Documente Academic
Documente Profesional
Documente Cultură
Chapter 21
Redox Review
Redox reactions: electron transfer processes
Oxidation:
Reduction:
O.N. is zero
Redox Review
Redox reactions: electron transfer processes
Oxidation:
Reduction:
O.N. is zero
Oxidation-reduction
Oxidation is loss of eO.N. increases (more positive)
Reduction is gain of eO.N. decreases (more negative)
Oxidation involves loss OIL
Reduction involves gain RIG
Redox
Oxidation is loss of ecauses reduction
reducing agent
Reduction is gain of ecauses oxidation
oxidizing agent
Oxidation-reduction
Oxidation is loss of eO.N. increases (more positive)
Reduction is gain of eO.N. decreases (more negative)
Oxidation involves loss OIL
Reduction involves gain RIG
Redox
Oxidation is loss of ecauses reduction
reducing agent
Reduction is gain of ecauses oxidation
oxidizing agent
2.
Examples
Acidic conditions:
MnO 4(aq)
2
Fe (aq)
acid
2
Mn (aq)
3
Fe (aq)
Basic conditions:
Ag (s)
CN (aq)
O 2(g)
Ag(CN) 2(aq)
base
Types of cells
Voltaic (galvanic) cells:
a spontaneous reaction generates electrical energy
Electrolytic cells:
absorb free energy from an electrical source to
drive a nonspontaneous reaction
Common Components
Electrodes:
conduct electricity between cell and
surroundings
Electrolyte:
mixture of ions involved in reaction or
carrying charge
Salt bridge:
completes circuit (provides charge balance)
Electrodes
Anode:
Oxidation occurs at the anode
Cathode:
Reduction occurs at the cathode
Active electrodes: participate in redox
Inactive:
sites of ox. and red.
17_360
e
Porous disk
Oxidation
e
(a)
Reducing
agent
Anode
Reduction
Oxidizing
agent
(b)
Cathode
N.B. The galvanic cells which consists of the zinc rod dipping
into a ZnSO4 solution and the copper electrode dipping
into a CuSO4 solution is Daniell cell.
Its formula is:
Salt bridge and its function. Its usually an inverted U-tube
filled with concentrated solution of inert electrolyte. The
essential requirements of electrolyte are:
a) The mobility of the anion and cation of the electrolyte
should be almost same.
b) The ions of the electrolyte are not involved in
electrochemical change.
c) The ions do not react chemically with the species of the
cell.
Generally, salts like KCl, KNO3, etc. are used. The seturated
solutions of these electrolytes are prepared in agar agar
jelly or gelatin. The jelly keeps the electrolyte in semisolid phase and thus prevents mixing.
The important functions of the salt bridge are:
a) Salt bridge completes the electrical circuit.
b) Salt bridge maintains electrical neutrality of two half cell
solution.
The accumulation of charges in the two half cells
(accumulation of extra positive charge in the solution
around the anode according to the realizing of Zn2+ in
excess and accumulation of extra negative charge in the
solution around the catode due to excess of SO42- ) is
prevented by using salt bridge, which provides a passage
for the flow of the charge in the internal circuit.
Zn
1- metal
2 - solution
+
-
+
+
+
+
+
+
(-)
- - - --CuSO4
+
-
+
+
+
+
+
+
(-)
- - - --CuSO4
Electrochemistry
Standard Potentials
Electrochemistry
Constructing a Cell Diagram
Because voltaic cells are cumbersome to describe in words, a
line notation called a cell diagram has been developed
In a cell diagram
the identity of the electrodes and the chemical contents of the
compartments are indicated by their chemical formulas, with the anode
written on the far left and the cathode on the far right;
phase boundaries are shown by single vertical lines;
the salt bridge, which has two phase boundaries, is shown by a double
vertical line;
Heres a cell diagram for Zn/Cu cell:
Salt Bridge
Cathode
Electrochemistry
The standard cell potential for a redox reaction, Ecell, is a measure of the
tendency of the reactants in their standard states to form the products in
their standard statesit is a measure of the driving force for the reaction
(voltage)
The standard cell potential is the reduction potential of the reductive
half-reaction minus the reduction potential of the oxidative halfreaction (Ecell = Ecathode Eanode).
Calculations for the standard potential for the Zn/Cu cell represented by
the cell diagram:
Zn(s) | Zn2+(aq, 1 M) || Cu2+(aq, 1M) | Cu(s)
Cathode: Cu2+(aq) + 2e Cu(s)
Anode:
Ecathode =
0.34 V
Eanode = + 0.76 V
1.10 V
Electrochemistry
These experimental facts demonstrate that Cu2+ is a stronger oxidizing agent
than Zn2+.
Electrochemistry
To measure relative electrode potentials, we must establish an
arbitrary standard.
That standard is the Standard Hydrogen Electrode (SHE).
The SHE is assigned an arbitrary voltage of 0.000000 V
The potential of a half-reaction measured against the SHE under
standard conditions is called the standard electrode potential for that
half-reaction.
Figure 21.11A
The relation between Ecell and log Q for the zinccopper cell.
If the reaction starts with [Zn2+] < [Cu2+] (Q < 1), Ecell is higher than the
standard cell potential.
As the reaction proceeds, [Zn2+] decreases and [Cu2+] increases, so
Ecell drops. Eventually the system reaches equilibrium and the cell can
no longer do work.
21-73
Thermodynamic calculations
Free Energy and Cell Potential
0
wmax G nFE
n:
F:
G RTlnK nFE
RT
so E
lnK
nF
0
At equilibrium: G0 = 0 and K = Q
At 298 K:
0.0592
E
logK
n
0
Nernst Equation
Under nonstandard conditions
0
G G RTlnQ
0
E cell
RT
E
lnQ
nF
298K
E cell
0.0592
E
lnQ
n
or
E E0
0.059
log [ Mn (aq) ]
n
Nerst equation
Ox / Re d
0
Ox / Re d
RT
ln a
nF
RT
2.3
0.059, that
F
Ox / Re d
0
Ox / Re d
0.059
lg a
n
aA bB cC dD
The Nerst equation may be written as:
Where
is the standard free energy for the reaction.
Significance. The above equation helps us to predict the
feasibility of the cell reaction. For a cell reaction to be
spontaneous,
must be negative. This means that E must
be positive for a spontaneous cell reaction.
0.059
E E
log a A z
n
0
KCl, AgCl | Ag
Fe3+ , Fe2+ | Pt
Fe3+ + e = Fe2+
FeCl3 + FeCl2
E Fe3 / Fe2 E
0
Fe3 / Fe 2
0.059 lg
aFe3
aFe2
Quinonhydrone electrode
(the third reference electrode)
642, 64()2, H+ | Pt
642 + 2+ + 2 = 64()2
Ecell
aC6 H 4 (OH ) 2
0.059
E
lg
2
2
C6 H 4O2
0
Ecell E 0.059 lg aH
0
Quinonhydrone
H+
ClEcell
u Kt u An 0.059 a1
lg
u Kt u An n
a2
where a1 > a2
HCl 0.1
-
+
+
+
+
+
+
+
+
+
(+)
>
AgNO3, C1
Concentration Cells
. . . a cell in which both compartments
have the same components but at
different concentrations
17_366
e
e
Ag
e
Porous
disk
0.1 M Ag +
0.1 M NO 3
Anode
e
Ag
1 M Ag +
1 M NO 3
Cathode
17_369
Reference solution of
dilute hydrochloric acid
Thin-walled membrane
Concentration Cell
Cell potential depends on concentration.
Concentration Cell is a cell in which both
compartments have the same components
but at different concentrations.
The difference in concentration is the only
factor that produces a cell potential and
the voltages are typically small.
Figure 17.9 A Concentration Cell That Contains a Sliver Electrode and Aqueous Silver Nitrate in Both Compartments
Concentration Cells
A concentration cell exploits the effect of concentration
changes on cell potential.
The cell has the same half-reaction in both cell
compartments, but with different concentrations of
electrolyte:
Cu(s) Cu2+(aq; 0.10 M) + 2e[anode; oxidation]
Cu2+(aq; 1.0 M) Cu(s)
[cathode; reduction]
Cu2+(aq; 1.0 M) Cu2+(aq; 0.10 M)
21-
Oxidation half-reaction
Cu(s) Cu2+(aq, 0.1 M) + 2eReduction half-reaction
Cu2+(aq, 1.0 M) + 2e- Cu(s)
Overall (cell) reaction
Cu2+(aq,1.0 M) Cu2+(aq, 0.1 M)
21-
21-
21-
+
0.0592 V log [Ag ]dil
[Ag+]conc
1
4.0x10-4
0.0592 log
0.010
= 0.0828 V
Figure 21.13
21-
21-
Species Detected
Typical Sample
NH3/NH4+
CO2/HCO3-
Blood, groundwater
F-
Br-
I-
Milk, pharmaceuticals
NO3-
K+
H+
Electrochemistry
Commercial Galvanic Cells
Galvanic cells can be self-contained and portable and can
be used as batteries and fuel cells
1. A battery (storage cell) is a galvanic cell (or a series of galvanic
cells) that contains all the reactants needed to produce electricity.
2. A fuel cell is a galvanic cell that requires a constant external
supply of one or more reactants in order to generate electricity.
Electrochemistry
Two basic kinds of batteries
1. Disposable, or primary, batteries in which the electrode reactions are
effectively irreversible and which cannot be recharged
2. Rechargeable, or secondary, batteries, which form an insoluble product
that adheres to the electrodes; can be recharged by applying an electrical
potential in the reverse direction, which temporarily converts a
rechargeable battery from a galvanic cell to an electrolytic cell
Batteries
Lithium-iodine battery
Water-free battery
Consists of two cells separated by a
metallic nickel mesh that collects
charge from the anodes
The anode is lithium metal, and the
cathode is a solid complex of 2
Electrolyte is a layer of solid Li that
allows Li+ ions to diffuse from the
cathode to the anode
Highly reliable and long-lived
Used in cardiac pacemakers, medical
implants, smoke alarms, and in
computers
Disposable
Fuel Cells
A galvanic cell that requires an external supply of reactants
because the products of the reaction are continuously removed
Does not store electrical energy but allows electrical energy to
be extracted directly from a chemical reaction
Have reliability problems and are costly
Used in space vehicles
21-
Figure 21.15
Anode (oxidation):
Alkaline battery.
21-
Figure 21.16
Anode (oxidation):
Ecell = 1.6 V
The mercury battery uses HgO as the oxidizing agent instead of
Ag2O and has cell potential of 1.3 V.
21-
Figure 21.17
Lithium battery.
The primary lithium battery is widely used
in watches, implanted medical devices,
and remote-control devices.
Anode (oxidation):
3.5Li(s) 3.5Li+ + 3.5eCathode (reduction):
AgV2O5.5 + 3.5Li- + 3.5e- Li3.5V2O5.5
Overall (cell) reaction:
AgV2O5.5 + 3.5Li(s) Li3.5V2O5.5
21-
Figure 21.18
Lead-acid battery.
21-
Cathode (reduction):
PbO2(s) + 3H+(aq) + HSO4-(aq) + 2e- PbSO4(s) + 2H2O(l)
Overall (cell) reaction (discharge):
PbO2(s) + Pb(s) + H2SO4(aq) 2PbSO4(s) + 2H2O(l) Ecell = 2.1 V
Overall (cell) reaction (recharge):
2PbSO4(s) + 2H2O(l) PbO2(s) + Pb(s) + H2SO4(aq)
21-
Figure 21.19
Anode (oxidation):
Cathode (reduction):
21-
Figure 21.20
Lithium-ion battery.
Anode (oxidation):
LixC6(s) xLi+ + xe- + C6(s)
Cathode (reduction):
Li1-xMn2O4(s) + xLi+ + xe- LiMn2O4(s)
Overall (cell) reaction:
LixC6(s) + Li1-xMn2O4(s) LiMn2O4(s)
Ecell = 3.7 V
21-
Fuel Cells
In a fuel cell, also called a flow cell, reactants enter the
cell and products leave, generating electricity through
controlled combustion.
Reaction rates are lower in fuel cells than in other
batteries, so an electrocatalyst is used to decrease
the activation energy.
21-
Figure 21.21
Anode (oxidation):
21-