Chng III

K THUT PHN TCH TH TCH (PHNG PHP CHUN )

Ts. Pham Tran Nguyen Nguyen ptnnguyen@hcmus.edu.vn

K THUT PHN TCH TH TCH (PHNG PHP CHUN )

III.1 Mt s khi nim III.2 ng cong chun III.3 Cht ch th trong phng php phn tch (PPPT) th tch III.4 Cc cch chun thng dng 4.1. Chun trc tip 4.2. Chun ngc 4.3. Chun th 4.4. Chun gin tip 4.5. Chun lin tip hay phn on III.5 Cch tnh kt qu trong PPPT th tch III.6 Sai s h thng trong PPPT th tch
2

III.1 Mt s khi nim

PPPT th tch: pp nh lng cu t X da trn php o th tch Cu t X (Cx ?) + dd chun C (bit CT) s nh phn hay php chun C + X A + B : p. chun Chun acid-base (acidbase titrations) Chun phc (complexometric titrations) Chun oxy ha kh (redox titrations) Chun ta (precipitation titrations)
3

C + X A + B : p. chun im tng ng (equivalent point): thi im C tc dng va ht vi X: # mol C = Vt x CT # mol X = ? Da vo h s t lng ca pt # mol X Da vo nh lut ng lng: nC = nX

xc nh im tng ng bng cht ch th (dd i mu, xut hin ta ) im kt thc chun (endpoint): khi c s thay i ca cht ch th sai s trong chun im tng ng cn c xc nh thng qua php o mt s i lng ha l: in th, dn in, mt dng : PPPT ha l

iu kin p dng pppt th tch Bit t l p. gia cht chun (C) v cht cn phn tch (X) Tc p. chun phi nhanh C pp xc nh im cui thch hp vi chnh xc chp nhn c V d:

Ag + (aq ) + SCN - (aq )

AgSCN(s)

Cht chun C = KSCN Cht ch th Fe3+ Fe(SCN)2+ (mu )

5

III.2 ng cong chun (titration curve)

ng biu din s bin i nng hay logarit ca nng mt cu t no trong dd ca qu trnh chun theo lng cht chun thm vo. C+XA+B
Biu din s bin thin ca [C], [X], [A] theo lng cht chun C thm vo

[C]

[X]

[A]

Vtd

Vc

Vtd

Vc

Vtd

Vc
6

III.2 ng cong chun (titration curve)

C+XA+B Biu din s bin thin ca log[C], logX], log[A] theo lng cht chun C thm vo
Log[C] Log[X] im tng ng
K=108 K=1010

im tng ng

C (mmol)

C (mmol)
7

ng cong chun acidbase

ng cong chun phc

ng cong chun ta

8 ng cong chun th oxy ha kh

ng cong chun nhit cho phn ng ta nhit

9

III.3 Cht ch th trong PPPT th tch

3.1 nh ngha:
Cht ch th (indicator, Ind) l hp cht HC hay VC c cu trc thay i theo nng mt cu t Z no trong dd.

Ind + Z

IndZ

Du hiu bin i cu trc: s i mu ca dd, s xut hin hay bin mt ca ta no trong dd

3.2 Phn loi Cht ch th nng ion Cht ch th oxy ha kh (REX-OX) Cht ch th hp ph
10

Cht ch th nng ion

y l cht ch th c c cu v tnh cht thay i theo nng ion no trong dd: Z l H+ (OH-): Ind l cht ch th acid-baz, c dng trong phng php trung ha v o mu x pH

HInd Ind + M n+

Ind + H + MInd n +

Z l ion Mnn+ v IndZ l kt ta: Ind l cht ch th to ta

Z l ion Mnn+ v IndZ l cht phc: Ind l cht ch th to phc, dng rng ri trong phng php chun phc

Ind + M n+

MInd n +
11

Ch th acid-baz hay ch th pH
Ind l acid hay baz yu, c th thay i mu sc theo pH ca dd. Ind ny c dng trong phng php trung ha v o mu x pH.

HInd Ind + H +

[ Ind ][ H + ] [ HInd ] ki = [ H + ] = ki [ HInd ] [ Ind ] [ Ind ] pH = pki + lg [ HInd ]

Mu dd c quyt nh ty thut vo t s [Ind]/[HInd] v gi tr ca t s ny ph thuc vo pH ca mi trng. Khi t s [Ind]/[HInd] t n 1/10 hay 10 th dd c s chuyn mu. Khong chuyn mu: pH = pki 1

12

13

Cht ch th oxy ha kh (REX-OX) Mu sc thay i theo kh nng cho nhn in t ca mi trng, hay theo s thay i th oxy ha kh ca h c gi cht ch th oxy ha kh.
C ch:

Ind (ox) + ni e Ind (kh) pH xc nh: 0.059 [ Ind (ox)] Ei = Ei0 + lg ni [ Ind (kh)]
V ch th c nng rt nh nn th ca dd c quyt nh bng cc cp Ox/Kh. S thay i ca th lm t l Ind(Ox)/Ind(Kh) thay i dd s c mu ca dng oxy ha hay dng kh khi nng dng ny hn nng ca dng kia 10 ln Khong chuyn mu:

E = Ei0 0.059 / ni

14

15

Cht ch th hp ph:
Phm nhum HC c tnh acid-baz, c kh nng hp ph trn b mt ta, lm ta nhum mu c trng.

Cht ch c to thnh trong qu trnh chun

Trong qu trnh chun , im cui cn c th c x nh vo cc du hiu xut hin do bn thn ca tc cht hay sn phm Chun cht kh (khng mu) = MnO4-, khi d MnO4 dd cn chun s c mu hng tm. Chun cht kh (khng mu) = BrO3-, khi d BrO3 dd cn chun s c mu vng nu. Chun cht kh (khng mu) = Ce4+, khi d Ce4+ dd cn chun s c mu vng.
16

III.4 Cc cch chun thng dng

4.1 Chun trc tip (direct titration)
Dung dch (dd) chun C c cho vo dd cha cu t X C+XA+B # ng lng gam C ~ # ng lng gam X
CN = m 1000 . dlg V(ml)

17

III.4 Cc cch chun thng dng

4.2 Chun ngc (back titration)
Cho lng tha dd chun C vo dd cha cu t X nh lng lng tha C bng dd chun C1 n im cui C+X A+B C + C1 D + E # ng lng C ~ # ng lng (X + C1) Dng phng php chun ngc khi: 1. Khng c cht ch th thch hp cho p. C + X 2. iu kin tin hnh p. C + X c bit: nhit cao, thi gian tip xc di
18

V d: Xc nh nng ca formaldehyde, H2CO bng I3H 2 CO(aq ) + 3OH - (aq) + I3 (aq)

HCO-2 (aq ) + 3I- (aq) + 2H 2 O (l ) (1)

Phn ng chun trc tip chm dng lng tha I32I3 (aq) + 2S2 O3 (aq) 2S4 O6 (aq) + 3I- (aq) (2)

# ng lng H2CO = ?
# ng lng I3- (1) = # ng lng I3- - # ng lng I3- (2)

V d: Xc nh hm lng CaCO3 c trong 4g phn bng lng tha 200ml dd HCl 0.5N. Bit sau phn ng, lng tha HCl cn li phn ng chun ht vi 50 ml dd NaOH 0.5N.

CaCO3 + 2 HCl CaCl 2 + CO 2 + H 2 O (l ) (1)

HCl + NaOH NaCl + H 2 O (2)

# g lng CaCO3 = ? = # g lng HCl (1) # g lng HCl (1) = # g lng HCl - # g lng HCl (2) # g lng HCl = NHCl x VHCl = 0.5 x 0.2 = 0.1 # g lng HCl (1) = # g lng NaOH = NNaOHx VNaOH = 0.5 x 0.05 = 0.025 # g lng CaCO3 = 0.1 0.025 = 0.075 khi lng CaCO3 = # g lng CaCO3 x dlg(CaCO3) = 3.75g ln 0.25 g tp cht

4.3 Chun th (displacement titration)

Cho dd AC1 vo dd cha cu t X, to p. thay C1 bng X nh lng lng tha C bng dd chun C1 n im cui AC1 + X AX + C1 Lng C1 phng thch c chun bng dd chun C C1 + C D + E # g lng X ~ # g lng C = # g lng C1

21

V d: Xc nh nng ca Ca2+

Ca 2+ (aq ) + Y 4- (aq )

CaY 2 (aq ), Y 4- = EDTA

khng c thuc th thch hp nu chun trc tip dng lng tha phc Mg2+ vi EDTA

Ca 2+ (aq) + MgY 2- (aq)

chun Mg2+ phng thch

CaY 2 (aq ) + Mg 2+ (aq ) MgY 2 (aq)

22

Mg 2+ (aq) +Y 4- (aq)

EDTA = EtylenDiamineTetraAxetic

Cng nghip ty ra : To phc vi ion Ca2+, Mg2+, kim loi nng Lm sch nc : To phc vi ion Ca2+, Mg2+ (gim cng ca nc). Trong nhip nh : s dng Fe(III)EDTA nh l cht oxiha. Cng nghip dt : To phc vi kim loi nng, my ty trng vi. Ha hc nng nghip : Phn bn st, km v ng, c bit l vng vi. K thut trng cy trong nc : Fe(EDTA) c s dng ha tan st trong gii php dinh dng cho cy trng.
http://www.h2vn.com/community/index.php?topic=2788.msg26798#ixzz0Ew3cwOvG&A
23

4.4 Chun gin tip (indirect titration)

Cu t X c chuyn thnh hp cht khc c CTPT xc nh v mt thnh phn no ca pt c th chun bng pp thch hp V d: xc nh lu hunh trong than

S(s) + O2 ( g ) SO2 ( g ) SO 2 ( g ) + H 2 O 2 (aq) H 2SO 4 (aq) H 2SO 4 (aq) + 2OH - (aq ) SO 4 2 (aq ) + 2H 2 O (l)

4.5 Chun lin tip hay phn on

24

III.5 Cch tnh th tch trong PPPT th tch

5.1 Nguyn tc chung: da vo nh lut ng lng

C+X A+B CC .VC = CX .VX

Cc , Cx: nng ng lng ca cht chun C v cu t X Vc , Vx: th tch ca 2 dd C v X (ml) 5.2 Cc biu thc tnh: Mu lng Mu rn
25

5.2 Cc biu thc tnh:

Mu lng a. Ly Vx (ml) mu, chun bng Vc (ml) dd chun c nng ng lng Cc

Cc .Vc C (X) ; CM (X) = N (1) Vx n M C(g/l) = C N (X) dlg(X) = C N (X) x (2) n C N (X) =
b. Ly V(ml) mu m c pha long thnh V1 (ml) dd long; dng Vx (ml) dd long chun bng Vc (ml) dd chun c nng ng lng Cc

Cc .Vc V1 (3) Vx V M C(g/l) = C N (X) dlg(X) = C N (X) x (4) n C N (dddd ) =

26

5.2 Cc biu thc tnh:

Mu rn a. Cn a (g) mu, ha tan v chun bng Vc (ml) dd chun c nng ng lng Cc

%X = CC .VC .103

100 dlg(X) (5) a

b. Cn a (g) mu, ha tan v nh mc thnh V1(ml) dd long; ly Vx (ml) dd long em chun bng Vc (ml) dd chun c nng ng lng Cc

%X = CC .VC .103

V1 100 dlg(X) (6) VX a

Biu thc 1-6 c p dng tnh kt qu cho pp chun trc tip v chun th.
27

Vi chun ngc, s dng biu thc

CC .VC = CX .VX + CC1 .VC1 CX =

CC .VC CC1 .VC1 VX

(7)

Mt s trng hp, vic tnh kt qu thng qua chun a. chun ca mt cht Tx: s gam hay miligam cht X trong 1 mililit dd:

TCX (g/ml) =

m m hay T(mg/mL) = i1000 (8) V V

b. chun theo cht xc nh TC/X: s gam hay miligam cht X tc dng va vi 1 mililit dd chun c nng CC

TCX (g/ml) =

TC/X = THCl/NaOH = 0.00401g 0.00401g NaOH s c tc dng va vi 1 ml dd HCL 0,1 N. 28

CC dlg(X) (9) CC = 1000.TC/X /dlg(X) (10) 1000

V d: Mt dd soda (Na2CO3) k thut cha bit nng , c pha long bng nc n vch mc ca bnh nh mc c dung tch 250 ml. Chun 25ml dd ny khi c mt methyl da cam th tn mt 22.45 ml dd chun acid HCl 0.1095N. Tnh tng hm lng Na2CO3 ra gam c trong dd soda ban u

V d: Tnh hm lng % ca Na2B4O7.10 H2O c trong mu borax k thut, bit rng chun 0,2298 g borax th tn mt 10,60 ml dd HCl 0,1060 N

III.6 Sai s h thng trong PPPT th tch

6.1 Sai s do p.ng chun c hng s cb khng ln
K C + X A + B

Hng s cb K cng ln, mc phn ng din ra cng hon ton sai s h thng % cng b v ngc li K = 108-109: % 0.01% K = 106-107: % 0.1% K < 105: % > 1% 6.2 Sai s do dng c o th tch, do my o hoc ha cht 6.3 Sai s ch th % = S (mili) ng lng ca X cn li x 100% S (mili) ng lng ca X ban u

31

Titrimetry: Any method in which volume is the signal. Titrant: The reagent added to a solution containing the analyte and whose volume is the signal. Equivalence point: The point in a titration where stoichiometrically equivalent amounts of analyte and titrant react. End point: The point in a titration where we stop adding titrant. Indicator: A colored compound whose change in color signals the end point of a titration.