(A convenient method: decompose the process into subprocesses.

)
G= +RTlnK
Ⅰ

0
Ⅱ
= +RTln

Zn =1
Zn Ⅲ =1
()()
− 2 (2) 2 (2)
2𝑒 2𝑒
−
Inhomogeneous Conc.

()+(Zn,l)Zn(s) (s) (Zn,r)+()

)
(Zn,l)(Zn,r)

2F

=()+2(2)-{(()+2(2)}

+ + +=0
+ +=0
(Without salt bridge: thermodynamic viewpoint)

𝑍𝑛 𝑍𝑛 ( )
−
2+¿ 𝐶 𝑙 ¿

𝐶𝑙 ( 2 𝐶 𝑙 )
𝑍𝑛 ( )
−
2+¿ 𝐶 𝑟 ¿

𝐶𝑙 ( 2 𝐶 𝑟 )
𝑍𝑛
cathode anode

Assume
2+¿ (𝑎𝑞 ,𝐶 𝑟 ) ¿
𝑍𝑛
−
𝐶𝑙 ( 𝑎𝑞, 2 𝐶 𝑙 )

−
2+¿ (𝑎𝑞 ,𝐶 𝑙 )+2 𝑒 ( 𝑍 𝑛 , 𝑙) → 𝑍 𝑛 ( 𝑠 ) ¿
𝑍 𝑛
2 +¿ ( 𝑎𝑞 , 𝐶𝑟 ) ¿
𝑍 𝑛 ( 𝑠 ) → 2 𝑒− ( 𝑍 𝑛, 𝑟 ) + 𝑍 𝑛
electrode reaction would be accompanied by the transfers

𝑡 2 +¿ (𝑎𝑞 , 𝐶 𝑟 ) → 𝑡
+ ¿𝑍
2 +¿ ( 𝑎𝑞, 𝐶
𝑙)
¿
¿
¿

+ ¿ 𝑍𝑛 𝑛
¿

− −
2 𝑡 − 𝐶𝑙 ( 𝑎𝑞 ,2 𝐶 𝑙 ) →2 𝑡 − 𝐶𝑙 ( 𝑎𝑞 ,2 𝐶 𝑟 )

Quasi – thermodynamic arguments to predict the cell voltage of the concentration

cell with transference because it is not at thermodynamic equilibrium.

if at a thermodynamic equilibrium at the electrodes:

① =①-② 2+ ¿ ( 𝑎𝑞 , 𝐶𝑟 ) ¿

⇒ 𝑍𝑛 ( )⇄ 𝑍𝑛
2+ ¿ 𝑎𝑞 , 𝐶 𝑙 ¿
−
2+¿ (𝑎𝑞 , 𝐶 𝑟 )+2 𝑒 ( 𝑍 𝑛, 𝑟 ) ⇌ 𝑍 𝑛 ( 𝑠 ) ¿
② 𝑍𝑛

Since at pseudo – equilibrium in the electrolyte :

(electrochemical equilibrium constants)

On account of junction potential difference, two solution chambers are

at different potentials.
 𝐹 ∆ 𝐸𝑛
𝑅𝑇
¿𝑒

When this cell functions galvanically to the end,

and .

Since is a function of ,
(Consider the following hypothetical situations)

if the membrane were permeable only to cations,

→ ∆ 𝐸𝑛 =0
if it were permeable only to anions,

(null potential with salt bridge)

 High conc Low 이온만 통과시키는 diaphram
(Ⅰ conc
( ->
)Zn 2 +¿ ¿ 2 +¿ ¿ Zn
Ⅱ
𝑍𝑛 ❑ − 𝑍 𝑛❑ − )
= 0.0

𝟐 𝒆 2 𝐶𝑙 𝟐 𝑪𝒍2− 𝐶𝑙
− −
𝟐𝒆 + RTln + F(- ) = + RTln
Cathode α β phase An-
phase ode = -

(Ⅰ) = -(α) - 2(l)

(Ⅰ) +  (Ⅱ)  +
(Electrolyte) 2 (α) -> (β) (Ⅱ) =(β) + 2(r)
= =
= 2 β) - 2 (α)
(electrolyte)
= + +
= + + {2 β) - 2 (α)} =2 (β) - 2 (α)
= +2RTln + + =0
= RTln = 3RTln <0
전자에너지 변화 : -2F )=- (should be) (at electrochemical equilibrium)

= -(α) - 2(l) +(β) + 2(r) + 2 (β) - 2 (α)

= RTln + RTln

= RTln +2RTln +2RT )=0

2F )=RTln =RTln = 3RTln <0

 (Ⅰ High con ( + RTln
)Zn Low2 +¿
con 2 +¿ ¿ Ⅱ
Zn = -
𝑍 𝑛❑−
¿
− 𝑍𝑛
− ❑ )
𝟐 𝒆 2 𝐶𝑙 2 𝐶𝑙 −
𝟐𝒆
Cathode α β phase An-
phase ode = -(α) - 2(l)
(Ⅰ) +  (Ⅱ)  + = -(β) - 2(r)
(Electrolyte) = [2 -2 [-
At electrochemical equilibrium
2 ()  () = + + =0
= RTln + RTln +RTln
( )  ()
= RTln + RTln +RTln
= = = RTln +RTln
= RTln + RT ( ) = 0
= [2 -2 [-
2FE= RTln = 3
=3

= + + [2 -2

[-

= RTln = RTln

= RTln = RTln = 3

전자 에너지 변화

-2F ) = -

2FE= 3
Consider P + q : P+q =0
a=m (m=) (=pm) (=qm)
=p +q
=+RTln+ F = +RTln : = exp()
= = =() ()
= : ( show that = where =P+q+(p+ q)RTln)

{liquid junction potential}

α phase β phase
평형조건 ) =  - =ln or = (1)
• Liquid junction potential is formed due to the transport rate of cations and anions.
• We have to consider the transference number (transport number) to find the liquid junction potential.

When employing the convenient method (decomposition of a total process into subprocesses),
the liquid junction potential is taken care of automatically by the term.

Liquid junction potential - =

 = [ - - RTln ]
α phase β phase > 0 when > , i.e, (β)
Zn Zn
lo
Hig 𝑆𝑂 4 w
2−
h
Cath- an-
ode ode

(At an earlier stage) (At a later stage)

α β α β
Hig lo sam sam
h w e e
2− 2− ❑ 2−
𝑆𝑂244−𝑡 ❑𝑆𝑂 24 −
𝑆𝑂 𝑆𝑂 4 𝑡 𝑆𝑂 4
− −

(α) > (β) for electrochemical equilibrium (α) = (β)

= (α) - (β) > 0 = (α) - (β) = 0
= + > = + = =0

When = 0 , no generation of electricity at the expense of

chemical energy
 Daniell Cell
= [ - - RTln ] =1.102V >0
α phase β phase
Cu lo Zn -0.76 0.34
Hig w 2−
h 𝑆𝑂 4
> 0 even if > , i.e, (β)
Cath- An-
ode ode

(At an earlier stage) (At a later stage)

α β α β
Hig lo low Hig
h w h
2− 2− ❑ 2−
𝑆𝑂244−𝑡 ❑𝑆𝑂 24 −
𝑆𝑂 𝑆𝑂 4 𝑡 𝑆𝑂 4
− −

(α) > (β) for electrochemical equilibrium (α) < (β) for electrochemical equilibrium
= (α) - (β) > 0 = (α) - (β) < 0
= + > = + <

When = 0 , no generation of electricity at the expense of

chemical energy
 solution (Fickian diffusion)

α β 𝑡+ ¿ ❑
≫ 𝑡❑
− ¿
− −
𝐶𝑙 ¿
𝐻 +¿
❑
𝐶𝑙 ¿
❑
𝐻 +¿
❑
❑
(α) < (β)
High 𝑡+ ¿
❑ low
¿ +¿ ¿
= (α) - (β) < 0

𝑡 𝐻 ❑−
❑
−
𝐶𝑙 ❑

Contrary to the cases of the Daniell cell and the concentration cell (Zn/Zn), which are composed of coupled subprocesses,
This case is a single subprocess.

If we consider , (α) < (β).

For , (α) > (β).
Since , the effect of movement dominates.

HCl :

For the case of Fickian diffusion: cation 이 이동하는 곳의 electric potential 증가하고
anion 이 이동하는 곳의 electric potential 감소한다 .
For non-Fickian diffusion: the above statement is invalid: we have to consider the coupling of subpro-
cesses.
☆ liquid junction potential 구할 때 주의 할 요소들

1. Liquid junction potential 은 이온들의 이동에 의해 생성되므로 Gibbs energy balance 에 (transport number) 를 고려함

2. 이온의 움직임은 chemical species 의 chemical energy 를 transport number 에 비례해서 변화시키고 electric energy 는 그 지점의 electric potential 에 의해
결정 : - = =ln ( electrochemical equilibrium 일 때 =0 or =)
위의 식에 이온이동 고려하면
- = =ln

3. Electrochemical Gibbs free energy 의 변화가 zero 라는 조건을 이용할 때는 이온과 counter ion 의 움직이는 방향을 고려해야 함 .
Counter ion 은 electroneutrality 를 만족시키려고 이온의 반대 방향으로 움직임 .
3 번 방법 2 번 방법
α β
𝑎
❑
− 𝑎
❑
−
𝑎+¿ ❑
¿ 𝑎+¿ ❑
¿
(α ( 방향
) 고려함 ❑ ❑
𝑎+¿ ❑
¿ 𝑎 β❑
+¿) ¿
𝑎− 𝑎−
동일한 결과 !
(= 0= -) (- )= ln + ln
+ RTln
Cathode ln + ln
α phase
❑
α 𝑡− β α β (=-) = (- ) ln

( Ⅰ)
𝑎α❑− phase 𝑎❑− 𝑎+¿ ¿ (Ⅱ) 𝑎+¿ ¿
Cathode
❑ ❑

= RTln = RTln
+=0
( 적용
RTln + RTln =RTln + F(- )
예) α β : =0.391
(=-)=RTln + F(- )(+ )
=RTln+RTln F(- ) +¿ ¿ +¿ ¿ : = 0.490
2RTln +RTln + F(- )=0
𝐻 ❑ 𝐻 ❑ 에 적용해 볼 것
(- )=(2-1) ln =(- ) ln
− −
𝐶𝑙 ❑ 𝐶𝑙 ❑
high conc low
conc
>
- =(- ) ln < 0
(Application to the battery analy-
sis) 이온만 통과시키는 막
High con Low
(Ⅰ con
(
= 0.0
)Zn 2 +¿ ¿ 2 +¿ ¿ Zn
Ⅱ
𝑍𝑛 ❑ 𝑍𝑛 ❑ )(r)
(l) − −
𝟐𝒆 𝟐 𝑪𝒍
−
𝟐𝒆
Cathode α β phase An-
phase ode
(Ⅰ) +  (Ⅱ) Zn+

(electrolyte)
: 2 (α)  (β) : 방향고려 해야함 ( 이동 )

= -(α)-2(l), =(β)+2(r)
=2(β) - 2(α)
+ + ()
= -(α)-2(l)+(β)+2(r)+2(β) - 2(α)
= RTln +2RTln +RTln
= = RTln +2F(- )0
2F(- )= 3RTln <0

이 경우 voltage 는 liquid junction potential 이 없는 경우와 같음

 𝑍𝑛
Salt bridge()
High con
(Ⅰ Low con (
) Ⅱ
)
+¿¿ +¿¿
>> Zn 𝑲 𝑲
) − )
Because transport number is
𝑪𝒍
) 2)
proportional to the concentra- −
tion 𝟐𝒆
−
𝑪𝒍
− 𝟐𝒆
Excess
α conc β
phase phase

과량의 가 electroneutrality 유지 시킴  ) 와 2) 의 이동 없음
= 0, =0 : , 만 nonzero

(- ) due to , Salt
= ln + ln ln + ln = 0 = bridge
 Concentration cell with a salt
bridge

𝑍𝑛
High con (Ⅰ) () + (l) Zn(l)
(Ⅰ Low con ( (Ⅱ) () () + (r)
) Ⅱ
)
+¿¿ +¿¿
Zn 𝑲 𝑲 ( 전해질 )
) − )
𝑪𝒍 )  2)
−
) 2)
𝒆 =1.0 since = 0.0

Excess
α conc β
phase phase

소량의 2 가 α 에서 salt bridge 를 통과해서 β 로 이동

이 경우는 이온만 통과시키는 membrane 이용한 경우와 동일

2F(- ) =2F (- )= 3RTln < 0
(3 번 방법 )

𝑍𝑛
(Ⅰ ( (Ⅰ) () + (l) Zn(l)
) α β Ⅱ (Ⅱ) Zn(r)  () + (r)
phase phase )
Zn High con ( 전해질 )
Low
2 +¿con
¿ 2 +¿ ¿ 𝑡❑
𝑍𝑛 ❑ 𝑍𝑛 ❑ )  2)
−

𝟐𝒆
−
−
𝑡+ ¿ ¿
❑

) 2) 𝟐𝒆 ()  ()

+ + 0
= RTln +RTln +RTln
= RTln + 2F (- ) = RTln + 2F (- )
= RTln + 2F(- ) =0

2F(- = 3RTln >0

liquid junction potential 이 없으면

2F (- ) = 3RTln
liquid junction potential
2F (- )=2F (- -2F(- ) = - 3RTln < 0
 (2 번 방법 )
Salt bridge 이용한 경우와 동일
(Ⅰ) () + (l) Zn(l) 2F (- ) = 3RTln
(Ⅱ) Zn(r)  () + (r)
( 전해질 ) )  2)

Then, liquid junction potential may be found by considering

( 전해질 ) 2) 2)  (- ) = ln (-1=- )
() ()  (- ) = ln ()

(- ) = ln + ln
ln +ln

= ln = - ln < 0 ( the same as previous result)

Then 2F(- = 2F(- ) + 2F(- )

= 3(1- )RTln = 3RTln (the same result as the previous one)

mea- w/c liq- Liquid

sured uid junction
junction poten-
poten- tial
tial
Oxygen ion transferring through

Figure 3.9 The zirconia-based oxygen-concentration cell responds to the ratio of the partial pres-
sures of oxygen at its two electrodes.

Ⅰ) cathode
(left)
Ⅱ) anode (right)

(overall reaction: Ⅰ- Ⅱ)
𝑂 2 (𝑔¿¿ 𝐿)⇌ 𝑂 2 (𝑔¿¿ 𝑅)¿¿
Electrodes

How to determine ?

working electrode (WE) : electrode of interest.

reference electrode (RE) : 기준 potential 결정
∆ E= EWE − E ℜ
electrode potential or half cell potential

Typical reference potentials : have constant activities

1) standard hydrogen electrode (SHE)

2) saturated calomel electrode (SCE) at

3) silver/silver chloride electrode

at
Standard electrode potential
(WE)
(RE)

∆ 𝐸 𝑛 =𝐸𝑤𝑜𝑟𝑘 − 𝐸 𝑟𝑒𝑓

(Nernst equation)

: standard electrode potential

may be found from values (both data are tabulated)

Example of standard electrode potential : given

＊ if >0 , it is equivalent to <0 , meaning spontaneous forward reaction.

Figure 3.6 The Daniel cell

(Daniel cell)

left electrode
right electrode

For the reaction , left-right,

Therefore, left electrode is cathode and right electrode is anode.

Cu − − Zn
2𝑒 2𝑒

Zn electrode at higher electron population → lower potential

𝜙𝐶𝑢 > 𝜙 𝑍𝑛
Figure 6.3 An electrochemical series.
구리전극 Cu2+(aq) + 2e- Cu(s) ECu = 0.34 + +

아연전극 Zn2+(aq) + 2e- Zn(s) EZn = -0.763 +

electrochemical couple or redox couple

𝐸𝑐𝑒𝑙𝑙=𝐸 𝑐𝑎𝑡h𝑜𝑑𝑒−𝐸𝑎𝑛𝑜𝑑𝑒
Versions of the Nernst equation
−
𝑜𝑂+ ⋯ + 𝑛 𝑒 ⇌ 𝑟𝑅+ ⋯
null potential

For the reaction (reference electrode is SHE : )

+ ¿ (𝑎𝑞 )¿
2 +¿ ( 𝑎𝑞 ) + 𝐻 2 ( 𝑔 ) +2 𝐻 2 𝑂 ( 𝑙 ) → 𝐶𝑢 ( 𝑠 ) +2 𝐻 3 𝑂 ¿
𝐶𝑢
∆ 𝐺= 𝐺𝐶𝑢 +2 𝐺 𝐻 3
¿
𝑂 − 𝐺𝐶 𝑢 2 +¿ 𝑜 𝑜 ¿
− 𝐺 𝐻 −2 𝐺 𝐻 𝑂 ¿
2 2

()
 −
𝑣 𝐴 𝐴+𝑣 𝐵 𝐵+ …+𝑛 𝑒 ⇌+𝑣
⇌ 𝑍 Z+ 𝑣 𝑌 𝑌 +…

Nernst equation

: formal electrode potential, conditional electrode potential

Various shapes of working electrodes

Figure 6.7 Cross-sectional diagrams of four common electrode shapes: (a) an inlaid disk electrode,
(b) a hemispherical electrode, (c) a hanging drop electrode and (d) a tubular band electrode. The
figures have been scaled to represent configurations with identical electrode | solution interfacial
areas.
※ Donnan membrane equilibrium

(I) (II)
K+ K+
Cl- Cl-
R-
R- : impermeable
,= K+, Cl- : permeable

electrochemical potential should be the same at equilibrium

(*)

(**)
 Donnan membrane potential
(caused by R-)
From (*) and (**), we find
or =
C+(I) = C-(I) + CR(I) , C+(II) = C-(II)

>1 : () >0