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1.
Suy ra : [Ag+] =
11,,77..
Khi cho d 0,1ml dung dch Cl- vo dung dch, tng ng vi nng Cl- t c
l 10-3M.
HgY
Hg
EMY
Echit
chit
HgY
Hg
Hng s bn:
in cc ch th: in cc Hg
in cc so snh: in cc calomen
Eo = Ech th - Echun
Tnh [Hg2+]
Khi thm dung dch chun Y vo ta c Y s tham gia vo c hai cn bng (1) v (2)
Ta c : [Hg2+] =
Echit
MY
Ta c c dng phng trnh Nerst
0,04
02
00
Kkb
0,246
.01
09
05
.64(10
.1.
Ta xt mt v d khc : Ag+ + 2CN- = Ag(CN)2Hng s khng bn ca phc:
chun . Gi s thm 0,5ml dung dch AgNO 3 1N vo 100ml dung dch KCN 0,1N.
y vic to phc, nng ion CN- gim ti khi [CN-] = 0,09N cn nng ion
phc mi to thnh s bng [Ag(CN)-2] = 0,005N . T y ta c :
[Ag+]= 10-21 .
Ta c : [Ag+]= 10-21 .
Ta c : [Ag+]= 10-21 .
0,04
[4Kkb
Ag
,
96
.
(0.00
Khi thm 4,95ml Ag+
Ta c : [Ag+]= 10-21 .
Th tng ng :
[ Ag
Echi thi = 0,8 + 0,058lg
C th m t th chun nh sau :
im
tng
Fe2+ + Sn4+
ddSn4+
DD Fe3+
Th tiu chun ca cc in cc nh sau :
E0Fe3+/Fe2+ = 0,77v , E0Sn4+/Sn2+ = 0,15v
Nu nhng mt in cc Pt vo dung dch v tin hnh kho st s bin thin th
trong dung dch. Ta thy th bin thin ca dung dch c th tnh :
+ Khi qu trnh chun c mt na c ngha l thm c 25ml Sn 2+ lc ny
nng Fe3+ cn li l 0,05N v nng Fe2+ cng to c l 0,05N
3
[0Fe
,05
01
2
[0Fe
,09
05
E = 0,77 + 0,058lg = 0,77 + 0,058lg
E = 0,77V
[0,00
0
0Etd
,1.
[0,09
10
cn li l 1% tng ng vi 0,001N. Nng Fe2+ to thnh l 0,099N
E = 0,77 + 0,058lg = 0,654v
vo nng Sn4+ v nng Sn2+ cn nng Fe3+ v Fe2+ khng thay i. Nng
Sn4+ lc ny l 0,05N
4
[,0059
0,05
,0
[0[Sn
2
[0Sn
,200
E = 0,15 + lg= 0,15+ lg=0,24v
Ag+ + I- = AgI
Sau : Ag+ + Cl- = AgCl
Khi AgCl bt u kt ta cng vi AgI th [Ag+] trong dung dch l :
[Ag+]= 10-16/[I-] = 10-10/[Cl-] suy ra : [I-]/[Cl-]= 10-6. Chng t khi bt u qu trnh
chun Cl- th I- chun hon ton.
I.
1.in
tr,
2.
Cng tc, 3. Ac
quy, 4. in k, 5.
in
cc
calomen, 6. Bnh
chun , 7. in
cc Pt
u im ca phng php ny l cc thit b n gin v vic tin hnh nhanh.
Thiu st ca phng php l th ca cc ch th v qu trnh bin thin th ph
thuc vo cc cht in ly l c trong dung dch.
2.2 Phng php chun vi hai cc kim loi
Phng php chun vi hai cc kim loi da trn tnh tr ca cc lm bng cc
kim loi tr nh Pt. Pd, W i vi s thay i thnh phn im tng ng.
Nhng cc ny c th xem nh nhng in cc so snh .
1. Bnh chun , 2.
in k, 3. c quy, 4.
Cng tc, 5. in tr,
6. in cc Wonfram,
7. Cnh khuy, 8.
in cc Platin
Khi chun theo s trn vic thm mt git thuc th cui cng im tng
ng gy ra s sai lch bt thng ca kim in k. Phng php chun vi hai
in cc kim loi tin dng cho tt c cc loi chun in th. Phng php ny
cho php tin hnh phn tch nhanh, thit b chun n gin. Nhc im ca
phng php l khng c du hiu chng t sp ti im tng ng.
NaCl.
5.2. Phng php xc nh:
5.2.1. i vi cc sn phm cha t hn 5 % natri clorua:
Cho 5,00 g (hoc 5,00 ml nu nng c tnh theo khi lng trn th tch) mu
th chun b trong 1.1.1 hoc 1.1.2, hoc 50,0 g trong 1.1.3 cho vo cc c m
250 ml. Thm nc n khong 50 ml nu s dng mu th chun b trong 1.1.1
hoc 1.1.2 ( lm tan chy cht bo ca mu nh b th dng nc si). Thm 50
ml HNO3 (1 + 49). Chun nh trn, s dng buret 10 ml nu hm lng natri
clorua nh hn hoc bng 1 %.
% NaCl = ml AgNO3 nng 0,0856 M/10
Khi nng AgNO3 khc vi 0,0856 M th tnh nh sau
% NaCl = ml AgNO3 x C/0,0856/10
Trong C l nng mol ca dung dch AgNO3 dng chun
5.2.2. i vi cc sn phm cha bng hoc ln hn 5 % natri clorua:
Cho 5,00 g (hoc 5,00 ml nu nng c tnh theo khi lng trn th tch) mu
th chun b trong 1.1.1 hoc 1.1.2, cho vo bnh nh mc 100 ml v pha long
bng nc n vch. Trn u v chuyn dch lng cha t 50 mg n 250 mg NaCl
cho vo cc c m 250 ml . Nu mu th c chun b theo 1.1.3 th chuyn phn
dch lng cn cha t 50 mg n 250 mg NaCl sang cc c m 250 ml. Chun
theo nh trn, bt u t on pha long bng nc n khong 50 ml.
% NaCl = F x ml AgNO3 nng 0,0856 M/10
Trong F l h s pha long = 100/ml phn dch lng chun nu mu th
chun b trong 6.1.1 hoc 6.1.2, hoc 50/g mu th c chun b theo 6.1.3.
Khi nng AgNO3 khc vi 0,0856 M th tnh nh sau:
% NaCl = F x ml AgNO3 x C/0,0856 / 10
Trong C l nng mol ca dung dch AgNO3 dng chun .
5.2.3. Trng hp chung:
Cn chnh xc phn mu th nu (cn di 5 g mu nu hm lng NaCl bng
hoc ln hn 5 %, pha long n 100 ml). S dng dung dch AgNO 3 khong 0,1 M,
c chun ha chnh xc nh trn, khng iu chnh nng mol v chun
nh trn
% NaCl = ml AgNO3 x M AgNO3 x 0,05844 x 100/g mu th
Trong M l nng mol ca dung dch chun AgNO3 dng.
Nu mu th chun qu th thm chnh xc mt th tch dung dch chun NaCl
v hon thnh chun . iu chnh th tch dung dch AgNO 3 theo th tch dung
dch chun NaCl thm vo.