BI GING

HA PHN TCH

1. i cng v phn tch th tch 1.1.Bn cht ca phng php

xc nh nng ca mt dung dch cht A(gi l cht nh phn), ngi ta thm dn mt dung dch cht B(gi l cht chun hay thuc th) bit nng vo mt th tch chnh xc dung dch cht A cho n khi hai cht phn ng va vi nhau. T th tch dung dch cht B dng tnh c nng ca dung dch cht A.

- Cht A(cht nh phn) l cht cn xc nh nng - Cht B(cht chun hay thuc th) bit nng - Cho hai cht phn ng va vi nhau vi nhng th tch xc nh - Da vo nh lut ng lng tnh nng ca dung dch cht A.

0 1 0 2 0 3 0 4 0 5 0

D dich B

D dich A

 Theo nh lut ng lng ta c :

0

VA . NA = VB . NB NA = Trong : VA, VB : l th tch ca dung dch A v B NA, NB : l nng ng lng ca dung dch cht A v cht B
V B .N B VA

1 0 2 0 3 0 4 0 5 0

D dich B

D dich A

1.2. Nhng khi nim c bn

1.2.1. S chun
Qu trnh thm dn dung dch B vo dung dch A gi l s chun .

1.2.2. im tng ng
im tng ng l im m dung dch cht A phn ng va vi dung dch cht B.

V d : Khi chun HCl bng NaOH : HCl + NaOH = NaCl + H2O Khi lng NaOH phn ng ht vi lng HCl th trong dung dch ch c nc v mui NaCl. Vy im tng ng ng vi gi tr pH = 7

1.2.3. Cht ch th
pht hin im tng ng trong phng php phn tch th tch ngi ta thng dng nhng cht ch th khc nhau. Cht ch th l nhng cht c mu sc thay i khi phn ng t n im tng ng.

1.2.4. im kt thc chun

im m cht ch th gy ra nhng bin i m mt quan st c, cho ta bit phn ng n vng gn im tng ng th ngng chun c gi l im kt thc. Ni chung, im kt thc thng khng trng vi im tng ng. im kt thc cng gn vi im tng ng th php nh lng cng chnh xc.

1.3. Phn loi cc phng php phn tch th tch

Ty theo bn cht ca phn ng gia thuc th v cht nh phn ngi ta chia thnh cc phng php sau :
1.3.1. Phng php trung ha Phn ng nh lng l phn ng trao i proton hay phn ng axit - baz HA + BOH = AB + H 2O

1.3.2. Phng php oxy ha kh

Phn ng nh lng l phn ng trao i electron gia mt cht oxy ha v mt cht kh Ox1 + Kh2 = Kh1 + Ox2

1.3.3. Phng php kt ta

Da vo phn ng kt ta gia thuc th v cht cn nh lng to ra mt hp cht t tan. Thng dng nht l phng php to thnh kt ta bc halogenua X + Ag+ = AgX

1.3.4. Phng php to phc

Da vo phn ng to thnh phc cht gia thuc th v cht cn nh lng. Hay dng l phng php to thnh phc vi xyanua v complexon. Na2H2Y + Men+ = Na2MeY + 2H +

2. Phng php trung ha

2.1. C s ca phng php
Phng php trung ha l phng php phn tch nh lng da trn nhng phn ng cho nhn proton gia axit baz HA + BOH = AB + H 2O

 Nhn xt : - Trong qa trnh chun , pH ca dung dch bin i. - Ti im tng ng c s bin i t ngt ca pH v ta thu c mt dung dch c pH nht nh hoc vng axit, hoc trung tnh, hoc kim. - xc nh im tng ng ngi ta phi dng nhng cht ch th axit- baz hay gi l cht ch th pH.

2.2. Cht ch th
L nhng cht c mu sc thay i theo s bin i pH ca mi trng. L nhng cht hu c c tnh axit yu, baz yu . Trong dung dch c cn bng sau : HInd + H2O = Ind + H3O + Ty thuc vo gi tr pH ca dung dch m cht ch th dng axit hoc dng baz v mu ca hai dng ny l khc nhau Khong pH chuyn mu : pH = pKa(HInd) 1 n pKa(HInd) + 1
(Nng 2 dng axit v baz hn km nhau 10 ln)

Mt s cht ch th thng dng

Yu cu i vi cht ch th
Tan trong nc hoc trong cn nng l 104 M n 105 M mu phi xut hin kh r Mu phi chuyn nhanh, r trong mt khong pH kh hp Khong pH chuyn mu phi gn hoc cha gi tr pH im tng ng ca phn ng chun ( t nht phi nm trong bc nhy ca pH ) Bn vng iu kin thng.

2.3. ng cong chun Bc nhy pH - Cch chn cht ch th

2.3.1. Kho st ng cong chun axit mnh bng baz mnh V d : Chun 100 ml dung dch HCl 0,1 N (CA) bng dung dch NaOH 0,1 N (CB). Phng trnh phn ng : HCl + NaOH = NaCl + H2O

K tht tin hnh qu trnh nh lng

Buret : Dd NaOH 0,1N Bnh nn : Dd HCl 0,1N Tin hnh chun bng cch nh t t dd NaOH xung bnh nn Tnh gi tr pH ti tng thi im Xy dng ng cong chun Chn cht ch th thch hp
0 1 0 2 0 3 0 4 0 5 0

Ddich NaOH 0,1 N

Ddich HCl 0,1N

ng cong nh lng (ng cong chun )

pH
14

9,7

4,3

100

V NaOH ( ml )

NHN XT :
th biu din s thay i gi tr pH ca dung dch vo lng NaOH cho vo dung dch HCl, gi l ng cong nh lng hay ng cong chun Trong qu trnh nh lng ban u pH bin i t t, gn im tng ng ( khi thiu v tha 0,1 % NaOH ) c s bin i t ngt ca pH ( t 4,3 n 9,7 ) gi l bc nhy pH ca ng cong chun .

Cch chn cht ch th :

Ba cht ch th phenolphtalein, metyl , bromotymol xanh, u c khong pH chuyn mu nm trong bc nhy ca ng cong nh lng nn u c th chn c ba cht ch th ny, tuy nhin khong pH chuyn mu ca bromotymol xanh cha pH ti im tng ng nn chn cht ch th ny l tt nht v sai s ca php chun l nh nht.

2.3.2. Kho st ng cong chun axit yu bng baz mnh

V d : Chun 100 ml dung dch CH3COOH 0,1 N ( CA ) c pKa =4,75 bng dung dch NaOH 0,1 N ( CB ) Phng trnh phn ng : CH3COOH + NaOH = CH3COONa + H2O Cch tin hnh tng t th nghim trn

CU HI LNG GI
1. Kho st ng biu din nh lng v chn cht ch th cho cc trng hp : a . Chun baz mnh NaOH 0,1N bng axit mnh HCl 0,1N b . Chun baz yu NH4OH 0,1N (c pKB = 4,76) bng axit mnh HCl 0,1N 2. Mt hn hp gm hai axit HCl v CH3COOH cha bit nng . Bng dung dch NaOH 0,1N v cc cht ch th bit, hy xc nh nng ca tng axit trong hn hp trn.

NH LNG BNG PHNG PHP OXY HA KH

1. C s ca phng php
1.1. nh ngha Phng php chun oxy ha - kh l phng php da trn phn ng gia cht oxy ha v cht kh ca hai h oxy ha - kh khng lin hp. Phng trnh phn ng : n2 Ox1 + n1 Kh2 = n2 Kh1 + n1 Ox2

1.2. c im ca phn ng oxy ha - kh :

Xy ra hon ton v theo mt t lng nht nh Xy ra nhanh, nu chm cn phi tm iu kin thch hp tng tc ca phn ng ln nh un nng, dng cht xc tc v.v Phi chn lc, nu trong dung dch chun c mt cc ion l phi tm cch che hoc tch n ra. Phi c cch v cht ch th thch hp xc nh c im cui ca qu trnh chun .

1.3. Cht ch th
* Cht ch th loi 1: L cc cht hu c c tnh cht oxy ha - kh c mu dng oxy ha v dng kh khc nhau v mu thay i ph thuc vo th oxy ha ca dung dch

 Qu trnh oxy ha-kh ca cht ch th loi 1 c biu din bng phn ng tng qut : Ind ox + ne = Ind kh Th oxy ha kh ca h oxy ha kh tnh theo phng trnh Nerst :

Mt s cht cht ch th thng dng

Cht ch th Dng oxy ha Mu Dng kh E0 (v) Khi [H+] = 1

trung tnh Xanh metylen

Xanh da tri

Khng mu Khng mu

+ 0,24 + 0,53

Diphenylamin
Eric glusin A Ax phenylantranilic Feroin

Tm xanh
Tm Xanh da tri

Khng mu
Khng mu Khng mu

+ 0,76
+ 1,00 + 1,08 + 1,14

* Cht ch th loi 2
L cc cht c kh nng cho php nhn ra im cui ca s chun , nhng s i mu khng ph thuc vo th ca dung dch. Th d : Dng dung dch KMnO4 chun cc cht kh nh Fe2+, C2O42 , H2O2 v.v, sau im tng ng nu d mt git dung dch KMnO4 th dung dch s nhum mu hng.

1.4. ng chun Cch chn cht ch th

ng chun trong phng php oxy ha kh l ng biu din s ph thuc th oxy ha (E) ca dung dch vo th tch (V) ca dung dch chun thm vo. ng chun cho bit bc nhy th ca qu trnh chun , qua s chn c cht ch th thch hp cho qu trnh chun . Mun v ng chun ta phi tnh c th ca dung dch sau mi ln thm thuc th (theo phng trnh Nests).

2. ng dng
2.1. Phng php nh lng bng Iot : Xc nh hm lng Vitamin C
Phng trnh phn ng :
0 1 0 2 0 3 0 4 0

Ddich I2

C6H8O6 +

I2 C6H6O6 +

2HI

5 0

Cch tin hnh - Buret : Dung dch I2 - Bnh nn : Dung dch vitamin C + ch th h tinh bt

Ddich vitamin C + Ho tinh bot

Tin hnh chun cho n khi dung dch trong bnh nn chuyn t khng mu sang mu xanh nht bn vng
c th tch dung dch I2 phn ng. Tin hnh lm 3 ln, ly kt qu trung bnh v tnh hm lng ca vitamin C ( g/l ). Bit E vitamin C = 88 Vy :

2.2. Xc nh kh ca nc Nc trong t nhin ( sng, sui, ao, h... ) ngoi cc tp cht v c cn c nhiu tp cht hu c c ngun gc ng vt, thc vt ... Nhng tp cht hu c ny c tnh kh v chnh chng gy nn bn ca nc. Thng thng ngi ta hay dng phng php oxi ha kh hay phng php thuc tm xc nh kh ca nc.

Nguyn tc : Dng phng php tha tr xc nh lng cht kh.

0 1 0 2 0 3 0 4 0 5 0

KMnO Ddich I2 4

Ddich vitamin C + Ho tinh bot

-Nc NC

-H2SO4

PHNG PHP CHUN TO PHC

Phng php complexon

Da trn s to phc cng cua ca cc ion kim loi vi nhm complexon dn xut ca axt aminopolycacboxylic (ph bin dinatri ca axt etylendiamin tetraaxetic - EDTA). Ch th mu l nhng axt hu c yu hoc baz yu cha nhng nhm mang mu v ch mu. Mu ca ch th v mu ca phc phi khc nhau, d phn bit. pH phi thch hp cho ch th v phn ng to phc xy ra hon ton. Ch th thng dng: eriocromen T, murexit, xylen da cam

Complexon III (chelaton, trilon B) l mui dinatri ca EDTA (etylen diamin tetra axit axetic)

Vit tt l Na2H2Y

Trong dung dch complexon III phn ly theo phng trnh sau : Na2H2Y = 2 Na+ + H2Y2

Khng ph thuc vo ha tr ca ion kim loi, complexon u phn ng vi ion kim loi theo t l 1:1 theo cc phng trnh phn ng sau :
Men+ + H2Y2= MeY(n 4) + 2 H+ Me2+ + H2Y2 = MeY2 + 2 H+

Me3+ + H2Y 2 = MeY

Me 4+ + H2Y 2 = MeY

+ 2 H+
+ 2 H+

 V d : Ca2+ + H2Y2 = CaY2 + 2 H+ Al3+ + H2Y2 = AlY + 2 H+ Th4+ + H2Y2 = ThY + 2 H+ Phn ng gia ion kim loi v complexon thng gii phng ra ion H+ lm cho pH ca dung dch thay i trong qu trnh chun do nh hng nhiu n kh nng to phc ca ion kim loi v vy khi chun phi gi cho pH ca dung dch trong mt khong pH nht nh thch hp cho s to phc, mun vy phi dng dung dch m.

Cht ch th
Dng nhiu nht l cht ch th mu kim loi. Cht ch th mu kim loi l nhng cht mu hu c, c kh nng to phc mu vi cc ion kim loi v trong nhng iu kin nht nh mu ca cc phc khc mu ca cht ch th t do. Nhng cht ch th mu kim loi c dng trong chun complexon phi tha mn cc iu kin sau :

- Phc ca cht ch th vi ion kim loi phi khng bn bng phc ca complexon vi ion kim loi. - Mu ca phc gia cht ch th vi ion kim loi phi khc mu ca cht ch th t do. - S i mu phi xy ra nhanh v r rt gn im tng ng ca qu trnh chun - Cht ch th phi c phn ng c trng vi tng ion kim loi.

Cc cht ch th kim loi

Eriocrom T en ( ETOO ) ; Murexit ; Xylen da cam ; axit sunfosalixilic thy r c ch chuyn mu ca cht ch th kim loi trong chun complexon ta ly mt v d c th : chun Mg2 + bng complexon III pH = 11 vi cht ch th l ETOO (k hiu l HInd )

* Trc khi chun : Trong dung dch c ion Mg2+ v ETOO

HInd = MgInd+ + H+ xanh nho * Khi chun Mg2+ + H2Y2 = MgY2 + 2 H+ Khi H2Y2 phn ng ht vi ion Mg2+ t do, mt git H2Y2 d s phn ng vi phc MgInd+ (v phc MgInd+ km bn hn phc complexonat magie MgY2 ) theo phn ng : MgInd+ + H2Y2 = MgY2 + HInd + H+ nho xanh + Mg2+

1 0 2 0 3 0 4 0 5 0

NaHI2Y Ddich 2

2-

2+ Ddich vitamin C - Mg

- Ho ETOO + tinh bot

ng dng phng php chun complexon xc nh cng ca nc

cng ton phn ca nc l tng mui canxi v magie tan trong nc. Ta c th xc nh cng ton phn ca nc bng complexon III vi cht ch th Eriocrom T en. (Xem THHH i cng)

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