Lecture 39

Chapter 20 Electrochemistry
 Chapter 20: Electrochemistry
Electrochemistry is the study of the relationships between electricity
(movement of charge) and chemical reactions.

It includes the study of both spontaneous and nonspontaneous processes.

Two incredibly important processes:

1. Using electrons to make stuff (electrolytic cells).

Examples: Electroplating. Production of Aluminum.

2. Using chemical reactions to produce electricity (Galvanic or voltaic

cells).
Batteries.

Liquid fuels (like gasoline): chemical energy stored in atoms/compounds

Batteries: Electrical energy stored in atoms/ compounds.
2
First step: Where to the electrons come from?
Where do they go?
Must Assign Oxidation Numbers (as a Reminder)

1. Elements (pure substance) = 0

2. Monatomic ion = charge
3. F: –1
4. O: –2 (unless peroxide = –1)
5. H: +1 (unless a metal hydride = –1)
6. The sum of the oxidation numbers equals the overall
charge (0 in a compound).

3
 Oxidation Numbers in “REDOX” reactions
§ To keep track of which chemical species loses electrons and what gains them,
we assign oxidation numbers.
§ If the oxidation number increases for an element, that element is oxidized
(loss of electron).
§ If the oxidation number decreases for an element, that element is reduced
(gain of electron).

Oxidation number:

§ H+ (reduced) causes oxidation of something else (here, Zn). Thus, it is

called an “oxidizing agent”
§ Zn (oxidized) causes reduction of something else (here H+). Thus, it is
called a ”reducing agent”.
4
 Balancing Redox Equations:
The Half-Reaction Method

1) Make two half-reactions

(oxidation and reduction).
2) Balance elements other than O and H.
3) Balance O and H using H2O/H+.
4) Add electrons to balance charges.
5) Multiply by common factor to make
electrons in each half-reaction equal.
6) Add the half-reactions.
7) Simplify by dividing by
–
common factor or
converting H to OH if basic.
+

8) Double-check:
1) Element balance
2) charge balance!

5
 The Half-Reaction
Consider Method
the reaction between MnO4– and C2O42–:
+7 +3 Reduction
+2 Half-Reaction
+4
Example: MnO4–(aq) + C2O42–(aq) ¾¾® Mn (aq) + CO2(aq)
2+

2 half reactions: MnO4 ¾¾® Mn – 2+

Mn is reduced (+7 ® +2) Reduction Half-Reaction

• Assigning oxidation
C is oxidized numbers shows
(+3 ® +4). that Mn
is
The C is MnO
andmanganese
reduced (+7 ® +2)Reduction is¾¾®
–
balanced;
4Half-Reaction
oxidized Mn2+
to balance
(+3 ® +4).
the oxygen,
Reduction weHalf-Reaction
must add four waters to
the right side:
MnO – ¾¾® Mn2+
The manganese is balanced; to balanc
4
Reduction Half-Reaction
the oxygen,
a. Balance atoms other than O The manganese we must add four waters t
is balanced;
and H a. Balance atoms other than
Thethe right
manganese 4 ¾¾®
MnOside:– Mn2+ + 4
is balanced; toHbalance
2O
O and H the oxygen, we must add four waters to
to balance the oxygen, we must add four waters to
b. Balance
a.OBalance
with water.
atoms other the
thethan right side: the
4 ¾¾®
right side: MnO – Mn2+ we+ 4 add
H2O
b. Balance O with water. To balance hydrogen,
O and H 8 H + + MnO – ¾¾® Mn2+ + 4 H O
c. Balance +H with H+
To 8H+ the
balance to the left
4
hydrogen, side:
we add 8H
2
+ to the left side:
c. Balance H with H
a. Balance atoms other than MnO 4 ¾¾®
– Mn2+ + 4 Hwe 2O add
b. Balance O with water. To balance the hydrogen,
O d.
and H
Balance charge To balance
+ the charge, we add 5e – to
c. Balance H with H + 8H
8 H to+ the
+ MnO left
4 side:
– ¾¾® Mn + 4 H2O
2+
with e- the
To left side:the hydrogen, we add
balance
b. Balance O with water.
d. Balance charge with e- + To balance
+ the charge, we add 5e– to the left side:
c. Balance H with H 8H to8 the
H+ +left
MnOside:– ¾¾® Mn2+ + 4 H O
4 2
5e + 8 H + MnO4 ¾¾® Mn + 46 H2O
– + – 2+

+ – 2+
 An example:
The Half-Reaction Method–
Consider the reaction between MnO4 and C2O42–:
Example: +7 +3 +2 +4
MnO4–(aq) + C2O42–(aq) ¾¾® Mn2+(aq) + CO2(aq)
Oxidation Half-Reaction
Mn is reduced (+7 ® +2) and C is oxidized (+3 ® +4).
• Assigning oxidation numbers shows
Oxidation
that Mn is
Half-Reaction
a. Balance atoms other than O and H
reduced (+7 ® +2) and C is oxidized (+3 ® +4).
2– ¾¾® CO
Oxidation
C O Half-Reaction
Oxidation Half-Reaction
2 4 2
Oxidation Half-Reaction
Oxidation Half-Reaction
a. Balance atoms other than O To balance the carbon, we add a coefficient of 2:
and H To balance the carbon, we add a
2– ¾¾® 2 CO
b. Balance O with water. coefficientCof 2O2:4 2
b. Balance O with water. C2O4 ¾¾® 2 CO2
2–
c. Balance H with H +
b. Balance O with water
c. Balance H with(skip)
H+ The oxygen is now balanced as well.
The oxygenC2O4is2–now ¾¾® balanced
2 CO2as well.
d. Balance
c. Balance H withcharge ToThe
H+ (skip)with e- There is nooxygen
balance is now balanced
thereaction.
H in the charge, we mustas add well.
d. Balance charge with e- twoToelectrons
balanceto thethecharge, we must add
right side:
d. Balance charge with e- two electrons
To balance the charge, to we the
mustright side:
add two electrons
to the right side:
C2O42– ¾¾® 2 CO2 + 2e–
C2O42– ¾¾® 2 CO2 + 2e–
7
 8 H + MnO4 ¾¾® Mn + 4 H2O
d. Balance charge with e-To balance the charge, we must add
The Half-Reaction Method: combine
two electrons theright
to the twoside:
half-reactions
d. Balance charge To balance the charge, we add 5e– to
with e- the left side:
Oxidation Half-Reaction C2O42– ¾¾® 2 CO2 + 2e–
Combine the half reactions
5e– + 8 H+ + MnO4– ¾¾® Mn2+ + 4 H2O
Reduction Half-Reaction
Combineand the balance:
half reactions
The number of electrons must be equal on each
Balance the half reactions. Combine
side,:
the half reactions
and balance:
and
multiply5 the
C2O
2–balance:
first ¾¾® by
4 reaction 105,CO 2 + 10e
second by –2:
10e– +516 – ¾¾® 2 Mn–2+ + 8 H O
C2H +2
O+42– MnO410
¾¾® CO2 + 10e 2

10e – + 16 H+ + 2 MnO – ¾¾® 2 Mn2+ + 8 H O

10e – + 16 H + + 2 MnO –4+ 5 C O 2– ¾¾® 2
Add the two reactions When we add these together,
4 2 we
4 get
Cancel out common species 2 Mn2+ + 8 H2O + 10 CO2 +10e–
(10 e-):
When we add these together, we get
10e– + 16 H+ + 2 MnO4– + 5 C2O42– ¾¾®
10eThe
– + only
16 Hthing that 2appears
+ + 2 MnO –Mn2+ + on both
8 H2–O +sides
4 + 5 C2O4 2 ¾¾®
10 COis the
2 +10e
–
electrons. Subtracting 2+ them, we are left with
2 Mn + 8 H2O + 10 CO2 +10e–
The final equation: 16 H+ + 2 MnO4– + 5 C2O42– ¾¾®
2 Mn2+ + 8 H2O + 10 CO2
(Verify that the equation is balanced by counting atoms
and charges
Verify that the equation is balanced by on each side
counting of the and
atoms equation.)
charges on each side!
8
 Spontaneous
Spontaneous REDOXRedox
reactionreaction
metallic zinc
rod
metallic
copper
forming
CuSO4
solution

9
 Galvanic (Voltaic) Cell
Galvanic
Instead of letting electrons (Voltaic)
go from Cell to the other directly,
one molecule
we redirect them through a wire and SEPARATE the two half reactions.
But what if you SEPARATED the two half reactions?
A setup
Electrons thenlike this is acalled
run through ELECTROCHEMICAL
an one
wire from half reaction to the other.CELL.
A setup like this is called an ELECTROCHEMICAL CELL.

electrons flow
to this side (positive)!
from this side…
(—) (+)

OXIDATION SIDE: REDUCTION SIDE:

!! !!
Cu(2+aq ) + 2e− ↽!⇀
! Cu( s )
!⇀
−
! Zn( aq ) + 2e
2+
Zn( s ) ↽

ANODE BRIDGE
BRIDGE CATHODE
ANODE
the half side of a cell where allows
allowsions
ions to
to flow
flow CATHODE
the half side of a cell where
theOXIDATION
the half side of occurs
a cell totoclose
close the
the circuit
circuit the
the half side of a cell
REDUCTION occurs
where the OXIDATION occurs (eachside
(each sidemust
must remain
remain where the REDUCTION occurs
electrically
electrically neutral)
neutral)
10
Daniell Cell (~1830s)

11
 Mnemonics…
Mnemonics...
Reduction always occurs at the cathode
Reduction always occurs at the cathode
Oxidation
Oxidation always occurs
always occurs the anode
at anode
at the

Two trickstoto
Two tricks remember
remember this: this:

1) Consonants with consonants, vowels with vowels:

Reduction at the Cathode

Oxidation at the Anode

REDCAT
2)
REDuction at the CAThode
12
 ELECTROMOTIVE FORCE (EMF)
As Water flows spontaneously Down a waterfall…
electrons flow spontaneously one way in a redox reaction,
Both from high to low potential energy.

§ electromotive force (emf) or

Oxidation
§ cell potential designated Ecell.
§ The potential difference between the
anode and cathode
§ The relative propensity of one species to
oxidize, versus another specie’s
Ecell propensity to reduce.

§ measured in volts (V).

§ volt = one joule per coulomb
§ (1 V = 1 J/C).
Reduction

“If the Gibbs free energy is negative for a

redox reaction, you’ve got an Electromotive
Energy ≡ Potential × Current × Time Force.”
13
 A Daniell cell at standard conditions gives a difference of po
1.1 V, with the zinc side more negative than the copper side
Standard Cell Potential/Reference cell potential will flow from the zinc to the copper.
Eo = 1.1 V
The standard conditions for electrochemical
negative electrode positive electrode
reaction: anode cathode
§ The concentration of all solutions is 1 M
§ Gas pressures are 1 bar (often 1 atm is used)
§ T = 25 oC (298 K), unless otherwise noted

Such “standard cell potentials” are denoted Eo.

Standard
Reference Hydrogen
electrode Electrode (SHE)
(standard hydrogen
The “ZERO” electrode-SHE)
for electrical potentials:

!! 1
H(+aq ) + e− ↽!⇀
! H 2( g )
§ All cell potentials are relative. 2

§ You need an arbitrary standard:

when [H+] = 1 M (pH = 0) and
§ the REDUCTION potential for hydrogen P(H2is) =0 1V:bar,
then we define the potential
§ Every other potential is relative to hydrogen.
of this half-reaction as being

2H + (aq, 1M) + 2e ¾® H2(g, 1 atm)

– 0.0 volts, precisely.

Every other electrical potential is

E =0V
o
then referenced relative to this
electrode.
14
 Standard
By international convention, Cell Potentials
the standard half-cell potential of
reactions
All standardare compiled
half-cell as reduction
potentials potential.
are compiled as reduction potential.

the species the reduced form

being reduced of that species
Ex:
(
Standard Cell )
Potentials
!!
Cu(2+aq ) + 2e− ↽!⇀
! Cu( s )
o
Ered Cu 2+ / Cu = 0.34 V vs. SHE

a reduction reaction
a reduction the reference
Since oxidation reactions arepotential
reduction reactions run backwards.
potential
The standard potential of an oxidation reaction
The standard potential of an oxidation reaction is the negative of the reduction.
is the
Just run negative
it backwards, of the
the reduction.
sign changes.
The more positive the reduction potential is, the easier it is for the
species to accept an electron / be reduced 2+ / act as an oxidant.
Ex: !!
Zn(2+aq ) + 2e− ↽ ⇀
!! ( s )
Zn E o
red (
Zn )
/ Zn = −0.76 V vs. SHE
a reduction reaction this is what we find in a redox table

!!
Zn( s ) ↽!⇀
! Zn( aq ) + 2e
2+ −
( )
Eoxo Zn / Zn 2+ = −Ered
o
(
Zn 2+ / Zn )
an oxidation reaction = 0.76 V vs. SHE
(inverse of reduction!) 15
 potential potential
Standard Reduction Potentials
The more positive the reduction potential is, the easier it is for the
Here’s the table you’ll get.
species to accept an electron / be reduced / act as an oxidant.
Standard Reduction Potentials (vs. SHE) at 25 oC, in Aqueous Solutions

More “positive” Eo (
E o F2 / F − ) = 2.87 V (
E o Fe 3+ / Fe ) = −0.04 V

Bestoxidants
oxidants (O ,H / O ) ( )
+
= 2.08 V E o CO 2 ,H + / CO = −0.11 V
§ Better
o
E 3 2

E o
(S O / SO ) 2− 2−
= 2.01 V E o
( Pb / Pb )
2+
= −0.13 V

Easiestto to
be reduce
2 8 4

§ Easiest reduced Eo ( Ag / Ag ) 2+ +
= 1.98 V Eo (Sn / Sn )
2+
= −0.13 V

( Au / Au ) +
= 1.83 V ( Ni / Ni) = −0.25 V
Electron grabbers.
o o 2+

§ Electron grabbers
E E
Eo (Co / Co ) 3+ 2+
= 1.82 V Eo (V / V )
3+ 2+
= −0.26 V

§ Better cathode Eo ( H O ,H / H O)
2 2
+
2 = 1.76 V Eo (Co / Co )
2+
= −0.28 V
E o
( PbO ,H ,SO / PbSO )
2
+ −
4 4 = 1.69 V E o
( In / In )
3+
= −0.34 V
Eo ( Au / Au ) 3+
= 1.52 V Eo ( Eu / Eu )
3+ 2+
= −0.35 V
E o
( MnO ,H / Mn ) −
4
+ 2+
= 1.51 V E o
( PbSO / Pb,SO )
4
2−
4 = −0.36 V
Eo (Cl / Cl )
2
−
= 1.36 V E o ( PbI2 / Pb ) = −0.37 V
E o
(Cr O ,H / Cr )
2
2−
7
+ 3+
= 1.33 V o
(
E Cd / Cd 2+
) = −0.40 V
Eo (O ,H / H O)
2
+
2 = 1.23 V (
E o Cr 3+ / Cr 2+ ) = −0.42 V
E o
( IO ,H / I )
−
3
+
2 = 1.20 V E o
( Fe / Fe )
2+
= −0.44 V
Eo ( Br / Br )
2
−
= 1.07 V Eo (Cr / Cr )
3+
= −0.74 V
Eo ( NO ,H / NO) −
3
+
= 0.96 V Eo ( Zn / Zn )
2+
= −0.76 V
E o
( Hg / Hg ) 2+
= 0.85 V E o
( H O / H ,OH )
2 2
−
= −0.83 V
Eo ( Ag / Ag ) +
= 0.80 V Eo ( V / V)
2+
= −1.13 V
E o
( Fe / Fe ) 3+ 2+
= 0.77 V E o
( Mn / Mn )
2+
= −1.19 V
Eo (O ,H / H O )
2
+
2 2 = 0.70 V Eo ( Al / Al)
3+
= −1.66 V
E o
(I / I )
2
−
= 0.54 V E o
( Eu / Eu )
3+
= −1.99 V
Eo (I / I )
− −
= 0.53 V Eo ( Mg / Mg )
2+
= −2.37 V
More “negative” Eo
3

E o
(Cu / Cu ) +
= 0.52 V E o
( Na / Na )
+
= −2.71 V

(O / OH ) (Ca / Ca )
§ Better reducers
−
Eo 2 = 0.40 V Eo 2+
= −2.87 V

(
E o ⎡⎣ Fe ( CN )6 ⎤⎦ / ⎡⎣ Fe ( CN )6 ⎤⎦
3− 4−
) = 0.36 V Eo (Sr / Sr )
2+
= −2.90 V
o
(
E Cu / Cu 2+
) = 0.34 V E o
( Ba / Ba )
2+
= −2.91 V § Best reducers
Easiest to oxidize
E o ( AgCl / Ag ) = 0.22 V Eo (K / K )
+
= −2.93 V
§ Electron
Easiest givers
to reduce
o
(
E Cu / Cu 2+ +
) = 0.16 V E o
( Rb / Rb )
+
= −2.98 V

(
E o Sn 4+ / Sn 2+ ) = 0.15 V Eo (Cs / Cs)
+
= −3.03 V § Better anode
Electron givers
E o
(H +
/ H2 ) = 0.00 V E o
( Li / Li)
+
= −3.04 V
 Standard
Standard Cell Cell Potentials
Potentials
Standard Cell Potentials
Standard
Therefore:
Therefore: the the total
total
Cell
potential is
potential
Potentials
Therefore: the total potential is the DIFFERENCE of the reductio
is the
the DIFFERENCE
DIFFERENCE of of
thethe
reduction potentials
reduction
between the cathode and the anode (always “Reduction” part first):
potentials between
potentials betweenthe cathode
the cathodeand theand
anode:
the anode:
Therefore: the total potential is the DIFFERENCE of the reduction
potentials between ⎛ cathode
o theo cathode ⎛ ⎞ the
and o ⎛ anode:
anode ⎞ anode
Etot = Ered
o ⎜ ⎟ + Eox ⎜ ⎞
cathode o ⎛
⎟
⎞
Etot ⎝=reduction
o
Ered ⎜ ⎠ + Eox ⎜⎠
⎝ oxidation
⎟ ⎟⎠
⎛ ⎝ reduction
cathode ⎞ ⎠ ⎛ ⎝
anode ⎞
oxidation
o
Etot = Ered
o
⎜⎝ reduction ⎟⎠ + E o
ox ⎜
⎝ oxidation ⎟⎠
o ⎛
cathode ⎞ o ⎛
anode ⎞
Etot = Ered ⎜
o
⎟ − Ered ⎜ ⎟⎠ anode
o ⎝ oxidation ⎛ cathode
⎠ ⎞
⎝ reductiono ⎛ ⎞
Etot = E⎛redcathode
o
⎜ ⎞ ⎟ −⎛Eanode
red ⎜ ⎞ ⎟⎠
Etot = Ered ⎜
o o ⎝ oxidation ⎠
− Ered ⎜
o ⎝ reduction
⎟ ⎟⎠
red ( Cu / Cu ) = 0.34 V vs. SHE
ex: Daniell Cell ⎝Eoxidation
o 2+ ⎠ ⎝ reduction

(E (Cu ( ) / Cu ) = 0.34
) V vs. SHE
—
Zn(ex: ex:
Zn 2+
s ) Daniell
( aq )Daniell
2+
Cell
Cell( aq ) Cu
Cu (s) o
Ered Zn
o
E/redZn2+Cu
2+ 2+
= −0.76 = 0.34
/ CuV vs. SHE V vs. SHE
!#"ex: #$Daniell !#" Cell
#$ o
—
( )
anode half-cell cathode half-cell red
Zn( s ) Zn2+(2+aq ) Cu 2+
2+ ( aq ) Cu ( s ) — oE o = 1.10/ Zn
2+ V vs.=SHE
−0.76 V vs. SHE
Zn#
!
! # "
Zn#
( s )"
# $
$
( aq
anode half-cell
) Cu
!
!#
( aq#
)"
"
Cu#
#
( s )$
$
cathode half-cell
E o
red ( / Zn ) = −0.76 V vs. SHE
E
red
Zn
Zn
tot
2+

tot =V
anode half-cell cathode half-cell o
E
E = 1.10
o 1.10 V vs. SHE
vs. SHE
tot
17
 Galvanic
Galvanic CellCell Example
Example
Start with: unbalanced redox reaction
Build a galvanic cell using the unbalanced redox reaction:

Cr2O 2−
7( aq )
+ I −
( aq )
!
↽!⇀
!! Cr( aq ) + I2( s )
3+

is spontaneous in acidic conditions.

Lets build a galvanic cell using this reaction.
We need to:
We need to:
A. Define the reaction occuring at the anode (oxidation),
B. Define the reaction at the cathode (reduction)
A.the
C. Show Define theof reaction
direction occuring at the anode (oxidation),
electron migration
D. Show the direction of ion migration
B.the
E. Show Define
signs ofthe
the reaction
electrodes at the cathode (reduction)
C. Show the direction of electron migration
D. Show the direction of ion migration
E. Show the signs of the electrodes 18
 Start with: unbalanced redox reaction
Galvanic Cell Example
Cr2O 2−
7( aq )
+ I − !!⇀
( aq ) ↽!! ( aq ) + I2( s )
Cr 3+

Oxidation numbers: +6 -1 +3 0
Galvanic Cell Example
A. Define the reaction occurring at the anode (oxidation),
is 2−
spontaneous in acidic3+conditions.
B. Define the reaction
Cr O +I
7( aqbuild
2 Lets )
−
at the cathode
)
!!
↽!⇀
! Cr
(reduction)
(aaqgalvanic ( aqusing
) +I
( s ) reaction.
cell 2this
The balanced redox reaction is
The
We
balanced
need to:
redox reaction is
oxidation
oxidation: 6I−- ↽
6I !!⇀
!! 3I 3I
+ 6e
2 +− 6e-
Anode ( aq ) 2( s )

+6 A.2−Define the
2- +
+ reaction
− !!occuring
⇀ 3+ at the anode (oxida
reduction:
Reduction Cr2O
+6Cr
2 O77( aq+ 14H+(+
14H + 6e
aq )6e
- ↽!! 2Cr3+
2Cr )++7H
7H22O
O(l)(l )
Cathode
B. Define the reaction at the ( aq
) cathode (reduction)
total: C. Show
Cr2O 2− + 6I − the direction
+ 14H + !
↽!⇀
!of2Cr
! electron
3+
+ migration
3I + 7H 2O(l )
7( aq ) ( )
aq ( )
aq ( )
aq 2( s )
D. Show the direction of ion migration
E. Show the signs of the electrodes
As always,
the oxidation occurs at the anode,
the reduction occurs at the cathode.

We need to: 19
 Example:
Example:
Example:
Last lecture
Last lecture we
we
Galvanic
Last lecture we claimed
claimed
claimed
that theCell
that
that thethe Example
following
following
redox reaction was
following
redoxredox reaction
reaction was was
spontaneous as written:
spontaneous
spontaneous as written:
The balanced redoxwritten:
reaction is
Cr2O2−2−
7( aq )
+ 6I −
+ 14H + !
↽ !⇀
!! 2Cr ( aq ) + 3+
3+
3I2( s ) + 7H 2O(l )
− (−aq ) +( aq+ )
! ! ⇀
O ) ++6I
Cr2O
Cr 2−
6I + 14H
+ 14H aq ) ↽! !
!!
↽ ⇀
2Cr
! !
3+
2Cr + 3I2( s+) +3I7H 2O + 7H 2O(l )
2 77((aq
aq ) ( aq )
( aq ) ( ( aq ) ( aq ) ( aq ) 2( s ) ( l )

From the table:

From the
From thetable:
table:
From the table:
o
(
2−
)
Ered Cr2O 7 / Cr 3+ = 1.33 V vs. SHE most POSITIVE of the two: reduction
Eredo
(( Cr O 2−
/
)
Cr )
3+
= 1.33 V vs. SHE most POSITIVE of the two: reduction
(( )
2 7−
Ered
o
o Ered I2 /2−
Cr O I /= Cr0.54
3+ V vs. SHE
= 1.33 V vs. most NEGATIVE of the two: oxidation
SHE most POSITIVE of the two: reductio
2 7−
)
Ered I2 / I = 0.54 V vs. SHE
o
most NEGATIVE of the two: oxidation

( )
positive:
So the total
− potential:
Ered I2 / I = 0.54 V vs. SHE
o
most NEGATIVE of the two:spontaneous!
oxidation
positive:
So the total potential:
Etoto
= Eredo
( Cr2O 2− / Cr )
3+
− E o
( I) / I −
= 1.33 V − 0.54 V = 0.79 Vspontaneous!
( ) ( )
7 red 2
positi
So Etheo
tot = total
E o
red potential:
Cr O
2 7
2−
/ Cr 3+
− E o
red I 2 / I −
= 1.33 V − 0.54 V = 0.79 V spontan
o
Etot = Ered
o
(
Cr2O 2−
7 / Cr 3+
− E)o
red I 2(/ I −

C. Show the direction of electron migration

)
= 1.33 V − 0.54 V = 0.79 V
D. Show the direction of ion migration from the salt bridge
E. Show the signs of the electrodes 20
 Potential and Thermodynamics
A galvanic cell is just another chemical reaction.

Therefore:
The laws of Thermodynamics should apply Exactly as it did
for any other chemical reaction.

This means the relationships between Work, Free Energy

and Equilibrium should be exactly the same as for any
other chemical reaction

21
 For any electrical current:
Potential and Thermodynamics
Potential and(coulomb
Work( joule) = Charge transferred Thermodynamic
) × Cell potential ( volt )
First, let’s look at electrical work. For any electrical current:
The work obtained from a galvanic cell is therefore:
Charge transferred = transferred (coulomb) × Cell potential (volt)
otential and Thermodynamicsvolt
Work(joule) = Charge
moles of electrons transferred (n) x charge of one mole of electrons
1 Charge
Work(
mole joule) = Charge
oftransferred
electrons = moles transferred (
of electrons transferred
= 96,485 coulombs coulomb ×(F):
(n) x charge
= 1 Faraday )
Cellof potential
one mole of ( )
work obtained from a galvanic cell is therefore:
electrons = 96,485 coulombs = 1 Faraday (F):

Work =
F = (1.602…× 10 C ) × ( 6.022…× 10 mol ) = 96485… C ⋅ mol
nFE −19
o 23 −1 −1

joule) =!Charge
###"### $ !###
transferred ( coulomb
"###) × Cell
$ potential ( volt )
maximum work = −ΔG
charge of 1 electron # of electrons per mole o
From basic Thermodynamics:
Work = nFE o
From basic Thermodynamics:
maximum work = −ΔG o

So: ΔG o
= −nFE o
asic Thermodynamics: maximum work = −ΔG
spontaneous reactions: negative oΔG o / positive Eo!

The ⇒standard
spontaneous free energynegative
reactions: depends ΔGo onand the equation
positive Eo! used to represe
heo reaction:
Gwe =
The
−nFE if
cell potential we
o does multiply
NOT change
spontaneousthe reaction
though: by
it remains
reactions: two,
always
negative ΔG then
othe
/ we
same need
noE
positive matter
o! TWIC
how
write the equation!
as much energy to do the change. The cell potential does NOT
ndard
change free
§ Energy is energy
though: depends
it remains
an EXTENSIVE onwhereas
always
property, the the
equation
sameisused
potential no to represent
matter
an INTENSIVE how we writ
property...)
22
ntial and Thermodynamics
Work = nFE o

Thermodynamics
Potential also
and gave the relationship between Free En
Thermodynamics
o gave andFrom
the the basic Thermodynamics:
Equilibrium
relationship Constant:
between Free Energy maximum work = −ΔG
amics
Constant:also
The gave the
relationship relationship
between the standard between Free
free energy and theEnergy
standard redox
uilibrium Constant:o
potential:
So: ΔG = −nFE o spontaneous reactions: negative ΔGo / po

The The standard

relation between the free
free energyΔG o
=
depends
energy and the −RT onln
equilibrium K
the equation used to
constant:
ΔGthe=reaction:
o
−RToln ifKwe multiply the reaction by two, then we ne
ΔG = −RT ln K
as much energy to do the change. The cell potential does
change
Equating though:
the two So:it
relationships: −nFE
remains
o
=
always −RT ln
the same K no matter how
−nFE o
= relationship
−RToln(energy
the equation! K the is an EXTENSIVE property, whereas p
Yielding −nFE =property…)
the
So:an INTENSIVE −RT lnstandard
between K redox potential and equilibrium
constant:
RT
RT or: E o
= ln K
E = Eln
o
o K RT nF
or: nF = ln K
nF
23
verything we’ve done only applies at standard conditions.
The Nernst Equation
-All reactants at 1 M concentration
-Temperature at 298 K.
-GasesAllallthe
at 1relationships
atm. that we derived only applies under standard conditions.
-All reactants at 1 M concentration
Why? -T=298 K.
The Nernst
-Gases all at 1 atm. Equation
ecause we’re using the Standard Reduction
otential:
Why?
So: Because we are using the Standard Reduction Potential:
−nFE = −RT
Whato happens ifln
the
K reactionAnd
is not under
those are “standard conditions”?
all at standard
-what if the concentrations of the solutions are not all 1 M?
conditions.
nd those are all atifstandard
What happens conditions.
the reaction is not under “standard conditions”?
Theif equation
What that gives
the concentrations of the potentialare
the solutions in non-standard
not all 1 M? conditions is
called the NERNST EQUATION:
NERNST EQUATION: The equation that gives the potential under non-standard
conditions
Q = reaction quotient
[products]
RT Q=
E=E −
o
lnQ [reactants]
potential under nF
any conditions
specific concentrations used
potential under
(if all concentrations = 1 M,
standard conditions 24
then Q = 1 and ln Q = 0)
 - The Nernst Equation - Example
Using the Nernst Equation: Calculate the cell potential when the
concentration ofTheZn2+ ions inEquation
Nernst the anode-half-cell
Example has increased to
1.5 M and the- concentration of Cu2+ Calculate
Using the Nernst Equation: ions in the cathode
the cell potentialhalf-cell
when the
Using the
has decreased concentration
Nernst Equation:
to 0.50 M. of Zn 2+ ions in the anode half-cell has increased to
Calculate the cell potential when the concentration
of Zn ions in the
2+ 1.5anode
M and half-cell
the concentration of Cuto 1.5
has increased 2+ ionsMinand
the the
cathode half-cell
concentration
hascathode
of Cu2+ ions in the decreased to 0.50
half-cell M.decreased to 0.50 M.
has
RT
ernst Equation
E = E − E = ElnQ -o −Example
o
RT
lnQ
nFThenFNernst Equation - Ex
The standard cell potential for a Daniell
.0257V cell at 25 oC is 1.10 V:
The standard cell1.1V
potential for alnQ
Daniell cell at 25 C is 1.10 V:
o
The standard cell potential forE a= Daniell
− the
ost” constant potential until
reaction is all completed! -
Using cell2Nernst Equation:
at 25 oC is 1.10 V: Calculate the cell potent

( ) ( )
=
concentration of Znmost
2+ ions in the anode half-cell has
= 0.34 V vs. SHE
o 2+
o
E Cu / Cu 2+ E Cu / Cu 0.34 V vs. SHE
most
1.5 M and the positivepositive Ered: cathode
Ered: of
concentration cathode side
side
Cu2+ ions in the cath
o 2+
o
(
E ( Zn / Zn ) = −0.76 V vs. SHE
2+
)
E Zn / Zn = −0.76has decreased
V vs. SHE to 0.50
most M.
negative Ered: anode side
most negative Ered: anode side
he potential drops significantly when the ions in one of the
Remember: standard conditionscell
The standard mean that [Znfor
potential 2+] a
=Daniell
1.0 M incell
theat 25 oC
half-cell (here, the Cu2+ in the cathode side) are almost
Remember: standard
Remember: anode
standard conditions
half-cell meanthat
AND
conditions that
[Cu
mean [Zn ]=
2+]2+=
RTthat 1.0
1.0 MM
[Znin2+in
the
] the
= anode
cathode
1.0 M half-cell
half-cell.
in the
depleted
AND that [Cu ] = 1.0 M in the cathode half-cell.
2+ E = E o
− lnQ
anode half-cell AND that [Cu2+] = 1.0 M nF in the cathode half-cell.
−1 −1
8.314 JK mole (298K ) 1.5M
Zn( s ) + Cu( aq ) ⎯⎯
2+
→ Zn( aq ) + Cu( s )
2+ E = 1.1V − ln
2(96485Coulombs / mole) 0.5M
start with 1M Cu2+ and 1 M Zn2+, when the reaction .0257V
E = 1.1V − ln 3
be completed, there will be 0 M Cu2+ left and 2 M 2
Zn2+ produced… E = 1.1V − 0.014V = 1.086V 25
 The Nernst Equation - Example
The Nernst Equation - Example

.0257V
1.2 “almost” constant potential until E = 1.1V − lnQ
the reaction is all completed! 2

1.0

the potential drops significantly when the ions in one of the

0.8 half-cell (here, the Cu2+ in the cathode side) are almost
Cell Potential (V)

depleted

0.6
Zn( s ) + Cu(2+aq ) ⎯⎯
→ Zn(2+aq ) + Cu( s )
0.4
if we start with 1M Cu2+ and 1 M Zn2+, when the reaction
will be completed, there will be 0 M Cu2+ left and 2 M
Zn2+ produced…
0.2

0.0
1.0 1.2 1.4 1.6 1.8 2.0
2+
Concentration of Zn in anode half-cell (M) 26
 Concentration
What if we built a Galvanic Cells
cell using the same redox reaction on the
anode and cathode? You can do this because they are separated.
What if we built a Galvanic cell using the same redox reaction on the anode
anddo
If we cathode? You by
that, then candefinition
do this because they arepotential
the standard separated.will be zero.

For any such cell the standard potential is zero.

Then what’s the point?
But: the concentration difference in the two half-cells is directly related to the
potential.
The concentration difference in the two half-cells is directly related
to the potential. Therefore a concentration difference is measured by
Therefore,difference.
a potential a concentration
Superdifference is measured by a potential difference.
easy to measure.

RT [anode ions] ⎫ if these two are different,

E= E − o
ln ⎬ then E will not be zero!
=0! nF [cathode ions] ⎭
Cells like this are called CONCENTRATION CELLS.
Cells like this are called
CONCENTRATION CELLS.

27
 Concentration Cells
Concentration Cells
Example: We build a galvanic cell by putting two
wires of zinc metals in two different zinc sulfate
Concentration Cells
solutions: one at 0.10 M and the other at 1.90 M.
Zinc

What is the total potential of this cell?

Example: We build a galvanic cell by putting two wires of zinc metals
Which
in two side is thezinc
different cathode and
sulfate which one
solutions: oneis at
the0.10 M and the other at
Zn2+
anode?
1.90 M. What is the total potential of this cell? Which side is the
cathode and which one is the anode? ZnSO
Low concentration High concentration

RT [anode ions]
E=− ln
nF [cathode ions]
.0257V 0.1
E=− ln
2 1.9
E = .0006V
28
Concentration Cells: pH meters
Concentration cells have another very important application: they form the basis for
one of the most accurate ways of measuring pH.

All we need is a redox reaction which depends on the concentration of H+ ions

29
 pH pH Meters
Meters
Concentration Cells: pH meters pH Meters
In meter,
In a pH a pH the
meter,
a pHthe
Inmeasured measured
potential
meter, comespotential
the measured frompotentialcomes
the difference from
in [H
comes +] ion
from the
the
concentrations onInboth
a pHsides
difference of [H
+meter,
in the+]thin
the glass
measured
ion membrane ofon
potential
concentrations the sensing
comes
both from
sideselectrode.
thethe thin
of
difference in [H ] ion concentrations on both sides of the th
difference in [H +] ion concentrations on both sides of the thin
glass membrane of the sensing electrode.
glass membrane of the ofsensing
glass membrane electrode.
the sensing electrode.
We can think of the redox reactions as being:
We can think of the redox reactions as being:
We can Wethink of the
can think of
+
redox
the redoxreactions
reactions +as asbeing:
bein
RT [H ]out [H ]out
[H ]in
+ E = − RT ln+ [H +] + = −0.02569 V ln [H ++]
=+]in RT
E = − [H
F ln]out in = −0.02569 V ln [H
[H ]out 1 M]outout
1=M E = − ln F + [H =]in−0.02569 V ln 1 M
[H +
[H+]in
= 1M
F make
To [Hthings
]in simpler, let’s change1 the M
1M To make
To make things
logarithm things simpler,
to a base 10:let’s
simpler, change
let’s changethe the
To make things
logarithm
logarithm totoasimpler,
abase
base let’s change
10:10:
+
the
[H ]out = ? M
+ E = −2.30 × 0.02569 V log10 [H ]out
logarithm to a base 10:
E = −2.30 × 0.02569 V log+10 [H + ]out
[H+]out = ? M
(
= 0.0592 V × − log10 [H ]out )
[H+]out = ? M E = −2.30 ×
= 0.0592
0.02569 (
V × −Vloglog
= 59.2 mV × pH 10 10the out
[H +
[H
]
+
)
]out changes by 59.2
potential

= 0.0592= 59.2
(
V ×mV−×log pH [Hevery
10 )
+ thetime the pH changes by on
] potential changes by 59.2
every
outtime the pH changes by on

= 59.2 mV × pH
The potential changes bythe potential
59.2 mV everychanges by 59
every
time the pH changes by one time
unit! the pH changes by
30
 pH Meters
pH Meters
Concentration
pH meter electrode
Example: Cells:
A pHismeter
calibrated pHtometers
electrode show a potential
is calibrated to show a poten
0.000 V when introduced
difference of 0.000 V when in a pH = 1 solution.
introduced in a The
pH = 1 solution. T
Example: A pH meter electrode is calibrated to show a potential difference of
ter issame
then
0.000 used
pH
V when meteron aissolution
introduced inthen 1 of
a pH =used unknown
on a
solution. pHpHand
solution
The same of unknown
meter is then usedpH a
e of the
potential
on a solution isunknown
difference
of reported to the
of potential
pH and bedifference
is+296 mV;
reported
of what
to be
potential is+296tomV;
is reported be what
+296 mV; what is the pH of the unknown solution?
unknown
the pHsolution?
of the unknown solution?
+ +
E = −2.30 × 0.02569EV= log
−2.30
10 ×
[H ]
0.02569
out V log10 [H ]out
(
= 0.0592 V × − log10
= [H +
) (
]out V × − log10 [H + ]out
0.0592 )
ating pH 1 is Calibrating
0 V: pH 1 is 0 V:
E 1=is59.2
Calibrating pH 0 V: mV × (1) −E = 59.2
Cal = 0 mV × (1) − Cal = 0
59.2 = Cal 59.2 = Cal
= 59.2 mV × pH − 59.2V
E = 59.2 mV × pH −E 59.2V
296 + 59.2 = 355.2 =296 + 59.2
59.2 mV ×= 355.2
pH = 59.2 mV × pH
pH = 6 pH = 6
31
32
 Electrolysis
Galvanic (voltaic) cells: production of electrical energy from the energy of a
chemical reaction
Electrolysis: Use of electrical energy to create chemical reactions. Nonspontaneous
reactions can occur IF outside electricity is used to drive the reaction.

If spontaneous reaction occurs:

Cathode: EoRed (Cl2/Cl-) = 1.36 V Cathode: EoRed (Ni2+/Ni) = -0.25 V
Anode: EoRed (Na+/Na) = -2.71 V Anode: EoRed (Na+/Na) = -2.71 V

EoTot = EoRed (Cl2/Cl-) - EoRed (Na+/Na) = 4.07 V EoTot = EoRed (Ni2+/Ni) - EoRed (Na+/Na) = 4.07 V

Non-spontaneous can occur by the addition of external voltage source.

33
Faraday’s
Faraday’s Law
Law of
of Electrolys
Electrolysis
Faraday’s Law of Electrolysis

Faraday madea anumber

Faraday made number of important
of important
Faraday made
observations
observations about
about a electrolysis,
number
electrolysis, ofwhich
which important
can be
observations
can about
all be summarized
summarized by this electrolysis,
“law”: by this “law”: whic
can allamount
“The be summarized
of substanceby this is“law”:
created
“The amount of substance created is
directly
directlyproportional to the
proportional to theelectrical
electrical
“The amount
charge
charge passed of substance
passed through
through cell.” created
thecell.”
the
directly proportional to the electric
Michael Faraday
charge passed through the −1cell.”
charge ( C ) × molar mass ( g ⋅ mol )
1791 - 1867 (England)

mass ( g ) =
Michael Faraday
(
n × F C ⋅ mol )
−1

Michael Faraday

(
1791 - 1867
1791(England)
charge ( C ) × molar mass g ⋅ mol−
- 1867

mass ( g ) =
(England)

( )
Number of electrons required −1
to make one n × ofFsubstance
mol C ⋅ mol
34
 Using Faraday’s Law
Using Faraday’s Law
Quantity of charge (C) Faraday constant
= F = 96,485 C/mol
Current (A) × time (s)

Moles of electrons balanced

half-reaction

Moles of substance formula

weight

Mass (g) of substance

produced

35
 Electrolysis - Examples
Example - Faraday’s Laws.
Electrolysis - Examples

Example - Faraday’s
Example- Laws.
Faraday’s Laws.
A solution of copper(II) sulfate is electrolyzed by applying a larg
A solution of copper(II) sulfate is electrolyzed by applying a large enough
enough
A potential;potential;
solution of currentwhat
copper(II)
what current
sulfate
would 404would
is electrolyzed
deposit deposit
metal404
by applying
mg of copper a mg
largeof coppe
if operated
metal
enough at theforcathode
potential;
continuously what
5.0 of thewould
hrs? current cell ifdeposit
operated
404 mgcontinuously
of copper for 5.0
metal at the cathode of the cell if operated continuously for 5.0 hrs?
half − cell reaction : 2+Cu(2+aq )− + 2e− → Cu s
half − cell reaction : Cu( aq ) + 2e → Cu s

grams
grams Cu Cu 0.404g0.404g −3 −3
moles Cu
moles Cu = = = = =
= 6.36x106.36x10
Atomic
Atomic weight
weight Cu Cu
63.54663.546
− −3 −2
molese e=− moles
moles = moles Cu ×Cun =×6.36 × 2 =−31.27x10
n = 6.37x10
6.37x10 moles −2 moles
× 2 = 1.27x10
− −2
charge = mol e × −F = 1.27x10
charge = mol e × F = 1.27x10 −2
moles(96486 coulombs/mole)=1227
moles(96486 C
coulombs/mole)=12
Definition of current: 1 A = 1 C s-1

Calculate the current: 1 A = 1227 C/5 hrs = 1227/(3600x5 s) A = 68 mV

36
 current of 250,000 A. How long would it take to produ
Q2. Sea water is electrolyzed at a- potential of 5.0 V and a
1000 Typical Problems Electrolysis
currentkg of of Cl2 gas?
250,000 A. How How long much
wouldNaOHit take toisproduce
produced at
Sea water
1000 kgis of cathode?
electrolyzed
Cl2 gas? at How What
a potential
much of 5.0 Venergy
NaOH and a is ofused?
iscurrent
produced 250,000 A. How
at the
long would it take to produce 1000 kg of Cl2 gas? How much NaOH is produced at
cathode? What energy is used?
the cathode? What energy is used?
oxidation: − 2Cl− ⎯⎯
→ Cl− 2 + 2 e−
oxidation : oxidation: − 2Cl ⎯⎯ →− Cl2 +E2oe= −1.359 V vs. SHE
− ( aq ) → Cl 2( g )− + 2e
2Cl +E o = −1.359
−
) →
oxidation : 2Cl( aqreduction: Cl 2( g )
+ 2e + 2H − + 2e ⎯V ⎯
→ vs.H
SHE
reduction:+ 2H
− + 2e ⎯⎯ → Ho 2 2
reduction
reduction : : 2H2H
+
+ +− 2e → H
→ E = 0 V vs. SHE
− + = 0 V+vs. SHE
o
( aq ) ( aq )
2e H 2( −
g) 2( E
g )
2Cl 2Cl + 2H +⎯ ⎯ ⎯ ⎯→
→ ClKINETICS
2H 2 + H 2Cl 2 + H 2 MATTER!
KINETICS
MATTER!

E ((ClCl2/ Cl
o
Ered
o
/ Cl) ) = 1.359
2
−
−= 1.359
V vs.VSHE
vs. SHE
The oxidation
KINETICS
also occur,
The
MATTER!
of water intoof
oxidation O2water
but in practice it is MUCH
also occur,
could into O
2
red The oxidation
than the of waterbutinto in- practice
of ClO 2 could
it is M
Cl2, also
E o ( H +/ H ) = 0.000 V vs. SHE
+
slower oxidation into

Ered ( H / H 2 ) = 0.000 V vs. SHE

o
red 2 occur,
so the but slower
latter than
inshuts
practice
down the
it the oxidation
is MUCH
oxidation of Cl- i
slower
of water.soWethe latter
cannot Clshuts
of predict Cldown
- intowhich the ox
E ( O ,H / H O ) = 1.230 V vs. SHE
o + than the oxidation 2, so the
reaction
shutsisof going
water. to be
We the fastest
cannot ofpredict
water. w
( )
red 2
+
2 latter down the oxidation
Ered O 2 ,H / H 2O = 1.230 V vs. SHE
o
reaction
We cannot predict
without checking experimentally.
is going
which to be
reaction the fas
is going
without
to be the fastest checking
without experiment
checking
experimentally.

37
 Typical Problems - Electrolysis
Typical Problems - Electrolysis
Q2. Sea water
Q2. Sea water is is electrolyzed
electrolyzed
Typical Problems at
ataapotential
potentialofof5.0
- Electrolysis
5.0VVand
anda a
current
current of 250,000
of 250,000 A. A.How
Howlonglongwould
woulditittake
taketotoproduce
produce
Sea water is electrolyzed at a potential of 5.0 V and a current of 250,000 A. How
1000
long1000
kg
would kg
of to
of
it take
Clproduce
Cl 2 gas? How
2 gas?1000
How muchNaOH
kgmuch
NaOH
of Cl2 gas? How is
isproduced
much
produced atatthe
the
NaOH is produced
at the cathode? What cathode? Whatenergy
energy is used?
cathode? What energyisisused?
used?
mass
mass 1000 × 10 3
3 g
1000 × 10 g
1) mol of Cl = = = 1.41× 10 4
1) mol of Cl22 = molar mass= 70.9054 g ⋅ mol−1−1= 1.41× 10 mol
4 mol
molar mass 70.9054 g ⋅ mol
mol of e−− = mol of Cl × n = 1.41× 10 4 4 mol × 2 = 2.82 × 104 4 mol
mol of e = mol of Cl2 × n = 1.41× 10 mol × 2 = 2.82 × 10 mol
2

charge == mol
charge of ee−− ××FF==2.82
mol of 2.82××10 mol××96485
104 4mol 96485CC⋅ mol −1 −1 = 2.72 × 10
⋅ mol 9
= 2.72 × 10 9 C C
× 99
time = charge == 2.72 × 10 C ==1.09
charge 2.72 10 C
1.09××10
104 4s s==3.0
3.0hrs
hrs
current 250,000
current 250,000AA

2) 1 mol Cl produced→
Cl22 produced molHH+ +consumed
→22mol consumed→→2 2mol
molOH
OH− −
produced
produced
nNaOH = 2n
2nClCl22 == 22××1.41× mol==2.82
104 4 mol
1.41×10 2.82××10104 4mol
mol

38
 Typical Problems - Electrolysis
Q2. Sea water isTypical electrolyzed
Problems - at a potential of 5.0 V and a
Electrolysis

current
Sea water is of 250,000
electrolyzed at aA. Howoflong
potential would
5.0 V and it take
a current to produce
of 250,000 A. How
long would it take to produce 1000 kg of Cl2 gas? How much NaOH is produced at
1000 kg of Cl 2 gas? How much NaOH is produced at the
the cathode? What energy is used?
cathode? What energy is used?

3) 3) potential ×=charge
Energy = Energy charge=5× × 2.72 × 10=9 C
V voltage × 10
= 1.36
2.72 × 10910CJ × 5 V = 1.36 × 1010 J
note: this equals 3770 kWh of electricity, which would cost about $550 in Michigan these days.
Note:
A 1000 kg this
of Clequals ~3,770
2 gas costs kWh
about $1,000 ofdays.
these electricity,
A huge partwhich would
of the cost cost
goes into the
compressing
average Michigan
the gas into cylinders. 1000customer aboutCl$575
kg of uncompressed 2 takes athese
volume days. Theliters,
of 0.3 million costwhich
to buis a
a ton
tenth of volume
of the chlorine of anis currently
olympic pool... less than $400: not a very good idea to
make your own chlorine (safety concerns aside!).
Note: this equals ~3,770 kWh of electricity, which would cost 1000 kg of Cl2 gas
costs about $1,000 these days. A huge part of the cost goes into compressing
average Michigan customer about $575 these days. The cost to buy
the gas into cylinders. 1000 kg of uncompressed Cl2 takes a volume of 0.3
million liters, which is a a ton of chlorine is currently less than $400: not a very
good idea to make your own chlorine (safety concerns aside!).

39
 Batteries
Batteries
• Strictly speaking, a
BATTERY is a collection
of electrochemical cells
Strictly speaking, a BATTERY is a in series, but
connected
collection of electrochemical cells
the term is often used
connected in series, buteven
the term is often
for single cells
used even for single cells
• From Kirchhoff’s 2nd law,
we know that the total
From Kirchhoff’s 2nd law, we know that the
potential of elements in
total potential of elements in is
series series is theof the
the SUM
SUM of the individual potentials.
individual potentials.

• This is how large

potentials
This is how large potentials (bigger
(bigger than
than ~1
V) are obtained. ~1 V) are obtained.

40
 “alkaline”manganese.
• Cathode: means “basic”)

•••Cathode:
Cathode: manganese.
Irreversible Alkaline
manganese.
chemistry: Batteries
non-rechargeable
• Irreversible
Irreversible•chemistry:
Irreversible
The
chemistry:
chemistry:
half
non-rechargeable
non-rechargeable
two non-rechargeable
reactions of the standard alkaline battery:
The
The
1.The two half two
two half
ofreactions
half
reactions reactions of the
the standard
ofalkaline
the standard battery:alkaline
standard alkaline battery:
battery:
Zn(s) + 2OH (aq) → ZnO(s) + H2O(l) + 2e [Eoxidation° = +1.28 V]
− −

Zn+4
Zn (s) +
+ 2OH (aq) →
→ ZnO (s) + +3
HH22O (l) + 2e −− [Eoxidation° = +1.28 V]
Oxidation: (s) 2OH−−(aq) ZnO (s) + O(l) + 2e [Eoxidation° = +1.28 V]
2MnO2(s) + H2O(l) + 2e− → Mn2O3(s) + 2OH−(aq) [Ereduction° = +0.15 V]
+4
+4 +3
+3
Reduction: 2MnO
2MnO2(s)
2(s) +
+ H
H 2 O
O(l)
2 (l) +
+ 2e
2e −− →
→ Mn
Mn 22O 3(s) +
O3(s) + 2OH (aq) [E
2OH−−(aq) reduction°° =
[Ereduction = +0.15
+0.15 V]
V]

Total: Zn
Alkaline Batteries
Overall reaction:
(s) + 2MnO
Overall 2(s) ⇌ ZnO(s) + Mn2O3(s) [Ecell = +1.43 V]
reaction:
Overall reaction:
Zn (s) +
Zn(s) + 2MnO 2(s) ⇌
2MnOCathode.
2(s) ⇌ ZnOZnO(s)(s) +
+ Mn
Mn22O 3(s) [E
O3(s) cell =
[Ecell = +1.43
+1.43 V]
V]
Where the reduction takes place
The typicalMnO battery
2 —> Mn O
2 is rated at 1.5 V. What’s the deal?
3

The
The typical
typical battery
battery isis rated
rated at
at 1.5
1.5 V.
V. What’s
What’s the
the deal?
deal?

Anode.
Where the oxidation takes place Zn —> Zn2+ 41
wikipedia
 Lead-Acid Battery
Lead-Acid Battery
Lead-Acid
supplyingLead-Acid
Battery
A 12 V lead-acid automotive battery
Battery
consists of 6 galvanic cells in series (each
Lead-Acid
2 V)
Battery
+ • A− 12 V lead-acid automotive
Pb( s ) PbSO 4( s )
Pb( s ) PbSO
H ,HSO(H
aq+) ,HSO −+battery) PbO
4( aqPbO consists
2( s )
− PbSO
PbSO of
Pb ( s ) Pb( s ) Pb
6 4galvanic
!##" !### #"$
Pb
##( s )4$PbSO
( s ) ( aq ) 4( s ) H4(aq
) !!
aq )
(cells ,HSO
in
##
2(##
s )4 aq "
( ##
series
"
4( s##
PbO
) (each ) ( s ) $ 4( s )
PbSO
$ 2( s ) supplying 2 (s)
!##"##
ANODE ANODE $ !##"##$
CATHODE
ANODE V) CATHODE
CATHODE

ANODE: Pb( s ) + HSO −

−
(
! )
!!
↽
!
⇀
!
⇀!• Cathodes:
PbSO ( ) + H +
(
lead(IV)
) + 2e
+
−
oxide
+ −
(PbO2)
Pb( s ) ++4HSO
: ANODE: Pb4((saq) +) ↽
4 aq
HSO ! !−
PbSO
packed
4( aq+)
!
↽ !
4
! ⇀
s
! on
PbSO
4−( s )
+ aq
H
lead +
grids
4((aq
+2 s) )
+ H 2e
( aq ) + 2e −

CATHODE: PbO 2( s+4 ) + HSO −

4( aq )
+ 3H ( aq ) + 2e ↽! !! ⇀! PbSO 4(+2
s)
+ 2H +2 2 O( l )
+4
DE:CATHODE:
PbO + PbO 2−( s ) + HSO
HSO
s ) ( s ) + PbO 2(4s () aq
2(Pb
+ •
3H
−
− 4( aq ) +
Anodes:
+ )2HSO 4( aq( aq
+
+ + 3H+ lead
2e
+
(!
− !
aq!↽) +metal
⇀ !! ⇀
2e
!
− !!
↽
PbSO !⇀ !+PbSO + 42H
( + 2H O
s ) 2 O 2 (l )
TOTAL: ) ) 2H ( aq ) ↽ ! ! 2PbSO 4( s )
2H
4 ( )2 (l )
s O (l )
TOTAL: Pb( s ) + PbO 2•( s )Electrolyte:
− sulfuric+ acid
−+ 2HSO 4( aq+) + ! !!(H
aq ) ↽!!
2H!(⇀ SO4)
⇀22PbSO + 2H 2O(l )
: ⎛ 2+ Pb
( + PbO
s) +
0 + 2HSO 4( aq ) + 2H( aq ) ↽!! 2PbSO 4( s )
2( s−) ⎞
4( s )
+ 2H 2O(l )
E o
Pb SO 4 ,H / Pb ,HSO 4 = −0.356 V vs. SHE (most negative = anode)
⎝red
⎠
o4+ ⎛ ⎞ = −0.356 V vs. SHE (most negative = anode)
2+ 0
+
o E ⎛ red Pb0SO−4,,H
2+
+ / Pb ,HSO ⎞ =−41.685
⎝2 −⎞ ⎠ V vs. SHE (most positive = cathode)
Ered Pb+O ,HSO 3H / Pb SO
⎝ ⎠
O ,H / Pb ,HSO = −0.356 V vs. SHE (most negative = anode)
4 4

( cathode) −−⎠Ered
4 4
E o
=⎛ o
E 4+ o
( anode
+ ) ( ⎞ ) ( )
2+ = 1.685 V − −0.356 V = 2.041 V
Ered Pb O 2 ,HSO 4 , 3H / Pb SO 4 = 1.685 V vs. SHE
cello red
(most positive = cathode)
⎝ 2+
⎞ ⎠
O 2 ,HSOo −4 , 3Ho+ / Pb SO 4 = o1.685 V vs. SHE (most positive = cathode)
Ecell = Ered ( cathode )⎠− Ered ( anode ) = (1.685 V) − ( −0.356 V) = 2.041 V
42
E o
cathode − E o
anode = 1.685 V − −0.356 V = 2.041 V
 Lead-Acid Battery

Advantages of Lead-acid battery:

- Redox species (those that exchange electrons) are in the solid state: Pb, PbO2, -
and PbSO4.
- Gives more stable current
- Faster discharge, means a lot of current at once.

Rechargable.
- Applying an external source of energy to reverse the reaction (what the the
alternator does)
- For this to work well, it is critical that the solids form on the electrodes: if they
crystalize and fall off the electrode, then the battery cannot be fully recharged.

What are the disadvantages?

•Very heavy (full of lead).
•Toxic (lead)
•Bulky
•Stores comparatively little energy for size and weight.
•Why do we still use them?
43
 Lithium-Ion
• Anode: Lithium-Ion Batteries
Lithium-Ion BatteriesBatteries
Lithium-Ion Batteries
Li Li CoO LiCoO +

• Anode: • ( graphite) 2( s ) 2( s

Lithium-Ion Batteries
Anode:
! ! ⇀ +
+ −
Li
•Anode:
Anode:
( graphite) ↽ ! ! Li ( graphite) e Li + + CoO
Li LiCoO 2( s )
Li( graphite
( + Li ) CoO 2( s ) LiCoO
Li) CoO LiCoO 2( s ) 2( s )
graphite
Li !
↽ !!⇀! Li +
+ e −
Li
Li( graphite !!
↽ ! ⇀ !
+
( graphite
Li ) + + (e −
graphite) ( graphite) 2( s ) 2( s )
•• Cathode:
)
Anode:
Li ( graphite) ↽! !! ⇀
! (Li
graphite )
( graphite) + e −

Li( graphite) Li+ CoO 2( s ) LiCoO 2( s )

+4 !• !Cathode:
⇀ ++ + −
−
• Cathode:
LiCoO
• Cathode:
( graphite) ↽ +
!
+4 ! Li
Li
2( s )CoO ( CoO
( graphite+) + e
+ Li 2)
e
+ e−
+4
+4 Cathode: 2( s ) (CoO2 )
+ −e−
CoO•+4
CoO +
Cathode:
2(Li
+
+ Li
CoO+
+
e +3+3
2( s )
s)
(CoO (
2)
2 ) !
↽!↽! ⇀! !⇀
!+3!LiCoO
! LiCoO2 2
+ −
CoO 2( s ) + Li(CoO2 ) +!e!⇀ LiCoO
! ! ⇀ ↽!! +3 2
• Li +↽ !
ions!migrate
LiCoO through
•• Li
+3
Li ions migrate
+ ! !
↽!!
a
⇀ LiCoOthrough
membrane
2
(all
2
solid)
+ions migrate through
a membrane (all solid)
• Li • ions migrate through
o
+ a membrane E ~ 3.8
(all Vsolid)
Li ions
+
o • migrate through
cell

a membrane
aE Ecellcell~~3.83.8
membrane
o V solid)
V(all
(all solid)
• o• Ecell ~ 3.8
E•cell ~ 3.8• V
o
Because
V lithium is so
• • •LiBecause
+Because
Because
ions migrate
light, packs a lot of
lithium
energy lithium
through
per isbattery
so
a is somass(all
membrane Liu,solid)
• light, packs a lot of lithium is so Neale, Cao. Materials Today, 19, 109-123 (2016)
light,
• Because
light, packs
lithium
packs ais lot
so of
perabattery
lotso oflight,
Because lithium is packs a lot of energy per battery mass
energy mass Liu, Neale, Cao. Materials Today, 19, 109-123 (2016)
light,energy
packs per
a lotbattery
energy per battery mass
of mass Liu, Neale, Cao. Materials Today, 19, 109-123
Liu, Neale, Cao. Materials Today, 19, 109-123 (2016)
44
energy per battery mass Liu, Neale, Cao. Materials Today, 19, 109-123 (201
 Fuel Cells
An electrochemical cell where oxidant and reductant can be continuously added!

Fuel Cells
Much more efficient than combustion (“burning” the fuel):
• An electrochemical cell A hydrogen Fuel Cell:
where oxidant and INPUT: hydrogen and oxygen
§ More work (electricity)
reductant almost
can beno heat. OUTPUT: electricity and water
continuously added!
o
Ecell ~ 1.23 V
§ Fuel cell efficiency:
Much65-80%
• more efficient than
combustion (“burning” the
fuel): engine: about 30%
§ Internal combustion

• more work (electricity)

A hydrogen Fuelalmost
Cell: no heat.
INPUT: hydrogen and oxygen
• Fueland
OUTPUT: electricity cellwater
efficiency:
65-80%
Eo ~1.23 V
• Internal combustion
engine: about 30%

45
 Electricity in Biology

The Galvanis demonstrating

that a (dead) frog leg can be stimulated
with electrical impulses

Luigi Galvani
Lucia Galeazzi Galvani
1737-1798 (Italy)
1743-1788 (Italy)

46
Electricity and Biology

A potential can come from a

simple difference in the
concentration of ions.

No Redox reaction has to

happen.

Any current of ions will do…

It doesn’t have to be electrons.

47
 Potential

en.wikipedia.org/wiki/Action_potential
48
en.wikipedia.org/wiki/Cardiac_action_potential