An Introduction to

Electrochemistry

Redox Reaction
ox1 + red2 <=> red1 + ox2

1
 Outline
1. Review
 Concepts: Redox Reaction, Cell, Potential
 Balance an Equation
 Nernst Equation
2. Redox Titration
3. Potentiometry
4. Voltammetry and Electrochemical Sensor

12.1 Balancing Oxidation-

Reduction Reactions
• Mass Balance: the amount of each element present at the
beginning of the reaction must be present at the end.
• Charge Balance: electrons are not lost in a chemical
reaction.
Half Reactions
• Half-reactions are a convenient way of separating
oxidation and reduction reactions.

2
 Half Reactions
• The half-reactions for
Sn2+(aq) + 2Fe3+(aq)
Sn4+(aq) + 2Fe3+(aq)
are
Sn2+(aq)
Sn4+(aq) +2e-
2Fe3+(aq) + 2e-
2Fe2+(aq)
• Oxidation: electrons are products.
• Reduction: electrons are reagents.

Balancing Equations by the Method of Half Reactions

• Consider the titration of an acidic solution of Na2C2O4
(sodium oxalate, colorless) with KMnO4 (deep purple).

3
How?

1. Write down the two half reactions.

2. Balance each half reaction:
a. First with elements other than H and O.
b. Then balance O by adding water.
c. Then balance H by adding H+.
d. Finish by balancing charge by adding electrons.
3. Multiply each half reaction to make the number of electrons equal.
4. Add the reactions and simplify.
5. Check!

Balancing Equations by the Method of Half Reactions

16H+(aq) + 2MnO4-(aq) + 5C2O42-(aq)
2Mn2+(aq) + 8H2O(l) + 10CO2(g)

4
Exercise:

Try to Balance:
Sn+2 + Fe+3 <=> Sn+4 + Fe+2
Fe+2 + MnO4- <=> Fe+3 + Mn+2

Sn+2 + Fe+3 <=> Sn+4 + Fe+2

5
Fe+2 + MnO4- <=> Fe+3 + Mn+2

Important Redox Titrants and the

Reactions
Oxidizing Reagents (Oxidants)
(1) Potassium Permanganate

MnO4 + 8H + + 5e
 Mn 2+ + 4H 2O

MnO4 + 4H + + 3e
 MnO2 (s) + 2H 2O

MnO4 + e  MnO4

2

6
 Important Redox Titrants and the
Reactions
Oxidizing Reagents (Oxidants)
(2) Potassium Dichromate

Cr2O7 + 14H + + 6e
 2Cr 3+ + 7H 2O

2

Cr2O7 + 3U 4 + + 2H +  2Cr 3+ + 3UO2 + H 2O

2
2+

Important Redox Titrants and the

Reactions
Oxidizing Reagents (Oxidants)
(2) Potassium Iodate

1
IO3 + 6H + + 5e
 I2 + 3H 2O

7
 Important Redox Titrants and the
Reactions
Reducing Reagent ( Reductants )
(2) Potassium Iodide

1
I
 I 2 + e

2

Important Redox Titrants and the

Reactions
Reducing Reagent ( Reductants )
(2) Sodium Thiosulfate

2S2O32- S4O62- +2e

8
 12.2 Nernst Equation

• Voltaic cells consist of

– Anode: Zn(s)
Zn2+(aq) + 2e2
– Cathode: Cu2+(aq) + 2e-
Cu(s)
– Salt bridge (used to complete the electrical circuit): cations
move from anode to cathode, anions move from cathode to
anode.
• The two solid metals are the electrodes (cathode and
anode).

9
The salt bridge allows charge transfer through the solution and prevents mixing.

Fig. 12.1. Voltaic cell.

10
 Galvanic Cells

anode cathode
oxidation reduction

spontaneous
redox reaction

19.2

11
• This rearranges to give the Nernst equation:
RT
E = E°
lnQ
nF

• The Nernst equation can be simplified by collecting all

the constants together using a temperature of 298 K:
0.0592
E = E°
logQ
n

• (Note that change from natural logarithm to base-10 log.)

• Remember that n is number of moles of electrons.

Nernst Equation
aA + bB + ne- <=> cC + dD

0.0592 [C]c[D]d
E= Eo - ---------- log ----------------
a b
at 25oC
n [A] [B]

0.0592 [Re d]
E = E0
log
n [Ox]

12
 Standard Electrode Potentials

Standard reduction potential (E0) is the voltage associated

with a reduction reaction at an electrode when all solutes
are 1 M and all gases are at 1 atm.

Reduction Reaction

2e- + 2H+ (1 M) H2 (1 atm)

E0 = 0 V

Standard hydrogen electrode (SHE) 19.3

Standard Reduction (Half-Cell) Potentials

• The SHE is the cathode. It consists of a Pt electrode in a

tube placed in 1 M H+ solution. H2 is bubbled through the
tube.
• For the SHE, we assign
2H+(aq, 1M) + 2e-
H2(g, 1 atm)
• E°red of zero.
• The potential of a cell can be calculated from standard
reduction potentials:
E°cell = E°red (cathode)
E°red (anode)

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Standard Reduction (Half-Cell) Potentials

• Consider Zn(s)
Zn2+(aq) + 2e-. We measure Ecell

relative to the SHE (cathode):
E°cell = E°red(cathode) - E°Ox(anode)
0.76 V = 0 V - E°red(anode).
• Therefore, E°red(anode) = -0.76 V.
• Standard reduction potentials must be written as
reduction reactions:
Zn2+(aq) + 2e-
Zn(s), E°red = -0.76 V.

14
 12.3 Cell Diagram
anode//cathode
Zn/ZnSO4 (0.1 M)//CuSO4 (0.2
M)/Cu

If a cell,
Ecell = Ecathode - Eanode

if Ecell => positive, spontaneous as written

15
The more positive the E o, the better oxidizing agent is the oxidized form (e.g., MnO4 -).
The more negative the Eo, the better reducing agent is the reduced form (e.g., Zn).

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

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12.4 Redox Titration Curve

12.4 Redox Titration Curve

17
 12.4 Redox Titration Curve

Derivation of a titration curve

Fe+2 + Ce+4 <=> Ce+3 + Fe+3
EXAMPLE: Derive the titration curve for
50.00 mL of 0.0500 M Fe+2 with 0.1000 M
Ce+4 in a medium that is 1.0 M in H2SO4.

EXAMPLE: Derive the titration curve for 50.00

mL of 0.0500 M Fe+2 with 0.1000 M Ce+4 in a
medium that is 1.0 M in H2SO4.

Fe+2 + Ce+4 <=> Ce+3 + Fe+3

E = Eo - (0.0592/n) log([red]/[ox])
At 0.00 mL of Ce+4 added, initial point
no Ce+4 present; minimal, unknown [Fe+3];
thus, insufficient information to calculate E

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 Derive the titration curve for 50.00 mL of 0.0500 M Fe+2 with
0.1000 M Ce+4 in a medium that is 1.0 M in H2SO4.
Fe+2 + Ce+4 <=> Ce+3 + Fe+3
At 15.00 mL of Ce+4 added, VFeMFe > VCeMCe

VCe MCe (15.00 mL)(0.1000 M)

[Fe+3] = --------------- = ----------------------------
VFe + VCe (50.00 + 15.00)mL

= 2.308 x 10-2 M

EXAMPLE: Derive the titration

curve for 50.00 mL of 0.0500 M
Fe+2 with 0.1000 M Ce+4 in a medium
that is 1.0 M in H2SO4.

Fe+2 + Ce+4 <=> Ce+3 + Fe+3

At 15.00 mL of Ce+4 added, VFeMFe > VCeMCe
[Fe+3] = 2.308 x 10-2 M
VFe MFe - VCe MCe
[Fe+2] = ------------------------
VFe + VCe

19
 EXAMPLE: Derive the titration
curve for 50.00 mL of 0.0500 M Fe+2
with 0.1000 M Ce+4 in a medium that
is 1.0 M in H2SO4.

Fe+2 + Ce+4 <=> Ce+3 + Fe+3

At 15.00 mL of Ce+4 added, VFeMFe > VCeMCe
[Fe+3] = 2.308 x 10-2 M
(50.00 mL)(0.0500 M) - (15.00 mL)(0.1000 M)
[Fe+2] = --------------------------------------------------------
(50.00 + 15.00)mL
= 1.54 x 10-2 M

EXAMPLE: Derive the titration

curve for 50.00 mL of 0.0500 M Fe+2
with 0.1000 M Ce+4 in a medium that
is 1.0 M in H2SO4.

Fe+2 + Ce+4 <=> Ce+3 + Fe+3

At 15.00 mL of Ce+4 added, VFeMFe > VCeMCe
[Fe+3] = 2.308 x 10-2 M [Fe+2] = 1.54 x 10-2 M
for Fe+2 -> Fe+3 Eo = 0.69 v
0.0592 [Fe+2]
o
Ecell = Ecell - ----------- log -----------
n [Fe+3]

20
 EXAMPLE: Derive the titration
curve for 50.00 mL of 0.0500 M Fe+2
with 0.1000 M Ce+4 in a medium that
is 1.0 M in H2SO4.

Fe+2 + Ce+4 <=> Ce+3 + Fe+3

At 15.00 mL of Ce+4 added, VFeMFe > VCeMCe
[Fe+3] = 2.308 x 10-2 M [Fe+2] = 1.54 x 10-2 M
for Fe+2 -> Fe+3 Eo = 0.69 v
0.0592 1.54 x 10-2
Ecell = 0.68 v - ---------- log ----------------- v = 0.69 v
1 2.31 x 10-2

EXAMPLE: Derive the titration

curve for 50.00 mL of 0.0500 M Fe+2
with 0.1000 M Ce+4 in a medium that
is 1.0 M in H2SO4.

Fe+2 + Ce+4 <=> Ce+3 + Fe+3

At 25.00 mL of Ce+4 added,
VFeMFe = VCeMCe, equivalence point

nFe EFeo + nCe ECeo 1(1.44) + 1(0.68)

Ecell = ----------------------- = ------------------------ v
nFe + nCe 1 + 1
= 1.06 v

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EXAMPLE: Derive the titration
curve for 50.00 mL of 0.0500 M Fe+2
with 0.1000 M Ce+4 in a medium that
is 1.0 M in H2SO4.

Fe+2 + Ce+4 <=> Ce+3 + Fe+3

At 26.00 mL of Ce+4 added, VCeMCe > VFeMFe
VFe MFe (50.00 mL)(0.0500 M)
[Ce+3] = ---------------- = -------------------------------
VFe + VCe (50.00 + 26.00)mL
= 3.29 x 10-2 M

22
EXAMPLE: Derive the titration
curve for 50.00 mL of 0.0500 M Fe+2
with 0.1000 M Ce+4 in a medium that
is 1.0 M in H2SO4.

Fe+2 + Ce+4 <=> Ce+3 + Fe+3

At 26.00 mL of Ce+4 added, VCeMCe > VFeMFe
[Ce+3] = 3.29 x 10-2 M
VCe MCe - VFe MFe
[Ce+4] = ---------------------------
VFe + VCe

EXAMPLE: Derive the titration

curve for 50.00 mL of 0.0500 M Fe+2
with 0.1000 M Ce+4 in a medium that
is 1.0 M in H2SO4.
Fe+2 + Ce+4 <=> Ce+3 + Fe+3
At 26.00 mL of Ce+4 added, VCeMCe > VFeMFe
[Ce+3] = 3.29 x 10-2 M
(26.00 mL)(0.1000 M) - (50.00 mL)(0.0500 M)
[Ce+4] = -------------------------------------------------------
(50.00 + 26.00)mL
= 1.32 x 10-3 M

23
 EXAMPLE: Derive the titration
curve for 50.00 mL of 0.0500 M Fe+2
with 0.1000 M Ce+4 in a medium that
is 1.0 M in H2SO4.

Fe+2 + Ce+4 <=> Ce+3 + Fe+3

At 26.00 mL of Ce+4 added, VCeMCe > VFeMFe
[Ce+3] = 3.29 x 10-2 M [Ce+4] = 1.32 x 10-3 M
for Ce+4 -> Ce+3 Eo = 1.44 v
0.0592 [Ce+3]
o
Ecell = Ecell - ----------- log ----------
n [Ce+4]

EXAMPLE: Derive the titration

curve for 50.00 mL of 0.0500 M Fe+2
with 0.1000 M Ce+4 in a medium that
is 1.0 M in H2SO4.

Fe+2 + Ce+4 <=> Ce+3 + Fe+3

At 26.00 mL of Ce+4 added, VCeMCe > VFeMFe
[Ce+3] = 3.29 x 10-2 M [Ce+4] = 1.32 x 10-3 M
for Ce+4 -> Ce+3 Eo = 1.44 v
0.0592 3.29 x 10-2
Ecell = 1.44 v - ------------ log --------------- v = 1.39 v
1 1.32 x 10-3

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25
26
 Electrochemical Methods: Potentiometry
•Reference Electrodes
•Indicator Electrodes
• pH Electrodes
• Ion-Selective Electrodes

Reference Electrodes
• A half-cell with a constant potential that is used as a
comparison for other measurements.
• Made of some stable chemical species, is readily
available and usually simple to use.
• Should be non-toxic if you are going to use it in a
biological system.
• Should be rugged and portable if you are going to use it
in the field!
• Several Varieties:
– S.H.E
– Ag/AgCl
– Calomel

27
 S.H.E. (again)
• Cell made with hydrogen gas and hydrogen ion using a Pt
electrode
• Not practical for regular use due to the hydrogen gas
• Assigned a standard potential of zero by definition

Ag/AgCl
• Constructed of a silver wire, coated with silver
chloride, in a solution containing silver chloride
– Sometimes AgCl is in solution saturated with KCl
– Saturated KCl keeps the chloride activity constant and
helps keep the electrode stable
AgCl(s) + e
 Ag(s) + Cl
(aq )

E° = 222mV (Relative to S.H.E.)

E (sat. KCl) + 197 mV (relative to S.H.E.)

RT
E = E°

RT
ln[Cl
] = 0.05916@25°C
nF nF

IF we replace ln with base ten log!

28
29
 Calomel (S.C.E)
• Calomel is mercury (I) chloride
• One of the most common reference
electrodes

Hg2Cl2(s) + 2e
 Hg(1) + 2Cl
(aq )

E° = 268 mV (relative to S.H.E.)

E (sat. KCl) = 241 mV (relative to S.H. E.)

RT
E = E°
ln[Cl
]2
nF

30
 Conversions among different
scales (different electrodes)
• The reduction potential for iron (III)
under standard conditions is ? (look it
up)
– What is it if measured compared to the
Ag/AgCl reference electrode?
– A saturated calomel electrode?

Indicator Electrodes
• Used for indicating • Metal Electrodes
the potential caused – Gold
by some chemical
– Platinum
species as compared
– Carbon
to the reference • ?
electrode. • Solid carbon
• Usually connected to • Carbon Paste
the + (cathode) side – Analyte of Interest
of the potentiometer • Ion Selective
• Made of a variety of – Glass membrane
often allegedly, but – Crystalline
never actually, inert • Solid State

materials. – Liquid Membrane

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 Typical Metal
Electrode
Arrangement

pH (Glass Membrane) Electrodes

• One of the simpler ion-selective electrodes (ISE)
• Hydrogen Ion imparts a charge across a hydrated
glass membrane

• Generally include an internal reference electrode

(Ag/AgCl) and a separate Ag/AgCl electrode for
sensing the charge imparted by the hydrogen ions

• Not as simple to use as you think!

32
33
 Basic Nernst Equation of a pH Electrode
(only the pH sensing cell, not the reference electrode)….

A + 
E pH cell = constan t +
x0.05916 x log H outside 
 A H + inside 

The constant is cancelled out by calibration in similar

Ionic strength solutions

is an efficiency factor that cancels out by calibration in similar
Ionic strength solutions.
So, what really matters are the activities of hydroben ions!
Don’t forget, electrodes respond to ACTIVITIES, even if we pretend
That they are concentrations to simplify our calculations.

34
 Ionic Activity and Concentration
Debye and Huckel in 1923

Ionic Activity ai = ri C

Activity coefficient
0.51z 2 I

log ri =
1+ I

Ionic Strength

ISFET pH electrode
(Ion Selective Field Effect Transistor)

35
 What does 0.05916 mean?
• It is a constant, if there is a one-
electron reaction
• It can be considered as the
equivalent of a constant of 59.16 mV (relative
pH
mV readings)
100.00 2.00
• A pH meter is a high-impedance
potentiometer (measures voltage) 159.16 3.00

• A pH change of “1” imparts a 218.32 4.00

change in 59.16 mV to the 277.48 5.00
potential recorded by the pH 336.64 6.00
meter! 395.80 7.00
• 1 pH unit change= 59.16 mV

Errors in pH Measurement….
1. Junction potential due to the salt bridge and differences in junction
potentials over time due to contamination of the junction
• Overcome by regular recalibration
2. Sodium Error will result in high concentration of sodium solutions. The
sodium can also impart a charge across the glass membrane.
3. Acid error (strong acids) can saturate or contaminate the membrane
with hydrogen ion!
4. Equilibration Error is overcome by letting the electrode equilibrate with
the solution
5. Dried out glass membrane (ruins electrode)
6. Temperature. Since temperature affects activities, it is best to have all
solutions at the same, constant temperature!
7. Strong bases. Strongly basic solutions (>pH 12) will dissolve the glass
membrane!
8. Uncertainty in your buffer pH due to normal weighing, diluting errors.

36
 Ion Selective Electrodes……
• Selectivity Coefficient
– Defines how an ISE responds to the species of
interest versus some interfering species
• Interferences cause a signal (voltage) to be imparted on the
electrode that is NOT the result of the ion or chemical
species of interest
– You want the selectivity coefficient to be as SMALL
as possible
electrode response to X
k(A,X ) =
electrode response to A
Where X is the interfence and A is the analyte

E = constan t

0.05916
n
( )
log AA +  ( k(A ,X )  AX )

Examples of Electrodes / Interferences

37
 Solid State Electrodes
• Uses a small amount of a doped crystal to transport charge from
the solution to an inner electrode
• The inner (sensing) electrode can be a Ag/AgCl electrode, and a
separate Ag/AgCl electrode can be present
– Combination electrode
• You can use a separate reference electrode also.

38
• Typical equation (Fluoride Electrode):
E = constan t
  0.05916  log( AF
outside )

• Use:
– Prepare calibration and sample solutions to
similar ionic strengths and temperatures
– Connect ISE and reference electrode to
potentiometer (pH meter in mV mode)
– Record potentials of calibration solutions
– Prepare calibration curve
– Measure potential of sample solutions and
calculate fluoride activity!

39
 Liquid Membrane ISE’s

• Replace the solid

state crystal
with a liquid
ion-exchanger
filled membrane
• Ions impart a
charge across
the membrane
• The membrane
is designed to be
SELECTIVE for
the ion of
interest……

40
 Voltammetry
Voltammetry can be used to
• Study electroactivity of ions and molecules at the
electrode/solution interface
• Probe coupled chemical reactions and measure
electron transfer rates
• Examine electrode surfaces

An electrochemical cell consists of a working (analyzing) electrode, an auxiliary

(counter) electrode, and a reference electrode. The control device is a potentiostat.

Clarifications of disk electrodes:

In quiescent solutions,

Conventional-sized Microelectrode Ultramicroelectrode Nanode

(>mm) (>25 mm) (0.1-25 μm) (nm)

In flowing or agitated solutions,

Rotating disk electrode, channel electrode, wall-jet electrode, and flow-through

tubular electrode.

Disk Working Electrode Pt/Au wire or coil auxiliary electrode

Imbedded In Teflon or Kel-F

41
 Stripping Analysis
In anodic stripping voltammetry (analysis), analytes are reduced and deposited into (onto) an
electrode. They are reoxidized during the stripping step.

e.g. Cd2+(aq) + 2e = Cd(Hg) Deposition Step

Cd(Hg) – 2e = Cd2+ (aq) Stripping

In the deposition step, solution is stirred or the electrode is rotated.

In cathodic stripping voltammetry, typically anions are oxidized and deposited onto an
electrode with subsequent stripping via a negative potential scan.

2I- + 2Hg -2e = Hg2I2 at a Hg electrode (deposition step)

Hg2I2 + 2e = 2 Hg + 2I- (cathodic stripping, reduction)

Because sample analytes are preconcentrated from a large-volume dilute solution into (onto)
a small-volume electrode under forced convection, trace analysis (enhanced sensitivity) can
be realized.

Tissue-based biosensor
(voltammetric)

catechol

PPO: polyphenol oxidase

42