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Giao Trinh Hoa Phan Tich PDF
Giao Trinh Hoa Phan Tich PDF
GIO TRNH
HA HC PHN TCH
(DNG CHO CC H KHNG CHUYN HA)
TS. Nguyn ng c
2
M U
3
Sinh hc, Khoa hc Mi trng, Y hc, Nng hc c kin thc c bn nht v Ha
phn tch, gip cho h c vn kin thc trong qu trnh hc tp trn gh nh trng
cng nh sau khi ra trng c th bt tay vo cng vic chuyn mn ca h,
iu kin lm vic vi nhng cng vic lin quan n ha Phn tch.
Khi bin son gio trnh ny khng th trnh khi nhng thiu st. Chng ti
mong c s ng gp kin ca cc bn ng nghip v cc em sinh vin.
Thng 5 nm 2008
Tc gi
4
PHN TH NHT
C S L THUYT HA PHN TCH
CHNG 1:
DUNG DCH CHT IN LY - CN BNG HA HC
1.1. CHT IN LY V S IN LY
1.1.1. nh ngha v s in ly v cht in ly
- S in ly l qu trnh phn t phn ly thnh ion cn cht in li l cht c
kh nng phn li thnh ion khi ha tan vo nc lm cho dung dch dn c in.
V d: NaCl, HCl ha tan trong nc hay trong dung mi phn cc khc.
V d:
5
c trng cho kh nng phn ly ca cc cht trong dung dch, ngi ta dng
hai i lng l in ly v hng s in ly.
a. in ly l t s gia phn nng in ly v phn nng ban u.
6
Khi thm 2 milimol Fe2+ vo 1 lt dng dch cha 1 milimol I3-, mu gim
nhanh, ngha l phn ng xy ra theo chiu nghch.
7
Nu phn ng M, N, P, Q thc hin trong dung dch v gi NM, NN, NP, NQ l
nng phn mi ca cc cht M, N, P, Q th ta c:
8
Kt gi l hng s phn ly axit (gi tt l hng s axit).
Cn bng phn li ca baz:
KD gi l hng s phn b ca I2
1.2.3.5. Cn bng ha tan ca cht kh - nh lut Henri
Qu trnh nghch:
10
Hng s cn bng t hp thu c khi cng cc cn bng vi nhau bng tch
cc hng s cn bng ring l.
Gii phng trnh (g) cho php nh gi X v t (c), (e) ta tnh c nng
cn bng cc cu t trong dung dch.
11
cho tin ta ghi s tnh ton nh sau:
Cn bng: MX ' Mn+ + Xn- (K)
Nng ban u (mol/1) C O O
Nng phn li: (C) (mol/l) - x +x +x
Nng ln: ([ ]) (mol/l) c-x x x
Theo LTDKL:
Vy ta chp nhn:
12
1.3. HOT
Theo thuyt v cht in li mnh ca bai - Huken, vi nhng dung dch
long v rt long khong cch gia cc con cch xa nhau, lc tng tc gia cc
ion l khng ng k, c tnh bng cng thc:
13
Nu 0,01 0,2. Ta tnh lgf theo (1.12).
V d: Tnh hot ca ion Ca2+ trong dung dch bao gm CaCl2 0,01M v
NaNO3 0,01M.
Gii:
Tnh h s hot f:
14
1.4.2. Phn ng oxy ha kh
1.4.3. Phn ng kt ta
15
1.5.1.3. Nng ng lng gam/ lt, cn gi l nng ng lng, k hiu l
N ch ra c bao nhiu ng lng gam cht tan trong mt lt dung dch. V d
dung dch KMnO4 0,1N ngha l trong 1 lt dung dch c 0,1 ng lng KMnO4.
0,004 (g/ml) ngha l 0,004g cht nh phn Cl- tc dng va vi lu dung dch
chun AgNO3.
1.5.1.6. Mi lin h gia cc loi nng :
Nu gi nng % ca dung dch l C%, khi lng ring ca dung dch l d,
P l phn t gam cht tan, D l ng lng gam cht tan, ta c:
Cc v d:
1. Trn 500ml dung dch HNO3 30% vi 500ml dung dch HNO3 10% thu c
dung dch HNO3 bao nhiu % (cho d1 = 1,2g/ml, d2 = l,05g/ml).
p dng (1.19) ta c:
2. Cn bao nhiu ml dung dch HNO3 25% (d = 1,19) trn vi dung dch HNO3
5 %(d = 1,04) c 1 lt dung dch HNO3 10%
p dng (1.19):
Vy ta ong 448ml axt c, chuyn ton b sang bnh 2 lt, trng bnh bng
17
nc ct v thm nc ct n vch mc, ri y kn np bnh, o i o li
trn u dung dch.
b. Vi nng M, N.
Gi s phi trn V1 ml dung dch th nht c nng mi l M1 (hoc nng
ng lng N1) vi V2 ml dung dch th hai c nng mi l M2 (hoc nng
N2) c dung dch c nng l M (hoc N) th tch l V = V1 + V2 (ml). Khi
ta c:
Cc V d:
1. Pha 2 lt dung dch H2SO4 0,5 M vi 1 lt dung dch H2SO4 0,1 M c dung
dch bao nhiu M.
p dng cng thc (1.20) thay s vo ta c:
2. Cn bao nhiu mililt dung dch NaOH 0,5N trn vi 1 lt dung dch NaOH
0, l c 2 lt dung dch NaOH 0,2N.
p dng (1.20) ta c:
V1 = 600ml
3. Pha 2 lt dung dch HCl 0,1N t axt HCl 0,5M.
y cng l s pha long dung dch trong nc l dung dch th hai c nng
bng khng. Do p dng (1.20) ta c:
Vy cn ong chnh xc 0,4 lt dung dch HCl 0,5M, chuyn ton b sang bnh
nh mc 2 lt trng bnh chuyn ht HCl sang bnh nh mc thm nc n
vch mc, o u bng cch y np kn vo o ln o xung.
18
CU HI - BI TP CHNG 1
1.1. Vit phng trnh phn ng dng ion thu gn xy ra (nu c) trong cc
dung dch nc sau:
1.2. Trn 20,00 ml dung dch Ba(OH)2 0,0211M vi 40ml dung dch Na2SO4
0,0153M. Hy Cho bit nng gc, nng ban u v nng cn bng ca
cc ion trong dung dch (coi phn ng xy ra hon ton).
1.3. Vit biu thc nh lut tc dng khi lng i vi cc cn bng sau:
19
CHNG 2:
PHN NG AXIT - BAZ
Baz:
Trung tnh:
Lng tnh:
20
c trng bng hng s phn li Kb.
Cp:
V:
Cp:
S mol proton nc nhn l [H3O+] bng s mol proton [OH-] cho v 1 phn t
H2O khi cho i 1 proton th bin thnh ion OH- nn phng trnh bo ton proton
l [H3O+] = [OH-]
V d 2: Xt dung dch HCl nng C mol/l.
Trong dung dch c hai axit l HCl v H2O v 1 baz l H2O. Trong xy ra
cc qu trnh sau:
21
S mol proton H2O nhn bng s mol proton HCl cho v H2O cho:
22
Phng trnh bo ton proton ca dung dch ny:
y l phng trnh tng qut tnh [H+] trong dung dch, n l phng trnh
bc 3 ca [H+]. Do tnh pH trong cc dung dch nc, ta phi dng cch gii
gn ng.
2.3.1. Dung dch axt mnh c nng Ca.
T (2.5) ta c:
24
2.3.5. Dung dch gm 1 axit yu v 1 baz yu (dung dch m)
2.3.5.1. nh ngha: Dung dch m l dung dch c gi tr pH khng thay i
hoc thay i rt t khi thm mt lng nh axit mnh hoc mt lng nh baz
mnh vo dung dch , k c khi pha long dung dch.
V d h m axtat 1 M:
25
2.3.6. Dung dch axit a chc: H3PO4, H2SO3, H2CO3.
Loi axit a chc ny phn li theo nhiu nc ?
Cn nc th 3 c tnh (Na3PO4):
V d 2: Tnh pH ca dung dch NH3 0,1 M. Cho KNH3 = 10-4,8. p dng (2.9)
ta c:
V d 3: Tnh pH ca dung dch thu c khi thm 15ml HCl 0,1M vo 20ml
dung dch NH3 0,1M. Cho KNH3 = 10-4,8
Phn ng xy ra: HCl + NH3 = NH4Cl
Nng hai cht u bng nhau v u l 0,1 M nn th tch tiu tn phi
tng ng nhau. Do th tch HCL trung ha NH3 l 15ml, lng NH3 cn l
26
5ml, y l mt baz yu, dung dch cn c NH4Cl to thnh l 15ml v l mt axt
yu. Dung dch thu c l mt h m.
p dng (2.10):
V d 4: Tnh pH ca dung dch thu c khi thm 20ml KOH 0,1 M vo 25ml
dung dch HCOOH 0,1 M. Cho Ka = 10-4
Phn ng xy ra:
Cng tng t bi trn, ta thy dung dch sau phn ng cn d HCOOH l 5ml,
lng mui HCOOK to thnh l mt baz yu c nng tng ng nng
KOH thm vo. Do dung dch thu c l h m.
p dng (2.10), ta c:
27
Tch s ion ca dung mi.
Ru etylic:
Axit focmic:
V pKi = pH + pS
Trong dung mi nguyn cht pH = pS =1/2 pKi
Dung dch s c phn ng axt khi [H2S+] > [S-] hoc pH < pS, s c phn ng
baz khi [H2S+] < [S-] hoc pH > pS
Ni chung trong dung mi ny pH c xc nh trong phm vi pH = 0 cho n
pH = PK(HS). Trong bng (2.1) c cho c tnh axit - baz ca mt s dung mi
lng tnh.
Bng 2.1. c im axit - baz ca mt s dung mi lng tnh.
Dung mi Ionlioni Ionliat Ki Thang pH pH trung
(HS) bnh
H2SO4 H3SO4+ HSO4- 10-3,8 0 - 3,8 1,9
HCOOH HCOOH+ HCOO- 10-6 0 - 6,0 3,0
CH3OH CH3OH+ CH3O- 10-16,7 0 - 16,7 8,35
C2H5OH C2H5OH2+ C2H5O- 10-19
28
Trong nc HCL l mt axt mnh, nhng trong dung mi axt axtc bng c
tnh baz rt yu nn HCl li l mt axit yu.
29
CU HI V BI TP CHNG 2
2.1. Tnh [OH-], pH, pOH i vi dung dch axt c nng [H+] = 0,0010M,
coi h s hot cc cu t bng 1.
2.2. Thm 300ml H2O Vo 200ml dung dch HCl c nng ln H+ 0,10M.
Tnh pH ca dung dch sau khi pha long.
2.3. Tnh pH, pOH v [H+], [OH-] ca dung dch HCl 1,0.10-3M.
2.4. Trn 200ml dung dch HCl c pH = 2,0 vi 300ml d HNO3 c pH = 3,0.
Tnh pH ca dung dch thu c.
2.5. Nh 1 git HCl 3,4.10-3 M vo 300,00 ml nc. Tnh pH ca dung dch,
bit th tch 1 git l 0,03ml.
2.6. Tnh [H+], [OH-], pH ca dung dch thu c khi thm 20,0 ml dung dch
NaOH l,00.10-3M vo 80,00 ml dung dch HCl 2,5.10-4 M.
2.7. Tnh pH ca dung dch HCOOH 0,1M.
2.8. Tnh nng ca dung dch CH3COO- phi c trong dung dch sao cho pH
= 3,0.
pH= 3,0 << 7,0. Vy s phn li ca nc l khng ng k.
30
CHNG 3:
PHN NG TO PHC
31
3.1.2. Cch gi tn phc cht:
S ch s phi t + tn phi t + tn ion trung tm + tn ion cu ngoi.
- [Cu(NH3)4]SO4: Tetramino ng (II) sun pht.
- K3[Fe(CN)6]: Kali hexa xyanua st (III)
Tn ca phi t: X-halogien nua; OH - hyroxo; NO3- nitrato; H2O - aqu;
NH2(NH3- NH) amino; CO - cacbonyl.
3.1.3. Hng s bn v khng bn ca phc cht:
Trong :
l HSKB nu 6, cn
Ngc li:
th c gi l hng s bn nc 1 (3.4)
cn:
32
c gi l hng s bn nc 2 (3.5)
v
c gi l hng s bn nc 6 (3.6)
Cn phn ng:
c gi l hng s bn tng hp (3.7)
33
nng i vi ion kim loi v i vi phi t.
3.2.1. Phi t rt d so vi ion trung tm.
t c iu phi tnh ton bng nhng phng php gn ng thch
hp.
Khi phc to thnh s c th c s phi tr cao nht (v CL >> CM).
Ta c nng cn bng phi t bng nng ban u ([L] CL)
V d 1: Tnh nng cn bng cc cu t trong dung dch AgNO3 0,01M,
NH3 1,00 v NH4NO3 1,00M. Cc qu trnh xy ra trong dung dch:
Xt cc iu kin gn ng.
Tnh gn ng pH ca dung dch.
T cn bng (3) ta c:
34
Vy phc tn ti trong dung dch ch yu l Ag(NH3)
T lp lun trn ta c th tnh gn ng nh sau:
- Xc nh thnh phn gii hn:
Xt cc iu kin gn ng.
- Mi trng axt, c th b qua s to thnh phc Hiroxo ca ion Cd2+.
- C Cl >> C Cd , cc gi tr lg khng qu ln v khng chnh lch nhau nhiu.
2+
(1 2 3 4).
35
Khi tnh gn ng, phi k s c mt ca tt c cc dng phc cloro ca Cd2+
p dng nh lut bo ton nng ban u i vi ion Cd2+ ta c:
Vic kim tra bng cch thay cc kt qu tnh c vo phng trnh (5) cho
thy:
-3
C Cd 2 + = 9,975.10 M so vi gi tr ban u ( C Cd 2+ = 0,010) th sai s l khng
ng k (-0,25%).
Nu thay cc kt qu tnh c vo phng trnh nh lut bo ton nng
i vi ion Cl- th:
Suy ra:
Sai s:
36
V d: Thm 1 git (0,03 ml) dung dch NH4CNS 0,10M vo 1,00ml dung
dch FeCl3 0,100M khi c mt HCl 1 M (coi th tch thay i khng ng k khi
thm thuc th). Tnh nng cn bng cc cu t trong dung dch.
Xt cc iu kin gn ng.
V nng ln H+ ln nn c th b qua s phn li ca ion NH4+ v s to
phc hidroxo ca Fe3+.
V C 3+ >> CSCN- nn c th coi phn ng to thnh phc FeSCN2+ l ch
Fe
yu:
37
Vic kim tra cho thy:
38
[Y,] l tng cc nng cn bng ca cc dng tn ti ca Y4-, tr phc MYn-4,
tc l:
39
Trong
v ca EDTA l:
Thay [MgY2-] = 0,01 - [Mg] v [Y] = 0,01 + [Mg] vo biu thc ca hng s
bn iu kin:
40
Gi s [Mg'] << 0,01 th:
Tnh (H).
Ta tnh (H) tng t nh v d 1. Khi [H+] = 10-9, ta tnh c (H) = 101,28.
Ta tnh c Ni ( NH ) = 1 + 1.1 [NH3] + + 1.5 [NH3] thay cc gi tr , [NH3]
3
41
Nh vy trong dung dch m NH3 + NH4Cl c nng NH3 kh ln, c pH =
9, ion Ni2+ va to phc vi EDTA va to phc vi NH3 nhng khi tnh MY ta
thy gi tr hng s rt ln chng t Ni2+ to phc nh lng vi EDTA.
3.4. PHC CHT CA CC ION KIM LOI VI AXIT
ETILENDIAMINTETRAAXETIC.
Trong s cc cht to phc vng cng (Chelate) vi cc ion kim loi th nhm
thuc th hu c c tn chung l complexon c ng dng rt rng ri trong ha
phn tch, cc complexon l nhng dn xut ca cc axit aminopolycacboxilic.
V d: Nitrylotriaxetic hay complexon I.
42
Bng 3.1. Hng s to thnh ca cc complexonat kim loi
Cation KL Phc conplexonat lg
43
cch nh lng vi EDTA.
Ta hy tnh pH ca dung dch phi bng bao nhiu khi trn hai th tch bng
nhau ca dung dch ton kim loi Mn+ v dung dch EDTA c nng bng nhau Co
th 99,9% lng ion kim loi to phc complexonat l MYn-4.
Khi trn hai th tch bng nhau ca dung dch EDTA v ca dung dch Mn+ th
C0
nng ca chng gim i mt na, bng . Theo nh lut bo ton khi lng
2
th:
Nh vy, mun cho 99,9% lng ion kim loi to phc complexonat th hng
2.106
s bn iu kin ca phc phi bng . Ta hy tnh pH ' bng gi tr .
C
Ta bit, theo nh ngha:
44
Phng trnh biu din i lng (H) l phng trnh bc 4 i vi [H+]:
45
NiY2- 1010,62
CuY2- 1010,8
ZnY2- 108,5
CdY2- 108,46
Hg2- 1013,8
PbY2- 1010,04
AlY- 108,13
FeY- 1017,1
VY- 1017,9
ThY- 1015,2
46
3.5. NG DNG PHN NG TO PHC TRONG HA HC PHN TCH
3.5.1. Phn tch nh tnh cc cht
Cc phn ng mu c trng thng c s dng pht hin cc ion.
a. Cc phc ca ion kim loi vi amoniac. V d Cu(NH3)42+ mu xanh m
dng pht hin ion Cu2+, phc Co2+ vi NH3 c mu vng CO(NH3)62+ b oxi
ha bi khng kh hoc H2O2 to thnh phc CO(NH3)63+ c mu hng c trng.
Phc thioxyant kim loi, v d Fe(SCN)n(3-n) (n = 1 -5) c mu mu c
trng c dng pht hin Fe3+. Phc Co(SCN)42- c mu xanh t bn trong
nc nhng bn vi dung mi hu c (axeton, cc ancol, ete etylic) v vy phn
ng gia Co2+ vi SCN- khi c mt dung mi hu c c dng pht hin Co2+.
b. Cc thuc th hu c c dng pht hin ion kim loi kh phong ph:
Pht hin Ni2+ bng imetyl glyoxim, Al3+ bng Alizarin hoc Aluminon, Fe2+
bng O - phenantrolin hoc , ' dipiridin....
3.5.2. Xc nh nh lng cc ion kim loi.
a. EDTA l thuc th quan trng c dng xc nh nh lng nhiu ion
kim loi.
b. Phn ng mu gia nhiu thuc th hu c vi cc ion kim loi c dng
nh lng trc quang hoc chit trc quang cc ion kim loi. V d nh lng
Ni2+ bng imetylglyoxim, Fe3+ bng SCN-, Al3+ bng Aliuminon, Pb2+ bng
ithizon v Cu2+ bng ietyl ithiocacbamat... Cd2+ bng Amoni Pirolidin ithio
cacbamt (APDC).
3.5.3. Ha tan cc kt ta kh tan, tch cc ion.
Nhiu thuc th to phc c s dng ha tan cc kt ta. V d AgCl tan
trong NH3 do to phc Ag(NH3)2+; Cu(OH)2 tan trong NH4Cl do to phc
Cu(NH3)42+; - cng o c tnh ny m ngi ta c th s dng cc thuc th to
phc tch cc ion, v d dung NH3 d tch hn hp Fe3+, Al3+ v Cu+ do
Fe3+, Al-3+ c chuyn vo kt ta Hydroxit Fe(OH)3, Al(OH)3, cn Cu2+ c
gi li trong dung dch di dng phc Cu(NH3)42+.
3.5.4. Che cc ion cn tr
Mt trong cc ng dng quan trng ca phc cht trong phn tch ha hc l
che cc ion cn tr. Khi mt thuc th c kh nng phn ng vi ion B cng c
mt trong dung dch cha ion phn tch A th ta ni n ion B cn tr phn ng ca
A vi thuc th. loi tr nh hng ca B ta phi kt ta B vi mt thuc th
thch hp.
47
Mt bin php tch cc l "che" ion B, ngha l khng cn tch B m chuyn n
sang to phc vi mt thuc th khc n khng cn tr phn ng chnh. Cht
c a vo lm trit tiu hoc km hm phn ng cn tr c gi l cht
che.
V d: ion Fe3+ cn tr n phn ng gia Co2+ v SCN- ta che n bng cch
cho Fe3+ to phc vi F- v phc FeF63- bn hn nhiu phc Fe(CNS)nn-3 trn.
Cht che phi c kh nng to phc bn vi ion cn tr n khng cn tc
dng vi thuc th chnh dng nh lng, ion cn xc nh, mt khc bn
ca phc gia cht che v ion cn nh lng phi rt b khng gy cn tr cho
phn ng chnh. Chng hn, vic tm ion Cd2+ trong dung dch cha ion Cu2+, Co2+,
Ni2+ bng Na2S khng thc hin c v cc ion ny cho kt ta sunfua mu en
khng cho php nhn ra kt ta CdS mu vng. che cc ion ny ngi ta dng
KCN, v cht che ny to ra cc phc bn Cu(CN)42-, Co(CN)42-; Ni(CN)42- khng
phn ng vi Na2S, trong khi phc Cd(CN)42- km bn, Cd2+ phn ng vi
Na2S.
48
CU HI - BI TP CHNG 3
3.5. Tnh nng CH+ lm gim nng Ag(NH3)2+ 0,1M xung cn 1,0
10-6 M, Ag(NH3)+ = 103,32.
3.6. Thm 1ml dung dch NH4SCN 0,10M vo 1ml dung dch Fe3+ 0,01M v F-
1,00M. C mu ca phc xut hin hay khng ? Bit rng mu ch xut hin khi
CFeCN2+ > 7.10-6M v dung dch c axit ha va s to phc Hiroxo ca
Fe(III) khng xy ra. Cho CFe3+ (= 0,0 1) < CF (= 1).
3.1. Hng s bn tng cng ca cc phc to bi ion Hg2+ v ion 1- ln lt l:
1.1 = 109,05, 1.2 = 1017,33, 1.3 = 1019,74 v 1.4 = 1021,0. Tnh cc hng s bn v
khng bn tng nc ca cc phc .
3.8. Tnh nng cn bng ca cc ion v phn t trong dung dch Cd(ClO4)2
10 M v KI 1 M. Trong dung dch c HClO4 Cd2+ khng to phc c vi
-3
49
Phc ca Hg2+ v Cl- c logart hng s bn tng cng l 6,74 v 13,22.
3. 11. Tnh nng cn bng ca ion Fe3+ v FeY- trong dung dch hn hp
Fe3+ 10-2M v Na2H2Y 10-2M c pH = 2,0, FeY = 1025,1.
3.12. Cn phi thm NH3 vo dung dch AgNO3 10-2M n nng cn bng
no gim nng Ag+ t do xung 10-8M. Phc ca Ag+ v NH3 c logant hng
s bn tng cng ln lt l 3,32 v 7,24.
50
CHNG 4
PHN NG KT TA
51
4.1.2. tan (S) ca kt ta, quan h gia S v T.
tan (S) ca cht tan l nng mol/l ca cht trong dung dch bo ha.
Gia S v T c mi quan h:.
52
S = 16.10-6 mol/l kt qu ny cho thy gi thit trn l ng. Vy tan ca
PbSO4 trong dung dch Na2SO4 l 1,6.10-6 v thy rng tan ca n nh hn trong
H2O rt nhiu, c th ti
Gi s: S << 0,1 th
53
Chng hn kt ta AmBn trong dung dch c ion H+ c kh nng phn ng vi
B v c cht to phc L c kh nng to phc vi A, trong dung dch c cc ion
bng:
A to phc vi L:
- B phn ng ph vi H+
K1, K2 l hng s khng bn ca phc HB, H2B cng l hng s phn li ca axit
HB v H2B.
- Nu gi S l tan ca kt ta th:
54
V d: Tnh tan ca CaF2 trong dung dch HCl 10-2M cho KHF = 6.10-4 v
TCaF2 (trong nc) = 4.10-11.
Trong nc:
55
K1 kh ln, phn ng (4) xy ra d dng. Trong khi phn ng kt ta Cu2S
xy ra kh khn:
Cc qu trnh xy ra:
Trong dung dch B, Fe3+ tn ti ch yu di dng phc Floro (CF- >> CFe3+).
T cn bng (4) ta c:
56
Gi s
Ta c:
Vy vn c kt ta Fe(OH)3
4.2.4. nh hng ca nhit .
V qu trnh ha tan thu hoc ta nhit, n nh hng khng c qui lut nn
khng c nhng biu thc nh lng chung. S thay i tan mt cht theo
nhit c lin quan ti hiu ng nhit khi ha tan. i vi nhng cht thu nhit
khi ha tan th tan s tng theo nhit , th d PbI2 tan nhiu khi un nng.
tan ca AgCl 1000C ln gp 25 ln tan ca n 100C. i vi nhng cht ta
nhit th ngc li, tan gim khi nhit tng. Th d CaSO4.0,5H2O 600C c
tan ln gp 3 ln tan ca n 1000C.
4.2.5. nh hng ca kch thc ht kt ta.
i vi cng mt lng cht kt ta c dng ht nh tan nhiu hn kt ta c
dng ht ln v b mt ca cc tinh th nh c cc gc, cnh, cc ion v tr gc,
cnh d tan hn nhng v tr khc v cc ion v tr bn trong b gi cht hn.
Ngoi cc yu t k trn, cn c yu t khc nh qu trnh sp xp tinh th t
dng ny sang dng khc bn hn.
4.3. KT TA PHN ON.
Nu trong dung dch c cha hai hay nhiu con c kh nng to c kt ta
cng vi mt con khc, nhng cc kt ta hnh thnh c tan khc nhau th khi
thm cht lm kt ta vo dung dch cc kt ta ln lt c to thnh. l s
kt ta phn on.
n gin cho vic tnh ton, cc v d sau ta b qua s l thp phn ca
cc i lng tch s tan.
V d 1: Cc ion Cl-, I- u c kh nng to kt ta vi ion Ag+, nhng c tch
s tan khc nhau.
Ta c:
57
Khi thm AgNO3 vo dung dch hn hp gm Cl- v I-, v TAgI << TAgCl nn
u tin AgI kt ta v khi AgCl bt u kt ta, hai phn ng xy ra trong cng
mt dung dch nn t hai biu thc (a) v (b) ta c: khi trong dung
58
Tc l t khi nng Cl- trong dung dch nh hn hng vn ln nng
Cr)42-
Theo cc d liu ca bi ton khi Ag2CrO4 bt u kt ta th:
59
Khi lc cc kt ta keo gp rt nhiu kh khn v cc ht keo thng nh nn
phi dng loi giy lc mn, rt kh chy. Khi ra kt ta keo, cht in li dng
lm ng t keo b loi bt mt phn, kt ta c th tr li trng thi keo hin
tng ny gi l s ti keo hay pptin ha. V vy khi ra kt ta keo phi chn
cht in li thch hp trnh s ti keo.
4.5. S HA TAN CC KT TA KH TAN TRONG NC.
Qu trnh ha tan xy ra ngc vi qu trnh to kt ta, mun c qu trnh ha
tan xy ra cn lm gim tch s con ca cht t tan xung i lng b hn tch s
tan ca hp cht bng cc bin php sau:
- Ha tan kt ta trong axt hoc kim.
- Chuyn kt ta sang phc cht bn t phn li.
- Chuyn ion ca cht t tan sang dng oxi ha kh.
- Chuyn hp cht t tan ny sang hp cht t tan khc c kh nng tan d trong
thuc th thch hp.
4.5.1. Ha tan kt ta trong axt v kim
4.5.1.1. Ha tan cc hyroxit
a. Cc hyroxit kim loi tan trong cc axit to thnh mui tan v nc t phn
li. tan ph thuc tch s tan ca hyrxit v hng s phn li ca axit.
V d 1: Mg(OH)2 (pTS = 10,9) tan d trong c cc axt rt yu (NH4+ c DKa
= 9.24).
Nhng Fe(OH)3 (TS= 10-37) ch tan trong t mnh, khng tan trong cc axt yu
nh NH4+.
60
V d 2: nh gi tan ca CaCO3 trong axt axetic.
61
[H+] << [HCO3-] do c th coi nng ln HCO3- sinh ra do (5) l ch yu.
Vy c th chp nhn cch tnh gn ng trn. tan ca CaCO3 trong dung
dch bo ha CO2 l 7,3.10-3, trong khi tan CaCO3 trong nc l 7.10-5 M.
b. Cc oxalat c kh nng tan trong cc axt mnh, nhng kh tan trong axt
yu. Chng hn CaC2O4 kh tan trong axt axetic yu hn nhiu so vi axt oxalic
(pK1 = 1,25; pK2 = 4,27).
V d 4:
d. Cc sunfua c tch s tan khc nhau nn tan trong cc axit cng rt khc
nhau:
62
CdS 26, 1 9, 18 Tan d trong HCl > 1 M
CuS 35,2 -15,28 Kh tan trong HCl
HgS 51,8 -31,88 Kh tan trong HCl
Li dng tnh tan khc nhau trong cc axt m ta c th thit lp cc iu kin
tch cc mui sunfua.
V d 5: Thit lp nng HCl tch CdS v CuS.
Phn ng ha tan CdS trong HCl.
ho tan hon ton v d 0,10 mal CdS cn thit lp nng HCl bng bao
nhiu?
Gii ra ta c C = 0,73M
Trong iu kin ny CuS khng tan. V d trong HCl 2M th:
Tng t trn ta c:
63
th...
V d, mt s ion to c phc bn vi NH3 do c th dng NH3 ho
tan kt ta hyroxit ca nhiu ion kim loi: Cu(OH)2, Zn(OH)2, Ag2O, Cd(OH)2.
Mt s mui ca cc kim loi ny cng tan c trong NH3, v d AgCl tan d
dng trong NH3:
Tuy vy AgI, Ag2S, CuS, Zns, CdS c tch s tan qu b nn khng th tan
trong NH3:
Cng vy, HgS khng tan trong HCl bi v tch s tan ca HgS qu b, mc
du Hg2+ to phc bn vi ion Cl-:
Vic nh gi gn ng theo cn bng trn cho thy tan ca HgS trong HCl
1 M vo c S 3,3.10-9M. tan ny rt b mc du ln gp nhiu ln so vi
tan ca HgS trong nc (= 10-26M).
4.5.3. Ho tan kt ta trong thuc th oxi ho - kh
Nu ion ca kt ta c tnh oxy ho th c th s dng phn ng oxy ho kh
ho tan kt ta bng mt thuc th thch hp. tan ph thuc tch s tan ca
kt ta v bng hng s cn bng ca phn ng oxy ho kh. V d cc kt ta
sunfua kim loi c kh nng tan trong HNO3:
64
Thay cc i lng ny vo biu thc tnh K ta c:
65
Phn ng xy ra rt nhanh v k rt ln.
4.5.4. Ho tan cc kt ta kh tan bng cch chuyn chng sang hp cht
khc d tan trong thuc th thch hp
Mt s kt ta kh tan trong cc thuc th thng thng, V d: BaSO4,
CaSO4, SrSO4 rt kh tan trong cc axit. C th chuyn chng sang mui Cacbont
tng ng tan d trong axit.
Nu tch s tan ca mui to thnh b hn tch s tan ca hp cht cn chuyn
ho th qu trnh chuyn ho xy ra d dng. Cn nu ngc li s chuyn ho xy
ra kh khn hn.
V d 6: Tnh nng Na2CO3 phi ly 1 lt dung dch ny c th chuyn
ho hon ton cc mui sau:
a) 0.010 mol CaSO4
b 0,0 10 mol BaSO4
chuyn ho mui sunft thnh cabonnat ngi ta cho kt ta sunfat tc dng
vi mui cacbonat tan, V d: Na2CO3
66
trng hp (1) ch cn nng Na2CO3 0,010M l . Cn trng hp (2)
th cn nng Na2CO3 ln gp 50 ln. Thc t chuyn ho c th phi dng
Na2CO3 bo ho v chuyn nhiu ln, mi ln u phi un nng dung dch.
67
CU HI V BI TP CHNG
68
4.8. Ngi ta dng 20ml dung dch NH4NO3 ra kt ta MgNH4PO4. Hy
tnh nng dung dch NH4NO3 theo phn trm khi lng khi ra khng mt
qu 0,01mgMgO.
4.9. Tnh nng ion H+ t nht cn phi c trong dung dch CaCl2 0,02M v
K2C2O4 0,1 M CaC2O4 khng kt ta.
Nu dung dch gm CaCl2 2.10-2M, HCl 10-2M v K2C2O4 10-2M th CaC2O4 c
kt ta c khng?
4.10. Tnh tan ca cc sunphua sau: Ag2S, Cu2S, PbS v HgS trong nc, c
k n tng tc ca ion ca kt ta vi cc ion ca H2O.
69
CHNG 5
PHN NG OXY HO - KH
70
Bc 1: Cht kh l As2S3; Cht oxy ha l HNO3
Bc 2 v 3: thnh lp phng trnh electron v cn bng:
71
iu kin tiu chun, T = 25oC + 273 = 298o, F: 96.500C. ng thi chuyn
lnK = 2,3.lgK; R = 8,314 J/mol.K
72
5.2.2.1. nh hng ca nng
Xt chiu phn ng
a) Khi
b) Khi
Cho
T (1) ta c 2 bn phn ng:
a) Khi
Ta c:
5.2.2.2. nh hng ca s kt ta
Xt chiu phn ng:
73
Do c kt ta CuI to thnh m TCuI = 10-12 rt b nn nng Cu+ trong dung
dch gim mnh, lm th E, tng ln:
T (2) ta c:
75
1II.6
Vy E
'o
Co 3 + / Co 2 +
=E o
Co 3 + / Co 2 +
+ 0,0591 lg II
1 .6
10 4,39
'o
ECo 3+
/ Co 2 +
= 1,84 + 0,0591 lg = 0,05V ( ECo
'o
3+
/ Co 2 +
l th tiu chun iu kin)
1035, 21
Nh vy hot tnh oxi ha cu Co3+ gim, hot tnh kh ca Co2+ tng ln.
5.3. HNG S CN BNG CA PHN NG OXI HO KH.
Xt hai bn phn ng sau:
Nh vy lc cn bng ta c:
76
Thay cc gi tr: F = 96.500C, lnK = 2,3lgK, R = 8,314J/mol.K,T = 298K
Ta c:
Khi n1 = n2 = n th:
Bi gii:
Theo (5.7):
77
CU HI - BI TP CHNG 5
78
trong dung dch nng ln H+ l 1M.
Cho 0
ECe 4+
/ Ce3+
= 1,55V , 0
ECr O 2 / 2 Cr 3+
2 7
= 1,36V
0
E MnO
/ Mn2 +
= 1,51V , 0
E Fe 3+
/ Fe 2 +
= 0,77V
4
E I02 = 0,54V ,
2l
79
PHN TH HAI
CC PHNG PHP PHN TCH HA HC
CHNG 1
PHN TCH KHI LNG
80
Mg2P2O7 hp cht c to thnh sau khi nung dng kt ta v em cn xc
nh hm lng ca Mg c gi l dng cn. Phng php phn tch khi lng
Mg nh trn c gi l phng php kt ta. Phng php kt ta l phng
php c s dng ph bin nht trong phn tch khi lng.
xc nh CO2 trong qung ccbnt ngi ta phn hy lng mu CaCO3
bng axit trong mt dng c ring:
81
cao ti khi c khi lng khng i chuyn chng thnh Fe2O3 hoc Al2O3 l
nhng dng cn phi tha mn nhng yu cu sau:
- Phi c cng thc xc nh, c thnh phn khng i t khi sy hoc nung
xong n khi cn n trn cn phn tch. Th d, dng cn khng c ht m,
khng hp th kh CO2 c trong khng kh, khng b phn hy bi nh sng...
tha mn yu cu ny cn phi tin hnh phn tch theo nhng k thut nht nh.
H s chuyn (cn gi l h s phn tch) cng nh th cng tt. Th d, c th
xc nh Cr3+ di dng cn l BaCrO4 hoc Cr2O3. Gi s, sai s tuyt i khi cn
BaCrO4 v Cr2O3 u l 1 mg, nhng khi cn dng Cr2O3 th sai s l 52 x 2/152
= 0,7mg Cr, cn khi cn dng BaCrO4 th sai s l 52x1/253,3 = 0, 20mg Cr, nh
hn trng hp trc 0,7/0,2=3,5 ln.
1.3. CCH TNH KT QU TRONG PHN TCH KHI LUNG
a/ H s chuyn cn gi l h s phn tch
Thng thng dng cn khng phi l dng cn xc nh hm lng, v vy, t
khi lng ca dng cn tnh khi lng ca dng cn xc nh hm lng. Do ,
tin cho vic tnh kt qu phn tch, ngi ta a ra khi nim h s chuyn.
l i lng m ta cn phi nhn khi lng ca dng cn vi n c khi
lng ca dng cn xc nh, thng thng h s chuyn l t s ca khi lng
ca mt, hai hoc nhiu nguyn t hoc phn t hoc tn ca dng cn xc nh v
khi lng phn t ca dng cn. Ni cch khc h s chuyn ch ra c bao nhiu
gam nguyn t (cht) cn nh phn trong 1 gam dng cn. Trong trng hp cn
xc nh Si th h s chuyn t SiO2 (dng cn) thnh Si dng cn xc nh l:
Nu p (g) mu cha trong v (ml) dung dch m ly ra v (ml) phn tch th:
83
CHNG 2
PHN TCH TH TCH
Ta cho phenolphtalein vo bnh nn cha HCl, dung dch khng mu. Nhng
khi lng HCl ht th 1 git NaOH d xung s lm dung dch chuyn sang mu
hng do phenolphtalein tc dng vi OH-.
2.1.1.2. Cc yu cu ca phn ng dng trong phn tch th tch
Do qu trnh chun din ra nhanh li i hi nhn bit i mu tc khc
kt thc chun ng lc nn phn ng trong phn tch i hi cc yu cu sau:
a) Phn ng phi hon ton: C ngha l phn cht cn li sau khi kt thc
nh phn nh hn sai s cho php.
V d: Sai s 0,1% l cho php c. iu c ngha l tc phn ng
phi ln, qua tnh ton v qua thc t tc phn ng phi ln hn 106.
Nu phn ng din ra khng hon ton th phi c bin php thc y phn ng
84
bng cch to phc hoc kt ta vi sn phm, v d:
hoc axit mnh s phn ng vi CrO42- (cht ch th) theo phn ng:
85
th nm trong bc nhy pH ca php chun , v d Phenolphtalein,
metyldacam.
b) Chun oxy ho kh (cn gi l phng php oxy ho kh): Phng php
ny c da trn vic xc nh nng cc cht oxy ho (hoc cht kh) bng
cc cht kh (hoc oxy ho) ch th ca php chun l cht ch th oxy ho kh
c khong th i mu nm gn hoc gn gn trong bc nhy th.
V d chun Fe2+ bng dung dch chun Cr2O7.
Sau khi lng Fe2+ (di bnh nn) ht th Cr2O72- d s phn ng vi iphenyl
quan, lm cho n bin i t khng mu sang mu tm xanh. Khi ta kt thc
nh phn.
c) Chun kt ta (phng php kt ta): Sn phm to thnh l kt ta, song
vn nhn bit c s i mu ch th no . V d vic xc nh Cl- bng
AgNO3, khi d AgNO3 n s phn ng vi K2CrO4 (l Cht ch th di bnh
nn):
86
b) Chun gin tip: l vic xc nh nng cht nh phn thng qua
sn phm to thnh gia A (dung dch nh phn) v B (dung dch chun).
V d:
(P l phn t gam ca cht tan n l i lng c trng cho tng loi phn
ng).
- Trong phn ng trung ho, n: S mol H + (hoc OH-) ca axit(hay baz) trao
i.
87
- Trong phn ng oxy ho kh, n = s electron m cht oxy ho (hoc cht
kh) trao i.
chun
88
V d 1: C bao nhiu gam Ba(OH)2 ho tan trong 250ml dung dch nu chun
20ml dung dch ny ht 22,4ml dung dch HCl 0,09884N? Ta c phn ng
chun :
90
V vy trong mi trng axit v trung tnh phenolphtalein tn ti ch yu di
dng lacion khng mu, trong mi trng baz tn ti ch yu di qui non mu
hng, nhng trong mi trng kim mnh li tn ti dng khng mu.
Metyl da cam c th tn ti trong dung dch di cc dng sau:
1/10 - 10. Ni cch khc khi nng ca dng axit chnh lch vi nng dng
baz khong 10 ln th ta ch thy c mu ca dng c nng ln. Thay i t
s nng :
vo biu thc (2.7), ta c:
91
Nh vy, khong i mu m mt ta nhn thy c l 2 n v pH. Tuy nhin
i vi mt s cht ch th mt ta c th nhn c s i mu nh hn 2 n v,
ngha l khi t s nng ca cc dng nh hn 10 ln. i vi cht ch th loi
IndOH, ta cng lp lun tng t xc nh khong pH i mu. Trong bng sau
y l mt s cht ch th axit - baz quan trng nht.
Bng 2. Mt s cht ch th axt-baz quan trng
Tn thng dng Khong i mu pKa Mu ca dng axit-baz
Thimol xanh 1,2 - 2,8 1,65 vng
Metyl vng 2,9 - 4,0 3,55 - vng
Metyl da cam 3,1 - 4,4 3,46 da cam
Bromcresol xanh 3,8 - 5,4 4,66 Vng - xanh
Metyl 4,2 - 6,3 5,00 - vng
Bromcresol ta 5,2 - 6,8 6,12 Vng - ta
Bromthimol xanh 6,2 - 7,6 7,10 Vng - xanh
Phenol 6,8 - 8,4 7,81 Vng -
Cresol ta 7,6 - 9,2 8,40 Vng - ta
Phenolphtalein 8,3 - 10 9,15 K0 - hng
Thimolphtalein 9,3 - 10,5 9,90 K0 - xanh
Alizann vng GG 10 - 12 11,00 K0 - vng
i vi loi cht th th c mu tc l ch mt trong hai dng axit - baz lin
hp c mu, chng hn cht ch th loi HInd m dng HInd khng mu th mu
ca dung dch s do nng dng c mu Ind- quyt nh. Nu C l gi tr m
nng Ind- cn t ti ta nhn ra mu ca n v Co l nng ban u ca
cht ch th th pH ca dung dch ti mu ca Ind bt u xut hin l:
92
2.2.1.2. ng nh phn
ng nh phn trong chun axit - baz l ng biu din s lin h gia
nng cn bng ca ion H+ v lng axit hoc baz chun . Thit lp c
phng trnh nh phn ta c th v c ng thy c s bin thin pH
ca dung dch trong qu trnh chun , chn cht ch th thch hp cho vic
chun v khi c phng trnh ng phn nh ta d dng tnh sai s ch th.
a. ng nh phn khi chun axit mnh bng baz mnh: Gi s chun
V0 ml axit mnh HA nng Co (mol/l) bng dung dch chun baz mnh NaOH
hoc KOH nng C (mol/1).
Phng trnh phn ng chun l:
93
Phng trnh trn cho ta thy nng [H+] bng nng axit cha c chun
b pha long bng V ml dung dch chun NaOH c thm vo. Tuy nhin,
iu ny ch ng khi tng i xa im tng ng. Cng gn n im tng
ng ta phi k n s phn ly ca nc. Ti im tng ng khi F = 1, t
(2.14) ta c:
94
c quy c l bc nhy ca ng nh phn. Trong trng hp ny bc
nhy ca ng nh phn l 5,4 n v pH (9,70 - 4,30)
- Da vo bc nhy ca ng nh phn ta c th d dng chn cht ch th.
Trong trng hp ny ta chn bt k cht ch th pa no c pT nm trong bc
nhy. Tc l trong khong pH t 4,3 - 9,7 ta u nhn ra im tng ng vi
sai s khng vt qu 0,1 %.
95
phng trnh trn c n gin ha thnh:
96
im cui tc l theo pT ca cht ch th. i vi trng hp chun axit mnh
bng baz mnh t phng trnh (2.14) ta c:
Th d 2: Nu chun dung dch HCl 0,1M bng dung dch NaOH 0,1 M th
cn kt thc trong khong pH no sai s ch th khng qu 0,1 %. i vi sai s
- 0,1 % tc l S = - 0,001: ngha l lng NaOH thm vo cha . p dng cng
thc (2.20), ta c:
97
Nh vy, mun sai s ch th khng vt qu 0,1 % ta phi kt thc chun
trong khong pH t 4,3 v 9,7 hay ni cc khc l dng cc cht ch th c pH nm
trong khong 4,3 - 9,7.
b. Chun n t yu bng baz mnh
Phn ng chun :
Phng trnh trn l phng trnh bc 3 theo [H+] nhng trong cc giai on
ca qu trnh chun n c n gin ha.
Khi cha chun F = 0, V = 0 trong dung dch Axt nng C, ta b qua
nng ln OH-, phng trnh (2.22) c bin i thnh:
T (2.26) suy ra c:
98
Trong phng trnh (2.27), 1 - F ng vi phn axt HA cn li cha c chun
, cn F ng vi phn axit c chun sinh ra baz A- lin hp vi n.
v vy, phng trnh chnh l phng trnh tnh pH ca dung dch m gm axit
HA v baz lin hp A-.
Ti im tng ng F = 1, ta c dung dch A-, nn [OH-] >> [H+] v phng
trnh (2.22) tr thnh:
100
Cng axit (pKa) pH tng ng Bc nhy pH pH
3,0 7,85 5,7 10,0 4,3 v
4,0 8,35 6,7 10,0 3,3 v
5,0 8,70 7,7 10,0 2,3 v
7,0 9,85 9,7 10,3 0,43 v
9,0 10,85 10,84 10,9 1 0,06 v
Qua cc kt qu trn ta thy, cc dung dch axt cng nng nhng c pKa
khc nhau th vi axit cng yu, tc c pKa cng ln th pH ti im tng ng
cng ln hn 7 nhiu v bc nhy pa ti im ng ng cng ngn. Khi pKa
bng 9 th thc t khng c bc nhy. i vi axit c pKa bng 7 bc nhy pH
cha t c 0,5 n v pH; nn kh chn c cht ch th c th phn bit
c s i mu bng mt thng. i vi axit c pKa bng 8 hoc 9 th khng th
chun c v khng th chn c cht ch th.
- Bc nhy ca ng nh phn cn ph thuc vo nng ca axit cn
chun v nng ca dung dch chun baz mnh.
Ta hy tnh nc nhy ng nh phn khi chun cc dung dch
CH3COOH pKa = 4,75 c cc nng l 1,0; 0,1; 0,01; 0,001M bng cc dung
dch chun NaOH cng nng . Trong trng hp ny gi s bc nhy ng vi
F - 1 = 0,002; tc l chun thiu v tha 0,2% lng axit cn chun . Sau
khi gii phng trnh (a), ta c cc kt qu sau:
Nng CH3COOH v NaOH pH bc nhy pH
100 M 7,45 - 11,0 3,55 v pH
0,10 M 7,45 - 10,0 2,55 v pH
0,01 M 7,44 - 9,0 1,50 v pH
0,001 M 7,37 - 7,8 0,43 v pH
Qua cc v d trn ta thy bc nhy cng ngn nu nng axit cng nh. Cc
dung dch nng nh hn 0,001M gn nh khng c bc nhy, nn nu chun
s mc sai s ch th rt ln hoc khng th chn c cht ch th.
Phng trnh tnh sai s ch th khi chun axt yu bng baz mnh: T
phng trnh ng nh phn ta rt ra phng trnh tnh sai s cht ch th:
101
Nn im cui gn im tng ng th:
a) Trng hp pH = 4:
V [H+] = 10-4 v [OH-] = 10-10 nn c th b qua s hng th hai trong phng
trnh (2-31) tnh sai s:
102
Sai s rt nh v ch ch chun tha 0,02% lng axit.
V d 2: tnh sai s chun dung dch CH3COOH 10-3M bng dung dch
NaOH cng nng v kt thc chun khi pH = 7,5.
p dng phng trnh (2.28) tnh pH im tng ng:
103
phn n axt mnh. Bc nhy di hay ngn cn ph thuc vo cng baz v
nng ca n, baz cng yu th bc nhy cng ngn, nng baz cn nh
phn cng nh bc nhy cng cng ngn.
Ta hy dng phng trnh (2.34) tnh pH ti im tng ng v pH bc
nhy (vi qui c chun thiu v tha 0,2% lng baz) khi chun dung
dch NH3 c nng khc nhau 1 M; 0,1 M; 0,001 M bng dung dch HCl cng
nng .
Ti im tng ng tc l khi F = 1, phng trnh (2.34) c n gin ha
khi b qua [OH-] cnh [H+], Ka= KNH4+ = 10-9,25 cnh [H+] v C0 = C nn khi -
tr thnh v ta c:
V d: Tnh sai s khi chun dung dch NH3 0,1 M bng dung dch HCl
0,1M dng cht ch th c pT bng a) 5; b) 4,0.
104
a) Trng hp kt thc chun khi pH = 5. Ta tnh pH ti im tng ng
pHt = 4,78 - 0,5lg0,1 = 5,28
Khi pH = 5,0 tc l [H+] = 10-5 nn c th b qua [OH-] cnh [H+] v b qua
KNH4+ cnh [H+]. V pH ny gn pH ti im tng ng v v C = Co nn thay
105
Nhn 2 v ca phng trnh trn vi ta c:
106
Bin i, chuyn v ta tnh ra H+:
Phng trnh (2.40) trn cng l phng trnh bc 3 theo [H+] nhng trong giai
on ca qu trnh chun n c th n gin ha. Khi ang chun nc th
hai, cn xa im tng ng th 2 ta c th b qua c [H+], [OH-], [A2-] v
[H2A] nn (2.40) c n gin ha thnh:
v suy ra
107
Phng trnh (2.41) chnh l phng trnh tnh pH ca dung dch h m HA
v A2- trong biu thc (2.41), 2- F1 ng vi nng HA- cn li cha b trung ha.
Cn 1-F ng vi nng phn HA- b trung ha thnh A2-. st im tng
ng th 2 ta c th b qua c [OH-], [H2A], [HA-] nn phng trnh ng
nh phn cn l:
Ti im tng ng th 2,
108
Hnh2.3. ng nh phn dung dch H2C2O4 0,1M
bng dung dch chun NaOH 0,1M.
e. nh phn a baz bng n axit mnh:
Chng ta xt trng hp c th: nh phn dung dch CO32- mt tia baz rt
thng gp trong thc t. V d: phi chun dung dch (Vo ml) Na2CO3 nng
Co bng dung dch chun HCl nng mi C. Phng trnh ng nh phn:
Chun CO32- theo nc th nht:
Phng trnh trn l phng trnh tng qut, n cng c n gin ha trong
tng giai on ca qu trnh chun .
- Khi cha chun F = 0, ta b qua c [H+] cnh [OH-], [H2CO3] cnh
[CO32-] nn (2.45) c n gin ha thnh:
109
T phng trnh trn suy ra:
V d 1: Tnh sai s ch th khi chun dung dch Na2CO3 0,1M bng dung
dch HCl 0,1 M. Theo nc th nht khi dng cht ch th c pT = 9.
p dng phng trnh (2.47) tnh F - 1 ti im pH = 9 ta c S = - 0 0477
tc l sai s bng -4,77%.
V d 2: Tnh sai s ch th khi dng cht ch th c pT = 4 nhn ra im
tng ng khi chun dung dch Na2CO3 0,1M bng dung dch chun HCl
0,1M. Gi thit l ton b CO2 cn li trong dung dch.
tnh sai s ta dng phng trnh (2.50) tnh F - 2. Khi thay [H+] = 10-4, C
= Co = 0,1 vo ta tnh c:
110
F - 2 = - 0,00146 = -0,0015.
tc l sai s thiu 0,075%.
V d 3: Cn thm bao nhiu ml dung dch HCl 0,05M vo 20 ml dung dch
Na2CO3 0,1M pH ca dung dch thu c bng a) 9,0 v b) 5,0. (Gi s khi pH
bng 5,0 ton b kh CO2 cn li trong dung dch.) c) khi pH = 5,0 em un si
dung dch lng CO2 trong dung dch khng ng k th pH ca dung dch bng
bao nhiu v khi thm tip HCl 0,1M th cn thm tip bao nhiu ml HCl vo
pH ca dung dch = 4,0. Gi s lc ny nng CO2 cng khng ng k.
a) Gi th tch dung dch HCl cn thm vo pH ca dung dch thu c bng
9,0 l V. tnh V ta dng phng trnh (2.47):
112
im tng ng ca phn ng chun ngi ta cng dng cc cht ch th.
113
phng trnh trn. Gii phng trnh , sau khi c n gin ha cc i
lng nh bn cnh cc i lng ln ta c V2 = 99,37 ml.
Nh vy nu chun H3PO4 theo mt nc da vo s i mu ca cc cht
ch th c pT = 4, pT = 9 th th tch theo thc nghim l Vo = 99,37 - 59,43 =
39,94 ml. Theo u bi, v nng ca H3PO4 = 2 ln nng NaOH nn th tch
NaOH ng vi im tng ng khi chun theo mt nc l 20x2 = 40,00ml.
Do sai s i vi H3PO4 l:
Trong phn trn (2.48) chng ta bit rng c th chun a baz Na2CO3
bng dung dch chun HCl dng 2 cht ch th l phenolphtalein (vi im tng
ng th nht) v metyl da cam (vi im tng ng th hai). V vy, ta cng
c th chun dung dch hn hp NaOH v Na2CO3 bng dung dch chun HCl,
hai cht ch th tng t nh chun dung dch hn hp HCl + H3PO4 bng
dung dch chun NaOH trnh by trong phn trn. Khi phenolphtanein i mu
ta chun NaOH v nc th nht ca Na2CO3.
t th tch dung dch hn hp hai baz trn l Vo, nng dung dch chun
HCl l C, th tch dung dch HCl khi phenolphtalein i mu l V1, khi metyl da
cam i mu l V2, th tch dung dch HCl dng chun mt nc ca Na2CO3
l V2 V1 (Cc th tch c tnh t im 0 ca buret). Th tch HCl chun
NaOH l V1 - (V2 V1) = 2V1 - V2. Do biu thc tnh nng tng cht l:
V d 2: Cn thm bao nhiu ml dung dch cho 0,05M vo 100ml dung dch
hn hp NaOH 0,1M + NaHCO3 0,02M pH ca dung dch hn hp thu c
114
bng a) 9,0 v b) 4,0. bit H2CO3 c pK1 = 6,35; pK2 = 10,3.
t th tch dung dch hai baz l Vo, nng HCl l C, th tch dung dch
chun HCl thm vo pH t c 9,0 l V1, t c pH = 4 l V2 (V1, V2
tiu c tnh t im ca buret). Nng ca NaOH trong hn hp l Co, ca
Na2CO3 l Co.
a) Tnh th tch HCl cn thm vo pH = 9,0.
Phng trnh bo ton proton xut pht t H2O v HCO3-:
Khi [H+] = 10-9, ta b qua c [H+], [H2CO3], [OH-] dng phng trnh trn,
nn n ch cn:
dung dch [H+] = 10-4, th phng trnh (b) c n gin ha khi b qua
[OH-], [CO32-] thnh:
115
Th tch dung dch chun HCl dng chun NaOH l
238,1 - 41,5 = 196,56.
Nng ca dung dch NaOH l
sai s l:
Bng phng php tng t, chng ta c th chun dung dch hn hp
NaOH + Na3PO4 bng dung dch chun HCl dng hai cht ch th l phenolphtalein
(khi chun ton b NaOH v Na3PO4 thnh Na2HPO4) v metyl da cam (khi
chun Na2HPO4 thnh NaH2PO4).
2.2.2. Phng php chun to phc
Cc phng php chun to phc da trn phn ng to phc ca cc cht.
Trong phn tch th tch, ngi ta thng dng cc phng php chun to
phc sau y:
Phng php thy ngn II. Phng php ny da trn phn ng to phc bn
gia con Hg2+ vi cc anion clorua, bromua, iodua v xianua. Th d:
Phng php bc: Phng php ny da trn phn ng to phc ca ion Ag+
v ion xianua.
116
2.2.2.1. Cht ch th trong phng php complexon
xc nh im tng ng ca phng php chun complexon, ngi
ta dng mt s loi cht ch th, loi cht ch th c s dng nhiu nht (c ti
hng chc cht khc nhau) c gi l cht ch th mu kim loi. y chng ta
ch xt loi cht ny.
Cc cht ch th mu kim loi l nhng cht mu hu c c kh nng to vi
cc ion kim loi phc cng cua c mu v trong nhng iu kin xc nh mu ca
phc khc vi mu ca cht ch th t do. Cc cht ch th mu kim loi thng
l nhng axit hu c yu hoc baz yu, phn t ca chng cha nhng nhm
mang mu v tr mu nn cng l nhng cht ch th pH. Do c im k trn mu
ca cht ch th loi ny bin i theo pM (pM = - lg[Mn+]) v theo pH ca dung
dch.
Khi chn cht ch th cho s chun mt ion kim loi no bng phng
php complexon, ngi ta phi chn pH thch hp (bng cch dng cc dung dch
m thch hp) phn ng to complexonnat kim loi xy ra hon ton, cht ch
th t do v phc ca cht ch th vi ion kim loi phi c mu khc nhau, d phn
bit v s i mu ca cht ch th phi xy ra rt gn im tng ng, bn
ca phc gia kim loi vi Complexon bn hn vi ch th.
Khong i mu ca cht ch th mu kim loi l khong tm trong c th
xy ra s bin i mu ca cht ch th.
Gi s Ind l dng ca cht ch th to vi ion kim loi phc mu. Da vo cn
bng:
117
Ion Ind3- cn phn ng vi ion H+ to thnh nhng dng axit c mu khc
nhau:
118
vo pH ca dung dch, khi pH < pK2 cht ch tn ti trong dung dch ch yu di
dng H2Ind mu . Khi pK2<PH<pK3 cht ch th tn ti ch yu trong dung dch
di dng HInd2- mu xanh v khi pH > pK3 cht ch th trong dung dch tn ti
ch yu di dng Ind3- mu da cam.
Da vo phng trnh (2.56) ta c th v c gin s ph thuc ca
khong i mu ca cht ch th vo pH ca dung dch. Trn hnh 2.4 l gin
i vi trng hp ET - 00 - Mg2+.
Cng nh trong phng php trung ha chn cht ch th thch hp cho s
chun mt ion kim loi no , trong phng php complexon ngi ta cng
da vo ng nh phn hoc vic tnh sai s ch th.
Trn hnh 2.4 l gin biu din s ph thuc khong i mu ca ET - 00
i vi ion Mg2+ v pH ca dung dch. Da vo th ny v ng nh phn khi
chun magi ta thy c vic chn iu kin nh th no (chn pH dung dch
nh th no) khong i mu nm trong bc nhy ca ng nh phn.
Phng trnh (2.57) l phng trnh ng nh phn khi chun ln kim loi
M bng dung dch chun EDTA. Bng phng trnh ta c th tnh chnh xc M
theo F t suy ra theo cng thc:
120
phng trnh bc 2, nhng n c th c n gin ha trong tng giai on ca
qu trnh chun :
- Trc v tng i xa im tng ng, nu kh ln. [Y'] s khng ng
k cnh [M'], phng trnh (2.57) c n gin ha thnh:
121
0,01M. Phc Mg2+ vi EDTA c = 108,7.
Trong dung dch ny c ion Mg2+ thc t ch to phc vi EDTA do hng s
bn iu kin ca phc l:
122
Hnh 2.5. ng nh phn khi chun dung dch Mg2+ 0,01M
Th d: Nu quy c bc nhy l hiu pMg khi F tng t 0,99 - 1,01 th bc
nhy khi chun Mg2+ 0,01M pH bng 10 bng dung dch EDTA cng nng
l 1,4 n v pMg, bc nhy khi chun dung dch 0,1M cng pH bng
dung dch EDTA cng nng l 2,4 n v pMg. Hng s bn iu kin ph
thuc vo pH ca dung dch. Th d i vi ion Mg2+ khi tng pH nu hng s bn
iu kin cng ln th bc nhy cng di. Da vo ng nh phn v gin
i mu ca cht ch th cho vic chun mt tn kim loi bng EDTA. Th
d theo gin 24 ti pH bng 10 cht ch th ET - 00 i mu trong khong tng
t 4,3 - 5,7; khong nm trong bc nhy ca ng nh phn ca cc dung
dch Mg (II) 0,1 M v 0,01 M bng dung dch chun EDTA cng nng .
2.2.2.3. Mt s cht ch th quan trng dng trong cc phng php chun
complexon
Ngy nay ngi ta tng hp c hng chc thuc th hu c lm cht ch
th mu kim loi trong chun complexon. Sau y l mt s cht ch th quan
trng nht c s dng rng ri trong cc phng th nghim phn tch v s lng
cc cht ch th rt nhiu, nn tnh ph bin ca cc phng php chun
complexon ngy cng c m rng v ngi ta ni cc phng php chun
complexon l ht nhn ca phn tch th tch hin i.
Eriocrom en T (ET- 00)
l mui natri ca axit (1-oxi -2 -naphtylazo)-6-nitro-2-naphtol-4- sunfonic.
Cng thc cu to ca cht ch th l:
123
ET - 00 l cht mu, cht ch th t do c mu khc nhau ph thuc pH ca
dung dch ha tan n. Cht ch th l a axit H3Ind. Khi pH = 6 cht ch th c mu
nho, trong dung dch c pH nm trong khong 7 - 11 n c mu xanh bic, khi
pH = 11,5 n c mu da cam. V H3Ind c pK1 = 6,3; pK2 = 11,5 5.
ET - 00 to phc hoc hng vi cc ion kim loi Mg2+, Zn2+, Cd2+ thng
c dng chun trc tip cc ion trong mi trng c pH = 10 dng hn
hp m NH3 - NH4+. Ngoi ra n cn c dng nh phn gin tip cc ion
kim loi khc nh nh phn Ni2+, Pb2+ bng phng php chun ngc vi
mui Zn2+ (pH = 10), chun Ca2+ pH = 10 bng cch thm phc MgY2- vo.
Murexit
Murexit l mui amoni ca axit pupuric C8H5O6N5. Trong mi trng axit
mnh anion H4Ind- c cng thc cu to nh sau:
Anion H4Ind- ca Murexit trong dung dch axit mnh, axit pupuric l a axit c
pK1 = 0, pK2 = 9,2, v pK3 = 10,9. Nn mu ca cc dng ca cht ch th ph
thuc vo pH ca dung dch.
Trong dung dch nc c pH < pK2 cht ch th c mu tm, trong khong
pH t pK2 - pK3 c mu tm hoa c v khi pH = pK3 cht ch th c mu xanh tm.
Murexit to phc vi cc ion kim loi sau: vi Ca2+ khi pH = 12 phc mu ;
vi Co2+, Cu2+ v Ni2+ khi pH trong khong 7 - 9 (dung dch m amoniac) phc
c mu da cam; vi ion Ag+ trong dung dch m NH3 pH = 10 - 11,5 phc c mu
.
Murexit l cht ch th tt cho vic chun trc tip cc ion Ca2+, Cu2+, Ni2+
v Ag+.
124
2.2.2.4. Phng php bc. Chun xianua
Trong phng php to phc ny ngi ta chun dung dch xianua bng
dung dch chun bc thut.
Trong qu trnh chun , trc im tng ng, trong dung dch c d cc
ion CN- nn xy ra cc phn ng to phc:
125
Phng php chun kt ta da trn vic s dng cc phn ng to thnh
cc hp cht kh tan (kt ta). Cc phn ng kt ta c s dng phi tha mn
cc yu cu sau:
- Kt ta c to thnh trong phn ng chun phi thc t khng tan, tc l
phn ng phi hon ton v theo mt t lng xc nh.
- Tc to thnh kt ta phi ln, tc l khng to thnh dung dch qu
bo ha.
- Phn ng phi chn lc, ngha l nh hng ca cc qu trnh cng kt, hp
ph, kt ta theo phi khng ng k.
- Phi c cht ch th thch hp xc nh c im tng ng. Tuy s
lng cc phn ng kt ta rt nhiu nhng thng khng tha mn cc yu cu
trn nn a s cc phn ng ch c p dng trong phn tch nh tnh cn rt
t c p dng trong phn tch nh lng. Trong thc t phn tch, ngi ta
thng ch dng cc phng php chun kt ta sau:
- Phng php bc, trong dng dung dch chun AgNO3 chun cc ion
halogenua Cl-, Br-, I- v thioxianat SCN-
Khi thm vo dung dch phn tch V ml dung dch chun (1) xy ra th cc
ion Ag+ v X- c nng cn bng lin h vi nhau bng cc h thc sau:
126
Trong , U l s mol kt ta ng vi 1 lt dung dch.
t tc l phn lng anion X- c chun ri ly (3) tr i
(2) v nhn 2 v ca phng trnh nhn c vi ta c:
127
dch chun AgNO3 0,1M.
F Cl- 0,1M Cl- 10 M I- 0,1 M
pCl pAg pCl pAg pI pAg
0,50 1,48 8,52 0,48 9,52 1,48 14,52
0,90 2,28 7,72 1,28 8,72 2,28 13,72
0,99 3,30 6,70 2,30 7,70 3,30 12,70
0,999 4,30 5,70 3,30 6,70 4,30 11,70
1,000 5,00 5,00 5,00 5,00 8,00 8,00
1,01 6,70 3,30 7,70 2,30 12,70 3,30
1,10 7,70 2,30 8,70 1,30 13,70 2,30
1,50 7,97 0,03 7,67 0,33 15,67 0,33
v ng nh phn trong v d ny ta tnh ph hoc pH theo F khi F =
0,999 ta p dng cng thc (2.63) tnh ph v t ph tnh pH. Khi F = 1,01 ta
dng cng thc (2.65) rt st im tng ng nu mun tnh ta dng cc cng
thc (2.62) v (2.63).
Trn bng (2.62) l cc gi tr tnh c ca ph, pH v tri khi chun cc
dung dch cc dung dch Cl-, I- bng cc dung dch AgNO3 cng nng .
2.2.3.3.ng nh phn
Ta thy cc ng nh phn cc dung dch Cl- v I- bng dung dch chun
AgNO3 cng nng l cc ng c bc nhy theo ph ti vng st im tng
ng v ng nh phn i xng qua im tng ng. Ti im tng
ng nng ca cc ion to nn kt ta bng nhau. Nng dung dch cng
ln, tch s tan ca kt ta cng b th bc nhy pAg ti im tng ng cng
ln (hnh 2.6).
128
Hnh 2.6. ng nh phn cc dung dch Cl- v I-
bng cc dung dch chun AgNO3 cng nng .
V d 1:
Tnh sai s khi chun dung dch Cl- 0,1M bng dung dch chun Ag+ cng
nng nu kt ta chun khi pAg = 4,3. Ly tch s tan ca AgCl- l 10-10.
Kt thc chun pAg = 4,3 tc l khi [Ag+] = 5.10-5. p dng phng trnh
129
(2.69) ta c
V d 2:
Chun dung dch NaCl 0,1 M bng dung dch chun AgNO3 0,1 M.
Mun sai s chun khng vt qu 0,2% th phi kt thc chun trong
khong ph no? Cho TAgCl = 10-10.
Ta phi tnh ph khi F - 1 = 0,002.
Khi F - 1 = -0,002.
131
trn ng nh phn ch c mt bc nhy pH ng vi s chun tng s c hai
axit ch hu nh khng c bc nhy pH im tng ng th nht i vi s
chun mt mnh HCl. vng gn im tng ng th nht th CH3COOH
bt u s chun sinh ra CH3COO- to thnh mt h m (CH3COOH +
CH3COO-) nn pH bin thin rt t t lm ng nh phn khng c bc nhy
pH im tng ng th nht .
Trong phn trn chng ta bit, i vi dung dch H3PO4 l a axit c pK1 <<
pK2 << pK3 v pK2 = 7,21 khng qu nh nn ta c th chun c tng nc
ca dung dch axit vi hai cht ch th l metyl (cho nc th nht) v
phenolphtalein (cho nc th hai). V vy, trong trng hp ny ta c th chun
c hn hp hai axit HCl v H3PO4 dng hai cht ch th . Khi thm dn dung
dch NaOH vo dung dch hn hp 2 axit , u tin HCl b chun :
132
mu vi mt cht khc chng hn tt to mu xanh vi h tinh bt th cng dng
cht (h tinh bt) lm cht ch th cho phn ng chun tt hoc dung dch
cht kh bng dung dch chun tt. Trng hp ny h tinh bt khng tham gia
phn ng oxi ha - kh. Trong i a s cc trng hp cht ch th trong phng
php oxi ha - kh l nhng cht oxi ha - kh m dng oxi ha v dng kh ca
n c mu khc nhau. V vy, mu ca cht ch th ph thuc vo th oxi ha - kh
ca dung dch. Mi cht ch th oxi ha - kh cng c mt khong i mu. Ta hy
xt mt cht ch th oxi ha - kh. Gia dng oxi ha v dng kh ca n c cn
bng trao i electron.
133
c s dng di dng dung dch HCl long. Cht ch th ny c th oxi ha -
kh tiu chun l +O,97V. Dng oxi ha mu xanh nht, dng kh c mu .
Feroin:
Phc ca Fe2+ vi 1,10 - phenaltrolin:
Cht ch th ny c cng thc cu to l:
Dung dch cht ch th c chun b bng cch ha tan 1,26 g phenal - trong
clohydrat v 0,695 g FeSO4 trong 100 mi nc. Cht ch th ny c Eo l + 1,06V.
Dng oxi ha mu xanh nht, dng kh mu .
Axit fenylantranilic Cht ch th ny c cng thc cu to l:
134
Phn ng trao i electron ca tng cht trong cp ca n:
Phng trnh bo ton electron ca dung dch xut pht t sn phm phn ng
(Ce3+, Fe3+), khi thm V ml dung dch Ce4+ vo Vo ml dung dch Fe2+:
Ta bit rng:
nn suy ra:
Nn (4) tr thnh:
135
Chia t v mu s ca v phi phng trnh (4') vi Fe2+, ta c:
T suy ra:
qu nh ta c:
137
Hnh 2.7. ng nh phn dung dch Fe2+ 0,1M
bng dung dch Ce4+ 0,1M.
Cn ch l i vi c hai h va xt h s ca cht oxi ha v cht kh lin
hp trong phng trnh trao i electron l bng nhau nn cc phng trnh thit
lp tnh th khng ph thuc vo nng ca cc cht. Tuy nhin i vi
trng hp cc h s.bt i xng th cc kt qu s khc i. Ta hy tnh th trong
qu trnh chun dung dch Fe2+ bng dung dch chun Cr2O72- trong mi trng
axit.
b. Chun Fe2+ bng Cr2O72- Gi s ta cn v ng nh phn khi chun
dung dch Fe2+ 0,1M bng dung dch chun K2Cr2O70,03M trong mi trng axit
c [H+] = 1M. Bit cc th tiu chun
138
Phn ng gia Fe2+ v Cr2O72- xy ra rt hon ton v th tiu chun ca hai cp
khc nhau nhiu (K = 1066,1). Do , trc im tng ng ta b qua c
[Cr2O72-] bn cnh [Fe2+] trong phng trnh (2.75), phng trnh cn:
Kt hp vi phng trnh
Sau im tng ng. Khi F> 1, ta b qua nng [Fe2+] trong phng trnh
(2.77) v tnh th theo phng trnh Nernst ca h Cr2O72-/Cr3+:
Trong
139
Hnh 2.8. ng nh phn dung dch Fe2+ 0,1N
bng dung dch Cr2O72- 0,2M
140
2.3.1.2. ng dng v tnh ton
Phng php trung ho c dng xc nh nng cc baz t axit gc
hoc ngc li. V d, dng H2C2O4 tiu chun xc nh nng NaOH vi ch
th l phenolphtalein, sau li dng NaOH xc nh nng HCl, CH3COOH
vi ch th phenolphtalein, ri t HCl ta li xc nh nng NH4OH vi ch th
metyl da cam. xc nh nng ca chng ngi ta tin hnh chun trc
tip H2C2O4, HCl, CH3COOH bng NaOH v chun trc tip NH4OH bng HCl
v tnh ton trc tip theo cng thc ca nh lut ng lng.
Nu coi:
142
Cn nng chung ca hn hp HCl v H3PO4:
b) Xc nh cng ca nc:
* cng tm thi ca nc c tnh bng s mt ng lng gam mui
cacbonat axit magi v canxi trong mt lt nc
xc nh KTT ngi ta chun trc tip nc cng bng dung dch chun
H vi ch th metyl da cam, phn ng chun xy ra:
Khi metyl da cam i mu th dng chun v ghi th tch HCl tiu tn (V1).
Do :
chun ngc.
u tin, kt ta ton b Me2+ bng hn hp NaOH, Na2CO3 bit nng
trn, khi th tch hn hp l Vh2
143
* cng vnh cu (KVC) ca nc l tng mt ng lng gam mui Me2+ t
do, c sn trong mt lt nc. Do :
Do phi chun trc tip bng. Khi H2C2O4 phn ng ht th dung dch
KMnO4 d s nhum dung dch thnh mu hng nht, lc khng tan th dng
chun . Ta tnh nng KMnO4 theo cng thc.
Cui cng chun lng H2C2O4 gii phng ra bng KMnO4 theo phn ng
trn:
144
Theo cc phng trnh phn ng trn th:
145
- Phi cho KI d I2 sinh ra c ho tan do to phc KI3 (Poliiodua), ng
thi cht oxi ho phn ng ht.
Khng c tin hnh chun trong mi trng axit mnh v gy ra phn ng
ph:
- Khng c tin hnh chun trong mi trng kim mnh v khi sinh
phn ng ph:
146
Chun trc tip Cl- nh dung dch chun AgNO3 vi ch th K2CrO4:
Khi dung dch chuyn t c trng sang hng nht lc khng tan th dng
chun .
Phng php Mor ch c chun trong mi trng trung tnh hoc kim
yu v nu trong mi trng axit mnh th vai tr ch th ca CrO42- b bin mt do
c phn ng.
Dung dch phi vng mt Ba2+, Bi3+, Pb2+ v chng cng to kt ta gch vi
CrO42-. Ngoi ra dung dch phi vng mt mui amoni, v n s ho tan AgCl do
to phc vi AgCl.
2.3.3.2. Phng php Vothard
Xc nh Cl- bng cch chun ngc bng AgNO3.
- u tin cho Cl- kt ta bi Agno3d
147
Vic tnh ton nng Cl- theo phng php ny c phc tp hn.
Vit tt l Na2H2Y
Ch th ca phng php l Eriocrom en T (vit tt l ET_OO) hay Murexit.
V phc ca ch th vi kim loi km bn hn phc ca Trilonb vi kim loi nn
khi cho dung dch trilonb xung dung dch cha phc kim loi vi ch th (Meind),
th phc ny b ph hu v ion kim loi s to phc vi Trilonb.
Ton b qu trnh chun c m t bng s sau:
- Cho ch th (Eriocrom en T) vo dung dch cha ion kim loi th ion kim loi
phn ng vi ch th:
Sau chun dung dch cha ion kim loi bng Trilonh th ion kim loi t do
s phn ng vi Trilonb.
148
- Mi phn ng chun u sinh ra H+ nn ta phi thm hn hp m amoni
vo n nh pH ca dung dch, hn hp m amoni c pH = 8 -10, nh vy mu
ca phc bn.
- Php chun thng hay dng xc nh cng ca nc v trong nc
c rt nhiu Ca2+, Mg2+.
- Tnh ton theo phng php chun trc tip:
Nh vy ion kim loi lin kt vi Trilonb nh hai lin kt chnh vi hai nhm a
x tt v hai lin kt phi tr vi 2 nguyn t N nn phc ny bn khng mu v
tan trong nc.
2.3.4.2. Phng php thu ngn chun cc halogennua
Ion Cl- to phc kh bn vi Hg2+ (1 = 5,5.106, 2 = 3.106).Do nu chun
dung dch clonla bng Hg2+ th trong qu trnh chun xy ra phn ng :
149
CU HI V BI TP CHNG 2
2.1. Phn tch th tch v s chun l g? Tnh ton ca phn tch th tch
da trn c s no? Cho v d.
2.2. Bn cht v phm vi ng dng ca phng php trung ho, cch pha ch
dung dch chun ca phng php trung ho.
2.3. Cht ch th ca phng php trung ha, oxi ho kh kt ta v to phc.
2.4. Nhn xt v cc dng ng cong chun ca phng php trung ho.
2.5. ng dng ca phng php trung ho.
2.6. Nhn xt v bc nhy ca ng cong chun pH, oxi ho kh v quy
tc chn ch th.
2.7. Bn cht ca phng php oxi ho kh. Nng dng oxi ho v dng
kh nh hng th no n bc nhy th.
2.8. Hy trnh by cch xc nh im tng ng trong phng php oxi ho
kh.
2.9. So snh v ng cong chun trung ho v chun oxi ho kh.
2.10. So snh s ging v khc nhau v php o Pemanfanat v php o
Bicromat.
2.11. Ch th mu ca oxi ho kh l g? H tinh bt c phi l cht ch th ny
khng?
2.12. Bn cht v c im v ng dng ca php o Iod.
2.13. Bn cht c im v ng dng ca php chun kt ta.
2.14. Bn cht c im v ng dng ca php chun Komplexon.
2.15. pha dung dch chun Na2CO3 ngi ta cn chnh xc mt lng l,325g
mui Na2CO3 tinh khit sau em ho tan trong bnh nh mc 250ml v thm
nc n vch mc. Tnh chun v nguyn chun ca dung dch thu c.
2.16. Pha long 2,9ml H2SO4 iu kin 96%(d= 1,84 g/ml) trong bnh nh
mc 1 lt s thu c dung dch c nguyn chun bng bao nhiu?
2.17. Khi chun dung dch Na2CO3 bng HCl 0,12N th ht 22ml axit. Tnh
s gam Na2CO3 trong dung dch v t suy ra chun ca HCl theo Na2CO3.
2.18. Tnh (khng k s thay i th tch) bc nhy pH khi chun 20ml dung
150
dch NH4OH 0,2N bng dung dch HCl 0,2N cho KNH3 = 10-4,75
2.19. Tnh (khng k s thay i th tch) bc nhy th v th ti im tng
ng khi chun 100ml dung dch FeSO4 0,1N bng dung dch chun KMnO4
0,1N trong mi trng axit c nng ln H+ l 1 mol/l, cho
0
EMnO
/ Mn2 +
= 1,51V , E Fe
0
3+
/ Fe2 +
= 0,77V
4
2.20. Hi c bao nhiu gam canxi trong 250 ml dung dch CaCl2, bit rng nu
cho 40 ml dung dch (NH4)2C2O4 vo 25ml dung dch CaCl2 th sau khi tch kt
ta phi dng ht 15ml dung dch KMnO4 0,02N chun lng (NH4)2C2O4
khng tham gia phn ng, cho Ca= 40.
2.21. Chun hn hp NaOH, Na2CO3 bng dung dch H2SO4 0,1N, chia lm hai
phn bng nhau:
a) Phn th nht chun bng Phenolphtalein ht 20ml axit H2SO4
b) Phn th hai chun bng metyl da cam ht 25 ml. Tnh thnh phn % ca
hn hp, cho H = 1, C = 12, O = 16, Na = 23.
2.22. Tnh p Ag v p Cl khi chun 25 ml dung dch AgNO3 0,1 M bng
dung dch chun NaCl 0,1M ti cc im khi thm 24,0; 25,0; 26,0ml NaCl cho
AgCl = 10-10.
2.23. Tnh sai s mc phi khi chun 50 ml dung dch AgNO3 0,1 M bng
AgNO3 0,1M nu kt thc khi pAg = 4,9 v bng 5,25.
2.24. Thm 20 ml H2C2O4 0,25M vo mt mu cn 1,2340g PbO2 kh PbO2
Pb2+ v ho tan PbO. Trung ho dung dch bng NH3 ton b Pb2+ kt ta ht
dng mui oxalat. Nc lc em chun bng dung dch KMnO4 0,04M ht 10ml.
Kt ta lc c em ho tan trong axit v chun bng KMnO4 ht 30ml. Tnh
thnh phn% khi lng ca PbO v PbO2 cho PbO = 223,2 v PbO2 = 239,2.
2.25. Tnh sai s mc phi khi chun dung dch HCl 0,1M bng dung dch
NaOH 0,1M nu kt thc chun pH = 3,0 v pH = 11.
2.26. Tnh sai s mc phi khi chun dung dch CH3COOH 0,1 M bng
dung dch NaOH 0,1 M nu kt thc chun pH = 6,0 v pH = 11.
V d 2: Tnh nng cn bng pH = 11 ca cc cu t trong dung dch
2+
Mg c nng ban u 0,01M v EDTA c nng ban u l 0,02M. Trong
th d trn, ta tnh c hng s bn iu kin ca phc MgY2- trong dung dch
c pH = 11 l = 108,28.
Phng trnh bo ton khi lng ca Mg2+:
151
v ca EDTA l:
vo biu thc ca
hng s bn iu kin:
152
C: L nng cht tan (mol/l)
l: L chiu dy lp dung dch, tnh bng cm.
: L h s hp th phn t l h s tt ca dung dch khi nng C l 1 mol/1
v chiu dy dung dch = 1cm. l mt i lng khng i c trng cho mi
cht mu v ph thuc vo bc sng ca nh sng chiu vo, bn cht ca cht
tan, nhit dung dch v tng ng vi mt quang ca dung dch c nng
mol/l ca cht nghin cu.
Thc nghim xc nh vi nhiu hp cht mu thy thng khng vt
qu 2.105.
154
- Nu Kkb nh th ion Men+ to phc nhiu, dng t do t, lm cho chnh
xc ca phng php tng thm, nhy tng, v ch cn nng Men+ rt long
to phc mu.
V d: Me + nR = MeRn
156
nh lut Bia, n c th tin hnh nhanh, khng cn dng c phc tp. Song
phng php c hn ch ch l ch bit c gn ng nng ca dung dch
kho st nm trong khong hai dung dch tiu chun k nhau. Nhng dung dch
mu tiu chun thng khng..bn, cn nu thay bng dung dch gi hoc knh
thy tinh mu gi th gp kh khn trong vic tuyn la ng mu sc ca chng.
b. Phng php chun o mu (kp i).
- Ni dung v nguyn tc: y l phng php phn tch gin tip, ngi ta so
snh mu ca hai dung dch tnh trng lun lun c th tch bng nhau. Mt bn
l dung dch mu nghin cu cha bit nng , c th tch ban u xc nh cn
mt bn l nc v thuc th to mu c th tch ban u tng ng.
Sau tin hnh chun : thm vo bn nc v thuc th dung dch tiu
chun bit nng t buret xung. Ngi ta thm vo bn dung dch mu
nghin cu mt th tch H2O tng ng th tch dung dch chun cho xung
cng nh mt buret th 2.
157
phn ng to mu bit u dng c, m ch c mt s phn ng to mu m
bo c iu kin nh: sinh mu tc thi v s to mu khng gn lin vi nhng
qu trnh ha hc ph thuc khc.
V d: phn ng to phc mu sau:
158
- Tia sng t ngun sng qua thu knh to thnh 2 tia.
+ Mt tia i qua cu vt bn phi ng dung dch mu kho st qua trc thy
tinh lng knh, knh lc ri tp trung vo na tri ca th trng.
+ Tia kia qua cu vt tri ng dung dch mu tiu chun, ri tr thy tinh (2 tr
thy tinh lun nhng trong dung dch), tip n lng knh, knh lc v tp trung
vo na phi ca th trng.
Ngi ta iu chnh tr thy tinh ln xung sao cho khi quan st th knh thy
mu ( sng) ca hai na th trng bng nhau.
nhng ca tr thy tinh vo dung dch su, nng l b dy ca dung dch
kho st v tiu chun c phn nh trn thang ca my.
- u nhc im ca phng php.
Phng php cn bng l phng php o mu bng mt chnh xc nht. Song
phng php ny ch c th p dng phn bit nhng dung dch mu tun theo
nh lut c bn ca php o mu, phng php i hi dng c c bit t sc k
Duy bt.
e. ng dng ca phng php o mu bng mt.
ng dng quan trng nht l xc nh pH dung dch, da trn nguyn tc
dy tiu chun.
Mun xc nh pH ca dung dch m cng nh dung dch nghin cu, ta dng
mt b cht ch th c khong pH i mu khc nhau. Bng cch th ln lt tng
cht ch th, ta xc nh c gn ng pH ca dung dch nghin cu Sau xc
nh chnh xc pH. Chn mt dy tng ng cc dung dch m cng nh dung
dch nghin cu. Nhng dung dch no c mu bng nhau l c tr s pH bng
nhau.
chnh xc phng php o mu ch quan ph thuc vo nhy ca mt
ngi quan st. Cc phng php ny lm mt mi mt nu phn tch nhiu. Cho
nn thun li hn vi vic t ng ha cn dng phng php o mu quang
in.
1.1.3.2. Phng php o mu quang in.
a. Nguyn tc chung: Cc phng php o mu quang in u da trn s
nguyn tc chung sau y:
159
Dng sng i qua cu vt (hoc ng th) ng y dung dch mu kho st. nh
sng qua dung dch b tip thu bi t bo quang in, trong nng lng nh sng
bin thnh nng lng in. Dng in c pht sinh khi c o bng
ganvanmt c nhy cao. T bo quang in l dng c trong quang nng
c bin thnh in nng.
Stltp ch ra: Cng dng in c pht sinh di tc dng ca nng
lng nh sng ln t bo quang in t l thun vi cng nh sng.
b. Cc phng php o mu quang in
* o ph trc tip: o hp th A ca dung dch, tnh nng C ca dung
dch da vo gi tr E11 bit trc (tra cu).
160
- Phng php ng chun:
Chun b mt thang tiu chun vi nng tng dn C1, C2, C3
o MQ ca cc dung dch ny A1, A2, A3 o mt quang Ax ca dung
dch c Cx.
Dng ng chun A = f(c), t php ni suy th ta tnh Cx.
A to phc vi L:
- B phn ng ph vi H+
161
- Nu gi S l tan ca kt ta th:
Cch xc nh Cx:
Cch 1: Ko di th v bn tri, ct trc honh ti u, l Cx.
Cch 2: T O k 1 ng ph song song vi th. T Ao k 1 ng thng
song song trc honh, ct ng ph ti M. T M k vung gc trc honh ti Cx.
Tuy nhin trong thc t phn tch c rt nhiu yu t nh hng n kt qu o
mt quang nh lng d thuc th, pH mi trng, cc cation l...
Tm li: thc hin mt php o quang hon chnh cho mi php xc nh
hm lng cc nguyn t, tc l tm ra qui trnh phn tch thch hp cho cc
nguyn t, nh ha hc phn tch phi thc hin tt cc bc sau y:
Gi s mun xc nh Cr3+ trong mu nh php o quang, chng ta cn thc
tu cc bc nghin cu sau y:
1. Nghin cu s to phc ca ion kim loi vi thuc th, v d Cr6+ vi 1,5 -
iphenylcabcbazide ( max = 542 nm).
* Kho st ph hp th ca phc mu tm gia Cr6+ v 1,5
Difphenuycacbazide, gm:
* Xc nh pH ti u Qua kho st, pH = 1,5 2,5 (pH = 2,0).
* Kho st nh hng ca lng d thuc th n s to phc (V = 2ml).
* nh hng ca thi gian (t = 10 - 15') n bn ca phc.
* Kho st s tun theo nh lut Bia ca phc Cr(6+) vi 1,5D phenylcacbaz
(C = 0 - 4 mg/l).
* Kho st nh hng cc ion l: Pb2+, Zn2+, Fe2+, Fe3+, Mn2+... Ch Fe2+, Fe3+
v Cu2+ nh hng (nh hng hn c l Fe3+), loi tr cc ion a lng Ca2+, Al3+,
Ba2+, Mg2+ khng nh hng.
162
T ta tm cch loi tr cc yu t nh hng: Fe3+ dng phng php che
bng cch cho to phc bn vi PO43- (trong mt s trng hp khc che bng CN-
, F-...); cn loi tr nh hng ca Cu2+ bng cch cho kt ta trc n bng thuc
th thch hp (cufferon).
2. Xy dng ng chun da trn cc d kin a kho st trn.
3. Pha cc mu gi ri xc nh nguyn t cn phn tch, t kt qu tnh sai s
(x l kt qu thng k ng chun theo phng php bnh phng ti thiu).
Xc nh chnh xc ca php phn tch v kt lun dng c hay khng dng
c qui trnh chn.
4. Xc nh hm lng cc nguyn t trong mu thc.
1.2. PHNG PHP PH HP TH NGUYN T(AAS)
1.2.1. Nhng vn chung v ph hp th nguyn t
1.2.1.1. S xut hin ph hp th nguyn t (cha tha ng cn ni r hn)
Khi nguyn t trng thi c bn, nng lng ca n l ngho nn nht.
Nhng khi trng thi kch thch (th kh, hi) nguyn t t do hp th c nng
lng v sinh ra ph gi l ph hp th nguyn t
Nu gi nng lng tia sng b nguyn t hp th l E th chng ta c:
163
Nu gi D l cng ca vch ph hp th nguyn t, t cng thc:
I = I0.e-(KVN.L) chng ta c:
164
1.2.2. Nguyn tc trang b ca php o AAS.
Da trn chc nng ca b phn thit b AAS nguyn tc trang b cho php o
gm:
Phn 1: Ngun pht tia bc x cng hng chiu vo mi trng hp th
cha cc nguyn t t do ca nguyn t. l cc n HCL (Holow Cathod
Lamp), cc n phng in khng in cc EDL (Electrodeless Discharge Lamp)
hay ngun pht bc x lin tc c bin iu.
Phn 2: H thng nguyn t ha mu phn tch. l k thut nguyn t ha
bng ngn la F-AAS (Flame Atomic Absorption Spectrophotometry) v k thut
nguyn t ha khng ngn la ETA-AAS (Electro Thermal Atomization Atomic
Absorption Spectrophotometry) gm 2 b phn l b phn dn mu vo bung
aerosol ha v b phn thc hin qu trnh Aeroxol.
Phn 3: My quang ph lm nhim v thu, phn li v chn tia sng cn c
hng vo nhn quang in pht hin tn hiu AAS ca vch ph.
165
gia I0 v phn cng sng I i qua mi trng c tnh theo cng thc:
166
+ mg/l hay g/ml.
+ mg/ kg hay g/g
- Nng ppm v c s ca n: Nng ppm (part per milion), nng phn
triu cng c biu th theo hai cch.
+ Vi mu rn nu trong 1g cha 10-6 g cht phn tch th gi tr ny (10-6g)
c gi l 1ppm. Uc s ca ppm l ppb - nng phn t.
+ Vi mu lng trong 1 lt c cha 10-6g mu phn tch th cng tng ng 1
ppm hay 1 mg/l (hay 1 g/ml).
d. Khi nim v nhy:
- nhy tuyt i l lng gam (khi lng) nh nht ca nguyn t phn
tch c trong mi trng hp thu cn thu c cng ca vch ph hp thu
chn chim 1% ton bng hp th, hay bng 3 ln dao ng ca tn hiu nn.
Mi nguyn t v mi vch ph s c nhy khc nhau.
- nhy tng i cn gi l nhy nng n l nng nh nht c
trong mu c th pht hin c tn hiu hp th ca n theo mt vch ph nht
nh chn v tn hiu ny phi bng 1% ca bng hp th ton phn, hay bng 3
ln dao ng ca gi tr nn.
e. Gii hn pht hin:
- Gii hn pht hin tng i ca mt nguyn t theo mt vch ph nht nh
c xem l nng nh nht ca nguyn t trong mu phn tch cn c th
pht hin c tn hiu hp th ca n theo vch ph trong mt iu kin
chn.
- Gii hn pht hin tuyt i ca mt nguyn t l khi lng ti thiu ca
nguyn t trong mi trng hp th ca n cng trong mt iu kin nht nh
chn pht hn c tn hiu hp th ca n.
e. Khong xc nh:
- Trong AAS, vic nh lng mt nguyn t l da vo phng trnh c bn.
D = a.Cb (1.21)
Trong mi quan h ny, D ch ph thuc tuyn tnh vo C khi b = 1, ngha l
khi nhit C l rt nh, khi chng ta c th vit.
167
Khong nng C ca nguyn t phn tch ng ng vi phng trnh (1.20)
c gi l khong xc nh ca nguyn t theo phng php nu. Trong
khong nng ny th quan h gia D v C c dng y = ax.
1.2.3.2. Cc phng php phn tch AAS.
a. Phng php ng chun
Chun b 5 mu u c nng tng
dn C1 C2 C3 C4 C5
Chn cc iu kin ph hp ngun n
(HCL) bc sng (nm) o ca n,
rng khe o (nm) cng bng n
(mA), nhit nguyn t ha mu, hn
hp kh t, tc dn mu (l/pht).
Tin hnh o ta c cc gi tr A1,
A2, A3, A4, A5.
Tnh Cx nh php ni duy t th
b. Phng php thm chun:
Nguyn tc ca phng php ny l
ngi ta dng ngay mu phn tch lm nn chun b mt dy mu u bng
cch ly mt lng mu phn tch nht nh v cho thm vo nhng lng nht
nh ca nguyn t cn xc nh theo tng bc nng (theo cp s cng). V d
lng thm vo l C1, C2, C3
Ta c dy mu u l:
168
Cng chn cc iu kin th nghim nh trn ri tin hnh o cc dung dch
trn ta c A0, A1, A2, A3, A4 tng ng v xy dng th A C.
Cch xc nh nng :
+ Cch 1: Ko di ng chun, ct trc honh ti C0 th OC0 l nng Cx.
+ Cch 2: T O k ng song song ng chun. T A0 k ng song song
vi trc honh ct ng chun ti M. T M k vung gc vi trc honh, ct M
ti X ta c Cx phi tm.
169
CHNG 2
I CNG V SC K
170
2.1.2.3. Theo k thut v phng tin sc k
- Sc k trn ct.
- Sc k lp mng.
- Sc k trn giy.
2.1.3. S tch sc k v sc
Xt qu trnh tch hai cht A, B trn ct (hnh 2.1).
171
2.2. C S L THUYT CA SC K.
hai cht c tch hon ton khi nhau ta thy:
- Hai pic phi cch xa nhau ngha l hai cht phi c tc di chuyn khc
nhau r rt (hay b lu gi mnh yu khc nhau r rt trn ct): sc (b) (hnh
2.3)
- Hai pic phi gn (hp v cn i) ngha l khng c s dong pic (hay s m
di) (sc (c)) (hnh 2.3).
172
mu qua ct sc k ti detector v cho pic trn sc (tnh t lc tim n khi xut
hin nh ca pic).
Thi gian cht (tM) l thi gian cn mt cht khng b gi li trn ct.
tR cng ln, cht tan b lu gi cng mnh v tc di chuyn qua n cng nh.
b) H s phn b K
V t ta c: tR = tM (l + K)
Khc vi K, K khng nhng ph thuc vo bn cht cc pha, bn cht ca cht
tan, vo nhit m cn ph thuc vo c im ca ct (t l VS/VM ca ct).
Nu K cng ln tc di chuyn cng thp. tch mt hn hp cc cht,
ngi ta thng chn ct, pha ng, cc iu kin phn tch khc sao cho K cc
cht nm trong khong t 1 - 8. Nu K > 8 th thi gian phn tch qu di. Nu K
< 1 pic s xut hin qu sm d ln vi pic khc.
Tc di chuyn t i ca hai cht: c c trng bi tha s chn lc hay
h s chn lc .
173
chng c dng tng t nh ng cong phn b chun Gauss thu c khi ta v
ng cong ph thuc gia gi tr ca kt qu cc th nghim lp v tn s xut
hin cc kt qu (hnh 2.4).
b = 1/2 chiu rng pha sau ca lc, a = 1/2 chiu rng pha trc.
174
S dong pic hay s m rng di l hin tng c bit quan trng trong sc k
v c nghin cu qua thuyt v a v thuyt ng hc. S dong pic l kt qu
ca s di chuyn nhanh chm khc nhau ca cc phn t ca cng mt cht khi i
qua ct st k. Cc lc ra mun bao gi cng t hn. Mt ct sc k tt s cho cc
lc nhn.
2.2.3. phn gii v cc yu t nh hng.
phn gii l i lng o mc tch hai cht trn mt ct sc k.
Xt trng hp tch hai cht A v B (hnh 2.6).
175
2.2.4. Thi gian phn tch
l yu t quan trng nht. t c phn gii RS xc nh th cn thi
gian phn tch l bao nhiu. Mun vy ta dng cng thc.
177
* Hng s trao i ion:
- Vi anionit.
* Dung lng trao i c trng cho kh nng trao i ca ion cht tan vi 1g
iont. N ph thuc vo bn cht cht hp ph, dung mi v nhit .
* ng dng: tch cc cht hu c v v c.
2.3.2. Sc k lng trn mt phng
Qu trnh sc k c tin hnh trn mt t giy hay mt lp bt vi v c
gi trn mt mt tm knh, cht do hay kim loi. Bn thn lp mng c th l pha
tnh hay ch l cht mang gi pha tnh trn . Ph bin nht l sc k lp
mng.
2.3.2.1. Sc k lp mng.
Dng th tinh khit ca sn phm, c dng trong cc th nghim lm
sng, trong nghin cu sinh hc, ha sinh. N c tin hnh trn mt bn thy
tinh c ri mt lp mng dnh chc ca cc ht bt mn.
a. Trang b.
* Cht hp ph: silicagel (0,07 - 0,1 mm), Al2O3, thch cao, celuloza, bt poli
axt...
* Bn mng: - Bn mng dnh chc (cht hp ph trn thm cht kt dnh
(thch cao, tinh bt), n l knh c cc c khc nhau).
- Bn mng khng dnh chc, ri bt c hot ng thch hp ln tm knh v ri
bng mt a thp.
* Dung mi phi tinh khit: hexan, heptan, xyclohexan, cacbon tetra clorua.
* Bnh sc k: C th dng cc bnh chuyn dng hoc cc l rng ming, bnh
hnh tr thng thng.
178
b. Qu trnh chun b v k thut sc k.
* Chun b:
- Bn mng v bnh sc k thch hp.
- Chm dung dch ln lp mng.
- t bn sc k vo bnh.
- Hin hnh sc ph.
2.3.2.2. Sc k giy.
a. Trang b:
* Giy sc k: c lm bng mt loi gy c bit. Bt giy c ch ha
bng hn hp axt v c HCl + HF cc si xenluloz phi thng v dung mi di
chuyn chm trn giy ny.
* Dung mi:
- Pha tnh l nc c pha axt, kim, cc dung dch m hay cc dung mi phn
cc.
- Pha ng thng t phn cc hn pha tnh: butanol, ancolbenzilc, benzen,
axeion.
b. Qu trnh tch v k thut sc k.
* Bnh sc k: lm bng b can thy tinh hay l ming rng.
* Chun b bn mng v bnh sc k thch hp.
Cho dung mi vo bnh, quanh thnh bnh lt giy lc bo ha dung mi
c nhanh hn. Nu tin hnh sc k phn b th chun b dung mi v bnh
tng t nh sc k giy.
Vi lp mng dnh chc c th nh du ng xut pht mp di
khong 1cm. Dng micropipt hay ng mao qun chm ln nhng im cch nhau
t nht 1 cm. Vt chm phi gn.
* Xc nh h s chm: Rf
Trong : Lx l vt di chuyn ca di
Lm l vt di chuyn ca dung mi, c tnh t im xut pht
n vch cui cng ca n. H s chm Rf khng ph thuc vo
179
nng m ch ph thuc nhit iu kin tin hnh, pH mi
trng vo bn cht ca cht phn tch.
180
CHNG 3
CC PHNG PHP PHN TCH IN HO
Trong phn tch in ho ngi ta chia ra nhiu phng php sau: Phng php
do th, phng php cc ph, phng php in phn, phng php in trng
lng, phng php in dn.... Tuy nhin chng ta ch nghin cu hai phng
php o th v phng php cc ph.
3.1. PHNG PHP O TH
3.1.1. Th in cc
Trong trng hp tng qut, xt phn ng:
3.1.1.1. Cch xc nh th in cc
xc nh th in cc ca bn phn ng: M2+ + 2e = M0(s)
y M0 l kim loi to ra 1 in cc dng mch o th hnh 3.1.
- C H+ tham gia:
182
- C OH- tham gia
3.1.1.2. Mch in ha
* Mch in ha phn ra 2 loi: mch ganvanc, mch in phn.
* Mch in ha gm c 2 dy dn gi l hai in cc nhng vo hai dung dch
cht in ly, mt in cc gi l catot, in cc kia gi l anot, y xy ra qu
trnh oxi ha.
* Cch k hiu: M/M2+(ymol) // H+ (x mol) / Pt, H2 (p at).
3.1.2. Cc loi in cc
3.1.2.1. in cc so snh
L loi in cc tr m th thay i t khng ng k.
Thng dng l in cc calomen v in cc bc clourua.
a. in cc calomel // Hg2Cl2bh, KCl (x M) / Hg, Pt (X l nng mi ca KCl
trong dung dch).
Phn ng in ha trn 2 in cc.
183
in cc ny thng c ch to vi dung dch KCl bo ha, th 250C (o
vi in cc Hydro chun) l 0,197V. C hai in cc ny lun sn c trn th
trng.
3.1.2.2. in cc ch th
Chia lm hai nhm: - in cc ch th kim loi.
- in cc mng chn lc ion.
a. in cc ch th kim loi.
* in cc loi 1, cho cation: in cc ny dng xc nh nng trong
dung dch. N gm 1 dy dn kim loi nhng vo dung dch mui ha tan ca kim
loi . V d:
184
+ Mt in cc AgCl nm trong bn thy tinh mng. Mng thy tinh ny to
ra th in cc ph thuc vo pH ca dung dch.
- Mch o pH.
- Khi ni in cc thy tinh vi in cc calomel bo ha (Electrod Calomel
Saturation (SCE)) ta c mch in ha o pH dung dch SCE // H3O+ = a1/mng
thy tinh / H3O+ = a2, Cl-, AgCl bo ha / Ag.
in cc thy tinh.
E = L + 0,059 lg aH+ (L l mt hng s a = 1).
Tnh cht ca in cc thy tinh nhy vi pH c nghin cu u tin
(1906) bi nh ha hc. M.Cremer.
* in cc mng chn lc ion:
Mng rn l 1 mng dn in ion, c th l:
+ n tinh th LaF3 chn lc ion F-.
+ a tinh th Ag2s.
+ Tinh th hn hp cha cc mui khc nhau ca ion Ag+ hay S2-
phn tn trong nn Ag2S
- Mng lng to nn in cc phc tp hn. N gm hai ng ng tm. ng
trong ng dung dch in cc Ag/AgCl. Gia 2 thnh ng c cht trao i ln
lng v c. Phn di ng l cht do gi cht lng trao i ln.
185
chn lc. V d Ca2+ (nhng vo mui CaCl2: mng cht do (2) gi cht trao i
ln ng gia hai ng ng tm (3)). y l mt cht lng hu c khng bay hi,
khng ha tan trong H2O. Phn ng chn lc vi ion Ca2+, in cc mng lng
chn lc ion Ca2+ hin c vi cht trao i ln l dieste ca axit phosphoric ha tan
trong mt dung mi phn cc. Cn bng qua mng l:
186
em gi tr ny vo (3.6)
* o pH vi in cc thy tinh:
Khi in cc so snh l in cc calomel v in cc ch th l in cc thy
tinh. Th ca in cc thy tinh.
b. Chun o th.
u im: - nhy cao
- Dng c vi dung dch mu c
- Khng c sai s ch quan.
Yu cu: Ging chun th tch thng thng.
187
* Chun o th khng dng.
y l phng php c in: Trong qu trnh chun ngi ta o sc in
ng ca mch galvanc khng c dng i qua (i = 0). Chun ny c th thc
hin vi cc phn ng c bn cht ha hc khc nhau
* Chun axt baz: dng in cc ch th cho s thay i pH ca dung dch -
thng dng l in cc thy tinh.
* Chun kt ta: chun halogen bng ion Ag+ ngi ta dng in cc
bc lm in cc ch th.
- Phn ng chun :
188
Vi in cc kim loi M0 khi c mt H2Y2- phn ng in ha sau d dng xy
ra:
Sau khi phn ng (e) kt thc, ion M2+ c d (c thm vo) cho phn ng
in cc mi:
Do E1 = E2 nn t (k) v (e) ta c:
189
vi microampe - tc l lm phn cc in cc, nh lm tng nhanh qu trnh
cho nhn electron trn in cc - lm qu trnh nhanh t n cn bng, v vy th
n nh nhanh, lp li tt. Gi tr th ph thuc vo tr s dng phn cc.
- C th phn cc nut hay phn cc catot.
- C th dng 2 in cc ging nhau trong cng mt dung dch nhng phi lm
phn cc c 2 in cc.
3.2. PHNGPHP CC PH V CHUN AMPE
3.2.1. Phng php cc ph
3.2.1.1. C s ca phng php cc ph
Nu t mt hiu th vo hai cc nhng vo dung dch cht in li v tng dn
th hiu , ban u dng in chy qua dung dch hu nh khng i. Khi hiu
in th tng n mt gi tr phn hu cht in li th cng dng s tng
ln mt cch t ngt. Gi tr th hiu gi l th phn hu.
Nu dng mt trong hai cc c b mt nh (thng dng catt git thu ngn)
cn cc kia c b mt ln, th khi cho dng mt chiu qua dung dch, cc c b
mt nh xy ra s bin thin nng (do cht in li phn hu); v b mt in cc
qu nh nn mt dng in cc ln.
Cng vi s tng th hiu gia hai cc, cng dng chy qua dung dch v
mt dng trn cc nh tng ln, th con b kh vng st vi b mt cc nh
tng ln nn lm gim nng ca ion b kh xung. Tip tc tng th hiu
gia hai cc ln th s tng mt dng trn in cc nh dn ti kt qu l n
mt lc tt c cc ion c chuyn n canh u b phng in. S b sung cc ion
t dung dch cho lp in cc xy ra chm hn qu trnh phng in trn b mt
in cc. Khi s tng tip hiu in th gia hai cc s khng gy ra c s
tng ng k cng dng in chy qua dung dch.
3.2.1.2. Dng khuch tn trn in cc git Hg.
Cc ph l qu trnh in phn dung dch nghin cu trong nhng iu kin
c trng, l:
a. in cc: Dng in cc git thy ngn lm ch th. l in cc c din
tch b mt nh nn mt dng kh ln (A/cm2). Nh khi in phn, khu
vc gn in cc nng ln tham gia phn ng gim nhanh, t n cn bng,
to ra dng gii hn.
in cc so snh c b mt kh ln, ln hn nhiu in cc ch th. V vy mt
dng b. gn in cc s thay i nng ion rt nh, khng nh hng n
190
ng cong dng th. Nh vy trong cc ph, in cc git thy ngn b phn cc
to ra sng cc ph, cn in cc so snh khng b phn cc.
Git Hg c to ra t mt mao qun di (5-10cm) ng knh trong l
0,05mm. Nu bu thy ngn cao 50cm, dng chy to ra cc git Hg ging nhau
c ng knh 0,5 1mm. Phn ng in ha xy ra trn git ny. S thnh cng
ca cc ph ph thuc trc ht vo lp li ca git Hg.
b. Cht in li nn: vic chuyn cc ion tham gia phn ng in ha trn in
cc do nhiu yu t tc ng nh: Lc ht tnh in, khuy trn c hc, s khuch
tn do gradient nng .
Trong iu kin cc ph phn cc catot git Hg, ngi ta thm mt cht in ly
tr vo dung dch lm nn cc ph. l cht in ly to ra 1 cation khc tham gia
phn ng kh canh hn ion cn xc nh, nng li cao hn nhiu (gp 100 -
1.000 ln ion tham gia phn ng in cc). l cht in li nn nh KCl, KNO3,
R4 NX.
Cc cation ca nn di chuyn n in cc nhng khng tham gia phn ng
in cc ( th cho). Chng trn b mt in cc, to nn lp in kp. Do
trng in canh b chn bi cation nn cho nn cation kh cc ch c th tip cn
in cc nh qu trnh khuch tn. V vy dng to ra gi l dng khuch tn...
Ngoi ra cn cc dng khc nh dng xc tc, dng ng hc.
c. Trong iu kin cc ph nh trn, th t ln 2 in cc c thay i lin
tc t 0-2V, dng khuch tn i qua dung dch khong 1 - 100 A. Tr s dng ny
trong cng iu kin ph thuc vo th phn cc: th hin qua s chnh lch nng
trong lng dung dch C v nng trn b mt in cc C*. Khi tt c cc ion
trn b mt in cc b kh ht tc l C = 0, dng khuch tn in cc c gi l
dng khuch tn gii hn. Gi tr trung bnh ca dng ny ( i a) c m t bi
phng trnh Ilcovic:
191
xc nh th i d tuyn tnh vi nng .
1. Dng d 2. Kh nn K+
3. Th phn hy ca Cd2+ 4. Dng khuch tn ca Cd2+
5. Dng gii hn i ca Cd2+
192
e. nh hng ca cc yu t n sng cc ph.
- nh hng ca cht nn:
- nh hng ca s to phc: Khi c mt ca cht to phc sng cc ph s
chuyn v pha m hn.
- nh hng ca c tnh thun nghch.
3.2.1.3. Dng khuch tn trn in cc rn.
Khi cn lm vic th dng trn + 0,3V - tc l dng phn ng oxi ha anot
trn in cc ch th - ngi ta dng vi in cc rn - trong nhng iu kin nht
nh c th ghi c dng khuch tn.
Thng dng nht l in cc Pt. Qu th hydro trn in cc Pt b. Ion H+ b
kh th - 0,1V. Nhng qu th oxi kh ln, v vy c th kho st sng oxy ha
nut n +1,3V.
in cc rn c th ng yn (in cc tnh) hay quay.
a. Trn in cc rn tnh:
Dng i qua vi in cc rn ph thuc vo nhiu yu t:
1. Ngun in 1 chiu 4 6V
2. Bin tr:
3. Vn k
4. Ganva nomt
5. in cc git Hg
6. Anot Hg.
Th t ln in cc thay i t 0 3V c do nh vn k (3). Dng i qua
in cc git Hg (5) c o bng Ganvanomt 4 (4).
* in cc so snh: calomel, in cc HgSO4, in cc AgCl...
194
3.2.1.5. ng cc ph
ng cc ph l ng biu din s ph thuc ca gi tr cng dng
chy qua dung dch (biu din trn trc honh) c dng nh trn hnh 3.7 v 3.8.
195
gi tr th trn trc honh c gi l th na sng E1/2, n c trng cho th cn
thit t c na dng gii hn. Th na sng khng ph thuc vo nng
ca cht tan v ch ph thuc vo bn cht ca ion b kh. Do th na sng
c s dng phn tch nh tnh cc ion c
mt trong dung dch.
3.2.1.6. Catt git thu ngn
1. ng ng thu ngn v dy platin lm
tip xc; 2. Bu cha thu ngn ni vi canh
git thu ngn; 3. ng dn bng cao su ni bu
cha thu ngn vi mao qun bng thu tinh; 4.
Mao qun thu tinh qua git thu ngn
(catt thu ngn) chy ra; 5. Bnh in phn; 6.
Lp thu ngn c ni vi dy tip xc bng
platin (nut thu ngn); 7. ng nhnh dn
kh hidro hoc nh vo loi oxi
196
dng t cc ny n cc kia c thc hin bng cc ion ca mui tan . Nhng
tn di tc dng ca dng in, cation chuyn ti nut. Tc chuyn ng
ca cc ion di tc dng ca dng in ph thuc vo nhiu yu t nh: hiu th
gia hai cc, bn knh v in tch ca ion phn tch, nng ca n trong dung
dch... Do s vn chuyn ca cc ion di tc dng ca dng in s lm sai
lch qu trnh xc nh cc ph v gy tr ngi ln cho qu trnh phn tch.
lm gim s chuyn vn , ngi ta thm vo dung dch phn tch mt
mui khc m s phn hu n ch bt u hiu th ln hn so vi hiu th cn
thit i vi cht cn xc nh, th cc cation ca nn cng chuyn ng ti canh,
nhng chng khng b phng in ti th c t vo. V vy phn ln ca
cht tham gia vo s chuyn ng b gim i.
Nu nng mui thm vo ln hn so vi nng cht phn tch, th thc t
tt c dng u c vn chuyn bi ion ca mui c thm vo. Trong trng
hp ny, tc chuyn ng ca cc ion cht phn tch di tc dng dng in
gn nh bng khng v c th b qua.
Mui tr c thm vo loi tr s vn chuyn ca ion cht phn tch di
tc dng ca dng in gi l nn cc ph.
cho dng in mt chiu chy qua dung dch khng gy ra s vn chuyn
ng k ca cc ion cht phn tch th nng ca nn phi ln hn t 100 - 1000
ln nng mui cn cn xc nh. Do phng php cc ph c ng dng
rng ri phn tch cc tp cht c hm lng khng ng k trong dung dch.
3.2.1.8. Phm vi ng dng ca phng php phn tch cc ph.
Dng phng php phn tch cc ph c th xc nh c cc cht v c cng
nh hu c, nu chng c th b kh hay b oxi ho trn b mt cc cc khi c
dng in mt chiu i qua. Do phn tch cc ph c ng dng rng ri trong
cc phng th nghim ho phn tch ca cc c s nghin cu khoa hc v ca cc
nh my. Trong thi gian gn y, phng php cc ph s dng cc vi in cc
rn quay c s dng ngy cng nhiu. Ti nay c nhiu phng php phn tch
cc ph hin i xc nh c nhng lng nh ti 10-9 - 10-10 nh cc ph sng
vung, cc ph xung vi phn, cc ph von ampe ho tan, cc ph xc tc...
3.2.1.9. Quy trnh ca phng php phn tch cc ph
phn tch mt cht no bng phng php cc ph, trc ht cn chuyn
n vo dung dch. Sau to nn mi trng cn thit v tch cc cht ngn cn s
xc nh cc ph.
iu bt tin nht i vi phn tch cc ph l trong dung dch phn tch c cc
197
cht c th kh gn vi th kh ca nguyn t cn xc nh hoc c th thp hn
oxi ho tan trong dung dch, chng s cn tr php xc nh. tch cc cht ngn
cn, ngi ta s dng cc phn ng kt ta, to phc, oxi ho kh, tch bng sc
k... tch oxi ho tan l cht cng b kh trn canh, ngi ta cho kh hidro hay
nh qua dung dch ui oxi. i vi cc dung dch kim ngi ta dng cht kh
l Na2SO3.
Vic chn ng cht lm nn cho cc ph c ngha ln. Vic ny thng
c gii quyt bng thc nghim.
Dung dch chun b phn tch, tch cc cht cn tr c cho vo bnh
in phn. ng mch dng mt chiu v tng th gia 2 cc ln mt cch t t v
ghi s bin i dng ph thuc vo in th. Da vo cc d kin thu c ta v
ng cc ph.
3.2.1.10. Cc phng php phn tch cc ph
phn tch nh lng bng phng php cc ph, ngi ta dng phng
php ng chun, phng php mu chun v phng php thm.
Khi s dng phng php ng chun, ngi ta ghi cc cc ph ca mu
dung dch chun. Da vo chiu cao sng cc ph ca mu phn tch (ghi trong
iu kin cng vi iu kin khi ghi cc ph cc mu chun) ri xc nh nng
ca n theo mu chun.
Trong phng php mu chun, ngi ta ch ghi cc ph ca mt dung dch
chun (Cch) ri xc nh chiu cao ca sng cc ph mu chun (hch) sau ghi
cc ph mu phn tch (trong cng iu kin nh ghi mu chun) c nng Cx v
xc nh chiu cao hx ca sng cc ph . Tnh nng ca dung dch phn tch
bng cng thc:
198
3.2.2. Chun ampe.
Chun Ampe thc hin trong hai iu kin:
- Mt trong cc phn ng, c kh trn catot Hg hoc oxi ha trn in cc
rn.
- Tr s dng khuch tn gii hn t l vi nng i d = K.C
C th s dng cc loi phn ng: Kt ta to phc v oxy ha kh cho chun
ny vi 2 phng php k thut - chun vi in cc ch th v chun vi
2 in cc ch th.
3.2.2.1. Chun ampe vi mt in cc ch th.
Bnh chun (1) ni vi in cc so snh (2) qua cu mui (3). in cc ch
th (4) c phn cc nh ngun (5). Dng qua mch c o bng galvanomet
(6) trong qu trnh chun bng dung dch t buret (7).
199
a) Cht cn nh lng cho dng kh catt.
b Cht chun cho phn ng trn catt.
c) C cht khun l cht cn nh lng cho phn ng trn in cc.
d) Trn th chn, cht cn nh lng cho dng oxy ha cn lng d cht
chun cho dng kh (id,c).
. e) Cht cn nh lng cho dng kh id,c cn dung dch chuyn cho dng oxi
ha id,a.
c dng khuch tn gii hn id th lm phn cc in cc ch th phi ri
vo khong th to dng id ca thnh phn cho phn ng in cc, thng m hn
0,1 - 0,3V so vi tr s E1/2.
Hnh 3.12. Trnh by cch xy dng ng cong chun ampe t ng cong
I-V cho trng hp (a).
200
E l tr s in th lm phn cc in cc trc honh l % cht c chun .
3.2.2.2. Phng php ampe kp
Trong chun ampe kp, c 2 in cc ch th c nhng trc tip vo dung
dch phn tch. Hai in cc ging nhau. Gia hai in cc c s chnh lch th
trn in cc xy ra cc phn ng in ha, t c dng in qua mch th phn
cc khng ln: 0,01 0,1V.
Dng ng cong chun ph thuc vo tnh cht thun nghch ca cc h
(cht cn chun v cht chun) cng nh tr s th lm phn cc hai in cc.
* V d: Kho st chun ln Fe(II) bng Ce4+
- Khi cha thm Ce4+ trn anot xy ra qu trnh oxy ha Fe(CN)4-, cn trn
catt Fe(CN)63- b kh. Khi thm Ce4+ vo ion [Fe(CN)6]3- tng ln nn dng qua
mch tng ln. T s dng t cc i khi nng hai ion bng nhau, tc l chun
c 50% ion Fe(CN)64-. Sau nng cht kh gim ko theo gim dng
qua mch.
- im tng ng dng i 0 bi nng cht kh [Fe(CN)6]4 rt b.
- Sau im tng ng Ce4+ c d trong dung dch nn trn anot oxy ha Ce3+
cn trn catt kh Ce4+. Dng qua mch li tng ln (hnh 3.13a).
y ta c hai h thun nghch:
202
PHN TH T
SAI S TRONG PHN TCH
X L S LIU THC NGHIM
I. CC NH NGHA V SAI S
Trong phn tch vic nh gi cc kt qu l mt trong nhng bc khng th
thiu c ca cc qu trnh phn tch. Trong bc ny vic tnh sai s l quan
trng nht v n cho ta bit kt qu phn tch thu c ng v chnh xc ti mc
no.
C th ni rng khng bao gi chng ta c th tin hnh mt php phn tch m
kt qu thu c li hon ton khng mc sai s. iu c ngha l chng ta
khng th bit c gi tr thc ca mt i lng cn xc nh. Chng ta ch c
th c gng thc hin phn tch sao cho sai s nh nht, kt qu thu c cho ta
mt gi tr chp nhn c tt nht bng phng php thng k hc ta c th xc
nh c gii hn trong cha gi tr thc ca i lng cn xc nh vi mt
mc xc sut cho trc. Gi s chng ta tin hnh xc nh mt i lng no
n ln bng mt quy trnh phn tch duy nht (ta ni php xc nh c lp li n
ln), cho ta cc kt qu tng ng x1, x2, x3 xn. Gi tr trung bnh s hc x ,
thng khc vi gi tr thc ca i lng cn xc nh:
203
Th d khi lng ca cht A cha trong mt mu l 45,2 mg, ca cht B cha
trong mt mu tng t l 215,4 mg. Gi tr xc nh c theo cng mt phng
php ca A l 45,8 mg v B l 216,0 mg. Nh vy sai s tuyt i khi xc nh A
v B u nh nhau bng +0,6 nhng ta thy ngay l php xc nh B ng hn v
xc nh 216 mg mi ch sai 0,6 mg trong khi khi xc nh A th ch vi 45,8
mg sai s 0,6 mg.
Sai s tng i s ch ra vic xc nh B chnh xc hn xc nh A:
Vi A, S% = (+0,6/45,2).100 = 1,3%
Vi B, S% = (0,6/216,4).100 = 0,3%
Ty thuc vo nguyn nhn gy ra sai s, ngi ta dng khi nim sai s h
thng v sai s ngu nhin.
Sai s h thng hoc sai s xc nh l nhng sai s do nhng nguyn nhn c
nh gy, v vy n lun c du + hoc -. Sai s h thng c th do chnh phng
php khng ng (do cc dng c o lng nh cn, dng c o th tch nh buret,
pipet hoc bnh nh mc khng ng th tch trn vch chia; do ha cht khng
tinh khit; do xc nh nng dung dch chun sai; do ngi tin hnh phn tch
khng c k nng ngh nghip thiu kinh nghim phn tch).
Sai s ngu nhin l nhng sai s gy nn bi nhng nguyn nhn khng c
nh, khng bit trc, thay i khng theo quy lut, khi dng, khi m, th d do
ngi phn tch mt lc no thiu tp trung hoc tin hnh thao tc i khi thiu
cn thn, s thay i v nhit , p sut kh quyn ni lm phn tch.
Ta c th tn c sai s h thng, t loi tr c nguyn nhn gy ra sai
s bng nhng bin php thch hp nh sa cha hiu chnh dng c my mc,
pha li v kim tra li cc dng c, dung dch chun v iu ch li ha cht dng
lm thuc th v..v.
i vi cc sai s ngu nhin ta khng th bit trc loi tr cc nguyn
nhn gy ra n m ch c gng gim sai s ti mc ti thiu bng cch phn
tch tht cn thn v tng s ln phn tch ri cui cng s l cc s liu bng
phng php thng k ton hc. Sai s h thng phn nh, ng ca phng
php phn tch, sai s ngu nhin phn nh phn tn ca cc kt ta phn tch
tc l lch gia cc gi tr ring l v gi tr trung bnh tc l phn nh lp
li.
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Hnh 1. ng v lp li ca phng php phn tch
a. lp li v ng u thp; b. ng cao, nhng lp li thp; c. lp
li cao nhng ng thp; d. ng cao v lp li cng cao.
Sau y chng ta nu ra nhng khi nim ton hc c lin quan trc tip n
vic x l cc d kin thc nghim theo phng php thng k ton hc.
II. CC I LNG TRUNG BNH
Trung bnh s hc. Gi s tin hnh n ln phn tch c cc gi tr ca i
lng no (c th dng, m) x1, x2, x3 xn. Gi tr trung bnh s hc x c
xc nh bng h thc:
Thng thng trung bnh nhn c biu th di dng logarit thp phn,
tin cho vic tnh ton:
205
III. CC I LNG C TRNG CHO PHN TN.
Khi tin hnh nhiu php phn tch tc l tin hnh lp li th nghim ta thu
c mt dy cc d kin thc nghim. Cc khi nim sau y c trng cho
phn tn cc d kin .
lch trung bnh
Phng sai:
Phng sai l trung bnh cng ca cc bnh phng nhng hiu gia cc gi tr
ring l v gi tr trung bnh tc l:
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lch chun gi tr trung bnh
Phng sai ca gi tr trung bnh bng phng sai chia cho s th nghim
H s bin ng
Gi s tin hnh phn tch lp li n ln ta c cc gi tr kt qu x1, x2, x3
xn. T cc biu thc ton hc c trnh by trn ta tnh c x v S. H s bin
ng V ca phng php phn tch c xc nh bng h thc:
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Bng 1. Tn xut phn b cc kt qu thc nghim
Khong th tch, ml S ln xut hin % xut hin
9,969 ti 9,971 3 6
9,962 ti 9,974 1 2
9,975 ti 9,977 7 14
9,978 ti 9,980 9 18
9,981 ti 9,983 13 26
9,984 ti 9,986 7 14
9,987 ti 9,989 5 10
9,990 ti 9,992 4 8
9,993 ti 9,995 1 2
209
Tuy nhin trong thc tin phn tch, s th nghim thng nh lch chun
tnh theo cng thc (11.12) nn phi dng cc chun khc. l chun studentt
tm bin gii tin cy
210
nh vy, gi tr thc nm trong khong x - < < x + .
Vi xc sut tin cy no c biu th theo n v tuyt i nh x . nu
biu th theo n v tng i (%) th ta c:
v (20) c dng:
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2,25; 2,11; 3,21; 2,38; 2,32. C nn loi b gi tr no khng.
Trc ht sp xp cc gi tr tng dn, ta thy gi tr b nht l 2,11 v gi tr
ln nht ln 3,2 1. Kim tra gi tr 3,2 1.
212
6 5,99 5,14 4,76 4,53 4,39 4,28 4,15 4,06 4,00
7 5,59 4,74 4,35 4,12 3,97 3,87 3,73 3,63 3,57
8 5,32 4,46 4,07 3,84 3,69 3,58 3,44 3,34 3,23
9 5,12 4,26 3,36 3,63 3,48 3,37 3,23 3,13 3,07
10 4,96 4,10 3,71 3,48 3,23 3,22 3,07 2,97 2,3 1
11 5,84 3,98 3,59 3,36 3,20 3,09 2,95 3,86 2,79
12 4,75 2,88 3,49 3,26 3,11 3,00 2,85 2,76 2,69
15 4,54 3,08 3,29 3,06 2,90 2,79 2,64 2,55 4,48
20 4,35 3,49 3,10 2,87 2,71 2,60 2,45 2,35 2,28
3- Tnh S:
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TI LIU THAM KHO
1. Nguyn Tinh Dung (2001), Ha hc phn tch, Cn bng ion trong dung
dch, Nxb Gio dc, H Ni.
2. Trn T Hiu (1984), Bi tp ha phn tch, Nxb i hc v Trung hc
chuyn nghip.
3. Trn T Hiu (1999), Phn tch trc quang, Khoa Ha - Trng i hc
Khoa hc T nhin - i hc Quc gia H Ni.
4. Phm Gia Hu - Trn T An (2002), Ha hc phn tch, tp 1 + 2, Trng
i hc Dc H Ni.
5. Nguyn Vit Huyn (1999), C s cc phng php phn tch in Ha,
Khoa Ha, Trng i hc khoa hc t nhin - i hc Quc gia, H Ni.
6. Phm Lun (2006), Phng php phn tch ph nguyn t, Nxb i hc
Quc gia H Ni,
7. T Vng Nghi (2001), Ha hc phn tch phn I, Nxb i hc Quc gia, H
Ni.
8. Trnh Xun Sen (2006), in ha hc, Nxb i hc Quc gia, H Ni
215
MC LC
217