiu chun hoc khng th tin hnh chnh xc phn ng trc tip gia chng. Tu theo cc phn ng xy ra trong qu trnh thao tc chun m chia chun gin tip thnh 3 loi: - Chun ngc. - Chun th. - Chun th, ngc. * Chun ngc Cn gi l chun nghch. L php chun s dng 2 dung dch tiu chun, u tin cho cht cn xc nh phn ng vi mt lng chnh xc v ly d ca dung dch tiu chun th nht, sau lng d ca dung dch tiu chun ny c xc nh li bng mt dung dch tiu chun th hai. V d: xc nh ion Cl- trong mi trng axit (phng php Fonha) (mc 8.3, chng III, cho n tc dng vi dung dch tiu chun AgNO3 ly d: HNO3 AgCl + NO3- , Cl + AgNO3 = sau chun li lng AgNO3 d bng dung dch tiu chun KCNS: AgNO3 + KCNS = AgCNS + KNO3 Chun ngc thng c dng khi: - Phn ng gia cht cn xc nh v thuc th xy ra chm. V d: phn ng gia ion Al3+ vi complexon III, y, chun lng d complexon III bng dung dch tiu chun ZnSO4: chm 3+ Al + Na2H2Y d = AlY- + 2Na+ + 2H+ Zn2+ + Na2H2Y d = ZnY2- + 2Na+ + 2H+
- Khi khng c ch th thch hp xc nh im tng ng. V d: phn ng chun xc nh ion Cl- ni trn khng th dng K2CrO4 lm ch th v kt ta nu Ag2CrO4 khng hnh thnh trong mi trng axit. - Khi chun nhng cht d bay hi, khng bn. V d: khi xc nh H2O2, ion SO32- bng KMnO4, cho cc cht phn ng vi KMnO4 ly d sau lng d ca KMnO4 c chun bng dung dch tiu chun ion Fe2+. Trong chun ngc, s ng lng gam ca dung dch tiu chun 1 (tc1) bng tng s ng lng gam cht cn xc nh v s ng lng gam ca tiu chun 2 (tc2), tc tho mn biu thc: Vx . Nx = Vtc1 . Ntc1 - Vtc2 . Ntc2 Trong chun ngc, cc phn ng xy ra l cng loi, do ng lng gam cc cht tham gia phn ng c tnh theo loi phn ng chun s dng (mc 3.1 chng III). * Chun th Khi cht cn xc nh v dung dch tiu chun khng phn ng vi nhau (v d: 2+ ion Ca khng phn ng vi KMnO4) hoc phn ng khng theo mt nh lng nht nh (v d: phn ng gia K2Cr2O7 vi Na2S2O3 trong mi trng axit mnh), th th nh lng cht cn xc nh bng mt cht th 3 l cht c phn ng nh lng vi dung dch tiu chun. V d: xc nh ion Pb2+ bng chun vi dung dch tiu chun ion Fe2+ theo phng php oxi ho kh l khng thc hin c, v ion ion Pb2+ khng phn ng vi ion Fe2+. Tin hnh chun nh sau: cho vo dung dch ion Pb2+ lng K2CrO4 ly d , s kt ta nh lng ion Pb2+ di dng PbCrO4, sau ho tan lng PbCrO4 thu c trong axit H2SO4 long v chun lng ion Cr2O72- gii phng ra bng dung dch tiu chun ion Fe2+: (1) Pb2+ + K2CrO4 = PbCrO4 + 2K+ (phn ng th) 2+ 2+ 2PbCrO4 + 2H = 2Pb + Cr2O7 + H2O (2) Cr2O72- + 6Fe2+ + 14H+ = 6Fe3+ + 2Cr3+ + 7H2O (3) (phn ng chun ) Nh vy, thay cho vic chun ion Pb2+, xc nh lng ion CrO42- tng ng vi lng ion ch. Trong chun th lun tho mn mi quan h: s ng lng gam ca cht cn xc nh bng s ng lng gam cht tiu chun: Vx . Nx = Vtc . Ntc, d s dng mt ln hay nhiu ln th. ng lng gam ca cc cht tham gia phn ng c xc nh da vo c ch phn ng th v phn ng chun . Chng hn, nh v d trn: Pb2+ = MPb2+/3, v theo cc phn ng th (1), (2) trn, th 2 ion Pb2+ c thay bng 1 ion Cr2O72-, m theo phn ng chun (3) trn th 1 ion Cr2O72- nhn 6e c ngha rng phn ng ca 1 ion Pb2+ tng ng vi phn ng ca 3e. * Chun th, ngc l cch chun phi hp gia chun th vi chun ngc. Trong chun th, ngc, ng lng gam ca cc cht tham gia phn ng tnh theo phng php chun th cn s ng lng gam ca chng tnh theo phng php chun ngc.
V d: chun xc nh ion Ca2+ bng dung dch tiu chun KMnO4. Cho ion Ca phn ng vi dung dch tiu chun (NH4)2C2O4 ly d, lc b kt ta, dung dch thu c c chun bng dung dch tiu chun KMnO4: Ca2+ + (NH4)2C2O4 d = CaC2O4 + 2NH4+ (phn ng th) 5(NH4)2C2O4 d + 2KMnO4 + 16H+ = 10CO2 + 2Mn2+ + 2K+ + 10NH4+ + 8H2O (phn ng chun ) Cc phn ng trn cho thy: 1 ion Ca2+ c th bi s mt i ca 1 ion C2O42-, 1 ion C2O42- khi tham gia phn ng chun nhng 2e, do , 1 ion Ca2+ tng ng vi 2e, suy ra: Ca2+ = MCa2+/2. Cng theo cc phn ng trn c: VCa2+.NCa2+ = V(NH4)2C2O4. N(NH4)2C2O4 - VKMnO4.NKMnO4.
2+
4. CCH PHA DUNG DCH TIU CHUN Tt c cc ho cht dng trong phn tch phi m bo sch tinh khit phn tch (TKPT) hoc tinh khit ho hc (TKHH). Trong phn tch thng thng, ch dng loi sch tinh khit phn tch. pha ch mt dung dch tiu chun cn phi bit cc tiu ch sau: * Dung dch tiu chun cn pha s dng cho chun no, t xc nh ng lng gam () ca cht cn pha. V d: khi pha dung dch KMnO4 cn bit n dng cho chun trong mi trng axit hay baz; nu dng chun trong mi trng axit mnh th: KMnO4 = MKMnO4/5, nu dng chun trong mi trng kim th: KMnO4 = MKMnO4. * Nng v lng dung dch cn pha l bao nhiu, t tnh lng cn cn. V d: pha 2 lt dung dch KMnO4 0,1N dng cho chun oxi ho trong mi trng axit mnh. C: MKMnO4 = 158,038; KMnO4 = MKMnO4/5= 31,6075. Nh vy, lng cn s l: w = . N . V = 31,6075 . 0,1 . 2 = 6,3215 g. * Ho cht dng pha l cht gc hay khng phi l cht gc, tm ra cch pha v cch bo qun. Cht gc l cht bo m cc tiu chun: - Phi tinh khit v phng din ho hc, tinh khit phi t 99,9%, tc phi t tinh khit TKPT hoc TKHH. - Phi bn trng thi rn, trng thi lng cng nh trong dung dch. y l yu t rt quan trng, n m bo cho vic ly chnh xc lng ho cht tnh cng nh s bo qun chng sau khi pha. Chnh v th, m hng lot cc ho cht sch nh NaOH rn (d ht m v ht CO2), HCl 35%, HNO3 65% (d bay hi), H2SO4 95% (d ht m), KMnO4, AgNO3 (d b nh sng phn hu) khng phi l cht gc. - Thnh phn ca ha cht phi ng ng vi cng thc ho hc, nu c nc kt tinh th phi bit s phn t nc kt tinh. V d: CuSO4.5H2O, th chc chn 1 phn t CuSO4 phi ngm 5 phn t H2O - ng lng gam ca ho cht cng ln cng tt, sai s cn l nh nht. V d: gia H2C2O4.2H2O v H2C2O4, nn dng H2C2O4.2H2O pha dung dch axit oxalic tiu chun gc, v c ng lng gam ln hn.
Khi pha dung dch tiu chun t ho cht gc ch cn cn chnh xc lng tnh ton bng cn phn tch v ho tan vo bnh nh mc c dung tch bng th tch cn pha s c dung dch tiu chun c nng cn pha. Nu ho cht dng pha khng phi l cht gc th ch cn cn tng i chnh xc lng cn cn c tnh thm t 5 10% bng cn k thut v em pha. Dung dch thu c c nng gn ng. Nng ng ca dung dch ny cn c xc nh bng chun vi dung dch tiu chun khc. y, c 2 cch pha: - Cch 1: Pha dung dch c nng chnh xc gn bng vi nng cn pha. Lng cn tnh c pha vo trong cc hoc trong bnh nh mc thnh dung dch c th tch cn pha, lc b kt ta nu c. Dung dch thu c c chun li kim tra nng bng dung dch tiu chun khc. V d: pha1 lt dung dch NaOH 0,1000N dng cho chun trung ho. V NaOH rn d ht m nn n khng phi l cht gc. Do vy, khi cn cn cn tng khong 5 10% so vi lng phi cn, tc t 4g thnh khong 4,2g 4,4g, ri pha vo bnh nh mc 1 lt. Dung dch thu c c chun li bng dung dch cht gc H2C2O4 0,1000N hoc dung dch HCl 0,1000N tiu chun xc nh chnh xc nng ca n. - Cch 2: Pha dung dch c nng ng vi nng cn pha N. Lng cn tnh c pha vo trong cc vi th tch dung mi chnh xc (Vml) nh hn th tch cn pha, thu c dung dch c nng N cao hn nng cn pha N. Dung dch thu c c chun li kim tra nng bng dung dch tiu chun khc, ri t kt qu thu c tnh ra lng dung mi (VH2O) cn thm vo lng dung dch cn (V1) li theo biu thc III- 5: (III- 5) VH2O (ml) = [(N/N) 1]. V1 (ml) y: N nng dung dch pha. N nng dung dch cn pha. V1 th tch dung dch pha cn li cn pha long, bng th tch dung dch ban u V tr i s ml dng cho chun kim tra. V d: pha khong1 lt dung dch NaOH 0,1000N dng cho phn ng trung ho. Cng nh cch 1, cn khong 4,2g 4,4g NaOH rn ri pha vo mt th tch chnh xc b hn th tch cn pha, v d: 800 ml. T dung dch thu c ht 2 ln, mi ln 25 ml, chun vi dung dch H2C2O4 0,1000N ht trung bnh, v d: 30,0 ml. Nh vy, dung dch pha c nng 0,1200N cao hn nng cn pha. Do , cn thm nc ct vo dung dch pha, lng nc c tnh theo biu thc III- 5: N = 0,1200 ; N = 0,1000; V = 800 (2 . 25) = 750 ml; VH2O cn thm = 150 ml. Nh vy, khi cho thm 150 ml H2O vo 750 ml dung dch pha cn li s c 900 ml dung dch NaOH vi nng chnh xc 0,1000N. Cch pha th 2 phc tp hn cch pha th 1, nhng rt thun tin cho vic tnh ton, nht l trong phn tch hng lot mu, v y, tr s nng l nhng s chn. Hin nay, vi s hon thin ca cng nghip ho cht, sn xut sn cc ng chun (fixanan) nh: ng fixanan HCl 0,1N; KCNS 0,1N Vic pha dung dch tiu chun t cc ng fixanan rt n gin: ch cn ho tan ton b lng cha trong ng thnh mt th tch xc nh theo ch dn s c dung dch c nng chnh xc nh ghi trn ng. V d: pha mt ng fixanan HCl 0,1N thnh mt lt dung dch s c dung dch HCl c nng chnh xc 0,1N m khng cn chun li.
5. CCH TNH KT QU PHN TCH Phng php phn tch th tch l phng php da trn nh lut ng lng. Trong phn ng chun khng c s d tha ca cht cn xc nh hay thuc th, ni cch khc s ng lng gam ca cc cht tham gia phn ng l bng nhau, tc: wA/A = wB/B , (III6) Trong : wA, wB khi lng ca cc cht A, B tham gia phn ng, A, B ng lng gam ca cc cht A, B. ng dng cc biu thc I- 2 v III- 6 , c th vit: wA/A = VB . NB . 10-3 (nu cn mt lng mu v em chun ton b, V tnh bng ml) hoc: VA . NA = VB . NB (khi ht mt lng dung dch mu mang chun ). T khi lng w (g) ca cht A c xc nh bng biu thc III- 7: wA = A . VB . NB . 10-3 (g) (III- 7) V d 1: C bao nhiu gam Ba(OH)2 ho tan trong 250 ml dung dch, nu chun 20 ml dung dch ny ht 22,4 ml dung dch HCl 0,09884N? Gii: Phn ng chun : Ba(OH)2 + 2HCl = BaCl2 + 2H2O do : Ba(OH)2 = MBa(OH)2/2 = 171,35/2 = 85,675 (g). p dng biu thc III- 7, khi lng w ca Ba(OH)2 trong 20 ml dung dch mu l: w = 85,675. 22,4. 0,09884.10-3 = 0,190 (g) v trong 250 ml dung dch mu l: 0,190.(250 : 20) = 2,275 (g). V d 2: Tnh phn trm H2C2O4 trong mu, nu cn 0,200 g mu v ho tan vo 50 ml dung dch. Chun dung dch ny trong mi trng axit ht 30,5 ml KMnO4 0,10N. Gii: Phn ng chun : 5H2C2O4 + 2KMnO4 + 6H+ = 10CO2 + 2K+ + 2Mn2+ + 8H2O do : H2C2O4 = MH2C2O4/2 = 90/2 = 45 p dng biu thc III- 7, khi lng w ca H2C2O4 trong 0,2000 g mu l: w = 45. 30,5. 0,10. 10-3 = 0,1372 (g). Suy ra% % H2C2O4 trong mu l: % H2C2O4 = (0,1372: 0,2000). 100 = 68,60%. 6. NG CHUN
6.1. nh ngha
Trong chun , nng ca cc cht trong dung dch lun thay i. S thay i ny dn n hng lot cc i lng vt l, ho hc cng thay i tr s ca mnh. Do , theo di s thay i ca cc i lng vt l, ho hc c th cho bit nng cc cht trong dung dch. V d: khi chun xc nh HCl bng NaOH th hng lot cc i lng nh nng ca HCl, NaOH, H+, OH- thay i dn n pH dung dch thay i hay cc i lng vt l khc nh dn in ca dung dch, in th dung dchthay i ph thuc vo lng NaOH a vo h chun . Do c nhiu i lng vt l, ho hc gn lin vi h chun , cho nn, tu tng phng php chun m s dng i lng theo di thch hp. Thng thng, trong phng php trung ho dng i
lng pH, trong phng php oxi ho kh dng i lng in th dung dch E, trong phng php kt ta dng cc i lng pX (pX = -lg[Xn-]), pM (pM = -lg[Mm+]), trong phng php to phc dng i lng pM, pX. th biu din s ph thuc ca mt i lng vt l, ho hc no c lin quan n nng cc cht tham gia phn ng chun ln th tch dung dch tiu chun a vo c gi l ng chun . Tuy vy, tu theo loi phn ng chun m chn mi quan h thch hp. Thng thng, trong phng php trung ho l ng biu din ph thuc: pH = f(Vtc); trong phng php oxi ho kh: E = f(Vtc); trong phng php kt ta, to phc: pM = f( Vtc), pX = f(Vtc). Cng c th biu din ng chun di dng hm i lng o ph thuc ln % chun . Tr s ca pH, E, pM, pX ti im tng ng c gi l ch s pT. Vic nghin cu ng chun c ngha rt ln trong vic tin hnh chun , n gip cho vic xc nh t chnh xc cao v chn ch th thch hp cho chun . Qu trnh chun tri qua 4 giai on: cha chun , chun trc im tng ng, chun ti im tng ng, chun sau im tng ng. mi giai on, thnh phn cc cht trong dung dch chun ging nhau, nn xy dng ng chun chnh l thit lp cc biu thc ton biu din s ph thuc ca i lng theo di ca tng giai on ln th tch dung dch tiu chun s dng hay ln % chun . Vic tnh chi tit ch cn l s thay s vo cc biu thc ton c.
6.2. ng chun trung ho

Cc axit c chia thnh cc nhm theo mnh yu ca chng: axit mnh (Ka 1), axit trung bnh Ka t 10-2 10-3, axit yu Ka t 10-4 10-10 v rt yu Ka < 10-10. Tng t, cc baz cng c chia thnh cc nhm theo mnh yu ca chng: baz mnh (Kb 1), baz trung bnh Kb t 10-2 10-3, baz yu Kb t 10-4 10-10 v rt yu Kb < 10-10. Ngoi ra, cc axit, baz tham gia phn ng chun trung ho c th l cc axit, baz n chc, a chc, c th nm trong hn hp nhiu axit hoc nhiu baz, do , trong phng php chun trung ho c th gp cc loi chun : chun axit mnh bng baz mnh v ngc li, chun axit yu bng baz mnh, chun baz yu bng axit mnh, chun axit yu bng baz yu v ngc li, chun hn hp axit, hn hp baz hoc axit a chc bng baz mnh hay axit mnh ng chun trung ho l ng biu din s ph thuc pH dung dch ln th tch dung dch tiu chun a vo trong qu trnh chun : pH = f(Vtc) hay l ln % chun : pH = f(% chun ). Mi dng chun khc nhau s c ng chun khc nhau. Trong thc t s dng ch cn bit gn ng ng chun nn trong tnh ton cho php dng cc biu thc tnh gn ng pH dung dch. a. Cch tnh pH ca mt s dung dch Trong dung dch, c th s dng nh ngha axit, baz ca Arrhenius hoc nh ngha tng qut hn ca Bronsted. Song, vic chn nh ngha tin cho tnh ton pH dung dch ph thuc vo tng trng hp c th, v d: trong mi trng nc, i vi cc axit, baz in hnh nh: HCl, H3PO4, NaOH, NH4OH s dng nh ngha ca Arrhenius n gin hn, cn i vi cc axit, baz nh ion NH4+, ion CO32- nn s dng nh ngha ca Bronsted. * pH dung dch axit mnh: Gi thit c axit mnh HA, theo Arrhenius, trong dung dch nc ca n c hai cn bng:
HA = H+ + AH2O H+ + OHT mi quan h cn bng vt cht c: = [HA] + [A-] = [HA] + [H+] - [OH-] = [HA] + [H+] - KH2O/[H+] Suy ra: [H+]2 + [H+]([HA] - CHA) - KH2O = 0 9)
CHA
(III- 8) (III-
Nu coi s phn li ca axit mnh HA l hon ton th [HA] = 0 v KH2O CHA, s c [H+] = CHA NHA v pH = - lg[H+] = -lgCHA (III10) Trong thc t, s dng my o pH o pH dung dch. Do cc my o thng dng c chnh xc 0,02pH, v th vic tnh pH theo biu thc III- 10 ch c ngha khi pH < 6,3, nu pH > 6,3 s khng th b qua [OH-] do nc phn li v nng [H+] phi tnh theo biu thc III- 9. * pH dung dch baz mnh: Gi thit c baz mnh BOH, theo Arrhenius, trong dung dch nc ca n c hai cn bng: BOH = OH- + B+ H2O H+ + OHT mi quan h cn bng vt cht c: CBOH = [BOH] + [B+] = [BOH] + [OH-] - [H+] = [BOH] + [OH-] - KH2O/[OH-] 11) Suy ra: [OH-]2 + [OH-]([BOH] - CBOH) - KH2O = 0 12)
(III(III-
Nu coi s phn li ca baz mnh BOH l hon ton th [BOH] = 0 v KH2O CBOH, s c [OH-] = CBOH NBOH v pOH = - lg[OH-] = -lgCBOH, T : pH = 14 - pOH = 14 + lg[OH-] = 14 + lgCBOH (III13) Cng nh trn trnh by, do cc my o pH thng dng c chnh xc 0,02pH, v th vic tnh pH theo biu thc III- 13 ch c ngha khi pH > 7,7, nu pH < 7,7 s khng th b qua [H+] do nc phn li v nng [OH-] phi tnh theo biu thc III12. * pH dung dch axit trung bnh v yu: Gi thit c axit HA, theo Arrhenius, trong dung dch nc ca n c hai cn bng: HA = H+ + AH2O H+ + OHS phn li ca axit c biu th bng hng s phn li Ka: Ka = ([H+][A-])/[HA] T mi quan h cn bng vt cht c:
(III- 14)
CHA = [HA] + [A-] = [HA] + [H+] - [OH-] = [HA] + [H+] - KH2O/[H+] (III- 8) Thay cc mi quan h ca III- 8 vo III- 14 s c: [H+] = Ka{CHA - [H+] + KH2O/[H+]}/{[H+] - KH2O/[H+]} (III- 15) tnh c chnh xc nng ca ion H+ cn gii phng trnh bc 3, l iu khng d thc hin. Vic gii c th n gin ho nh sau: s c: Nu coi [OH-] [H+], th CHA = [HA] + [H+] v thay n vo biu thc III- 15 [H+]2 + Ka[H+] - KaCHA = 0 (III- 16) Khi s phn li ca HA l khng ng k (i vi axit yu v rt yu) v CHA
ln, c th coi [H+] CHA hay [HA] CHA, th biu thc III- 16 c n gin ho thnh biu thc III- 17 v pH dung dch c xc nh bng biu thc III- 18: [H+] = (Ka . CHA )1/2 (III- 17) pH = (1/2)pKa - (1/2)lgCHA (III- 18) Khi o pH, thng mc sai s 5%, nn vic tnh pH theo biu thc III- 18 c coi l ng, nu pH tnh c tho mn iu kin: pH > pCHA + 1,3, ( y, pCHA = - lgCHA), nu khng, phi tnh [H+] theo biu thc III- 16 hoc biu thc III- 15. * pH dung dch baz trung bnh v yu: Gi thit c baz BOH, theo Arrhenius, trong dung dch nc ca n c hai cn bng: BOH OH- + B+ H2O H+ + OHS phn li ca baz c biu th bng hng s phn li Kb: Kb = ([OH-][B+])/[BOH] (III- 19) T mi quan h cn bng vt cht c: = [BOH] + [B+] = [BOH] + [OH-] - [H+] = [BOH] + [OH-] - KH2O/[OH-] (III-
CBOH 11)
Thay cc mi quan h ca III- 11 vo III- 19 s c: [OH-] = Kb{CBOH - [OH-] + KH2O/[OH-]}/{[OH-] - KH2O/[OH-]} (III- 20) tnh c chnh xc nng ca ion OH cng cn gii phng trnh bc 3, l iu khng d thc hin. Vic gii c th n gin ho nh sau: Nu coi [H+] [OH-], th CBOH = [BOH] + [OH-] v thay n vo biu thc III- 20 s c: [OH-]2 + Kb[OH-] - KbCBOH = 0 (III- 21) Nu s phn li ca BOH l khng ng k (i vi baz yu v rt yu) v CBOH ln, c th coi [OH-] CBOH hay [BOH] CBOH, th biu thc III- 21 c n gin ho thnh biu thc III- 22 v pH dung dch c xc nh bng biu thc III- 24: [OH-] = ( Kb . CBOH )1/2 (III - 22) pOH = (1/2)pKb - (1/2)lgCBOH (III - 23) pH = 14 - pOH = 14 - (1/2)pKb + (1/2)lgCBOH (III24)
Nh ni trn, khi o pH, thng mc sai s 5%, nn vic tnh pOH theo biu thc III- 24 c coi l ng, nu pOH tnh c tho mn iu kin: pOH > pCBOH + 1,3, ( y, pCBOH = - lgCBOH)), nu khng, phi tnh [OH-] theo biu thc III- 21 hoc III- 20. * pH dung dch cha cp axit baz lin hp ca axit hoc baz trung bnh v yu: Trong dung dch nc, theo Bronsted, cp axit baz lin hp ca axit hoc baz trung bnh v yu vi nng ca axit l CHA v ca baz l CA- s to ra h m pH. S tong tc gia chng vi nhau th hin qua cc phng trnh: HA H+ + AA- + H+ HA Cc mi quan h ny c thit lp bi hng s cn bng Ka (III- 14). T mi quan h cn bng vt cht c: CHA = [HA] + [A-] = [HA] + [H+] - [OH-] [HA] = CHA - [H+] + [OH-] 25) (III- e1) (III- e2)
(III-
(IIICA- = [A-] + [HA] = [A-] + [OH-] - [H+] [A-] = CA- - [OH-] + [H+] 26) Do , phng trnh III- 14 c vit thnh: [H+] = Ka{CHA - [H+] + [OH-]}/{CA- - [OH-] + [H+]} (III27) Nu [OH-] < 5% [H+], [H+] < 5% CHA v [H+] < 5% CA- (5% l sai s ca my o pH), cc biu thc III- 25 v III- 26 c n gin ho thnh: [HA] = CHA v [A-] = CA-. Thay cc gi tr ny vo biu thc III- 27 s c: = {[H+] CA-}/CHA Ka (III- 28) Log ho biu thc III- 28 v chuyn v s c: pH = pKa - lg(CHA /CA- ) (III- 29) * pH dung dch mui thu phn: - Khi trong dung dch nc c mui BA to bi axit yu HA v baz mnh BOH. Mui BA b thu phn: BA + H2O = HA + B+ + OH(III- f) Theo Bronsted, c th coi BA nh l mt baz yu. Do , c th s dng biu thc III- 24 vi vic thay CBOH bng CBA v pKb = 14 - pKa tnh pH dung dch mui BA (III- 27). pH = 7 + (1/2)pKa + (1/2)lgCBA (III- 30) - Khi trong dung dch nc c mui BA to bi baz yu BOH v axit mnh HA. Mui BA b thu phn: BA + H2O = BOH + H+ + A(IIIg) Theo Bronsted, c th coi BA nh l mt axit yu. Do , c th s dng biu thc III- 18 vi vic thay CHA bng CBA v pKa = 14 - pKb tnh pH dung dch mui BA: pH = 7 - (1/2)pKb - (1/2)lgCBA (III- 31) * pH dung dch mui lng tnh:
l mui c th ng vai tr nh mt axit v nh mt baz. Cc mui ny hnh thnh do trung ho cha hon ton cc axit hoc cc baz a chc, v d nh cc mui NaH2PO4, NaHCO3 Vic tnh pH dung dch ca cc mui ny c th c minh ho cho trng hp mui BHA hnh thnh t axit H2A (c hai hng s phn li Ka1 v Ka2) v baz mnh BOH. Trong dung dch, mui BHA phn li thnh ion HA-, ion ny tham gia cc phn ng nh mt axit: HA- H+ + A2- vi Ka2 = [H+].[A2-]/[HA-] 32) v nh mt baz: HA- + H+ H2A vi K = [H2A]/[H+].[HA-] = 1/Ka1 (III-
(III33) Trong dung dch, nng [H+] s bng tng lng [H+] do HA- phn li ra (tc bng [A2-] v nc phn li ra (tc bng [OH-] tr i lng [H+] tham gia phn ng vi HA- to H2A (tc bng [H2A]): [H+] = [A2-] - [H2A] + [OH-] = [A2-] - [H2A] + KH2O/[H+] (III34) Thay [A2-] v [H2A] t III- 30 vo III- 28 v III- 29 s c: (III[H+] = {Ka1(Ka2[HA-] + KH2O)/(Ka1 + [HA-])}1/2 35) Thng thng [HA-] KH2O, [HA-] Ka1, nn biu thc III- 35 c th rt gn thnh: [H+] = (Ka1Ka2)1/2 . Nh vy: pH = (pKa1 + pKa2)/2 (III- 36) Vi trng hp tng qut ca ion HmAn-: HmAn- Hm-1A(n+1)- + H+ v HmAn- + H+ Hm+1A(n-1)-, c th vit: (IIIpH = (pKan + pKan+1)/2 37) Trong : Kan l hng s axit phn li ra gc mui HmAn-, Kan+1 l hng s axit m gc mui HmAn- s phn li c gc Hm-1A(n+1)-. b. ng chun axit mnh bng baz mnh Khi chun axit mnh HA c th tch dung dch VHA v nng NHA (CHA) bng dung dch baz mnh BOH c nng NBOH (CBOH), v d, chun 100 ml HCl 0,1N bng dung dch NaOH 0,1N, ng chun c xc nh nh sau: * pH khi cha chun : Dung dch ch cha axit mnh HA phn li hon ton: HA = H+ + A-, nn s dng biu thc III- 10 tnh pH dung dch. Thay s, theo v d nu trn, c: pH = - lg [H+] = -lg CHA = -lg0,1 = 1 * pH trc im tng ng: Vic a BOH vo dung dch HA dn n phn ng: HA + BOH = BA + H2O lm gim nng axit HA, nhng, axit vn cn d v n quyt nh pH dung dch. Nng axit HA d s bng:
38) s c:
[HA] = (VHA . NHA - VBOH . NBOH)/(VHA + VBOH) Tng t nh trn: [H+] = [HA]d, do , pH dung dch l: pH = - lg[(VHA . NHA - VBOH . NBOH)/(VHA + VBOH)]
(III-
Thay s, theo v d nu trn vi 50% chun , tc s dng 50 ml NaOH 0,1N, pH = - lg[(100. 0,1 - 50. 0,1)/(100 + 50)] = 1,48 * pH ti im tng ng: Ton b axit HA c trung ho bng lng va baz mnh BOH, nn, trong dung dch ch c mui trung tnh BA v H2O. Do , pH dung dch l pH ca nc v bng 7. * pH sau im tng ng: Lng BOH a vo sau im tng ng tr thnh lng baz d. BOH l baz mnh phn li hon ton: BOH = B+ + OHnn, pH dung dch ph thuc vo nng BOH d. pH c tnh theo biu thc III- 13. Nng BOH d l: [BOH] = (VBOH . NBOH - VHA . NHA)/(VHA + VBOH) Do , pH dung dch c xc nh bng biu thc III- 39: pH = 14 - pOH = 14 - lg[BOH] = 14 lg[(VBOH . NBOH - VHA . NHA)/(VBOH + VHA)] (III39) Thay s, theo v d nu trn vi 150% chun , tc s dng 150 ml NaOH 0,1N, s c: pH = 14 lg[(150. 0,1 - 100. 0,1)/(100 + 150)] = 12,30 ng dng cc biu thc III- 10, III- 38 v III- 39 tnh ton pH trong mt s chun cho cc s liu ghi trong bng B.1.3. Biu din cc s liu ca bng B.1.3 trn th, c hnh H.1.3. Bng B.1.3: S bin thin pH dung dch trong chun 100ml HCl vi cc nng khc nhau bng NaOH 0,1N Trng thi % chun chun Cha chun 0 50 Trc im 90 tng 99 ng 99,9 Ti im 100 tng ng 100,1 Sau im 101 tng 110 ng 150 Vn dng biu thc III- 10 III- 38 HCl 0,1N 1,00 1,48 2,30 3,30 4,30 7,00 III- 39 9,70 10,70 11,70 12,30 pH HCl 0,01N 2,00 2,30 3,04 4,04 5,04 7,00 8,96 9,96 10,96 11,70 HCl 0,001N 3,00 3,30 4,00 5,00 6,00 7,00 8,00 9,00 10,00 10,69
T hnh H.1.3 c nhn xt: 1- ng chun l ng cong i xng qua im 100% chun v pH = 7. 2- Gn im tng ng, pH dung dch thay i mnh khi a mt lng nh dung dch tiu chun vo. Khong thay i ca pH c gi l bc nhy ca ng cong chun . ng vi mt sai s cho trc ( 0,1%, 1%) s c mt bc nhy tng ng trn ng cong v r rng sai s cng ln th bc nhy cng di. V d: Vi NHA = 0,1N, NBOH = 0,1N, vi sai s 1% c bc nhy t pH = 3,3 n pH = 10,7; cn vi sai s 0,1% bc nhy ch cn l t pH = 4,3 n pH = 9,7.
Hnh H.1..3: ng chun axit mnh bng baz mnh: 1. HCl 0,001N; 2. HCl 0,01N; 3. HCl 0,1N 3- Bc nhy ng cong chun ph thuc vo nng cc cht tham gia phn ng, nng cng ln th bc nhy cng di. V d: Cng sai s 0,1% v cng chun bng NaOH 0,1N, vi nng ban u ca HCl l 0,1N c bc nhy: pH = 4,3 10,7, nhng vi nng HCl 0,01N th bc nhy ch l: pH = 5,04 8,96. Do , khng nn pha long dung dch khi chun . Nu c th, nn dng dung dch tiu chun vi nng cao thi gian chun khng ko di. Tuy nhin, khi dng dung dch tiu chun vi nng cao cn lu n sai s got d (mc 6. 6 chng III).
c. ng chun baz mnh bng axit mnh Khi chun baz mnh BOH c th tch dung dch VBOH v nng NBOH (CBOH) bng dung dch axit mnh HA c nng NHA (CHA) , v d, chun 100 ml NaOH 0,1N bng dung dch HCl 0,1N, ng chun c xc nh nh sau: * pH khi cha chun : Dung dch ch cha baz mnh BOH phn li hon ton: BOH = OH- + B+ Do c: [OH-] = CBOH NBOH, v th pH c tnh theo III- 13. Thay s, theo v d nu trn, s c: pOH = - lg [OH-] = -lg CBOH = -lg0,1 = 1, do pH = 14 - 1 = 13. * pH trc im tng ng: Vic a HA vo dung dch BOH dn n phn ng: BOH + HA = BA + H2O lm gim nng baz BOH, nhng, baz vn cn d vi nng baz BOH d s bng: [BOH] = (VBOH . NBOH - VHA . NHA)/(VHA + VBOH) Do pH dung dch c xc nh bng biu thc III- 39. Thay s, theo v d nu trn vi 50% chun , tc s dng 50 ml HCl 0,1N, s c: pH = 14 lg[(100. 0,1 - 50. 0,1)/(100 + 50) = 12,52 pH ti im tng ng: Ton b lng baz BOH c trung ho bng lng va axit mnh HA nn trong dung dch ch c mui trung tnh BA v H2O. Do , pH dung dch l pH ca nc v bng 7. * pH sau im tng ng: Lng HA a vo sau im tng ng tr thnh lng axit d. V HA l axit mnh phn li hon ton, nn, nng ca n c tnh theo biu thc: [HA] = (VHA . NHA - VBOH . NBOH)/(VHA + VBOH) Do pH dung dch c tnh theo III- 38. Thay s, theo v d nu trn vi 150% chun , tc s dng 150 ml HCl 0,1N, s c: pH = - lg[(150. 0,1 - 100. 0,1)/(100 + 150)] = 1,70 ng dng cc biu thc III- 13, III- 39 v III- 38 tnh ton pH trong mt s chun thu c cc s liu ghi trong bng B.2.3. Bng B.2.3: S bin thin pH dung dch trong chun 100ml NaOH vi cc nng khc nhau bng HCl 0,1N Trng thi chun Cha chun Trc im tng ng % chun 0 50 90 99 99,9 Vn dng biu thc III- 13 III- 39 NaOH 0,1N 13,00 12,52 11,70 10,70 9,70 pH NaOH 0,01N 12,00 11,70 10,96 9,96 8,96 NaOH 0,001N 11,00 10,69 10,00 9,00 8,00
Ti im tng ng Sau im tng ng
100 100,1 101 110 150
III- 38
7,00 4,30 3,30 2,30 1,48
7,00 5,04 4,04 3,04 2,30
7,00 6,00 5,00 4,00 3,30
Biu din cc s liu ca bng B.2.3 trn th, c hnh H.2.3. T hnh H.2.3, tng t nh trong chun axit mnh bng baz mnh, c nhn xt sau: 1. ng chun l ng cong i xng qua im 100% chun v pH = 7. ng chun baz mnh bng axit mnh c dng ngc li (i xng gng qua trc i qua im 100% chun ) vi ng chun axit mnh bng baz mnh (hnh H.1.3). 2. Gn im tng ng, pH dung dch thay i mnh khi a mt lng nh dung dch tiu chun vo. Khong thay i mnh ca pH c gi l bc nhy ca ng cong chun . ng vi mt sai s cho trc ( 0,1%, 1%) s c mt bc nhy tng ng trn ng cong v r rng sai s cng ln th bc nhy cng di. V d: vi NBOH = 0,1N, NHA = 0,1N, vi sai s 1% c bc nhy t pH = 10,7 n pH = 3,3; cn vi sai s 0,1% bc nhy ch cn l t pH = 9,7 n pH = 4,3. 3. Bc nhy ng cong chun ph thuc vo nng cc cht tham gia phn ng, nng cng ln th bc nhy cng di. V d: cng sai s 0,1% v cng chun bng HCl 0,1N, vi nng ban u ca NaOH l 0,1N c bc nhy: pH = 10,7 - 4,3, nhng vi nng NaOH 0,01N th bc nhy ch l: pH = 8,96 - 5,04. Do , cng nh khi chun axit mnh bng baz mnh khng nn pha long dung dch khi chun . Nu c th, nn dng dung dch tiu chun vi nng cao thi gian chun khng ko di. Tuy nhin, khi dng dung dch tiu chun vi nng cao cn lu n sai s git d (mc 6. 6 chng III).
Hnh H.2..3: ng chun baz mnh bng axit mnh: 1. NaOH 0,001N; 2. NaOH 0,01N; 3. NaOH 0,1N. d. ng chun axit yu bng baz mnh Khi chun axit yu HA vi th tch VHA v nng NHA (CHA) bng baz mnh BOH c nng NBOH (CBOH) theo phng trnh: HA + BOH = BA + H2O ng chun c xy dng nh sau: * pH khi cha chun : Trong dung dch ch c axit yu HA phn li mt phn: HA H+ + A-, nn pH dung dch c tnh theo III- 18 hoc t III- 16, III- 15. * pH trc im tng ng: Trong dung dch c mui BA v axit yu HA d to nn cp axit baz lin hp. Nu [HA] cn li ln hn 0,1% so vi CHA, tnh pH dung dch nh i vi hn hp m pH (biu thc III- 29) v trong trng hp ny c th l III- 40: (IIIpH = pKa - lg([HA]/[BA]) = pKa lg[(VHA . NHA - VBOH . NBOH)/(VBOH . NBOH)] 40) Nu [HA] cn li nh hn 0,1% so vi CHA, tnh pH dung dch vi vic s dng biu thc III- 27. * pH ti im tng ng: Trong dung dch tn ti mui BA v H2O. V mui BA l mui ca axit yu vi mt baz mnh, nn, n b thu phn: BA + H2O HA + BOH cho mi trng kim. Do , pH dung dch mui BA c xc nh bng biu thc III30 v trong trng hp ny c th l III- 41: pHt = 7 + (1/2)pKa + (1/2)lg[(VHA . NHA)/(VHA + VBOH)] (III- 41) * pH sau im tng ng: Trong dung dch d BOH, l baz mnh. Nu s d ca BOH ln hn 0,1% ca CBOH, c th b qua s thu phn ca mui BA v pH dung dch s c tnh gn ng theo biu thc III- 39. Nu s d ca BOH nh hn 0,1% ca CBOH, khng th b qua s thu phn ca mui BA v pH dung dch s c tnh theo biu thc III- 27. Kt qu tnh pH ca chun mt s axit yu bng baz mnh c minh ho trong bng B.3.3 v dng ng chun ca chng c minh ha bng cc hnh H.3.3 v H.4.3.
Bng B.3.3: S bin thin pH dung dch trong chun 100ml axit yu CH3COOH (pKa = 4,76) nng 0,1N bng NaOH 0,1N Trng thi chun Cha chun Trc im tng ng % chun 0 50 90 99 99,9 100 100,1 101 110 150 Vn dng biu thc III- 18 III- 40 III- 27 III- 41 III- 27 III- 39 pH 2,88 4,76 5,72 6,76 7,80 8,73 9,70 10,70 11,70 12,52
Hnh H.3..3: ng chun axit yu CH3COOH (pKa= 4,76) 0,1N bng baz mnh NaOH 0,1N.
Hnh H.4..3: ng chun axit yu khc nhau bng baz mnh: 1. ClCH2COOH (pKa= 2,85); 2. CH3COOH (pKa= 4,76); 3. H3BO3 (pKa= 9,23). T cc hnh H.3.3 v H.4.3 c nhn xt nh sau: 1. ng chun l dng ng cong bt i xng, lch v pha mi trng kim, im tng ng c pH ln hn 7. iu ny rt r khi xem xt trong khong sai s 0,1%. 2. Axit cng mnh th bc nhy ca ng cong chun cng di v i vi axit yu c pKa > 10 ng cong khng c bc nhy. 3. Cc nhn xt khc cng ging nh cc nhn xt 2, 3 ca ng cong chun axit mnh bng baz mnh. e. ng chun baz yu bng axit mnh Khi chun baz yu BOH vi th tch VBOH v nng NBOH (CBOH) bng axit mnh HA c nng NHA ( CHA) theo phng trnh: BOH + HA = BA + H2O ng chun c xy dng nh sau: * pH khi cha chun : Trong dung dch ch c baz yu BOH phn li mt phn: BOH OH- + B+, nn pH dung dch c tnh t III- 24 hoc t III- 21, III- 20. * pH trc im tng ng: Trong dung dch c mui BA v baz yu BOH d to nn cp axit baz lin hp. Nu [BOH] cn li ln hn 0,1% so vi CBOH, tnh pH dung dch nh i vi hn hp m pH (biu thc III- 29) v trong trng hp ny c th l III- 42: pH = pKa - lg([BA]/[BOH]) = 14 - pKb lg[(VHA . NHA)/(VBOH . NBOH - VHA . NHA)] (III42) Nu [BOH] cn li nh hn 0,1% so vi CBOH tnh pH dung dch theo biu thc III- 27. * pH ti im tng ng:
Trong dung dch tn ti mui BA v H2O. V mui BA l mui ca baz yu vi mt axit mnh nn n b thu phn: BA + H2O HA + BOH cho mi trng axit. Do pH dung dch mui BA c xc nh bng biu thc III- 31 v trong trng hp ny c th l III- 43: pHt = 7 - (1/2)pKb - (1/2)lg[(VBOH . NBOH)/(VBOH + VHA)] (III43) * pH sau im tng ng: Trong dung dch d HA, l axit mnh. Nu s d ca HA ln hn 0,1% ca CBOH, c th b qua s thu phn ca mui BA v pH dung dch s c tnh gn ng theo biu thc III- 38. Nu s d ca BOH nh hn 0,1% ca CBOH, khng th b qua s thu phn ca mui BA v pH dung dch s c tnh theo biu thc III- 27. Kt qu tnh pH ca chun mt s axit yu bng baz mnh c minh ho trong bng B.4.3 v dng ng chun ca chng c minh ha bng cc hnh H.5.3 v H.6.3. T cc hnh H.5.3 v H.6.3 c nhn xt nh sau: 1. ng chun l dng ng cong bt i xng, lch v pha mi trng axit, im tng ng c pH nh hn 7. iu ny rt r khi xem xt trong khong sai s 0,1%. 2. Baz cng mnh th bc nhy ca ng cong chun cng di v i vi baz yu c pKb > 10 ng cong khng c bc nhy. 3. Cc nhn xt khc cng ging nh cc nhn xt 2, 3 ca ng cong chun baz mnh bng axit mnh. Bng B.4.3: S bin thin pH dung dch trong chun 100ml baz yu NH4OH (pKb = 4,74) nng 0,1N bng HCl 0,1N Trng thi chun Cha chun Trc im tng ng % chun 0 50 90 99 99,9 100 100,1 101 110 150 Vn dng biu thc III- 24 III- 42 III- 27 III- 43 III- 27 III- 38 pH 11,13 9,26 8,31 7,26 6,22 5,28 4,31 3,32 2,38 1,70
Hnh H.5..3: ng chun baz yu NH4OH (pKb = 4,74) 0,1N bng axit mnh HCl 0,1N:
Hnh H. 6..3: ng chun baz yu bng axit mnh: 1. Dietylamin (pKb= 3,02); 2. Amoniac (pKb= 4,74); 3. Anilin (pKb=9,38)
T cc hnh v H.3.3 - H.6.3 c nhn xt: Khi chun axit yu bng baz mnh cng nh khi chun baz yu bng axit mnh, trc im tng ng, trong dung dch u tn ti h m pH nn pH thay i chm. Do , d dng nhn thy rng vic chun axit yu bng baz yu hoc ngc li s dn n ng cong chun khng c bc nhy (v trc v sau im tng ng trong dung dch lun tn ti h m pH lm pH thay i chm). Chnh v iu ny, nn trong thc t khi chun theo phng php trung ho ch dng dung dch tiu chun l cc axit, baz mnh ng chun c bc nhy ln. e. ng chun hn hp nhiu axit n chc hoc axit a chc bng baz mnh hoc chun hn hp nhiu baz n chc hoc baz a chc bng axit mnh ng chun hn hp nhiu axit n chc cho bc nhy ring r gn im tng ng ng vi vic chun ca tng axit ch khi cc axit ny c hng s axit khc nhau r rt (vi sai s % = 0,1% th Ka1/Ka2 104), (v d: hn hp axit HCl (phn li hon ton) v CH3COOH (Ka = 1,74.10-5)), nu cc hng s axit Ka1 khc nhau khng nhiu (v d: cc axit hu c dy axit focmic nh HCOOH vi Ka = 1,8.10-4 v CH3COOH vi Ka = 1,74.10-5) ), th ng chun c chung mt bc nhy. iu ny cng ng cho chun axit a chc, bi v axit a chc phn li theo tng nc v mi nc phn li khc nhau c th c coi l s phn li ca mt axit khc. V d: Axit HnA phn li nh sau: HnA
-
Hn-1A- + H+
2-
(nc 1), (nc 2),
Hn-1A Hn-2A
+ H
(nc n) HA(n-1)- An- + H+ pH ca dung dch axit HnA c tnh theo cc biu thc III- 10 (cho axit mnh) hoc cc biu thc III- 16 v III- 18 (cho axit yu). Cc ion gc mui Hn-1A-, Hn-2A2-,.HA(n-1)c gi l cc gc mui lng tnh v pH ca cc dung dch cha cc ion ny c tnh gn ng theo biu thc III- 37. Vi baz a chc B cng c th vit tng t : B + H+ BH+ BH ..
+
(nc 1)
2+
+ H
BH2
(nc 2)
(nc n) BHn-1(n-1)+ + H+ BHnn+ pH ca dung dch baz B c tnh theo cc biu thc III- 13 (cho baz mnh) hoc cc biu thc III- 21 v III- 24 (cho axit yu). Cc ion gc mui Hn-1A-, Hn-2A2-,.HA(n-1)c gi l cc gc mui lng tnh v pH ca cc dung dch cha cc ion ny c tnh gn ng theo biu thc III- 37. Vic xy dng ng chun cho c hai trng hp cng tng t nh khi xy dng ng chun axit bng baz mnh hoc chun baz bng axit mnh, ch c khc mt iu l i vi axit a chc c th coi y l hn hp ca nhiu axit n chc c cng nng mol/lt v tng t i vi baz a chc c th coi nh chun hn hp nhiu baz n chc c cng nng mol/lt.
Vic xy dng ng chun c th c minh ho qua v d chun 20ml dung dch axit H3PO4 0,1M (H3A) (vi cc hng s axit: Ka1 = 7,6.10-3 (pKa1 = 2,12); Ka2 = 6,2.10-8 (pKa2 = 7,21); Ka3 = 4,2.10-13 (pKa3 = 12,38)) bng NaOH 0,1N. * pH khi cha chun : V nc 1 ca axit H3PO4 phn li trung bnh nn [H+] ca dung dch c xc nh bng biu thc III- 16 vi CH3A = 0,1N: [H+]2 + Ka1[H+] - Ka1CH3A = 0, thay s s c: [H+]2 + 7,6.10-3 [H+] - 7,6.10-3. 0,1 = 0, gii ra s c: [H+] = 3,12.10-2, pH = 1,50. Nu s dng biu thc III- 18, s tnh c pH = 1,58, nh hn pCa + 1,3 = 2,3, khng tho mn iu kin. * pH trc im tng ng 1: Trong dung dch tn ti hn hp H3PO4 v NaH2PO4 to thnh h m pH, nn pH c tnh bng biu thc III- 40 vi pKa l pKa1. V d, khi chun 50% ca nc 1, s c: pH = 2,12 lg[(20. 0,1 - 10. 0,1)/(10. 0,1)] = 2,12 * pH ti im tng ng 1: Dung dch ch cha NaH2PO4 l mui lng tnh, nn pH c xc nh bng biu thc III- 37 vi vic s dng pKa1 v pKa2 ca axit H3PO4. Thay s s c: pH = (2,12 + 7,21)/2 = 4,66 * pH sau im tng ng 1 v im tng ng 2: Trong dung dch tn ti ng thi NaH2PO4 v Na2HPO4 to thnh h m pH, nn, pH c tnh theo biu thc III- 40 vi pKa = pKa2 vi [NaH2PO4] = (2VH3PO4 . MH3PO4 VNaOH . NNaOH)/(VH3PO4 + VNaOH) (III44) [Na2HPO4] = (VNaOH . NNaOH VH3PO4 . MH3PO4)/(VH3PO4 + VNaOH) (III45) V d, khi chun 50% ca nc 2, s c: pH = 7,21 lg[(2. 20. 0,1 30. 0,1)/(10. 0,1)] = 7,21 * pH ti im tng ng 2: Dung dch ch cha Na2HPO4 l mt cht lng tnh nn pH dung dch c xc nh bng biu thc III- 37 vi vic s dng pKa2 v pKa3 ca axit H3PO4. Thay s s thu c: pH = (7,21 + 12,38)/2 = 9,80 * pH sau im tng ng 2 v trc im tng ng 3: Trong dung dch tn ti ng thi Na2HPO4 v Na3PO4 to thnh h m pH, nn, pH c tnh theo biu thc III- 40 vi pKa = pKa3 vi [Na2HPO4] = (3VH3PO4 . MH3PO4 VNaOH . NNaOH)/(VH3PO4 + VNaOH) (III46) [Na3PO4] =(VNaOH . NNaOH 2VH3PO4 . MH3PO4)/(VH3PO4 + VNaOH) (III47) V d, khi chun 50% ca nc 3, s c: pH = 12,38 lg[(3. 20. 0,1 50. 0,1)/(10. 0,1)] = 12,38 Vic tnh ton tip theo khng c ngha, v axit HPO42- (pKa3 = 12,38) qu yu, khng th chun c.
ng chun axit H3PO4 bng NaOH c biu din bng hnh v H.5.3. ng ny c 3 im tng ng nhng ch c hai bc nhy ng vi vic chun nc 1 v nc 2, cn chun nc 3 s khng c bc nhy v axit th 3 qu yu. Tng t c th xy dng ng chun baz a chc bng axit mnh vi vic s dng biu thc III- 48: pKa + pKb = 14, (III- 48) trong Ka v Kb l cc hng s axit v baz ca mt cp axit baz lin hp.
6.3. ng chun oxi ho kh
Hnh H.7..3: ng chun axit H3PO4 bng NaOH
L ng biu din s ph thuc th in cc dung dch E ln th tch dung dch tiu chun a vo trong qu trnh chun (E = f(Vtc)) hay l ln % chun (E = f(% chun )). C rt nhiu phn ng oxi ho kh c dng trong chun , song, c th phn chng thnh 2 nhm nh sau: - Phn ng oxi ho kh, trong cc cp oxi ho kh trao i s electron nh nhau. C th, vi cc phn ng ring phn III c1 v III c2 c m = n, vi a = a, b = b, v d: Fe2+ + Ce4+ = Ce3+ + Fe3+ Fe3+ + e = Fe2+ Ce4+ + e = Ce3+
hoc vi a a, b b, v d: 2Na2S2O3 + I2 = 2NaI + Na2S4O6 S4O62- + 2e = 2S2O32I2 + 2e = 2I - Phn ng oxi ho kh, trong cc cp oxi ho kh trao i s electron khng nh nhau. C th, i vi phn ng ring phn III- c1 v III- c2 vi m n, vi a = a, b = b, v d: 5Fe2+ + KMnO4 + 8H+ = 5Fe3+ + K+ + Mn2+ + 4H2O Fe3+ + e = Fe2+ MnO4- + 8H+ + 5e = Mn2+ + 4H2O hoc vi a a, b b, v d: 6Fe2+ + K2Cr2O7 + 14H+ = 6Fe3+ + 2K+ + 2Cr3+ + 7H2O Fe3+ + e = Fe2+ Cr2O72- + 6e + 14H+ = 2Cr3+ + 7H2O ng chun ca mi nhm c nhng c im khc nhau. Kh nng tham gia phn ng oxi ho kh ca cc cht ph thuc rt nhiu vo iu kin mi trng, do , n gin cho vic xy dng ng chun , thng gii hn iu kin phn ng chun lun c nh. V d: nu trong phn ng c s tham gia ca ion H+, thng qui c [H+] = 1 iong/l. a. ng chun oxi ho kh ca trng hp m = n, a = a, b = b Nh vy, i vi h ny tn ti: a = a = b = b = 1. Chun xc nh cht kh 1 c th tch Vkh1, nng Nkh1 bng dung dch cht oxi ho 2 c nng Nox2 s theo phng trnh: ( III- d ) kh1 + ox2 = ox1 + kh2 Th E ca dung dch c th c xc nh theo biu thc: E = E0ox1/kh1 + (0,059/m)lg([ox1]/[kh1]) ( III- 49 )
(III- 50) E = E0ox2/kh2 + (0,059/n)lg([ox2]/[kh2]) Tuy nhin, cn chn la biu thc thch hp, c th d dng tnh c nng ca cc cht trong biu thc t nhng d liu chun . Thng thng, da vo s d tha ca cc cht tham gia phn ng chn. V d: vi chun xc nh cht kh 1 bng cht oxi ho 2, khi trong dung dch cn d cht kh 1, chn biu thc III- 49, khi trong dung dch c d cht oxi ho 2, chn biu thc III- 50. ng chun c xy dng nh sau: * E khi cha chun : Trong dung dch ch c cht kh 1, nn, E dung dch c tnh da vo nng cc cht oxi ho kh ca cp 1 (biu thc III- 49). Thay s c: (III- 51) E = E0ox1/kh1 + (0,059/m)lg[0/(Nkh1/m)] V cha chun , nn [ox1] = 0 v E = - . Nhng, trong thc t, E c mt gi tr xc nh, v mi trng nc bn thn ion H+ ng vai tr cht oxi ho, n s oxi ho cht kh 1 to ra cht oxi ho 1, nh vy, [ox1] > 0. * E trc im tng ng: Lc ny, trong dung dch d cht kh 1, nn tnh E theo cp ox1/kh1 (biu thc III- 49).
hoc
Thay d liu s c biu thc III- 52: E = E ox1/kh1 + (0,059/m)lg([ox1]/[kh1]) = = E0ox1/kh1 + (0,059/m)lg{[(Vox2 . Nox2)/m]/[(Vkh1 . Nkh1 Vox2 . Nox2)/m]} (III52) * E ti im tng ng (Et): Trong dung dch nng ca cc cht oxi ho cng nh cht kh ca c hai cp oxi ho kh nm trng thi cn bng v rt nh, nn E c tnh da vo c hai phng trnh tnh th oxi ho kh III- 49 v III- 50: Et = E0ox1/kh1 + (0,059/m)lg([ox1]/[kh1]) Et = E0ox2/kh2 + (0,059/m)lg([ox2]/[kh2]) (v m = n). Nhn c 2 v ca 2 phng trnh ny vi m, ri cng chng vi nhau, s c: 2mEt = mE0ox1/kh1 + mE0ox2/kh2 + 0,059 lg([ox1] [ox2]/[kh1] [kh2]) Theo phng trnh III- d, ti im tng ng phi tho mn: [kh1] = [ox2] v [ox1] = [kh2]. Thay [ox2] v [kh2] bng [kh1] v [ox1] vo phng trnh trn, thu c: 2mEt = mE0ox1/kh1 + mE0ox2/kh2 + 0,059 lg([ox1] [kh1]/[kh1] [ox1]) hay: Et = ( E0ox1/kh1 + E0ox2/kh2 )/2 (III- 53) * E sau im tng ng: Trong dung dch d cht oxi ho 2, v vy, th in cc dung dch c tnh n gin da vo th ca cp oxi ho kh th 2 (biu thc III- 50). Thay d liu s c: E = E0ox2/kh2 + (0,059/m)lg([ox2]/[kh2]) = E0ox2/kh2 + (0,059/m)lg{[(Vox2 . Nox2 Vkh1 . Nkh1)/m]/[(Vkh1 . Nkh1)/m]} (III- 54) C th minh ho vic xy dng ng chun oxi ho kh ca trng hp m = n, a = a, b= b thng qua trng hp chun 20 ml FeSO4 0,1N bng dung dch Ce(SO4)2 0,1N. Chun xy ra theo phng trnh: Fe2+ + Ce4+ = Ce3+ + Fe3+ Nh vy, m = n = 1. Gi cp Fe3+/Fe2+ l cp ox1/kh1, cp Ce4+/Ce3+ l cp ox2/kh2; cc s liu tnh ton c ghi trong bng B.5.3. ng chun c dng nh hnh H.8.3.
0
b. ng chun oxi ho kh vi trng hp m n, a, = a, b = b Nh vy, i vi h ny tn ti: a b. Chun xc nh cht kh 1 c th tch Vkh1, nng Nkh1 bng dung dch cht oxi ho 2 c nng Nox2 s theo phng trnh: ( III- e ) akh1 + box2 = aox1 + bkh2 Th E ca dung dch c th c xc nh theo cc biu thc III- 49, III- 50. Vic chn la biu thc thch hp nh nu trng hp trn. Bng B.5.3: Th in cc dung dch khi chun 20 ml FeSO4 0,1N bng dung dch Ce(SO4)2 0,1N ( E0Fe3+/Fe2+ = 0,77V, E0Ce4+/Ce3+ = 1,44V) Trng thi chun Cha chun % chun 0 1 Vn dng biu thc III- 51 E (V) 0,53
Trc ng
im
tng
10 50 90 99 99,9 100 100,1 101 110 200
III- 52
III- 53 III- 54
0,71 0,77 0,83 0,89 0,95 1,10 1,26 1,32 1,38 1,44
* E khi cha chun : Ging trng hp trn, th in cc E c xc nh bng biu thc III- 49. * E trc im tng ng: Tng t nh trn E c xc nh bng biu thc III- 50. * E ti im tng ng (Et): Tng t nh phn trn, c th vit: Et = E0ox1/kh1 + (0,059/m)lg([ox1]/[kh1]) Et = E0ox2/kh2 + (0,059/n)lg([ox2]/[kh2]) [kh1] = (a/b)[ox2] [ox1] = (a/b)[kh2] Tip tc bin i s c: (m + n) Et = mE0ox1/kh1 + nE0ox2/kh2
Et = (mE0ox1/kh1 + nE0ox2/kh2)/(m + n) (III- 55) * E sau im tng ng: Tng t nh phn 6.3.a trn, E c tnh theo biu thc III- 50. Thay d liu s c: E = E0ox2/kh2 + (0,059/n)lg{[(Vox2 . Nox2 Vkh1 . Nkh1)/n]/[(Vkh1 . Nkh1)/n]} (III56) C th minh ho vic xy dng ng chun oxi ho kh ca trng hp m n, a, = a, b, = b thng qua trng hp chun 20 ml FeSO4 0,1N bng dung dch KMnO4 0,1N trong mi trng c [H+] = 1iongam/l. Chun xy ra theo phng trnh; 5Fe2+ + KMnO4 + 8H+ = 5Fe3+ + K+ + Mn2+ + 4H2O Nh vy, cp Fe3+/Fe2+ l cp ox1/kh1, trao i 1e, tc m = 1, cp MnO4-/Mn2+ cp ox2/kh2, trao i 5e, tc n = 5. Cc s liu tnh ton c ghi trong bng B.6.3. ng chun c dng nh hnh H.8.3.
hay
Bng B.6.3: Th in cc dung dch khi chun 20 ml FeSO4 0,1N bng dung dch KMnO4 0,1M ( E0Fe3+/Fe2+ = 0,77V, E0MnO4-/Mn2+ = 1,51V) Trng thi chun Cha chun Trc ng im tng % chun 0 1 10 50 90 99 99,9 100 100,1 101 110 200 Vn dng biu thc III- 51 III- 52 E (V) 0,53 0,71 0,77 0,83 0,89 0,95 1,39 1,48 1,49 1,50 1,51
Ti im tng ng Sau im ng tng
III- 55 III- 56
T hnh H.8.3 c nhn xt: 1. ng chun l ng cong i xng qua im 100% chun v Et khi hai cp oxi ho kh trao i s e nh nhau (n = m) v bt i xng khi hai cp oxi ho kh trao i s e khc nhau (n m). 2. Gn im tng ng, E dung dch thay i mnh khi a mt lng nh dung dch tiu chun vo. Khong thay i mnh ca E c gi l bc nhy ca ng cong chun . Bc nhy ph thuc vo: - Sai s phn tch: Sai s cng ln th bc nhy cng di, - chnh th oxi ho kh tiu chun ca hai cp oxi ho kh: S chnh ny cng ln th bc nhy cng di.* - Nng dung dch khng c nh hng n bc nhy.
6.4. ng chun kt ta
Trong thc t s dng rt t cc phn ng kt ta tin hnh chun . Ph bin nht l s dng cc phn ng to cc kt ta AgCl, AgBr, AgI, AgCNS v i khi BaSO4, PbCrO4 trong vic xc nh cc ion to nhng mui trn. Nh vy, phng trnh phn ng c th vit di dng tng qut: (III- e) Mn+ + Xn - = MX vi tch s tan: TMX = [Mn+] [Xn-] ng chun kt ta l ng biu din s ph thuc pX = f(Vtc), hoc pM = f(Vtc) hay pX = f(% chun ) hay pM = f(% chun ). Khi chun xc nh ion Xn- c nng Nx, th tch Vx bng dung dch ion Mn+ c nng NM, ng chun c xy dng nh sau: -----------------------------------------------------------------------------------------------------------* chnh th tiu chun ca hai cp oxi ho kh cng ln th hng s cn bng K ca
phn ng cng ln. Vi phn ng III- c, lgK = am.(Eoox1/kh1 - Eoox2/kh2)/0,059 ; am l tng s electron trao i trong phn ng.
Hnh H. 6.3: ng chun oxi ho kh: a- Chun ion Fe2+ bng ion Ce4+ (m = n = 1); b- Chun ion Fe2+ bng ion MnO4- (m = 1, n = 5) * pX khi cha chun : Trong dung dch ch c ion Xn - nn pX c xc nh bng biu thc III- 57: pX = - lg CX = - lg(NX/n) (III- 57) (n - ch s ng lng, trong chun AgNO3 xc nh cc ion Cl-, Br-, I-, CNS-, n = 1). * pX trc im tng ng: Khi a dung dch tiu chun Mn+ vo dung dch Xn- th nng Xn- gim. pX c xc nh bng biu thc III- 58: pX = -lg[Xn-] = -lg{[(VXn-NXn- - VMm+NMm+)/(VXn- + VMm+)]/n} (III58) * pX ti im tng ng: Nng ion Xn- v ion Mn+ l tng ng nhau v c coi l tan ca kt ta MX (MX Mn+ + Xn- ). V tch s tan TMX = [Xn-] [Mn+] = [Xn-]2 [Xn-] = (TMX)1/2 do :
pX = (lgTMX)/2 (III- 59) *pX sau im tng ng: Vic a d dung dch tiu chun Mn+ vo dung dch chun lm cho cn bng III- e chuyn dch sang bn phi, do nng ion Xn- tip tc gim. Nng ion Xnlc ny l: [Xn-] = TMX/ [Mn+] = TMX/ [(VMm+ . NMm+ - VXn- . NXn-)/ n (VMm+ + VXn-) tc (IIIpX = - lg[TMX (VMm+ + VXn-).n/(VMm+ . NMm+ - VXn- . NXn-)] 60) C th minh ho vic xy dng ng chun kt ta thng qua trng hp chun 20 ml Cl- 0,1N bng dung dch AgNO3 0,1N (TAgCl = 1,78.10-10). Chun xy ra theo phng trnh: Cl- + AgNO3 = AgCl + NO3Cc s liu tnh ton c ghi trong bng B.7.3. Bng B.7.3: pCl dung dch khi chun 20 ml Cl- 0,1N bng dung dch AgNO3 0,1N (TAgCl = 1,78.10-10) Trng thi chun Cha chun Trc im tng ng % chun 0 10 50 90 99 99,9 100 100,1 101 110 150 Vn dng biu thc III- 57 III- 58 pCl 1,00 1,04 1,48 2,28 3,30 4,30 4,87 5,45 6,45 7,43 8,95
III- 59 III- 60
ng chun kt ta c dng nh hnh v H.9.3. T hnh v H.9.3 c nhn xt: 1. ng chun l ng cong i xng qua im pX = (-lgTMX )/2 v 100% chun . 2. Tng t nh phng php trung ho, gn im tng ng pX thay i mnh to ra bc nhy ca ng cong. Bc nhy ph thuc vo: - Sai s phn tch: Sai s cng ln th bc nhy cng ln, - Hng s TMX: TMX cng nh, bc nhy cng ln. - Nng cc cht tham gia phn ng: Nng cc cht tham gia phn ng cng ln, bc nhy cng ln.
Hnh H.9.3: ng chun cc halogenua bng AgNO3: 1. Cl - 0,1N; 2. Br- 0,1N; 3. I- 0,1N; 4. Cl- 0,01N
6.5. ng chun to phc

Trong chun xc nh cc i tng nng nghip, thng dng phn ng chun ca complexon III (Na2H2Y) xc nh cc ion kim loi Mm+: Mm+ + Na2H2Y = MYm-4 + 2Na+ + 2H+, (III- f) vi k hiu Na2H2Y l L, pH mi trng l c nh v b qua in tch, c th vit ngn gn phng trnh III- f nh sau: M + L = ML, (III- f) vi hng s cn bng K: K = [ML]/[M] [L] (III- 61) v nng cc cht trong dung dch: CM = [M] + [ML] (III- 62) CL = [L] + [ML] (III- 63)
Vic xy dng ng chun cho trng hp xc nh ion Mm+ c nng NM v th tch VM bng dung dch tiu chun complexon III c nng NL nh sau: * pM khi cha chun : Khi cha chun , dung dch ch c ion Mm+. Ch s ng lng n ca ion Mm+ l 2, nn nng mol/l ca ion Mm+ l: [M] = CM = NM/2 do : pM = - lg(NM/2) (III- 64) * pM trc im tng ng: Khi cho dung dch tiu chun L vo dung dch chun , th nng ion Mm+ s gim. Bng vic gii h 3 phng trnh III- 61, III- 62, III- 63 c th xc nh c nng ion Mm+. Song, vic gii chnh xc h 3 phng trnh ny kh phc tp. Cch gii n gin gn ng nh sau: Nu coi phn ng III- f l hon ton th s mol ca phi t L bng s mol ca phc cht ML, nn c th vit: [ML] = VL. NL/2(VM + VL) Do , t biu thc III- 62 s c: [M] = [(VM.NM - VL.NL): (VM + VL)]/2 pM = - lg{[(VM .NM - VL.NL): (VM + VL)]/2} (III- 65) * pM ti im tng ng: Theo phng trnh III f c: [L] = [M] v theo biu thc III- 62 c: [ML] = CM [M] = [VM . NM/2(VM + VL)] [M] Thay [L] v [ML] vo biu thc III- 61 s c: K = {[VM . NM/2(VM + VL)] [M]}/[M]. [M] (III- 66) hay: (III- 67) K [M]2 + [M] VM . NM/2(VM + VL) = 0 m+ Gii phng trnh III- 67 s c nng ca ion M v t suy ra pM. Trong trng hp phc cht bn c th coi [ML] CM th: [ML] = CM - [M] VM . NM/2(VM + VL) v khi biu thc III- 66 c vit thnh: K [M]2 = VM . NM/2(VM + VL) t : [M] = [VM . NM/2K (VM + VL)VL)]1/2 hay: pM = (1/2)lgK (1/2)lg[VM . NM/2(VM + VL)] (III- 68) m+ Vic tnh pM theo biu thc III- 68 c chp nhn khi lng ion M d nh hn sai s cho php (thng thng vi sai s 1%). * pM sau im tng ng: Trong dung dch d L nn c th coi nng t do ca ion Mm+ l khng ng k so vi nng [ML], tc: [ML] = VM . NM/2(VM + VL) [L] = (VL. NL VM . NM)/2(VM + VL) thay cc gi tr ny vo biu thc III- 61 v bin i tip s c:
hay: 69)
[M] = [(VM . NM)/2]/[K(VL. NL VM . NM)/2] pM = lgK lg[VM . NM/(VL . NL VM . NM)] (III-
C th minh ho vic xy dng ng chun to phc thng qua trng hp chun 20 ml Mm+ 0,01N bng dung dch Na2H2Y 0,01N vi cc hng s K khc nhau ca phc cht MY. Chun xy ra theo phng trnh III- f. Cc s liu tnh ton c ghi trong bng B.8.3. ng chun to phc ML c dng nh hnh v H.10.3. Bng B.8.3: pM dung dch khi chun 20 ml Mm+ 0,02N bng dung dch complexon III (Na2H2Y) 0,02N Trng thi chun Cha chun Trc im tng ng Ti im tng ng Sau im tng ng % chun 0 50 90 99 99,9 100 100,1 101 110 150 Vn dng biu thc III- 64 III- 65 pM ng vi cc hng s K khc nhau 108 2,00 2,48 3,28 4,30 5,15 6,00 7,00 7,70 1010 2,00 2,48 3,28 4,30 5,30 6,15 7,00 8,00 9,00 9,70 1012 2,00 2,48 3,28 4,30 5,30 7,15 9,00 10,00 11,00 11,70 1016 2,00 2,48 3,28 4,30 5,30 9,15 13,00 14,00 15,00 15,70 1020 2,00 2,48 3,28 4,30 5,30 11,15 17,00 18,00 19,00 19,70
III- 68 III- 69
Hnh H.10.3: ng chun complexon III Qua c nhn xt: 1. ng chun l ng cong i xng qua im 100% chun v pM = {lgK lg[VM . NM/2 (VM + VX)]}/2 2. Tng t nh cc phng php chun khc, xung quanh im tng ng pM thay i nhanh v to ra bc nhy. Bc nhy ph thuc vo: - Sai s phn tch: Sai s cng ln th bc nhy cng ln, - Hng s cn bng K: K cng ln, bc nhy cng ln. - Nng cc cht tham gia phn ng: Nng cc cht tham gia phn ng cng ln, bc nhy cng ln.
6.6. Nhn xt chung v ng chun . ng dng ca ng chun

a. Nhn xt chung v ng chun T cc dng ng chun trung ho, oxi ho kh, kt ta v to phc c nhn xt chung nh sau: 1. ng chun c 2 dng: dng i xng v dng bt i xng qua im ch s chun pT (pHt , Et, pXt, pMt, pXt) v 100% chun . Dng i xng nhn c: - Trong chun trung ho: khi chun axit mnh bng baz mnh v ngc li. - Trong chun oxi ho kh: khi cc cp oxi ho kh ring phn trao i cng s electron. - Trong chun kt ta v chun to phc: khi cc cht tham gia phn ng vi h s phn t nh nhau. Dng bt i xng nhn c: - Trong chun trung ho: khi chun axit yu bng baz mnh hoc chun baz yu bng axit mnh. - Trong chun oxi ho kh: khi cc cp oxi ho kh ring phn trao i khng cng s electron. - Trong chun kt ta v chun to phc: khi cc cht tham gia phn ng vi h s phn t khc nhau. 2. Xung quanh im tng ng (pT v 100% chun ), cc i lng pH, E, pX, pM c s thay i mnh tr s o v to nn bc nhy ca ng chun pH, E, pX hoc pM. ng vi mi sai s cho trc c mt bc nhy ring, bc nhy ny cng ln khi sai s cng ln, v d: trong chun trung ho pH1% > pH0,1%. 3. Bc nhy ng chun ph thuc vo hng s cn bng ca phn ng chun . Hng s cn bng cng ln, bc nhy cng di. V d: Chun axit mnh
bng baz mnh c bc nhy di hn chun axit yu bng baz mnh, chun kt ta vi TMX cng nh th bc nhy cng di 4. Bc nhy ng chun ph thuc vo nng dung dch cc cht tham gia phn ng, nng cng ln bc nhy cng di. Ring trong chun oxi ha kh th bc nhy t ph thuc vo nng . 5. Khi chun hn hp nhiu cht th thu c ng chun vi nhiu bc nhy tng ng vi tng cht, bc nhy trc l ca cht hot ng mnh hn. Tuy vy, cc bc nhy ch r rng tch ra khi nhau khi hng s cn bng ca cc phn ng m chng tham gia khc nhau r rt. V d: Vi sai s 0,1%, cc hng s cn bng ca cc phn ng phi hn km nhau 104 ln. b. ng dng ca ng chun ng chun c nhiu ng dng trong thc t nh: 1. Xc nh sai s chun . V d: khi chun trung ho dng chun ti mt gi tr pHkt no th sai s chun l bao nhiu? xc nh sai s ch cn dng ng cong chun tng ng. T trc tung (pH) xc nh pHkt v trn trc honh tm tr s phn trm chun tng ng vi pHkt, cui cng l tnh sai s %: sai s% = % chun - 100. 2. Chn cht ch th thch hp m bo chun vi chnh xc cho trc. Cht ch th mu c dng phi c khong i mu nm trong bc nhy ca ng chun (mc 7.1 chng III) v c gng sao cho ch s chun pT nm gia khong i mu. 3. Chn cch thao tc chun thch hp. i vi ng cong chun i xng c th chun theo c 2 chiu m vn t c chnh xc nh nhau nu cng dng mt tr s chun . V d: chun axit mnh bng baz mnh hoc ngc li, nu dng chun pH = 5 th vic chun theo chiu tng pH (a baz vo axit) hay chiu gim pH (a axit vo baz) u cho kt qu nh nhau. i vi ng cong bt i xng th ch c mt cch chun sao cho tr s i lng o thay i t phn bin i chm sang phn bin i nhanh, v nh hng ca git d l khc nhau mi phn ng cong. C th: khi chun axit yu bng baz mnh th phi a baz mnh vo axit, chun baz yu bng axit mnh th phi a axit mnh vo baz, hay, trong chun oxi ho kh b tr dung dch ca cp trao i electron t hn trn buret, v d, chun xc nh ion Fe2+ bng K2Cr2O7 th a ion Fe2+ vo dung dch K2Cr2O7). 4. Chn nng thch hp ca cc dung dch tham gia phn ng. Bc nhy ng cong chun cng di khi nng cng ln, nn trnh s pha long dung dch chun mt cch khng cn thit v nn s dng dung dch tiu chun c nng cao. Song, khng nn dng nng qa cao ca dung dch tiu chun trnh sai s git d (git d l git dung dch cht tham gia phn ng gy ra s i mu ca ch th, v khng phi ton b git ny tham gia phn ng). V d: chun xc nh NaOH bng HCl, nu dng HCl 0,1N ht 20 ml, cn nu dng HCl 1N ht 2 ml, th sai s do git d (1 git tng ng vi 0,03 ml) gy nn s l: - Trong trng hp dng HCl 0,1N: e% = (0,03 . 100)/20 = 0,15 % - Trong trng hp dng HCl 1N: e% = (0,03 . 100)/2 = 1,5 %
7. CH TH C rt t cc phn ng chun , m , bn thn cc cht tham gia phn ng c mu v t n ch th im tng ng nh s xut hin hoc s bin mt ca cht mu ny. V d: chun cc cht kh bng dung dch tiu chun KMnO4, th li dng mu tm ca KMnO4 lm ch th im tng ng, khi mu tm hng xut hin s dng chun . Cc phn ng chun ny c gi l cc phn ng t ch th. Cc chun loi ny c chnh xc rt cao, v sai s y ch l sai s git d. Trong i b phn cc trng hp chun , nhm xc nh im tng ng phi dng ch th. Ch th l mt hp cht hay mt dng c o c a vo dung dch chun . Ti im tng ng hay xung quanh im tng ng, ch th bng s thay i tnh cht ca mnh bo hiu im kt thc chun . Trong phn tch th tch hay dng ch th l nhng cht mu hay cht to mu (gi chung l ch th mu).
7.1. Phn loi ch th

Da vo s tn ti ca dng mu, cc ch th c chia thnh ch th mt mu v ch th hai mu: Ch th mt mu l loi ch th m trong mt pha ch c mt dng ca ch th c mu. V d: - Ch th phenolphtalein, trong dung dch mu dng axit ca n khng mu cn mu dng baz ca n mu hng. - Ch th K2CrO4 dng trong phng php Mo, v hai dng K2CrO4 (dung dch mu vng) v Ag2CrO4 (kt ta nu ) nm hai pha khc nhau. Ch th hai mu l loi ch th m trong mt pha c hai dng mu ca ch th. V d: ch th metyl , trong dung dch mu dng axit ca n c mu cn mu dng baz ca n mu vng. Da theo phn ng ca ch th, cc ch th mu c chia thnh 4 nhm: 1. Ch th axit baz, l cc hu c c mu, c tnh axit, baz yu v mu ca cc dng axit, dng baz l khc nhau, s chuyn mu l chuyn t mu dng axit sang mu dng baz v ngc li ph thuc vo pH mi trng chun . V d: ch th metyl ni trn, c mu dng axit l mu , mu ca dng baz l mu vng, nh vy mu chuyn t vng sang khi gim pH dung dch v ngc li t sang vng khi tng pH dung dch. 2. Ch th oxi ho kh, l cc cht mu c tnh oxi ho kh v mu ca cc dng oxi ho, dng kh l khc nhau, s chuyn mu l chuyn t mu dng oxi ho sang mu dng kh v ngc li ph thuc vo in th E ca dung dch. V d: ch th diphenylamin, trong mi trng axit, n c mu dng oxi ho l mu tm than, mu ca dng kh l khng mu, nh vy mu chuyn t tm than sang khng mu khi gim E dung dch v ngc li t khng mu sang tm than khi tng E dung dch. 3. Ch th kt ta, l cc cht c th to cc kt ta c mu vi cc cht tham gia phn ng chun . V d: chun xc nh ion Cl- bng AgNO3 theo phng php Mo dng ion CrO42- lm ch th, v n to kt ta mu nu Ag2CrO4 vi ion Ag+. 4. Ch th to phc, l cc ho cht c th to phc mu vi cc cht tham gia phn ng chun , tc mu ch th t do khc vi mu ca phc cht gia ch th vi cht tham gia phn ng chun . S chuyn mu l chuyn t mu dng ch th t do sang mu dng phc cht ca ch th v ngc li ph thuc nng ca cc cht tham
gia phn ng chun . V d: ch th eriocrom T en, ti pH = 10, c mu xanh da tri, song, phc cht ca n vi ion Mg2+ c mu nho, nh vy mu chuyn t xanh da tri sang mu nho khi tng nng ion Mg2+ v ngc li t nho sang xanh da tri khi tng nng complexon III, hay ch th h tinh bt trong chun it da trn s to phc cht xanh tm than ca n vi it, ch th Fe(NO3)3 trong chun Fonha da trn s to phc cht mu mu ca ion Fe3+ vi ion CNS-. Nh vy, s i mu ca mi ch th u gn lin vi nng ca cc cht tham gia phn ng chun , hay ni mt cch khc ph thuc vo tr s ca cc i lng o ca dung dch, v d, pH, E, pX, pM Khi cc tr s ny thay i dn n mu ca dung dch thay i.
7.2. Khong i mu ca ch th
Khi chun , tr s chun lin tc thay i lm cho cc thnh phn ca ch th thay i dn n mu sc thay i. Tuy vy, trong chun thng dng mt nhn bit s thay i mu m kh nng ca mt ch c hn, n ch c th nhn c mu sc trong nhng gii hn nht nh ca nng cht mu. Khong nng gii hn li ph thuc vo tr s chun . Khong tr s chun m mu ca ch th thay i mt con ngi nhn bit c, c gi l khong i mu ca ch th. Khong i mu ca ch th ph thuc vo ch th mt mu hay hai mu. a. i vi nhm ch th mt mu Vi loi ch th ny, khng c s pha trn mu gia cc dng ca ch th, nn s nhn c mu ca mt ph thuc vo nng ca dng mang mu. Thng mt nhn c mu khi trong dung dch c nng ca dng mang mu khong 10-5 10- 6 mol/lt. V d: vi ch th phenolphtalein ch nhn thy mu hng khi nng dng baz ca ch th ny trong dung dch l > 10- 6M. b. i vi nhm ch th hai mu y, c s pha trn mu, nn, vic nhn thy thay i mu ca mt ph thuc vo t l nng cc dng mang mu ca ch th. Thng mt ch nhn thy mu ca mt dng no khi n chim khong 1/10 tng lng cht mu. V d: vi ch th axit baz: HInd H+ + Ind CInd = [HInd] + [Ind] mt nhn thy mu chuyn sang mu ca dng [Ind-] khi: ([Ind-]/CInd ) 1/10 v khng thy s chuyn na khi ([Ind-]/CInd ) 9/10 v t s ny thay i ph thuc vo pH dung dch. * Vi ch th axit baz: Nu k hiu ch th axit baz c dng axit l HInd v dng baz l Ind-, c: HInd H+ + IndKaHInd = [H+] [Ind-]/ [HInd] (III- 70) Bin i biu thc III- 70 s c: pH = pKaHInd - lg{[HInd]/[Ind-]} (III- 71) Nh trn ni, s i mu m mt nhn c xy ra khi lng ca mt dng no chim 1/10 tng lng mu, hay t l [Ind-]/[HInd] bin i t 1/9 n 9/1. T , biu thc III- 71 c vit thnh biu thc III- 72: pH = pKaHInd 1 (III- 72) vi hng s phn li:
v c gi l khong i mu ca ch th HInd; hng s pKaHInd c gi l ch s ch th ca ch th axit baz. V d: ch th metyl c pKa = 5, th s i mu ca n xy ra trong khong pH: 4 - 6. * Vi ch th oxi ha kh: Thng gp cc ch th oxi ha kh l nhng cht hu c c tnh oxi ho kh: Indox + ne = Indkh c c trng bi th in cc EInd (III- 73): EInd = E0 Indox / Indkh + (0,059/n)lg{[Indox]/[Indkh]} (III73) Vi l lun tng t nh phn ch th axit baz, s c khong i mu ca ch th oxi ho kh l: (III- 74) E = E0 Indox / Indkh 0,059/n v E oIndox / Indkh c gi l ch s ch th ca ch th oxi ho kh. V d: ch th diphenylamin (ox + 2e = kh) c Eo = 0,76V, th s i mu ca n xy ra trong khong E: 0,73 0,79V. * Vi ch th to phc: S to phc mu ca ch th vi ion kim loi M: M + aInd = M(Ind)a ( y, b qua in tch ca cc ht), c c trng bi hng s bn biu kin Kb (v ch th Ind c th phn ng vi H+): Kb = [M(Ind)a]/[M][Ind]a (III- 75) S i mu xy ra khi c t l ([Ind]/[M(Ind)a] bng 1/9 hay 9/1, nh vy bng vic bin i biu thc III- 75 c: pM1/9 = lgKb - 1 v pM9/1 = lgKb + a (III- 76) nh vy, khong i mu ca ch th l t pM1/9 n pM9/1 hay c tr s t lgKb - 1 n lgKb + a. Gi tr lgKb cng c gi l ch s ch th ca ch th to phc. * Vi ch th kt ta: V dung dch ch th v sn phm kt ta gia ch th vi cht xc nh thuc hai pha khc nhau, nn c th coi ch th nh l ch th mt mu, do lng kt ta cng phi t n mt lng nht nh mt mi nhn c. V th, nu chun vi dung dch long s rt kh nhn mu. Khong i mu ca ch th tnh theo cc biu thc III- 72, III- 74 v III- 76 hon ton mang tnh cht l thuyt. Trong thc t, khong i mu ca cc ch th khng nh nhau do s nhy cm ca mt vi tng loi mu sc c khc nhau. V d: Mt nhy cm vi tt c cc loi mu xanh nhng rt km nhy vi mu vng. Cho nn, i vi mt ch th, thao tc chun khc nhau c th cho sai s khc nhau. V d: Khi dng ch th metyl da cam, nu chun theo chiu gim pH, mt c th nhn thy s i mu khi ch c 5% dng mu , nhng chun theo chiu tng pH th ch nhn c mu vng khi trong dung dch c ti 20 30% dng mu vng, do , sai s chun s ln hn sai s trng hp trn.
7.3. Nguyn tc chn ch th

chun t chnh xc cho trc, cn chn ch th p ng cc yu cu sau:
- u tin chn cc phn ng t ch th trnh sai s ch th. V d: trong chun pemanganat dng lun mu tm ca ion MnO4- lm mu ch th. - Khong i mu ca ch th nm trn trong hoc t nht c mt phn nm trong bc nhy ca ng chun . V d: chun axit mnh bng baz mnh hoc ngc li vi sai s 0,1% (bc nhy pH t 4,3 n 9,7) c th dng cc ch th metyl da cam (pKa = 3,46), metyl (pKa = 5), qu (pKa = 7), phenolphtalein (pKa = 9) Nu khng c ng chun th tnh sai s ch th (xem chng V) chn ch th ph hp. - Ch th phi c cc mu tng phn nhau r rt (max 70nm) nh vy mt mi d dng nhn thy s chuyn mu. Nhng cp tng phn mu mt rt d nhn bit l: khng mu c mu, mu xm c mu hoc xanh . ng dng hiu bit ny b tr chun sao cho quan st mu d nht, v d: khi chun trung ho axit mnh bng baz mnh vi ch th phenolphtalein nn baz trn, mu ch th chuyn t khng mu sang mu . - Nng ch th phi va mt nhn thy s thay i mu, nhng, khng qu ln dn n sai s chun , v thc cht phn ng ch th l phn ng cnh tranh vi phn ng gia cht cn xc nh v cht tiu chun.
8. CC PHP CHUN THNG DNG
8.1. Chun trung ho

y, c 2 php chun : chun axit v chun kim. a. Chun axit L php chun vi dung dch tiu chun l cc dung dch axit mnh, dng xc nh cc cht c tnh baz (cc baz, cc mui baz). Dung dch tiu chun thng c dng l cc dung dch axit mnh HCl, HNO3 v H2SO4. Cc dung dch ny thng c pha t cc axit HCl, HNO3, H2SO4 c (TKPT). Bi v, cc axit c ny khng phi l cht gc, do chng d bay hi (HCl, HNO3 c) hay d ht m (H2SO4 c), nn dung dch sau khi pha xong cn c chun li bng dung dch cc cht gc nh KHCO3 (KHCO3 = MKHCO3), Na2CO3 khan (Na2CO3 = MNa2CO3/2), Na2B4O7.10H2O (Na2B4O7.10H2O = MNa2B4O7.10H20/2) vi ch th metyl da cam. Mt cch pha khc l dng cc ng fixanan, v d: ng fixanan HCl, HNO3, H2SO4. b. Chun kim L php chun vi dung dch tiu chun l cc dung dch kim mnh, dng xc nh cc cht c tnh axit (cc axit, cc mui axit). Dung dch tiu chun thng l cc dung dch kim mnh: NaOH, KOH, Ba(OH)2. Cc dung dch ny thng c pha t NaOH, KOH, Ba(OH)2 rn, l nhng cht khng phi l cht gc do chng d ht m v hp th CO2. Do , dung dch thu c sau khi pha cn lc v chun li xc nh nng bng dung dch tiu chun gc nh dung dch H2C2O4 (H2C2O4 = MH2C2O4/2) vi ch th phenolphtalein v c bo qun kn trong cc bnh bng polyetylen. Trong nhng chun m lng mui cacbonat khng nh hng n kt qu phn tch th khng cn tch cacbonat (v d: vi chun kt thc ti pH 4), cn cc chun m lng mui cacbonat c nh hng th cn loi
chng i bng cch cho vo dung dch NaOH, KOH mt t mui BaCl2 v lc ly dung dch, sau mi xc nh nng ca cc dung dch ny. c. Cc cht ch th thng dng trong chun trung ho Thng dng ch th l cht hu c c tnh axit yu, baz yu v c mu dng axit khc mu dng baz (bng B.9.3). Bng B.9.3: Cc cht ch th thng dng trong chun trung ho Tn ch th Bromthymol xanh Metyl da cam Metyl Phenol Phenolphtalein Cch pha cho 100ml dung dch 0,1g trong cn 20% 0,1g trong nc 0,1g trong cn 60% 0,1g trong cn 20% 0,1g trong cn 50% pKaHInd 7,30 3,46 5,00 8,00 9,00 Khong i mu (pH) 6,2 7,6 3,1 4,5 4,2 6,2 6,8 8,4 8,0 10,0 Mu ca cc dng axit baz vng vng khng mu xanh vng chanh vng
d. ng dng chun trung ho

Chun trung ho thng c ng xc nh cc cht c tnh cht axit, baz. Chun c th tin hnh chun trc tip hoc chun ngc. Trong i b phn cc trng hp, thng dng chun trc tip. Trong trng hp xc nh cc cht t tan (cc mui khng tan), cc cht rn, cc cht kh hoc cc cht phn ng chm vi thuc th (v d: xc nh este), thng tin hnh chun ngc. V d: xc nh CaCO3, MgCO3, cho chng tc dng vi dung dch tiu chun HCl ly d, xc nh kt ta (NH4)3P(Mo3O10)4 (amoni molybdatophotphat), cho cht ny tc dng vi dung dch tiu chun NaOH ly d hoc khi xc nh este th un nng hn hp este vi NaOH ly d; sau lng d ca axit hoc baz c xc nh bng dung dch tiu chun NaOH hoc HCl. Bng chun trung ho c th xc nh hn hp cc baz hoc hn hp cc axit vi vic chn ch th thch hp da trn s khc nhau v baz, axit ca chng. V du: chun xc nh hn hp NaOH v Na2CO3 bng HCl: vi ch th phenolphtalein, chun xc nh NaOH v nc 1 ca Na2CO3, cn vi ch th metyl da cam s chun ng thi NaOH v c 2 nc ca Na2CO3. T lng tiu tn HCl ca 2 ln chun suy ra hm lng NaOH v Na2CO3 trong mu.
8.2. Chun oxi ho kh
y, cng c 2 php chun : chun oxi ha v chun kh. a. Chun oxi ho L php chun vi dung dch tiu chun l dung dch cc cht oxi ha, dng xc nh cc cht kh. Dung dch tiu chun thng dng l KMnO4, K2Cr2O7, I2, Ce(SO4)2, t hnh thnh cc phng php chun pemanganat, chun bicromat, chun it Cc cht gc thng dng H2C2O4, K2Cr2O7, Ce(SO4)2. b. Chun kh L php chun vi dung dch tiu chun l dung dch cc cht kh, dng xc nh cc cht oxi ho.
Dung dch tiu chun thng dng l FeSO4, Ti2(SO4)3, Na2S2O3 t hnh thnh cc phng php chun st (II), chun titan, chun thiosunphat Cc cht gc thng dng K2Cr2O7, KIO3, Ce(SO4)2. c. Ch th thng dng trong chun oxi ho kh Trong chun oxi ho kh thng s dng 3 loi ch th: t ch th, ch th khng lin quan n in th dung dch v ch th c lin quan n in th dung dch. * T ch th: l chun vi dung dch tiu chun KMnO4 trong mi trng axit. Mt git d KMnO4 lm dung dch chuyn t khng mu sang mu hng, bo s kt thc ca chun . * Ch th khng lin quan n in th: Cht ch th to phc mu vi mt dng oxi ha kh ca cht cn xc nh hoc thuc th. Khi d mt git dung dch tiu chun s xy ra s chuyn mu. V d: chun it vi ch th h tinh bt th s chuyn mu l do vic to ra hay mt i mu xanh tm than ca phc cht it h tinh bt * Ch th lin quan n in th: l cc ch th c tnh oxi ho kh. S chuyn mu ca n lin quan cht n th in cc ca dung dch. Tu theo tng phn ng chun m chn ch th thch hp. Mt s ch th thng dng c nu bng B.10.3.
Bng B.10.3: Cc cht ch th thng dng trong chun oxi ha kh Tn ch th Cch pha cho 100ml dung dch EoInd S e trao i 1 1 2 2 Mu ca cc dng oxi ho kh xanh tm tm tm khng mu khng mu khng mu
Fe(II)(ophenan1,485g ophenanthrolin + 1,11 throlin)3 (ferroin) 0,695gFeSO4.7H2O Benzidin 1g trong H2SO4 c 0,92 Diphenylamin Axit N phenylanthranylic nghip 1g trong H2SO4 c 0,2g trong nc 0,76 1,08
d. Mt s chun oxi ha kh thng dng trong phn tch i tng nng * Chun pemanganat (permanganatomet): y l phng php chun vi dung dch tiu chun KMnO4 v thng tin hnh trong mi trng axit (pH 0) theo phng trnh phn ng: KMnO4 + 5e + 8H+ = K+ + Mn2+ + 4H2O (tm hng) (khng mu) o E MnO4-/ Mn2+ = 1,51V, ([H+] = 1M) KMnO4 = MKMnO4/5
lm mi trng cho chun ny, dng axit H2SO4 m khng dng axit HCl. Tng t, chun khng c tin hnh nu mu cha ion Cl-, bi v, th in cc ca clo EOCl2 / 2Cl- = 1,36V, nh hn th in cc ca cp MnO4-/Mn2+, nn ion MnO4- oxi ho c ion Cl-: 2MnO4- + 10Cl- + 16H+ = 5Cl2 + 2Mn2+ + 8H2O Trong trng hp khng th loi tr c ion Cl-, th cho vo dung dch chun MnSO4, hn ch nh hng ca ion Cl-. Vi chun pemanganat khng cn dng cht ch th, v bn thn ion MnO4- c mu tm hng, s xut hin hoc mt mu tm hng bo hiu im kt thc chun . Do trong chun trc tip lun b tr KMnO4 trn buret. Pemanganat l mt cht oxi ha mnh nn dng chun pemanganat c th xc nh c nhiu cht bng nhng cch chun khc nhau: + Chun trc tip: Xc nh c nhng cht tham gia phn ng trc tip vi ion MnO4- nh: Sn2+, Fe2+, AsO33-, Sb3+, Ti2+, Ti3+, [Fe(CN)6]4-, NO2-, H2O2, H2C2O4, ancol + Chun ngc: Dng xc nh cc cht kh km bn trong mi trng axit, do to cht bay hi, d phn hu, nh S2-, SO32-, I-. Trong trng hp ny, cho KMnO4 d vo dung dch chun v lng d ca KMnO4 c xc nh li bng dung dch tiu chun FeSO4. Chun ngc cng cn dng xc nh cc cht oxi ha nh MnO2, PbO2, K2Cr2O7, H2O2 Trc tin, cho cc cht ny phn ng vi dung dch tiu chun H2C2O4 hay FeSO4 ly d, sau lng d ca H2C2O4 hay FeSO4 c xc nh bng chun pemanganat. + Chun th: Cc ion kim loi Ca2+, Sr2+, Ni2+, Co2+, Mn2+, Cd2+, Cu2+ khng phn ng vi ion MnO4-, nhng li to kt ta hon ton vi ion C2O42-, thu ly kt ta ri ho tan trong axit H2SO4 v chun lng axit H2C2O4 gii phng ra bng KMnO4. + Cch pha dung dch tiu chun KMnO4: V KMnO4 rn d b phn hu bi nh sng v nhit cao nn n khng phi l cht gc. Sau khi ho tan lng cn tnh vo nc ct, yn trong bng ti v ni mt 72 gi ri cht ly phn dung dch trong hoc lc dung dch bng phu lc s hoc thu tinh (khng lc qua giy lc). Dung dch thu c mang chun li bng dung dch tiu chun gc H2C2O4 nhit 60 80oC (v nhit thp, phn ng xy ra chm): 60oC 80oC + 2KMnO4 + 5H2C2O4 + 6H = 10CO2 + 2K+ + 2Mn2+ + 8H2O v bo qun trong cc bnh mu nu ni ti v nhit thp. * Chun bicromat (bicromatomet): L php chun vi dung dch tiu chun K2Cr2O7 v tin hnh trong mi trng axit (pH 0) theo phng trnh phn ng: K2Cr2O7 + 6e + 14H+ = 2K+ + 2Cr3+ + 7H2O EoCr2O72-/ 2Cr3+ = 1,36V, ([H+] = 1M) K2Cr2O7 = MK2Cr2O7/ 6 Mi trng axit c duy tr bng axit H2SO4 hoc axit HCl. Khc vi phng php chun pemanganat, trong chun ny ion Cl- khng gy nh hng n kt qu phn tch. Nhng khi tin hnh chun nhit cao, th ion Cl- s gy nh hng, v lc ny bicromat oxi ha c ion Cl-, gii phng Cl2.
xc nh im tng ng phi dng ch th mu nh: diphenylamin, diphenylbenzidin, natri diphenylaminsulfonat, axit N - phenylantranylic, v mu da cam ca ion Cr2O72- c cng mu thp v trong chun , ion mu xanh Cr3+ c to thnh cng c cng mu thp. Chun bicromat c dng xc nh cc ion c tnh kh nh Fe2+, Sn2+ (chun trc tip) hoc cc hp cht hu c (glyxerin, etanol, mn) (chun ngc). Pha dung dch tiu chun K2Cr2O7: Bi v K2Cr2O7 l cht gc, nn vic pha dung dch tiu chun rt n gin, ch cn cn chnh xc lng tnh ri ho tan n trong bnh nh mc c th tch bng th tch cn pha. * Chun it - thiosunphat: L phng php chun vi dung dch tiu chun l dung dch it theo phng trnh phn ng: I2 + 2e = 2I(pH = 0 8) o E I2/2I- = 0,54V , I2 = MI2/2 v dung dch Na2S2O3 tiu chun theo phng trnh phn ng: S4O62- + 2e = 2S2O32EoS4O62-/S2O32- = 0,09V Phn ng gia I2 v Na2S2O3 xy ra theo phng tnh sau: I2 + 2Na2S2O3 + 2NaI + Na2S4O6 , do Na2S2O3 = MNa2S2O3 Phng php chun it thiosunphat c s dng xc nh hng lot cc cht kh v cc cht oxi ha c tnh oxi ho kh trung bnh bng nhiu cch chun . + Chun trc tip: Thng dng xc nh cc cht kh (c th oxi ha kh nh hn th oxi ha kh ca I2) nh cc ion: S2O32-, CN-, AsO33-, Sb(III). Cc chun tin hnh trong mi trng axit vi ch th l h tinh bt; khi d I2, h tinh bt s chuyn t khng mu sang mu xanh tm than. + Chun ngc: Dng chun nhng cht kh d b oxi ho bi oxi ca khng kh (SO32-, S2) hoc nhng cht hu c (nh cc du bo) c ni i phn ng chm vi I2. Sau khi cho cc cht cn xc nh phn ng hon ton vi dung dch tiu chun I2 ly d, th lng I2 d c chun bng dung dch tiu chun Na2S2O3 vi ch th l h tinh bt (dung dch chuyn mu t mu xanh tm than sang khng mu). + Chun th: Dng xc nh cc cht oxi ha nh: ClO3-, BrO3-, IO3-, AsO43-, Cr2O72-, 2CrO4 , MnO4-, [Fe(CN)6]3-, Fe3+, Cu2+, Cl2, H2O2, MnO2, PbO2 Da trn nguyn tc: cc cht ny oxi ha ion itua trong mi trng axit gii phng ra I2, sau lng I2 c xc nh bng dung dch tiu chun Na2S2O3 vi ch th h tinh bt. Bng cch ny cng c th chun cc cht to kt ta vi ion CrO42- nh Ba2+, Pb2+ + Cch pha dung dch tiu chun I2 v Na2S2O3: Dung dch tiu chun I2 dng cho chun trc tip v chun ngc c pha t lng it thng hoa tnh trc trong dung dch KI 1% ( tng tan v bn ca dung dch, v y xy ra phn ng I2 + KI KI3). Sau , nng chnh xc ca dung
dch c xc nh bng dung dch tiu chun Na2S2O3. Dung dch c bo qun trong bnh mu v ni ti, mt. Trong trng hp chun ngc c th dng bin php iu ch trc tip I2 trong dung dch bng phn ng: KIO3 + 5KI + 6H+ = 3I2 + 6K+ + 3H2O KIO3 = MKIO3/6 y, ch cn ly chnh xc mt lng KIO3 (KIO3 l cht gc) tng ng vi lng I2 cn c v cho tc dng vi dung dch KI d trong mi trng axit H2SO4 hoc axit HCl. Dung dch tiu chun Na2S2O3 c pha t Na2S2O3.5H2O. V Na2S2O3.5H2O khng phi l cht gc nn dung dch sau khi pha cn c xc nh li nng bng dung dch tiu chun gc K2Cr2O7, KBrO3 hay KIO3 bng cch cho cc dung dch tiu chun gc K2Cr2O7, KBrO3, KIO3 phn ng vi KI d trong mi trng axit: K2Cr2O7 + 6KI + 14H+ = 3I2 + 8K+ + 2Cr3+ + 7H2O K2Cr2O7 = MK2Cr2O7/6 KBrO3 + 6KI + 6H+ = 7K+ + 3I2 + Br- + 3H2O KBrO3 = MKBrO3/6 ri chun lng I2 gii phng ra bng dung dch Na2S2O3 vi ch th h tinh bt. Dung dch Na2S2O3 sau khi pha xong c b sung vi git CHCl3 chng vi khun n lu hunh. Khi s dng phng php it - thiosunphat cn lu : - Chun ch tin hnh pH = 0 8, bi v pH thp hn 0, axit HI c th t phn hy to thnh I2 (2HI H2+I2), cn pH > 8 s xy ra phn ng: I2 + 2OH- IO- + I- + H2O gy mt it hoc cho phn ng ph bi kh nng oxi ha mnh ca IO-. - Do phn ng ca I2 vi cht kh hoc ca I- vi cht oxi ha thng xy ra chm, nn cn c thi gian cho phn ng xy ra hon ton. - It d bay hi, nn khng chun vi dung dch nng v khi chun gin tip, phi y kn bnh phn ng trong khi I2 phn ng vi cht kh hay khi iu ch I2. - B mt mt s cht kt ta, cht keo c kh nng hp th I2,, nn khi chun cn lc k, nht l gn im tng ng. - Phc cht it h tinh bt ch thun nghch khi nng it thp, nn khi chun gin tip phi chun khng c ch th n khi nng it cn rt thp (mu vng nht) mi cho ch th vo v chun tip. - Dung dch KI d b oxi khng kh oxi ha: 4I- + O2 + 2H2O I2 + 4OHnn trong chun th cn lm mu trng. Cng do phn ng ny, m trong chun gin tip s mt mu ca ch th ch cn bn trong 30 giy, v sau , mu c th s ti xut hin. - Dung dch Na2S2O3 khng bn trong mi trng axit mnh: Na2S2O3 + 2H+ = 2Na+ + S + SO2 nn n c b tr buret v nh t t vo bnh phn ng. - Nng ca cc dung dch tiu chun I2 v Na2S2O3 cn c kim tra thng xuyn. * ng dng chun oxi ha kh:
Di y trnh by nguyn tc xc nh mt s ion hay hp cht thng gp trong nng nghip bng chun oxi ha kh. + Xc nh ion Fe3+: Ion Fe3+ c kh v ion Fe2+ bng SnCl2 (lng SnCl2 d c oxi ha bng HgCl2), sau chun lng Fe2+ to thnh bng dung dch tiu chun KMnO4 hay K2Cr2O7 trong mi trng axit. Ion Fe3+ cng c xc nh bng chun it thiosunphat. Trc ht cho ion 3+ Fe phn ng vi KI ly d, ri chun lng I2 gii phng ra bng Na2S2O3 vi ch th h tinh bt. + Xc nh ion Cu2+: Ion Cu2+ c xc nh bng chun it thiosunphat. Trc tin cho Cu2+ tc dng vi KI ly d trong mi trng pH 3 4 v vi s c mt ca KCNS, sau chun lng I2 gii phng ra bng Na2S2O3 vi ch th h tinh bt. + Xc nh ion Ca2+: Ion Ca2+ c xc nh gin tip bng chun pemanganat da trn vic th ion Ca2+ bng lng tng ng CaC2O4. Sau ho tan CaC4O4 trong mi trng axit H2SO4 v chun lng axit H2C2O4 gii phng ra bng KMnO4. + Xc nh mn trong t: Cho t tc dng vi dung dch tiu chun K2Cr2O7 ly d trong mi trng axit H2SO4 50% nhit 200oC. Lng d ca K2Cr2O7 c chun li bng dung dch tiu chun FeSO4. + Xc nh ch s it ca du bo: Ho tan du bo trong clorophoc, cho vo dung dch I2 ly d. Sau 15 pht chun lng it d bng Na2S2O3 vi ch th h tinh bt.
8.3. Chun kt ta
S lng phn ng to kt ta nhiu nhng ch c rt t cc phn ng tho mn cc iu kin ca phng php phn tch th tch. Trong phn tch cc i tng nng nghip, thng ch s dng phn ng ca dung dch tiu chun AgNO3 chun xc nh cc ion nhm halogenua Cl-, Br-, I- v CNS- (X-): Ag+ + X- = AgX Phng php chun ny gi l chun bc (argentomet). Chun bc thng c tin hnh theo hai cch: chun trc tip (phng php Mo, phng php Fajans) v chun ngc (phng php Fonha). a. Phng php Mo (Mohr) Dng xc nh cc ion Cl-, Br- (X-) vi ch th K2CrO4. Do cc kt ta AgCl, AgBr c tan nh hn tan ca kt ta Ag2CrO4 (TAgCl = 1,78 . 10-10, TAgBr = 1,5 . 1012 , TAg2CrO4 = 1,1 . 10-12), nn cc kt ta AgCl, AgBr hnh thnh trc v ch khi n im tng ng kt ta Ag2CrO4 mi hnh thnh: AgNO3 + X- = AgX + NO3trng 2Ag+ + CrO42- = Ag2CrO4 nu Trong chun , b tr AgNO3 trn buret, nn s chuyn mu l t kt ta mu trng sang kt ta mu nu. Trong phng php Mo cn lu :
- Chun ch tin hnh mi trng c pH 6,5 10, bi v mi trng kim pH > 10 s xy ra phn ng: 2Ag+ + 2OH- = Ag2O + H2O lm tiu tn thuc th gy nn sai s, cn trong mi trng axit kt ta Ag2CrO4 khng hnh thnh, nn khng c phn ng ch th. - Do chun trong mi trng trung tnh, nn cc ion gy nhiu nh CO32-, PO43- cn phi c tch trc khi chun . - im kt thc chun ph thuc vo nng ch th, nn cn tnh nng K2CrO4 cn thit cho tng chun . V d: Chun xc nh ion Cl-, ti im tng ng c: pCl = - lg(TAgCl)1/2 = 4,88 = pAg+, tc nng [Ag+] = 1,3 . 10-5 M. Nh vy, Ag2CrO4 kt ta, nng CrO42- ti im tng ng l: [CrO42-] = TAg2CrO4/[Ag+]2 = 1,1.10-12/(1,3.10-5)2 = 6,5.10-3 M. - Khng dng phng php ny chun xc nh cc ion I-, CNS- v cc kt ta AgI, AgCNS hp ph mnh ion CrO42- nn s chuyn mu ca ch th khng r rng. b. Phng php Fonha (Volhard) Phng php da vo s chun xc nh ion Ag+ bng dung dch tiu chun KCNS hay NH4CNS vi ch th l Fe(NO3)3. Ti im tng ng, trong dung dch xut hin mu hng ca phc cht [FeCNS]2+: Ag+ + KCNS = AgCNS + K+ trng (ti pH 1 KCNS + Fe(NO3)3 = [FeCNS]2+ + K+ + 3NO32) hng Phng php Fonha dng chun trc tip CNS-, nhng cng c dng xc nh cc ion Cl-, Br-, I- (song, ch yu l chun ion Cl-) bng chun ngc. Khi xc nh ion Cl-, cho vo dung dch phn tch c pH 1- 2 dung dch tiu chun AgNO3 ly d. Lng d ca ion Ag+ c xc nh bng chun vi dung dch tiu chun KCNS hay NH4CNS vi ch th l ion Fe3+ nh trnh by trn. So vi phng php Mo trong xc nh ion Cl-, phng php Fonha tin hnh chun gin tip nn sai s ln hn, nhng c u im l chun tin hnh trong mi trng axit nn nh hng ca cc ion CO32-, PO43- khng tn ti, do cc kt ta Ag2CO3, Ag3PO4 khng hnh thnh trong mi trng axit (pH = 1 - 2). Phng php Fonha cng c dng xc nh cc ion PO43-, CrO42-, song, trc khi chun lng ion Ag+ d cn lc b kt ta. Dung dch tiu chun AgNO3, KCNS, NH4CNS c pha t cc ha cht tng ng. Nhng v cc ha cht ny khng phi l cht gc, do b nhit v nh sng phn hu (AgNO3) hoc b oxi khng kh oxi ho (KCNS, NH4CNS), nn dung dch pha xong cn chun li bng dung dch tiu chun gc NaCl theo phng php Mo hoc Fonha.
8.4. Chun complexon

Vic s dng rng ri thuc th hu c vo Ha phn tch m rng phm vi ng dng ca chun to phc. Khong 30 nm gn y, xut hin nhiu cng trnh nghin cu v s to phc ca cc hp cht cha nhm aminopolycacboxylic, cc hp cht ny c gi chung l cc complexon. Thng s dng 3 hp cht sau: CH2 COOH
N CH2 COOH CH2 COOH axit nitriltriaxetic (complexon I) HOOC CH2 CH2 COOH N CH2 CH2 N HOOC CH2 CH2 COOH axit etylendiamintetraaxetic (complexon II , EDTA) N CH2 CH2 N NaOOC CH2 CH2 COOH dinatri etylendiamintetraaxetat (complexon III, Na2EDTA, Na2H2Y, Trilon B) Cc hp cht complexon u to phc cht bn vi hng lot cc ion kim loi vi thnh phn phn t 1:1, nn chng u c th s dng lm thuc th trong chun xc nh cc ion kim loi. Song, hp cht complexon III c s dng nhiu nht, v phc ca n vi ion kim loi rt bn (bng B.11.3), n d tan trong nc hn complexon II v tinh th Na2EDTA. 2H2O c th c coi l cht gc. S to phc ca complexon III vi cc ion kim loi c th hin qua phng trnh: Na2H2Y + Mm+ = MY m-4 + 2H+ + 2Na+ y, quy nh: Na2EDTA = MNa2EDTA/2, nn Mm+ = MMm+/2. EDTA l mt axit hu c 4 ln axit vi pKa1 = 2,0, pKa2 = 2,76, pKa3 = 6,16 v pKa4 = 10,26, nn s to phc MYm-4 s ph thuc vo pH mi trng. Phc cht cng bn th cng c kh nng hnh thnh pH thp hn. Da trn kh nng ny c th chia cc phc cht thnh 3 nhm: - Nhm phc cht hnh thnh mi trng axit mnh (pH 1 2): gm phc cht ca i b phn cc ion kim loi nng ha tr +3, +4 nh Fe3+, Cr3+, Th4+ - Nhm phc cht hnh thnh mi trng pH > 4: gm phc cht ca i b phn cc ion kim loi nng ha tr +2 nh: Zn2+, Pb2+, Cu2+, Co2+, Ni2+, Fe2+v ion Al3+. - Nhm cc phc cht hnh thnh mi trng pH 10: gm phc cht ca cc 2+ ion Ca , Mg2+, Ba2+, Sr2+. y l c s ca vic chun phn on cc ion kim loi. Bng B.11.3. Hng s bn phc cht ca mt s ion kim loi vi axit etylendiamintetraaxetic Cation Ag+ Pb2+ Hg2+ Cu2+ Cd2+ Ni2+ Co2+ Fe2+ Fe3+ Phc cht AgY 3PbY 2HgY 2CuY 2CdY 2NiY 2CoY 2FeY 2FeY lg KMYm-4 7,2 18,04 21,8 18,8 16,46 18,62 16,31 14,33 25,1 Cation Mn2+ Al3+ Zn2+ Ca2+ Sr2+ Ba2+ Mg2+ Cr3+ Th4+ Phc cht MnY 2AlY ZnY 2CaY 2SrY 2BaY 2MgY 2CrY ThY lg KMYm-4 14,04 16,13 16,5 10,96 8,63 7,76 8,69 24,0 23,2 HOOC CH2 CH2 COONa
a. Ch th trong phng php chun to phc Cc cht ch th l cc hp cht to phc cht mu vi ion kim loi: ( y b qua in tch) M + aInd M(Ind)a, nn thng gi cc ch th mu loi ny l ch th mu kim loi. Ti im tng ng, dung dch tiu chun (v d: dung dch complexon III) phn ng vi phc cht M(Ind)a: Na2H2Y + M(Ind)a = MYm-4 + aInd + 2Na+ + 2H+ lm mu ca dung dch chuyn t mu ca phc cht M(Ind)a sang mu ca ch th t do Ind. s chuyn mu xy ra, bt buc phc cht MYm-4 phi bn hn phc cht M(Ind)a. Do phn ng to cc phc cht MYm-4 v M(Ind)a ph thuc vo pH mi trng, nn mun cho phn ng ch th nhy cn duy tr pH gi tr thch hp bng dung dch m pH. Trong chun complexon, thng dng cc cht ch th mu l cc hp cht hu c c tnh axit, baz v to phc cht mu vi ion kim loi, nh vy i vi mt ch th c th c nhiu mu ng vi tng dng ca ch th: mu dng axit, mu dng baz, mu dng phc cht. Cho nn mt ch th tho mn c iu kin ca cht ch th (mc 7.2 chng III) cn duy tr pH dung dch gi tr xc nh. V d: Vi ch th ericrom T en (H2Ind-): pH = 6,3 pH = 11,5 H2 Ind HInd2 Ind3 xanh vng da cam v mu ca phc cht vi ion kim loi l mu nho, nn cn tin hnh chun pH 10 vi dung dch m amoni, s chuyn mu ca ch th l r rt nht: xanh . Mt s ch th thng dng cng nh phm vi ng dng ca chng c trnh by bng B.12.3. b. ng dng chun complexon III Chun complexon III c th tin hnh theo 3 cch: chun trc tip, chun ngc, chun th. * Chun trc tip: c dng khi phn ng to phc xy ra nhanh, thun nghch v c ch th thch hp. bng B.12.3 trnh by cc ion kim loi c xc nh trc tip bng nhng ch th khc nhau. Bng B.12.3. Mt s ch th thng dng trong chun complexon III Cch pha ch ch Ion kim loi c th xc nh trc tip Murexit 1% trong NaCl Ca2+ Cu2+, Ni2+, Co2+ Eriocrom T en 1% trong NaCl Mg2+, Mn2+, Zn2+, Cd2+, Pb2+ Xylenol da cam 0,5% trong etanol Bi3+, Th4+ Hg2+, Cd2+, Zn2+ Fluorexon 2% trong nc Ca2+ Axit sunphosalixylic 5% trong nc Fe3+ Tn ch th pH mi trng pH 12 10, m amoni 10, m amoni 13 56 12 2
* Chun ngc: Dng xc nh cc ion kim loi to phc chm vi complexon III nh Al3+, Cr3+ hoc xc nh cc ion d b thu phn, hoc khng c ch th thch hp. Trong trng hp ny, thng cho cc ion cn xc nh phn ng vi lng dung dch tiu chun ly d, sau lng dung dch tiu chun d c chun bng MgSO4 vi ch th eriocrom T en hoc bng cc dung dch tiu chun khc nh ZnSO4, Pb(NO3)2 nu phc cht ca cc ion ny km bn hn phc cht ca cc cht cn xc nh. * Chun th: Dng xc nh mt s ion kim loi to phc cht MYm-4 bn hn phc cht ca ion Mg2+ (MgY2-). y, cho ion cn xc nh phn ng vi phc cht MgY2-: Mm+ + MgY2- = MYm-4 + Mg2+ 2+ sau lng ion Mg gii phng ra c chun bng complexon III vi ch th eriocrom T en. Chun complexon III cho php xc nh nhiu ion trong hn hp da trn s chun phn on v s che cc ion gy nhiu. Chun phn on da trn s khc nhau v bn ca cc phc cht pH khc nhau. Gi thit trong hn hp c nhiu ion th tin hnh chun xc nh cc ion M4+ ti pH < 1 (Ti4+, Zr4+), chun cc ion M3+ ti pH 2 3 (Fe3+, Bi3+), sau chun cc ion M2+, Al3+ ti pH 3 5, cn cc ion Ca2+, Mg2+, Sr2+ c chun cui cng ti pH 10. V d: chun xc nh hn hp Fe3+, Mg2+, u tin chun xc nh ion Fe3+ pH = 2 vi ch th axit sunphosalyxilic, sau chun tip ion Mg2+ ti pH = 10 vi ch th eriocrom T en. Chun vi s che cc ion gy nhiu l da trn s to phc cht bn ca cc ion gy nhiu vi cc phi t khc nhau; cc phc cht ny bn hn phc cht MYm-4 nn cc ion kim loi gy nhiu s khng tham gia phn ng vi complexon III. V d: Dng KCN c th che: Fe3+, Cd2+, Hg2+, Cu2+, Zn2+, Ag+, Ni2+, Co2+. Dng trietanolanmin che Fe3+, Al3+. Dng F- che Al3+ , Ti4+, Fe3+, Zr4+ Tm li, chun complexon III vi cc cch thao tc khc nhau cho php xc nh hng lot cc ion v phng php ny cng ngy cng c ng dng nhiu trong phn tch nh lng. Di y l nguyn tc chun mt s ion thng gp trong nng nghip. + Xc nh ion Fe3+: Dung dch cha ion Fe3+ c trung ha v pH = 2 v un n nhit 60oC. Sau khi cho vo dung dch vi tinh th axit sunphosalixylic, th chun ion st (III) bng complexon III n khi mu dung dch chuyn t mu hng sang khng mu hoc mu vng nht (mu ca phc cht FeY-). nh hng ca mu vng ca phc cht FeY- l khng ng k, cn chun vi dung dch long ( 0,001M). + Xc nh cng ca nc (Xc nh ion canxi v ion magie): Dung dch cha cc ion Ca2+ v Mg2+ th c iu chnh v pH 10 bng dung dch m amoni v c chun bng complexon III vi ch th eriocrom T en (t sang xanh).
Cn nu xc nh ring ion Ca2+, th dung dch c iu chnh v pH = 12 (ion Mg s b kt ta di dng Mg(OH)2 v khng tham gia phn ng) v chun xc nh ion Ca2+ bng complexon III vi ch th murexit (t mu sang mu tm). + Xc nh ion Al3+: Cho vo dung dch (pH = 4) cha ion Al3+ lng complexon III ly d. Sau khi pha long dung dch v cho thm pyridin, lng complexon III d c chun bng dung dch ZnSO4 tiu chun vi ch th eriocrom T en (t mu xanh sang mu ). + Xc nh ion PO43-: Ion PO43- c kt ta di dng MgNH4PO4. 6H2O v c ha tan li bng axit HCl. Sau khi cho vo dung dch lng complexon III ly d v chnh pH v pH = 10 bng dung dch m anioni, th lng d ca complexon III c chun bng dung dch tiu chun MgSO4 vi ch th eriocrom T en n khi dung dch chuyn t mu xanh sang mu . + Xc nh ion SO42-: Cho vo dung dch lng BaCl2 ly d, lc b kt ta BaSO4. Cho vo dung dch lc lng complexon III ly d v iu chnh pH v pH = 10 (m amoni), ri chun lng complexon III d bng dung dch tiu chun MgSO4 vi ch th eriocrom T en n khi dung dch chuyn t mu xanh sang mu .
2+
9. U NHC IM CA PHNG PHP PHN TCH TH TCH Phng php phn tch th tch c nhng u nhc im chnh sau: - u im: - Trang thit b dng trong phn tch n gin v khng t tin nn, c kh nng ph cp cao. - chnh xc cao, nn cng c dng lm phng php chun kim tra cc phng php khc v kim tra cc dung dch m. - C th dng phn tch nhiu ion v c. - Tc phn tch cao, cao hn phng php phn tch khi lng kt ta nhiu ln. - C kh nng t ng ho, nu s dng ch th l cc cng c o. - Nhc im: - chnh xc khng bng phng php phn tch khi lng kt ta. - Ph ng dng khng ln nh phng php phn tch khi lng kt ta. Nhiu phn ng to kt ta khng c s dng trong chun .
Cu hi n tp
1. Nhng yu cu ca phn ng chun ? 2. Phn loi cc phng php chun ? Cch tnh ng lng gam ca cc cht tham gia phn ng chun ? 3. Cch pha ch dung dch tiu chun? 4. Cc loi nng thng dng trong phn tch th tch? Cch tnh kt qu phn tch? 5. ng chun l g? Cch xy dng ng chun ca tng phn ng chun ? 6. S i mu ca ch th dng trong chun ? Cch chn ch th? 7. ng dng ng chun trong vic chn ch th v trong xc nh sai s ch th?
8. Cc php chun thng dng (chun trung ho, chun oxi ha kh, chun kt ta, chun to phc), nguyn tc v phm vi ng dng ca chng?
Bi tp
1. Cn cn chnh xc bao nhiu gam H2C2O4.2H2O (TKPT) pha c 2 lt dung dch tiu chun 0,1N dng trong chun xc nh KMnO4 trong mi trng axit. (p s: 12,6000gam). 2. Tnh s gam Na2CO3 (TKPT) pha 250 ml dung dch, bit rng chun 20 ml dung dch ny th ht 30 ml dung dch HCl 0,05N nu kt thc chun ti pH = 8,3. Cho: cc hng s axit ca H2CO3 l Ka1 = 4,5.10-7; Ka2 = 4,8.10-11. (p s: 1,9875gam). 3. Chun 20 ml dung dch hn hp hai axit H2SO4 v H3PO4. Nu kt thc chun ti pH = 4,66 th ht 15 ml dung dch NaOH 0,1N. Nu kt thc chun ti pH = 9,8 th ht 25 ml dung dch NaOH 0,1N. Tnh nng mol/l ca mi axit trong hn hp u. Cho: cc pKa ca H3PO4 l pKa1 = 2,12; pKa2 = 7,21; pKa3 = 12,38; axit H2SO4 in li hon ton. (p s: H2SO4 0,0125M, H3PO4 0,05M). 4. Chun 20 ml dung dch CH3COOH 0,1N bng dung dch NaOH 0,1N. Nu php chun mc sai s: 1%, th khi kt thc chun pH ca dung dch bng bao nhiu? Bit pKa ca CH3COOH = 4,76. (p s: pH 0,1% = 6,76, pH +0,1% = 10,7). 5. Cho 50ml dung dch NaOH 0,1N vo 90 ml dung dch CH3COOH 0,07N, tnh pH dung dch sau phn ng! Cn thm vo bao nhiu ml dung dch NaOH 0,1N na th ti im tng ng? Bit pKa ca CH3COOH = 4,76. (p s: pH = 5,34, 13ml NaOH 0,1N). 6. Cn 6 gam mu gm NaOH, Na2CO3 v H2O pha thnh 1 lt dung dch. Bit rng, chun 25ml dung dch ny th ht 16,5 ml dung dch HCl 0,1N nu kt thc chun ti pH 8,3 vi ch th phenolphtalein); cn khi cng chun lng trn, nhng kt thc chun ti pH = 4 (ch th metyl da cam) th ht 20,5 ml dung dch HCl 0,1N. Tnh % khi lng cc cht trong mu phn tch? Bit: H2CO3 c pKa1 = 6,35; pKa2 = 10,32. (p s: 33,33% NaOH, 28,26% Na2CO3, 38,41% H2O). 7. T dung dch HCl 0,3 N v dung dch NH4OH 0,2N, tnh th tch mi dung dch cn ly pha c 250 ml dung dch m c pH = 8,46. Bit: pKb ca NH4OH = 4,74. (p s: 89,3ml HCl, 160,7ml NH4OH). 8. T dung dch CH3COOH 1M v dung dch CH3COONa 1M, hy tnh th tch cn ly cc dung dch pha 250 ml dung dch m CH3COOH/CH3COONa 1M c pH = 5,08. Bit: pKa ca CH3COOH = 4,76. (p s: 83,3ml CH3COOH, 166,7ml CH3COONa). 9. Cn 1,2 gam mu cha Na2CO3, NaHCO3 v tp cht tr ho thnh 250 ml dung dch. Chun 50 ml dung dch ny, nu kt thc chun ti pH = 8,3 th ht 5,7 ml dung dch HCl 0,2N, nu kt thc chun ti pH = 4 th ht 15,2 ml dung dch HCl 0,2 N. Tnh % khi lng ca mi mui trong mu phn tch. Bit: H2CO3 c pKa1 = 6,35; pKa2 = 10,32. (p s: 50,35% Na2CO3, 26,6% NaHCO3). 10. Cn 0,588gam K2Cr2O7, ho thnh 300 ml dung dch. Cn bao nhiu ml dung dch ny, khi thm KI d v H2SO4 long ri chun lng I2 gii phng ra ht 25,16 ml dung dch Na2S2O3 0,1N. (p s: 62,9ml). 11. Ho tan 4,895 g mu ch cha KCl v NaCl thnh 500 ml dung dch. Chun 25 ml dung dch ny ht 20 ml dung dch AgNO3 0,1N. Tnh % khi lng ca CaCl2 trong mu. (p s: 76% KCl).
11. Ho tan 2,062g mu ch cha CaCl2 v MgCl2 thnh 500 ml dung dch. Chun 25 ml dung dch ny ht 35 ml dung dch AgNO3 0,1N. Tnh % khi lng ca KCl trong mu. (p s: 53,83% KCl). 12. Thm 40 ml dung dch (NH4)2C2O4 0,1N vo 25 ml dung dch cha ion Ca2+. Lc b kt ta, ly phn dung dch. Tin hnh chun dung dch ny trong mi trng H2SO4 long ht 15 ml KMnO4 0,15N. Tnh s gam ion Ca2+ c trong 1 lt dung dch. (p s: 1,4g ion Ca2+). 13. Ho tan 5 gam mu cha ion Pb2+ thnh dung dch ri kt ta ton b lng ion Pb2+ di dng PbCrO4. Ho tan kt ta bng H2SO4 long v thm KI d. Chun lng I2 gii phng ra ht 25 ml dung dch Na2S2O3 0,2N. Tnh % khi lng Pb trong mu. (p s: 6,9% Pb). 14. Ha tan hon ton 0,2425 gam mu ch cha mui ca cc ion Ca2+ v Mg2+ thnh 500 ml dung dch. Ly 20 ml dung dch ny v iu chnh pH n 10 ri chun ht 11,75ml dung dch complexon III 0,016N vi ch th eriocrom T en. Nu chun 10 ml dung dch ny pH = 12 vi ch th murexit ht 4,85 ml dung dch Trilon B ni trn. Tnh % khi lng ca Ca v Mg trong vi. (p s: 32% Ca, 4,06% Mg). 15. Tnh s ml dung dch ch th K2CrO4 0,5M cho vo 20 ml dung dch NaCl 0,1N, khi chun xc nh ion Cl- bng dung dch AgNO3 0,05N th mc sai s + 0,1%. Bit: TAgCl = 1,78.10-10; T Ag2CrO4 = 1,1.10-12. (p s: 0,12ml). 16. Ho tan 0,0202 gam vi ri kt ta hon ton ion Ca2+ di dng CaC2O4. Ho tan kt ta bng dung dch H2SO4 long d ri thm vo 35 ml dung dch KMnO4 0,0366N. Lng KMnO4 d c chun bng 9,57 ml dung dch FeSO4 0,1N. Tnh % khi lng ca Ca trong mu phn tch. (p s:31,9%). 17. Mt mu nc khong ch cha mui hydrocacbonat v sunphat ca cc ion Ca2+ v Mg2+. Chun 100ml nc ny vi ch th metyl da cam (pHkt = 4) ht 20,5 ml dung dch HCl 0,04N. Mt khc, sau khi un nng ri chun 50 ml nc khong ny pH = 10 vi ch th eriocrom T en th ht 20 ml dung dch Trilon B 0,025N. Tnh cng ton phn v cng vnh cu ca nc khong. (p s: cng tm thi K = 8,2, cng vnh cu K = 10). 18. Ho tan 5 gam mu c cha ng thnh 250ml dung dch ion Cu2+. Ly 25 ml dung dich ny cho tc dng vi dung dch KCNS v KI ly d. Chun lng I2 gii phng ra ht 15 ml dung dch Na2S2O3 0,1N. Tnh % khi lng Cu trong mu. (p s:19,2% Cu).
Chng IV PHN TCH CNG C

1. PHN LOI PHNG PHP Phn tch cng c l cch thng gi ca phn tch bng cng c gm cc phng php phn tch m dng cc my o nh gi v theo di cc i lng vt l, ho hc lin quan n h phn tch. Phn tch cng c l lnh vc rt rng bao gm nhiu phng php khc nhau, da vo tng tc ca cht cn phn tch vi cc tc nhn phn tch v tnh cht c trng ca i lng o c th chia thnh cc nhm c bn sau: cc phng php quang hc, cc phng php o in t, cc phng php tch, cc phng php nhit.
1.1. Nhm phng php quang hc

Da trn s tng tc ca cht cn phn tch vi cc bc x in t hoc s pht ra cc bc x in t ca cht cn phn tch. Vt th c cu to bi cc nguyn t v cc phn t. S tng tc ca chng vi cc bc x in t rt khc nhau v cho cc hiu ng quang hc khc nhau. Vic o cc hiu ng quang hc ny s gip phn tch c cc cht. Da trn hiu ng quang hc khi vt cht tng tc vi bc x in t c th chia cc phng php quang hc thnh hai nhm chnh: - Cc phng php quang ph, l cc phng php d trn s trao i nng lng gia vt cht v bc x in t. - Cc phng php khng quang ph, l cc phng php da trn s thay i mt s tnh cht quang hc ca bc x in t di tc ng ca vt cht cn nghin cu, song, nng lng ca bc x in t khng b thay i. a. Cc phng php quang ph Bc x in t (nh sng) l khi nim rt rng gm tp hp ca cc ht photon (ht nh sng, tia nh sng) c nng lng khc nhau. Xp theo nng lng ca tia bc x in t t cao xung thp cao s c cc loi tia chnh sau: tia v tr, tia , tia rnghen, tia t ngoi, nh sng nhn thy, tia hng ngoi, bc x nhit, sng v tuyn, sng raio Vt cht nghin cu lun cha cc ht electron, proton, neutron. trng thi bnh thng, cc ht ny lun nm trn cc qu o xc nh ph thuc vo nng lng ca n, nhng khi n nhn thm nng lng (bc x in t, nhit, cng) n c th thay i qu o v hu qu l dn n cc hiu ng quang hc tip theo, l vt cht hp th bc x in t hoc pht ra bc x in t. Khi vt cht hp th bc x in t s to ra quang ph hp th, cn khi vt cht pht ra bc x in t s to ra quang ph pht x. Tu theo bc x in t m vt cht hp th hoc pht ra c th o c, xy dng cc phng php o nh: quang ph hp th rnghen, quang ph pht x rnghen, quang ph hp th nguyn t, quang ph pht x nguyn t, quang ph hp th phn t vng t ngoi v kh kin, quang ph hunh quang, quang ph hp th hng ngoi, phng php cng hng t ht nhn.
b. Cc phng php khng quang ph Ngoi nng lng ca mnh bc x in t cn cc tnh cht khc nh hng truyn, mt phng truyn ca n. Khi bc x chuyn t mi trng ny sang mi trng khc cc tnh cht ny cng thay i theo, to ra cc hiu ng quang hc nh s chit quang, s phn cc quang. Vic o cc hiu ng ny cho cc phng php: phng php o chit quang v phng php o phn cc.
1.2. Nhm cc phng php in t

Da trn vic theo di cc tnh cht in, t ca h cn phn tch hoc tng tc ca cc cht cn phn tch vi cc i lng in t, t cho cc phng php o in v cc phng php o t. Phng php o in da trn cc qu trnh vt l, ha hc xy ra trn in cc v trong dung dch gia hai in cc. Cc qu trnh ny gn lin vi s bin i cc i lng vt l nh: in th (E), dng in (I, i), in tr (R), in dung (C), tr khng (L), dn in (S) Nhng i lng vt l k trn u lin quan n nng v bn cht ca cht phn tch. Thng qua vic o cc i lng vt l ny c th xc nh c thnh phn nh tnh, thnh phn nh lng cc cht cn phn tch trong h. Da vo mi quan h ca i lng vt l o c vi cht cn phn tch xy dng nhiu phng php o in khc nhau: phng php o in th, phng php cc ph, phng php von ampe, phng php in khi lng, phng php o dn in, phng php in di
1.3. Nhm cc phng php tch

i b phn cc phng php phn tch ho hc v nhiu phng php phn tch cng c cn c s tch cc phn gy nhiu trc khi tin hnh cc php o. C th tch cht gy nhiu hoc thnh phn cn phn tch ra khi hn hp. Phng php tch khng ch loi b thnh phn gy nhiu m cn c th lm giu mu. Cc phng php tch thng dng l phng php kt ta, phng php in phn, phng php chng ct, phng php chit, phng php sc k.
1.4. Nhm cc phng php nhit

Da trn s phn hu hoc chuyn cu trc ca cht cn phn tch di s tc ng ca nhit. Nhit m din ra phn ng ho hc gi l nhit phn hu, nhit chuyn ho, n biu th yu t nh tnh ca cht cn phn tch. Khi lng vt cht b mt i do s phn hu bi nhit cho bit yu t nh lng ca vt cn phn tch. Trong khun kh cho php ca gio trnh, di y ch trnh by v nguyn tc ca cc phng php hp th vng t ngoi v nh sng nhn thy, phng php o in th v phng php chit. 2. PHNG PHP QUANG PH HP TH PHN T VNG T NGOI V NH SNG NHN THY Trong t nhin, cc phn t lun lun c cc dng chuyn ng: chuyn ng quay ca cc phn t, dao ng ca cc electron lin kt, s chuyn orbitan ca electron trong phn t. ng vi cc dng chuyn ng s c cc dng nng lng tng ng c trng cho phn t. Gia cc dng chuyn ng, nu so snh ln nng lng th c: Nng lng chuyn ng quay (Er) nh hn nng lng dao ng (Eo) v nng lng chuyn dch orbitan (Ee): Er<E0<Ee.
Nng lng ca tia t ngoi v nh sng nhn thy tng ng vi nng lng Ee, nn n to nn s dch chuyn electron t orbian ny sang orbitan khc (thay i trng thi orbitan) to nn quang ph. Khi vt cht hp th bc x in t c quang ph hp th vng t ngoi v kh kin, thng c gi l quang ph hp th dch chuyn electron. Vng nh sng t ngoi v nh sng nhn thy gm cc sng c bc sng t 200 800 nm (2000 8000 AO) c nng lng kch thch cc electron lin kt dch chuyn t orbitan lin kt sang orbitan phn lin kt. Vng nh sng ny c chia thnh 3 vng nh vi cc bc sng nh sng ( ) khc nhau: - Bc sng <200nm - vng t ngoi chn khng - Bc sng t 200 n 400nm - vng t ngoi gn - Bc sng t 400 n 800nm - vng nh sng nhn thy. Thng thng hay s dng vng nh sng t ngoi v nh sng nhn thy, v d khng ch iu kin o. Phng php o vi di bc x in t c cc bc sng t 400 n 800nm cn c gi l phng php trc quang so mu hay ngn gn l phng php so mu. Phng php so mu da trn s chuyn thnh phn xc nh thnh hp cht hp th nh sng vng nhn thy ri o lng hp th nh sng, t suy ra hm lng thnh phn cn phn tch.
2.1. C s l thuyt ca phng php so mu

a. nh lut Bug - Lambe- Bia Gi s tn ti mt mi trng ng nht c chiu dy l l cha cht mu c kh nng hp th nh sng. Cho tia sng n sc c bc sng v cng Io i qua mi trng (tia sng ny khng b phn x, khc x v tn x). Sau khi b mi trng hp th, dng sng yu i v ch cn cng I. Quan h gia Io v I c xc nh theo nh lut Bug - Lambe- Bia: (IVI/Io=10- lC 1) t A = -lg I/Io v gi l hp th quang, th: A = lC (IV- 2) Trong : - l h s hp th nng , h s ny ch ph thuc vo bn cht ca cht mu v bc sng nh sng hp th, nu nng C c tnh bng mol/lt th l h s hp th phn t gam v thng khng ln hn 2.105, nu C tnh bng nng % th l h s hp th % - l l chiu dy ca tng hp th nh sng, o bng cm, - C l nng cht mu, c th l nng M, %, mg/ml Nh vy, nh lut Bug - Lambe - Bia pht biu nh sau: hp th quang ca dung dch hp th mu l t l thun vi chiu dy ca tng hp th mu v nng cht mu c trong tng . nh lut Bug - Lambe - Bia cn c gi l nh lut Lambe - Bia, hp th quang A cn c gi bng mt thut ng khc l mt quang D. b. Tnh cht ca nh lut Bug - Lambe - Bia: Tnh cht quan trng nht ca nh lut ny l tnh cng tnh. Tnh cng tnh ny c th hin theo 3 hng sau: - Tnh cng tnh theo chiu dy ca tng hp th mu:
Nu c th chia tng hp th mu thnh n phn nh th tng hp th quang ca cc tiu phn l hp th quang ca ton b dung dch mu. Tc: A = lC = l1C +l2C + + lnC = Cni=1 li, (IV3) trong : l = l1 + l2 + + ln. ng dng tnh cht ny, c th tng hp th quang ca dung dch mu long bng vic s dng ng mu (cuvet) c kch thc hn ln hoc gim hp th quang ca dung dch mu c bng vic s dng cuvet c kch thc nh ln, vic o hp th quang t chnh xc cao. Trong thc t, ch sn xut cc cuvet c dy t 0,1 n 10cm, thng l cuvet 1cm. Khng dng cc loi cuvet nh hn 0,1cm, v lc ny rt kh rt dung dch vo cuvet; khng dng cc loi cuvet ln hn 10cm, v lc ny s khc x nh sng qu ln gy sai s phn tch. - Tnh cng tnh theo nng cht hp th mu: Nu c th chia nng cht hp th mu thnh n phn nh th tng hp th quang ca cc tiu phn l hp th quang ca ton b dung dch mu. Tc: (IVA = lC = lC1 +lC2 + + lCn = lni=1 Ci, 4) trong : C = C1 + C2 + + Cn ng dng tnh cht ny, c th tng hp th quang ca dung dch mu long bng vic cch cho thm cht mu hoc gim hp th quang ca dung dch mu c bng pha long dung dch mu hay ly lng cht mu t hn lm phn tch, vic o hp th quang t chnh xc cao. - Tnh cng tnh theo thnh phn cc cht hp th mu: Nu trong dung dch c n cht hp th mu v mi cht mu u tun th nh lut Bug - Lambe - Bia th tng hp th quang ca cc cht mu l hp th quang ca ton b dung dch mu. Tc: A = lC = 1lC1 +2lC2 + + nlCn = l.ni=1 i Ci (IV5) ng dng tnh cht ny c th c th gii bi ton phn tch nhiu cht mu trong dung dch phn tch. Dng my o xc nh hp th quang. chnh xc ca my o l cao nht khi A = 0,4343. Song, trong khong A t 0,15 - 0,7, sai s o l khng ng k, do khi o A cn iu chnh chiu dy tng hp th hay nng cht mu gi tr A o c nm trong khong . Ngoi vic o A, cn c th o truyn quang T%: T% = (I/Io).100. Tuy nhin, php o ny t c s dng trong phn tch nh lng, v hm s T% = f(C) khng tuyn tnh nh hm s A = f(C). Thng ch dng o T% khi cn chnh my o. Lu : T% = 100 th A = 0. c. Phm vi ng dng ca nh lut Bug - Lambe - Bia: nh lut Bug - Lambe - Bia ch tuyn tnh trong cc iu kin sau: + nh sng i qua dung dch mu l nh sng n sc, v i vi cc nh sng c cc bc sng khc nhau th h s hp th mu ca cht mu khc nhau dn n hp th quang o c s khc nhau. Tc, ng vi hai bc sng 1 v 2 c: A1 = + Vi mt khong nng cht mu. th biu din s ph thuc A = f(C) thng c cc dng nh trong cc hnh H.1a.4, H.1b.4.
1.l.C A2 = 2.l.C.
Nguyn nhn to ra cc dng ny nh sau: - Dng 1: y l ng l thuyt. - Dng 2: nng qu cao, cc cht mu che khut nhau dn n hp th quang dung dch b gim. - Dng 2, 3: nng qu cao, cc cht mu cu trc li to ra cht mi c h s hp th khc vi cht mu nng thp, dn n hp th quang dung dch tng (dng 3) hoc gim (dng 2). - Dng 4: i vi cc cht phn tch m mu ca n c c nh to phc cht mu, song, hng s bn khng ln, th nng thp ca cht cn phn tch phn ng to mu cha xy ra hoc xy ra khng hon ton, dn n hp th quang b gim. Cn nng cao th nguyn nhn li nh cc dng ng 2, 3. Do khi o cn kim tra s tuyn tnh ca nh lut xc nh khong dung dch cn o. i vi cc dng ng 2, 3, nng o l t 0 n C1, cn vi dng ng 4 l t C1 n C2.
a b Hnh H.1a.4, H.1b. 4: Mt s dng ng A = f(C) +Dung dch mu l dung dch tht, tc trong dung dch khng c kt ta, huyn ph hay nh tng, v cc ht ny tn x mnh nh sng v lm thay i cng nh sng i ra khi cuvet chiu vo b phn o. + iu kin o l thng nht mi mu, v o so mu l php o so snh. Khi iu kin o thay i c th dn n: - Nng cht mu thay i. V d: Khi s dng dung mi l cc cht d bay hi, nu thi gian o khng nh nhau, lng dung mi bay i khng nh nhau dn n nng bin i khc nhau, to nn sai s phn tch. - Thay i dng cht mu. V d: Khi o mu vng ca ion CrO42-, nu pH dung dch thay i chuyn sang mi trng axit, trong dung dch hnh thnh ion Cr2O72- c mu da cam: 2 CrO42- + 2H+ = Cr2O72- + H2O, vng da cam lm sai lch s o.
+ Khng pha long dung dch mu, nht l i vi cc phc cht mu khng bn v khi pha long phc cht mu b phn li, v d: ML M + L lm cho phc cht mu thay i v cng mu cng nh dng mu (mu ca dng ML sang mu ca dng L)
2.2. Nhng yu cu i vi phc cht mu

Trong nhiu trng hp cht cn phn tch khng c mu hoc cng mu khng ln, phi to mu cho chng bng cc phn ng thch hp. Vic to mu thng da trn cc phn ng to phc cht c mu. Phn ng c la chn phi tho mn cc yu cu sau: * Phc cht phi c bn ln: Phc cht cng bn th nh hng ca s pha long v cc phn ng ph cng gim nn php o t chnh xc cao. Ngoi ra, khng cn phi dng qu d thuc th, cho php gim chi ph phn tch. * Phc cht phi c h s hp th phn t gam ln: Phc cht c h s hp th gam ln th php o s nhy cao, cho php phn tch lng nh vi chnh xc cao hn, v d: phc cht [Cu((NH3)4]2+ c = 500, cn phc cht ca ion Cu2+ vi dithizon c = 5000, do , php o vi phc cht Cu dithizon s nhy hn 10 ln. *Phc cht phi c thnh phn xc nh: Tc trong dung dch ch c mt phc cht mu hnh thnh, bi v mi cht mu c mt gi tr v nh vy, khi trong dung dch hnh thnh nhiu cht mu th tnh tuyn tnh ca nh lut Lamba - Bia s b vi phm khi qui nng cht phn tch v mt dng cht mu no . Mun cho trong dung dch ch tn ti mt cht mu cn chn cc iu kin phn ng thch hp nh: - Dng thuc th phi c tnh chn lc cao, tc ch to mu vi mt ion nht nh. V d: xc nh ion Fe3+ trong hn hp vi cc ion Al3+, Ca2+, Mg2+, th chn thuc th l KCNS v tin hnh phn ng mi trng axit pH = 2, v ch c ion Fe3+ to phc cht mu, cn cc ion khc khng phn ng. - Thuc th phi c nng xc nh bo m ch c mt phc cht mu c hnh thnh, bi v phn ng to phc cht thng xy ra theo nhiu bc. V d: phn ng to phc cht mu gia ion Fe3+ v ion CNS- xy ra nh sau: Fe3+ + 2CNS- = [Fe(CNS)2 ]+, khi [CNS-]d = 1,2.102
M Fe3+ + 3CNS - = [Fe(CNS)3], Fe3+ + 4CNS - = [Fe(CNS)4]-,

1
khi [CNS-]d = 4.10-2M khi [CNS-]d = 1,6.10khi [CNS-]d = 7.10-1M
M Fe3+ + 5CNS - = [Fe(CNS)5]2-,
Theo s bin i ca nng thuc th m mu sc ca phc cht bin i t mu vng sang mu . Do , ch c mt loi phc cht mu hnh thnh phi cho lng d thuc th nh nhau c dung dch phn tch v dung dch tiu chun. - pH mi trng phi n nh mt gi tr nht nh, bi v cc ion kim loi trong dung dch chu s thu phn: Mm+ + H2O M(OH)(m-1)+ + H+
M(OH)(m-1)+ + H2O M(OH)2 (m-2)+ + H + v ligand (phi t) (L) thng l cc axit, baz nn s to phc cht gia cc cation Mm+ v cc phi t L ph thuc vo pH mi trng. V d: Phn ng to phc cht mu gia cc ion Fe3+ v CNS- ch xy ra pH < 2,5, v pH cao hn th ion Fe3+ b thu phn: Fe3++ 3H2O = Fe(OH)3 + 3H+ Hay phn ng to phc cht mu gia ion Fe3+ v axit salyxilic (sal) xy ra nh sau: Fe3+ + sal = [Fe(sal)]+ + 2H+ pH < 4 tm pH 4 9 Fe3+ + 2sal = [Fe(sal)2]- + 4H+ Fe3+ + 3sal = [Fe(sal)3]3- + 6H+ pH > 9 vng Nn, trong phn tch so mu ion Fe3+ vi thuc th axit salyxilic thng tin hnh ti pH = 2 2,5. * Phc cht mu phi bn vi thi gian kp o hp th quang: Thi gian thch hp o l khi hp th quang dung dch t cc i v khng i. Thi gian bn ca cht mu cng di cng tt, t nht phi t t 5 10 pht. ng biu din s ph thuc A = f(t) thng c 2 dng H.2a.4 v H.2b.4. Nh vy, vi dng ng nh hnh H.2a.4 th thi gian o l t 0 t1, hnh H.2b.4 l t t1 t2, cc khong thi gian ny u phi t t 5 n 10 pht tr ln. Nu phc cht km bn vi thi gian th c th dng thang mu gi. Thang mu gi l dy dung dch c mu v cng mu ging mu dung dch kho st nhng mu bn hn. Thang mu gi thng c pha t cc hp cht v c. V d: kho st mu da cam ca caroten c th dung dch K2Cr2O7 pha thang mu gi.
a b Hnh H.2a.4 v H.2b.4: ng biu din ph thuc A= f(t)
2.3. Ph hp th v chn bc sng o

* Ph hp th: Ph hp th l ng biu din s ph thuc ca gi tr hp th quang A hoc vo bc sng nh sng. Trong vng nh sng nhn thy, thng gp ph hp th vi mt cc i (hnh H.3.4).
Hnh H.3.4: Ph hp th ca thuc th v phc cht mu: 1- Thuc th, 2- Phc cht mu Ph hp th l thng tin rt quan trng c ng dng trong phn tch nh tch v nh lng. Trong phn tch nh tnh: Ph hp th l mt thng s c trng cho mi cht nn qua vic xc nh ph hp th c th xc nh c thnh phn nh tnh ca dung dch phn tch. Tuy vy, khng s dng ph hp th trong phn tch nh tnh cc cht v c. Trong phn tch cc hp cht hu c, cng ch dng ph hp th kim tra sch ca cc cht thng qua so snh ph hp th ca cht cn phn tch vi ph hp th ca cht chun. Trong phn tch nh lng: Dng ph hp th chn bc sng o hp th quang. * Chn bc sng o hp th quang: Chn bc sng o hp th quang l mt khu rt quan trng trong phn tch nh lng bng phng php so mu, v n c nh hng ln n chnh xc v nhy ca php phn tch. Vic chn bc sng o da trn cc nguyn tc sau: + Trng hp dung dch ch c cht phn tch hp th mu cn thuc th khng hp th mu, th chn bc sng o ( ), hp th quang t gi tr cc i, v y nh hng ca bc sng o n kt qu phn tch l nh nht. Bc sng o ng vi gi tr A cc i gi l max. + Trng hp thuc th cng hp th mu, th c th chn bc sng o theo 1 trong 2 cch sau: - Cch th nht: chn bc sng o sao cho hiu h s hp th phn t gam ca phc cht mu v ca thuc th ( ) t gi tr cc i. - Cch th hai: chn bc sng o sao cho ng thi hiu h s hp th phn t gam ca phc cht mu v ca thuc th ( ) t gi tr cc i v t s phc cht mu/ thuc th cng t cc i. Trong trng hp ny, i khi cng phi hi lng vi gn vi gi tr cc i. + Trng hp phn tch hn hp nhiu cht mu:
Da trn s cng tnh ca nh lut Lambe - Bia (biu thc IV- 5), c th xc nh n cht mu cng mt lc nu o hp th quang ca dung dch phn tch n bc sng i ( i = 2, 3,, n) khc nhau. Nh vy, khi biu din hp th quang tng bc sng s c n phng trnh th hin mi tng quan A 1, A 2, ., A n vi cc nng ca n cht mu. Gii h phng trnh bc nht ny s thu c cc gi tr nng ca cc cht mu. Thng thng hay chn cc bc sng ng vi s hp th cc i ca tng cht mu. V d: Xc nh ng thi chlorophyl a v chlorophyl b trong dung dch da vo vic o hp th quang 2 bc sng 662nm ( max ca chlorophyl a) v 644nm ( max ca chlorophyl b). * To nh sng n sc: Hin nay, c 3 phng php to nh sng n sc, l dng knh lc, dng lng knh v dng mng. Ph bin nht l 2 phng php dng knh lc v dng lng knh, v sn phm to ra c gi thnh r cho php sn xut cc my o vi gi thnh r. + Phng php dng knh lc: l dng c lm bng knh trong ho tan nhng cht mu c th hp th mt phn nh sng trng, do , ch cho phn nh sng cn thit i qua. B lc ny c phn gii 20 100 nm tu theo tng knh lc, v th, khi cn o hp th quang mt bc sng c th, khng th dng loi my o vi phng php to nh sng n sc ny. Hin nay, thng cc my o c thit k vi 5 - 7 knh lc cho vng nh sng nhn thy. + Phng php dng lng knh: y l phng php tch nh sng da trn s khc x ca cc tia nh sng khi i qua lng knh. nh sng trng khi i qua lng knh s b tch ra thnh cc nh sng mu khc nhau. phn gii t 0,1 - 0,5nm, t chnh xc cn thit cho o hp th quang ca mt bc sng c th.
2.4. o so mu
a. My so mu My o c hai loi, loi 1 tia sng (H.4a.4) v loi hai tia sng (H.4b.4). Loi 1 tia sng n gin, r tin, song, khng th t ghi quang ph (ph hp th), thng dng trong o ng dng, o phn tch nh lng. Loi 2 tia sng cho php t ghi quang ph, song, t tin, thng dng trong nhng nghin cu c bn gm c nghin cu phn tch nh tnh v phn tch nh lng. to nh sng trng dng n si t vonphram, to nh sng t ngoi dng n thu ngn hoc n deuteri. Cuvet dng cho o vng nh sng nhn thy c lm t thu tinh thng, song, cho o vng nh sng t ngoi gn phi lm t thu tinh thch anh.
b Hnh H.4a.4, H.4b.4: S my o so mu: a- loi 1 tia sng, b- loi 2 tia sng b. Cc phng php so mu * Phng php so mu bng mt: Mt c kh nng nh gi mc bng nhau ca hai cng nh sng, nn thc cht phng php so mu bng mt l dng mt so snh cng mu ca dung dch phn tch vi cng mu ca dung dich tiu chun. Thng phng php ny c chch xc khng cao (sai s khong 5 - 10% hoc ln hn tu tng mu), song, tin hnh n gin v nhanh, rt thch hp cho phn tch ti hin trng. tin hnh xc nh cc cht c th s dng cc phng php sau: + Phng php dy tiu chun: Ly 6 ng nghim ng nht, cho vo y dung dch tiu chun ca cht cn xc nh vi lng tng dn. Sau , thm dung dch thuc th v cc ho cht cn thit khc n th tch bng nhau s nhn c dy tiu chun vi cng mu tng dn (c gi l dy mu chun). Cho mt lng dung dch phn tch vo ng nghim khc (ging ng lm dy tiu chun) v cng tin hnh tng t nh lm vi ng tiu chun. em so snh ng phn tch vi dy mu chun, nu mu ging mu ca ng tiu chun no th hm lng cht phn tch bng hm lng ca cht c trong ng tiu chun, nu mu ca ng phn tch nm gia mu ca hai ng tiu chun th hm lng cht phn tch bng trung bnh cng lng cht c trong hai ng tiu chun. + Phng php pha long: Ly 2 ng nghim nh nhau, cho vo ng 1 dung dch tiu chun v vo ng 2 dung dch phn tch. Tin hnh to mu nh nhau cho c hai ng. Nu mu ca hai ng khng nh nhau, th cho thm dung mi vo ng c mu m hn n khi mu hai ng bng nhau. Ghi th tch ca c hai ng. Lng cht phn tch c tnh theo biu thc IV- 6: (IV- 6) wpt = wtc.Vpt/Vtc , Trong : wtc - l khi lng cht tiu chun, wpt - l khi lng cht phn tch, Vtc - l th tch dung dch ca ng cha cht tiu chun, Vpt - l th tch dung dch ca ng cha cht phn tch. Phng php ny ch dng cho phn tch cc cht mu bn, khng b phn hu do s pha long. + Phng php chun so mu: Ly hai ng nghim nh nhau. Cho vo ng th nht dung dch phn tch, cho thm cc thuc th v ho cht khc to mu ri v ln th tch V. Cho vo ng th hai ch c thuc th v cc ho cht khc v cng ln th tch V. Dng buret nh tng git dung dch tiu chun nng cao ( cho s thay i th tch sau ny l khng ng k, <10%) vo ng 2 cho n khi mu ca hai ng nh nhau. Da vo lng dung dch tiu chun dng suy ra hm lng cht cn phn tch. * Phng php so mu bng my:
Dng my o chnh xc hp th quang A ca dung dich cht mu, ri t hp th quang o c suy ra cht cn phn tch theo nh lut Lambe - Bia. My o c chnh xc rt cao, sai s thng khng vt qu 2%, do vic to mu phi tin hnh trong cc bnh nh mc dung tch 25 100ml. Phng php o c nhy ln (c th o mu ca dung dch c nng 10-6M), nn c s dng nhiu trong phn tch vi lng. Khi o phi chnh bc sng o v gi tr chn. Thng s dng hai phng php o: phng php ng chun v phng php thm vo. + Phng php ng chun: Vic chun b cc bnh mu chun c tin hnh nh lm thang chun trong phng php so mu bng mt, song, thay cho vic dng ng nghim s dng cc bnh nh mc c dung tch 25ml, 50ml. 100ml. o hp th quang ca dy chun v dng th ph thuc A = f(C) (qua cng xc nh gii hn khong tuyn tnh ca nh lut Lambe-Bia (cc hnh H.1a.4, H.1b.4). Chun b bnh mu dung dch phn tch tng t nh trn v o hp th quang ca n: Apt. T th biu din A = f(C) (cc hnh H.1a.4, H.1b.4) v gi tr ca Apt suy ra nng dung dch phn tch. Phng php ng chun rt thch hp cho phn tch hng lot mu. Tuy vy, phng php ny b nh hng bi cc ion l c trong dung dch phn tch. + Phng php thm vo: Ly hai bnh nh mc. Cho vo bnh th nht dung dch cn phn tch v tin hnh phn ng mu. o hp th quang ca dung dch Apt. Cho vo bnh th hai cng vi lng dung dch phn tch nh bnh mt nhng c thm mt lng xc nh dung dch tiu chun ca cht cn xc nh v tin hnh phn ng hin mu. o hp th quang ca dung dch A. Khi lng cht cn phn tch c xc nh bi biu thc IV7: wpt = wtc.(Apt/(A Apt) (IV7) trong : wtc - l khi lng cht tiu chun, wpt - l khi lng cht phn tch, A - l hp th quang ca bnh gm cht cn phn tch v cht tiu chun, Apt - l hp th quang ca bnh ch c cht cn phn tch. Phng php thm vo ch thch hp cho trng hp phn tch t mu (1 2 mu). Phng php ny t b nh hng bi cc ion l c trong dung dch phn tch. 3. PHNG PHP O IN TH
3.1. t vn
Phng php o in th l da trn vic o th in cc ca in cc nhng trong dung dch phn tch, th ca in cc ny l hm ca nng cht cn phn tch: E = f(C). Nh vy, t gi tr th o c ca in cc c th suy ra nng cht cn phn tch. in cc ny c gi l in cc o (in cc lm vic, in cc ch th). Phng php o in th c tin hnh theo cch o trc tip (tc thng qua hiu in th o c tnh ra hm lng cht cn phn tch), v d: o pH, o cc ion Ag+, Cl- v mt s ion khc hoc cch o gin tip, v d: chun vi vic s dng phng php o hiu in th xc nh im tng ng. Cch o th hai c ng
dng rng ri trong chun trung ho, chun kt ta, chun to phc v c bit trong chun oxi ho kh.
3.2. in cc
C th chia in cc theo c ch hot ng lm hai nhm chnh: 1- nhm c th in cc hnh thnh do xy ra s trao i e trn bn in cc, 2- nhm in cc c th in cc hnh thnh do s trao i hoc khuch tn ion qua li bn in cc. a. Nhm c th in cc hnh thnh do xy ra s trao i e trn bn in cc y l cc in cc c th in cc c hnh thnh do phn ng trao i e xy ra trn in cc. Th ny c xc nh bi cc phng trnh Nerst I: E = EOMm+/M + (0,059/m)lg[Mm+], (IV8) cho phn ng: Mm+ + me = M, v phng trnh Nerst II hoc Nerst - Peterson: E = EOox/kh + [0,059/(m-n)]lg([ox]a/[kh]a), (IV9) v d: cho phn ng: aMm+ + a(m-n)e = aMn+ Cc in cc loi ny li c chia thnh hai nhm nh: 1- in cc h ng tnh v 2- in cc h khng ng tnh. + in cc h ng tnh: Cc cht tham gia phn ng u tan trong dung dch. in cc c lm bng kim loi tr nh Pt. Nhm in cc ny dng o in th ca h, , xy ra phn ng oxi ho kh: aox + ane akh hoc aox + amH+ + ane akh + (m/2)H2O Th in cc ca in cc c xc nh bi phng trnh Nerst II (IV- 9). in cc loi ny c dng o nng ca cc cht tham gia phn ng oxi ho kh trong dung dch. + in cc h khng ng tnh: Mt trong hai cht tham gia phn ng oxi ha kh nm trong dng rn. in cc dng trong cc trng hp ny c lm t chnh cc kim loi hot ng M, hoc Pt ph kim loi hot ng, hoc ph cht khng tan ca kim loi hot ng. (Khi nim kim loi hot ng l kim loi c cc ion tham gia phn ng cn theo di). Nh vy, c cc dng tng tc sau: - Kim loi M v ion Mm+ hoc phc cht ca n. in cc c cu trc: Mm+ | M, c gi l in cc loi I. Th in cc ca in cc c xc nh bi phng trnh Nerst I (IV- 8). in cc loi ny c dng o nng ca cc ion Mm+. - Kim loi M v mui khng tan MXm hoc cc hidroxit M(OH)m khng tan. in cc c cu trc: MXm | M, M(OH)m | M, c gi l in cc loi II. Th in cc ca in cc cng c xc nh bi phng trnh Nerst I, tuy nhin, c s tham gia ca cc anion X hoc cc ion OH-: E = EOMm+/M + (0,059/m)lg[Mm+], song, do c phn ng to kt ta, v d: MXn, m+ nn [M ] = TMXm/[X-]m. Thay gi tr ny vo biu thc IV- 8 s c: E = EOMm+/M + (0,059/m)lg TMXm/[X-]m. V TMXm l hng s, nn nhp lgTMXm vi EOMm+/M ri t thnh hng s mi EoMm+/M v nh vy biu thc IV- 8 tr thnh: 10) E = EOMm+/M - 0,059lg [X-]. (IV-
Nh vy, nng anion X- cng tng th in cc ca in cc cng gim. in cc loi ny dng o nng cc ion Mn+ , X-, OH-. - Kim loi M to mui khng tan MXm, anion X to mui khng tan vi ion kim loi M di dng MXn, kim loi M ng vai tr nh mt in cc. in cc c cu trc: M|MXn | MXm, c gi l in cc loi III. Th in cc ca in cc ny c tnh theo biu thc IV- 8 cho ion M vi s tham gia ca anion X v ion kim loi Mm+. in cc loi ny dng o nng ion ca kim loi M. b. Nhm c th in cc hnh thnh do xy ra s trao i hoc khuch tan ion qua bn in cc: y l nhm in cc hot ng da trn s trao i, khuch tn cc ion qua mng. Khi hai bn mt mng trao i c s khc bit v nng ca mt ion no c th trao i qua mng th trn mng s xut hin mt th in cc. Th in cc ny c gi l th in cc mng v c biu din bi biu thc: E = EO + (RT/nF)lg (C1/C2), (IV- 11) Trong : R- hng s kh, T- nhit Kenvin, F- hng s Faray, C1, C2 nng ca cht cn nghin cu hai bn b mt mng (lun t C1> C2). Cc hng sn xut in cc lun sn xut in cc vi tiu chun sao cho RT/nF 0,059. Trong nhm ny c cc in cc thu tinh v in cc mng chn lc. + in cc thu tinh: in cc l bu thu tinh mng bn trong cha dung dch c ion trng vi ion cn phn tch (v d HCl dng cho o ion H+). Th in cc ca in cc l kt qu ca s trao i ion qua mng thu tinh. in cc thu tinh c hai loi: loi in tr ln v loi in tr nh tu theo loi thu tinh v dy ca mng thu tinh. Hin nay, sn xut uc cc in cc cho vic xc nh H+, cc ion kim loi kim (Na, K..), cc kim loi kim th, km + in cc mng chn lc: Mng c dng ph bin l mng nha silicon, trn phn tn cc mui khng tan ca ion cn xc nh, v d: BaSO4 cho cc ion SO42-, AgCl hay AgI cho ion Cl- hay ion I-... Mng c dy khong 0,5 2mm c gn ln ng thu tinh. Bn trong ng cha dung dch long ca ion ging nh ion cn phn tch, v d: KI 10-3M cho xc nh ion I-. Hin nay, sn xut cc loi in cc khc nhau phc v xc nh chn lc khong 50 ion: clorua, itua, bromua, xyanua, florua, sunphua, sunphat, photphat, nitrrat, canxi , nhm, km, niken, magie, ng, bc
3.3. o in th
Khng th o trc tip c th n cc ca mt in cc no , v th, phi s dng php o so snh vi mt in cc bit gi tr th ca n. in cc bit th ca n c gi l in cc so snh. in cc ny phi c th n nh trong iu kin o. Nh vy, thit b o in th gm: in cc lm vic, in cc so snh v dng c o hiu in th. a. in cc so snh + in cc so snh tiu chun l in cc hydro chun: in cc c cu trc l mt thanh Pt c ph mt lp PtO2 nhng trong dung dch c hot ca H+ = 1 (aH+ =1), c h ny c t trong bu kh quyn hydro vi p sut 1atm (Pt(PtO2) | aH+, H2). nhit 20o C, th in cc ca in cc c qui nh l bng 0.
in cc tiu chun hydro rt cng knh, nn trong phn tch ng dng thng dng cc in cc khc d ch to v bn hn nh in cc calomen v in cc bc bc clorua. + in cc calomen: y l loi in cc so snh tt nht v c s dng nhiu nht. N thuc vo in cc loi II, c cu trc l Hg2Cl2(bo ho),KCl | Hg(Pt). Phn ng ca in cc l: Hg2Cl2(rn) + 2e = 2Hg + 2ClTu theo nng KCl np trong in cc m n c cc gi tr in th khc nhau. Thng thng s dng cc nng ca KCl: bo ho, 1M v 0,1M, trong nng bo ho c s dng nhiu nht. nhit 25o C, th in cc ca cc loi in cc ny nh sau: in cc calomen 0,1M KCl +0,335V in cc calomen 1M KCl +0,280V in cc calomen KCl bo ho +0,241V + in cc bc-bc clorua: Cng thuc vo nhm cc in cc loi II. in cc c cu trc AgCl(bo ho),KCl | Ag, hoc AgCl(bo ho),KCl | Pt m bc. Phn ng ca in cc nh sau: AgCl(rn) + e = Ag + ClTh in cc ca n cng ph thuc vo nng KCl np trong in cc Thng s dng cc loi in cc vi nng ca KCl: 0,1M, 1M v bo ho. nhit 25o C, th in cc ca cc loi in cc ny nh sau: in cc bc - bc clorua 0,1M KCl +0,290V in cc bc - bc clorua 1M KCl +0,236V in cc bc - bc clorua KCl bo ho +0,197V b. in cc o C th s dng cc loi in cc m t ti mc 3.2 chng IV n trn. Tuy vy, tu theo phn ng cn theo di hoc cht cn xc nh m chn la loi in cc thch hp. C th: + Theo di phn ng trung ho: Thng s dng in cc thu tinh. + Theo di phn ng oxi ho kh: Thng s dng in cc lm bng cc kim loi tr nh Pt, Au. + Theo di phn ng kt ta v to phc: Thng s dng cc loi in cc loi II v loi III.
3.4. ng dng phng php o in th trong phn tch

Bng phng php o in th c th xc nh nh lng trc tip hoc gin tip cc ion, cc hp cht khc nhau. Trong phng php trc tip, t s o in th suy ra nng cht cn phn tch. Cn trong phng php gin tip, phng php o in th c s dng lm ch th xc nh im tng ng cho cc php chun . Xc nh nh lng trc tip cc ion bng phng php o in th vi vic s dng cc in cc c in th biu din bng phng trnh Nerst i vi nhiu ion l khng th thc hin c, v in cc o cho chng khng thun nghch trong khong rng ca nng . Do trong thc t, ch c th xc nh trc tip c cc ion H+ trong khong rng nng v trong khong hp hn cc ion Ag+ vi in cc Ag, ion clorua vi in cc bc-bc clorua.
S dng cc in cc thu tinh, in cc mng c th cho php xc nh trc tip chn lc v nh lng i vi cc ion nu trn trong khong nng t 10-1 -10-4M. Di y trnh by mt php o c nhiu ng dng trong thc tin, l php o pH. o pH: Xc nh pH bng phng php o in th c tin hnh rt nhanh v ng tin cy. Tu theo my o v in cc s dng, chnh xc ca php o c th t 0,1, 0,01, 0,001 pH iu kin thng trong khong rng ca thang pH cng nh nhit cao, p sut ln. Vic o pH c th c t ng ho hon ton. nhit 20OC, pH ca dung dch c xc nh bng biu thc: pH = (Ex - Ess)/0,059, (IV- 12) Trong : Ex l hiu in th ca h, Ess l th in cc ca in cc so snh. Hin nay, thng dng in cc ch th o pH l in cc thu tinh. chnh xc ca in cc thu tinh ph thuc vo thnh phn thu tinh ch to ra n, v d: loi thu tinh thng l thu tinh Na, cn loi c bit l c thm Li2O v mt s oxit khc. in cc lm bng thu tinh thng cho chnh xc ca php o 0,1 pH trong khong pH n 10, 11, cn i vi loi thu tinh Li c th t chnh xc ti 0,05 0,1 pH trong khong pH n 12, 13. in th ca in cc thu tinh l khng hon ton tuyn tnh vi pH, chng dao ng trong khong 56 n 58mV cho 1 n v pH, v th trc khi tin hnh o pH dung dch phn tch, cn hiu chnh gi tr ca my o bng cc dung dch chun pH. Khi hiu chnh my o cn chn dung dch pH chun c pH nm trong khong pHo 2. Trong bng B.1.4 l mt s dung dch pH chun dng cho hiu chnh my o pH (pH-mt). Bng B.1.4: Mt s dung dch pH chun Dung dch 0,1M HCl 0,01M HCl + 0,09M KCl 0,03 M monokali tactrat 0,1M monokali tactrat 0,05M monokali phtalat 0,01M CH3COOH + 0,01M NaCH3COO 0,025M KH2PO4 + 0,025M Na2HPO4 0,05M Na2B4O7.10H2O 0,05 CaCl2 + 2M NaCl + Ca(OH)2 bo ho Ca(OH)2 bo ho 4. PHNG PHP CHIT pH 25O 1,085 2,075 3,567 3,719 4,010 4,714 6,855 9,180 11,82 12,45
4.1. Khi nim

Nguyn tc tch ca cc phng php chit l da trn s ho tan ca nhng cht cn tch gia 2 pha hoc 2 tng. Pha l khi nim ch s tn ti trng thi vt cht, nh vy c 3 pha: rn, lng, kh tng ng vi 3 trng thi ca vt cht. Tng l khi nim ch ranh gii tn ti ca cc cu t to thnh pha, v d: hn hp nc v du ho to chung thnh pha lng gm tng nc v tng du ho khng trn ln vo nhau.
4.2. Chit cht rn bng cht lng
Cn gi l phng php trch li. y, thnh phn cht gy nhiu hoc thnh phn cn phn tch c chit ra khi hn hp bng dung mi thch hp. V d: khi phn tch ion Hg2+ di dng kt ta HgS vi thuc th H2S, th kt ta thng b ln nguyn t S. lm sch kt ta, khng th lm cho S bay hi v HgS b thng hoa theo, do , chit S bng CS2 hoc nitrobenzen. Khi phn tch cht bo trong nng sn c th chit n bng petrolejete , sau phn tch cht bo. Khi phn tch cc mui ho tan trong t th chit chng bng nuc ct
4.3. Chit cht lng bng cht lng

y l phng php rt thng dng, cho php tch khi lng ln cht gy nhiu cng nh lng nh cht cn phn tch. Trong phng php ny, s dng dung mi chit l cc hp cht hu c chit cc cht ho tan trong nc. Sau khi chit, thng dng chit rt ph hp vi mt php o no , v d: chit phc cht mu hng Zn dithizon vo CCl4, ri o hp th quang ca dung dch chit bng phng php so mu. Trong qu trnh chit, cht b chit chuyn vo dung mi hu c n khi t c cn bng. V d: vi cht A, nng ca chng hai tng hu c (hc) v nc (nc) c cn bng nh sau: (Anc ) (Ahc ) v t s nng cn bng ca cht A trong hai tng c gi l hng s phn b K: (IVK = [A]hc/[A]nc 13) Hng s ny c gi l hng s phn b l thuyt v cn c gi l h s phn b Q. Trong Ho phn tch, kt qu phn tch c biu din di dng t l ton phn nn thng dng hng s phn b thc nghim K (cn c gi l t s phn b q) c xc nh bng t s nng phn tch ca cht A trong tng hu c (Ahc ) v trong tng nc (Anc): K = CAhc /CAnc , (IV14) bi v cht b chit trong dung dch nc hoc trong dung dch hu c c th tn ti nhiu dng. V d: khi chit ion Zn2+ di dng phc cht Zn - dithizon, trong tng dung mi hu c c phc cht Zn - dithizon, trong tng nc: c ion Zn2+, phc cht Zn - dithizon, do trong v d ny c: K = [Zn - dithizon]hc/[Zn - dithizon]nc K = [ Zn - dithizon]hc/([Zn2+] + [Zn - dithizonnc) Hiu qu ca vic chit thng c biu din bng % chit (E%) v c xc lp nh sau: Gi s s mol ca cht A l X c phn b thnh Xhc mol trong tng hu c v Xnc mol trong tng nc, th tch tng hu c l Vhc v ca tng nc l Vnc th c: X = Xhc + Xnc E% = (Xhc/X).100 Vi cc d liu trn cng c: K = (Xhc/Vhc)/(Xnc /Vnc) T mi quan h gia E% v K c xc lp bi biu thc IV - 15: E% = (100. K)/(K+Vnc/Vhc) (IV - 15)
Biu thc IV- 15 cho they, nu hng s phn b thc nghim K ln hoc th tch dung mi hu c rt ln, th ch cn chit mt ln l c th t E% chit gn 100%. Song trong thc t, hng s K v lng dung mi hu c khng ln cho php ch chit mt ln, lc ny cn s dng phng php chit nhiu ln, nh vy, hiu qu ca vic s dng dung mi chit s cao hn. V d: Khi chit bng n ln chit vi th tch ca hai tng khng i s c : E% = 100.{1 - [Vnc/(K Vhc+Vnc)]n} (IV- 16) T cho thy, khi chia dung mi chit thnh nhiu phn chit th hiu qu chit s cao hn. iu ny rt c li khi s dng cc dung mi c t l phn b nh hoc cc dung mi t tin. Trong Ho phn tch thng chit tch cc cht v c ra khi nhau thng qua vic chit cc phc cht dng ni phc (v d: [Al(8-hydroxiquinolin)3]) hoc cc hp cht axociat (ht cng hp) (v d H[FeCl4]) khng mang in tch ca chng. Do phn ng to phc cht thng gii phng ra ion H+, nn khi cc ion khc nhau cng to phc vi mt phi t th bn ca phc cht cng khc nhau ph thuc vo pH ca mi trng. V th, bng s iu tit pH mi trng c th tch chn lc cc ion ra khi nhau. V d: vi hn hp ion Al3+ v Mn2+ c th cho chng to phc cht vi 8-hydroxiquinolin, ri chit phc cht ca ion Al3+ trc pH 3 4 (lc ny s to phc cht ca ion Mn2+ khng xy ra), sau chit phc cht ca ion Mn2+ pH 6 7.
Cu hi n tp
1. nh lut Bug - Lambe Bia? Phm vi ng dng ca chng? 2. Tnh cng tnh ca ca nh lut Bug - Lambe Bia? v ng dng tnh cht ny? 3. Ph hp th v ng dng ca n ? 4. Nguyn tc ca cc phng php so mu bng mt v bng my? 5. Cc loi in cc dng trong o in th dung dch? 6. Nguyn tc xc nh pH bng phng php o in th. 7. Hng s phn b, hng s phn b thc nghim, % chit l g? Biu thc tnh ca chng?
Bi tp
1. So mu bng mt xc nh cht X theo phng php pha long. Khi th tch ca ng mu phn tch v ng mu chun l V1, th mu ca ng phn tch nht hn. Sau khi cho thm V2 ml nc vo ng mu chun th mu ca hai ng l nh nhau. Hy tnh khi lng cht mu X trong ng phn tch, nu bit khi lng cht mu X trong ng chun l a mg. (p s: a.V1/(V1 + V2). 2. Xc nh h s hp th nh sng ca cht mu X, o hp th quang ca 2 dung dch cht mu X: o mu dung dch 1 c nng C1 = 10-4M vi cuvet 5 cm c A = 0,60 v o mu dung dch 2 c nng C2 = 4. 10-4M vi cuvet 1cm c A = 0,48. Hi: c ph thuc vo cuvet v nng cht mu khng? (p s: khng). 3. So mu bng mt xc nh cht X c khi lng mol phn t M theo phng php dy tiu chun, c mu ca ng phn tch ging ng mu c cha V ml dung dch tiu chun nng C mol/l. Nu th tch dung dch cht X ly phn tch l VX ml, th khi lng cht X trong 1 lt dung dch l bao nhiu? (p s: a = M.(VC/VX).1).
4. So mu bng mt xc nh cht X c khi lng mol phn t M theo phng php dy tiu chun, c mu ca ng phn tch ging ng mu c cha a mg cht mu chun. Nu th tch dung dch cht X ly phn tch l VX ml, th nng mol/l ca dung dch cht X l bao nhiu? (p s: a/MVX). 5. So mu bng mt xc nh cht X c khi lng mol phn t M theo phng php dy tiu chun, c mu ca ng phn tch nm gia hai ng mu c cha a1 v a2 mg cht mu chun. Nu th tch dung dch cht X ly phn tch l VX ml, th nng mol/l ca dung dch cht X l bao nhiu? (p s: (a1 + a2)/2MVX). 6. hp th quang ca hai dung dch phc ca ion Cu2+ vi NH3 c nng C1, C2 c o cng bc sng trong hai cuvet c dy l1, l2 (l1 l2). Hai dung dch ny c cng hp th quang khi no? (p s: C1 = l2C2/l1). 7. nh lng ion Cu2+, cho n to phc vi NH3 ri so mu bng mt, kt qu cho thy mu ca ng kho st m hn mu ca ng tiu chun cha 0,0295 mg ion Cu2+. Th tch dung dch hai ng bng nhau v bng 20 ml. Nu pha long ng kho st n th tch 24 ml th cng mu ca 2 ng bng nhau. Tnh nng mol/l ca ion Cu2+ trong dung dch phn tch ban u bit rng ly 4 ml dung dch phn tch to mu. (p s: 1,383.10-4M). 8. So mu xc nh ion Fe3+ vi thuc th KCNS bng phng php ng chun, ly vo cc bnh nh mc 100 ml ln lt 2,0; 4,0; 6,0; 8,0; 10,0 ml 10-3M dung dch ion Fe3+. hp th quang ca cc dung dch mu tiu chun ln lt l: 0,13; 0,29; 0,40; 0,56; 0,68. Hy tnh nng M ca dung dch mu, nu hp th quang ca bnh mu lm t dung dch mu phn tch l 0,35, bit rng khi ln mu ly 15 ml dung dch phn tch. (p s: 3,5.10-4M). 9. o hp th quang ca dung dch mu gm 2 cht mu X v Y ti 2 bc sng 1 v 2 c cc gi tr tng ng l 0,35 v 0,48. Tnh nng dung dch theo mol/l ca hai cht X, Y. Bit: vi cuvet 1cm, dung dch 2.10-4 M ca cht X c A 1 = 0,22, A 2 = 0,64 v dung dch 2.10-4 M ca cht Y c A 1 = 0,46, A 2 = 0,34. (p s: CX = 9,27.10-5M, CY = 1,078.10-4M). 10. Cn 1g mu cha ion PO43- ri ho tan thnh 1000ml dung dch. Ly 2ml dung dch ny to mu xanh molybden th o c A = 0,40. Thang mu chun c cc tr s ca A ng vi cc hm lng ca ion PO43- nh sau: mg PO43- 0 0,001 0,002 0,003 0,004 A 0,151 0,250 0,352 0,450 0,553 Hy tnh thnh phn % ca ion PO43- trong mu! (p s: 0,0125%). 11. Cho cht X c phn b trong hai dung mi nc v dung mi hu c vi th tch bng nhau. Sau khi t cn bng, lng cht X trong dung mi nc l 10mmol v trong dung mi hu c l 50mmol. Hy tnh: a Hng s phn b thc nghim K. b- Tnh % chit ( E%), khi cc th tch tng nc v tng hu c bng nhau. (p s: K = 5, E% = 83,33%). 12. Nu chit 100mmol cht X t 100 ml dung dch nc vi hiu sut 90% bng 1 ln chit v bng 2 ln chit th th tch dung mi hu c cn l bao nhiu? Bit hng s phn b thc nghim K = 5. (p s: 180ml; 63,4ml).
Chng V SAI S TRONG HO PHN TCH

1. SAI S Trong Ho phn tch, thu c kt qu cui cng ngi phn tch phi tin hnh rt nhiu thao tc v mi thao tc u c th mc sai st dn n s sai lch kt qu phn tch so vi gi tr thc ca mu. Sai s phn tch chnh l s sai lch gia kt qu thu c so vi gi tr thc. Sai s l s kin m ngay c ngi phn tch cn thn nht, s dng phng tin, dng c cng nh my mc phn tch hon ho nht cng khng th trnh c. Sai s thng c ln khc nhau v do nhiu nguyn nhn khc nhau gy nn. Khng th trnh c sai s nhng c th hn ch tc hi ca n nu nm c nguyn nhn v qui lut pht sinh ca n chn gii php phn tch tt nht.
1.1. Phn loi sai s

Da vo ln, tnh cht v nguyn nhn gy nn, sai s c chia thnh 3 loi: - Sai s ngu nhin, - Sai s h thng. - Sai s ng tic (sai s th). a. Sai s ngu nhin L nhng sai s rt nh v khng c qui lut, thng gp trong khi tin hnh tng bc phn tch. Hu qu ca n l lm cho kt qu ca cc ln phn tch song song c khc nhau cht t, nhng kt qu trung bnh ca cc ln phn tch ny khng gy ra sai s ng k so vi gi tr thc (sai s nh hn hoc bng sai s cho php). Tp hp kt qu ca nhiu ln phn tch lp li ny c gi l tp hp mc sai s ngu nhin. Nguyn nhn ca sai s ngu nhin khng th xc nh c, khng l gii c. Thng qui cho s hnh thnh sai s ny l do nhng s bin i rt nh ca mi trng trong qa trnh o nh nhng thay i nh ca nhit , p sut, m Sai s ngu nhin khng th loi b c m ch c th dng ton thng k xc nh khong tn ti ca gi tr kt qu phn tch. b. Sai s h thng L loi sai s c hng lm cho kt qu phn tch lun ln hn hoc lun nh hn gi tr thc vt qu sai s cho php. C nhiu nguyn nhn gy ra sai s h thng nh: * Do dng c, thit b o khng chnh xc, ho cht khng sch: Gy ra s o lun sai vi gi tr thc. V d: Bnh nh mc c dung tch ghi trn bnh l 100ml, nhng trong thc t ch c 99,5ml. Nh vy, khi dng bnh ny pha ho cht, dung dch thu c lun c nng ln hn theo tnh ton l 100/99,5 ln. Hoc khi pha 1 lit dung dch CuSO4 0,02N t CuSO4.5H2O (theo nhn ghi), nhng trong thc t do bo qun CuSO4.5H2O chuyn thnh CuSO4.4H2O; nu pha theo lng tnh vi CuSO4.5H2O s cho dung dch c nng 0,0216N ln hn 0,02N.
khc phc loi sai s ny cn cn chnh dng c, thit b o, kim tra ho cht trc khi tin hnh th nghim. Nu sau khi lm th nghim mi pht hin ra sai s th: - Tt nht l lm li phn tch. - Trong trng hp khng th lm li phn tch, th c th hiu chnh kt qu bng h s xc nh. Trong trng hp trn vi s sai s o ca bnh, kt qu phn tch thu c c hiu chnh bng cch nhn vi h s 100/99,5. * Do phng php: Php o lun cho kt qu ln hn hoc nh hn gi tr thc. V d: Dng phn ng khng hon ton s lun mc s m (-). khc phc loi sai s ny cn chn li phng php phn tch, nu khng th chn li phng php, cn tnh ton sai s ca phng php hoc lm mu kim tra vi i tng chun (cht chun) v sau chnh l kt qa phn tch theo sai s tnh. V d: Khi phn tch N trong cc hp cht hu c vi cc vng thm cha N bng phng php Kendan (Kjeldahl); thng qu trnh cng ph mu khng chuyn ho 100% N v NH3, v th phi s dng cc ho cht sch c tnh cht tng t cht cn phn tch lm mu chun. Phn tch mu chun s cho h s hiu chnh hiu chnh kt qu phn tch trong thc t. * Do s thin lch ca ngi lm phn tch: Sai s ny do c nhn ngi phn tch gy nn do thiu kinh nghim hoc c s thin v khi quan st v tin hnh th nghim hoc tnh ton sai. V d: Khi chun nhn bit sai v s chuyn mu ca ch th. khc phc loi sai s ny ngi phn tch cn phi t sa mnh cho cc thao tc tht chun xc. c. Sai s ng tic (sai s th) Sai s ny thng ln, khng c qui lut v gy nh hng ln n kt qu cui cng. Nguyn nhn gy ra sai s ny l: * Do chn phng php phn tch khng n nh: V d: Khi so mu chn phn ng km bn vi thi gian hoc b tc ng ca khng kh hoc khi phn tch theo phng php khi lng kt tu s dng kt ta c kh nng hp th cht bn qa ln kh ra sch Cch khc phc l thay i phng php hoc n nh iu kin o * Do ngi lm phn tch cu th, khng cn thn: Nh khi lm phn tch khng tun th qui trnh, khi lm th nghim nh , nhm ln ho cht; nhm ln khi tnh ton khc phc loi sai s ny ngi phn tch cn phi t sa mnh cho cc thao tc tht chun xc. Trn quan im thc tin sai s cng c th c chia thnh hai nhm: sai s chnh l c v sai s khng chnh l c. Sai s h thng do dng c, thit b v ho cht v sai s h thng do phng php l loi sai s chnh l c thng qua con ng thc nghim hoc thng qua tnh ton. Sai s ngu nhin l loi sai s khch quan khng chnh l c, song, n rt nh nn c chp nhn. Sai s th l sai s khng chnh l c v phi c loi ra khi tnh ton kt qu.
1.2. Biu din kt qu phn tch v sai s

a. Biu din kt qu phn tch
Gi s mt i lng cn phn tch c gi tr thc l c xc nh n ln vi cc kt qu ca mi ln lp li l xi ( i = 1, 2,, n), c th biu din sai s bng sai s tuyt i hoc sai s tng i. b. Sai s tuyt i Sau khi loi tr sai s th, kt qu phn tch l gi tr trung bnh (x ) ca cc kt qu thuc nhng ln phn tch lp li: _ x = (ni = 2 xi)/n Sai s tuyt i (k hiu l dx) s l: dx = x - (V- 2) (V-1)
Nh vy, sai s tuyt i c th mang du m hoc dng. Thng sai s tuyt i c biu din di dng gi tr tuyt i, tc dx = x - (V- 3)
n v ca dx chnh l n v o kt qu phn tch. Sai s tuyt i thng c dng khi biu din kt qu phn tch di dng khong xc nh x dx, v d: khi cn 100mg mu trn cn phn tch c sai s 0,1mg, th lng cn cn c l 100,0 0,1 (mg). Bng sai s tuyt i c th nh gi chnh xc ca php phn tch. Khi xc nh mt ch tiu no ca mt mu bng cc phng php khc nhau, th phng php no c sai s tuyt i nh hn s c chnh xc cao hn. V d 1: khi cn 100,0mg mu trn 2 loi cn cn phn tch c sai s 0,1mg, tc dx = 0,1mg v cn thng c sai s 1mg, tc dx = 1mg, nh vy cn trn cn phn tch c chnh xc cao hn v dx nh hn. Tuy nhin, khi xc nh cc ch tiu khc nhau vi cc hm lng khc nhau th sai s tuyt i khng th cho bit r thng tin v chnh xc ca phng php o. V d 2: khi xc nh mu cha 60,01% SiO2 v mt mu khc cha 0,10% As u mc sai s tuyt i dx = 0,05%, r rng khng th coi vic xc nh As c chnh xc nh l xc nh SiO2 ch v c dx nh nhau. Mt khc khng th dng sai s tuyt i so snh chnh xc ca cc phn tch m kt qu c biu din vi cc n v o khc nhau. V d 3: so snh kt qu phn tch ca mu 1 c x1 = 40,0mg, dx = 0,1mg vi mu 2 c x2 = 20,00% v dx = 0,05% l khng th thc hin c. V th, c th nh gi tt hn chnh xc v c th so snh cc kt qu phn tch biu din bng cc n v o khc nhau dng sai s tng i. c. Sai s tng i L t s gia sai s tuyt i v gi tr thc . Sai s tng i c biu din theo phn trm e% hoc sai s %: e% = (dx/).100 (V- 4) Trong thc t, thng khng bit gi tr thc tr khi phn tch mu chun, v th sai s tng i thng c biu din di dng:
e% = (dx/x).100 (V- 5) Sai s tng i thng dng biu din chnh xc ca kt qu phn tch. Trong v d 2 nu trn, sai s e% ca phn tch SiO2 l 0,083%, ca phn tch As l 50%, nh vy, vic phn tch SiO2 l chnh xc hn phn tch As. Cn vi v d 3, c hai php o u mc sai s tng i 0,25%, nh vy c chnh xc nh nhau. Nh vy, tu theo yu cu m biu din kt qu phn tch vi sai s tuyt i hoc sai s tng i. 2. L THUYT V SAI S Vic tnh ton sai s phn tch theo cc biu thc V- 1 - V- 5, thng ch dng cho tnh ton kt qu tng cng on phn tch. Trong thc t, khi tin hnh phn tch, ngi phn tch trin khai rt nhiu thao tc lin tip nhau c kt qu cui cng. Mi thao tc mc mt sai s nht nh v sai s ny th hin trong kt qu cui cng. S th hin ca chng c xc lp bng l thuyt sai s. Nu mi bc i trong phn tch cho kt qu x1, x2,,xn, sai s dx ca chng l dx1, dx2,, dxn v sai s % ca chng l ex1, ex2,, exn , kt qu cui cng ca phn tch l y c biu din nh l hm ca cc xi: y = f(x1, x2,, xn), l thuyt sai s ni nh sau: y = f(x1, x2,, xn] dy = (y/x1).dx1 + (y/x2).dx2 + + (y/xn).dxn v ey = (lny/x1).dx1 + (lny/x2).dx2 + + (lny/xn).dxn Nh vy, nu qu trnh phn tch l tng i s cc cng on th: (Vy = x1 x2 dy = dx1 + dx2 v ey = dy/y 6) Nu qu trnh phn tch l gi tr thu c nhn vi hng s th: y = kx dy = kdx v ey = ex (V- 7) Nu qu trnh phn tch l tch hoc thng ca cc cng on th: dy = ey.y v ey = ex1 + ex2 y = x1.x2 hoc y = x1/x2 (V- 8) Nu qu trnh phn tch l hm m, hm cn ca cc cng on th: (V- 9) y = xn dy = n.xn-1.dx v ey = nex Vic p dng cng thc no hoc t hp cc nhm cng thc ph thuc vo vic xc nh cc mi tng quan trong tin hnh phn tch. V d: khi cn mu, trc tin phi cn b (x1) ri cn b + mu (x2), khi lng cn ca mu y = x2 x1. Nu sai s ca cn l dx, p dng biu thc V- 6 s c: dy = dx + dx= 2dx, suy ra ey = [2dx/(x2 x1)]100. ng dng l thuyt sai s c th tnh c sai s phn tch khi bit sai s ca tng cng on v xc nh c cng on no gy ra sai s ln nht c bin php lm gim sai s phn tch. V d: pha1 lt dung dch tiu chun CuSO4.5H20 10-4M. Chn la cch pha trong hai cch sau: 1 - pha trc tip t lng cn, 2- pha long t dung dch m c nng 10-3M, vi vic s dng cn phn tch c chnh xc 0,1mg v cc dng c thu tinh tiu chun, sai s cho php 0,1%. Cch 1: Khi lng mol phn t ca CuSO4.5H20 l 249,685g, vy lng cn pha1 lt dung dch tiu chun c nng 10-4M l: 249,685. 1. 10-4g tc 24,9685mg 25,0mg,
nh vy sai s cn l: 2.0,1.100/25 = 0,8% (theo biu thc V- 6), qu ln so vi sai s cho php 0,1%. Cch 2: Lng cn pha1lt dung dch tiu chun c nng 10-3M l: 249,685. 1.103 g tc 249,685mg 249,7mg, nh vy, sai s cn l: 2.0,1.100/249,7 = 0,08% (theo biu thc V- 6), nh hn sai s cho php (0,1%). Nu coi vic ly 100ml dung dch 10-3M ny ri pha long thnh 1000ml s mc sai s rt nh so vi sai s cho php, th theo cc biu thc V- 6 v V- 7 c sai s ca cch pha th 2 l 0,08% chnh l sai s cn, nh hn sai s cho php. Nh vy: khi pha dung dch c nng qu nh nn dng phng php pha long t dung dch m c nng cao hn khng mc sai s cn qu ln. 3. NG, CHNH XC V TIN CY CA KT QU PHN TCH y l 3 ch tiu nh gi kt qu phn tch.
3.1. ng
Phn tch l ng khi kt qu thu c trng vi gi tr thc. S sai lch gia kt qu thu c v gi tr thc th hin ng ca php phn tch, gi tr ny cng nh th ng cng cao. Trong Ho phn tch thng sai lch ny cho php nh hn hay bng 0,1%, nhng trng hp c th c th cho php cao hn.
3.2. chnh xc
Mt cch gi khc l lp li hay hi t. Khi tin hnh phn tch nhiu ln lp li (i ln) mt mu vi mt phng php, cc kt qu phn tch thu c thng cng khc nhau v khc vi gi tr thc mt tr s dxi. Khong gi tr m cc kt qu xi phn b c gi l hi t ca php phn tch. Nu khong cng nh, th php phn tch c hi t cng cao; cn khong cng ln, th hi t cng nh hay phn tn cao (php phn tch c th mc sai s th).
3.3. tin cy
tin cy l tiu ch phi hp bi ng v hi t. Php phn tch c coi l tin cy cao, khi va cho kt qu c ng cao v va c hi t cao ca cc gi tr xi. Trong phn tch mu thc t, i b phn cc mu khng c trc gi tr thc cho nn thng chn cc phng php c hi t cao mc d c th mc sai s h thng. Cn phng php tuy cho kt qu ng, nhng, phn tn ln khng c chp nhn, v kh c c s m bo rng ln phn tch lp li tip theo s vn cho ng nh c (v thng ch c th lp li mt s ln rt hn ch). ng, hi t v tin cy c ng dng trong vic xc nh s ln phn tch nhc li ti thiu cn thc hin. Nu phng php phn tch c hi t cao th s ln nhc li c th t cn nu c phn tn cao th s ln nhc li phi nhiu. Thng thng, khi xy dng phng php phn tch mi cn nhc li t nht 7 ln, cn khi phn tch vi phng php c xc nh (khi phn tch hng lot mu) c th gim s ln nhc li xung 3 hoc 2, v ch trong nhng trng hp nu trn mi c th dng ton thng k xc nh sai s th, sai s h thng.
Hnh H.1..5 Minh ha ng, hi t: a- c ng v hi t cao, bkhng c ng nhng c hi t cao, c- c ng nhng khng c hi t. 4. TNH TON SAI S H THNG DO PHNG PHP Nh trn ni: sai s h thng do phng php c th tnh c v c th s dng kt qu sai s tnh c kim tra phng php phn tch hoc chnh l kt qu phn tch, nn vic tnh ton sai s h thng l cn thit. Trong phng php phn tch ho hc hoc ha l thng s dng cc phn ng ho hc thch hp tch hoc chuyn ha cht cn phn tch, song, do cc phn ng ny khng bao gi hon ton nn c nh hng n chnh xc ca php phn tch. Hai nguyn nhn chnh gy sai s h thng do phng php thng gp trong Ha phn tch l: - Do s cn bng ca phn ng ho hc. - Do kt thc phn ng khng ng im tng ng, v d: ch th phn ng khng ng im tng ng.
4.1. Sai s h thng do s cn bng ca phn ng ho hc gy nn

Tt c cc phn ng ho hc xy ra, v d gia hai cht A (cht cn phn tch) v cht B (thuc th) theo phng trnh (V- a), u c s cn bng lm cho phn ng khng hon ton. a) A + nB ABn S cn bng ny c c trng bi hng s cn bng K: K = [ABn]/ [A] [B]n (V(V-
10) (trong phn ng to kt ta BAn th K c thay bng T v c K = 1/T). Do vy, sau phn ng lun c mt lng cht A d v y chnh l ngun sai s v c gi l sai s do phng php. Sai s ny c th tnh l thuyt c t biu thc V- 10. T biu thc V- 10 c: [A] = [ABn]/K[B]n (V- 11) Nu gi nng phn tch ca cht A l CA, s c: CA = [A] + [ABn] thay biu thc ny vo biu thc V- 11 c: (V[A] = (CA [A])/K.[B]n CA/K.[B]n 12) nu coi [A] CA.
Nh vy, sai s tng i ca phng php do phn ng xy ra khng hon ton s l: e% (V- 13) = 100[A]/CA= 100/ K[B]n
(trong phn ng to kt ta BAn, e% = T . 100/[B]n). Nu gi nng cht A khi cha phn tch l COA, th tch dung dch ban u l VO v th tch dung dch lc t cn bng l Vcb th sai s tng i cn c biu din nh sau: e% = 100[A] . Vcb/ COA . VO (V- 14) T hai biu thc V- 13 v V- 14 cho thy mun phn ng xy ra hon ton hay sai s nh nht cho php th cn c K ln, [B] ln (hay phi dng thuc th d) v khng nn lm long qu i dung dch khi phn tch. Nhn xt ny c ng dng nhiu trong phng php tch bng s to kt ta, bng s to phc, bng s chit nhm thit lp iu kin cn cho s cn bng xy ra. V d 1: phn ng V- a xy ra hon ton vi sai s e 0,1% th KAB phi l bao nhiu, nu khng dng d thuc th B, COA = 0,1M, VO = 100ml, Vcb = 200ml. Gii: Theo bi ra c phng trnh: A + B = AB. Do khng dng d thuc th nn ti im cn bng: [A] = [B], t biu thc V- 14 c: 0,1 100([A] . 200)/(0,1 . 100) [A] 5 . 10-5 tc [B] 5 . 10-5M thay [B] 5 . 10-5M vo biu thc V- 13 c K 2 . 107. V d 2: Khi lm kt ta 96 mg ion SO42- bng BaCl2 ti pH = 4, th sai s phn tch do phn ng khng hon ton l bao nhiu? Nu [Ba2+]d = 10-5 M, V = 200ml, TBaSO4 = 1,1.10-10. Gii: BaCl2 + SO42- = BaSO4 + 2Cl2+ TBaSO4 = [Ba ] [SO42-]. T c: [SO42-] = TBaSO4/[Ba2+] = 1,1.10-10/ 10-5 10-5 . Do sai s e% l: e% = 100{[SO42-].V.MSO42-}/wSO42- = 100.10-5. 0,2 . 96/ 96 . 10-3 = -0,2% (M)
4.2. Sai s h thng do ch th gy nn
Trong qu trnh phn tch, nht l trong chun thng dng ch th xc nh im tng ng (hoc im kt thc chun ) ca phn ng V- a. Nu ch th phn ng ng im tng ng s c sai s bng khng, song, thng ch th phn ng trc hoc sau im tng ng gy nn sai s ch th v sai s ny mang tnh cht sai s h thng. Sai s ch th c th tnh c v kt qu ca php tnh ny cho cch chn ch th thch hp v cch thao tc thch hp. Trong chun , c th tnh sai s tng i e% theo biu thc III- 2. Vic tnh ton sai s c tin hnh theo cc bc sau: Bc 1: T ch th dng tnh tr s chun ti im kt thc (pTkt: pHkt, Ekt pXkt ) theo cc biu thc III- 72, III- 74, III- 76 v II- 4.
Bc 2: T phn ng chun tnh ch s chun ti im tng ng (pT: pHt, Et, pXt). Bc 3: So snh pTkt v pT chn biu thc tnh pTkt (theo mc 3. 6 chng III) Bc 4: T biu thc ton chn tnh th tch dung dch tiu chun dng v cui cng tnh sai s (theo III- 2). Lu : D dung dch tiu chun mc sai s h thng dng (+), d cht cn xc nh mc sai s h thng m ( -). V d 1: Khi chun 20ml NH4OH 0,1N bng HCl 0,1N dng metyl (pKa = 5) lm ch th. Hy tnh sai s chun . Cho pKbNH4OH = 4,74. Gii: Bc 1: Tnh pHkt: Dng chun khi ch th i mu (vng ) hay khi t mu bn, tc 2 gi tr pH = pKa 1: pH = 6 v pH = 4. Bc 2: Tnh pHt theo biu thc III- 43: pHt = 7 - (1/2) pKb - (1/2)lgCm = = 7 - 4, 74/2 - (1/2)lg{(VNH4OH . NNH4OH)/[VNH4OH/(VNH4OH . NNH4OH/ NHCl)]} = 5,28 Bc 3: So snh pHkt v pHt: pHkt = 6 > pHt d NH4OH, kt thc trc im tng ng, vy mc sai s h thng -. pHkt = 4 < pHt d HCl, kt thc sau im tng ng, vy sai s h thng +. Bc 4: Tnh ln ca sai s: a) Ti pHkt = 6: S dng biu thc III- 42: pH = pKa lg{[NH4Cl]/[NH4OH]} = 14 4,74 lg[VHCl . NHCl/(VNH4OH . NNH4OH VHCl . NHCl)] 6 = 9,26 + lg{[(VNH4OH . NNH4OH)/VHCl . NHCl] 1 ]} Thay s vo tnh, c: VHCl = 20/(1 + 5,5 . 10-4) e% = 100{[ 20/(1 + 5,5 . 10-4)] 20}/20 = 0,06 % b) Ti pHkt = 4: S dng biu thc III- 38 : pHkt = 4 = lg[(VHCl . NHCl VNH4OH . NNH4OH)/(VHCl + VNH4OH)], thay s vo s c: VHCl = 20,04 ml e% = [(20,04 20)/20].100 = +0,2% V d 2: Chun 20ml ion Fe2+ 0,1N bng dung dch ion Ce4+ 0,1N trong mi trng axit vi ch th [Fe(II)(O-phenanthrolin)2)]2+ (ox + 1e = kh). Hy tnh sai s chun . Cho EoFe3+/Fe2+ = 0,77V, EoCe4+/Ce3+`= 1,44V, EoIndox/Indkh = 1,11V. Gii: Bc 1: Tnh Ekt: ng dng biu thc III-74. Khi dng chun dung dch chuyn t mu sang mu xanh hoc mu xanh bn, tc 2 gi tr Ekt1 = 1,11 0,059 1,05 v Ekt2 = 1,11 + 0,059 1,17. Bc 2: Tnh Et: ng dng biu thc III- 53, thay s s c: Et = (EoFe3+/Fe2+ + EoCe4+/Ce3+)/2 = (0,77 + 1,34)/2 = 1,10 Bc 3: So snh Ekt vi Et thy Ekt1 < Et, , nh vy, d ion Fe2+ (mc sai s -); Ekt2 > Et, nh vy, d ion Ce4+ (mc sai s +). Bc 4: Tnh sai s: + Ti Ekt1 = 1,05V: S dng biu thc III- 52, thay s c: Ekt1 = EoFe3+/Fe2+ + 0,059lg[VCe4+ . NCe4+/( VFe2+ . NFe2+ - VCe4+ . NCe4+)] 1,05 = 0,77 + 0,059lg[VCe4+/ ( 20 - VCe4+)] VCe4+ 20ml. Nh vy, e% 0%.
+ Ti Ekt2 = 1,17V: S dng biu thc III- 54, thay s c: Ekt2 = EoCe4+/Ce3+ + 0,059lg[(VCe4+ . NCe4+ - VFe2+ . NFe2+)/ (VFe2+ . NFe2+)] 1,17 = 1,44 + 0,059lg[(VCe4+ - 20)/20] VCe4+ 20ml. Nh vy e% 0%. V d 3: Ly 50 ml dung dch cha Cl-, cho vo y 0,55 ml K2CrO4 0,1M v chun xc nh Cl- bng 5 ml AgNO3 0,01N. Hy tnh sai s chun ny! Cho TAgCl = 1,78.10-10, TAg2CrO4 = 1,1.10-12. Gii: Bc 1: Tnh pClkt: [CrO42-] =(0,55 . 10-1)/( 50 + 0,55 + 5) 10-3 M, suy ra: [Ag+] cn kt ta Ag2CrO4 l: [Ag+] = {TAg2CrO4/[CrO42-]}1/2 10-4,5 M pAg = 4,5 pClkt 5,5. Bc 2: Tnh pClt: [Cl-]t = (TAgCl)1/2 = 1,33.10-5 pCl = 4,88 = pAg Bc3: So snh pClkt v pClt cho thy pClkt > pClt, tc im kt thc xy ra sau im tng ng. Bc 4: Tnh sai s: pAg = - lg[(VAg+ . NAg+ - VCl- . NCl-)/(VAg+ + VCl-)]. Thay s c: pAg = 4,5 = - lg[(5 . 0,01 - 50 . NCl-)/55] NCl- = 9,65 . 10-4 N. Sai s e% l: e% = 100.(VAg+ . NAg+ - VCl- . NCl-)/(VCl- . NCl-) = 100.(5 . 0,01 - 50 . 9,65 . 10-4)/(50 . 9,65 . 10-4) = 3,62%
Cu hi n tp
1. Sai s phn tch l g? S phn loi sai s v cc cch biu din sai s? 2. L thuyt v sai s? ng dng l thuyt ny? 3. ng, chnh xc, tin cy ca kt qu phn tch? ng dng cc tiu chun ny trong vic xc nh cch tin hnh phn tch? 4. Cch tnh sai s h thng?
Bi tp
1. Sau khi lm kt ta 80mg ion Ca2+ bng (NH4)2C2O4 ti pH = 10, kt ta c ra 5 ln mi ln 10ml nc. Hy tnh sai s phn tch ion Ca2+ do s ho tan ca kt ta khi ra! Cho TCaC2O4 = 2,3.10-9. (p s: -0,12%). 2. Tnh sai s khi chun 20 ml dung dch CH3COOH 0,1N bng dung dch NaOH 0,1N vi vic s dng phenolphtalein (pKa = 9) lm ch th im kt thc chun . Cho pKa ca CH3COOH = 4,76. (p s: ti pH 8: -4%, ti pH 10: +0,2%). 3. Tnh sai s khi chun 20 ml dung dch HCl 0,1N bng dung dch NaOH 0,1N khi kt thc chun : a) pH = 4; b) pH = 10. (p s: -0,2%, +0,2%) 4. Chun 20 ml dung dch Fe2+ 0,1N bng dung dch tiu chun Ce4+ 0,1N vi ch th benzidin (ox + e = kh) s mc sai s l bao nhiu? Bit: EoFe3+/Fe2+ = 0,77V, EoCe4+/Ce3+`= 1,44V, EoIndox/Indkh = 0,92. (p s: 1. 0,3%, 2. 0%)
5. Chun 20 ml dung dch NaCl 0,1N bng dung dch tiu chun AgNO3 0,1N vi ch th K2CrO4 c nng trong dung dch trc khi chun l 0,1 M th s mc sai s l bao nhiu? Bit: TAgCl = 1,78. 10-10 ; T Ag2CrO4 = 1,1.10-12. (p s: 0,02%) 6. Nu chit 100mmol cht X t 200 ml dung dch nc bng 50ml dung mi hu c th sai s thu hi cht X l bao nhiu? Bit hng s phn b thc nghim K = 10. (p s: 28,6%). 7. kim tra phng php Kejdal xc nh N cn 5 mu mi mu l 0,1320g (NH4)2SO4 tinh khit v em phn tch. Kt qu thu c nh sau: 0,0275g, 0,0279g, 0,0281g, 0,0277g, 0,0275g. Hy tnh sai s tuyt i, sai s tng i ca phng php! (p s: d = 0,0026g, sai s% 0,93%).
Ti liu tham kho

1. Alecxep V. N. (1971): Phn tch nh lng, tp I, II, III. NXB Gio dc, H Ni. 2. Nguyn Thc Ct, T Vng Nghi, o Hu Vinh (1980): C s l thuyt Ho hc phn tch. NXB i hc v trung hc chuyn nghip, H Ni. 3. Eckschlager K. (1971): Chyby chemickch rozboru (ting Tip) (Sai s phn tch ho hc). NXB Ti liu k thut, Praha. 4. Trn T Hiu (1973): Gio trnh Ho phn tch, tp I, II. Trng i hc Tng hp H Ni. 5. Holzbecher Z. v cc tc gi (1968): Analytick chemie (ting Tip ) (Ho phn tch). NXB Ti liu k thut, Praha. 6. Lialikov Iu. X. (1974): Nhng phng php phn tch ho l (ting Nga). NXB Ho hc, Maxcva. 7. Lurie Ju. (1975): Handbook of Analytical Chemistry. Mir Publishers, Moscow. 8. Murasova V. I., Tananaeva A. N., Khobiakova R. Ph. (1976): Phn tch nh tnh ring (ting Nga). NXB Ho hc, Maxcva. 9. H Vit Qu (2001): Phn tch l ho. NXB Gio dc, H Ni. 10. Nguyn Trng Sn, Hong Xun Lc (1991): Gio trnh Ho v c - phn tch. NXB i hc v gio dc chuyn nghip, H Ni. 11. Nguyn Vn Tu, V Vn Soan (1990): Gio trnh C s l thuyt Ho hc. NXB i hc v gio dc chuyn nghip, H Ni. 12. Phm Ngc Thu, Phm Hng Anh (1996): Gio trnh Ho phn tch. Trng i hc Nng nghip I.
Cc bng ph lc
Ph lc 1: Tch s tan ca mt s kt ta
Tn hp cht AgBr Ag2CO3 Ag2C2O4 AgCl Ag2CrO4 AgI Ag3PO4 Ag2SO4 Al(OH)3 AlPO4 BaCO3 BaC2O4 BaCrO4 BaF2 Ba3(PO4)2 Tch s tan (T) 5,3.10-13 8,2.10-12 3,5.10-11 1,78.10-10 1,1.10-12 8,3.10-17 1,3.10-20 1,6.10-5 1,0.10-32 5,8.10-19 5,1.10-9 1,1.10-7 1,2.10-10 1,1.10-6 6,0.10-39 -lgT 12,28 11,09 10,46 9,75 11,95 16,08 19,89 4,80 32,00 18,24 8,29 6,96 9,93 5,98 38,22 Tn hp cht CuCO3 CuC2O4 Cu(OH)2 CuS FeCO3 FeC2O4 FeS Fe(OH)3 FePO4 Hg2Cl2 HgO HgS (en) HgS () MgCO3 MgC2O4 Tch s tan (T) 2,5.10-10 3,0.10-8 2,2.10-20 6,3.10-36 3,47.10-11 2,0.10-7 5,0.10-18 3,2.10-38 1,3.10-22 1,3.10-18 3,0.10-26 1,6.10-52 4,0.10-53 2,1.10-5 8,6.10-5 -lgT 9,60 7,50 19,66 35,20 10,46 6,70 17,3 37,50 21,89 17,88 25,52 51,80 52,40 4,67 4,10
BaSO4 CaCO3 CaC2O4 CaCrO4 CaF2 Ca(OH)2 Ca3(PO4)2 CaSO4 CdCO3 CdC2O4 Cd(OH)2 CdS CoCO3 CoC2O4 Co(OH)2 CoS CoS Cr(OH)3 CrPO4 (tm) CrPO4 (lc)
1,1.10-10 4,8.10-9 2,3.10-9 7,1.10-4 4,0.10-11 5,5.10-6 2,0.10-29 9,1.10-6 5,2.10-12 1,5.10-8 5,9.10-15 7,9.10-27 1,4.10-13 6,3.10-8 2,0.10-15 4,0.10-21 2,0.10-25 6,3.10-31 1,0.10-17 2,4.10-23
9,97 8,32 8,64 3,15 10,40 5,26 28,70 5,04 11,30 7,80 14,23 26,10 12,84 7,20 14,80 20,4 24,70 30,20 17,00 22,62
MgF2 MgNH4PO4 Mg(OH)2 Mg3(PO4)2 MnCO3 MnC2O4 MnNH4PO4 Mn(OH)2 MnS NiCO3 NiC2O4 Ni(OH)2 NiS NiS PbCO3 PbC2O4 PbCl2 PbCrO4 Pb(OH)2 PbS
6,5.10-9 2,5.10-13 6,0.10-10 1,0.10-13 1,8.10-11 5,0.10-6 1,0.10-12 1,9.10-13 2,5.10-10 1,3.10-7 4,0.10-10 2,0.10-15 3,2.10-19 1,1.10-24 7,4.10-14 4,8.10-10 1,6.10-5 1,8.10-14 1,1.10-20 2,5.10-27
8,19 12,60 9,22 13,00 10,74 5,30 12,00 12,72 9,60 6,87 9,40 14,70 18,50 24,00 13,13 9,32 4,79 13,75 19,96 26,60
Ph lc 1: Tch s tan ca mt s kt ta (tip)

Tn hp cht PbSO4 PbClF ZnCO3 ZnC2O4 Tch s tan (T) 1,6.10-8 2,8.10-9 1,4.10-11 1,5.10-9 -lgT 7,80 8,55 10,84 8,80 Tn hp cht Zn(OH)2 Zn3(PO4)2 ZnS ZnS Tch s tan (T) 7,1.10-18 9,1.10-33 2,5.10-22 1,6.10-24 -lgT 17,15 32,04 21,60 23,80
Ph lc 2: Hng s axit, hng s baz ca mt s axit, baz

Tn axit Axetic CH3COOH Benzoic C6H5COOH Boric H3BO3 Cacbonic H2CO3 Cloaxetic Cl CH2COOH Etylendiamintetraaxetic (HOOCCH2)2 N-CH2-CH2N(CH2COOH)2 Ka 1,74.10-5 6,2.10-5 Ka1 5,8.10-10 Ka1 4,5.10-7 Ka2 4,8.10-11 1,4.10-3 Ka1 1,0.10-2 Ka2 2,1.10-3 Ka3 5,4.10-7 pKa 4,76 4,21 9,24 6,35 10,32 2,86 1,99 2,67 6,27
Focmic H COOH Oxalic H2C2O4 Phenol C6H5OH Photphoric H3PO4
Ka4 1,1.10-11 1,8.10-4 Ka1 5,6.10-2 Ka2 5,4.10-5 1,0.10-15 Ka1 7,6.10-3 Ka2 6,2.10-8 Ka3 4,2.10-13 Ka1 1,1.10-3 Ka2 4,0.10-6 1,1.10-3 Ka2 1,2.10-2 Ka1 9,1.10-4 Ka2 4,3.10-5 Ka1 7,4.10-4 Ka2 1,8.10-5 Ka3 4,0.10-7
10,95 3,75 1,25 4,27 15,0 2,12 7,21 12,38 2,95 5,40 2,95 1,94 3,04 4,37 3,13 4,76 6,40
o- Phtalic C6H4(COOH)2 Salixylic C6H4(OH)COOH Sunphuric H2SO4 Tartric HOOCCH(OH)CH(OH)COOH Xitric HOOCCH2C(OH)(COOH)CH2COOH
Ph lc 2: Hng s axit, hng s baz ca mt s axit, baz (tip)

Tn baz Amoni hidroxit NH4OH Anilin C6H5NH2 Dimetylamin (C2H5)2NH Hidrazin N2H4 Hidroxylamin NH2OH 8-Hidroxychinolin C9H7ON Piridin C5H5N Kb 1,76.10-5 4,2.10-10 1,1.10-3 9,8.10-7 9,6.10-6 1,1.10-9 1,5.10-9 pKb 4,76 9,38 2,97 6,01 8,02 8,99 8,82
Ph lc 3: Th oxi ho tiu chun ca mt s cht 25oC

Nguyn t Ag Ag AgBr Ag(CN)2AgCl AgI Al3+
+
Dng oxi ho
Al
+ne +e +e +e +e +e +3e
Dng kh Ag Ag + BrAg + 2CNAg + ClAg + IAl
Eo, V +0,7994 +0,071 -0,29 +0,224 -0,152 -1,66
Ba Br Ca Cd Ce Cl Co Cr
Cu
AlF63Ba2+ Br2 Ca2+ Cd2+ Cd (CN)42Cd(NH3)42+ Ce(SO4)32Cl2 Co2+ Co(NH3)62+ Cr3+ Cr2O72- + 14H+ Cu2+ Cu2+ Cu+ Cu (CN)42Cu(NH3)42+ F2
+3e +2e +2e +2e +2e +2e +2e +1e +2e +2e +2e +3e +6e +2e +e +e +2e +2e +2e
Al + 6FBa 2BrCa Cd Cd + 4CNCd + 4NH3 Ce3+ + 3SO422ClCo Co + 6NH3 Cr 2Cr3+ + 7H2O Cu Cu+ Cu Cu + 4CNCu + 4NH3 2F-
-2,07 -2,90 +1,087 -2,87 -0,402 --1,09 -0,61 +1,44 +1,359 -0,28 -0,42 -0,41 +1,33 +0,337 +0,153 +0,521 -0,43 -0,07 +0,287
Ph lc 3: Th oxi ho tiu chun ca mt s cht 25oC (tip)

Nguyn t Fe Dng oxi ho Fe3+ Fe3+ Fe2+ [Fe(CN)6 ]32H+ 2Hg2+ Hg2+ Hg22+ Hg2Cl2 Hg(CN)42I2 I3K+ Mg2+ Mn2+ MnO4- + 8H+ NO3 - + 2H+ NO3 - + 4H+ NO3 - + 10H+ Na+ Ni2+ Ni(NH3)62+ +ne +e +3e +2e +e +2e +2e +2e +2e +2e +2e +2e +2e +e +2e +2e +5e +e +3e +8e +e +2e +2e Dng kh Fe2+ Fe Fe [Fe(CN)6 ]4H2 Hg22+ Hg 2Hg 2Hg + 2ClHg + 4CN2I3IK Mg Mn Mn2+ + 4H2O NO2 + H2O NO + 2H2O NH4+ + 3H2O Na Ni Ni + 6NH3 Eo, V +0,771 -0,036 -0,440 +0,356 0,0000 +0,907 +0,850 +0,792 +0,2680 -0,37 +0,536 +0,545 -2,925 -2,37 -1,19 +1,51 +0,80 +0,96 +0,87 -2,713 -0,23 -0,49
H Hg
I K Mg Mn N Na Ni
Pb
Sn
O2 + 4H+ O2 +2H+ O2 + 2H2O H2O2 + 2H+ O3 + H2O Pb2+ PbBr2 PbCl2 PbI2 S S + 2H+ S4O62SO42- + 8H+ SO42- + 4H2O SO42- + 10H+ Sn2+ Sn4+
+4e +2e +2e +2e +2e +2e +2e +2e +2e +2e +2e +2e +6e +6e +8e +2e +e
2H2O H2O2 4OH2H2O O2 + 2OHPb Pb + 2BrPb + 2ClPb + 2IS2H2S 2S2O32S + 4H2O S + 8OHH2S + 4H2O Sn Sn2+
+1,229 +0,682 +0,401 +1,77 +1,24 -0,126 -0,274 -0,266 -0,0,346 -0,48 +0,14 +0,09 +0,36 -0,75 +0,31 -0,14 +0,15
Ph lc 3: Th oxi ho tiu chun ca mt s cht 25oC (tip)

Nguyn t
2+
Dng oxi ho Zn Zn (CN)42Zn(NH3)42+
Zn
+ne +2e +2e +2e
Dng kh Zn Zn + 4CNZn + 4NH3
Eo, V -0,763 --1,26 -1,04
Ph lc 4: Bc sng nh sng v mu ca chng

Bc sng nh sng (nm) 400 450 450 480 480 490 490 500 500 560 560 575 575 - 590 590 - 625 625 - 750 Mu sc nh sng b hp th Tm Xanh Xanh lc Lc xanh Lc Vng lc Vng Da cam nh sng b sung Vng lc Vng Da cam gch Tm Xanh Xanh lc Lc xanh
Ch thch: nh sng b hp th + nh sng b sung = nh sng trng
B GIO DC V O TO TRNG I HC NNG NGHIP I H NI NGUYN TRNG SN (Ch bin) NGUYN TH HNG LINH, BI TH VNH
GIO TRNH
HO PHN TCH
NH XUT BN NNG NGHIP
B GIO DC V O TO TRNG I HC NNG NGHIP I H NI NGUYN TRNG SN (Ch bin) NGUYN TH HNG LINH, BI TH VNH
GIO TRNH
HO PHN TCH
NH XUT BN NNG NGHIP
H NI - 2007

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B gio dc v o to Trng i hc nng nghip H Ni --------------------------

Pgs.ts. NGUYN TRNG SN (Ch bin) Nguyn Th Hng Linh, Bi Th Vnh

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch1

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch2

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch3

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch4

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch5

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch6

CHNG I CC KHI NIM C BN CA HO PHN TCH

2.1. Phn loi theo bn cht ca phng php phn tch

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch7

2.3. Chn la phng php phn tch

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch9

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch10

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch11

5.1. Phn tch nh tnh cc hp cht v c bng phng php ho hc

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch12

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch13

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch14

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch15

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch16

5.2. Phn tch nh tnh cc hp cht hu c bng phng php ho hc

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch17

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch18

5.3. Phn tch nh tnh cc hp cht bng phng php cng c

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch19

7.1. Dng c thu tinh

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch20

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch21

Hnh H.1.1 Bnh nh mc

Hnh H.2.1 Buret

Hnh H.3a.1 Pipet thng

Hnh H.3b.1 Pipet bu

Hnh H.4.1 ng ong

7.3. Ho cht tinh khit, nc ct

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch22

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch23

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch24

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch25

Chng II PHN TCH KHI LNG

1.1. Phng php tch

1.2. Phng php chng ct hoc t chy

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch26

1.3. Phng php nhit phn

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch27

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch28

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch29

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch30

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch31

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch32

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch33

2.4. Mt s k thut trong phng php phn tch khi lng kt ta

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch34

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch35

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch36

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch37

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch38

2.6. u nhc im ca phng php phn tch khi lng kt ta

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch40

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch41

CHNG II PHN TCH TH TCH

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch42

Trng i hc Nng nghip H Ni Gio trnh Ho Phn tch44

3.1. Phn loi phng php chun theo loi phn ng