Redox Reaction - the basics

ox1 + red2 <=> red1 + ox2

Ch.14-16
Oxidizing Reducing
Electrochemistry Agent Agent

Redox reactions: involve transfer of electrons from one

species to another.
Oxidizing agent (oxidant): takes electrons
Reducing agent (reductant): gives electrons

Redox Reaction - the basics Balance Redox Reactions (Half Reactions)

Reduced Oxidized

1. Write down the (two half) reactions.

ox1 + red2 <=> red1 + ox2 2. Balance the (half) reactions (Mass and Charge):
Oxidizing Reducing
a. Start with elements other than H and O.
Agent Agent b. Balance O by adding water.
c. balance H by adding H+.
Redox reactions: involve transfer of electrons from one d. Balancing charge by adding electrons.
species to another. (3. Multiply each half reaction to make the number of
Oxidizing agent (oxidant): takes electrons electrons equal.
Reducing agent (reductant): gives electrons 4. Add the reactions and simplify.)

Fe3+ + V 2+ → Fe 2+ + V 3+

Example: Balance the two half reactions and redox Important Redox Titrants and the Reactions
reaction equation of the titration of an acidic solution of
Na2C2O4 (sodium oxalate, colorless) with KMnO4 (deep
purple). Oxidizing Reagents (Oxidants)
MnO4-(aq) + C2O42-(aq) → Mn2+ (aq) + CO2(g)
(1) Potassium Permanganate
16H+(aq) + 2MnO4 +-(aq) →
5C2O42-(aq) −
MnO 4 + 8 H + + 5e − → Mn 2 + + 4 H 2 O
2Mn2+(aq) + 8H2O(l) + 10CO2(g)
−
MnO4 + 4 H + + 3e − → MnO2 ( s ) + 2 H 2O
Example: Balance
Sn2+ + Fe3+ <=> Sn4+ + Fe2+ MnO + e → MnO
− − 2−

4 4

Fe2+ + MnO4- <=> Fe3+ + Mn2+

1
Important Redox Titrants and the Reactions Important Redox Titrants and the Reactions

Oxidizing Reagents (Oxidants) Oxidizing Reagents (Oxidants)

(2) Potassium Dichromate (3) Potassium Iodate

2−
Cr2O7 + 14 H + + 6e − → 2Cr 3+ + 7 H 2O − 1
IO3 + 6 H + + 5e − → I 2 + 3 H 2O
2
2− 2+
Cr2 O 7 + 3U 4+ + 2H + → 2Cr 3+ + 3UO 2 + H 2O

Important Redox Titrants and the Reactions Important Redox Titrants and the Reactions
Reducing Reagent ( Reductants )
Reducing Reagent ( Reductants )
(1) Potassium Iodide
(2) Sodium Thiosulfate

2S2O32- S4O62- +2e¯

1
I → I 2 + e−
−

Galvanic Cells - Components Galvanic Cells - Line Notation

A galvanic (voltaic) cell uses a

spontaneous chemical reaction
to generate electricity.

– Electrodes (cathode
and anode).
– Salt bridge: cations
move from anode to
cathode, anions move
from cathode to
anode.
Line notation
Cd(s) | Cd(NO3)2 (aq) || AgNO3 (aq) | Ag(s)
Phase boundary Salt bridge Phase boundary

2
 Standard Electrode Potentials Standard Reduction (Half-Cell) Potentials
Standard hydrogen electrode (S.H.E.)
Standard reduction potential (Eo) is the voltage associated • The S.H.E. is the cathode. It consists of a Pt electrode in a
with a reduction reaction at an electrode when all solutes are tube placed in 1 M H+ solution. H2 is bubbled through the
1 M and all gases are at 1 atm. Cathode tube.
• For the S.H.E., we assign
2H+ (aq, 1M) + 2e- → H2 (g, 1 atm)
Reduction Reaction • E°red of zero.
• The potential of a cell can be calculated from standard
2H+ (1 M ) + 2e- H2 (1 atm)
reduction potentials:
Eo = 0V
E °cell = E °red (cathode ) − E °red (anode )

Standard Reduction (Half-Cell) Potentials Standard Potentials

We use hydrogen (S.H.E.)
• Consider Zn(s) → Zn2+(aq) + 2e-. We measure Ecell H +(aq) + e − ↔ 1/2H 2 ( g ) E ° ≡ 0.000
relative to the S.H.E. (cathode):
E°cell = E°red(cathode) - E°red(anode) We can measure Eº for other half-reactions, relative to
0.76 V = 0 V - E°red(anode). the hydrogen reaction, e.g. for silver:
• Therefore, E°red(anode) = -0.76 V. Ag +(aq) + e − ↔ Ag(s) E ° = 0.799
• Standard reduction potentials must be written as Standard reduction potentials are listed in Ap. H in
reduction reactions: your book. Eº for the H2 reaction is for the reaction
at 25º C
Zn2+(aq) + 2e- → Zn(s), E°red = -0.76 V.

Nernst Equation for a Half-Reaction

• The Nernst Equation relates the potential of the half
reaction to reagent concentrations
• For the half-reactions:
RT [B]
b

° E = E° − ln
aA + ne ↔ bB nF [A]a
-
E

aA + bB + ne - ↔ cC + dD E° RT [C] [D]
c d
E = E° − ln
nF [A ]a [B]b
RT
E = E° − ln Q
nF
# of moles of
electrons

3
 Nernst Equation for a Half-Reaction Nernst Equation for a Complete Reaction

At 298K (25oC)
ox1 + red2 <=> red1 + ox2
0.05916V
E = E° − log Q
n

E = E+ − E−

Example (Nernst) Example (Net Reaction)

• Find the voltage for the Ag-Cd cell and state if the reaction is
• Write the Nernst equation for the reduction of spontaneous if the right cell contained 0.50 M AgNO3(aq) and if
phosphoric acid to solid white phosphorous: the left contained 0.010 M Cd(NO3)2(aq)
H 3PO 4 + 5H + + 5e - ↔ 1/4P4 ( s) + 4H 2O E ° = -.402 • 1) 2Ag + + 2e − ↔ 2Ag( s) E+° = 0.799 V
0.05916 1 Cd + + 2e − ↔ Cd( s) E−° = −0.402 V
E = −0.402 − log
5 [ ]
[H 3PO 4 ] H + 5

• 2) E+ = 0.799 − 0.05916 log 1 = 0.781 V

• Note that multiplying the reaction by any factor
2 [0.50]2
does not affect Eº or the calculated E: • 3) E = −0.402 − 0.05916 log 1 = −0.461V
−
2 [0.010]
2H3 PO 4 + 10H + + 10e- ↔ 1/2P4 ( s) + 8H 2 O E ° = -.402
• 4) E = E+ − E− = 0.781 − ( −0.461) = +1.242 V
0.05916 1 • 5)
E = −0.402 − log
[ ]
+ −
10 [H 3PO 4 ]2 H + 10 2Ag + 2e ↔ 2Ag( s)
Cd + + 2e − ↔ Cd ( s ) Cd( s) + 2Ag + ↔ Cd 2+ + 2Ag( s)

Determination of the Equivalence Point Redox Titration Curve

Aox + Bred <=> Ared + Box EXAMPLE: Derive the
titration curve for 50.00 mL
At equivalence point, Ecell=0:
of 0.0500 M Fe2+ with 0.00,
0.0592 [A ] 0.0592 [B ]
15.00, 25.00, 26.00 mL
° °
EA − log red = EB − log red 0.1000 M Ce4+ in a medium
nA [ Aox ] nB [ Box ]
that is 1.0 M in HClO4.
Potential of saturated
Ared = Box and Bred = Aox at the equivalence point
calomel electrode is 0.241
o o V.
n A E A + nB E B Valid for simple
E= Redox expressions
n A + nB

4
 EXAMPLE: Derive the titration curve for 50.00 mL of
EXAMPLE: Derive the titration curve for 50.00 mL of 0.0500 M Fe2+ with 0.00, 15.00, 25.00, 26.00 mL 0.1000
0.0500 M Fe2+ with 0.00, 15.00, 25.00, 26.00 mL 0.1000 M M Ce4+ in a medium that is 1.0 M in HClO4.Potential of
Ce4+ in a medium that is 1.0 M in HClO4. Potential of saturated calomel electrode is 0.241 V.
saturated calomel electrode is 0.241 V.
Titration reaction: Fe2+ + Ce4+ <=> Ce3+ + Fe3+ Fe2+ + Ce4+ <=> Ce3+ + Fe3+
Fe3+ + e- <=> Fe2+ Eo = 0.767 V At 15.00 mL of Ce4+ added, VFeMFe > VCeMCe
Ce4++ e- <=> Ce3+ Eo = 1.70 V “Buffer region”

At 0.00 mL of Ce4+ added, initial point no Ce4+ present;

VCe M Ce
minimal, unknown [Fe3+]; thus, insufficient information to [ Fe 3+ ] =
VFe + VCe
calculate E
(15.00mL)(0.1000M )
0.0592 [ Fe 2+ ] = = 2.308 ×10 −2 M
E = E° − log − 0.241 (50.00 + 15.00)mL
n [ Fe 3+ ]

EXAMPLE: Derive the titration curve for 50.00 mL of EXAMPLE: Derive the titration curve for 50.00 mL of
0.0500 M Fe2+ with 0.00, 15.00, 25.00, 26.00 mL 0.1000 M 0.0500 M Fe2+ with 0.00, 15.00, 25.00, 26.00 mL 0.1000 M
Ce4+ in a medium that is 1.0 M in HClO4. Potential of Ce4+ in a medium that is 1.0 M in HClO4. Potential of
saturated calomel electrode is 0.241 V. saturated calomel electrode is 0.241 V.
Fe2+ + Ce4+ <=> Ce3+ + Fe3+ Fe2+ + Ce4+ <=> Ce3+ + Fe3+
At 15.00 mL of Ce4+ added, VFeMFe > VCeMCe At 15.00 mL of Ce4+ added, VFeMFe > VCeMCe
“Buffer region”
“Buffer region”
[ Fe 3+ ] = 2.308 ×10−2 M Half-reactions: Fe3+ + e- <=> Fe2+ Eo = 0.767 V
[ Fe3+ ] = 2.308 × 10 −2 M [ Fe 2+ ] = 1.538 ×10 −2 M
2+ V M −V M
[ Fe ] = Fe Fe Ce Ce 0.0592 [ Fe 2 + ]
VFe + VCe E = E° − log − 0.241
n [ Fe3+ ]
(50.00mL)(0.0500M ) − (15.00mL)(0.1000M )
= = 1.54 ×10 −2 M 0.0592 1.54 ×10 −2
(50.00 + 15.00)mL = 0.767 − log − 0.241 = 0.533V
1 2.038 ×10 −2

EXAMPLE: Derive the titration curve for 50.00 mL of EXAMPLE: Derive the titration curve for 50.00 mL of
0.0500 M Fe2+ with 0.00, 15.00, 25.00, 26.00 mL 0.1000 M 0.0500 M Fe2+ with 0.00, 15.00, 25.00, 26.00 mL 0.1000 M
Ce4+ in a medium that is 1.0 M in HClO4. Potential of Ce4+ in a medium that is 1.0 M in HClO4. Potential of
saturated calomel electrode is 0.241 V. saturated calomel electrode is 0.241 V.

Fe2+ + Ce4+ <=> Ce3+ + Fe3+ Fe2+ + Ce4+ <=> Ce3+ + Fe3+
At 25.00 mL of Ce4+ added, VFeMFe = VCeMCe, At 26.00 mL of Ce4+ added, VFeMFe < VCeMCe,
Equivalence point After equivalence point
Half-reactions: Fe3+ + e- <=> Fe2+ Eo = 0.767 V
VFe M Fe
4+ -
Ce + e <=> Ce 3+ Eo = 1.70 V [Ce3+ ] =
VFe + VCe
nFe EFe + nCe ECe
E= − 0.241 (50.00mL)(0.0500 M )
nFe + nCe = = 3.29 ×10 − 2 M
(50.00 + 26.00) mL
0.767 + 1.70
= − 0.241 = 1.23 − 0.241 = 0.99 V
1+1

5
 EXAMPLE: Derive the titration curve for 50.00 mL of EXAMPLE: Derive the titration curve for 50.00 mL of
0.0500 M Fe2+ with 0.00, 15.00, 25.00, 26.00 mL 0.1000 M 0.0500 M Fe2+ with 0.00, 15.00, 25.00, 26.00 mL 0.1000 M
Ce4+ in a medium that is 1.0 M in HClO4. Potential of Ce4+ in a medium that is 1.0 M in HClO4. Potential of
saturated calomel electrode is 0.241 V. saturated calomel electrode is 0.241 V.
Fe2+ + Ce4+ <=> Ce3+ + Fe3+
Fe2+ + Ce4+ <=> Ce3+ + Fe3+ At 26.00 mL of Ce4+ added, VFeMFe > VCeMCe
At 26.00 mL of Ce4+ added, VFeMFe < VCeMCe, After equivalence point
After equivalence point Half-reactions: Fe3+ + e- <=> Fe2+ Eo = 0.767 V
Ce4++ e- <=> Ce3+ Eo = 1.70 V
[Ce3+ ] = 3.29 × 10 −2 M
[Ce3+ ] = 3.29 × 10 −2 M [Ce 4+ ] = 1.32 × 10 −3 M
V M −V M
[Ce 4+ ] = Ce Ce Fe Fe 0.0592 [Ce 3+ ]
VFe + VCe E = E° − log − 0.241
n [Ce 4+ ]
(26.00mL)(0.1000 M ) − (50.00mL)(0.0500M )
= = 1.32 × 10 −3 M 0.0592 3.29 ×10 −2
(50.00 + 26.00)mL = 1.70 − log − 0.241 = 0.63 V
1 1.32 ×10−3

Galvanic Cells
A galvanic (voltaic) cell uses a spontaneous
Theoretical curve for chemical reaction to generate electricity.
titration of 100.0 mL
– Electrodes (cathode and
of 0.50 0 M Fe2+ with anode).
0.100 M Ce4+ in 1 M – Salt bridge: cations
HClO4. (p.330-331) move from anode to
cathode, anions move
from cathode to anode.
0.0592 [ Fe 2+ ]
E = E° − log − 0.241 – produces electricity
n [ Fe 3+ ]
when the cell reaction
0.0592 is not at equilibrium.
= 0.767 − log 1 − 0.241 = 0.526 V
1

Free Energy and Electrochemical Reaction E and Equilibrium Constants

• A galvanic cell produces electricity because the cell
• The free energy change, ∆G, for a chemical reaction at reaction is not at equilibrium
constant T, P equals the maximum possible electrical work
• At equilibrium, E for the net reaction can thus be
that can be done by the reaction on its surroundings.
related to K aA + ne - ↔ cC E+°
dD + ne - ↔ dD E-°
Work = − ∆G = E × q
E = E+ − E− = E+° −
.05916 [C] c
log a − E−° −
.05916 [B]
log d
b

∆G = − nFE n [A] n [D]

E = E° −
0.05916 [C] [D]
c d
log a b = E ° −
0.05916
at 25°C
• A spontaneous reaction (∆G<0) E>0 n [A] [B] n
log Q

• Think: how the equilibrium constant can be related to free 0.05916 nE °

E = 0 → E° = log K at 25°C
energy? n K = 10
0.05916
at 25° C
When the cell is at equilibrium, E=0 and Q=K

6
 Cells as Chemical Probes
Example: Find the equilibrium constant Two Equilibria: (1) Equilibrium between two half-cells
3+ 2+ 2+
(2) Equilibrium within each half-cell
Cu ( s ) + 2Fe ↔ Cu + 2Fe
AgCl ( s) + e − ↔ Ag (s ) + Cl - (aq,0.10M ) E+° = 0.222 V
This can be divided into two half reactions: 2 H + ( aq, ? M ) + 2e - ↔ H 2 ( g ,1.00bar ) E o- = 0 V
2Fe 3+ + 2e − ↔ 2Fe 2+ ( s) E+° = 0.771 V
•The half-reaction that you
Cu 2+ + 2e- ↔ Cu (s ) E o- = 0.339 V write must involve species that
appear in two oxidation states
in the cell.
E ° = E+° − E−° = 0.771− 0.339 = 0.432 V
•The reaction is in equilibrium
in the right cell is not the net
nE °
cell reaction:
(2)(0.432)
0.05916
K = 10 = 10 ( 0.05916) = 4 ×1014 AgCl( s ) ↔ Ag + (aq) + Cl − ( aq)

Important Biochemical Reactions

Survival Tips
Electrochemistry, chemical equilibrium, solubility,
complex formation, and acid-base chemistry • Formal potential,
Eº’, meant to
define potentials
(1) Write half-reactions and their standard potentials under conditions
(2)Write Nernst equation for the net reaction and put in of biochemistry
all the known quantities.
(3) Solve for the unknown concentration and use that
concentration in the chemical equilibrium equation to
solve the problems.

Ex. p.286-287

S.H.E.
Potentiometry (again)
• Potentiometry: the use of electrodes to measure voltages
from chemical reactions.
• Electroactive species: can donate or accept electrons at
an electrode; can be measured as the part of a galvanic
cell (analyte)
• Reference electrode: we then connect the analyte half- The standard reduction
potential, Eo, for each half-
reaction to a second cell with a fixed composition (known cell is measured when
potential), the 2nd half-cell is called reference electrode. different half-cells are
• Indicator electrode: responds to analyte connected to S.H.E.
- Metal electrodes: inert metals, e.g., Pt, Au S.H.E. || Ag+ (aq. =1) | Ag(s)
- Ion-selective electrodes: respond to specific analytes Standard means that the activities of all species are unity.
Not practical for regular use due to the hydrogen gas

7
Reference Electrodes Reference Electrodes
Detect Fe2+ /Fe3+ in solution:
a Pt wire (indicator
electrode) in the half-cell
and connect this half cell to
a 2nd half-cell at a constant
potential.

Reference Electrode

Indicator Electrode
Fe3+ + e - ↔ Fe 2+ E+° = 0.771 V
− ° The entire left half-cell containing
AgCl ( s ) + e ↔ Ag ( s) + Cl
-
E = 0.222 V
-
appropriate solutions and a salt bridge.
E+ = 0.771 − .059 log
[Fe ]2+

[Fe ]3+
E = E+ − E- Fe 3+ + e - ↔ Fe 2 + E+° = 0.771 V
E- = 0.222 - .059log[Cl ]
-
AgCl( s) + e ↔ Ag( s ) + Cl −
-
E-° = 0.222 V

Silver-Silver Chloride Electrode Saturated Calomel Electrode (S.C.E.)

Ag | AgCl Electrode :
AgCl( s) + e - ↔ Ag ( s) + Cl− E-° = +0.222 V
w/ saturated KCl E = +0.197 V
Hg | Hg2Cl2 Electrode:
• The difference in E is due to activity 1/2Hg 2 Cl 2 ( s) + e - ↔ Hg(l ) + Cl − E ° = +0.268 V
coefficients.
w/ saturated KCl E = +0.241 V
• A double junction electrode: avoid to
mix Cl- with the analyte

Voltage Conversions between Different Indicator Electrodes - Metal Electrodes

Reference Scales

• Metal electrodes: develop potential in response to a redox

reaction on their surface
• Pt is mostly inert, not participating in reactions
– It simply allows electron transfer to/from solution
• Platinum is the most common metal indicator electrode
Gold is also an inert metal indicator electrode
An indicator electrode has a potential of -0.351 V
with respect to an S.C.E., what’s its potential with
• Carbon electrodes are often used because many redox
respect to an S.H.E.? reactions are very fast on a carbon surface
- 0.351V + 0.241V = -0.110V

8
 Indicator Electrodes-Metal electrodes Example: 100.0 mL solution containing 0.100 M NaCl
• Metal electrodes: develop potential in response to a redox reaction on was titrated with 0.100 M AgNO3 and monitored with a
their surface S.C.E. What voltage reading would be observed after 65.0
• Inert metal indicator electrode: allows electron transfer to/from the mL? + −
Ag + Cl → AgCl( s )
solution but not participating in reactions, e.g., Pt (the most common
one), Au. Ve = 100.0 mL
• Silver Indicator Electrode E = 0.558 + 0.05916log Ag +[ ]
Ag + ( s ) + e- ↔ Ag( s ) E+° = 0.799 V [Cl ] = (0.350)(0.100 M) 100.0
−

165.0
= 0.021 M

1/2Hg 2Cl 2 ( s ) + e - ↔ Hg (l ) + Cl − E−° = 0.241 V

[Ag ] = [Cl
K −10
+ sp 1.8 ×10
= 8.5 ×10 −9
E = E+ − E− = 0.799 − 0.059 log
1
− 0.241 ] = 0.021
−

Ag + [ ]
E = 0.558 + 0.05916 log (8.5 ×10-9 ) = 0.081 V
E = 0.558 + 0.059 log Ag + [ ]

Ion Mobilities and Liquid Junction Potentials

Junction Potential

• Junction potential: A voltage difference develops whenever

dissimilar electrolyte solutions are in contact.
• Happens at the salt bridge/solution interface since different ions
have different mobilities in water.
• A major (fundamental) source of error in a potential measurement.

Ion-Selective
Glass Electrode (pH Combination Electrode)
Electrodes
(ISE)
• The most common ISE
• Responds
selectively to one • A glass membrane
ion using an ion- selectively binds H+
selective membrane • Two Ag|AgCl reference
• Do not involve electrodes measure the
redox reactions potential difference across
• The electric the glass membrane
potential across the • An ion-exchange
membrane depends
equilibrium is on the
on [analyte]
surface of the glass
• E is measured by
membrane
two reference
electrodes
0.05916
E = constant + log [C +
]
Out at 25°C n = charge of analyte Ag(s) | AgCl(s) | Cl - (aq) || H + (aqout ) | H + (aqin ), Cl − (aq) | AgCl( s ) | Ag( s)
n

9
 The Glass Membrane of a pH Electrode Errors in pH Measurement
•Cross section of the glass
membrane of a pH electrode. 1. Calibration standards (±0.01 pH)
2. Junction potential (~0.01 pH)
•H+ can diffuse into the
membrane to replace the 3. Junction potential drift (recalibrate every 2 hrs)
metal ions through binding 4. Sodium error (when [H+] is low and [Na+] is high)
to oxygen in glass (ion- 5. Acid error (strong acid, the glass surface is saturated
exchange equilibrium). with H+)
Response of the electrode : 6. Equilibration time (~30s with adequate stirring)
E = constant + β (0.0592) log[H ] +
Out
7. Hydration of glass (A dry electrode requires several
E = constant − β (0.0592) pH at 25 C
Out
O hours of soaking)
8. Temperature (calibrate at same T as measurement)
β: ~1.00, electromotive 9. Cleaning (remove hydrophobic liquid)
efficiency measured during
calibration.

Specifications for Electrochemical

Selectivity Coefficient Techniques
• The selectivity Advantages
response to X
k A,X = coefficient: the Linear response to analyte over wide dynamic range
response to A relative response of Nondestructive
the electrode to
k = 1× 10 −5 Short response times
K + , Na + different species
Unaffected by color/turbidity (limited matrix effects)
k = 0.44
K + , Cs +
Cheap
• The smaller k is, the
k = 2.8 Disadvantages
K + , Rb +
less interference there
is due to ion X Sensitivity (High detection limits)
Response of ion - selective electrode :
Not universal
E = constant ± β (
0.0592
n
[
) log a +
A
x
(k a )
A,X x
] at 25 C
O

Voltammetry
• A collection of techniques in which the relation between
current and voltage is observed during electrochemical
process.

• Can be used to
(1) Study electroactivity of ions and molecules at the
electrode/solution interface
(2) Probe coupled chemical reactions and measure electron
transfer rates
ip

(3) Examine electrode surfaces

[A]
• An electrochemical cell consists of a working (analyzing)
electrode, an auxiliary (counter) electrode, and a reference Calibration Curve
electrode. The control device is a potentiostat.

10
 Stripping Analysis
Anodic stripping voltammetry (ASV): analytes are reduced and
deposited into (onto) an electrode. They are reoxidized during the
stripping step.
e.g. Cd2+(aq) + 2e = Cd(Hg) Deposition Step
Cd(Hg) – 2e = Cd2+ (aq) Stripping

Cathodic stripping voltammetry (CSV): typically anions are

oxidized and deposited onto an electrode with subsequent stripping
via a negative potential scan.
e.g. 2I- + 2Hg -2e = Hg2I2 at a Hg electrode Deposition step
Hg2I2 + 2e = 2 Hg + 2I- cathodic stripping, reduction
Trace analysis (enhanced sensitivity) can be realized since sample
analytes are preconcentrated from a large-volume dilute solution into
(onto) a small-volume electrode under forced convection.

11