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Electrochemistry

Review
Oxidation

reduction reactions involve a


transfer of electrons.
OIL- RIG
Oxidation Involves Loss
Reduction Involves Gain
LEO-GER
Lose Electrons Oxidation
Gain Electrons Reduction

Solid lead(II) sulfide reacts with oxygen in


the air at high temperatures to form
lead(II) oxide and sulfur dioxide. Which
substance is a reductant (reducing
agent) and which is an oxidant
(oxidizing agent)?
A. PbS, reductant; O2, oxidant
B.

PbS, reductant; SO2, oxidant

C.

Pb2+, reductant; S2- oxidant


PbS, reductant; no oxidant
PbS, oxidant; SO2, reductant

D.
E.

Applications
Moving

electrons is electric current.


8H++MnO4-+ 5Fe+2 +5e Mn+2 +
5Fe+3 +4H2O
Helps

to break the reactions into half


reactions.
8H++MnO4-+5e- Mn+2 +4H2O
Fe+3 + e- )
In the same mixture it happens without
doing useful work, but if separate
5(Fe+2

Connected

this way the reaction starts


Stops immediately because charge builds
up.

-e- -

H+
MnO4-

e e
e- e-

Fe+2

Galvanic Cell
Salt
Bridge
allows
current
to flow
H+
MnO4-

Fe+2

Electricity

travels in a complete circuit

MnO4-

eFe+2

Instead

of a salt bridge

H+
MnO4-

Porous
Disk

Fe+2

ee

ee-

Anode
-

e
Reducing
Agent

Cathode
eOxidizing
Agent

Cell Potential
Oxidizing

agent pulls the electron.


Reducing agent pushes the electron.
The

push or pull (driving force) is called


the cell potential Ecell

Also

called the electromotive force (emf)


Unit is the volt(V)
= 1 joule of work/coulomb of charge
Measured with a voltmeter

0.76

H2 in
Anode
Zn+2 SO42

1 M ZnSO4

Cathode
H+
Cl1 M HCl

Standard Hydrogen Electrode


This

is the reference
all other oxidations
are compared to

E = 0

indicates standard
states of 25C,
H+
1 atm, 1 M
Clsolutions.
1 M HCl

H2 in

Calomel electrode:
Calomel electrode is the mercury-mercurous
chloride electrode. The potential of the calomel
electrode, on the hydrogen scale has been found to
vary with the concentration of the potassium
chloride solution used.

Construction:
It consists of a tube in the bottom of which is a
layer of mercury, over which is placed a paste of Hg
+ Hg2Cl2 . The remaining portion of cell is filled
with a solution of normal or decinormal or
saturated solution of KCl. A platinum wire dipping
into the mercury layer, is used for making electrical
contact. The side tube is used for making electrical
contact with a salt bridge.

Cell Potential
+ Cu+2 (aq) Zn+2(aq) + Cu(s)
The total cell potential is the sum of the
potential at each electrode.
Zn(s)

Ecell = EZn Zn+2 + ECu+2 Cu


We

can look up reduction potentials in a


table.
One of the reactions must be reversed,
so change it sign.

Cell Potential
Determine

the cell potential for a galvanic


cell based on the redox reaction.

Cu(s)

+ Fe+3(aq) Cu+2(aq) + Fe+2(aq)

E = 0.77 V
Cu+2(aq)+2e- Cu(s)
E = 0.34 V
Cu(s) Cu+2(aq)+2eE = -0.34 V
2Fe+3(aq) + 2e- 2Fe+2(aq) E = 0.77 V
Fe+3(aq) +

e- Fe+2(aq)

Reduction potential
More

negative E

more

easily electron is added


More easily reduced
Better oxidizing agent
More

positive E

more

easily electron is lost


More easily oxidized
Better reducing agent

Line Notation
solid Aqueous Aqueous solid
Anode on the left
Cathode on the right
Single line different phases.
Double line porous disk or salt bridge.
If all the substances on one side are
aqueous, a platinum electrode is
indicated.

For

the last reaction


Cu(s) Cu+2(aq)
Fe+2(aq),Fe+3(aq) Pt(s)

Cu

2+

Fe+2

In a galvanic cell, the electrode that


acts as a source of electrons to the
solution is called the __________;
the chemical change that occurs at
this electrode is called________.
a. cathode, oxidation
b. anode, reduction
c. anode, oxidation
d. cathode, reduction

Under standard conditions, which of


the following is the net reaction that
occurs in the cell?
Cd|Cd2+ || Cu2+|Cu
a. Cu2+ + Cd Cu + Cd2+
b. Cu + Cd Cu2+ + Cd2+
c. Cu2+ + Cd2+ Cu + Cd
d. Cu + Cd 2+ Cd + Cu2+

Galvanic Cell

1)
2)
3)
4)

The reaction always runs


spontaneously in the direction that
produced a positive cell potential.
Four things for a complete description.
Cell Potential
Direction of flow
Designation of anode and cathode
Nature of all the componentselectrodes and ions

Potential, Work and G


emf

= potential (V) = work (J) / Charge(C)

E = work done by system / charge


E = -w/q
Charge

is measured in coulombs.

=qE
Faraday = 96,485 C/mol e q = nF = moles of e- x charge/mole e -w

= -qE = -nFE = G

Potential, Work and G

G = -nFE

if

if

E > 0, then G < 0 spontaneous


E< 0, then G > 0 nonspontaneous

In

fact, reverse is spontaneous.


Calculate G for the following reaction:
Cu+2(aq)+ Fe(s) Cu(s)+ Fe+2(aq)
Fe+2(aq) +

e-Fe(s)

Cu+2(aq)+2e- Cu(s)

E = 0.44 V
E = 0.34 V

NERNST EQUATION
The Nernst equation was named after the
German chemist Walther Nernst who
established very useful relations between
the energy or potential of a cell to the
concentrations of participating ions

The Nernst Equation


G

= G +RTln(Q)

-nF

E = -nFE + RTln(Q)

E = E - RTln(Q)

nF

+ 3Mn+2(aq) 2Al+3(aq) + 3Mn(s)


E = 0.48 V
Always have to figure out n by balancing.
If concentration can gives voltage, then
from voltage we can tell concentration.
2Al(s)

The Nernst Equation


As

reactions proceed concentrations of


products increase and reactants decrease.
Reach equilibrium where Q = K and
Ecell = 0
0 = E - RTln(K)
nF
E = RTln(K)
nF

nF E = ln(K)
RT

Batteries are Galvanic Cells

Car

batteries are lead storage batteries.


Pb +PbO2 +H2SO4 PbSO4(s) +H2O

Batteries are Galvanic Cells

Dry

Cell
Zn + NH4+ +MnO2
Zn+2 + NH3 + H2O + Mn2O3

Batteries are Galvanic Cells

Alkaline

Zn +MnO2 ZnO+ Mn2O3 (in base)

Batteries are Galvanic Cells

NiCad

NiO2 + Cd + 2H2O Cd(OH)2 +Ni(OH)2

Electrolysis
Running

a galvanic cell backwards.


Put a voltage bigger than the potential
and reverse the direction of the redox
reaction.
Used for electroplating.

1.10
e

e-

Zn
1.0 M
Zn+2
Anode

1.0 M
Cu+2
Cathode

Cu

A battery
>1.10V

Zn
1.0 M
Zn+2
Cathode

e-

Cu

1.0 M
Cu+2
Anode

A way to remember
An

Ox anode is where oxidation occurs


Red Cat Reduction occurs at cathode
Galvanic cell- spontaneous- anode is
negative
Electrolytic cell- voltage applied to make
anode positive

Reversible & Irreversible cells:


Reversible electrochemical cells are the cells whose cell reactions
can be get reversed when an external emf greater than its capacity is
applied.
(A cell which obeys thermodynamic conditions of reversibility is
known as reversible cells).
For example 3 Daniel cell with Capacity 1.1 V, when an external emf
of 1.1 V is applied, the cell reaction stops.
Zn + Cu+2 ----------> Zn+2 + Cu
But when an increased amount of emf greater than 1.1 V is applied,
the cell reaction is get reversed.
Zn+2 + Cu -------> Zn + Cu+2
A cell of this type can be termed as Reversible cell.

Irreversible electrochemical cells are the cells


whose cell reactions can not be get reversed when
an external emf greater than its capacity is applied.
(A cell which does not obey thermodynamic
conditions of reversibility is known as irreversible
cells). For example, a cell which has Zn as an anode
and Ag as a cathode with sulphuric acid as an
electrolyte. The cell reaction at the anode is
Zn (s) ----------> Zn+2 (aq) + 2e
In the presence of electrolyte (H2SO4)
Zn + 2 H+ ----------> Zn+2 + H2
The cell reaction at the cathode
2 Ag + 2e- ----------> 2 Ag
When an external emf applied to the cell, the
chemical reactions are not reversed because one of
the products of the reaction H2 gas is escaped from
the reaction system. Dry cells are another familiar
example for this type of cells.