Title: ?20? ??? (Voltammetry)
1?20? ???(Voltammetry)
2- ??
- 1922 Heyrovsky??,1959??Nobel?
- 1934 ????(Ilkovic) ??????,??
- 50?????,????????
- 80?????,????,????
- ?? ????????????
3- ??????? ??????????-????????????
- ???(polarography) ???????????????????????????
- ??? ??????????????????????
- ????(????) ????,?????????,????????,???????????????
?? - ?????(????) ????,?????????,????????,???????????
4???
?????????????
idil-ir
??????
????
???? (A dropping mercury electrode)
????
5 ?????
6 ????
7- ??????
- ????? ???????????,?????????,??????,???????????0.3
V? - ??????
- ????,???????
- ?????,?????????
8????
???????
(?????????????,??????????)
9Fick????
????
x0
x xdx
Fick????
????
????
????t 0, x 0 CO C, CR 0 ????t
?0, x 0 CO C , CR C- C
t ?0, x ? CO C , CR 0
????
10??????????
??????
??
?????
11 ???????????Cottrell??
???????????3?????????,????,????
??????,?????????
??????,??????????????????????????????
,???????????????????????? ?
12???????????
?????
????(mg/s)
???????(mmol/L)
?A
?????????????(cm2/s)
????(s)
????????
????(Ilkovic)???
13?????????
????????????
- (1)?????m2/3t1/6
- (2)?? ???n?????
- (3)????? ??????
- ????????????
????
Ilkovic??
?????????
14- ??????????
- ????
- ???? ???????
- ????(????) ????????????????????? (10-5 mol/L)
- ?????????????????????
- ???? ???????????
- ????????????
- ??????????
- ????????????,????????????
- ??????????,??????????????,???????????
15- ????
- ???????(??????)
- ?? ??????
- ????????(N2,Ar?)
- ????
- ?? ???H??? ????????pH??
- ?? ????????????????
- ???????
- ?? ??????????????0.2 V
- ???????????,????????
- ?????
16???????
??????CO C, CR 0 ????????
k, k????D1/2, D? 1/2???
?
?
???? ?????????
17??????CR C, CO 0
?????? CO C O, CR C R
(id)c
(id)a
18??????,? ????????n??1/2 25ºC?,
????????(?????)n/0.059 ?????????????
id
19 ?????????????
Mn ne- Hg M(Hg) , Eo
(1)
Mn pL MLPn K
(2)
MLpn ne- Hg M(Hg) pL,
Eco (3)
??(1) ?????? (2) ???????,L0 L
20??????
????
???
?????,????????????,? i nFAkc ( MLpn -
MLpn 0 )
????
????
?????,?????????,? i nFAkcM(Hg) 0
21???????
????????
???????????,???????????,??????????
22??????
?????????????????????
???
????
????? ?????????? ????
???
???
????
???
23??????
1. ??????? ???
??????
????(????)
????
????
????
??(??????????)
24????? ??????????????,IR?????,??????,??????????????
??,???????????????,???????????
????? ?????????? ???????????????????? ???????????
??????
253. ????? ????? ????
????????
(1) ????????10-5 M
?????
(2) ??????????
??
??-???????
26i
t
Faraday???????
27 ????????????
(1) ???10-6 M (2) ???????
28 - ??????(?????) ?????????????
- ?????????????????????????????????,??????
?????????????
???? ?????
?? ??,0.2 V/min ??,0.25 V/s
???? ??? ???
????? S? ??
???????? ??? 1?
29?????
E
(1) ???
E?
a.
Randles-Sevcik equation
ip (2.69?105) n3/2 A C D1/2 v1/2
(25ºC)
b.
c.
iPc/iPa 1
30(2) ????
(3) ????
?????
Ep?v??
(1) ???10-6 M (2) ???????
31 - ?????????????????,???????????????,????????,???????
? - ????????????????,A?????,???????,????????,????????
???? ????
32?????
- ??????
- ?????????
- ????????
???
E
ic
????
i
???????
if
???10-7 M
??????????????????????
????
33??(??)???
??
??
34 35- Faraday?? if ? t-1/2
- ???? ic ? e-t
- ??????? i ? t-n (ngt1/2)
36???????
Square wave
voltammetry
37 ??(??)???
??????????????
38?????
i
C
39 ?????
????
40?????
- ?????(??)????,???,???????103?
- ????
- ??
- ??
???? ??????,???10-12 M, ??????????????
41 Multi-element Analysis
Cd2
Cu2
Cr3
Pb2
42????????????
43?????
- ???? ?????????????
- ??,???40??????
- ???
- ??????????n,D,C,E0,ks
- ??????
- ???????????
- ????
- ?????
44? ? ? ? ?
45?????
46- ??
- P569-570 9. 10. 11. 12. 13. 14
47- ????
- ???????5,7?????
- ????SCI???????,???????????????????????????
- ???????8,9?????
- ????SCI???????,??????DNA????????????
- ???????1000?
- ????4?22?
- ?????????(?????????????,????????),?????