Advanced Analytical Chemistry
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.
.
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---
---
A
B
M
X
Y
N
A
V
4πr2
{(4/3)πr3} = 3/r
r
r
1/ r2
1/r
r
---
---
---
Ox + ne
vf
Red
vb
vf = kfCOx(0,t)
v:
(
k:
(
C(0,t):
vb = kbCRed(0,t)
)
)
mol s-1 cm-2
cm s-1
Q = -nFN
F:
N:
Ox
Red
I = dQ/dt = -nFdN/dt = -nFAv
dN/dt = vA A:
I = -nFA(vf - vb)= -nFA(kfCOx(0,t) - kbCRed(0,t))
kf = Afexp(-ΔGf /RT)
kb = Abexp(-ΔGb /RT)
Af:
ΔGf :
ΔGf = ΔG0f + αnFE
α:
--0.5
ΔGb = ΔG0b - (1 - α)nFE
kf = Afexp(-ΔG0f /RT)exp(-αnFE/RT)
kb = Abexp(-ΔG0b /RT)exp((1 - α)nFE/RT)
Afexp(-ΔG0f /RT)
---E = 0
kf = kf0exp(-αnFE/RT)
Abexp(-ΔG0b /RT)
(E
)kf0
kb0
kb = kb0exp((1 - α)nFE/RT)
kf = kb
kf0exp(-αnFE0'/RT) = kb0exp((1 - α)nFE0'/RT) = k0
k0:
E0':
kf = k0exp(-αnF(E - E0')/RT)
kb = k0exp((1 - α)nF(E - E0')/RT)
I = -nFAk0(COx(0,t)exp(-αnF(E - E0')/RT)
- CRed(0,t)exp((1 - α)nF(E - E0')/RT)
---
t=0
C/
E1
E2
t = D 2C/ x2
t = 0, x ≥ 0 C = C0
x=0
C = 0; x
I = nFAD1/2C0 / (πt)1/2
I t
t
C
Cottrell
C0
(1)
<<
E = E0' + (RT/nF)lnCOx(0,t)/CRed(0,t)
(2)
>>
(3)
(1)
(2)
(WE)
WE
RE
CE
(RE)
NHE
H+ + e
1/2H2
0.0 V(pH = 0)
AgCl + e
KCl
(CE)
Ag + Cl0.199 V(vs. NHE)
IR
----E
E = Ea - IRs
Ea
I
Rs
-
E
I-E
2
Ox
Red
I / µA
1
Epa - Epc = 59/n (mV
Epa
0
-1
-3
E1/2 = (Epc + Epa)/2
DOx ~ DRed E1/2 = E0'
Epc
-2
Ox
0
Ipc =
2.69x105An3/2COxDOx1/2u1/2
Red
100
25oC)
200
E / mV
300
400
I
u
1/2
CV
Ox + ne
k
Red
Red
P
k:
5
Ox
Red
I / µA
k=0
0
Ox
-5
0
100
200
300
E / mV
Red
400
k
500
CV
Ox(
)
+ ne
Red(
)
Ip = n2F2AuΓ/(4RT)
Γ:
I/A
I u
ΔEp/2 = 3.53RT/(nF)
[= 90.6/n (mV, 25oC)]
E/V
CV
u
(1)
I = nFADC0{(πDt)1/2 + 1/r}
r
µm
mm
Cottrell
/V
S
/ nA
(2)
1 nA
10 mV/1 nA = 10 MΩ
10 mV
X
X+
X
X
2 µm
X+
X+
mm
Au
10
Pt
5 µm
CCD
RE
C1+ A1- (
) Xn+ C2+ A2- (
C1+ A1C2+ A2-
/
Xn+
) RE
Xn+
--/
RE
C1+ A1- (
) Xn+ C2+ A2- (
) RE
E = Δwoφ0Xn+ + (RT/nF)ln{aXn+(o)/aXn+(w)}
Δwoφ0Xn+ :Xn+
aXn+(o) aXn+(w)
n Xn+
Δwoφ0Xn+ = -ΔG0/nF
ΔG0 Xn+
Xn+
(TMA+)
1,6-
I / µA
TMA+: 0.4 mM
50 mV/s
: 0.07 cm2
E / mV
Δwoφ0TMA+ = 0.17 V
n2
n1 > n2
1
θi
λ0
---
00 nm
dp = (λ0/4π)(n12sin2θi – n22)-1/2
RE
CE
RE
CE
500 nm---0.5 µm
F
25µm
fL
µm
10 µm
µm
00 µm
10 µm
µ
µ
µ
µ
µ
1.
,
,
2.
,
,
,
,
3. K. Nakatani, T. Sekine, and T. Negishi , Encyclopedia of Surface and
Colloid Science, 1st Edition, Arthur Hubbard, Ed., Marcel Dekker, New
York, Vol. 3, p.3391-3401 (2002).

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