1501 Electrode Potential

The Spontaneity of Electron Transfer

Relationship between E , DG and Keq

Dr. Fred Omega Garces

Natural Science, Chemistry 251
Miramar College, SDCCD

Recommended:

1 Electrodes and Potentiometry October 2017

 Variable Concentration EMF Calculations
Example 20.51 (B&L, 8th ed)
Given: Redox reaction: Zn + Cd2+ g Zn+2 + Cd
i) Calculate the E for : Zn(s)|Zn+2 (aq, 1.0M)||Cd2+ (aq, 1.0M) |Cd(s)
ii) Calculate the emf for Zn(s)|Zn+2 (aq, 0.150M)||Cd2+ (aq,1.5M) |Cd(s)
(i) Calculate the E

Half Rxn (oxidation): (1) Zn+2 + 2e- D Zn(s) E red = - 0.76 V

Half Rxn (reduction): (2) Cd+2 + 2e- D Cd(s) E red = - 0.403 V

Net Rxn: Zn + Cd+2 (aq) g Zn+2 (aq) + Cd E cell = 0.357 V
or E (V) = E+ red (cathode) – E- red (anode) = -0.403 - (-0.76) = 0.357 V

(ii) Calculate the E (non-standard state)

E = E - RT ln Q = E - 2.303 RT log Q = E - .05916 log Q (Nernst Eqn)

nF nF n

ii) E = E (V) - 0.05916 (V) log [Zn+2] = 0.357 (V) - 0.05916 (V) log [.15] = 0.38658V
n [Cd+] 2 [1.5]

2 Electrodes and Potentiometry October 2017

 Variable Concentration EMF Calculations: Revisited
Given: Redox reaction: Zn + Cd2+ g Zn+2 + Cd
i) Calculate the E for : Zn(s)|Zn+2 (aq, 1.0M)||Cd2+ (aq, 1.0M) |Cd(s)
ii) Calculate the emf for Zn(s)|Zn+2 (aq, 0.150M)||Cd2+ (aq,1.5M) |Cd(s)

Half Rxn (oxidation): (1) Zn+2 + 2e- D Zn(s) E red = - 0.76 V

Half Rxn (reduction): (2) Cd+2 + 2e- D Cd(s) E red = - 0.403 V

Net Rxn: Zn + Cd+2 (aq) g Zn+2 (aq) + Cd E cell = 0.357 V

E (V) = E+ red (cathode) – E- red (anode) = -0.403 - (-0.76) V

i) E+red = -.403V - 0.05916 (V) log 1 . = -.39779V

n [Cd+2]

ii) E-red = -.76V - 0.05916 (V) log 1 . = -.7844 V

n [Zn+]
Previous Page
E (V) = E+ red (cathode) – E- red (anode) = 0.38661 V
3 Electrodes and Potentiometry October 2017
 Reference Electrode
Galvanic cells are coupled half reaction in which one of the reaction is an oxidation and
the other a reduction. If one of the half reaction is known, then it can be used as a
reference to determine the potential (or concentration) information at the other half-
cell. Consider the following-
Right Electrode (cathode): Fe+3 + e- D Fe2+ E+ = 0.771 V
Left Electrode (anode): AgCl(S) + e- D Ag(s) + Cl- (aq) E+ = 0.222 V Known

E (V) = E+ red (cathode) – E- red (anode) = E+ - E-

E+ = 0.771 V - 0.05916 log { [Fe2+] / [Fe3+] } n=1

E- = 0.222 V - 0.05916 log { [Cl-] }, Cl- is fixed by solubility of KCl
Ecell = E+ - E-
Ecell = (0.771 V - 0.05916 log { [Fe2+] / [Fe3+] } )
- (0.222 V - (0.05916/1)
+ 0.197 log.{ [Cl-] })
for sat KCl

Galvanic cells can be used to measure the [Fe2+] / [Fe3+] concentrations.

4 Electrodes and Potentiometry October 2017
 Galvanic Cells to Reference Electrode
In a reference electrode, the Platinum wire is the indicator electrode whose potential respond
to the quotient [Fe2+] / [Fe3+] . The reference provides a constant potential at the anode cell.

The silver-silver chloride electrode can be

simplified in the following schemes.

5 Electrodes and Potentiometry October 2017

 Silver and Calomel Reference Electrode

A reference electrode cannot be the standard hydrogen electrode since hydrogen gas
is required, instead Ag/AgCl or HgCl/Hg can be used as a reference.
Ag|AgCl: AgCl (s) + e- D Ag(s) + Cl- E+ = + 0.222 V (Appx)
electrode vs. SHE E (saturated KCl) = + 0.197 V

Calomel: ½ HgCl (s) + e- D Hg(l) + Cl- E+ = + 0.268 V (Appx)

electrode: vs. SHE E (saturated KCl) = + 0.241 V

6 Electrodes and Potentiometry October 2017

 Silver and Calomel Reference Electrode
How is the voltage calculated if different reference cell is used:
A potential of -0.461 V vs. Calomel electrode is read for a electrochemical process.
(1)What is potential versus Ag/AgCl ? (2) What is the voltage vs. SHE ?

A reference electrode cannot be the standard hydrogen electrode since hydrogen gas is
required, instead Ag/AgCl or HgCl/Hg can be used as a reference.
Ag|AgCl electrode: AgCl (s) + e- D Ag(s) + Cl- E+ = + 0.222 V (Appx)
vs. SHE E (saturated KCl) = + 0.197 V

Calomel: ½ HgCl (s) + e- D Hg(l) + Cl- E+ = + 0.268 V (Appx)

electrode: vs. SHE E (saturated KCl) = + 0.241 V

+ 0.197 V + 0.241 V
-0.461 Vs Calomel, SHE = -0.220 V

.220 V + .197 V = .417 V , so it is -0.417 V vs Ag/AgCl

7 Electrodes and Potentiometry October 2017
 …An analogy (Away From Home)
What is the potential of one electrode relative another electrode?
….the Electrode family

Buster is .461 miles from Stan C. Electrode. How far is Buster from Agnes C. Electrode?

Buster Stan
Agnes

0.461 mi
Agnes is .197 mi and Stan is .241 mi from home.

Buster is .461 mi west from Stan.

How far is Angie from Buster. (0.417 mi)
8 Electrodes and Potentiometry October 2017
 Silver and Calomel Reference Electrode
Voltage conversion between different reference:
A potential of -0.461 V vs. Calomel electrode is read for a electrochemical process.
(1) What is potential versus Ag/AgCl ? (2) What is the voltage vs. SHE ?
A reference electrode cannot be the standard hydrogen electrode since hydrogen gas is required,
instead Ag/AgCl or HgCl/Hg can be used as a reference.
Ag|AgCl electrode: AgCl (s) + e- D Ag(s) + Cl- E+ = + 0.222 V (Appx)
vs. SHE E (saturated KCl) = + 0.197 V

Calomel: ½ HgCl (s) + e- D Hg(l) + Cl- E+ = + 0.268 V (Appx)

electrode: vs. SHE E (saturated KCl) = + 0.241 V

-0.461 Vs Calomel, SHE = -0.220 V

.220 V + .197 V = .417 V , so it is -0.417 V vs Ag/AgCl

9 Electrodes and Potentiometry October 2017
 Silver and Calomel Reference Electrode
Voltage conversion between different reference:

SCE
-.461 V OV
Ag/AgCl
-.417 V OV

SHE
-.220V OV .197 V .241 V
SCE vs Ag/AgCl
.241 - .197 = 0.044V
0.461 - 0.044 = .417 ⇒ - .417, left of zero
SCE vs SHE
.241 - 0.0 = 0.241V
0.461 - 0.241 = 0.220 ⇒ - 0.220, left of zero
11 Electrodes and Potentiometry October 2017
 Indicator (counter or auxiliary) Electrode
There are two broad class of indicator electrodes: Metal and Ion selective.
Most common metal indicator electrode is platinum but other inert electrodes are Gold,
Pd, Carbon Glassy, sometimes Ag & Ni. Clean by dipping is Hot 8M HNO3 wash DI.
For silver (Ag) Indicator electrode-

To measure concentration of specific ion, i.e. Ag+

Ag electrode: Ag+ (aq) + e- D Ag(s) E+ = + 0.799 V

Coupled to the calomel reference half-cell
Calomel: ½ HgCl (s) + e- D Hg(l) + Cl- E- = + 0.241 V (Ref)
Ecell = E+ (Ox) - E-(rd)
Ecell = (0.799 V - 0.05916 log { 1 / [Ag+] } ) - (0.241 V)
Ecell = 0.558 + 0.5916 log [Ag+]

In essence, the Ecell measures [Ag+] conc.

12 Electrodes and Potentiometry October 2017

 Junction Potential
Migration of ions through membrane causes voltage difference.

13 Electrodes and Potentiometry October 2017

 Junction Potential
Differences in electrolyte solution results in difference in voltage called junction
potential. The small voltage variation resides at the end of the salt bridge. This
variation places limitation on the accuracy of voltage measurements.

Eobs = Ecell + Ejunction (Not known)

Junction potential occurs because

electrolyte will cross the membrane
to the main solution which inhibits
mobility of the ions.

In general there is a 59mV

response per pH unit change.

14 Electrodes and Potentiometry October 2017

 Indicator Electrodes
metal electrodes and Ion selective

Metal electrodes such as silver, carbon or platinum metals result in

redox taking place at the electrode surface.
Silver electrode: Ag+ + e- D Ag(s)
Platinum electrode: Fe(CN)6]3+ + e- D Fe(CN)6]2+

Ion-selective electrodes binds analyte ions but there is

no redox reaction taking place. The potential of the
electrode is measured as a functions of the
concentration of the analyte ions.

A classic example of an ion-selective electrode is the

glass pH electrode.
15 Electrodes and Potentiometry October 2017
 Ion Selective Electrode
An ion-selective electrode (ISE), also known as a specific ion electrode (SIE), is a transducer (or sensor) that converts the activity of a
specific ion dissolved in a solution into an electrical potential, which can be measured by a voltmeter or pH meter. The voltage is
theoretically dependent on the logarithm of the ionic activity, according to the Nernst equation. The sensing part of the electrode is
usually made as an ion-specific membrane, along with a reference electrode. Ion-selective electrodes are used in biochemical and
biophysical research, where measurements of ionic concentration in an aqueous solution are required, usually on a real time basis.
Shown are Ion Selective Electrodes used in water analysis. These electrodes allow for direct measurements of
Ammonium, Calcium, Cyanide, Fluoride, Lead, Nitrate, Potassium and Silver Sulfides.

Advantages of Ion-Selective Electrodes are:

Inexpensive and simple to use, in the field as well as the laboratory.
Wide concentration range - typically from less than one to several thousand parts per million.
Unaffected by sample color or turbidity.

ISE are routinely used for monitoring environmental pollution or water quality especially when the analysis simply involve
detection of ions below a particular threshold value, or where only the order of magnitude may be required. ISEs have have
accuracy of around 10% to as much as 2% (1-sigma) under ideal. Standard Addition or Sample Addition techniques).
Ion-Selective Electrodes measure the activity (or effective concentration) of ions in a solution, rather than the actual
concentration. Note that the activity is always less than the concentration because of inter-ionic interactions and the difference
between concentration and activity increases as the Ionic Strength increases. Remember that, activity is not significantly
different from the concentration in dilute solutions (i.e. with total ionic strength of less than about 0.01 Molar for monovalent
ions and 0.001 Molar for divalent ions). If measurements are to be taken at higher concentration then other techniques or
modification to minimize the difference at higher concentrations can be applied in the analysis, (e.g. by adding ionic strength
adjustment buffer, diluting the sample, or, most effectively, by using Standard Addition or Sample Addition techniques).
16 Electrodes and Potentiometry October 2017
 Ion Selective Electrode
Metal electrodes have disadvantage because of loss in response due to poisoning or mechanical failure. Many special
electrodes are use to test for a wide range of ion. These contain an insoluble membrane that can conduct current
and whose surface depends on the concentration of the ions. i.e., pH electrode.

Consider the liquid-base ion-selective electrode shown, the membrane is

an organic hydrophobic organic polymer, poly(vinyl chloride) impregnated
with a nonpolar liquid that softens the membrane and dissolves the ion- Inner
Region
selective ionophore (L), the complex (LC+) and a hydrophobic anion (R-).
Outer
The key is that the Ligand, L (ionophore) is soluble inside the membrane region
and selectively binds analyte ion. Almost all analyte inside the membrane
is bound in the complex LC+, which is in equilibrium with C+. C+ can
diffuse across the interface, as soon as a few C+ ions diffuse from the
membrane, there is an excess of positive charge , the imbalance creates
an the potential. [C+] D [C+]
inner outer

E = Constant + (0.05916/n)•log ( [C+] outer / [C+]inner )

E = Constant + (0.05916/n) • log Ao since Am constant

17 Electrodes and Potentiometry October 2017

 Ion Selective Electrode and pH Electrode

E = Constant + (0.05916/n) • log Ao, ,

Electrochemical difference for ion-selective electrode. In the equation, n is the charge of the analyte ion (negative
for anion, positive for cation), Ao is the activity in the outer solution.

For every factor of 10 (1-pH unit), a difference of 59.16mV across the pH electrode. i.e., 5.00 pH units would lead to
5.00 x 59.16 = 295.8 mV. For a charge aluminum cation, n = 3, so the potential difference is 59.16/3 = 19.72 mV.

Note that, (RT/F) [ln(10)] = 59.16mV at 298K, n=1

Example:
i) How much voltage across a pH electrode for a 4.63 pH reading at 25 C.
Answ: 4.63 x 59.16mV = 273.91 mV = 274mV
Note that, [RT ln(10)] / F = 59.16mV at 298K

ii) What would the voltage be for the same pH at 37 C?

Answ: (RT ln(10) / F) = 8.314 (310K) ln(10) / 96485 = 61.51 mV
4.63 x 61.51mV = 284.8 = 285 mV

18 Electrodes and Potentiometry October 2017

 pH Electrode
Components of the electrode:
1- Sensor of electrode, a bulb made from a specific
glass
2- AgCl precipitate inside the glass electrode
" [H+] %
3- Internal solution, usually 1 M HCl for pH
E = E° − 0.0592 log $ internal '
electrodes $[H+ ] '
# external &
4- internal electrode, usually silver chloride
electrode or calomel electrode
Since the internal [H] is constant at
5- body of electrode, made from non-conductive
glass or plastics. 1.0 M the equation becomes
" %
6- reference electrode, usually the same type as 4 1.0 M '
E = E° − 0.0592 log $
7- junction with studied solution, usually made from $[H+]
#
'
external &
ceramics or capillary with asbestos or quartz fiber.

The purpose of the silver-silver chloride electrode is to prevent the potential that E = E° + 0.0592 log [H+ ]external
develops from changing due to possible changes in the interior of the electrode. The
potential that develops is a membrane potential. For pH electrodes, it is the remember that pH = -log [H+ ] so
difference in the concentration of the hydrogen ions on opposite sides of the
membranes that cause the potential. There is no half-cell reaction involved. E = E° − 0.0592 pH
The Nernst Equation is-
20 Electrodes and Potentiometry October 2017
 Calibrating a Glass Electrode
Procedure:
- Calibrate with standard buffer solution so pH
of unknowns are in range of buffer solutions.

- The pH of an unknown can be determined by

interpolating between the buffer standards
based on the equation below.

- Note pH measurement errors.

21 Electrodes and Potentiometry October 2017

 Problem on Electrodes
A 10.0-mL solution of 0.050M AgNO3 was titrated with 0.025M NaBr in the cell.

SCE || titration solution | Ag (s)

Find the cell voltage for 0.1 and 30.0 mL of titrant. E (SCE) = 0.241

RT
Ve = 20.0mL Ag+ + e-  Ag (s) E° = 0.799 → E + = E + ° − lnQ , K sp (AgBr) = 5.0 ⋅ 10-13
nF
1 30.0 mL NaBr; Ag+ + Br- ! AgBr(s)
E + = 0.799 - 0.05916 log , E - °(SCE) = 0.241 V
[Ag ] +
s 0.5mmol .75 0
R -0.5 -0.5 +0.5
0.1 mL NaBr; Ag+ + Br-  AgBr(s) f 0 .25 -
s
R
f
.5mmol
-.0025
.4975
.00250
-.0025
0
0
+.0025
-
Answer 4.8 [e] 0
0.25
40mL
= 0.00625 M

.4975 K sp (5.0 ⋅ 10-13 )

[e] = 0.04926 = [Ag+ ] [Ag+ ] = = = 8.0 ⋅ 10-11 M
10.10 [Br ]
-
0.00625

(& $&
1 &$
1 $"
E = E + - E - = )0.799 - 0.05916 log % − 0.241 = 0.481V E = E + - E - = '0.799 - 0.05916 log
0.04926 &' # − 0.241
*& ($ 8.0 ⋅ 10-11 %$

E = − 0.039V

22 Electrodes and Potentiometry October 2017

 Problem on Electrodes
A 10.0-mL solution of 0.050M AgNO3 was titrated with 0.025M NaBr in the cell.

SCE || titration solution | Ag (s)

Find the cell voltage for 0.1 and 30.0 mL of titrant. E (SCE) = 0.241

RT
Ve = 20.0mL Ag+ + e-  Ag (s) E° = 0.799 → E + = E + ° − lnQ , K sp (AgBr) = 5.0 ⋅ 10-13
nF
1 30.0 mL NaBr; Ag+ + Br- ! AgBr(s)
E + = 0.799 - 0.05916 log , E - °(SCE) = 0.241 V
[Ag ] +
s 0.5mmol .75 0
R -0.5 -0.5 +0.5
0.1 mL NaBr; Ag+ + Br-  AgBr(s) f 0 .25 -
s
R
f
.5mmol
-.0025
.4975
.00250
-.0025
0
0
+.0025
-
Answer 4.8 [e] 0
0.25
40mL
= 0.00625 M

.4975 K sp (5.0 ⋅ 10-13 )

[e] = 0.04926 = [Ag+ ] [Ag+ ] = = = 8.0 ⋅ 10-11 M
10.10 [Br ]
-
0.00625

(& $&
1 &$
1 $"
E = E + - E - = )0.799 - 0.05916 log % − 0.241 = 0.481V E = E + - E - = '0.799 - 0.05916 log
0.04926 &' # − 0.241
*& ($ 8.0 ⋅ 10-11 %$

E = − 0.039V

23 Electrodes and Potentiometry October 2017