Introduction to Electrochemistry

(電化學概論)

Liquid Junction, ISE

2023/3/24
 Liquid Junction
V
e-
e-

Cu(s) Cu(s)

CuSO4 (dilute) CuSO4 (conc.)

Cu(s)|CuSO4(aq) (dilute) | CuSO4(aq)(Conc.) |Cu(s)

 Concentration Cells
• Concentration cells are among the simplest
electrochemical cells that can be devised
• The only difference between the two half-cells is the
concentration of the solutions in the electrodes bath
• The standard emf of this cell is zero
2+ 2+
Cu (s) Cu (aq) (c1 ) Cu (aq) (c 2 ) Cu (s)
RT a1
ÞE=- ln
2 F a2
 Liquid-Junction Potential

CuSO4 (a2) +++++

- - - - -

CuSO4 (a1) Cu2+ SO42-

?
 What is a Junction Potential?
• A junction potential develops at the interface between two
dissimilar electrolyte solutions
• Junction potentials are typically small and are found at each
end of the salt bridge connecting two half-cells
• They put a fundamental limit on the accuracy of direct
potentiometric measurement
𝐸!"#$%&$' = 𝐸($)) + 𝐸*+,(-.!,
• Figure shows that in water, Cl- has greater mobility than Na+
• The result is an electrical potential difference at the junction
between the NaCl and H2O phases
 What is a Junction Potential?
• Junction potentials are minimized by
choosing ions with similar mobilities
• Is KCl a good choice for a salt bridge?
Nernst-Plank Equation:
𝑑𝑐 𝑧 𝑑𝜑
𝐽 = −𝐷 − 𝑢𝑐
𝑑𝑥 𝑧 𝑑𝑥
 Nernst-Plank Equation
𝜇- = 𝜇/ + 𝑅𝑇𝑙𝑛𝑐 + 𝑧𝐹𝜑
𝑑𝜇- 𝑅𝑇 𝑑𝑐 𝑑𝜑
𝑓 𝑝𝑒𝑟 𝑚𝑜𝑙 = − =− − 𝑧𝐹
𝑑𝑥 𝑐 𝑑𝑥 𝑑𝑥
𝑅𝑇 𝑑𝑐 𝑑𝜑
𝑁0 𝜂𝑣 = − − 𝑧𝐹
𝑐 𝑑𝑥 𝑑𝑥
𝑅𝑇 𝑑𝑐 𝑧𝐹 𝑑𝜑
⇒𝑣=− −
𝑁0 𝜂𝑐 𝑑𝑥 𝑁0 𝜂 𝑑𝑥
[𝐽 = 𝑐𝑣; 𝜔 ≡ 1/𝑁0 𝜂]
𝑑𝑐 𝑑𝜑
𝐽 = −𝜔𝑅𝑇 − 𝑧𝐹𝜔𝑐
𝑑𝑥 𝑑𝑥
[𝐷 ≡ 𝜔𝑅𝑇; 𝑢 ≡ 𝑧 𝜔𝐹]
𝑑𝑐 𝑧 𝑑𝜑
𝐽 = −𝐷 − 𝑢𝑐
𝑑𝑥 𝑧 𝑑𝑥
 Assuming dc/dx = Constant
𝑑𝑐 𝑑𝜑
𝐽 = −𝜔𝑅𝑇 − 𝑧𝐹𝜔𝑐
𝑑𝑥 𝑑𝑥
𝑐.,' − 𝑐.,/ 𝑐.,' − 𝑐.,/ 𝑑𝜑
𝐽. = −𝜔. 𝑅𝑇 − 𝑧. 𝐹𝜔. 𝑐.,/ + 𝑥
𝑑 𝑑 𝑑𝑥
𝐼 = F 𝑧. 𝐹 𝐽. 𝐴
.
𝑐.,' − 𝑐.,/ 𝑐.,' − 𝑐.,/ 𝑑𝜑
= 𝐹𝐴 F 𝑧. −𝜔. 𝑅𝑇 − 𝑧. 𝐹𝜔. 𝑐.,/ + 𝑥
𝑑 𝑑 𝑑𝑥
.
𝑅𝑇 2
𝑑𝜑
= −𝐹𝐴 H F 𝑧. 𝜔. 𝑐.,' − 𝑐.,/ + 𝐹 F 𝑧. 𝐹𝜔. 𝑐.,/
𝑑 𝑑𝑥
. .
1 2
𝑑𝜑
+ 𝐹 F 𝑧. 𝜔. 𝑐.,' − 𝑐.,/ 𝑥 I
𝑑 𝑑𝑥
.
 Assuming dc/dx = Constant
Assume 𝐼 = 0
𝑅𝑇 2
𝑑𝜑
−𝐹𝐴 H F 𝑧. 𝜔. 𝑐.,' − 𝑐.,/ + 𝐹 F 𝑧. 𝐹𝜔. 𝑐.,/
𝑑 𝑑𝑥
. .
1 2
𝑑𝜑
+ 𝐹 F 𝑧. 𝜔. 𝑐.,' − 𝑐.,/ 𝑥 I=0
𝑑 𝑑𝑥
.
𝑅𝑇 2
𝑑𝜑
F 𝑧. 𝜔. 𝑐.,' − 𝑐.,/ + F 𝑧. 𝐹𝜔. 𝑐.,/
𝐹𝑑 𝑑𝑥
. .
1 2
𝑑𝜑
+ F 𝑧. 𝜔. 𝑐.,' − 𝑐.,/ 𝑥
𝑑 𝑑𝑥
.

𝐴 = F 𝑧. 𝜔. 𝑐.,' − 𝑐.,/ ; 𝐵 = F 𝑧. 2𝜔. 𝑐.,/

. .

𝐶 = F 𝑧. 2𝜔. 𝑐.,' − 𝑐.,/ = F 𝑧. 2𝜔. 𝑐.,' − 𝐵

 Assuming dc/dx = Constant
𝑅𝑇 𝑑𝜑 𝑥 𝑑𝜑
𝐴+𝐵 +𝐶 =0
𝐹𝑑 𝑑𝑥 𝑑 𝑑𝑥
𝑅𝑇 𝐴 𝑑𝑥
𝑑𝜑 = −
𝐹 𝐶𝑥+𝐵𝑑
𝐶
3"
M 𝑑𝜑 = 𝜑' − 𝜑/ = ∆𝜑
3!
𝑅𝑇 𝐴 ' 𝑑𝑥 𝑅𝑇 𝐴 𝐶 + 𝐵
=− M =− ln
𝐹 𝐶 / 𝑥+ 𝑑 𝐵 𝐹 𝐶 𝐵
𝐶
∑. 𝑧. 𝜔. 𝑐.,' − 𝑐.,/ 𝑅𝑇 ∑. 𝑧. 2𝜔. 𝑐.,'
⇒ ∆𝜑 = − ln
∑. 𝑧. 𝜔. 𝑐.,' − 𝑐.,/ 𝐹
2 ∑. 𝑧. 2𝜔. 𝑐.,/
𝑢.
∑. 𝑧.
𝑧. 𝑐.,' − 𝑐.,/ 𝑅𝑇 ∑. 𝑧. 𝑢. 𝑐.,'
⇒ ∆𝜑 = − ln
∑. 𝑧. 𝑢. 𝑐.,' − 𝑐.,/ 𝐹 ∑. 𝑧. 𝑢. 𝑐.,/
 Example
For two liquid phases containing respectively KCl and
HCl solutions both with mean ionic activities of 0.1

Element Mobility m2V-1s-1

K+ 7.61x10-8
H+ 3.63x10-7
Cl- 7.91x10-8
Numerical Experimental Values of the
Diffusion Potential
 Salt-Bridge

• The elimination of diffusion potentials in a practical

concentration cell with a salt-bridge
 Daniell Cell

oxidation (-) Zn(s)|Zn(aq)2+||Cu(aq)2+|Cu(s) reduction (+)

E = E right – E left
Goldman-Hodgkin-Katz (GHK) Equation
𝑑𝜑
= constant
𝑑𝑥
𝑅𝑇 ∑* 𝜔* 𝑐*,' + ∑4 𝜔4 𝑐4,/
∆𝜑 = − ln
𝑛𝐹 ∑* 𝜔* 𝑐*,/ + ∑4 𝜔4 𝑐4,'
• The Goldman–Hodgkin–Katz voltage equation, more
commonly known as the Goldman equation, is used in
cell membrane physiology to determine the reversal
potential across a cell's membrane, taking into account
all of the ions that are permeant through that membrane
∑ 7 ∑ & [𝑀 8 ]
𝑅𝑇 𝑃 $
* 6# [𝑀 ]
* !+- + 𝑃
4 0% 4 .,
∆𝜑 = 𝐸5 = ln
𝑛𝐹 ∑* 𝑃6$ [𝑀*7]., + ∑4 𝑃0&% [𝑀48]!+-
#

• 𝐸5 : membrane potential
• 𝑃: permeability
Structure and Function of Neurons
Membrane Potential

From Wikipedia
 Quiz
𝑅𝑇 ∑* 𝑃6$ [𝑀*7]!+- + ∑4 𝑃0&% [𝑀48].,
#
𝐸5 = ln
𝑛𝐹 ∑* 𝑃6$ [𝑀*7]., + ∑4 𝑃0&% [𝑀48]!+-
#

• 𝐸5 : membrane potential
• 𝑃: permeability
• For typical mammalian neuron cells, the ion concentration:
Potassium (K+) Sodium (Na+) Chloride (Cl-)
Outside 5.5 mM 135 mM 125 mM
Inside 150 mM 15 mM 9 mM
• The permeability
• PK : PNa : PCl = 1 : 0.04 : 0.45

Q: Please calculate the 𝐸5 if only K+ is under consideration

 pH measurement
• If the activity of the H3O+ ion appears in the overall
chemical equilibrium governing a galvanic cell, the
equilibrium potential of that cell can be used, at least
principally, as a measure of the pH-value
• The simplest, and in many ways the most important of
such equilibrium is the “hydrogen electrode”
• The hydrogen electrode Pt|H2|H3O+
• Electrode reaction
7 8
1
H9 O + e ⇌ H2 + H2 O
2
The potential at P = 1, 𝐸:/ $ |:' = 0
𝑅𝑇
𝐸:$ |:' = 𝑙𝑛𝑎:( <$ 𝑣𝑠 𝑆𝐻𝐸 ≡ −0.0591𝑝𝐻 𝑎𝑡 298𝐾
𝐹
 SCE as Reference Electrode

Hg | Hg 2 Cl 2 | KCl(sat.) || solution of pH = pH | H 2 | Pt
Df j : liquid junction potential
E = E H + |H - E SCE + Df j = - 0.0591 pH - ESCE + Df j
2

and
E + ESCE - Df j
pH = -
0.0591
Practice:
• If measured EMF is -0.8627 V, ESCE is taken as 0.2415 V,
and Δφj has been reduced to below ± 2 mV, then pH = ?
• pH=-(-0.8627+0.2415+/-0.002)/0.0591=10.51+/-0.03
 Other Types
• In alkaine media, the pH sensitivity of the mercury-
mercury oxide electrode can be exploited,
HgO + H2O + 2e8 ⇌ Hg + 2OH 8
𝐸 / = +0.097 𝑉 𝑣𝑠. 𝑆𝐻𝐸

• The electrode predominantly applicable in acid solutions

in the quinhydrone-electrode,
• Pt |C6H4O2,C6H4(OH)2|H3O+

𝐸 / = +0.097 𝑉 𝑣𝑠. 𝑆𝐻𝐸

Donnan Distribution
• Let the membrane separate
a purely inorganic solution of
NaCl on the left hand side
from a solution of an anionic
colloidal sol with Na ions
on the right hand side
• If two solutions of ions are
separated by a semi-
permeable membrane, an
electrochemical osmotic
equilibrium will be set up
leading to a potential drop
across the membrane
 Membrane Potential
• If ions in solution are in equilibrium with those present in
a membrane in contact with that solution, so that ion
exchange can occur, a potential drop at the phase
boundary between solution and membrane may happen
• Donnan potential appears as a result of Donnan
equilibrium, which refers to the distribution of ion species
between two ionic solutions separated by a
semipermeable membrane or boundary
• The boundary layer maintains an unequal distribution of
ionic solute concentration by acting as a selective
barrier to ionic diffusion
 Donnan Distribution
• For 𝑁𝑎7:
? ? ?? ??
𝜇=> $ + 𝐹𝜑 = 𝜇=>$ + 𝐹𝜑

• For 𝐶𝑙 8:
? & ?? &
𝜇@) − 𝐹𝜑 ? = 𝜇@) − 𝐹𝜑 ??
? ? ?? ??
⇒ 𝜇=> $ + 𝜇@)& = 𝜇=>$ + 𝜇@)&

𝜇. = 𝜇./ + 𝑅𝑇𝑙𝑛𝑎.
? ? ?? ??
⇒ 𝑎=> $ p 𝑎@)& = 𝑎=>$ p 𝑎@)&

(the so-called Donnan distribution)

• Based on electroneutrality
? ? ?? ?? ??
⇒ 𝑐=> $ = 𝑐@)& 𝑎𝑛𝑑 𝑐=>$ = 𝑐@)& + 𝑐(!))&
? ?? &
𝑅𝑇 𝑎 $ 𝑅𝑇 𝑎 @)
Δ𝜑 = 𝜑 ?? − 𝜑 ? = ln => ?? = ln ?
𝐹 𝑎=>$ 𝐹 𝑎@)&
Ion-Exchange Membrane

?
6 ?
𝑅𝑇 𝑎 =>$
𝜑 − 𝜑 = I ln 6
RT a 𝐹+ 𝑎=>$
D• jFor=dialysis:
(I )
ln( M )Na
F ? a Na
𝜑 |𝜑 6 |𝜑 ??
+

Δ𝜑'.>) = 𝜑 ?? − 𝜑 ? II
RT a Na +
Dj dial
== (𝜑D??j−𝜑 6
( 2)
-)D−j (𝜑=
(1)
? − 𝜑6 ln(
) I )
6 F 6 a Na +
𝑅𝑇 𝑎=>$ 𝑅𝑇 𝑎=>$
= ln ?? − ln ?
𝐹 𝑎=>$ 𝐹 𝑎=>$
?
𝑅𝑇 𝑎=> $
= ln ??
𝐹 𝑎=>$
 Haugaard Layer (HL)
• If a glass surface (e.g.
formed from a SiO2-CaO-
Na2O glass) is immersed in
water, some of the cations,
which are bound in the silica
network, are exchanged with
H3O+ ions in a thin layer at
the surface
• The “swelling process” is
complete after 24-48 hours
and the resultant “swollen
layer “ is termed the
Haugaard Layer (HL): it is 5
to 50 nm thick
 Operation of the Glass Electrode
• A thin glass membrane
(of thickness ca. 0.5 mm),
both of whose sides have
formed swollen layers, is
used to separate the
solution of unknown pH,
II, from a second solution,
I, whose pH is assumed
constant
• The electrical connection
between the two faces of
the membrane is
achieved through the
finite ionic conductivity of
the glass
Operation of the Glass Electrode
∆𝜑/(𝐼 − 𝐼𝐼) = (𝜑 ? −𝜑 :A,? ) − (𝜑 ?? − 𝜑 :A,?? )
:A,? :A,??
𝑅𝑇 𝑎 :( <$ 𝑅𝑇 𝑎 :( <$
= ln ? − ln ??
𝐹 𝑎:( <$ 𝐹 𝑎:( <$
??
𝑅𝑇 𝑎 :( <$
= ln ?
𝐹 𝑎:( <$
? ??
Putting log𝑎: (<
$ = −𝑝𝐻? ; log𝑎 :( <$ = −𝑝𝐻??
:A,??
𝑅𝑇 𝑎: <$
∆𝜑/ 𝐼 − 𝐼𝐼 = 𝑙𝑛 ??( + 0.0591(𝑝𝐻B − 𝑝𝐻?? )
𝐹 𝑎:( <$
asymmetry potential
pH Measurement with a Glass Electrode
• The most common ISE
• pH-sensitive part is the thin
glass bulb at the bottom of
the electrode
• Two reference electrodes
measure the electric
potential difference across
the membrane
pH Measurement with a Glass Electrode
• The salt bridge is the porous plug at the bottom right side
of the electrode
• Figure shows the structure of glass – the bulb of the ISE
• Negatively charged oxygen atoms bind cations such as
Na+, which can move sluggishly through the glass
pH Measurement with a Glass Electrode
• Each side of the glass membrane is hydrated (10 nm);
they are separated by a dry glass layer
• Metal cations, such as Na+, can diffuse out of the glass
in these hydrated regions and into the solution
• H+ can diffuse into the membrane and replace the metal
cations in an ion-exchange equilibrium
 pH Measurement with a Glass Electrode
• H+ is the main ion that binds significantly to the hydrated
gel layer
• The potential difference between the inner and outer
Ag|AgCl electrodes depends on the [Cl-] in each
compartment and on the potential difference across the
glass membrane
• [Cl-] is fixed in each compartment, and [H+] is fixed on the
inside of the membrane; therefore, the potential depends
only on the [H+]external
• The response of real glass electrodes is described by the
Nernst-like equation: (at 25 oC)
𝐸 = constant + 𝛽(0.05916)log𝐴:$
𝐸 = constant − 𝛽 0.05916 pH
• The value of β, the electromotive efficiency, is close to 1
and typically >0.98
 Calibrating a Glass Electrode
• 𝛃 and constant are
measured by calibrating the
electrode in at least two
solutions of known pH
• Using standard buffers, a
voltage is measured with the
electrode in each buffer:
𝐸 − 𝐸CB 𝐸D2 − 𝐸CB
=
pH − pHCB p𝐻D2 − pHCB

• To measure the pH of an
unknown:
𝐸EFGFHIF − 𝐸CB
p𝐻EFGFHIF − pHCB
𝐸C2 − 𝐸CB
=
pHC2 − pHCB
 Errors in pH Measurement
Standards. Limit us to ±0.01 pH unit
Junction potential. Exists at the porous plug near the bottom of the
electrode and gives an uncertainty of ~0.01 pH unit
Sodium error. When [H+] is low and [Na+] is high, the electrode
responds to [Na+], giving a measured pH lower than the actual pH
Acid error. In strongly acidic solutions, the glass is saturated with
H+ giving a measured pH higher than the actual pH
Equilibration time. Requires ~30 s with stirring to equilibrate with a
solution
Hydration of glass. A dry electrode must be soaked for several
hours before it responds correctly to H+
Temperature. A pH meter must be calibrated at the same
temperature at which the measurements will be made
“Errors 1 and 2 limit the accuracy of pH measurements with the glass
electrode to ±0.02 pH units, at best.”
 Indicator Electrodes
• In redox methods, an indicator electrode is used to sense the
presence or change in concentration of the oxidized and reduced
forms of a redox couple
Three types of indicator electrodes are used:
1. Metal electrodes develop an electric potential in response to a
redox reaction at the metal surface
⚬ Several metals, such as silver, copper, lead, cadmium, and
mercury, will participate in a reversible electron exchange and
can serve as indicator electrodes for their ions
⚬ In general, most other common metals, except noble metals,
are not satisfactory as indicator electrodes in ordinary
applications, usually because of oxide coatings on the surface
and other surface properties that hinder electron exchange
 Indicator Electrodes
2. Noble metals are chemically inert and can conveniently act
as collector electrodes for half-cell reactions that involve
charged species or gases
⚬ Platinum is the most common metal indicator electrode
because it is relatively inert
⚬ Gold and various types of carbon are also used as indicator
electrodes
⚬ Work best when their surfaces are large and clean
3. Ion-selective electrodes (ISEs) are not based on redox
processes but on the selective binding of one type of ion to a
membrane, which generates a potential
Indicator Electrodes
The reaction at the Ag indicator
electrode is:
Ag 7 + e8 ↔ Ag (K) 𝐸7/ = 0.799 𝑉

The calomel reference half-cell

reaction is:
1
Hg 2Cl2(K) + e8 ↔ Hg (M) +Cl8
2
𝐸8 = +0.241 𝑉

The Nernst equation for the entire cell

is:
𝐸 = 𝐸7 − 𝐸8
1
= 0.799 − 0.5916log 7 − 0.241
Ag
= 0.558 + 0.5916log Ag 7
 Example: Potentiometric Precipitation
Titration
• A 100.0 mL solution containing 0.10 M NaCl was titrated with
0.10 M AgNO3, and the voltage of the cell shown in Figure was
monitored. The equivalence volume is 𝑉$ = 100.0 mL. Calculate the
voltage after the addition of (a) 65.0 and (b) 135.0 mL of AgNO3
Solution
• The titration reaction is Ag 7 + Cl8 → AgCl
• (a) At 65.0 mL, 65.0 % of Cl8 has precipitated
• and 35.0 % remains in solution
8
100.0
Cl = 0.35 0.10 M = 0.0212 M
165.0
𝐾 1.8×10 8B/
#N
Ag 7 = = = 8.5×10 8O M
[𝐶𝑙 8] 0.212
𝐸 = 0.558 + 0.05916 log 8.5×108O = 0.081𝑉
 Indicator Electrodes
• (b) At 135 mL, there is an excess of 35.0 mL
of AgNO3 = 3.50 mmol Ag+ in a total volume
of 235.0 mL. Therefore, [Ag+] = (3.50
mmol)/(235.0 mL) = 0.0149 M
The cell voltage is
𝐸 = 0.558 + 0.05916 log 0.0149 = 0.450𝑉
• The silver electrode measures pAg:
𝐸 = 0.558 − 0.05916pAg
• A silver electrode is also a halide electrode if
solid silver halide is present
(𝑲𝒔𝒑 can be used to find an expression relating the cell voltage
to a halide ion, 𝐶𝑙 8 for example:
𝐾#N
𝐸 = 0.558 + 0.05916log
[𝐶𝑙 8]
 Ion-Selective Electrodes (ISE)
• Typical ion-selective
electrodes (ISEs) are about
the size of your pen
• ISE does not involve a redox
process
• ISE responds selectively to
one ion through a thin
membrane capable of
binding only that ion
• The figure shows a liquid-
based ion-selective
electrode
 Ion-Selective Electrodes (ISE)
• The ion-selective membrane is a hydrophobic organic
polymer containing a viscous organic solution, which
includes an ion-exchanger (ionophore) that selectively binds
the analyte cation, C+
• C+ is carried across the membrane by complexing with the
organic ligand L (the ionophore)
• The membrane also contains R-, a hydrophobic anion such
as (C6H5)4B-
• The inner filling solution contains a constant C+(aq)
concentration plus the counter-ion B-(aq)
• The outside analyte solution contains C+(aq) and the
counter-ion A-(aq)
• Two reference electrodes measure the potential difference
across the membrane
How Ion-Selective Electrodes (ISE) Work
• When the concentration of C+ in the analyte solution changes,
the voltage changes
• The potassium ISE uses valinomycin as the ligand
• Valinomycin is chosen because it has a high affinity for K+ and
a low affinity for other ions

Valinomycin 纈氨黴素
Ion Selective Electrodes (ISE)

• The existence of this membrane potential led to

the development of ISEs
RE (sample) | [A]samp(aq) | [A]int(aq) | RE (internal)
𝐸5$5 = 𝐸RFSTU − 𝐸KVWXMT
𝑅𝑇 𝑅𝑇
𝐸5$5 = 𝐸>#Y5 + 𝑙𝑛𝑎#>5N − 𝑙𝑛𝑎.,-
𝑛𝐹 𝑛𝐹
𝑅𝑇 𝑎.,-
𝐸5$5 = 𝐸>#Y5 − ln
𝑛𝐹 𝑎#>5N
How Ion-Selective Electrodes (ISE) Work
• Plugging in all constants and converting ln into log, where n is
the charge on the ion:
0.05916
𝐸 =𝑲+𝛽 log𝑎#>5N (volts at 25 HC)
𝑛
⚬ 𝐾: a constant that includes potentials of two reference
electrodes, junction potentials, asymmetry potential, and
the analyte’s activity in the internal solution

• Equation applies to any ion-selective electrode

• A difference of 59.16 mV develops across a glass electrode

for every factor-of-10 difference in [H+]; one pH unit

• A potential difference of 29.58 mV develops across a Ca2+

electrode for every factor-of-10 difference in [Ca2+]; one
pCa2+ unit
 Selectivity of Membranes
• A membrane potential results from a chemical interaction
between the analyte and active sites on the membrane’s surface
• Because the signal depends on a chemical process, most
membranes are not selective toward a single analyte
• The membrane potential is proportional to the concentration of
each ion that interacts with the membrane’s active sites
• The selectivity coefficient gives the relative response to a
species different than the analyte but with the same
charge:
response to 𝐈
𝐾0,? =
response to 𝐀
• If the response to each ion is Nernstian, then:
0.05916
𝐸 = constant − log 𝑎0 + F 𝐾0,? 𝑎?
𝑍0
Z
 Example: Using the Selectivity
Coefficient
• A fluoride ion-selective electrode has a selectivity coefficient
𝐾[& ,<:& = 0.1. What will the change in electrode potential
when 1.0×108\ M fluoride ion at pH 5.5 is raised to pH 10.5?
• Solution
⚬ At pH 5.5, the potential with negligible OH-
0.05916
𝐸 = constant − log 1.0×108\ = constant + 236.6 𝑚𝑉
𝑍0
⚬ At pH 10.5, the OH 8 = 3.2×108\ M
0.05916
𝐸 = constant − log 1.0×108\ + (0.1)(3.2×108\)
𝑍0
= constant + 229.5 𝑚𝑉
⚬ The change is 229.5 − 236.6 = −7.1 𝑚𝑉, which is quite
significant
⚬ The change is the same as the increase of [F-] by 32 %
 Selectivity Coefficient
• When the selectivity coefficient is 1.00, the membrane
responds equally to the analyte and the interferent
• A membrane shows good selectivity for the analyte when KA,I
is significantly less than 1.00
 Representative Examples

Glass membrane ISE for analytes other than H+

 Quiz
• A ion-selective electrode for NO2– has log KA,I values of –3.1
for F–, –4.1 for SO42-, –1.2 for I-, and –3.3 for NO3-
• Questions:
1. Which ion is the most serious interferent?
2. What activity of this interferent is the potential equivalent to
a solution in which the activity of NO2- is 2.75×10–4?