U3 Oxidation and Reduction PPT Watermark

Unit 3: Equilibrium acids and redox reactions
Topic 2: Oxidation and reduction

Subtopic:
Redox reactions
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Oxidation
GAIN OF OXYGEN
2Mg + O2 ——> 2MgO
magnesium has been oxidised as it has gained oxygen
REMOVAL (LOSS) OF HYDROGEN
C2H5OH ——> CH3CHO + H2
ethanol has been oxidised as it has ‘lost’ hydrogen

Reduction
GAIN OF HYDROGEN
C2H4 + H2 ——> C2H6
ethene has been reduced as it has gained hydrogen
REMOVAL (LOSS) OF OXYGEN
CuO + H2 ——> Cu + H2O
copper(II) oxide has been reduced as it has ‘lost’ oxygen
However as chemistry became more sophisticated, it

was realised that another definition was required
Oxidation/Reduction in terms of electrons
Oxidation and reduction are not only defined as changes in O and H
...
OXIDATION Removal (loss) of electrons ‘OIL’

species will get less negative or more positive
REDUCTION Gain of electrons ‘RIG’

species will become more negative or less positive
REDOX When reduction and oxidation take place
Oxidizing agent = substance that causes oxidation to occur.

The oxidizing agent is reduced.
Reducing agent = substance that causes reduction to occur
The reducing agent is oxidized.
Which one is the oxidising/reducing agent?
Mg + 2H+  Mg2+ + H2
Oxidised Reduced
Reducing agent Oxidising agent
Cr2O72- + 14H+ + 6Fe2+  2Cr3+ + 6Fe3+ + 7H2O

Reduced Oxidised
Oxidising agent Reducing agent
2MnO4¯ + 5C2O42- + 16H+  2Mn2+ + 10CO2 + 8H2O

Reduced Oxidised
Oxidising agent Reducing agent
2S2O32- + I2  S4O62- + 2I¯

Oxidised Reduced
Reducing agent Oxidising agent
REDOX agents
Oxidising agents Reducing agents

• Oxygen • Hydrogen
• Chlorine and other halogens • Carbon and carbon monoxide
• Iron (III) ion • Metals
• Hydrogen peroxide (H2O2) • Iron (II) ion
• Manganate (VII) ion • Iodide ion
(Permanganate ion MnO4-) • Thosulfate ion (S2O32-)
• Dichromate (VI) ion (Cr2O72-)
Oxidation states
Used to... tell if oxidation or reduction has taken place
work out what has been oxidised and/or reduced
construct half equations and balance redox equations
ATOMS AND SIMPLE IONS

The number of electrons which must be added or removed to become neutral
atoms Na in Na =
cations Na in Na+ =
0
+1
neutral already ... no need to add any electrons
need to add 1 electron to make Na+ neutral
anions Cl in Cl¯ = -1 need to take 1 electron away to make Cl¯ neutral
Q. What are the oxidation states of the elements in the following?

a) C (0) b) Fe3+ (+3) c) Fe2+ (+2)
d) O2- (-2) e) He (0) f) Al3+ (+3)

Rules for Determining Oxidation State
1. Free elements are assigned an oxidation state of zero.
2. The sum of the oxidation states of all that atoms in a species
must be equal to the net charge on the species.
3. The alkali metals (Li, Na, K, Rb, and Cs) in compounds are
always assigned an oxidation state of +1.
4. Fluorine in compounds is always assigned an oxidation state
of -1.
5. The alkaline earth metals (Be, Mg, Ca, Sr, Ba, and Ra) and
also Zn and Cd in compounds are always assigned an
oxidation state of +2.
6. Hydrogen in compounds is assigned an oxidation state of +1,
unless assigned to a metal then it is -1 (metal hydrides).
7. Oxygen in compounds is assigned an oxidation state of -2,
except for H2O2, where it is -1 (hydrogen peroxide).
8. Halogen in compounds is assigned an oxidation state of -1.
Oxidation states in molecules
MOLECULES
The SUM of the oxidation states adds up to ZERO
ELEMENTS H in H2 = 0 both are the same and must add up to Zero
COMPOUNDS C in CO2 = +4
O in CO2 = -2 1 x +4 and 2 x -2 = Zero
Explanation
• because CO2 is a neutral molecule, the sum of the oxidation states must be zero
• for this, one element must have a positive OS and the other must be negative
HOW DO YOU DETERMINE WHICH IS THE POSITIVE ONE?
• the more electronegative species will have the negative value

• electronegativity increases across a period and decreases down a group
• O is further to the right than C in the periodic table so it has the negative value
Problems:
A. The oxidation states of the elements other than O, H or F are
SO2 O = -2 2 x -2 = - 4 overall neutral S = +4
NH3 H = +1 3 x +1 = +3 overall neutral N=-3
NO2 O = -2 2 x -2 = - 4 overall neutral N = +4
NH4+ H = +1 4 x +1 = +4 overall +1 N=-3
IF7 F = -1 7 x -1 = - 7 overall neutral I = +7
Cl2O7 O = -2 7 x -2 = -14 overall neutral Cl = +7 (14/2)
NO3¯ O = -2 3 x -2 = - 6 overall -1 N = +5
NO2¯
SO32-
O = -2
O = -2
2 x -2 = - 4
3 x -2 = - 6
overall -1
overall -2
N = +3
S = +4
S2O32- O = -2 3 x -2 = - 6 overall -2 S = +2 (4/2)
S4O62- O = -2 6 x -2 = -12 overall -2 S = +2½ ! (10/4)
MnO42- O = -2 4 x -2 = - 8 overall -2 Mn = +6
What is odd about the value of the oxidation state of S in S4O62- ?

An oxidation state must be a whole number (+2½ is the average value)
Naming with oxidation states
THE ROLE OF OXIDATION STATE IN NAMING SPECIES
To avoid ambiguity, the oxidation state is often included in the name of a species
manganese(IV) oxide shows that Mn is in the +4 oxidation state in MnO2

sulphur(VI) oxide for SO3 S is in the +6 oxidation state
dichromate(VI) for Cr2O72- Cr is in the +6 oxidation state
phosphorus(V) chloride for PCl5 P is in the +5 oxidation state
phosphorus(III) chloride for PCl3 P is in the +3 oxidation state
Q. Name the following... PbO2 lead(IV) oxide

SnCl2 tin(II) chloride
SbCl3 antimony(III) chloride
TiCl4 titanium(IV) chloride
BrF5 bromine(V) fluoride
Determining redox with oxidation states
OXIDATION AND REDUCTION IN TERMS OF ELECTRONS
REDUCTION in O.S. INCREASE in O.S.

Species has been REDUCED Species has been OXIDISED
Q. State if the changes involve oxidation (O) or reduction (R) or neither (N)
Fe2+ —> Fe3+ O +2 to +3

I2 —> I¯ R 0 to -1
F2
C2O42-
—>
—>
F2O
CO2
R
O
0 to -1
+3 to +4
H2O2 —> O2 O -1 to 0
H2O2 —> H2O R -1 to -2
Cr2O72- —> Cr3+ R +6 to +3
Cr2O72- —> CrO42- N +6 to +6
SO42- —> SO2 R +6 to +4
Balancing redox half equations
STEPS:
Atom 1. Balance the atoms of the oxidation species
Oxn no. 2. Write oxidation states
e-1 3. Balance with electrons
H+ 4. Balance charge with H+
H2O 5. Balance H with H2O
Problem 1: Balance the half reaction of Iron(II) being oxidised to
iron(III).
Step 1 Fe2+ ——> Fe3+

Step 2 +2 +3
Step 3 Fe2+ ——> Fe3+ + e¯
Problem 2: MnO4¯ being reduced to Mn2+ in acidic solution.
Step 1 MnO4¯ ———> Mn2+

Step 2 +7 +2
Step 3 MnO4¯ + 5e¯ ———> Mn2+
Step 4 MnO4¯ + 5e¯ + 8H+ ———> Mn2+
Step 5 MnO4¯ + 5e¯ + 8H+ ———> Mn2+ + 4H2O
Problem 3: Cr2O72- being reduced to Cr3+ in acidic solution.
Step 1 Cr2O72- ———> Cr3+

Cr2O72- ———> 2Cr3+
Step 2 2 Cr at +6 2 Cr at +3
Step 3 Cr2O72- + 6e¯ ——> 2Cr3+
Step 4 Cr2O72- + 6e¯ + 14H+ ——> 2Cr3+
Step 5 Cr2O72- + 6e¯ + 14H+ ——> 2Cr3+ + 7H2O

Combining half equations
A combination of two ionic half equations, one involving oxidation and the other
reduction, produces a REDOX equation. The equations are balanced as follows...
Step 1 Write out the two half equations

Step 2 Multiply the equations so that the number of electrons in each is the same
Step 3 Add the two equations and cancel out the electrons on either side
Step 4 If necessary, cancel any other species which appear on both sides
Problem 1: The reaction between manganate(VII) and iron(II)
Step 1 Fe2+ ——>
MnO4¯ + 5e¯ + 8H+ ——>
Fe3+ + e¯
Mn2+ + 4H2O
Oxidation
Reduction
Step 2 5Fe2+ ——> 5Fe3+ + 5e¯ multiplied by 5

MnO4¯ + 5e¯ + 8H+ ——> Mn2+ + 4H2O multiplied by 1
Step 3 MnO4¯ + 5e¯ + 8H+ + 5Fe2+ ——> Mn2+ + 4H2O + 5Fe3+ + 5e¯
Step 4 MnO4¯ + 8H+ + 5Fe2+ ——> Mn2+ + 4H2O + 5Fe3+

Subtopic:
Electrochemical cells
Comparison of Electrochemical Cells
Cations are
Galvanic/voltaic Electrolytic
produced Cations go to
at the cathode the cathode
produces need
electrical power
two
current source
electrodes
anode (-)
conductive
anode (+)
medium
cathode (+) cathode (-)
reduction at
cathode DG > 0
salt bridge
oxidation at
DG < 0 anode
Voltaic cell
Electrolytic cell
Subtopic:
Galvanic cells
Subtopic:
Standard electrode potential
Electromotive force (EMF)
A voltaic cell produces a potential difference known as the
electromotive force (EMF). The cell potential or electrode potential (E)
is measured by comparing it to a standard which is the standard
hydrogen electrode (SHE).
The standard hydrogen electrode (SHE)
STANDARD ELECTRODE POTENTIALS (Eº) are the potential values determined by
comparison with the STANDARD HYDROGEN ELECTRODE which is the potential
created by 1 mole of hydrogen ions at 100kPa H2 at 298K, which has the Eº value
0.00V.
Hydrogen gas at
298K (25°C) 100kPa pressure
www.mrwengibchemistry.com Platinum
Solution of 1M H+(aq)
electrode
e.g. 1M HCl or 0.5M H2SO4
Glass tube with holes to
allow gas to escape
The standard hydrogen electrode is assigned an E° value of 0.00V.
Equilibrium reached: 2H+(aq) + 2e- ⇌ H2(g)

Measurement of E⁰ values
SALT BRIDGE
HYDROGEN
(100kPa)
ZINC PLATINUM
ELECTRODE
ZINC SULPHATE (1M) HYDROCHLORIC
ACID (1M)
In the diagram the standard hydrogen electrode is shown coupled up to a zinc half cell.
The voltmeter reading gives the standard electrode potential of the zinc cell.
conditions temperature 298K

solution conc. 1 Molar (1 mol dm-3) with respect to ions
gases 100kPa
salt bridge filled with saturated potassium chloride solution
it enables the circuit to be completed
The electrochemical series
E° / V
F2(g) + 2e¯ 2F¯(aq) +2.87
MnO4¯(aq) + 8H+(aq) + 5e¯ Mn2+(aq) + 4H2O(l) +1.52
Cl2(g) + 2e¯ 2Cl¯(aq) +1.36
Cr2O72-(aq) + I4H+(aq) + 6e¯ 2Cr3+(aq) + 7H2O(l) +1.33
Br2(l) + 2e¯ 2Br¯(aq) +1.07
Ag+(aq) + e¯ Ag(s) +0.80 REACTION MORE
LIKELY TO WORK
Fe3+(aq) + e¯ Fe2+(aq) +0.77
O2(g) + 2H+(aq) + 2e¯ H2O2(aq) +0.68 SPECIES ON LEFT
I2(s) + 2e¯ 2I¯(aq) +0.54 ARE MORE POWERFUL
OXIDATION AGENTS
Cu+(aq) + e¯
Cu2+(aq) + 2e¯
Cu2+(aq) + e¯
Cu(s)
Cu(s)
Cu+(aq)
+0.52
+0.34
+0.15
2H+(aq) + 2e¯ H2(g) 0.00
Sn2+(aq) + 2e¯ Sn(s) -0.14
Fe2+(aq) + 2e¯ Fe(s) -0.44
Zn2+ (aq) + 2e¯ Zn(s) -0.76
Layout If species are arranged in order of their standard electrode potentials you
get a series that shows how good each substance is at gaining electrons.
All equations are written as reduction processes ... i.e. gaining electrons
A species with a higher E° value oxidises (reverses) one with a lower value
The electrochemical series
E° / V
F2(g) + 2e¯ 2F¯(aq) +2.87
MnO4¯(aq) + 8H+(aq) + 5e¯ Mn2+(aq) + 4H2O(l) +1.52
Cl2(g) + 2e¯ 2Cl¯(aq) +1.36
AN EQUATION
Cr2O72-(aq) + I4H+(aq) + 6e¯ 2Cr3+(aq) + 7H2O(l) +1.33 WITH A
Br2(l) + 2e¯ 2Br¯(aq) +1.07 HIGHER E°
Ag+(aq) + e¯ Ag(s) +0.80 VALUE WILL
Fe3+(aq) + e¯ Fe2+(aq) +0.77 REVERSE AN
O2(g) + 2H+(aq) + 2e¯ H2O2(aq) +0.68
EQUATION
WITH A LOWER
I2(s) + 2e¯ 2I¯(aq) +0.54
VALUE
Cu+(aq) + e¯
Cu2+(aq) + 2e¯
Cu2+(aq) + e¯
Cu(s)
Cu(s)
Cu+(aq)
+0.52
+0.34
+0.15
2H+(aq) + 2e¯ H2(g) 0.00
Sn2+(aq) + 2e¯ Sn(s) -0.14
Fe2+(aq) + 2e¯ Fe(s) -0.44
Zn2+ (aq) + 2e¯ Zn(s) -0.76
Application Chlorine is a more powerful oxidising agent - it has a higher E°

Chlorine will get its electrons by reversing the iodine equation
Cl2(g) + 2e¯ ——> 2Cl¯(aq) and 2I¯(aq) ——> I2(s) + 2e¯
Overall equation is Cl2(g) + 2I¯(aq) ——> I2(s) + 2Cl¯(aq)
Will be
reduced,
gain
electrons
Will be
oxidized,
lose
electrons
Predicting with E⁰ values
• E° value can be used to predict the feasibility of
redox and cell reactions.
• In theory ANY REDOX REACTION WITH A

POSITIVE E° VALUE WILL WORK.
• In practice, it proceeds if the E° value of the reaction
is greater than + 0.40V.
• An equation with a more positive E° value reverse a

less positive one.
Problem 1: What happens if an Sn(s) / Sn2+(aq) and a Cu(s) / Cu2+(aq) cell are
connected?
Write out the equations Cu2+(aq) + 2e¯ Cu(s) ; E° = +0.34V

Sn2+(aq) + 2e¯ Sn(s) ; E° = -0.14V
the half reaction with the more positive E° value is more likely to work
it gets the electrons by reversing the half reaction with the lower E° value
therefore Cu2+(aq) ——> Cu(s) and
the overall reaction is Cu2+(aq)
Sn(s)
+ Sn(s)
——> Sn2+(aq)
——> Sn2+(aq) + Cu(s)
the cell voltage is the difference in E° values... (+0.34) - (-0.14) = + 0.48V
If the value is positive the reaction will be spontaneous

Subtopic:
Electrolytic cells
Inert electrolysis – General predictions
1. If the metal is high in the reactivity series you will get hydrogen
2. If the metal is low in the reactivity series you will get the metal
3. If the halide solution is concentrated you will get the halogen
(chlorine, bromine, iodine). With other common negative ions you
will get oxygen.
OH- > Cl- > SO42-
Products of electrolysis
Cathode
Formation of the metal or formation of hydrogen
Anode
Formation of the non-metal, formation of oxygen or
oxidation of the electrode
Using standard electrode potentials to
determine products of electrolysis
1. Determine which products go the cathode and which go to the
anode
2. For the cathode determine which cation has the most positive
electrode potential. This will be reduced (gain e-1). The higher the
positive potential value the more naturally a reaction will occur
(atom + e-1  ion).
3. For the anode reverse the reactions and electrode potential values
before determining which is the most positive and likely to occur
(ion atom + e-1).
4. Include all setting out!!! (as seen in examples below)
NOTE!
• The following 3 examples are from the IB data book that gave
different equations for water
• QCAA data book has:
Electrolysis of CuSO4(aq)
Ions present: Cu2+, SO42-, H2O(l)
From the data booklet (water must be on it’s own on one side of the equation, polyatomic
ions don’t react).
Cathode:
Most positive
Anode:
-1.23 Most positive
Final equation:
Electrolysis of NaCl(aq)
Ions present: Na+, Cl-, H2O(l)
From the data booklet (water must be on it’s own on one side of the equation).
Cathode: Most positive
Anode: -1.23 Most positive BUT…
-1.36
BUT for concentrations of >25% Cl2 is preferred.
Final equation:
Electrolysis of water
Water can be electrolyzed with weak sulphuric acid, (or weak NaOH).
Ions present: SO42-, H2O(l), H+
From the data booklet (water must be on it’s own on one side of the equation,
polyatomic ions don’t react).
Cathode:
Most positive
Anode: -1.23 Most positive
Final equation:
Factors affecting relative amounts of products
in electrolysis
Electroplating
Electroplating
1. The item to be coated is placed on the negative
electrode so that metal cations will be reduced.
2. The anode may be a metal block, often the solution
is cyanide.
3. The anode dissolves and releases cations into the
solution.
4. Temperature, current, constitution and
concentration of solution all controlled.
Electroplating applications
Jewellery – cheaper to coat with gold than make out of
pure gold
Tin cans – coating with tin protects the steal cans from
rusting
Car parts and tools – coating with nickel and chromium
decreases friction, prevents rust, and looks shiny
Galvanizing – coating with zinc prevents rusting. Used
on car bodies, pipes, wire, sheeting.
Other applications – Fuel cells
Anode:
Cathode:
Overall:

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Unit 3: Equilibrium acids and redox reactions

Topic 2: Oxidation and reduction

2Mg + O2 ——> 2MgO

magnesium has been oxidised as it has gained oxygen

C2H5OH ——> CH3CHO + H2

ethanol has been oxidised as it has ‘lost’ hydrogen

C2H4 + H2 ——> C2H6

ethene has been reduced as it has gained hydrogen

CuO + H2 ——> Cu + H2O

copper(II) oxide has been reduced as it has ‘lost’ oxygen

However as chemistry became more sophisticated, it

OXIDATION Removal (loss) of electrons ‘OIL’

REDUCTION Gain of electrons ‘RIG’

Oxidizing agent = substance that causes oxidation to occur.

Cr2O72- + 14H+ + 6Fe2+  2Cr3+ + 6Fe3+ + 7H2O

2MnO4¯ + 5C2O42- + 16H+  2Mn2+ + 10CO2 + 8H2O

2S2O32- + I2  S4O62- + 2I¯

Oxidising agents Reducing agents

ATOMS AND SIMPLE IONS

Q. What are the oxidation states of the elements in the following?

d) O2- (-2) e) He (0) f) Al3+ (+3)

ELEMENTS H in H2 = 0 both are the same and must add up to Zero

HOW DO YOU DETERMINE WHICH IS THE POSITIVE ONE?

• the more electronegative species will have the negative value

What is odd about the value of the oxidation state of S in S4O62- ?

manganese(IV) oxide shows that Mn is in the +4 oxidation state in MnO2

dichromate(VI) for Cr2O72- Cr is in the +6 oxidation state

phosphorus(V) chloride for PCl5 P is in the +5 oxidation state

Q. Name the following... PbO2 lead(IV) oxide

REDUCTION in O.S. INCREASE in O.S.

Fe2+ —> Fe3+ O +2 to +3

Step 1 Fe2+ ——> Fe3+

Step 1 MnO4¯ ———> Mn2+

Step 1 Cr2O72- ———> Cr3+

Step 3 Cr2O72- + 6e¯ ——> 2Cr3+

Step 5 Cr2O72- + 6e¯ + 14H+ ——> 2Cr3+ + 7H2O

Step 1 Write out the two half equations

Problem 1: The reaction between manganate(VII) and iron(II)

Step 2 5Fe2+ ——> 5Fe3+ + 5e¯ multiplied by 5

Step 4 MnO4¯ + 8H+ + 5Fe2+ ——> Mn2+ + 4H2O + 5Fe3+

Standard electrode potential

The standard hydrogen electrode is assigned an E° value of 0.00V.

Equilibrium reached: 2H+(aq) + 2e- ⇌ H2(g)

conditions temperature 298K

Application Chlorine is a more powerful oxidising agent - it has a higher E°

• In theory ANY REDOX REACTION WITH A

• An equation with a more positive E° value reverse a

Write out the equations Cu2+(aq) + 2e¯ Cu(s) ; E° = +0.34V

therefore Cu2+(aq) ——> Cu(s) and

——> Sn2+(aq) + Cu(s)

the cell voltage is the difference in E° values... (+0.34) - (-0.14) = + 0.48V

If the value is positive the reaction will be spontaneous

Anode: -1.23 Most positive BUT…

Ions present: SO42-, H2O(l), H+

Anode: -1.23 Most positive

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