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Redox

This document discusses electrochemistry and redox reactions. It introduces electron transfer as the basis of electrochemical processes. It explains the concepts of oxidation, reduction and oxidation states. Rules are provided for assigning oxidation states. Examples are given of redox reactions under acidic and basic conditions using the ion-electron method. Redox titrations are also discussed as a method to determine concentrations using redox reactions and stoichiometry.

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136 views14 pages

Redox

This document discusses electrochemistry and redox reactions. It introduces electron transfer as the basis of electrochemical processes. It explains the concepts of oxidation, reduction and oxidation states. Rules are provided for assigning oxidation states. Examples are given of redox reactions under acidic and basic conditions using the ion-electron method. Redox titrations are also discussed as a method to determine concentrations using redox reactions and stoichiometry.

Uploaded by

amitaggarwal78
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PPT, PDF, TXT or read online on Scribd
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Electrochemistry

Chemical reactions and Electricity

1
Introduction

Electron transfer
The basis of electrochemical processes is
the transfer of electrons between
substances.
A e - + B

Oxidation; the reaction with oxygen.


4 Fe(s) + 3O 2 (g) Fe2O3 (s)

Why is rust Fe2O3 , 2Fe to 3O?

2
Oxidation of Iron
Electron transfer of iron- Electron
transfer to oxygen
Fe Fe3+ + 3e- 1/2 O2 + 2e- O2-

Net reaction:
4 Fe(s) + 3O2(g) Fe2O3(s)
Fe(+3) O(-2)

Fe2O3 : Electrical neutrality

3
Oxidation States
Definition -
Oxidation Process- (charge increase)
Lose electron (oxidation)
i.e., Fe Fe+3 + 3e- (reducing agent)
Reduction Process-(charge decrease)
Gain electrons (reduction)
i.e., 1/2 O2 + 2e- O2- (oxidizing agent)
Redox Process is the combination of an
oxidation and reduction process.

4
Symbiotic Process
Redox process always occurs together. In
redox process, one cant occur without the
other.
Example: 2 Ca (s) + O2 2CaO
Which is undergoing oxidation ? Reduction?
Oxidation: Ca Ca+2
Reduction: O2 O-2

Oxidizing agent; That which is responsible to oxidize


another.
O2 ; Oxidizing agent; The agent itself undergoes reduction

Reducing agent; That which is responsible to reduce


another.
Ca; Reducing agent; The agent itself undergoes oxidation
5
Rules of Oxidation State Assignment
1. Ox # = 0: Element in its free
state (not combine with different
element)

2. Ox # = Charge of ion:
Grp1 = +1, Grp2 = +2, Grp7
= -1, ...
3. F = -1: For other halogens (-1)
except when bonded to F or O.
4. O = -2: Except with fluorine or
other oxygen.
5. H = +1: Except with electropositive
element (i.e., Na, K) H = -1.
Ox. # = charge of molecule or
ion.

Highest and lowest oxidation


numbers of reactive main-group
elements. The A group number
shows the highest possible
oxidation number (Ox.#) for a
main-group element. (Two
important exception are O, which
never has an Ox# of +6 and F,
which never has an Ox# of +7.)
For nonmetals, (brown) and
metalloids (green) the A group
number minus 8 gives the lowest
6
Detailed: Assigning Oxidation
Number
Rules for Assigning an Oxidation Number (Ox#)
General
General rules
rules
1. For an atom in its elemental form (Na, O2, Cl2 ) Ox# = 0
2. For a monatomic ion: Ox# = ion charge
3. The sum of Ox# values for the atoms in a compound equals zero.
The sum of Ox# values for the atoms in a polyatomic ion equals the
ion charge.

Rules for specific atoms or


or periodic
periodic table
table groups.
groups.
1. For fluorine: Ox# = -1 in all compounds
2. For oxygen: Ox# = -1 in peroxides
Ox# = -2 in all other compounds (except with
F)
3. For Group 7A(17): Ox# = -1 in combination with metals,
nonmetals (except O), and other halogens lower in the
group.
4. For Group 1A(1): Ox# = +1 in all compounds
5. For Group 2A(2): Ox# = +2 in all compounds
6. For hydrogen: Ox# = +1 in combination with nonmetals
Ox# = -1 in combinations with metals and
7 boron
Redox Reactions - Ion electron
method.
Under Acidic conditions
1. Identify oxidized and reduced species
Write the half reaction for each.

2. Balance the half rxn separately except H & Os.


Balance: Oxygen by H2O
Balance: Hydrogen by H+
Balance: Charge by e -

3. Multiply each half reaction by a coefficient.


There should be the same # of e- in both half-rxn.

4. Add the half-rxn together, the e - should cancel.

8
Example: Acidic Conditions
I- + S2O8-2 I2 + S2O42-
Half Rxn (oxid): I- I2
Half Rxn (red): S2O8-2 I2 + S2O42-
Bal. chemical and e- : 2 I- I 2 + 2 e-
Bal. chemical O and H : 8e- + 8H+ + S2O8-2 S 2 O4 2 - +
4H2O

Mult 1st rxn by 4: 8I- 4 I2 + 8e-


Add rxn 1 & 2: 8I- 4 I2 + 8e-
8e- + 8H+ + S2O8-2 S2O42- + 4H2O

8I- + 8H+ + S2O8-2 4 I2 + S2O42- + 4H2O

9
Redox Reactions - Ion electron
method.
Under Basic conditions
1, 2. Procedure identical to that under acidic
conditions
Balance the half reaction separately except H & Os.
Balance Oxygen by H2O
Balance Hydrogen by H+
Balance charge by e-

3. Mult each half rxn such that both half- rxn


have same number of electrons

4. Add the half-rxn together, the e- should


cancel.

5. Eliminate H+ by adding:
10 H+ + OH- H O
Example: Basic Conditions

H2O2 (aq) + Cr2O7-2(aq ) Cr 2+


(aq) + O2 (g)
Half Rxn (oxid): 6e- + 14H+ + Cr2O7-2 (aq) 2Cr3+ + 7
H 2O
Half Rxn (red): ( H 2O 2 (aq) O2 + 2H+ + 2e- ) x 3

8 H+ + 3H2O2 + Cr2O72- 2Cr+3 + 3O2 + 7H2O

add: 8H2O 8 H+ + 8 OH-

8 H+ + 3H2O2 + Cr2O72- 2Cr+3 + 3O2 + 7H2O


8H2O 8 H+ + 8 OH-

Net Rxn: 3H2O2 + Cr2O72 - + H2O 2Cr+3 + 3O2 + 8 OH-

11
Exercise

Try these examples:


1. BrO4- (aq) + CrO2- (aq) BrO3- (aq) + CrO42- (aq) (basic)

2. MnO4- (aq) + CrO42- (aq) Mn2+ (aq) + CO2 (aq) (acidic)

3. Fe2+ (aq) + MnO4- (aq) Fe3+(aq) + Mn2+ (aq) (acidic)

12
Redox Titration
Balance redox chem eqn: Solve problem using stoichiometric
strategy.
Q: 1.225 g Fe ore requires 45.30 ml of 0.0180 M KMnO 4. How pure is the ore
sample?

When iron ore is titrated with KMnO4 . The equivalent point results
when:
KMnO4 (purple) Mn2+ (pink)
Mn (+7) Mn(+2)

Rxn: Fe+2 + MnO4- Fe+3 + Mn2+

Bal. rxn: 5 Fe2+ + MnO4- + 8 H+ 5 Fe3+ + Mn2+ + 4 H 2O


Note Fe2+ 5 Fe3+ : Oxidized Lose e- : Reducing Agent

Mol of MnO4- = 45.30 ml 0.180(mol/L) = 0.8154 mmol MnO 4-

Amt of Fe:= 0.8154 mmol 5 mol Fe+2 55.8 g =


0.2275 g
1 mol MnO4- 1 mol Fe2+
% Fe = (0.2275 g / 1.225 g) 100 = 18.6 %

13
Redox Titration: Example

1. A piece of iron wire weighting 0.1568 g is converted


to Fe2+ (aq) and requires 26.24 mL of a KMnO 4 (aq)
solution for its titration. What is the molarity of the
KMNO4 (aq) ?

2. Another substance that may be used to standardized


KMNO4 (aq) is sodium oxalate, Na2C2O4. If 0.2482 g of
Na2C2O4 is dissolved in water and titrated with 23.68 mL
KMnO4, what is the molarity of the KMnO 4 (aq) ?

14

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