can discharge more than 50 V

Acetylcholine

Torpedo animal electricity

1. 50 billion nerve terminal emit acetylcholine in the botton side of membrane inside the wing
2. Acetylcholine cause soduim ion to surge through the membrane, result is rapid charge
separationand cause potentioal difference or voltage acros the membrane
3. This potential difference produce a current of as big of several amps in the surrounging see
water

THIS KINDS OF ANIMALS ARE RARE, BUT HUMAN LEARNED TO SEPARATE

CHARGE MECHANICALLY OR CHEMICALLY TO CREATE CELL, BATTERIES
AND …
 Electrochemistry
Coverage from Fundamentals of Analytical Chemistry, 9th Edition
Douglas A. Skoog
Donald M. West
F. James Holler Chapter 18
Stanley R. Crouch
Introduction to Electrochemistry
Chapter 19
Applications of Standard Electrode Potentials
Chapter 20
Applications of Oxidation/Reduction Titrations
Chapter 21
Potentiometry
Chapter 22
Bulk Electrolysis: Electrogravimetry and Coulometry
Dr. Kamyar Shameli Chapter 23
E-mail: [email protected] Voltammetry
Electrochemistry and Redox
 Oxidation-reduction: “Redox”
 Electrochemistry:
Study of the interchange between chemical change and electrical
work
 Redox reactions: electron transfer processes
 Oxidation: loss of 1 or more e- Reduction: gain of 1 or more e-
 Oxidation Numbers (O.N.)
imaginary charges
 1. Pure element O.N. is zero

 2. Monatomic ion O.N. Its charge

 3. Neutral compound: sum of O.N. is zero

 Polyatomic ion: sum of O.N. is ion’s charge
*Negative O.N. generally assigned to more electronegative element
 4. Hydrogen, assigned +1
(metal hydrides, -1)
 5. Oxygen, assigned -2
(peroxides, -1; OF2, +2)
 6. Fluorine, always -1
 Balancing Redox Reactions
1. Write separate equations (half-reactions) for oxidation and reduction
2. For each half-reaction
 a. Balance elements involved in e- transfer
 b. Balance number e- lost and gained
3. To balance e-
multiply each half-reaction by whole numbers
4. Add half-reactions/cancel like terms (e-)

5. Acidic conditions:
 a. Balance oxygen using H2O
 b. Balance hydrogen using H+
6. Basic conditions:
a. Balance oxygen using OH-
b. Balance hydrogen using H2O

6. Check that all atoms and charges balance

Examples

 Acidic conditions:

2 2 3
-
MnO 4(aq)  Fe(aq) 
 Mn (aq)
acid
 Fe(aq)

 Basic conditions:

 
Ag (s)  CN(aq)  O2(g) 
 Ag(CN) 2(aq)
base
 Redox
• Oxidation is loss of e- causes reduction, “reducing agent”
• Reduction is gain of e- causes oxidation, “oxidizing agent”
 Red-Ox reaction media
• Contact is the famous
Direct “silver tree” experiment
in which a piece of
Contact copper is immersed in
a silver nitrate solution

• The oxidizing agent

and the reducing
Electrochemical agent are physically
Cell separated from one
another
 You have to know ….
 Electrodes: conduct electricity between cell and surroundings
 Anode: Oxidation occurs at the anode
 Cathode: Reduction occurs at the cathode
 Electrolyte: mixture of ions involved in reaction or carrying charge
 Salt bridge: completes circuit (provides charge balance)
It isolates the reactants but maintains electrical contact between the
two halves of the cell
 Open circuit: When a voltmeter of high internal resistance is
connected as shown or the electrodes are not connected
externally, the cell is said to be at open circuit and delivers the full
cell potential. When the circuit is open, no net reaction occurs in
the cell, although we shall show that the cell has the potential for
doing work. The voltmeter measures the potential difference, or
voltage, between the two electrodes at any instant. This voltage is
a measure of the tendency of the cell reaction to proceed toward
equilibrium.
 OCV

ACS Appl. Mater. Interfaces, 2015, 7 (31)

pp 17008–17015
 Types of Electrochemical cells
Voltaic (galvanic) cells: a spontaneous reaction generates electrical energy
Electrolytic cells: absorb free energy from an electrical source to drive a
nonspontaneous reaction
17_360

e– e–

e– e–
Porous disk

Oxidation Reduction

e– Reducing Oxidizing e–
agent agent

(a) Anode (b) Cathode

Representing Cells Schematically
 A single vertical line indicates a phase boundary, or interface, at
which a potential develops.
 The double vertical lines represent two-phase boundaries, one at
each end of the salt bridge. There is a liquid-junction potential at
each of these interfaces. The junction potential results from
differences in the rates

1. If the measured value of E is positive, the right-hand electrode is positive with respect to
cell

the left-hand electrode, and the free energy change for the reaction in the direction being
considered is negative. Hence, the reaction in the direction being considered would occur
spontaneously if the cell were short-circuited or connected to some device to perform
work (e.g., light a lamp, power a radio, or start a car).
2. On the other hand, if E is negative, the right-hand electrode is negative with respect to the
cell

left-hand electrode, the free energy change is positive, and the reaction in the direction
considered (oxidation on the left, reduction on the right) is not the spontaneous cell
reaction.
3. E 0.412 V, and the oxidation of Cu and reduction of Ag occur spontaneously when the
cell 1
 Currents in Electrochemical Cells

1. Electrons carry
the charge within
the electrodes as
well as the
external
conductor.
By convention,
current, which is
normally
indicated by the
symbol I, is
opposite in
direction to
electron flow.
2. Anions and
cations are the Negative ions in the salt bridge
charge carriers move toward the anode; positive
within the cell. ions move toward the cathode
 Cell Potential
Cell Potential / Electromotive Force (EMF):
The potential difference between the electrodes of the cell in is a measure of the
tendency for the reaction to proceed from a nonequilibrium state to the condition
of equilibrium. The cell potential Ecell is related to the free energy of the reaction
G by

If the reactants and products are in their standard states, the resulting cell potential
is called the standard cell potential. This latter quantity is related to the standard
free energy change for the reaction and thus to the equilibrium constant by
n: number of moles of e-
F: Faraday’s constant
96485 C
mol of e-
work or electrical potential energy J
E cell   V
unit of charge moved C
 17_363

e– e–

e– e–
Ecell = +1.10 V

+ +
Zn 2 Cu 2
– –
SO 4 2 SO 4 2
Zn(s) Cu(s)
+ 2+
1.0 M Zn 2 1.0 M Cu
solution solution

Anode Cathode
E0cell
Cell Potential, E0cell
cell potential under standard conditions
elements in standard states (298 K), solutions:1 M, gases: 1 atm
The potential of a cell is the difference between two half-cell or single-
electrode potentials, one associated with the half-reaction at the right-
hand electrode (E ) and the other associated with the half-reaction at
right

the left-hand electrode (E ).

left

Cu2+ + 2e  Cu
E0 = 0.34 V vs. SHE

SO42 + 4H+ + 2e  H2SO3 + H2O

E0 = 0.20 V vs. SHE
 E0cell and DG0

E0cell > 0 DG0 < 0 Spontaneous

E0cell < 0 DG0 > 0 Not

E0cell = 0 DG0 = 0 Equilibrium

 Calculating E0cell
E0cell = E0cathode - E0anode

Br2(aq)+2V3+ +2H2O(l)  2VO2+(aq)+ 4H+(aq)+ 2Br-(aq)

Given: E0cell = +1.39 V

E0Br2 = +1.07 V

What is E0V3+ and is the reaction spontaneous?

 E0 values
More positive:
Stronger oxidizing agent
More readily accepts e-

More negative:
Stronger reducing agent
More readily gives e-

Stronger R.A. + O.A.  Weaker R.A. + O.A.

 Standard Hydrogen Reference Electrode

 For relative electrode potential data to be widely applicable and

useful, we must have a generally agreed-upon reference half-cell
against which all others are compared.
 easy to construct
 Reversible
 highly reproducible behavior.
The standard hydrogen electrode
(SHE) meets these specifications and
has been used throughout the world for
many years as a universal reference
electrode.

By convection the standard

hydrogen electrode is assigned a
value of 0.000 V at all
temperatures.
 Electrode Potential and Standard
Electrode Potential
 An electrode potential is defined as the potential of a cell in
which the electrode in question is the right-hand electrode and
the standard hydrogen electrode is the left-hand electrode.

The standard electrode

potential, E , of a half-reaction is
0

defined as its electrode potential

when the activities of the
reactants and products are all
unity.
 In contrast to the silver electrode, the cadmium electrode is
negative with respect to the standard hydrogen electrode.
Therefore, the standard electrode potential of the Cd/Cd2+
couple is by convention given a negative sign, and E 0 0.403 V.
Because the cell potential is
negative, the spontaneous
cell reaction is not the

Rather, the
spontaneous reaction is in
the opposite direction
 The magnitudes of these electrode potentials indicate the relative
strength of the four ionic species as electron acceptors (oxidizing
agents), that is, in decreasing strength, Ag1 . H1 . Cd21 . Zn21.

Remember:
1. An electrode potential is by definition a reduction potential. An
oxidation potential is the potential for the half-reaction written in the
opposite way. The sign of an oxidation potential is, therefore,
opposite that for a reduction potential, but the magnitude is the same.
2. The sign of an electrode potential is determined by the sign of the
half-cell in question when it is coupled to a standard hydrogen
electrode.
Effect of Concentration on Electrode
Potentials: The Nernst Equation
An electrode potential is a measure of the extent to which the
concentrations of the species in a half-cell differ from their equilibrium
values

For 25 C
 Calculation Nernst Equation
Typical half-cell reactions and their corresponding Nernst
expressions follow.
Ksp= 1.82 x 10-10
DG0, E0, and K
DG  RTlnK  nFE
0 0

RT
so E 
0
lnK
nF
 At equilibrium: DG0 = 0 and K = Q
 At 298 K:
0.0592
E 
0
logK
n
Limitations to the Use of
Standard Electrode Potentials

 Use of Concentrations Instead of Activities

 Effect of Other Equilibria
 Formal Potentials
Nernst Equation
 Under nonstandard conditions

DG  DG  RTlnQ0

 nFE  nFE  RTlnQ 0

RT
E cell E  0
lnQ
nF
0.0592
298K
E cell E  0
lnQ
n
Based on the
E0 values, for
Fe3+ and I3-,
which species
would you
expect to
predominate in
a solution
produced by
mixing iron(III)
andiodide ions?
 Concentration Cells

. . . a cell in which both compartments

have the same components but at
different concentrations
17_366

e– e–

e– Porous e–
disk
Ag Ag

0.1 M Ag + 1 M Ag +
– –
0.1 M NO 3 1 M NO 3

Anode Cathode
17_369

Reference solution of
dilute hydrochloric acid

Silver wire coated with

silver chloride

Thin-walled membrane
 Electrolysis

Forcing a current through a cell to

produce a chemical change for
which the cell potential is negative.
17_378

Electrodes of
graphite rods
To external
power source

Carbon
dioxide Molten Al 2O3/Na 3AlF 6
formed at mixture
the anodes
Molten
aluminum
Carbon-lined iron tank

Plug
 Stoichiometry

How much chemical change occurs with the flow

of a given current for a specified time?

current and time  quantity of charge 

moles of electrons  moles of analyte 
grams of analyte