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Chng 4. Phng php tnh nng cc cht trong nhng dung dch cn bng n gin Lm Ngc Th

C s ha hc phn tch. NXB i hc quc gia H Ni 2005.

T kho: Thnh phn ho hc, Hng s cn bng, Trng thi cn bng, C s ho phn tch.

Ti liu trong Th vin in t H Khoa hc T nhin c th c s dng cho mc ch hc tp v nghin cu c nhn. Nghim cm mi hnh thc sao chp, in n phc v cc mc ch khc nu khng c s chp thun ca nh xut bn v tc gi.

Mc lc
Chng 4 Phng php tnh nng cc cht trong nhng dung dch cn bng n gin .................................................................................... 2 4.1 Mt s lun im c s ............................................................................... 2 4.1.1 Thnh phn ho hc ca dung dch ......................................................... 2 4.1.2 Tnh cht axit - baz trong cc dung mi khc nhau ............................... 4 4.2 Phng php tnh nng cc cht trong nhng dung dch cn bng n gin.............................................................................................................. 6 4.2.1 Trng thi cn bng................................................................................. 6 4.2.2 Biu thc hng s cn bng .................................................................... 7 4.2.3 Nhng phng php biu th hng s cn bng ...................................... 8 4.2.4 Biu thc hng s cn bng ca nhng phn ng thng gp nht ......... 9

Chng 4 Phng php tnh nng cc cht trong nhng dung dch cn bng n gin
4.1 Mt s lun im c s

Phn ln nhng php nh lng c thc hin trong dung dch. Do , i tng ca ho phn tch bao hm l thuyt v dung dch. Tng quan v nhng lun im c bn ca l thuyt v dung dch c trnh by trong chng ny v cc chng tip theo. 4.1.1

Thnh phn ho hc ca dung dch

Trong ho hc phn tch ngi ta s dng rng ri c dung mi nc v dung mi hu c. Nhng dung mi khng phn cc nh tetraclorua cacbon v cc dn xut halogen ca n c s dng trong trng hp nu chnh cht cn phn tch khng phn cc. Nhng dung mi hu c vi phn cc trung gian c kh nng to lin kt hiro vi nhng cht tan (ru, xeton, ete) c s dng ph bin hn so vi nhng hp cht t phn cc hn, bi v s ln cc cht hu c v cc cht v c u tan c trong chng. Dng nh cc dung dch nc, trong s c dung dch axit v baz v c c s dng ph bin nht trong thc t phn tch. Do , trong khi trnh by lun im chng ta c bit ch n tnh cht ca cc cht tan trong nc. Nhng phn ng trong mi trng phn cc khng nc s c cp n km chi tit hn. 4.1.1.1 Cc cht in li

Cht in li l nhng cht ion ho trong dung mi to thnh mi trng dn in. Cht in li mnh ion ho hon ton, nhng cht in li yu ch ion ho mt phn. Nhng cht in li mnh v yu in hnh c dn ra bng 4.1.

4.1.1.2

Phn loi cc cht in li

Bng 4.1. Nhng cht in li mnh v yu in hnh Cht in li mnh Cht in li yu

1. Cc axit v c: HNO3, HClO4,

H2SO4a, HCl, HI, HBr, HClO3, HB2O3.

1. Nhiu axit v c nh H2CO3, H3BO3,


H3PO4, H2S, H2SO3.

2. Hiroxit ca cc kim loi kim v


kim th.

2. Phn ln cc axit hu c. 3. Amoniac v phn ln cc baz hu c. 4. Halogenua, xianat, thioxianat


Hg, Zn, v Cd.

3. Phn ln cc mui

H2SO4 phn li hon ton thnh ion HSO4 v H3O+ v do c xp vo cc cht in li mnh. Nhng cng cn nhn xt rng ion HSO4 l cht in li yu, ch phn li mt phn. 4.1.1.3 Qu trnh ion ho ca dung mi

Nhiu dung mi in hnh l nhng cht in li yu, nhng phn t ca chng phn ng vi nhau to thnh nhng ion (qu trnh c gi l qu trnh proton phn). Chng ta dn ra mt s v d: 2H2O 2CH3OH 2HCOOH 2NH3 H3O+ + OH
+ CH3 OH2 + CH3O

+ HCOOH2 + HCOO

+ NH4 + NH2

Ion dng to thnh khi nc t phn li c gi l ion hiroxoni. Proton ny lin kt vi phn t nc bng lin kt cng ho tr to nn bi i in t khng phn chia ca oxi. + + Trong dung dch cn tn ti c nhng ion hirat ho mnh hn nh H5 O2 v H7 O3 nhng nhng ion ny km bn hn H3O+. Ion hiro khng hirat ho khng th tn ti trong dung dch nc. nhn mnh bn cao ca proton hirat ho n gin, khi vit phng trnh phn ng vi s tham ra ca proton nhiu nh ho hc s dng k hiu H3O+. cho tin li nhng

ngi khc li k hiu proton bng biu tng H khng k ti mc hirat ho tht s ca n. K hiu n gin ho vic vit phng trnh phn ng c proton tham gia.

4.1.2 Tnh cht axit - baz trong cc dung mi khc nhau


S phn loi mang tnh lch s cc cht thnh axit v baz c hnh thnh trn c s nhng tnh cht c trng ca cc dung dch nc ca nhng hp cht y. S hin mu hoc mu xanh ca qu, mi v xc ca dung dch axit long, v ng v tnh x phng ca cc dung dch baz, s to mui khi tng tc axit vi kim l nhng tnh cht in hnh . Cui th k 19, Arrhenius ngh mt cch phn loi cht ch. ng nh ngha axit l cht cha hiro v phn li trong nc thnh ion hiro v anion; cn baz l hp cht cha nhm hiroxyl, cho ion hiroxyl v cation khi ho tan trong nc. Khi nim rt b ch cho php hnh thnh nhng c s nh lng ca thuyt axit - baz. C th nh gi cng axit - baz theo mc phn li ca chng trong dung dch nc. Ngoi ra, thuyt Arrhenius t c s cho s m t ton hc cn bng thit lp do kt qu tng tc ca axit v baz. Thiu st nghim trng ca thuyt Arrhenius l khng nh gi c vai tr ca dung mi trong qu trnh phn li. Bronsted v mt ngi hon ton c lp vi ng l Lowry (nm 1923) a ra quan nim tng qut hn v axit - baz. Theo thuyt Bronsted - Lowry, axit l cht c kh nng cho proton. Mt proton, ngha l chuyn thnh baz. Baz c gi l baz lin hp vi axit ban u. C th dng phn ng gia axit v nc lm v d in hnh. H2O + axit Baz lin hp + H3O+

Cn nhn mnh rng, nhng tnh cht axit ca mt cht bt k no ch th hin khi c mt cht nhn proton v tng t nh vy, mt cht ch th hin tnh baz khi c mt cht cho proton. Theo thuyt Bronsted - Lowry, c th din t phn ng trung ho bng phng trnh sau: Axit1 + Baz2 HCl + H2O HC2H3O2 + H2O
3 Al(H2O)6 + + H2O H2PO4 + H2O + NH4 + H2O

Baz1 + Axit2 Cl + H3O+


C2H3 O2 + H3O
+

2 Al(OH)(H2O)5 + + H3O

HPO2 + H3O 4

NH3 OH

+ H3O+
+ + NH4

H2O + NH3

5
2 H2O + CO3

OH

+ HCO3

Ta nhn thy rng axit c th l anion, l cation hoc hp cht trung ho in. R rng rng, nc ng vai tr cht nhn proton (baz) i vi nm hp cht u v ng vai tr cht cho proton (axit) i vi hai hp cht cui cng. Nhng dung mi c c tnh axit v tnh baz c gi l dung mi lng tnh. Axit (v c baz) khc bit nhau v c mc tng tc vi dung mi. V d, phn ng gia axit clohiric v nc, thc t xy ra n cng, do axit clohiric thuc loi axit mnh trong dung mi nc. Axit axetic v ion amoni phn ng vi nc mc yu hn, do hai cht ny l hai axit yu. Mc tng tc ca axit tan (hoc baz) vi dung mi, thc cht tu thuc vo kh nng cho hoc nhn proton ca n. V d, axit pecloric, clohiric, bromhiric trong dung dch nc thuc loi axit mnh. Nu ly axit axetic (bng axit axetic tinh khit 100%, thng c gi l axit axetic bng; n c kt tinh 16,7oC dng bng; lng nh tp cht ca nc lm h im ng bng xung r rt) lm dung mi thay cho nc, l cht nhn proton yu hn th ch c axit pecloric phn li hon ton trong n thnh ion v l axit mnh. Qu trnh phn li c th din t bng phng trnh: HClO4 + HC2H3O2 Axit1 + yu. Theo thuyt ca Bronsted - Lowry, nhng cht cho proton mnh nht (ngha l nhng axit mnh nht) cho proton to thnh nhng cht nhn proton yu nht (nhng baz lin hp yu nht). Tr li phn ng ca axit clohiric, axit axetic v ion amoni vi nc, ta thy rng ion clorua l baz yu nht, ion axetat l baz mnh hn, cn amoniac l baz mnh nht. L thuyt tng qut v dung dch bao hm khng ch cc cht c kh nng cho hoc nhn proton (axit v baz theo Bronsted - Lowry), m cn c m rng cho c nhng hp cht khng nht thit phi cha proton. ng dng cho nhng h nh th, l thuyt proton phn t ra c bit c ch. Trong trng hp ny, axit l cht bt k hoc l c cha trong thnh phn ca mnh cation c trng i vi mt dung mi nht nh hoc l phn ng vi dung mi to thnh ion . Mt cch tng t, baz l cht cho anion c trng i vi dung mi cho. Cn c mt quan im tng qut hn v bn cht ca axit v baz do Lewis a ra. ng nh ngha axit l cht nhn i in t v baz l cht cho i in t. Quan im ca Lewis cn i xa hn, khng gn cht nhng tnh cht axit - baz ca cc cht vi s c mt proton trong chng v do m rng ng k phm vi ca nhng qu trnh c th xp vo loi phn ng axit - baz. Quan nim ca Lewis thun li cho vic gii thch c ch phn ng hu c v Baz2
ClO4 + + H2C2H3 O2

Baz1 + Axit2

Cc axit clohiric, bromhiric trong axit axetic bng ch phn li mt phn v l cc axit

phn ng to phc. Cn vi phn ng axit - baz trong ho phn tch, thuyt Bronsted - Lowry kh nng gii quyt cc vn l thuyt v thc nghim. Khi xem xt cc vn axit - baz chng ta s da trn nhng khi nim ca Bronsted Lowry v s dng k hiu H3O+. Mt khc, khi vit phng trnh ho hc hoc l trong cc tnh ton v quan h trng lng, trong proton c ngha H+ l k hiu thun li hn cng s c s dng.

4.2 Phng php tnh nng cc cht trong nhng dung dch cn bng n gin
Phn ln cc phn ng c s dng trong ho phn tch u nhanh chng t ti trng thi cn bng ho hc l trng thi m cc cht phn ng v sn phm ca phn ng c t l xc nh v khng i. Bit nhng mi tng quan trong nhng iu kin thc nghim khc nhau, trong phn ln trng hp c th gii quyt c vn , phn ng c thun li cho mc ch phn tch khng v c vn la chn nhng iu kin cho php lm gim n cc tiu sai s phn tch. Biu thc i vi hng s cn bng l phng trnh i s, trong nng ca cc cht phn ng v sn phm ca phn ng lin h vi nhau qua mt vi i lng gi l hng s cn bng. Nh ho hc cn phi bit khai thc thng bo c li t hng s cn bng. Trong chng ny chng ta s nghin cu nhng tnh ton dng cho nhng h c mt cn bng chim u th. Nhng phng php tnh ton cn bng trong nhng h phc tp s c xt ti sau.

4.2.1 Trng thi cn bng


V d, chng ta xt cn bng: 2Fe3+ + 3I
2Fe2+ + I3

(4.1)

V tc v chiu su ca phn ng ny v bn phi c th d dng xt on theo mu da cam, ca ion triioua ( nng thp, ba cht cn li ca phn ng thc t khng mu). Nu, v d, thm 2 mmol st (III) vo mt lt dung dch cha 3 mmol ioua kali, mu xut hin ngay sau mt giy hoc t hn, cng mu tr thnh hng nh theo thi gian. iu chng t rng nng triioua khng bin i. Dung dch vi cng mu nh vy (v do , vi nng triioua nh vy) c th iu ch c bng cch thm 2 mmol st (II) vo mt lt dung dch cha 1 mmol ion triioua. Trong trng hp ny thy cng mu b gim i nhanh chng do kt qu ca phn ng:
2Fe2+ + I3

2Fe3+ + 3I

(4.2)

C th ly cu t ca phn ng c trong nhng t hp khc nhng nhng dung dch thu c th ng nht nh va m t. Khi thc hin ch i hi mt iu kin: lng cc thuc th thm vo trong mt lt dung dch phi c t l sau y:
S mmol Fe2+ = 2 s mmol I3

S mmol Fe3+ = 2/3 s mmol I S mmol Fe3+ + s mmol Fe2+ = 2,00 V d, thu c mt dung dch ng nht vi dung dch m t, c th trn 0,8 mmol st (II), 1,2 mmol st (III), 0,4 mmol ion triioua v 1,8 mmol kali ioua trong mt lt dung dch. Nhng v d dn ra ch r mi quan h nng trng thi cn bng ho hc, ngha l trng thi cn bng khng ph thuc vo con ng t ti trng thi . Mt khc, d dng ch ra rng, mi quan h nng bin i di tc dng ca mt s yu t. V d, khi bin i nhit , p sut (nu cht phn ng hoc sn phm phn ng l kh) hoc nng tng qut ca mt trong s cc cu t. Nhng bin i c th d on mt cch nh tnh trn c s quy tc Le Chatelier: Cn bng ho hc lun lun chuyn v pha chng li tc dng p t ln n. V d nh khi nng nhit s dn ti s bin i nng km theo s hp th nhit; s lm tng p sut s dn ti s to thnh cc cht c th tch chung nh. Trong ho hc phn tch, hiu ng quan trng nht l hiu ng c gy nn do s thm vo hn hp phn ng mt lng b sung ca mt trong cc cht tham gia phn ng. Trong trng hp ny, cn bng chuyn v pha lm mt i mt phn cht thm vo. V d, i vi cn bng ta ang nghin cu, thm st (III) vo s lm tng cng mu ca ion triioua v lm tng lng st (II) to thnh; ngc li, thm st (II) vo s gy nn hiu ng ngc li. Chuyn dch cn bng do bin i lng ca mt trong cc cht tham gia phn ng c gi l hiu ng tc dng trng lng. Nu nh c th nghin cu mt h bt k mc phn t chng ta s pht hin c rng, tng tc gia cc cht tham gia phn ng khng dng li ngay c khi cn bng thit lp. S hng nh ca t l nng ta quan st thy l kt qu ca s cn bng gia tc phn ng thun v phn ng nghch. iu c ngha l, cn bng ho hc l qu trnh ng hc.

4.2.2 Biu thc hng s cn bng


m t nh lng nh hng ca nng hoc p sut, nu cc cht phn ng trng thi kh, n trng thi cn bng ho hc, thun tin nht l s dng hng s cn bng. C th d dng rt ra biu thc hng s cn bng t nhng khi nim nhit ng. Hng s cn bng c ngha thc t quan trng bi v n cho php nh ho hc tin on hng v chiu su ca phn ng ho hc. Nhng cn thit phi nhn xt rng, biu thc hng s cn bng khng cho mt thng tin no v tc phn ng.

4.2.3 Nhng phng php biu th hng s cn bng


C hai phng php bin th hng s cn bng: cch biu th chnh xc (c gi l cch biu th nhit ng hc) v cch biu th gn ng, ch ng trong iu kin rt gii hn. Nhng nhng hng s gn ng li c ng dng rng ri bi v s dng chng rt n gin, mc d c kh nng phm sai s. 4.2.3.1 Nhng gi thit c chp nhn khi rt ra biu thc gn ng cho hng s cn bng Khi rt ra h thc gn ng cho hng s cn bng, ngi ta gi thit rng nng ca ion hoc phn t l yu t ng nht th hin nh hng ca chng n trng thi cn bng, ngha l mi ht x s mt cch c lp vi ht bn cnh. V d, trong phn ng (4.1) ngi ta gi thit rng, nh hng ca mi ion st (III) n trng thi cn bng l ng nht trong nhng dung dch rt long (khi m ion ch yu b bao quanh bi phn t nc trung ho) v c trong nhng dung dch rt c (khi m ngay st ion c nhng ht tch in khc). Dung dch hoc kh c nhng ion hoc phn t x s mt cch c lp i vi nhau c gi l dung dch l tng hoc dung dch tht. Dung dch l tng v tnh cht l tng rt t gp trong thc t. 4.2.3.2 Biu thc gn ng cho hng s cn bng

Chng ta xt trng hp tng qut ca cn bng ho hc: mM + nN pP + qQ (4.3)

y nhng ch hoa k hiu cc cht tham gia phn ng, cn nhng ch thng l h s hp thc. Phng trnh ch r rng m mol cht M phn ng vi n mol cht N to thnh p mol cht P v q mol cht Q. Hng s cn bng ca phn ng ny c biu din nh sau:
K=

[P ]p [Q ]q [ M]m [N ]n

(4.4)

y du ngoc vung l k hiu biu din nng phn t ca cc cht tan hoc p sut ring phn trong kh quyn nu cht phn ng l kh. Trong phng trnh (4.4), K l i lng bng s, ph thuc vo nhit , c gi l hng s cn bng. Nng sn phm phn ng, vit di dng phng trnh (4.3), c t t s v nng cc cht ban u c t mu s. Mi nng u c nng lu tha ln bc bng h s hp thc trong phng trnh phn ng. H qu l thuyt ca biu thc hng s cn bng ch r rng, trong cc du ngoc vung l nng tc thi t c trng thi cn bng l ng ch khng phi l nng khng thay i. mu s ca biu thc l nng cht trng thi tiu chun. Dung dch 1,00 mol/l ca cht tan c xem l trng thi tiu chun ca n. i vi nguyn t hoc cc hp cht tinh khit th l trng thi (rn, lng hoc kh) ca n 25oC v p sut 1 at. V d, nu P trong phng trnh (4.4) l cht tan:

[P] =

Nng P, mol/l 1, 00 mol/l

mu s l nng cht tan trng thi chun. H qu quan trng ca tnh tng i ca [P] l tnh khng th nguyn ca i lng ny cng nh ca hng s cn bng. Phng trnh (4.4) c th d dng rt ra t nhng khi nim nhit ng hc vi gi thit l cc cu t ca phn ng l l tng . Hng s cn bng nhit ng, phng trnh (4.4), c s dng xc nh thnh phn gn ng ca cc dung dch long trng thi cn bng. nh gi chnh xc hn cn phi s dng hng s nhit ng (hng s nhit ng c xt ti chng 5). Nhng tnh ton theo cc hng s gn ng khng phc tp v trong nhiu trng hp cho cc nh khoa hc thng tin kh v h.

4.2.4 Biu thc hng s cn bng ca nhng phn ng thng gp nht


Trong mc ny chng ta s xt nhng loi cn bng thng gp nht trong ho phn tch v nu ln nhng c im ca nhng hng s tng ng . 4.2.4.1 S phn li ca nc

Nhng dung dch nc lun lun c mt lng nh cc ion hiroxoni v hiroxyl do s phn li ca nc theo phn ng: 2H2O H3O+ + OH (4.5)

hnh dung hng s cn bng ca phn ng ny, chng ta s dng phng trnh (4.4):
H3 O+ OH K= H2O] [

Trong cc dung dch long trong nc, nng nc rt ln so vi cht tan nn c th xem l hng nh. V d, nu cho 0,1 mol hiro clorua sc qua mt lt nc [1000 g : 18 g/mol = 55,6 mol H2O], cn bng (4.5) chuyn v bn tri v s mol nc khng phn li tng t 55,6 n 55,7; nh vy, nu nng axit clohiric khng qu ln, nng nc r rng khng bin i. Do , [H2O] trong phng trnh (4.5), trong phn ln trng hp c th xem l i lng hng nh; khi c th vit: K[H2O]2 = K H2O = [H3O +][OH] y hng s K H2O c gi l tch s ion nc . (4.6)

10

25 C tch s ion nc c gi tr bng s l 1,01.10 ( thun tin chng ta thng s dng i lng gn ng K H2O = 1,00.1014). S ph thuc ca hng s vo nhit c dn ra bng 4.1. Nh tch s ion nc ta d dng tnh c nng cc hiroxyl v hiroxoni (ion hiro) trong cc dung dch nc. Bng 4.1 Nhit , oC 0 25 50 100
K H2 O

14

0,114.1014 1,010.1014 5,470.1014 49,000.1014

V d: Tnh nng ion hiro v ion hiroxyl trong nc nguyn cht 25oC v 100oC. V OH v H3O+ c to thnh ch l do s phn li ca nc nn nng ca chng phi bng nhau: [H3O +] = [OH] Thay vo phng trnh (4.6) ta c: [H3O+]2 = [OH]2 = K H2O [H3O+] = [OH] = K H2O 25oC [H3O+]2 = [OH]2 = 1,00.1014 = 1,00.107 ion.g/l = 7,00.107 ion.g/l

100oC [H3O+]2 = [OH]2 = 49.10 14

V d: Tnh nng ion hiro v ion hiroxyl trong dung dch NaOH 0,200M trong nc. V natri hiroxit l cht in li mnh, s ng gp ca n vo nng ion hiroxyl l 0,200M. S phn li ca nc cng to thnh nhng ion hiroxyl lng bng lng ion hiro. Do c th vit: [OH] = 0,200 + [H3O+] y [H3O+] l phn ng gp do dung mi phn li vo nng tng cng ca ion hiroxyl. So vi 0,200M nng ion OH ca nc nh, do :

11

[OH] 0,200 ion.g/l By gi chng ta c th tnh nng ion hiro theo phng trnh (4.6):
H3 O+ = 1,00.10 0,200
14

= 5,00.1014 ion.g/l

Nhn thy rng, s gn ng: [OH] = 0,200 + 5,00.1014 0,200 ion.g/l khng dn n sai s ng k. 4.2.4.2 Cn bng trong dung dch bo ha cht in li t tan

Trong dung dch nc bo ho mui t tan, mt hoc mt s cn bng c thit lp. V d, trong dung dch bo ho bc clorua: AgCl(r) AgCl(n) AgCl(n) Ag+ + Cl

y, AgCl(n) l nhng phn t khng phn li trong dung dch. C th din t hng s cn bng ca qu trnh u tin nh sau:
K=

[ AgCl ]n [ AgCl ]r

(4.7)

Nng AgCl tng rn l mt hng s bi v nng ca hp cht trng thi rn khng bin i (gi tr ca hng s ny theo nh ngha, bng 1,00). T y: K[AgCl]r = K1 = [AgCl]n (4.8)

T phng trnh (4.8) r rng l nng AgCl trong dung dch bo ho l khng i mt nhit nht nh. Hng s cn bng ca phn ng th hai c din t nh sau:
Ag + Cl K1 = [ AgCl ]n

(4.9)

thun tin ta nhn phng trnh (4.8) vi (4.9) v rt gn [AgCl]n: K1K2 = T = [Ag+][Cl] (4.10)

12

Tch s ca hai hng s, T, c gi l tch s tan. Nh vy, tch s tan l hng s cn bng ca phn ng tng cng: AgCl(r) Ag+ + Cl

Cn nhc mt iu rt quan trng l, cc phng trnh (4.8) v (4.10) ch dng c cho cc dung dch bo ho nm cn bng vi cht rn d khng tan. Phn ln cc mui v c t tan, thc t phn li hon ton trong cc dung dch nc, do so vi nng ca cc ion, nng ca cc phn t khng phn li gn bng khng (1) . iu kin , phn ng tng cng m t mt cch thch hp nht cn bng ca phn ng ho tan. Do nguyn nhn ny nn i vi phn ln cc cht v c, trong cc ti liu ch dn ra mt hng s (tch s tan) (xem mc lc). V d, khng c c s cho rng trong dung dch bo + ho bari ioat c Ba(IO3)2 hoc BaIO3 khng phn li. Do , cn bng: Ba(IO3)2 (r)
Ba2+ + 2IO3

S l cn bng duy nht tn ti v do ch cn ch ti hng s cn bng , ngha l:


[Ba2+][ IO3 ]2 = T

Di y dn ra nhng v d in hnh s dng biu thc tch s tan. Mt s v d khc s c xt ti trong chng 5 v 8. V d 1: C th ho tan bao nhiu gam bari ioat trong 500 ml nc 25oC? Cho bit tch s tan ca Ba(IO3)2 bng 1,57.109. Ba(IO3)2
(r)

Ba2+ +

2IO3

[Ba2+][IO3]2 = 1,57.109 = T T phng trnh m t cn bng, mi mol Ba(IO3)2 tan, phn li to thnh mt mol Ba2+, ngha l: tan (tnh bng mol) ca Ba(IO3)2 = [Ba2+] Mt khc, r rng l, nng ioat ln hn nng bari hai ln.
[ IO3 ] = 2[Ba2+]

Thay nng ioat bng nng Ba2+ vo phng trnh hng s cn bng ta c: [Ba2+](2[Ba2+])2 = 1,57.109
(1)

Quan im ny rt ph bin, tuy nhin khng phi lc no cng ng. C nhiu mui t tan v t phn li. Trong s , v

d c dy sunfua.

13

hoc: tan = 7,3.104 M

[Ba2+] = (1,57.109/4)1/3 = 7,3.104 mol/l

bit c tan ca Ba(IO3)2 tnh bng gam trong 500 ml, ta vit: tan = 7,3.104 [mmol Ba(IO3)2/ml] 500ml [0,487g/mmol Ba(IO3)2] = 0,178g/500ml y 0,487 l mili trng lng phn t ca Ba(IO3)2 . V d sau y minh ho nh hng ca ion cng tn c nguyn l Le Chatelier d on. V d 2: Tnh tan phn t ca Ba(IO3)2 trong dung dch Ba(NO3)2 0,02M.
Trong trng hp ny cn tnh tan theo [ IO3 ]:

tan ca Ba(IO3)2 =

1 [ IO3 ] 2

Ba(NO3)2 v Ba(IO3)2 cng sinh ra ion bari trong dung dch. Phn ng gp ca cht th nht l 0,02M, cn phn ng gp ca cht th hai bng tan phn t hoc bng [Ba2+] = 0,02M +
1 [ IO3 ] 2 1 [ IO3 ]. 2

Thay th i lng vo phng trnh tch s tan: (0,02 +


1 [ IO3 ]) [ IO3 ] = 1,57.109 2

Mun c nng chnh xc [ IO3 ] cn gii phng trnh bc 3. n gin cc php tnh i s, xut hin tm cch gii gn ng. i lng T nh nn tan ca Ba(IO3)2 nh, do c th gi nh rng, nng ion bari, thu c do s ha tan Ba(IO3)2 rn khng

ng k so vi nng ion bari t Ba(NO3)2. Ni cch khc,


1 [ IO3 ] 0,02. 2

1 [ IO3 ] << 0,02, v vy 0,02 + 2

Phng trnh dn ra trn y, lc ny c rt gn :


0,02[ IO3 ]2 = 1,57.109 [ IO3 ] = 2,8.104 mol/l

Gi thit rng:

14

[0,02 +

1 .2,8.104 ] 0,02 2

khng dn ti sai lm nghim trng, bi v thnh phn th hai ch bng khong 0,7% ca 0,02. Thng gi thit loi ny c th c coi nh l ng n nu s khc bit nh hn 5 10%. Vy: tan ca Ba(IO3)2 =
1 1 [ IO3 ] = .2,8.104 = 1,4.104 M 2 2

So snh kt qu thu c vi kt qu tan ca ioat bari trong nc nguyn cht, chng ta nhn thy rng s c mt mt lng nh ion ng dng h thp tan phn t ca Ba(IO3)2 xung khong 5 ln. V d 3: Ly mt v d khc phc tp hn, tnh tan ca Ba(IO3)2 trong dung dch thu c bng cch trn 200 ml dung dch Ba(NO3)2 0,01M vi 100 ml dung dch NaIO3 0,1M. Trc ht chng ta cn xc nh xem trong s cc thuc th, thuc th no d? Lng ban u ca cc thuc th l nh sau: Lng mmol Ba2+ = 200ml.0,01mmol/ml = 2,00 Lng mmol IO3 = 100ml.0,1mmol/ml = 10,00. Sau khi kt ta Ba(IO3)2:
IO3 d = 10,0 2(2,00) = 6,00 mmol

T y:

[ IO3 ] = 6,00mmol/300ml = 0,02 M

Cng nh trong v d u tin: tan phn t ca Ba(IO3)2 = [Ba2+] Nhng trong trng hp ny:
[ IO3 ] = 0,02 + 2[Ba2+]

y 2[Ba2+] l phn ng gp ca tan kt ta vo nng ioat. Sau khi gi thit rng:


[ IO3 ] 0,02

C th nhn c li gii s b:

15

tan ca Ba(IO3)2 = [Ba2+] =

T
2 IO 3

1,57.10 9 0,02
2

= 3,9.106

Gi thit ra khi tnh ton l hon ton chp nhn c. So snh nhng kt qu thu c trong hai v d trn, ta nhn thy rng d ioat lm gim tan Ba(IO3)2 mc ln hn so vi s d nh vy ca ion bari. 4.2.4.3 S phn li ca axit yu v baz yu

Khi ho tan axit yu hoc baz yu trong nc, xy ra s phn li mt phn. V d i vi axit nitr ta c th vit: HNO2 + H2O
H3O+ + NO2

H3O+ NO2 Ka = [HNO2 ]

y Ka l hng s phn li axit ca axit nitr. Hng s phn li baz ca amoniac c biu din tng t: NH3 + H2O
+ NH4 + OH

NH4 + OH Kb = [NH3 ]

Ta nhn thy rng, nng nc khng tham gia vo mt phng trnh no trong s cc phng trnh trn. Cng nh i vi tch s ion nc, ngi ta chp nhn rng nng dung mi l i lng ln v hng nh, do bao gm hm trong hng s cn bng Ka v Kb . Quan h gia hng s phn li ca mt cp axit - baz lin hp. Chng ta xt biu thc hng s phn li ca amoniac v axit lin hp ca n l ion amoni. C th vit: NH3 + H2O NH4+ + OH

NH4 + OH Kb = [NH3 ]

NH4+ + H2O

NH3 + H3O+

16 Ka =

[NH3 ] H3O+
NH4 +

Nhn hai biu thc, ta c:


KaK b =

[NH3 ] H3O+
NH4 +

NH4 + OH = H O+ OH 3 [NH3 ]

Bi v: [H3O+][OH] = Kn KaKb = Kn (4.11)

Mi quan h ng i vi tt c cc cp axit - baz lin hp. Trong phn ln cc bng hng s phn li, ngi ta a ra hoc hng s axit hoc hng s baz lin hp, bi v d dng tnh mt trong hai hng s theo gi tr ca hng s kia bng phng trnh (4.11). ng dng ca hng s phn li axit. Hng s phn li ca nhiu axit yu ph bin nht c dn ra ph lc IV. Nhng hng s ny c s dng ph bin tnh nng ion hiro v hiroxyl trong dung dch ca cc axit v baz yu. V d, khi ho tan mt axit yu HA trong nc ta c, cn bng: HA + H2O H3O+ + A

A H3 O+ Ka = [HA ]

Ngoi ra ion hiro cn phn li t nc: 2H2O H3O+ + OH

Thng nhng ion hiro sinh ra do phn ng th nht ngn cn s phn li ca nc n mc c th b qua, nng ion hiro v hiroxyl phn li ra t nc. iu kin , r rng l, axit phn li, c mi ion H3O+ to thnh mt ion A: [H3O+] [A] (4.12)

Ngoi ra, tng nng phn t ca axit yu v baz lin hp ca n phi bng nng ca phn t axit ban u bi v trong dung dch khng c cc cht khc cho A. Do : CHA = [A] + [HA] Sau khi thay phng trnh (4.12) vo (4.13) v chuyn v ta c: (4.13)

17

[HA] = CHA [H3O+]

(4.14)

Nu thay th [A] v [HA] bng cc biu thc ca chng t cc phng trnh (4.12) v (4.14) th hng s phn li axit c dng:
H3O+ Ka = CHA H3 O+
2

(4.15)

Phng trnh (4.15) c th chuyn thnh: [H3O+]2 + Ka[H3O+] KaCHA = 0 Gii phng trnh bc hai trn ta thu c:
H3O+ = K a + (K a + 4K aCHA 2

(4.16)

Gi thit rng [H3O+] nh hn rt nhiu so vi CHA th phng trnh (4.15) c th rt gn: [H3O+] = K a CHA (4.17) Sai s gy ra do gi thit ny s cng ln nu nng axit cng nh v hng s phn li cng ln. S khng nh ny c chng minh bng nhng d liu ca bng 4.2. Ta nhn thy rng, sai s do gi thit nu trn gy ra khong 0,5% khi t s (CHA/Ka) = 104. Sai s ny tng n khong 1,6% khi t s ny bng 103 v n 5% nu t s bng 102 v n 17% nu t s bng 10. Nhng d kin ny c dn ra bng th trn hnh 4.1. ng ch l, khi t s (CHA/Ka) << 1, nng ion hiro tnh c theo phng trnh gn ng s khng dn ti sai s c ngha. Trong thc t, thng ngi ta thc hin s rt gn gi thit v thu c gi tr gn ng ca [H3O+], sau cn phi so snh gi tr ny vi nng CHA trong phng trnh (4.15). Nu gi tr [H3O+] thu c lm bin i [HA] mt i lng nh hn sai s cho php trong cc php tnh (trong sch ny, phn ln trng hp l 5 10%).

18

Sai s tng i gy nn do gi thit CHA [H3O+] CHA (phng trnh (4.15)) c th xem nh tho mn. nhn c gi tr [H3O+] chnh xc hn cn gii phng trnh bc 2. V d: Hy tnh nng ion hiro trong dung dch axit nitr 0,12 M trong nc. Cn bng c bn trong dung dch: HNO2 + H2O Trong ph lc IV ta tm thy:
H3 O+ NO2 = 5,1.104 Ka = [HNO2 ]
H3O+ + NO2

V: T :

[H3O+] = [ NO2 ]; [HNO2] = 0,12 [H3O+]

H3 O+ = 5,1.104 + 0,12 H3 O

Gi thit rng [H3O+] << 0,120 mol/l ta tm c:


H3 O+ = 0,120 5,1.10 4 = 7,8.10 3 M

By gi cn kim tra tnh ng n ca gi thit (0,12 0,0078) 0,12; s khc nhau khong 7%. Sai s tng i cho php tnh [H3O+] nh thua i lng , v log(CHA/Ka) =

19

2,4. T hnh 4.1, ta thy rng sai s khong 3%. Nu cn chnh xc cao hn, cn phi gii phng trnh bc hai v ta thu c gi tr 7,6.103M. Bng 4.2 Sai s gy ra do gi thit cho rng H3O+ nh so vi CHA khi s dng phng trnh (4.15) i lng Ka i lng CHA i lng [H3O ] tnh theo gi thit
+

i lng [H3O+] tnh theo phng trnh chnh xc

Sai s (%)

1,00.102

1,00.103 1,00.102 1,00.101

3,16.103 1,00.102 3,16.102

0,92.103 0,62.102 2,70.102

244 61 17

1,00.104

1,00.104 1,00.103 1,00.102 1,00.101

1,00.104 3,16.104 1,00.103 3,16.103

0,62.104 2,70.104 0,95.103 3,11.103

61 17 5,3 1,6

1,00.106

1,00.105 1,00.104 1,00.103 1,00.102 1,00.101

3,16.106 1,00.105 3,16.105 1,00.104 3,16.104

2,70.106 0,95.105 3,11.105 9,95.105 3,16.104

17 5,3 1,6 0,5 0,0

V d: Tnh nng ion hiro trong dung dch hiroclorua anilin C6H5NH3Cl 2,0.104 M.
+ Trong dung dch nc, hp cht phn li hon ton ra Cl v C6 H5 NH3 . Axit yu + C6 H5 NH3 phn li nh sau: + C6 H5 NH3 + H2O

C6H5NH2 + H3O+

20 H3O+ [C6 H5 NH2 ] Ka = + C6H5NH3


+ Trong ph lc IV khng c hng s phn li ca C6 H5 NH3 nhng trong ph lc V ta tm thy hng s baz ca anilin C6H5NH2.

C6H5NH2 + H2O

+ C6 H5 NH3

+ OH

Kb = 3,94.1010 tnh Ka chng ta s dng phng trnh (3.11):


Ka = 1,00.10 14 3,94.10
10

= 2,54.105

Lm nh trong v d trc: [H3O+] = [C6H5NH2] [C6H5NH2] = 2,0.104 [H3O+] Gi thit rng [H3O+] << 2,0.104. Thay gi tr gn ng ca [C6H5NH2] vo biu thc hng s phn li:
H O+ 3 = 2,54.10 5 2,0.10 4
2

Ta tm thy:

[H3O+] = 7,1.105 mol/l.

So snh nhng i lng 7,1.105 v 2,0.104 ta thy rng, khi tnh [H3O+] ta b qua sai s ln (s dng hnh 4.1 ta tm thy sai s ln hn 20%). Sai s ln n nh vy nn phi s dng phng trnh chnh xc hn.
H O+ 3 = 2,54.10 5 2,0.10 4
2

Sau khi bin i thnh: [H3O+]2 + 2,54.105[H3O+] 5,08.109 = 0 Gii ra ta thu c:

21
5 5 2 9 H3 O+ = 2,54.10 + (2,54.10 ) + 4 5,08.10 2

[H3O+] = 6,0.105 mol/l ng dng hng s phn li ca baz yu. Nhng tnh ton dn ra trong cc phn trc c th d dng vn dng tnh nng ion hiroxyl trong cc dung dch baz yu. Dung dch nc ca amoniac biu l tnh baz trong phn ng: NH3 + H2O NH4+ + OH

D dng ch ra rng, ht chim u th trong dung dch l NH3. Hn na, i khi ngi ta gi nhng dung dch l dung dch hiroxit amoni theo thut ng cn c cng nhn cho n khi NH4OH cn c coi l dng cha phn li ca baz ch khng phi l NH3. Theo nh lut tc dng khi lng:
NH4 + OH Kb = NH3 ] [

Gi tr hng s cn bng tan khng ph thuc vo cng thc ca hp cht mu s, l NH3 cng thc ng hn hay NH4OH l cng thc dng trc y. V d: Hy tnh nng ion hiro trong dung dch NH3 0,075M. Cn bng chim u th trong dung dch l: NH3 + H2O NH4+ + OH

T cc bng ta tm thy hng s phn li ca baz (ph lc V):


NH4 + OH = 1,76.105 [NH3 ]

T phng trnh phn li trn: [NH4+] = [OH] v [NH4+] + [NH3] = CNH3 = 0,075 Thay th [OH] bng [NH4+] v bin i phng trnh th hai ta tm c: [NH3] = 0,075 [OH]

22

Thay cc gi tr vo phng trnh hng s phn li:


OH = 1,76.105 2 7,5.10 OH
2

Nu gi thit rng [OH] << 7,5.102, phng trnh trn c rt gn: [OH]2 [OH] = 1,15.103 mol/l V d: Tnh nng ion hiroxyl trong dung dch hippoclorit natri 0,01M. T phn ng tng tc gia OCl v nc: OCl + H2O c th vit:
Kb =

(7,5.102)(1,76.105)

HOCl + OH

[HOCl] OH
OCl

Trong ph lc V khng gi tr Kb nhng trong ph lc IV chng ta tm c hng s phn li axit ca HClO l 3,0.108. S dng phng trnh (4.11) chng ta c:
Kb = K n 1,00.1014 = = 3,3.10 7 8 Ka 3,0.10

Gii nh trong v d trn: [OH] = [HOCl] [OCl] + [HOCl] 0,01 nn: [OCl] = 0,01 [OH] 0,01 mol/l Gi thit rng [OH] << 0,01 mol/l v thay vo phng trnh hng s cn bng ta c:
OH = 3,3.107 0,01
2

[OH] = 5,7.105 mol/l

23

R rng l, gi thit khng dn ti sai s ln. 4.2.4.4 S to phc

Phn ng to phc ca cc ion phc tan l loi phn ng phn tch quan trng. Chng ta dn ra hai v d: Fe3+ + SCN Fe(SCN)2+

Fe(SCN)2+ K= Fe3+ SCN

Zn(OH)2 (r) + 2OH

Zn(OH)2 4

Zn(OH)2 4 K= 2 OH

K l hng s to phc hoc hng s bn ca phc. Hng s khng bn m t cn bng phn li ca ion phc. Hng s khng bn l nghch o ca hng s bn, v d:
K kb
3+ 1 Fe SCN = = K Fe(SCN)2+

Cn nhn xt rng, hng s bn ca Zn(OH)2 ch dng cho dung dch bo ho hiroxit 4 km t tan. ng thi cng cn nu r nng hiroxit km khng tham gia vo phng trnh hng s bn bi v nng cht rn l hng nh v bao hm trong hng s bn. Vi quan im nh vy, tt c mi lp lun tng t s c vn dng i vi phng trnh tch s tan. Hng s bn ca nhiu ion phc bit c dn ra trong ph lc VI. ng dng hng s bn s c minh ha bng v d sau y: V d: C th nhn thy mu thng thng ca FeSCN2+ trong dung dch nc nng phc 6.106M hoc ln hn. Nng KSCN nh nht, cn thit l bao nhiu pht hin 1 mg/ml st (III) trong nc t nhin. Chng ta tm c trong ph lc VI. Fe3+ + SCN K = 1,4.102 ngha l: Fe(SCN)2+

24 FeSCN2+ = 1,4.102 Fe3+ SCN

Chng ta biu din nng st (III) bng mol:


CFe3+ = 1mg 1 1 = = = 1,8.105 M 1 1000mg/g 55,8g/trng lng mol

iu kin gii hn pht hin ca phc [FeSCN2+] = 6.106 M. trng thi cn bng, st (III) hai trng thi: Fe3+ v FeSCN2+. Do :
CFe3 + = 1,8.10 M = [Fe ] + [FeSCN ]
5 3+ 2+

[Fe3+] = 1,8.105 [FeSCN2+] = 1,8.105 6.106 = 1,2.105 M Thay nng tm c vo phng trnh hng s bn ta xc nh c nng SCN cn thit.
6.10 6 = 1,4.102 [SCN ] = 0,0036M 5 1,2.10 SCN

Nh vy, nh dung dch KSCN c nng 0,0036 M hoc ln hn c th pht hin st (III) c nng 1 mg/ml hoc ln hn theo phn ng to thnh FeSCN2+. 4.2.4.5 Phn ng oxi ho kh

C th biu din hng s cn bng ca phn ng oxi ho kh bng phng php thng thng. V d: 6Fe2+ + Cr2O72 + 14H3O+
6

6Fe3+ + 2Cr3+ + 21H2O


2 14

K=

Fe3+ Cr3+
6

Fe2+ Cr O 2 H O+ 2 7 3

Nh trc y chng ta nhn xt, nng nc khng tham gia vo phng trnh. Ni chung, cc bng hng s cn bng ca cc phn ng oxi ho kh khng c thit lp bi v d dng thu c cc hng s ny t cc hng s c bn hn l th in cc tiu chun. Nhng tnh ton chi tit s c xt ti trong chng 13.

25

4.2.4.6

S phn b cht gia hai cht lng khng ho ln

Cn mt dng cn bng na c s dng trong phn tch l s phn b cht gia hai tng lng. V d, nu ta ly dung dch it trong nc vi mt dung mi hu c khng ho tan trong nc nh hexan hoc clorofom th mt phn iot c chit vo lp hu c. Cui cng cn bng c thit lp gia hai tng v c th hnh dung cn bng nh sau: I2 (n) I2 (hc) ;
K=

[I2 ]hc [I2 ]n

K, hng s cn bng ca phn ng ny, thng gi l hng s phn b hoc h s phn b. Cn bng phn b c ngha ln trong nhiu qu trnh phn chia. 4.2.4.7 Cn bng tng nc

Nhiu cht in li yu lin hp hoc phn li tng nc, c th vit hng s cn bng i vi mi nc. V d, nu thm amoniac vo dung dch ca ion bc th cui cng hai cn bng c thit lp, Ag+ v NH3 tham gia vo cc cn bng sau: Ag+ + NH3
+ AgNH3

+ AgNH3 K1 = + Ag [NH3 ]
+ AgNH3 + NH3 + Ag(NH3 )2

+ Ag(NH3 )2 K2 = + AgNH3 [NH3 ]

y K1 v K2 l nhng hng s bn tng nc ca hai phc cht. Nu nhn hai s K1, K2 vi nhau ta thu c hng s bn tng qut ca phc: Ag+ + 2NH3 Ag(NH3)2+

+ Ag(NH3 )2 2 = K1K 2 = + Ag [NH3 ]2

Hng s bn tng qut c k hiu l n, y n l s mol ca thuc th to phc lin kt vi mt mol cation. V d: Cd2+ + 3CN
Cd(CN)3

26
3 = K1K 2K 3 =
Cd(CN)3

Cd 2+ CN

Cd2+ + 4CN
4 = K1K 2K 3 K 4 =

Cd(CN)2 4

Cd(CN)2 4 Cd2+ CN
4

y K1, K2, K3 ,K4 l nhng hng s tng nc tng ng. Nhiu axit v baz rt quen bit, phn li tng nc. V d, trong dung dch axit photphoric tn ti nhng cn bng sau y: H3PO4 + H2O
H2PO4 + H3O
+

H3 O+ H2PO4 = 7,11.103 K1 = [H3PO4 ]


H2PO4 + H2O

HPO2 + H3O 4

2 H3 O+ HPO4 = 6,34.108 K2 = H2PO4

HPO2 + H2O 4

PO3 + H3O 4

H3 O+ PO3 4 = 4,2.1013 K3 = HPO2 4

T v d dn ra, r rng l gi tr bng s Kn ca mi nc phn li lin tip ca axit hoc baz gim dn. Cn bng loi ny c xt chng 10.

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