12 Topic 9 Reduction and Oxidation

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Topic 9

Reduction and Oxidation

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Definitions
Learn these off by heart

Anode: Where oxidation takes place. In electrolysis, it is the + electrode and anions are
attracted here.

Cathode: Where reduction takes place. In electrolysis, it is the – electrode and cations
are attracted here.

Electrolysis: Passage of electric current through an electrolyte. Amount of discharge is


affected by: 1) current; 2) charge on ion, 3) duration of electrolysis.

Electrolyte: A substance which does not conduct electricity when solid, but does when
molten or in aqueous solution and is chemically decomposed in the process.

Electrolytic cell: Used to make non-spontaneous redox reactions occur by providing


energy in the form of electricity from an external source.

Electroplating: A process of coating one metal with a thin layer of another metal, by
electrolysis.

Half cell: A metal in contact with an aqueous solution of its own ions.

Oxidation: The loss of electrons

Oxidizing agent: A substance that readily oxidizes other substances. Oxidizing agents
are thus reduced.

Reactivity: A measure of the readiness of a substance to gain or lose electrons. The


stronger the reducing agent or oxidizing agent, the more reactive it is.

Redox reaction: A reaction in which there is a transfer of electrons, i.e. reduction and
oxidation occurring simultaneously.

Reducing agent: A substance that readily reduces other substances. Reducing agents are
thus oxidized.

Reduction: The gain of electrons

Salt bridge: Allows the free movement of ions in a voltaic cell. Paper dipped in a
saturated solution of KNO3 is an example of a salt bridge.

Shorthand notation: For a voltaic cell. Example: Cu(s)/Cu2+(aq) || H+(aq) / H2(g)

Standard conditions: 298 K, 1 atm, 1.0 M.

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Standard electrode potential: The electrode potential of one half-cell compared against
another half-cell, by convention, the hydrogen half-cell, which is arbitrarily given a value
of 0 V.

Standard cell potential: Difference between the two standard electrode potentials of
the two half cells.

Standard hydrogen electrode: Arbitrarily assigned a potential of zero. Electrode


consists of an inert metal such as platinum dipped into a 1 M solution of HCl, where
hydrogen gas at 1 atm flows in.

Voltaic cell: Two different half-cells connected together to enable to electron


transferred during the redox reaction to produce energy in the form of electricity. The
electrons are produced at the half-cell that is most easily oxidized.

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Introduction to Oxidation and Reduction
Oxidation----Loss of electrons

Reduction ---- Gain of Electrons

LEO says "GER"

Loss of Electrons = Oxidation

Gain of Electrons = Reduction

OIL RIG  Oxidation is LOSS, Reduction is Gain

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Rules for Assigning Oxidation Numbers
1. Oxidation Numbers always refer to single
atoms
2. The oxidation number of an uncombined element i.e H2, Ne, Zn
is always 0
3. The oxidation number of Hydrogen is usually +1 i.e NH3, HCl

4. The oxidation number of Oxygen is usually -2 i.e H2O, SO2

5. The oxidation numbers of Alkali metals are +1, KCl, CaBr2


The Oxidation numbers of the Alkaline earth
metals are +2
6. Oxidation numbers on monatomic ions carry the K+, Cl-, O2-
charge of the ion
7. The sum of the oxidation numbers in a neutral i.e. H2SO4
compound is 0. In a polyatomic ion it equals
the charge of the ion H=+1, S= +6, O = -2

2(+1) + (+6) + 4(-2)=0

i.e. SO42-

S= +6, O = -2

(+6) +4(-2) = -2

Practice: Assign the oxidation numbers for each element in the following:

1. NO2 N= +4 O = -2

2. N2O5

3. HClO3

4. HNO3

5. Ca(NO3)2

6. KMnO4

7. Fe(OH)3

8. K2Cr2O7 .

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9. CO32-

10. CN-

11. K3Fe(CN)6

Use oxidation numbers to determine if a substance has been oxidized or reduced.

 An increase in the oxidation number indicates that an atom has lost electrons
and therefore oxidized.
 A decrease in the oxidation number indicates that an atom has gained
electrons and therefore reduced

Example

Zn + CuSO4  ZnSO4 + Cu

0 +2 +6-2 +2+6-2 0

Zn: 0  + 2 -- Oxidized

Cu: +2  0 -- Reduced

Practice: For each of the following reactions find the element oxidized and the element reduced

1. Cl2 + KBr  KCl + Br2

2. Cu + HNO3  Cu(NO3)2 + NO2 + H2 O

3. HNO3 + I2  HIO3 + NO2

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Oxidation States Practice

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Oxidation-Reduction Reactions

Oxidation-reduction (redox) reactions are reactions in which oxidation numbers change.


Oxidation numbers are either real charges or formal charges which help chemists keep track of
electron transfer. In practice, oxidation numbers are best viewed as a bookkeeping device.
 Oxidation cannot occur without reduction.
 In a redox reaction, the substance oxidized contains atoms which increase in oxidation
number. Oxidation is associated with electron loss (helpful mnemonic: LEO = Loss of
Electrons, Oxidation).
 The substance reduced contains atoms which decrease in oxidation number during the
reaction. Reduction is associated with electron gain (helpful mnemonic: GER = Gain of
Electrons, Reduction).
 An oxidizing agent is a substance which oxidizes something else: it itself is reduced! Also, a
reducing agent is a substance that reduces another reactant: it itself is oxidized.
 A disproportionation reaction is a reaction in which the same element is both oxidized and
reduced.

How to Assign Oxidation Numbers: The Fundamental Rules

 The oxidation number of any pure element is zero. Thus the oxidation number of H in H2 is
zero.
 The oxidation number of a monatomic ion is equal to its charge. Thus the oxidation number
of Cl in the Cl- ion is -1, that for Mg in the Mg+2 ion is +2, and that for oxygen in O2- ion is
-2.
 The sum of the oxidation numbers in a compound is zero if neutral, or equal to the charge if
an ion.
 The oxidation number of alkali metals in compounds is +1, and that of alkaline earths in
compounds is +2. The oxidation number of F is -1 in all its compounds.
 The oxidation number of H is +1 in most compounds. Exceptions are H2 (where H = 0) and
the ionic hydrides, such as NaH (where H = -1).
 The oxidation number of oxygen (O) is -2 in most compounds. Exceptions are O2 (where O =
0) and peroxides, such as H2O2 or Na2O2, where O = -1.
 For other elements, you can usually use the sum rule above to solve for the unknown
oxidation number.

Examples:

NO(g) has O = -2, so N = +2.

NO2 (g) has two oxygen atoms and each has O = -2.
Thus N + 2(-2) = 0, so N = +4.

SO42- has O = -2. Thus S + 4(-2) = -2. Solving the


equation gives S = -2 + 8 = +6.

K2Cr2O7 has K = +1 and O = -2. Thus 2(+1) + 2 Cr + 7(-


2) = 0; 2 Cr = 12; Cr = +6.

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Recognizing Oxidation-Reduction Reactions

Oxidation-reduction reactions are reactions in which


one type of atom increases in oxidation number (is oxidized) and another type of atom
decreases in oxidation number (is reduced). Thus to show that a reaction is a redox reaction,
you need to calculate oxidation numbers for the atoms in the reactants and products, and
document that changes are taking place. There are, however, a few useful generalizations.

 A large number (but not all!) of oxidation-reduction reactions contain one or more reactants
or products which are pure elements. Why is this true? Also, all electrochemical reactions
are redox reactions.
 Most acid-base reactions and most precipitation reactions are not redox reactions. Why?
Give some examples!

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Oxidation-Reduction Reactions

Oxidation-reduction (redox) reactions are reactions in which oxidation numbers change.


Oxidation numbers are either real charges or formal charges which help chemists keep track of
electron transfer. In practice, oxidation numbers are best viewed as a bookkeeping device.
 Oxidation cannot occur without reduction.
 In a redox reaction, the substance oxidized contains atoms which increase in oxidation
number. Oxidation is associated with electron loss (helpful mnemonic: LEO = Loss of
Electrons, Oxidation).
 The substance reduced contains atoms which decrease in oxidation number during the
reaction. Reduction is associated with electron gain (helpful mnemonic: GER = Gain of
Electrons, Reduction).
 An oxidizing agent is a substance which oxidizes something else: it itself is reduced! Also, a
reducing agent is a substance that reduces another reactant: it itself is oxidized.
 A disproportionation reaction is a reaction in which the same element is both oxidized and
reduced.

How to Assign Oxidation Numbers: The Fundamental Rules

 The oxidation number of any pure element is zero. Thus the oxidation number of H in H2 is
zero.
 The oxidation number of a monatomic ion is equal to its charge. Thus the oxidation number
of Cl in the Cl- ion is -1, that for Mg in the Mg+2 ion is +2, and that for oxygen in O2- ion is
-2.
 The sum of the oxidation numbers in a compound is zero if neutral, or equal to the charge if
an ion.
 The oxidation number of alkali metals in compounds is +1, and that of alkaline earths in
compounds is +2. The oxidation number of F is -1 in all its compounds.
 The oxidation number of H is +1 in most compounds. Exceptions are H2 (where H = 0) and
the ionic hydrides, such as NaH (where H = -1).
 The oxidation number of oxygen (O) is -2 in most compounds. Exceptions are O2 (where O =
0) and peroxides, such as H2O2 or Na2O2, where O = -1.
 For other elements, you can usually use the sum rule above to solve for the unknown
oxidation number.

Examples:

NO(g) has O = -2, so N = +2.

NO2 (g) has two oxygen atoms and each has O = -2.
Thus N + 2(-2) = 0, so N = +4.

SO42- has O = -2. Thus S + 4(-2) = -2. Solving the


equation gives S = -2 + 8 = +6.

K2Cr2O7 has K = +1 and O = -2. Thus 2(+1) + 2 Cr + 7(-


2) = 0; 2 Cr = 12; Cr = +6.

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Recognizing Oxidation-Reduction Reactions

Oxidation-reduction reactions are reactions in which


one type of atom increases in oxidation number (is oxidized) and another type of atom
decreases in oxidation number (is reduced). Thus to show that a reaction is a redox reaction,
you need to calculate oxidation numbers for the atoms in the reactants and products, and
document that changes are taking place. There are, however, a few useful generalizations.

 A large number (but not all!) of oxidation-reduction reactions contain one or more reactants
or products which are pure elements. Why is this true? Also, all electrochemical reactions
are redox reactions.
 Most acid-base reactions and most precipitation reactions are not redox reactions. Why?
Give some examples!

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Intro to Redox

1. 9.1.1 Define oxidation and reduction in terms of electron loss and gain. (1) a. How was
oxidation originally defined:

b. How do we now define oxidation and reduction?

c. How can you remember these simple definitions?

2. 9.1.2 Deduce the oxidation number of an element in a compound. (3)

a. Record the basic rules for assigning oxidation numbers:


i.

ii.

iii.

iv.

v.

vi.

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b. Determine the oxidation number for each element in the following reaction, then show the
oxidation and reduction half-reactions:

S(s) + O2(g)  SO2(g)

3. 9.1.3 State the names of compounds using oxidation numbers. (1)

4. 9.1.4 Deduce whether an element undergoes oxidation or reduction in reactions using


oxidation numbers. (3)

a. How can it be determined whether a reaction is considered to be a Redox equation?

NO2 KMnO4
N2O5 Fe(OH)3
HClO3 K2Cr2O7
HNO3 CO32-
Ca(NO3)2 K3Fe(CN)6

b. For each of the following reactions, first determine the oxidation state, then write the
oxidation and reduction half reactions for each:
i. Cl2 + KBr  KCl + Br2

ii. Cu + HNO3  Cu(NO3)2 + NO2 + H2O

iii. HNO3 + I2  HIO3 + NO2

c. Provide an example for an element which is both oxidized and reduced. What is this known as?

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Oxidation State Worksheet
In each of the following chemicals, determine the oxidation states of each element:

1) sodium nitrate ____________________________________

2) ammonia ____________________________________

3) zinc oxide ____________________________________

4) water ____________________________________

5) calcium hydride ____________________________________

6) carbon dioxide ____________________________________

7) nitrogen ____________________________________

8) sodium sulfate ____________________________________

9) aluminum hydroxide ____________________________________

10) magnesium phosphate ____________________________________

In each of the following reactions, determine what was oxidized and what was reduced.

11) Ca + H2O  CaO + H2

Element oxidized: ____________________________________

Element reduced: ____________________________________

12) 2 H2 + O2  2 H2O

Element oxidized: ____________________________________

Element reduced: ____________________________________

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Balancing Oxidation-Reduction Equations
A trial-and-error approach to balancing chemical equations involves playing with the equation
adjusting the ratio of the reactants and products until the following goals have been
achieved.

Goals for Balancing Chemical Equations

1. The number of atoms of each element on both sides of the equation is the same and
therefore mass is conserved.

2. The sum of the positive and negative charges is the same on both sides of the
equation and therefore charge is conserved. (Charge is conserved because electrons
are neither created nor destroyed in a chemical reaction.)

There are two situations in which relying on trial and error can get you into trouble. Sometimes
the equation is too complex to be solved by trial and error within a reasonable amount of time.
Consider the following reaction, for example.

3 Cu(s) + 8 HNO3(aq) 3 Cu2+(aq) + 2 NO(g) + 6 NO3-(aq) + 4 H2O(l)

Other times, more than one equation can be written that seems to be balanced. The following
are just a few of the balanced equations that can be written for the reaction between the
permanganate ion and hydrogen peroxide, for example.

2 MnO4-(aq) + H2O2(aq) + 6 H+(aq) 2 Mn2+(aq) + 3 O2(g) + 4 H2O(l)


2 MnO4-(aq) + 3 H2O2(aq) + 6 H+(aq) 2 Mn2+(aq) + 4 O2(g) + 6 H2O(l)
2 MnO4-(aq) + 5 H2O2(aq) + 6 H+(aq) 2 Mn2+(aq) + 5 O2(g) + 8 H2O(l)
2 MnO4-(aq) + 7 H2O2(aq) + 6 H+(aq) 2 Mn2+(aq) + 6 O2(g) + 10 H2O(l)

Equations such as these have to be balanced by a more systematic approach than trial and error.

The Half-Reaction Method of Balancing Redox Equations

A powerful technique for balancing oxidation-reduction equations involves dividing these


reactions into separate oxidation and reduction half-reactions. We then balance the half-
reactions, one at a time, and combine them so that electrons are neither created nor destroyed
in the reaction.

The steps involved in the half-reaction method for balancing equations can be illustrated by
considering the reaction used to determine the amount of the triiodide ion (I3-) in a solution by
titration with the thiosulfate (S2O32-) ion.

STEP 1: Write a skeleton equation for the reaction. The skeleton equation for the reaction on
which this titration is based can be written as follows.

I3- + S2O32- I- + S4O62-

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STEP 2: Assign oxidation numbers to atoms on both sides of the equation. The negative
charge in the I3- ion is formally distributed over the three iodine atoms, which means that the
average oxidation state of the iodine atoms in this ion is -1/3. In the S4O62- ion, the total
oxidation state of the sulfur atoms is +10. The average oxidation state of the sulfur atoms is
therefore +21/2.

I3- + S2O32- I- + S4O62-


-1/3 +2 -2 -1 +21/2 -2

STEP 3: Determine which atoms are oxidized and which are reduced.

STEP 4: Divide the reaction into oxidation and reduction half-reactions and balance these
half-reactions one at a time. This reaction can be arbitrarily divided into two half-reactions.
One half-reaction describes what happens during oxidation.

Oxidation: S2O32- S4O62-


+2 +21/2

The other describes the reduction half of the reaction.

Reduction: I3- I-
-1/3 -1

It doesn't matter which half-reaction we balance first, so let's start with the reduction half-
reaction. Our goal is to balance this half-reaction in terms of both charge and mass. It seems
reasonable to start by balancing the number of iodine atoms on both sides of the equation.

Reduction: I3- 3 I-

We then balance the charge by noting that two electrons must be added to an I 3- ion to produce
3 I- ions,

Reduction: I3- + 2 e- 3 I-

as can be seen from the Lewis structures of these ions shown in the figure below.

We now turn to the oxidation half-reaction. The Lewis structures of the starting material and
the product of this half-reaction suggest that we can get an S4O62- ion by removing two
electrons from a pair of S2O32- ions, as shown in the figure below.

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Oxidation: 2 S2O32- S4O62- + 2 e-

STEP 5: Combine these half-reactions so that electrons are neither created nor destroyed.
Two electrons are given off in the oxidation half-reaction and two electrons are picked up in the
reduction half-reaction. We can therefore obtain a balanced chemical equation by simply
combining these half-reactions.

(2 S2O32- S4O62- + 2 e-)


+ (I3- + 2 e- 3 I-)
I3- + 2 S2O32- 3 I- + S4O62-

STEP 6: Balance the remainder of the equation by inspection, if necessary. Since the overall
equation is already balanced in terms of both charge and mass, we simply introduce the symbols
describing the states of the reactants and products.

I3-(aq) + 2 S2O32-(aq) 3 I-(aq) + S4O62-(aq)

Redox Reactions In Acidic Solutions

Some might argue that we don't need to use half-reactions to balance equations because they
can be balanced by trial and error. The half-reaction technique becomes indispensable, however,
in balancing reactions such as the oxidation of sulfur dioxide by the dichromate ion in acidic
solution.

H+
SO2(aq) + Cr2O72-(aq)  SO42-(aq) + Cr3+(aq)

The reason why this equation is inherently more difficult to balance has nothing to do with the
ratio of moles of SO2 to moles of Cr2O72-; it results from the fact that the solvent takes an
active role in both half-reactions.

Practice Problem 3:

Use half-reactions to balance the equation for the reaction between sulfur dioxide and the
dichromate ion in acidic solution.

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The reaction between oxalic acid and potassium permanganate in acidic solution is a classical
technique for standardizing solutions of the MnO4- ion. These solutions need to be standardized
before they can be used because it is difficult to obtain pure potassium permanganate. There
are three sources of error.

 Samples of KMnO4 are usually contaminated by MnO2.


 Some of the KMnO4 reacts with trace contaminants when it dissolves in water, even when
distilled water is used as the solvent.
 The presence of traces of MnO2 in this system catalyzes the decomposition of MnO4- ion
on standing.

Solutions of this ion therefore have to be standardized by titration just before they are used.
A sample of reagent grade sodium oxalate (Na2C2O4) is weighed out, dissolved in distilled water,
acidified with sulfuric acid, and then stirred until the oxalate dissolves. The resulting oxalic
acid solution is then used to titrate MnO4- to the endpoint of the titration, which is the point at
which the last drop of MnO4- ion is decolorized and a faint pink color persists for 30 seconds.

Practice Problem 4:

We can determine the concentration of an acidic permanganate ion solution by titrating this
solution with a known amount of oxalic acid until the charactistic purple color of the MnO4- ion
disappears.

H2C2O4(aq) + MnO4-(aq) CO2(g) + Mn2+(aq)

Use the half-reaction method to write a balanced equation for this reaction.

Solutions of the MnO4- ion that have been standardized against oxalic acid, using the equation
balanced in the previous practice problem, can be used to determine the concentration of
aqueous solutions of hydrogen peroxide, using the equation balanced in the following practice
problem.

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Practice Problem 5:

An endless number of balanced equations can be written for the reaction between the
permanganate ion and hydrogen peroxide in acidic solution to form the manganese (II) ion and
oxygen:

MnO4-(aq) + H2O2(aq) Mn2+(aq) + O2(g)

Use the half-reaction method to determine the correct stoichiometry for this reaction.

Redox Reactions in Basic Solutions

Half-reactions are also valuable for balancing equations in basic solutions. The key to success
with these reactions is recognizing that basic solutions contain H2O molecules and OH- ions. We
can therefore add water molecules or hydroxide ions to either side of the equation, as needed.

The following equation describes the reaction between the permanganate ion and hydrogen
peroxide in an acidic solution.

2 MnO4-(aq) + 5 H2O2(aq) + 6 H+(aq) 2 Mn2+(aq) + 5 O2(g) + 8 H2O(l)

It might be interesting to see what happens when this reaction occurs in a basic solution.

Practice Problem 6:

Write a balanced equation for the reaction between the permanganate ion and hydrogen
peroxide in a basic solution to form manganese dioxide and oxygen.

MnO4-(aq) + H2O2(aq) MnO2(s) + O2(g)

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Reactions in which a single reagent undergoes both oxidation and reduction are called
disproportionation reactions. Bromine, for example, disproportionates to form bromide and
bromate ions when a strong base is added to an aqueous bromine solution.

OH-
Br2 Br - + BrO3-

Practice Problem 7:

Write a balanced equation for the disproportionation of bromine in the presence of a strong
base.

Molecular Redox Reactions

Lewis structures can play a vital role in understanding oxidation-reduction reactions with
complex molecules. Consider the following reaction, for example, which is used in the
Breathalyzer to determine the amount of ethyl alcohol or ethanol on the breath of individuals
who are suspected of driving while under the influence.

3 CH3CH2OH(g) + 2 Cr2O72-(aq) + 16 H+(aq) 3 CH3CO2H(aq) + 4 Cr3+(aq) + 11 H2O(l)

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We could balance the oxidation half-reaction in terms of the molecular formulas of the starting
material and the product of this half-reaction.

Oxidation: C2H6O C2H4O2

It is easier to understand what happens in this reaction, however, if we assign oxidation


numbers to each of the carbon atoms in the Lewis structures of the components of this
reaction, as shown in the figure below.

The carbon atom in the CH3 group in ethanol is assigned an oxidation state of -3 so that it can
balance the oxidation states of the three H atoms it carries. Applying the same technique to
the CH2OH group in the starting material gives an oxidation state of -1.

The carbon in the CH3 group in the acetic acid formed in this reaction has the same oxidation
state as it did in the starting material: -3. There is a change in the oxidation number of the
other carbon atom, however, from -1 to +3. The oxidation half-reaction therefore formally
corresponds to the loss of four electrons by one of the carbon atoms.

Oxidation: CH3CH2OH CH3CO2H + 4 e-

Because this reaction is run in acidic solution, we can add H+ and H2O molecules as needed to
balance the equation.

Oxidation: CH3CH2OH + H2O CH3CO2H + 4 e- + 4 H+

The other half of this reaction involves a six-electron reduction of the Cr2O72- ion in acidic
solution to form a pair of Cr3+ ions.

Reduction: Cr2O72- + 6 e- 2 Cr3+

Adding H+ ions and H2O molecules as needed gives the following balanced equation for this half-
reaction.

Reduction: Cr2O72- + 14 H+ + 6 e- 2 Cr3+ + 7 H2O

We are now ready to combine the two half-reactions by assuming that electrons are neither
created nor destroyed in this reaction.

3(CH3CH2OH + H2O CH3CO2H + 4 e- + 4 H+)


2(Cr2O72- + 14 H+ + 6 e- 2 Cr3+ + 7 H2O)

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3 CH3CH2OH + 2 Cr2O72- + 28 H+ + 3 H2O
3 CH3CO2H + 4 Cr3+ + 12 H+ + 14 H2O

Simplifying this equation by removing 3 H2O molecules and 12 H+ ions from both sides of the
equation gives the balanced equation for this reaction.

3 CH3CH2OH(g) + 2 Cr2O72-(aq) + 16 H+(aq) 3 CH3CO2H(aq) + 4 Cr3+(aq) + 11 H2O(l)

Practice Problem 8:

Methyllithium (CH3Li) can be used to form bonds between carbon and either main-group metals
or transition metals:

HgCl2(s) + 2 CH3Li(l) Hg(CH3)2(l) + 2 LiCl(s)

WCl6(s) + 6 CH3Li(l) W(CH3)6(l) + 6 LiCl(s)

It can be used also to form bonds between carbon and other nonmetals:

PCl3(s) + 3 CH3Li(l) P(CH3)3(l) + 3 LiCl(s)

or between carbon atoms:

CH3Li(l) + H2CO(g) [CH3CH2OLi] CH3CH2OH(l)

Use Lewis structures to explain the stoichiometry of the following oxidation-reaction, which is
used to synthesize methyllithium:

CH3Br(l) + 2 Li(s) CH3Li(l) + LiBr(s)

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How to Balance Equations for Oxidation-Reduction Reactions

Oxidation-reduction (redox) reactions are reactions in which oxidation numbers change.


Oxidation numbers are either real charges or formal charges which help chemists keep track of
electron transfer. In practice, oxidation numbers are best viewed as a bookkeeping device.
Oxidation cannot occur without reduction. In a redox reaction the substance which is
oxidized contains atoms which increase in oxidation number. Oxidation is associated with
electron loss (helpful mnemonic: LEO = Loss of Electrons, Oxidation). Conversely, the
substance which is reduced contains atoms which decrease in oxidation number during the
reaction. Reduction is associated with electron gain (helpful mnemonic: GER = Gain of
Electrons, Reduction).
Chemists often talk about oxidizing and reducing
agents. Be careful with these terms! An oxidizing agent is a substance which oxidizes
something else: it itself is reduced! Also, a reducing agent is a substance that reduces another
reactant: it itself is oxidized. A disproportionation reaction is a reaction in which the same
element is both oxidized and reduced.

How to Assign Oxidation Numbers: The Fundamental Rules

Rules for assigning oxidation numbers are as


follows:

• The oxidation number of any pure element is zero. Thus the oxidation number of H in
H2 is zero.

• The oxidation number of a monatomic ion is equal to its charge. Thus the oxidation
number of Cl in the Cl- ion is -1, that for Mg in the Mg+2 ion is +2, and that for
oxygen in O2- ion is -2.

• The sum of the oxidation numbers in a compound is zero if neutral, or equal to the
charge if an ion.

• The oxidation number of alkali metals in compounds is +1, and that of alkaline earths in
compounds is +2. The oxidation number of F is -1 in all its compounds.

• The oxidation number of H is +1 in most compounds. Exceptions are H2 (where H = 0)


and the ionic hydrides, such as NaH (where H = -1).

• The oxidation number of oxygen (O) is -2 in most compounds. Exceptions are O2


(where O = 0) and peroxides, such as H2O2 or Na2O2, where O = -1.

• For other elements, you can usually use rule (3) to solve for the unknown oxidation
number.

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Examples:

NO(g) has O = -2, so N = +2.

NO2(g) has O = -2, so N = +4.

SO42- has O = -2. Thus S + 4(-2) = -2. Solving the


equation gives S = -2 + 8 = +6.

K2Cr2O7 has K = +1 and O = -2. Thus 2(+1) + 2 Cr + 7(-


2) = 0; 2 Cr = 12; Cr = +6.

How to Balance Redox Reactions Using the Method of Half-Reactions

Oxidation-reduction reactions are often tricky to balance without using a systematic


method. We shall use the method of half-reactions which is outlined in detail below.

Method in Acidic (or Neutral) Solution

Suppose you are asked to balance the equation below:

NO2– + MnO4–  NO3– + Mn+2 (in acid solution)

Begin by writing the unbalanced oxidation and reduction half-reactions (you do not need to know
which is which):

NO2–  NO3–

MnO4–  Mn+2

Next, balance for atoms. First do this for atoms other than O and H. (Both equations above
are already balanced for N and Mn, so no change is needed in this example.) Then balance for O
atoms by adding H2O to the reaction side deficient in O:

H2O + NO2–  NO3–

MnO4–  Mn+2 + 4 H2O

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This leaves H atoms unbalanced. In acidic (or neutral) solution, balance for H atoms by adding
H+ to the side deficient in H:

H2O + NO2–  NO3– + 2 H+

8 H+ + MnO4–  Mn+2 + 4 H2O

The next step is to balance for charge. To do this, add electrons (e-) to the more positive
side:

H2O + NO2-  NO3- + 2 H+ + 2 e-

5 e- + 8 H+ + MnO4-  Mn+2 + 4 H2O

Now you need to multiply the equations by appropriate factors so that the number of
electrons lost in the oxidation half-reaction (LEO) is equal to the number of electrons gained in
the reduction half-reaction (GER):

5 x [ H2O + NO2-  NO3- + 2 H+ + 2 e- ]

2 x [ 5 e- + 8 H+ + MnO4-  Mn+2 + 4 H2O ]

Then, sum the above equations to obtain

5H2O + 5NO2- + 10 e- + 16H+ + 2MnO4-  5NO3- + 10H+ + 10 e- + 2Mn+2 + 8H2O

Finally, simplify by subtracting out species that are identical on both sides. Our final balanced
redox equation is

5 NO2- + 6 H+ + 2 MnO4- 5 NO3- + 2 Mn+2 + 3 H2O

Check this equation to confirm that it is balanced for atoms and balanced for charge.

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Method in Basic Solution

Suppose you are asked to balance the equation below:

I- + MnO4-  I2 + MnO2 (in basic solution)

Begin by writing the unbalanced oxidation and reduction half-reactions (you do not need to know
which is which):

I-  I2

MnO4-  MnO2

Next, balance for atoms. First do this for atoms other than O and H:

2 I- I2

MnO4-  MnO2

Then balance for O atoms by adding H2O to the reaction side deficient in O:

2 I- I2

MnO4-  MnO2 + 2 H2O

This leaves H atoms unbalanced. In basic solution (just as in acidic or neutral solution) first
balance for H atoms by adding H+ to the side deficient in H:

4 H+ + MnO4-  MnO2 + 2 H2O

In basic solution, follow this step by neutralizing the H+; do this by adding an equivalent amount
of OH- to both sides of the equation.

4 OH- + 4 H+ + MnO4-  MnO2 + 2 H2O + 4 OH-

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Then form water on the side which has both H+ and OH- (recall that H+ + OH-  H2O): in this
case we form 4 H2O on the left:

4 H2O + MnO4-  MnO2 + 2 H2O + 4 OH-

Next simplify the water by subtracting 2 H20 from both sides. The half-reactions are now:

2 I– I2

2 H2O + MnO4–  MnO2 + 4 OH–

At this point the equations should be balanced for atoms. The next step is to balance
for charge. To do this, add electrons (e–) to the more positive side:

2 I–  2 + 2 e–

3 e– + 2 H2O + MnO4–  MnO2 + 4 OH–

Now you need to multiply the equations by appropriate factors so that the number of
electrons lost in the oxidation half-reaction (LEO) is equal to the number of electrons gained in
the reduction half-reaction (GER):

3 x [ 2 I-  I2 + 2 e- ]

2 x [ 3 e- + 2 H2O + MnO4-  MnO2 + 4 OH- ]

Sum the equations to obtain

6 I- + 6 e- + 4 H2O + 2 MnO4-  2 + 6 e- 2 + 8 OH-

Finally, simplify by subtracting out species that are identical on both sides:

6 I- + 4 H2O + 2 MnO4-  I2 + 2 MnO2 + 8 OH-

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Check our final equation above to confirm that it is balanced for atoms and balanced for charge.

Exercises:

Balance the following redox reactions. In each case

• (a) give the balanced half-reactions; identify the oxidation half-reaction and the reduction
half-reaction.

• (b) give the balanced net reaction.

• (c) identify the oxidizing agent and the reducing agent.

_______________________________________________________________________

1. Cl2(g) + S2O32-(aq)  Cl-(aq) + SO42-(aq) in acid solution.

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Answers:

(a) S2O32-(aq) + 5 H20  2 SO42-(aq) + 10 H+(aq) + 8 e- (oxidation half-reaction – LEO);

Cl2(g) + 2 e- 2 Cl-(aq) (reduction half-reaction – GER).

(b) S2O32-(aq) + 5 H20 + 4 Cl2(g)  2 SO42-(aq) + 10 H+(aq) + 8 Cl-(aq)

(c) S2O32-(aq) is the reducing agent; Cl2(g) is the oxidizing agent.

_______________________________________________________________________

2. O3(g) + Br-(aq)  O2(g) + BrO-(aq) in basic solution.

Answers:

(a) Br - (aq) + H20 + 2 OH-(aq) BrO-(aq) + 2H2O + 2 e- or, after simplifying,

Br - (aq) + 2 OH-(aq) BrO-(aq) + H2O + 2 e- (oxidation half-reaction – LEO);

O3(g) + 2 H2O + 2 e-  O2(g) + H2O + 2 OH-(aq) or, after simplifying,

O3(g) + H2O + 2 e-  O2(g) + 2 OH-(aq) (reduction half-reaction – GER).

(b) Br - (aq) + O3(g)  BrO-(aq) + O2(g)

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(c) Br - (aq) is the reducing agent; O3(g) is the oxidizing agent.

_______________________________________________________________________

3. Balance the reaction, Br2(l)  Br-(aq) + BrO3-(aq) in basic solution.

Hint: this is a disproportionation reaction!

Answer: 6 Br2(l) + 12 OH- -(aq) + 2 BrO3-(aq) + 6 H2O

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How to Balance Redox Equations

1) Above each atom in the original equation write the atoms oxidation number.

2) Identify which atoms have changed their charge.

3) Write the half-reactions and make the number of electrons gained EQUAL the
number of electrons lost.

4) Rewrite the original equation with the new coefficients.

5) Add H+ and H2O (acidic) or H2O and OH– (basic) as needed to balance the number
of oxygen atoms and the charges.

6) Check that the sum of the charges on both sides of the equation are equal.

For Example:

Balance the following equation: Cr2+ + I2 ----> Cr3+ + I1-

Step 1 Cr2+ + I20 ----> Cr3+ + I1-

Steps 2 & 3 2 ( Cr2+ – 1 e- ---> Cr3+ ) Cr became more positive, it lost electrons
( I2 + 2e ---> 2 I1- ) I became more negative, it gained electrons

Step 4 2 Cr2+ + I20 ----> 2 Cr3+ + 2I1-

Step 5 Not needed

Step 6 (4 +) + ( 0 ) (6 +) + (2 -)
4+=4+
Equation is balanced!

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Even More Redox Equations to Balance

1) Fe2+ + MnO4  Fe3+ + Mn2+

2) NO3 - + I2  IO3- + NO2

3) H2O2 + I-  H2O + I2

4) C2H4 + MnO4-  Mn2+ + CO2

5) PbO2(s) + Cl-  Pb2+ + Cl2

6) As2S3 + NO3-  AsO43- + SO42- + NO

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Redox and Electrochemical Cells
1. Assign oxidation numbers to all elements in the following componds and ions:

a. NH4+ b. CuCl2 c. H2O d. SO2 e. Fe2O3

f. NO3- g. MnO2 h. PO43- i. K2Cr2O7 j. MnO4-

2. Use oxidation numbers to deduce which species is oxidised and which is reduced in the
following reactions:

a. Sn2+(aq) + 2Fe3+(aq) → Sn4+(aq) + 2Fe2+(aq)

b. Cl2(aq) + 2NaBr(aq) → Br2(aq) + 2NaCl(aq)

c. 2FeCl2(aq) + Cl2(aq) → 2FeCl3(aq)

d. H2O(l) + 2F2(aq) → 4HF(aq) + O2(g)

e. I2(aq) + SO3-(aq) + H2O(l) → 2I-(aq) + SO42-(aq) + 2H+(aq)

3. Identify the oxidizing and reducing agents in each of the following reactions:

a. H2(g) + Cl2(g) → 2HCl(g)

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b. 2Al(s) + 3PbCl2(s) → 2AlCl3(s) + 3Pb(s)

c. Cl2(g) + 2KI(aq) → 2KCl(aq) + I2(aq)

d. CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)

4. Deduce the half equations of oxidation and reduction for the following reactions:

a. Ca(s) + 2H+(aq) → Ca2+(aq) + H2(g)

b. 2Fe2+(aq) + Cl2(aq) → 2Fe3+(aq) + 2Cl-(aq)

c. Sn2+(aq) + 2Fe3+(aq) → Sn4+(aq) + 2Fe2+(aq)

d. Cl2(aq) + 2Br-(aq) → 2Cl-(aq) + Br2(aq)

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5. Use the half-reaction method to write balanced equations for the following reactions:

a. Magnesium reducing lead ions to lead metal

b. Sulfur dioxide being oxidised to sulfate through reducing iodine to iodide ions

c. Hydrogen peroxide oxidising iron(II) to iron(III) in acidic solution

d. Zinc reducing acidified dichromate(VI) ions to chromium(III)

e. Acidified permanganate(VII) ions oxidising methanol to CO2 and H2O

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6. If wine is left in an open bottle it often tastes ‘vinegary’ a few days later. This is
because of the oxidation of the ethanol to ethanoic acid (remember that?) by
atmospheric oxygen.

a. Write the half-equation for the oxidation of ethanol to ethanoic acid.

b. What is the intial and final average oxidation number for the carbons in this
change?

c. Write the half-equation for the reduction of oxygen in acidic solution.

d. Combine these to produce an overall equation for the reaction.

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Here is a small part of the reactivity series of metals:

Mg strongest reducing agent

Al

Zn

Fe

Pb

Cu

Ag weakest reducing agent

7. Refer to the reactivity series given above to predict whether the following reactions will
occur:

a. ZnCl2(aq) + 2Ag(s) → 2AgCl(s) + Zn(s)

b. 2FeCl3(aq) + 3Mg(s) → MgCl2(aq) + 2Fe(s)

We learned earlier that the tendency for the halogens to act as oxidizing agents decreases
down a group:

F2 strongest oxidizing agent

Cl2

Br2

I2 weakest oxidizing agent

8. Use the two reactivity series given to predict whether reactions will occur between the
following reactants and write equations where relevant.

a. CuCl2(aq) + Ag(s)

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b. Fe(NO3)2 + Al(s)

c. NaI(aq) + Br2(aq)

d. KCl + I2

9. a. Use the following reactions to deduce the order of reactivity of the elements w,
x, y, z putting the most reactive first.

w + x+ → w+ + x; y+ + z → no rxn; x + z+ → x+ + z; x + y+ → x+ + y

b. Which of the following reactions would you expect to occur according to the
reactivity series you established in a?

i. w + + y → w + y+ ii. w + + z → w + z+

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10. The following reactions are spontaneous as written.

Fe(s) + Cd2+(aq) → Fe2+(aq) + Cd(s)

Cd(s) + Sn2+(aq) → Cd2+(aq) + Sn(s)

Sn(s) + Pb2+(aq) → Sn2+(aq) + Pb(s)

a. State and explain which is the strongest oxidizing agent in the examples above.

b. State and explain which is the strongest reducing agent in the examples above.

c. State with a reason which of the following pairs will react spontaneously:

Sn(s) + Fe2+; Cd(s) + Pb2+; or Fe(s) + Pb2+.

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11. Draw a voltaic cell with one half cell consisting of Mg and a solution of Mg2+ ions and the
other consisting of Zn and a solution of Zn2+ ions. Label the electrodes with name and
charge, the direction of electron and ion movement and write equations for the reactions
occurring at each electrode.

12. Predict what would happen if an iron spatula was left in a solution of copper(II) sulfate
overnight.

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13. You are intending to construct an electrochemical cell using two metals chosen from
copper, iron, magnesium and zinc, in aqueous solutions of their salts. Explain how you
would use a reactivity series to choose the pair of metals that would produce the
greatest potential difference for the cell and predict which metal will be the anode and
which the cathode.

14. In each of the following half-reactions, give the species being reduced and the number
of electrons needed to balance the half-reactions:

a. AgBrO3 + ?e- → Ag + BrO3-

b. HCrO4- + 7H+ + ?e- → Cr3+ + 4H2O

c. WO3 + 6H+ + ?e- → W + 3H2O

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15. Identify the species in each of the following reactions that would receive electrons from
the cathode and that would lose electrons at the anode in each of the following galvanic cells:

a. Au3+(aq) + Zn(s)  Au+(aq) + Zn2+(aq)

b. 3 Pu6+(aq) + 2 Cr3+(aq)  2 Cr6+(aq) + 3 Pu4+(aq)

16. In electrolysis as well as in a battery, oxidation occurs at the _______________ and


reduction occurs at the _______________.

17. a. Write the two half-reactions for the electrolysis of molten NaCl and indicate which
reaction occurs at each electrode.

b. Write the overall equation for the electrolysis of NaCl(l).

756 Version 1 2012


Common Oxidizing Agents and Reducing Agents
In looking at oxidation-reduction reactions, we can focus on the role played by a particular
reactant in a chemical reaction. What is the role of the permanganate ion in the following
reaction, for example?

2 MnO4-(aq) + 5 H2C2O4(aq) + 6 H+(aq) 10 CO2(g) + 2 Mn2+(aq) + 8 H2O(l)

Oxalic acid is oxidized to carbon dioxide in this reaction and the permanganate ion is reduced to
the Mn2+ ion.

Oxidation: H2C2O4 CO2


+3 +4
Reduction: MnO4- Mn2+
+7 +2

The permanganate ion removes electrons from oxalic acid molecules and thereby oxidizes the
oxalic acid. Thus, the MnO4- ion acts as an oxidizing agent in this reaction. Oxalic acid, on the
other hand, is a reducing agent in this reaction. By giving up electrons, it reduces the MnO4- ion
to Mn2+.

Atoms, ions, and molecules that have an unusually large affinity for electrons tend to be good
oxidizing agents. Elemental fluorine, for example, is the strongest common oxidizing agent. F2 is
such a good oxidizing agent that metals, quartz, asbestos, and even water burst into flame in its
presence. Other good oxidizing agents include O2, O3, and Cl2, which are the elemental forms of
the second and third most electronegative elements, respectively.

Another place to look for good oxidizing agents is among compounds with unusually large
oxidation states, such as the permanganate (MnO4-), chromate (CrO42-), and dichromate (Cr2O72-
) ions, as well as nitric acid (HNO3), perchloric acid (HClO4), and sulfuric acid (H2SO4). These
compounds are strong oxidizing agents because elements become more electronegative as the
oxidation states of their atoms increase.

Good reducing agents include the active metals, such as sodium, magnesium, aluminum, and zinc,
which have relatively small ionization energies and low electro-negativities. Metal hydrides, such
as NaH, CaH2, and LiAlH4, which formally contain the H- ion, are also good reducing agents.

Some compounds can act as either oxidizing agents or reducing agents. One example is hydrogen
gas, which acts as an oxidizing agent when it combines with metals and as a reducing agent when
it reacts with nonmetals.

2 Na(s) + H2(g) 2 NaH(s)


H2(g) + Cl2(g) 2 HCl(g)

Another example is hydrogen peroxide, in which the oxygen atom is in the -1 oxidation state.
Because this oxidation state lies between the extremes of the more common 0 and -2 oxidation
states of oxygen, H2O2 can act as either an oxidizing agent or a reducing agent.

757 Version 1 2012


The Relative Strengths of Oxidizing and Reducing Agents

Spontaneous oxidation-reduction reactions convert the stronger of a pair of oxidizing agents


and the stronger of a pair of reducing agents into a weaker oxidizing agent and a weaker
reducing agent. The fact that the following reaction occurs, for example, suggests that copper
metal is a stronger reducing agent than silver metal and that the Ag+ ion is a stronger oxidizing
agent than the Cu2+ ion.

Cu(s) + 2 Ag+(aq) Cu2+(aq) + 2 Ag(s)


stronger stronger weaker weaker
reducing oxidizing oxidizing reducing
agent agent agent agent

On the basis of many such experiments, the common oxidation-reduction half-reactions have
been organized into a table in which the strongest reducing agents are at one end and the
strongest oxidizing agents are at the other, as shown in the table below. By convention, all of
the half-reactions are written in the direction of reduction. Furthermore, by convention, the
strongest reducing agents are usually found at the top of the table.

The Relative Strengths of Common Oxidizing Agents and Reducing Agents

K+ + e- K Best
2+ -
Ba + 2 e Ba reducing
2+ -
Ca + 2 e Ca agents
+ -
Na + e Na
2+ -
Mg + 2 e Mg
H2 + 2 e- 2 H-
Al3+ + 3 e- Al
Mn2+ + 2 e- Mn
2+ -
Zn + 2 e Zn
3+ -
Cr + 3 e Cr
S + 2 e- S2-
2 CO2 + 2 H+ + 2 e- H2C2O4
Cr3+ + e- Cr2+
Fe2+ + 2 e- Fe
2+ -
Co + 2 e Co
2+ -
Ni + 2 e Ni
2+ -
Sn + 2 e Sn
Pb2+ + 2 e- Pb
3+ -
Fe + 3 e Fe
2 H+ + 2 e- H2
2- -
S4O6 + 2 e 2 S2O32-

758 Version 1 2012


Sn4+ + 2 e- Sn2+
Cu2+ + e- Cu+
O2 + 2 H2O + 4 e- 4 OH-
Cu+ + e- Cu
I2 + 2 e- 2 I-
oxidizing MnO4- + 2 H2O + 3 e- MnO2 + 4 OH-
power O2 + 2 H+ + 2 e- H2O2 Reducing
increases Fe3+ + e- Fe2+ power
Hg22+ +2e -
2 Hg increases
Ag+ + e- Ag
2+ -
Hg + 2 e Hg
-
H2O2 + 2 e 2 OH-
HNO3 + 3 H+ + 3 e- NO + 2 H2O
Br2(aq) + 2 e -
2 Br -

2 IO3- + 12 H+ + 10 e- I2 + 6 H2O
CrO42- +8H +3e + -
Cr3+ + 4 H2O
Pt2+ + 2 e- Pt
MnO2 + 4 H + 2 e- +
Mn2+ + 2 H2O
O2 + 4 H+ + 4 e- 2 H2O
Cr2O72- + 14 H+ + 6 e- 2 Cr3+ + 7 H2O
Cl2(g) + 2 e- 2 Cl-
PbO2 + 4 H+ + 2 e- Pb2+ + 2 H2O
MnO4- + 8 H+ + 5 e- Mn2+ + 4 H2O
Au+ + e- Au
H2O2 + 2 H + 2 e- +
2 H2O
3+ - 2+
Co + e Co
Best S2O82- + 2 e- 2 SO42-
oxidizing O3(g) + 2 H+ + 2 e- O2(g) + H2O
agents F2(g) + 2 H+ + 2 e- 2 HF(aq)

Fortunately, you don't have to memorize these conventions. All you have to do is remember that
the active metals, such as sodium and potassium, are excellent reducing agents and look for
these entries in the table. The strongest reducing agents will be found at the corner of the
table where sodium and potassium metal are listed.

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Practice Problem 9:

Arrange the following oxidizing and reducing agents in order of increasing strength:

Reducing agents: Cl-, Cu, H2, H-, HF, Pb, and Zn

Oxidizing agents: Cr3+, Cr2O72-, Cu2+, H+, O2, O3, and Na+

Practice Problem 10:

Predict whether the following oxidation-reduction reactions should occur as written:

(a) 2 Ag(s) + S(s) Ag2S(s)

(b) 2 Ag(s) + Cu2+(aq) 2 Ag+(aq) + Cu(s)

(c) MnO4-(aq) + 3 Fe2+(aq) + 2 H2O(l)  MnO2(s) + 3 Fe3+(aq) + 4 OH-(aq)

(d) MnO4-(aq) + 5 Fe2+(aq)+ 8 H+(aq)  Mn2+(aq) + 5 Fe3+(aq) + 4 H2O(l)

760 Version 1 2012


Practice Problem 11:

Which of the following pairs of ions cannot exist simultaneously in aqueous solutions?

(a) Cu+ and Fe3+

(b) Fe3+ and I-

c) Al3+ and Co2+

Displacement Reactions

For each of the following, either complete the word equation or write ‘no reaction’

potassium + copper sulphate

iron + zinc sulphate

sodium + iron chloride

zinc + silver nitrate

lithium + sodium chloride

calcium + iron nitrate

sodium + potassium sulphate

761 Version 1 2012


More Redox Equations to Balance

1) Zn(s) + NO3-(aq)  Zn2+(aq) + N2(g)

2) IO3-(aq) + I-(aq)  I2(aq)

3) Ce4+(aq) + Cl-(aq)  Cl2(aq) + Ce3+(aq)

4) PH3(g) + CrO42-(aq)  CrO2-(aq) + P4(s)

5) F2(g) + H2O(l)  F- + O2(g)

6) H2O2(aq) + Cr(OH)3(s)  CrO42-(aq)

762 Version 1 2012


Oxidation and Reduction Practice
In each of the following equations, indicate the element that has been oxidized and the one that
has been reduced. You should also label the oxidation state of each before and after the
process:

1) 2 Na + FeCl2  2 NaCl + Fe

2) 2 C2H2 + 5 O2  4 CO2 + 2 H2O

3) 2 PbS + 3 O2  2 SO2 + 2 PbO

4) 2 H2 + O2  2 H2O

5) Cu + HNO3  CuNO3 + H2

6) AgNO3 + Cu  CuNO3 + Ag

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Redox Equations

1. 9.2.1 Deduce simple oxidation and reduction half-equations given the species involved in a
redox reaction. (3)

a. Using Cr2O72- as an example, demonstrate the steps for writing the proper half-reaction
for oxidation:
i.

ii.

iii.

iv.

v.

vi.

b. Using HNO2 as an example, demonstrate the steps for writing the proper half-reaction for
reduction:
i.

ii.

iii.

iv.

v.

vi.

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2. 9.2.2 Deduce redox equations using half equations. (3)

a. If given both the reduction and oxidation half equations, you should be able to balance and
simplify the equations. A common example is the oxidation of a primary or secondary alcohol (via
dichromate or manganate). Following Topic 10 again, if the half-equations for the oxidation of
methanol (and reduction of manganate)

2H2O + CH3OH  CO2 + H2O + 6H+ + 6e-


MnO4- + 8H+ + 5e-  Mn2+ + 4H2O

3. 9.2.3 Define the terms oxidizing agent and reducing agent. (1)

4. 9.2.4 Identify the oxidizing and reducing agents in redox equations. (2)
Reducing Agents (oxidized) Oxidizing Agents (reduced)
Hydrogen Oxygen

Carbon Ozone

Carbon Monoxide Chlorine

Metals Acidified KMnO4

Acidified K2Cr2O7

Acidified H2O2

Metal Ions

Hydrogen Ions

MnO2

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5. Often, chemical equations are difficult to balance based due to large and uneven numbers of
reacting and produced species. A systematic approach using the principles of redox may allow
you to balance such equations. Balance each of the following equations using this method:

a. Cu + HNO3 Cu(NO3)2 + NO + H2O

b. HNO3 + I2 HIO3 + NO2 + H2O

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Redox Equations
1) Complete the table below by filling in the charges on the ions. The first one has been
done for you.
2) Identify the charge on each species.

ZnSO4 Zn= +2 SO4= -2


PbSO4
HNO3
KBr
FeSO4
MgSO4
NaCl

3) Redox equations tell us what species have gained electrons, and which species have lost
electrons. The information below will help you to write redox equations.

1) Word equation
2) Symbol equation
3) Ionic equation
4) Write down the charges on each species
5) Identify the electron transfer (OILRIG).
If a species becomes more positive (0  +2) it has lost
electrons (oxidation).
If a species has become more negative (+2  0) it has
gained electrons (reduction).

Complete the missing information in the table for the reaction of Magnesium with Zinc
Sulphate.

Magnesium + Zinc Sulphate  Magnesium Sulphate +


Mg +  + Zn
+ Zn2+ + SO42-  + Zn
0 +2 -2
Mg: 0  +2 lost electrons, become oxidised.
Zn: gained electrons, become

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4) Identify what has been oxidised and reduced in the following reactions using the same
procedure as above.

a) Zinc reacting with Tin(II) Sulphate.

b) Magnesium reacting with Iron(II) Sulphate.

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Working with Oxidation & Reduction

1) What is the difference between oxidation and reduction? Include an example to show
what you mean.

2) How can you differentiate between an oxidizing agent and a reducing agent ?
3) In the reaction: 2 K + I2 2 KI , which chemical is the oxidizing agent and which
chemical is oxidized ?

4) For each of the following reactions, indicate whether the reaction is a REDOX or a
NONREDOX reaction.

a) Ba(NO3)2 + H2SO4  BaSO4 + 2 HNO3

b) H2O2 + MnO4-  O2 + Mn2+

c) HNO3 + I2  HIO3 + NO2 + H2O

d) H2CO3  H2O + CO2

5) A "redox" reaction is different from a "nonredox" reaction because:

a) only redox reactions are balanced by using H+ and water.


b) redox reactions are the more common reaction type.
c) in redox reactions the electrical charges of the atoms change.
d) in nonredox reactions the charges of the atoms change.

6) What is the oxidation number of carbon in each of the following substances?


a) C

b) CaC2

c) CO2

d) CO

e) CO3-2

7) Explain what happens to manganese in this equation:


I-1 + MnO4 -1  I2 + MnO2

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8) In the following redox reaction which element is oxidized and which is reduced?
4NH3 + 3Ca(ClO)2  2N2 + 6H2O + 3CaCl2

A. H is oxidized and N is reduced


B. Cl is oxidized and O is reduced
C. N is oxidized and Cl is reduced
D. Cl is oxidized and N is reduced
E. N is oxidized and O is reduced

9) Which one of the following is a redox reaction?


A) 2Al(s) + 3H2SO4(aq)  Al2(SO4)3(aq) + 3H2(g)
B) 2KBr(aq) + Pb(NO3)2(aq)  2KNO3(aq) + PbBr2(s)
C) CaBr2(aq) + H2SO4(aq)  CaSO4(s) + 2HBr(g)
D) H+(aq) + OH–(aq)  H2O(l)
E) CO32–(aq) + HSO4–(aq)  HCO3–(aq) + SO42–(aq)

10) Which of the following equations does not represent an oxidation-reduction reaction?
A) 3Al + 6HCl  3H2 + AlCl3
B) 2H2O  2H2 + O2
C) 2NaCl + Pb(NO3)2  PbCl2 + 3NaNO3
D) 2NaI + Br2  2NaBr + I2
E) Cu(NO3)2 + Zn  Zn(NO3)2 + Cu

11) Identify the element being oxidized in the following reaction.


4Al + 3O2  2Al2O3

12) Identify the oxidizing agent in the following reaction.


4Al + 3O2  2Al2O3

13) Identify the element being reduced in the following reaction.


2KBr + F2  Br2 + 2KF

14) Determine the oxidation number of each of the elements in Cs2Cr2O7?

15) Determine the oxidation number of each of the elements in K2TaF7?

770 Version 1 2012


REDOX WORD FRAME

Oxidation-reduction, or _______________________, reactions are an important

category of chemical reactions because they are what makes batteries work, they provide a way

for plants and animals to transfer and store energy in cells, they allow police officers to

measure the blood alcohol level of a driver, they explain why silver tarnishes, why iron rusts,

why the Statue of Liberty has turned green, and a myriad of other useful things. Oxidation was

originally only defined as the chemical combination of a substance with

________________________ but is now defined as any chemical change in which electrons

are _________________ by an atom. Reduction was originally defined as only the chemical

__________________ of oxygen but is now defined as any chemical change in which electrons

are ________________________ by an atom.

An oxidation reaction is always accompanied by a _________________________

reaction. The substance that undergoes oxidation is also called the _________________

agent. This is because it causes the reduction of the other element. The substance that

undergoes reduction is also called the ___________________________ agent. This is

because it causes the ______________________ of the other element.

All _______________________ replacement reactions are oxidation-reduction

reactions because one pure element replaces another atom in a compound. Combustion, double-

displacement, synthesis, and decomposition reactions can also be oxidation–reduction reactions.

A change in _______________________________ determines whether or not an oxidation-

reduction reactions has occurred.

An oxidation number can be assigned to an element in a substance according to a set of rules.

The oxidation number of a pure element is ______________. The oxidation number of a

monatomic cations can be determined from the ________________________

__________________. The oxidation state of oxygen is usually ______________. The

charge on a hydrogen ion is _________________. The oxidation states of all of the atoms in

a compound must add up to be ____________.

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The oxidation states of all of the atoms in an ion must add up to be the same as

_______________________________________. From the above rules, the oxidation

states of elements such as sulfur, nitrogen, and chlorine in covalent compounds can be

determined.

One way to describe how __________________________ are transferred between

elements in a redox reaction is to write _______________ reactions. The half reaction in

which electrons are a reactant is called _____________________________. The half

reaction in which electrons are a product is called ___________________________.

Word Bank:

-2

+1

electrons

gained

half

loss

lost

oxidation (2x)

oxidation state

oxidizing

oxygen

periodic table

redox

reducing

reduction (2x)

single

the ion’s charge

zero (2x)

772 Version 1 2012


Hi y’all ahm Erin Brockovich and ah want to talk to y’all about
chromium and ahxidation’.
Well now, I managed to use a relationship between humans and
chemicals to get the biggest settlement ever for a civil class action
lawsuit. You see, I could not understand why medical records were
being used by PG&E* in a real estate lawsuit in the town of Hinkley,
California. When I went and spoke to the residents of Hinkley, they
presented a variety of conditions (including throat cancer,
respiratory, liver and kidney problems, reproductory problems etc.)
that can be caused by the chromium 6 ion (which was present in
unlined ponds of wastewater.) When I went to see the scientists,
they told me that chromium is found naturally in the Earth, plants
and animals (including us humans), but not in its element form. However, chromium can have a variable
oxidation state in compounds (between -2 and +6) but most commonly it exists as chromium 3 (Cr3+, in
vegetables and meat) and chromium 6 (Cr6+, in industry.) Chromium 6 is used to stop rust forming, and
Insert picture of Erin Brockovich
when inhaled causes the health problems mentioned above. However, PG&E argued that chromium 6 is
here
turned into chromium 3 in the stomach, so the Hinkley residents were actually ingesting the non-toxic
chromium 3 form. What do you think? Can you help me write a letter to the residents of Hinkley
explaining the science behind their problems? Thank y’all very much!

*Pacific Gas and Electric

You will be graded according to the following stair of success:

Uses reactivity series to suggest why chromium prevents rust; constructs


A
general statement about oxidising ability and reactivity.

Independently creates a half equation for the process that PG&E claim happens in the
B
stomach and explain whether it is redox or not, and why.

Describes the reaction in the stomach as oxidation, reduction or redox, using different
C
definitions of oxidation and reduction in answer; uses books to describe redox (reduction
and oxidation) reactions

Suggests where chromium is found on the periodic table, giving a reason from text; suggests
D
whether chromium 3 or 6 is toxic.

Defines the words underlined correctly, using ideas about particles: gives own opinion about the
E
case. Suggests how the people ended up ingesting chromium.

773 Version 1 2012


Random Questions about Electrochemistry

1) What is a reducing agent ? What is an oxidizing agent ?

2) Which substance is the best reducing agent? Which is the best oxidizing agent?

3) When Ni and Fe are added to a solution that contains both Ni2+ and Fe2+, which will be
reduced and which will be oxidized?

4) Write the half-reactions that will occur if Cl2 and Br2 are added to a solution containing
Cl- and Br-. Is this reaction spontaneous?

5) What reaction happens at the anode ? At the cathode ? Give an example of each.

6) In a certain zinc-copper cell, the concentrations are [Cu2+] = 0.0100M and [Zn2+]= 1.0
M.
Zn(s) + Cu2+  Zn2+ + Cu(s)
If the standard cell potential is 1.10 V, what is the cell potential?

774 Version 1 2012


7) In the analysis of two water samples, cell potentials of 0.57 V and 0.82 were obtained.
Calculate the Cu2+ ion concentration for both samples. E° = 0.46V and the overall
reaction is
Cu(s) + 2 Ag+  Cu2+ + 2 Ag(s)

775 Version 1 2012


Reactivity
1. 9.3.1 Deduce a reactivity series based on the chemical behavior of a group of oxidizing and
reducing agents. (3)
a. Why do metals generally behave as reducing agents?

b. Provide an example of a replacement reaction where Mg takes the place of Cu2+ in the
compound CuSO4:

i. Write the Total Ionic Equation:

ii. Write the Net Ionic Equation:

iii. Provide each of the ½ reactions:

iv. Which metal is more reactive?

c. Describe and diagram a thermite reaction:

d. What happens when common metals are added to water? Use Na and H2O as an example:

2. 9.3.2 Deduce the feasibility of a redox reaction from a given reactivity series. (3)

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Reactivity Series
1. (a) The table shows what happens when four metals are added to the same volume of

dilute hydrochloric acid in a test tube.

Use the information in the table to help you decide which of these metals is

(i) the most reactive.

(ii) the least reactive.

(b) Zinc reacts with iron(II) sulphate solution in a displacement reaction.

(i) Why does this reaction occur?

(ii) Complete the word equation for the reaction.

zinc + iron(II) sulphate → .............................. + ..............................

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2. The list gives the order of reactivity of some metals.

(a) Iron is sometimes coated with zinc to prevent the iron rusting. The iron does not rust even
if the coating of zinc becomes damaged.

(i) What is the name given to this method of rust prevention?

(ii) Give one example where this method of rust prevention is used.

(iii) Explain how this method of rust prevention works.

778 Version 1 2012


(b) A student is given some solid nickel nitrate and several small pieces of magnesium, zinc,

iron, copper and silver. Describe and explain how he can find the position of nickel in the

reactivity series given above.

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3. Use information from the table to answer this question.

(a) When zinc is added to magnesium sulphate solution, no reaction occurs. Explain why.

(b) When iron filings are added to copper(II) sulphate solution, a reaction takes place.

(i) Write a chemical equation for this reaction.

(ii) Describe the colour changes during this reaction.

colour change of solid

colour change of solution

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(c) When copper is added to dilute sulphuric acid, no reaction occurs. When iron is added to
dilute sulphuric acid, hydrogen gas and iron(II) sulphate solution are formed. What does
this show about the reactivity of hydrogen compared to the reactivity of copper and the
reactivity of iron?

4. This question is about the reactions of the metals calcium, iron and zinc.

(a) Samples of each of the powdered metals were placed in separate beakers of water. Only
calcium reacted immediately.

Describe two observations that could be made during the reaction of calcium with water.
Write a chemical equation for the reaction.

(b) A reaction occurred when powdered zinc was heated in steam. Name the zinc compound
formed.

Write a chemical equation for the reaction.

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(c) Some powdered zinc was added to a solution of iron(II) sulphate.

(i) Write an ionic equation to show the reaction that occurs.

(ii) State the type of reaction occurring.

(d) Iron rusts slowly in the presence of water. Name one other substance that must be
present for iron to rust.

(e) Galvanising is one method used to prevent iron from rusting.

(i) Describe how a sheet of iron is galvanised.

(ii) A sheet of galvanised iron was scratched and left in the rain. The exposed iron did not
rust. Explain why.

782 Version 1 2012


Electrochemical Cells and the Activity Series

Write the appropriate half reactions and calculate the cell potential for each of the following
electrochemical cells

1. Copper and aluminum

2. Silver and zinc

3. Copper and nickel

4. Nickel and cadmium

5. Silver and aluminum

6. Magnesium and zinc

7. Lead and iron

8. Copper and magnesium

9. Magnesium and iron

783 Version 1 2012


10. Copper and iron

Use the electrochemical series to determine which of the following reactions can occur. For
those that occur write an appropriate balanced chemical reaction.

11. Zn + H2SO4

12. Mg + FeCl2

13. Pb + SnCl2

14. Mg + Fe SO4

15. Ag + Cu(NO3)2

16. A1 + CuSO4

17. Zn + AgNO3

784 Version 1 2012


18. Mg + Fe(NO3)2

19. Mg + NaCl

20. FeSO4 + Cu

785 Version 1 2012


Daniel’s Cell

1) If this is a standard cell, what is the concentration of the zinc sulphate solution?

2) What is the pressure and temperature in this standard cell?

3) Write down the 2 half equations for Zn2+ and Cu2+ from the data booklet. Include their
voltages.

4) How do you know the zinc electrode is the negative electrode?

5) If it is negative, electrons are being produced here. Does your equation in 3) show this?
If not reverse it and replace the ↔ with a . NB: You never have to reverse the sign for
the voltage.

6) How do you know the copper electrode is positive?

786 Version 1 2012


7) As it is positive electrons are attracted here. Does your equation in 3) show this? If not
reverse it and replace the <--> with a . If it does show the addition of electrons then
the forward reaction is correct; replace the ↔ with a 

.
8) Add the 2 half equations to get the equation for the cell.

9) Find the DIFFERENCE in the 2 voltages. This number must be positive in Chemistry.
___________V

10) Oxidised = _________ Oxidizing Agent: _________ Reduced:_______


Reducing Agent: ___________

11) Why does the zinc electrode get lighter?

12) Why does the concentration of the copper ions decrease?

13) What are the charge carriers in a) The wires _______________


b) the salt bridge __________________

14) Which direction do the potassium ions in the salt bridge move and why?
15) If 2 electrons go around the circuit:
a) How many zinc ions are produced? _________
b) How many copper atoms are produced? _______

16) If 2 MOLES of electrons go around the circuit:


a) How many zinc ions are produced? _______
b) How many moles of copper atoms are produced? _________

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17) Which electrode’s mass would change the most? Explain.

19 ) 1) HL: Electrochemical cells can be written in the following shorthand notation:

Cu/Cu2+║Zn2+/Zn

Most+ Most –

What does the ║ mean? ___________________

788 Version 1 2012


Activity Series Simulation
**DATA NOTEBOOK WILL BE ASSESSED**

(you can get to this link from my website, unit 8: Redox, first link under Labs)

http://www.chem.iastate.edu/group/Greenbowe/sections/projectfolder/flashfiles/redox/home.html

Purpose: To determine an activity series of various metals.

Procedures:

Describe briefly how you will determine the activity series. Include important details like the state of matter of
the reactants and how you will know that a reaction has taken place.

Data:

A large grid is the best with 8 rows (for each metal you are testing) and 9 columns for each solution you will
put the solid in. Some boxes of the grid will not be filled in.

Record not only if there is a reaction but before and after observations.

Click on microscopic views when available and describe what is happening.

Analysis

1. Give an order for your activity series and EXPLAIN. USE DATA in your explanation.
2. Compare to the actual activity series
3. Write half reactions for Fe (s) reactions
4. Write the net ionic reaction for iron reactions
5. For each half reaction state whether oxidation or reduction is occurring.
6. For each reaction state how many moles of electrons are transferred per mole of metal atoms.
7. If 2.00 g of aluminum completely reacts with a copper nitrate solution, what mass of copper would be
formed?
8. Give at least 3 changes you would see for the Aluminum + Copper nitrate reaction.
9. Using the activity series from your data book
a. Which of the following is the most powerful reducing agent?
i. Copper
ii. Magnesium
iii. Iron
iv. Zinc
b. Zinc reacts with dilute acids to liberate hydrogen. This is because
i. The zinc ion is a more powerful oxidizing agent than the hydrogen ion.
ii. They hydrogen ion is a more powerful oxidizing agent than the zinc ion.
iii. The zinc ion is a more powerful reducing agent than the hydrogen ion.
iv. The hydrogen ion is a more powerful reducing agent than the zinc ion.
c. Write the order of reactivity for halogens.
d. Why is the order for halogens different from alkali metals?
e. Br2 is brown, I2 is Pink, and Cl2 has a slightly yellowish green color. State and explain what
would you see when
i. Chlorine gas is bubbled through aqueous sodium bromide
ii. Bromine is added to sodium chloride
iii. Chlorine is bubbled through sodium iodide

789 Version 1 2012


Voltaic Cells Notes
1. 9.4.1 Explain how a redox reaction is used to produce electricity in a voltaic cell. (3)

a. For those of you not in physics, discuss a brief intro to charges:

b. Define Amperes and what it’s a measure of:

i. A large current could be produced from (two scenarios):

1.

2.

c. Define potential difference and what it means for the activity of a cell:

2. 9.4.2 State that oxidation occurs at the negative electrode (anode) and reduction occurs at
the positive electrode (cathode). (1)
a. Draw and Diagram a Voltaic (Daniell) Cell:

b. What purpose does the salt bridge serve?

790 Version 1 2012


c. A voltaic cell will continue until:

d. How can we remember which electrode is the Cathode and which is the Anode?

e. What does the voltage of a cell depend on?

f. Provide the shorthand notation for the Daniell cell and describe how to name them.

791 Version 1 2012


Electrolytic Cells Notes

1. 9.5.1 Describe, using a diagram, the essential components of an electrolytic cell. (2)

a. Diagram a simple Electrolytic Cell

2. 9.5.2 State that oxidation occurs at the positive electrode (anode) and reduction occurs at
the negative electrode (cathode). (1)

a. Define an electrolyte

b. During electrolysis, we still follow RedCat and AnOx, what does this mean?

3. 9.5.3 Describe how current is conducted in an electrolytic cell. (2)

a. How do we test conductivity?

b. What does it mean for a substance to be a conductor or an insulator?

792 Version 1 2012


4. 9.5.4 Deduce the products of the electrolysis of a molten salt. (3)

a. What happens when an electrical current passes through an ionic substance (molten or
solution)?
Diagram, and provide Redox half equations as Diagram, and provide Redox half equations as
well as the full equation, for the decomposition well as the full equation, for the decomposition
of PbBr2 of NaCl

Diagram, and provide Redox half equations as Diagram, and provide Redox half equations as
well as the full equation, for the decomposition well as the full equation, for electroplating a
of H2O material with Cu

793 Version 1 2012


Electrochemical Cell Tutorial

Open http://www.wwnorton.com/college/chemistry/gilbert2/contents/ch18/studyplan.asp in a browser and


click on Zinc-Copper Cell

**If the address above doesn’t work you can get to the site from my website. In the Redox unit under
assignments, click on Electrochemcial Cell tutorial.

Directions: Read through the entire tutorial and take notes. Some important notes to take are listed below (1-
10). You should read through all of the tutorial including the parts on the Nernst equation and answer the
questions at the end of the tutorial. However, you will not have to perform calculations using the Nernst
equation so you can skip these questions.

1. Sketch and label the electrochemical cell.


2. Which electrode (anode or cathode) is the negative terminal?
3. Which electrode is the positive terminal?
4. What process (oxidation or reduction) happens at the anode?
5. What process (oxidation or reduction) happens at the cathode?
6. What is current?
7. In what direction do the electrons flow?
8. What is a salt bridge used for?
9. What do you think would happen to the cell if there was no salt bridge?
10. Do you think the cell could continue to function forever? Explain.
11. Read the Chem 1 text book pg 663 to 666 and 673 to 682 and answer the questions on the worksheets
provided. Then come back to this worksheet.
12. In the electrochemical cell from the tutorial, a cell was made with copper and zinc. Which metal is
more active?
13. In the electrochemical cell from the worksheet, a cell was made with Platinum and Nickel. Which
metal is more active?
14. What is the relationship between how active a metal is and whether it is at the anode or cathode?
15. Sketch an electrochemical cell for Magnesium and Iron. You will need to use the activity series. The
sketch should identify
a. Positive and negative electrode
b. Cathode and anode
c. ½ reactions taking place at each electrode
d. the direction of electron flow
e. the direction of flow through the salt bridge

794 Version 1 2012


Voltaic Versus Electrolytic Cells

Do some research to answer the following questions. We will take up the answers as a class.

1. Valtaic cells have several other names, list two:

2. Define Anode:

3. Define Cathode:

4. Complete the following table comparing general properties of voltaic and electrolytic
cells.

Voltaic Electrolytic
Spontaneous? (Yes/No)
Anode (negative or positive)
Cathode (negative or positive)
Electrons flow from which
terminal?(negative/positive)
(anode./cathode)
Electrons flow towards which
terminal?
(negative/positive)
(anode/cathode)

795 Version 1 2012


5. How is spontaneity (or lack therefore) explained by the direction of flow of electrons?

6. Below is a diagram of a Voltaic Cell. Label the following components:


a. Anode + charge
b. Cathode + charge
c. Salt Bridge
i. What ions are found within the salt bridge?

d. Metal Ion Solutions


i. Which ions are present in solution at each terminual?

e. Zinc Metal, Copper Metal, Zinc Ion, Copper Ion


f. Direction of electron flow
g. Direction of Na+ flow
h. Direction of Cl- flow

6. Write the half reaction occuring at each terminal

7. What purpose does the salt bridge serve?

796 Version 1 2012


8. Below is a diagram of an Electrolytic Cell. Label the following components:

a. Anode + charge
b. Cathode + charge
c. Power Source
d. Direction of electron flow
e. Deduce and label the products of electrolysis of NaCl

9. State and explain one practical application of an electrolytic cell.

10. Redraw the voltaic cell from question 5 as an electrolytic cell.

797 Version 1 2012


Sodium Chemistry

798 Version 1 2012


799 Version 1 2012
Topic 9 Oxidation and Reduction IB Exam Questions
1. What happens at the negative electrode in a voltaic cell and in an electrolytic cell?

Voltaic cell Electrolytic cell


A. oxidation reduction
B. reduction oxidation
C. oxidation oxidation
D. reduction reduction
(Total 1 mark)

2. Consider how current is conducted in an electrolytic cell. Which statement is correct?

A. Electrons move through the electrolyte and the external circuit.

B. Ions move through the electrolyte and the external circuit.

C. Electrons move through the external circuit and ions move through the electrolyte.

D. Electrons move through the electrolyte and ions move through the external circuit.
(Total 1 mark)

3. Which species is oxidized in the following reaction?

2Ag+(aq) + Cu(s) → 2Ag(s) + Cu2+(aq)

A. Ag+

B. Cu

C. Ag

D. Cu2+
(Total 1 mark)

4. Which list represents the halogens in increasing order of oxidizing strength (weakest
oxidizing agent first)?

A. Cl2 I2 Br2

B. I2 Br2 Cl2

C. I2 Cl2 Br2

D. Cl2 Br2 I2
(Total 1 mark)

800 Version 1 2012


5. Which are redox reactions?

I. 2FeCl2 + Cl2 → 2FeCl3

II. Mg + 2HNO3 → Mg(NO3)2 + H2

III. H2O + SO3 → H2SO4

A. I and II only

B. I and III only

C. II and III only

D. I, II and III
(Total 1 mark)

6. Which compound contains nitrogen with an oxidation number of +3?

A. NH4Cl

B. HNO3

C. N2O4

D. KNO2
(Total 1 mark)

7. In the electrolytic cell shown, at which electrode will chlorine form, and what is the process
taking place there?

Electrode Process
A. P reduction
B. Q reduction
C. P oxidation
D. Q oxidation
(Total 1 mark)

801 Version 1 2012


8. Magnesium is higher in the reactivity series than zinc. In the cell shown, in which direction
do the electrons flow in wire X and which metal is oxidized?

Electron flow Oxidized


A. Zn to Mg Zn
B. Mg to Zn Zn
C. Zn to Mg Mg
D. Mg to Zn Mg
(Total 1 mark)

9. Outline two differences between an electrolytic cell and a voltaic cell.

...............................................................................................................................................
.

...............................................................................................................................................
.

...............................................................................................................................................
.

...............................................................................................................................................
.
(Total 2 marks)

10. (i) Define oxidation in terms of oxidation numbers.


(1)

802 Version 1 2012


(ii) Describe using a labelled diagram, the essential components of an electrolytic cell.
(3)

(iii) Explain why solid sodium chloride does not conduct electricity but molten sodium
chloride does.
(2)

(iv) Molten sodium chloride undergoes electrolysis in an electrolytic cell. For each
electrode deduce the half-equation and state whether oxidation or reduction takes
place. Deduce the equation of the overall cell reaction including state symbols.
(5)

803 Version 1 2012


(v) Electrolysis has made it possible to obtain reactive metals such as aluminium from
their ores, which has resulted in significant developments in engineering and
technology. State one reason why aluminium is preferred to iron in many uses.
(1)

(vi) Outline two differences between an electrolytic cell and a voltaic cell.
(2)

(Total 14 marks)

11. (a) Define oxidation in terms of electron transfer.

......................................................................................................................................

......................................................................................................................................
(1)

(b) Chlorine can be made by reacting concentrated hydrochloric acid with potassium
manganate(VII), KMnO4.

2KMnO4(aq) + 16HCl(aq) → 2MnCl2(aq) + 2KCl(aq) + 5Cl2(aq) + 8H2O(aq)

(i) State the oxidation number of manganese in KMnO4 and in MnCl2.

KMnO4 ..............................................................................................................

MnCl2 ................................................................................................................
(2)

(ii) Deduce which species has been oxidized in this reaction and state the change
in oxidation number that it has undergone.

...........................................................................................................................

...........................................................................................................................
(2)
(Total 5 marks)

804 Version 1 2012


Topic 9 IB Exam Question Markacheme
1. A
[1]

2. C
[1]

3. B
[1]

4. B
[1]

5. A
[1]

6. D
[1]

7. D
[1]

8. D
[1]

9. electrolytic cell converts electrical energy to chemical energy and


voltaic cell converts chemical energy to electrical energy / electrolytic
cell uses electricity to carry out a (redox) chemical reaction and
voltaic cell uses a (redox) chemical reaction to produce
electricity / electrolytic cell requires a power supply and voltaic
cell does not;

electrolytic cell involves a non-spontaneous (redox) reaction and


voltaic cell involves a spontaneous (redox) reaction;

in an electrolytic cell, cathode is negative and anode is positive and


vice-versa for a voltaic cell / electrolytic cell, anode is positive and
voltaic cell, anode is negative / electrolytic cell, cathode is negative
and voltaic cell, cathode is positive;

voltaic cell has two separate solutions and electrolytic cell has one
solution / voltaic cell has salt bridge and electrolytic cell has no salt bridge;

electrolytic cell, oxidation occurs at the positive electrode/anode and


voltaic cell, oxidation occurs at the negative electrode/anode/vice-versa;

If descriptions are reversed for electrolytic and voltaic cell, penalize


first marking point but award second marking point as ECF. 2 max
[2]

10. (i) increase in the oxidation number; 1

(ii) Annotated diagram of cell showing:


805 Version 1 2012
power supply/battery;
electrolyte;
cathode/negative electrode and anode/positive electrode;

(iii) (solid) ions in a lattice / ions cannot move;


(molten) ions mobile / ions free to move; 2

(iv) reduction occurs at the cathode/negative electrode and oxidation occurs


at the anode/positive electrode;
Cathode/negative electrode: Na+ + e– → Na;
Anode/positive electrode: 2Cl– → Cl2 + 2e– / Cl– → 12 Cl2 + e–;
Award [1 max] if the two electrodes are not labelled/labelled incorrectly
for the two half-equations.

Overall cell reaction: Na+(l) + Cl–(l) → Na(l) + 12 Cl2(g)


Award [1] for correct equation and [1] for correct state symbols.
Allow NaCl(l) instead of Na+(l) and Cl–(l). 5

(v) Al does not corrode/rust / Al is less dense/better conductor/more


malleable;
Accept Al is a lighter (metal compared to Fe).
Accept converse argument. 1

(vi) electrolytic cell converts electrical energy to chemical energy and voltaic
cell converts chemical energy to electrical energy / electrolytic cell uses
electricity to carry out a (redox) chemical reaction and voltaic cell uses a
(redox) chemical reaction to produce electricity / electrolytic cell requires
a power supply and voltaic cell does not;

electrolytic cell involves a non-spontaneous (redox) reaction and voltaic


cell involves a spontaneous (redox) reaction;

in an electrolytic cell, cathode is negative and anode is positive and vice-versa


for a voltaic cell / electrolytic cell, anode is positive and voltaic cell,
anode is negative / electrolytic cell, cathode is negative and voltaic
cell, cathode is positive;

806 Version 1 2012


voltaic cell has two separate solutions and electrolytic cell has one
solution / voltaic cell has salt bridge and electrolytic cell has no salt bridge;

electrolytic cell, oxidation occurs at the positive electrode/anode and voltaic


cell, oxidation occurs at the negative electrode/anode and vice-versa; 2 max
[14]

11. (a) Loss of (one or more) electrons; 1

(b) (i) (KMnO4) + 7;


(MnCl2) + 2;
Must have + sign for mark.
[1 max] if roman numerals or 7+ or 2+ used or if + signs
are missing. 2

(ii) Cl– / chloride / chlorine / Cl (has been oxidized) / HCl;


oxidation number from –1 to 0 / has increased by one;
If HCl is given for first mark, it must be clear that it is the Cl that
has the change of oxidation number. 2
[5]

807 Version 1 2012

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