CFE-Unit-2-Part-1

UNIT 2: ENERGY
Electrochemistry
Engr. Jose Nicko C. Rodriguez
Electrochemistry: Redox
CONTENT 01 Reaction
02 Voltaic Cell
03 Standard Electrode
Potentials
04 The Nernst Equation
05 Electrolytic Cell
ELECTROCHEMISTRY
It is defined as the study of the interchange
of chemical and electrical energy.
TWO PROCESSES:
- Generation of electric current from
chemical reaction.
- Use of current to produce chemical
change
REDOX REACTION
Involves a transfer of electrons from the
reducing agent to the oxidizing agent.
LEORA and GEROA
Oxidation: Loses electron = increase

oxidation number
Reduction: Gains electron = decrease
oxidation number
OXIDATION STATE/NUMBER
1. The oxidation state of an uncombined element is zero
2. The sum of the oxidation numbers in a chemical species is equal to
the charge on that species.
- The sum of the oxidation numbers in a neutral compound is zero
- Oxidation state of a monatomic ion = charge on the ion.
- Ionic compounds should be separated into their component ions
when assigning oxidation numbers.
- In covalent compounds the negative oxidation number is assigned
to the most electronegative atom.
OXIDATION STATE/NUMBER
3. The oxidation state of combined hydrogen is +1 except in
hydrides, in which oxidation state is -1.
4. The oxidation state of combined oxygen is -2 except in peroxides
and super oxides, in which the oxidations states are respectively, -1
and -1/2
EXERCISE
State the oxidation number of the designated element in each of the
following:
1. N in KNO3
2. K in K2CrO4
3. Cl in HClO4
4. S in SO42-
5. Pt in [PtCl6]2-
6. Fe in [Fe(H2O)6] 2+
OXIDATION AND REDUCTION
ANOX REDCAT
BALANCING HALF-REACTIONS
1. Assign oxidation numbers to each element.
2. Balance the oxygen atoms by adding the appropriate number of
water ( H2O) molecules to the opposite side of the equation.
3. Balance the hydrogen atoms (including those added in step 2 to
balance the oxygen atom) by adding H+ ions to the opposite side
of the equation.
4. Add up the charges on each side. Make them equal by adding
enough electrons ( e−) to the more positive side. (Rule of thumb:
e− and H+ are almost always on the same side.)
5. The e− on each side must be made equal; if they are not equal,
they must be multiplied by appropriate integers (the lowest common
multiple) to be made the same.
6. The half-equations are added together, canceling out the
electrons to form one balanced equation. Common terms should
also be canceled out.
If the reaction is being balanced in a basic solution, the above steps
are modified with the addition of one:
* Add the appropriate number of OH− to neutralize all H+ and to

convert into water molecules.
BALANCING NEUTRAL SOLUTION
BALANCING ACIDIC SOLUTION
BALANCING BASIC SOLUTION
EXERCISE
Balance the following half-reactions:
1. Cr2O72- (aq) ⟶ Cr3+(aq) (acidic medium)
2. MnO4- (aq) + Cl2 (aq) ⟶ Mn2+ (aq) + ClO3- (aq) (acidic solution)
3. H2O2 (aq) + Ni2+ (aq) ⟶ Ni3+ (aq) + H2O (acid solution)
4. SO2 (g) + I2 (aq) ⟶ SO3 (g) + I- (aq) (basic solution)
ELECTROCHEMICAL
CELL
- is a system consisting of two half-cell
reactions connected in such a way that
chemical reactions either uses or
generates an electric current.
VOLTAIC VS.
ELECTROLYTIC CELL
VOLTAIC CELL
- Any spontaneous redox reaction can
serve as a source of energy in voltaic
cell.
- It is an electrochemical cell in which a
spontaneous reaction generates an
electric current.
THE Zn-Cu 2+ CELL
CELL ABBREVIATION
Zn | Zn2+ || Cu2+| Cu
● Anode written on left ● , = separates different
ions/molecules in the same half cell
● Cathode written on right
with the same phase.
● | = phase boundary
● M = Molar concentration of ions
● || = salt bridge
● Zn = anode electrode
● Cu = cathode electrode
EXERCISE
Fe (s) + Ni2+ (aq) → Fe2+ (aq) + Ni (s)
a. Draw a sketch of the cell, labeling the anode, the cathode,
and the direction of the electron flow.
b. Write the half-cell reaction that takes place at the anode and
the cathode.
c. Write an abbreviated notation for the cell
EXERCISE
Cl2 (g) + Br- (aq) → Cl- (aq) + Br2 (l)
a. Draw a sketch of the cell, labeling the anode, the cathode,
and the direction of the electron flow.
b. Write the half-cell reaction that takes place at the anode and
the cathode.
c. Write an abbreviated notation for the cell
STANDARD ELECTRODE
POTENTIAL
- The driving force behind the
spontaneous reaction in a voltaic cell is
measured by the cell voltage.
- Cell voltage depends on the nature of
the redox reaction and the
concentration of the species involved.
STANDARD ELECTRODE
POTENTIAL
- standard cell voltage, E°, for a given cell
is that measured when the current flow is
essentially zero, all ions and molecules in
solution are at a concentration of 1 M,
and all gases are at a pressure of 1 atm.
STANDARD ELECTRODE
POTENTIAL
Eo = Eo red + Eoox
To obtain the standard voltage for an oxidation

half-reaction, all you have to do is change the
sign of the standard potential. Standard
voltages for forward and reverse half-
reactions are equal in magnitude but opposite
in sign.
Half-Reaction E °(V) Half-Reaction E °(V)
F2 +2e– → 2F– 2.87 O2 + 2H2O + 4e– → 4OH– 0.40
Ag2+ + e– → Ag+ 1.99 Cu2+ + 2e– → Cu 0.34
Co3+ + e– → Co2+ 1.82 Hg2Cl2 + 2e– → 2Hg + 2Cl– 0.27
H2O2 + 2H+ + e– → 2H2O 1.78 AgCl + e– → Ag + Cl– 0.22
Ce4+ + e– → Ce3+ 1.70 SO42– + 4H+ + e– → H2SO3 + H2O 0.20
PbO2 + 4H+ + SO42– + 2e– → PbSO4 + 2H2O 1.69 Cu2+ + e– → Cu+ 0.16
MnO4 + – 4H+ + 3e– → MnO2 + 2H2O 1.68 2H+ + 2e– → H2 0.00
2e– + 2H+ + IO4 –→ IO3 –+ 2H2O 1.60 Fe3+ + 3e– → Fe -0.036
MnO4 + – 8H+
+ 5e– → Mn2+ +
4H2O 1.51 Pb2+ + 2e–
→ Pb -0.13
Au3+ + 3e– → Au 1.50 Sn2+ + 2e– → Sn -0.14
PbO2 + 4H+ + 2e– → Pb2+ + 2H2O 1.46 Ni2+ + 2e– → Ni -0.23
Cl2 + 2e– → 2Cl– 1.36 PbSO4 + 2e– → Pb + SO42– -0.35
Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O 1.33 Cd2+ + 2e– → Cd -0.40
O2 + 4H+
+ 4e– →
2H2O 1.23 Fe2+ + 2e–
→ Fe -0.44
→
MnO2 + 4H+ + 2e– → Mn2++ 2H2O 1.21 Cr3+ + e– → Cr2+ -0.50
IO3– + 6H+ + 5e– → 1/2 I2+ 3H2O 1.20 Cr3+ + 3e– → Cr -0.73
Br2 + 2e– → 2Br– 1.09 Zn2+ + 2e– → Zn -0.76
VO2+ + 2H+ + e– → VO2+ + H2O 1.00 2H2O + 2e– → H2 + 2OH– -0.83
AuCl4– + e– → Au + 4Cl– 0.99 Mn2+ + 2e– → Mn -1.18
NO3– + 4H+ + 3e– → NO + 2H2O 0.96 Al3+ + 3e– → Al -1.66
ClO2 + e– → ClO2– 0.954 H2 + 2e– → 2H– -2.23
2Hg2+ + e– → Hg22+ 0.91 Mg2+ + 2e– → Mg -2.37
Ag+ + e– → Ag 0.80 La3+ + 3e– → La -2.37
Hg22+ + 2e– → 2Hg 0.80 Na+ + e– → Na -2.71
Fe3+ + e– → Fe2+ 0.77 Ca2+ + 2e– → Ca -2.76
O2 + 2H+ + 2e– → H2O2 0.68 Ba2+ + 2e– → Ba -2.90
MnO4 + e– → MnO42– 0.56 K+ + e– → K -2.92
I2 + 2e– → 2I– 0.54 Li+ + e– → Li -3.05
Cu + e– → Cu 0.52
SPONTANEITY OF
REDOX REACTIONS
To determine whether a given redox reaction
is spontaneous, apply a simple principle:
If the calculated voltage for a redox reaction is
a positive quantity, the reaction will be
spontaneous. If the calculated voltage is
negative, the reaction is not spontaneous.
EXERCISE
Find E0 values of the following spontaneous reactions:
Fe2+ + 2e- → Fe Eo = -0.44 V
V2+ + 2e- → V Eo = -1.19 V
EXERCISE
Find E0 values of the following spontaneous reactions:
Sn2+ + 2e- → Sn Eo = -0.14 V
Ag+ + e- → Ag Eo = +0.80 V
EXERCISE
Consider the voltaic cell in which the reaction is:
Ag+ + Cd → Ag + Cd2+
Calculate the Eo for the given reaction.
EXERCISE
Determine whether the following redox reaction below will occur:
Fe3+ + I- → Fe2+ + I2
Co2+ + Cu → Co + Cu2+
Effect of
Concentration on
Cell EMF
ELECTROMOTIVE
FORCE (EMF)
The force or electrical potential that pushes
the negatively charged electrons away from
the anode (− electrode) and pulls them toward
the cathode (+ electrode).
1J=1Cx1V
RELATIONSHIP OF G o
AND Eo
ΔG = - nFEcell
• ΔG = Free energy change (J)

• n = number of moles of electrons
transferred in the reaction
• F = Faraday’s constant (96, 485 C/mole e-)
• Eo = Cell potential (V)
EXERCISE
The standard cell potential at 25 °C is 1.10 V for the reaction:
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
Calculate the standard free-energy change (kJ) for this reaction
at 25 °C.
RELATIONSHIP OF K
AND Eo
ΔG = - nFEo
ΔG = - RTln(K)
nFEo = - RTln(K)
Eo = (RT/nF) ln(K)
EXERCISE
Consider the following reaction at 25oC:
3 Ag(s) + NO3-(aq) + 4H+(aq) → 3 Ag+(aq) + NO(g) + 2H2O
a. Find ∆Go
b. Find K
RELATIONSHIP OF Go, K,
AND Eo
∆𝐺° 𝐾 𝐸°𝑐𝑒𝑙𝑙 Reaction Under Standard-State

Conditions
Negative >1 Positive Favors formation of products.
=1 Reactants and products are equally

0 0
favored.
Positive <1 Negative Favors formation of reactants.

NERNST EQUATION
This is an equation correlating chemical
energy and the electric potential of a galvanic
cell or battery.
Ecell = Eocell – (RT/nF) ln(Q)

NERNST EQUATION
Reaction Under Standard-State
Q Ecell and Eocell
Conditions
The concentrations of products are
>1 Ecell < Eocell
high relative to those of reactants
The concentrations of reactant and
=1 Ecell = Eocell
product is equal
The concentrations of products low
<1 Ecell > Eocell
relative to reactants
NERNST EQUATION
Ecell = Eocell – (RT/nF) ln(Q)
Remember that gases enter Q as their partial

pressures in atmospheres. Species in water
solution enter as their molar concentrations.
Pure liquids and solids do not appear in the
expression for Q.
EXERCISE
Consider a voltaic cell in which the following reaction occurs:
O2(g, 0.98atm) + 4H+(aq, pH =1.24) + 4Br-(aq, 0.150M) → 2H2O + 2Br2(l)
a. Calculate E for the cell at 25oC
b. When the voltaic cell is at 35oC, E is measure to be 0.039 V.
What is the Eo at 35oC?
EXERCISE
Consider the voltaic cell at 25oC in which the reaction is
Zn(s) + 2H+(aq) → Zn2+ (aq) + H2(g)
It is found that the voltage is +0.56V when [Zn2+] = 0.85M and PH2 =
0.98 atm. What is the pH in the H2-H half-cell?
EXERCISE
Given the following reduction half-reaction:
Cr2O72- (aq) + 14 H+(aq) + 12e- → 2 Cr (s) + 7H2O
A current of 6.0 A and a voltage of 4.5V are used in the electroplating.
a. How many grams of chromium can be plated if the current is run for 48
minutes?
b. How long will it take (hr) to completely convert 215 mL of 1.25 M K2Cr2O7 to
elemental chromium?
c. How many kilowatt-hours of electrical energy are required to plate 1.0 g of
chromium?
THANK YOU!!!
ENGR. JOSE NICKO C. RODRIGUEZ

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UNIT 2: ENERGY

04 The Nernst Equation

LEORA and GEROA

Oxidation: Loses electron = increase

* Add the appropriate number of OH− to neutralize all H+ and to

To obtain the standard voltage for an oxidation

• ΔG = Free energy change (J)

∆𝐺° 𝐾 𝐸°𝑐𝑒𝑙𝑙 Reaction Under Standard-State

Negative >1 Positive Favors formation of products.

=1 Reactants and products are equally

Positive <1 Negative Favors formation of reactants.

Ecell = Eocell – (RT/nF) ln(Q)

Remember that gases enter Q as their partial

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