Chapter 17

Recommended Exercises and Problems

17-2 17-3
17-4 17-9
17-10 17-31
 iPhone
Glucose Monitor

Amperometric
Sensor
February 4, 2014 Issue
KS=Kenaf stem

Hibiscus
cannabinus
 Chapter 17
Electroanalytical
Techniques
Techniques which require current
to flow: Electrolysis
Four basic categories:

Electrogravimetry
Voltametry
Amperometry
Coulometry
 Current Measures the Rate of Reaction:

19 23
(1.6022 10 )(6.022 x 10 ) = 96485 /
160 zC 602 Z particles F
 C/s s

C/mol e-

Electron Electron
Depleted Rich

Cathode:
+ + = 2.71
22 () + 2 2 + 2 = 0.83
 Anode:
2 + 2 2 = 1.36
2 + 4+ + 4 22 = 1.23
 Anode: E
2 + 2 2 = 1.36 1.32
2 + 4+ + 4 22 = 1.23 2.2
22 () + 2 2 + 2

5000
= 0.026 2
2 96485
600 mL

2 mol e- / mol H2
Electrolytic Cell Battery

Electron Rich

Cathode Anode
reduction
 = + +
 Reaction
of interest

Counter Working
Electrode Electrode

Anode Cathode
 2+
C + 2 0.339

A 1.229

Convention:
Current is positive if reduction occurs
at the working electrode
Convention:

= +

Reduction Oxidation
Working electrode Counter electrode
Open Circuit Voltage
2+
1
2 + + 2 + 2+
2
0.059 1 0.059 1
= 0.339 2+
1.229 1/2
2 2 + 2
2

E (cathode) E (anode)

With 0.2 M Cu2+ and 1.0 M H+

0.059 1 0.059 1
= 0.339 1.229
2 0.2 2 1.0 1/2 1.0 2

= 0.318 1.229 = 0.911

 1
2 + 2+ + 2 + 2+
2
0.059 1 0.059 1
= 0.339 2+
1.229 1/2
2 2 + 2
2

E (cathode) E (anode)
With 0.2 M Cu2+ and 1.0 M H+
0.059 1 0.059 1
= 0.339 1.229
2 0.2 2 1.0 1/2 1.0 2

= 0.318 1.229 = 0.911

 2+
1 +
2 + + 2 + 2
2
= 0.318 1.229 = 0.911

What is G for this reaction?

 =
= 2 96485 0.911
= 176 /mol
1
2 + 2+ + 2 + 2+
2
Energetic Considerations
3 Important Processes

Overpotential a.k.a. overvoltage

Ohmic Potential
Concentration Polarization
Overpotential

The voltage required to overcome the

activation energy for a reaction at an electrode
Overvoltages associated with
gaseous products are among the
largest and most important
 Ohmic Potential

=
The resistance of ionic solutions can
be 100s -1000s of ohms
Conductance only depends on concentration, charge
and mobility
 Concentration Polarization
For our Cu2+ cell:
0.059 1
= 0.339
2 2+

At electrode surface

E (cathode) will be driven negative
Finally:

All 3 processes make the

electrolysis require more voltage in
order to sustain a given current
A few generalizations regarding overpotential

Increases with current density

Decreases with increasing temperature

Depends on electrode composition: most pronounced

with softer metals such as Sn, Pb, Zn and especially Hg

Larger for electrodes which produce gaseous products

 E

A 2 + 2 2 1.32
-0.83
C 22 () + 2 2 + 2
 What happens with NaBr?

C 22 () + 2 2 + 2 -0.828

A 2 () + 2 2 1.098

E = -0.828 1.078 = -1.906 V

2 + 2 2 = 2.890

2 + 2 2 = 1.360

2 + 2 2 = 1.098

2 + 2 2 = 0.620
 C 2+ + 2 0.339
A 1.229

E = 0.318 1.229 = -0.911 V


3 + 22 3 + 2 + 2

What are the two

half-reactions?
What is the open-circuit cell
voltage with no current
flowing?
What is the open circuit voltage?

: 22 + 2 2 + 2 = 0.828
: 3 + 2 3 = 0.535

[KI] = 0.010 M
5
3 = 3.0 10
pH = 10.00
2 = 1.00
 Open-circuit voltage:
= ()
0.059
= 0.828 2 2
= 0.591
2

0.059 3
= 0.535 = 0.579
2 3

E = -0.591 0.579 = -1.170 V

Overpotential + IR 0.5 V
 Electrogravimetry
Oliver Wolcott Gibbs, On the electrolytic precipitation
of copper and nickel as a method of analysis, Zeitschrift
fr analytische Chemie, October, 1864

0.6%
rsd!
 Electrogravimetric Analysis
Platinum Electrodes

O. W. Gibbs
1822-1908
 2+ + 2 0.339
C
A 1.229

E = 0.318 1.229 = -0.911 V

 1
2 + 2+ + 2 + 2+
2

-0.911 V
 2+
1 +
2 + + 2 + 2
2

0.6
How many amps are required to plate
out 1.0 g of Cu in 1 hour?

1
2 + 2+ + 2 + 2+
2

1.0 2 96485

= 0.84
3600 63.546 1
1 g of Cu plated in 1 hr:
 Chapter 17
Recommended Exercises and Problems

17-2 17-3
17-4 17-9
17-10 17-31
Voltammetry

The classical
polarographic
apparatus, Lingane
and Laitinen, 1939

Measure current
as a function of
voltage
Reduction
of 0.5 mM
Cu+ on Hg
electrode Eo = 153 mV
 = 0.356
Current vs Voltage 4 3
6 6 +
Ferrocyanide (FeII) Ferricyanide (FeIII)

Diffusion
Limited
Current

Eo

Constant 10 mM
ferricyanide
Voltammogram
Diffusion Limited Plateau Current
 Three Ways to reach an electrode surface:

(1) Diffusion through a concentration gradient

(2) Convection via stirring or boiling

(3) Migration by electrical repulsion or

attraction
1000 RPM 10-100 m

Concentration
gradient at the
electrode surface
 Bulk - Surface
At high enough voltage:

And:

Basis for Quantitative Analysis

The 3rd auxiliary
electrode carries
the current

Working Electrode
is a drop of Hg
The 3-electrode Cell Pt

Hg drop
Carbon
etc.
Common Working Electrodes

+0.04 to +1.14 V
SHE

B-doped diamond on Pt
Optically transparent
Sampled Current
Polarography
We measure the
faradaic current
after the charging
current has decayed
 on Hg

2+ + 2 = 0.380
5 mM Cd2+

1 M HCl blank

Supporting
electrolyte:
Minimizes
migration
Eo
Reduction of H+ to H2
Polarographic reduction of Oxygen
Nobel Prize
1959
 +
+ + () = 2.936

+ + ( ) = 1.975

Reduction into a Hg amalgam

is generally more favorable
than into the solid state
 + + = 1.69

1 96485
550
196.996 1.0 3600

= 74.8 75 hr
 Chapter 17
Recommended Exercises and Problems

17-2 17-3
17-4 17-9
17-10 17-31
 Amperometric Blood Glucose Monitor

Amperometry:
Measure the current
between two
electrodes which are
driving an
electrolysis reaction

3 Billion Dollars Annually

Amperometry

Fix voltage in this range

Annals of the New York Academy of Sciences, 1962
The Clark Oxygen Electrode

Father of the Biosensor

 0.7 V 2 + 2
+ + 2
2 2

() + +

KCl Ag/AgCl

Typical in
Pt blood

Teflon
Cerebral Oxygen in an awake cat
10 min
1958

Electrodes
1 mm apart
Blood Glucose Monitor, ca. 1960
Amperometric Blood Glucose Monitor

4 cm
 4 l

Disposable Test Strip

 Catalyst

Detected
At the working electrode:

Eo = 0.695 V
Ferricinium is regenerated at the working electrode:
Potential Interferents:
Ascorbic acid
Uric acid
acetaminophen
Idealized blood glucose and insulin levels
 iPhone
Glucose
Monitor

0.3 l
 March 3, 2015

TPAASH:
2,2, 2, (2,2,2nitrilotris(ethane-2,1-diyl)
tris((pyridin-2-ylmethyl) azanediyl)
triethanethiol
3-electrode
micro-electrode
 Normal Rat
Brain

Eo
Brain after
Cerebral
Ischemia
March 3, 2015
Electrode
Fabrication
Performance of
different electrodes for
the oxidation of 1 mM
ferrocenemethanol
 Chapter 17
Recommended Exercises and Problems

17-2 17-3
17-4 17-9
17-10 17-31
Chapter 20
Problems

20-7 20-11
20-14 20-17
20-28 20-33
 2+
1 +
2 + + 2 + 2
2

11.0 106 2 96485

= 0.0334 /
63.546

= 33.4 mA