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Chapter 20
Oxidation-Reduction Reactions
Some Common Reactions
The combustion of gasoline in an automobile
  engine requires oxygen
Burning of wood in a fireplace requires oxygen
The reactions that break down food in your
  body and release energy use oxygen
The oxide of hydrogen is water
Charcoal oxidizes when it burn forming CO2

Bleaching stains in fabric is still oxidation even
  though it does not burn.
Oxidation

When methane burns in air, it oxidizes and
 forms oxides of carbon and hydrogen.
   CH4(g) + 2O2(g)        CO2(g) + 2H2O(g)


When elemental iron turns to rust, it slowly
 oxidizes to compounds such as iron (III)
 oxide.
        4Fe(s) + 3O2(g)        2Fe2O3(s)
Reduction
Originally reduction meant a loss of oxygen
  from a compound
  2Fe2O3(s) + 3C(s)         4Fe(s) + 3CO2(g)
    iron oxide   carbon       iron      carbon dioxide




Reduction of iron ore to metallic iron involves
 the removal of oxygen from iron (III) oxide.
Involves heating the ore with carbon.
Question
What happens to magnesium and oxygen
 when they react to form magnesium oxide?
                                 +2   -2
         2Mg       +   O2       2MgO
       magnesium       oxygen   magnesium oxide


   Magnesium loses electrons to form Mg2+
     Oxygen gains electrons to form O2-
Electron Shift in Redox Reactions
The modern concept of oxidation and reduction
  have been extended to include many
  reactions that do not even involve oxygen.
Oxygen is the most electronegative element
 (besides fluorine)

When oxygen bonds with an atom of a different
 element (except fluorine), electrons from that
 atom shift toward oxygen.
Redox Reactions
Redox reactions are currently understood to
 involve any shift of electron between reactants.

Oxidation – a process that involves a complete or
 partial loss of electrons or a gain of oxygen.
• Results in an increase in the oxidation number of an atom


Reduction – a process that involves a complete or
 partial gain of electrons or the loss of oxygen.
• Results in a decrease in the oxidation number of an atom
Redox Reactions

  Oxidation and reduction always occur
            simultaneously.


The substance gaining oxygen or losing
          electrons is oxidized


The substance losing oxygen or gaining
         electrons is reduced.
Redox Reactions
During a reaction between a metal and a nonmetal,
 electrons are transferred from atoms of the metal
 to atoms of the nonmetal.
            Mg +      S       Mg2+S2-
         magnesium   sulfur   magnesium sulfide

2 electrons are transferred from a magnesium atom
  to a sulfur atom.
Magnesium atoms become more stable by the loss
 of electrons. Sulfur atoms become more stable
 by the gain of electrons
Redox Reactions
             Mg +      S          Mg2+S2-
          magnesium   sulfur      magnesium sulfide


Oxidation: Mg         Mg2+ + 2e- (loss of electrons)
Reduction: S + 2e-             S2- (gain of electrons)
Magnesium atom is said to be oxidized to a
 magnesium ion
Sulfur atom is said to be reduced to a sulfide ion.
Redox Reactions

When a metal combines with oxygen, it loses
 electrons
When oxygen is removed from the oxide of a metal,
 the metal gains electrons.
This knowledge is what led to the broader definition
 of oxidation and reduction as an exchange of
 electrons.
Redox Reactions

Reducing agent – the substance that loses the
 electrons
            Mg       +         S           MgS
        reducing agent
         oxidized


Oxidizing agent – the substance that accepts
 electrons
           Mg + S                MgS
                         oxidizing agent
                         reduced
Sample Problem

Silver nitrate reacts with copper to form copper nitrate
  and silver. From the equation below, determine what
  is oxidized and what is reduced. Identify the oxidizing
  agent and the reducing agent.

        2AgNO3 + Cu           Cu(NO3)2 + 2Ag

          Rewrite the equation in ionic form
  2Ag+ + 2NO3- + Cu           Cu2+ + 2NO3- + 2Ag
Sample Problem

   2Ag+ + 2NO3- + Cu          Cu2+ + 2NO3- + 2Ag

Oxidation: 2 e- are lost from copper when it
 becomes a Cu2+
Reduction: 2e- are gained by two silver ions which
 become neutral silver atoms.
2Ag+ + 2NO3- + Cu           Cu2+ + 2NO3- + 2Ag
oxidizing        reducing
Agent             agent
reduced          oxidized
Sample Problem

      2Na         +         S               2Na+     +   S2-
   oxidized              reduced
 reducing agent         oxidizing agent



4Al         +          3O2                  4Al3+    +   3O2-
Oxidized              reduced
Reducing agent        oxidizing agent

                      2I-                 I2 + 2e-
                             oxidation

                      Zn2+      +   2e-        Zn
                             reduction
Redox with Covalent Compounds
 Some reactions involve covalent compounds. In
   these compounds complete electron transfer
                 does not occur.
         2H2 (g) + O2 (g)      2H2O (l)

In each reactant hydrogen molecule, the bonding
  electrons are shared equally between the
  hydrogen atoms.
In water, however, the bonding electrons are
  pulled toward oxygen because it is much more
  electronegative than hydrogen.
Redox with Covalent Compounds

        2H2 (g) + O2 (g)       2H2O (l)

There is a shift of bonding electrons away from
 hydrogen, even though there is not a complete
 transfer.
Hydrogen is oxidized because it undergoes a
 partial loss of electrons.
Redox with Covalent Compounds
         2H2 (g) + O2 (g)        2H2O (l)

In oxygen, the bonding electrons are share
  equally between oxygen atoms in the reactant
  oxygen molecule.
When oxygen bonds to hydrogen in the water
 molecule, there is a shift of electrons toward
 oxygen.

Oxygen is thus reduced because it undergoes a
 partial gain of electrons.
Redox with Covalent Compounds



H         H     O        O           H   O   shift of bonding


e- shared           e- shared                e- away from H
equally             equally              H   and toward O

H is reducing       O is oxidizing
   agent               agent
Redox with Covalent Compounds
Some reactions involving covalent reactants or
 products, the partial electron shifts are less
 obvious.

General guideline for covalent reactants or
  products:
• for carbon compounds, the addition of oxygen
  or the removal of hydrogen is always oxidation
Processes Leading to
          Oxidation & Reduction
Processes Leading to Oxidation & Reduction
          Oxidation                     Reduction
Complete loss of electrons     Complete gain of electrons
(ionic reactions)              (ionic reactions)
Shift of electrons away from   Shift of electrons toward an
an atom in a covalent bond     atom in a covalent bond
Gain of oxygen                 Loss of oxygen
Loss of hydrogen by a          Gain of hydrogen by a
covalent compound              covalent compound
Increase in oxidation          Decrease in oxidation
number                         number
Corrosion

Iron, often used in the
form of the alloy steel,
corrodes by being
oxidized to ions of iron
by oxygen.

  2Fe(s) + O2 (g) + 2H2O (l)        2Fe(OH)2 (s)
4Fe(OH)2(s) + O2 (g) + 2H2O (l)       4Fe(OH)3 (s)

• Equations describe the corrosion of iron to iron
  hydroxides in moist conditions.
Corrosion

Water in the environment accelerates the rate
 of corrosion.
Corrosion occurs more rapidly in the presence of
 salts and acids.

Salts and acids produce electrically
 conducting solutions that make electron
 transfer easier.
Resistance to Corrosion

         Not all metals corrode easily.
Gold and platinum are called noble metals
 because they are very resistant to losing their e-
 by corrosion.

Other metals lose electrons easily but are
 protected from extensive corrosion by the
 oxide coating formed on their surface.

• Aluminum oxidizes quickly in air to form a
  coating of very tightly packed aluminum oxide
  particles.
Resistance to Corrosion

Iron also forms a coating when it corrodes
But the coating of iron oxide that forms is not
 tightly packed.

Water and air can penetrate the coating and
 attack the iron metal below it.

Corrosion continues until the iron object becomes
 only a pile of rust.
Controlling Corrosion

To prevent corrosion, the metal surface can
 be coated with oil, paint, plastic or another
 metal.

Coatings exclude air and water from the
 surface, preventing corrosion.

If coating is scratched or worn away, however, the
   exposed metal will begin to corrode.
Controlling Corrosion

      Another method of corrosion control
One metal is “sacrificed” or allowed to corrode, in
 order to save a second metal.

To protect an iron object, a piece of
 magnesium (or other active metal) may be
 placed in electrical contact with the iron.

When oxygen and water attack the iron object, the
 iron atoms lose electrons as the iron being to be
 oxidized.
Controlling Corrosion

Because magnesium is a better reducing agent
 than iron and is more easily oxidized

the magnesium immediately transfers electrons
  to the iron, preventing their oxidation to iron
  ions.

Magnesium is “sacrificed” by oxidation and
 protects the iron in the process.
Controlling Corrosion

Sacrificial zinc and magnesium blocks are sometimes
 attached to piers and ship hulls to prevent corrosion
 damage in areas submerged in water.
Underground pipelines and storage tanks may be
 connected to magnesium block for protection

It is easier and cheaper to replace a block of
  magnesium or zinc than to replace a bride or a
  pipeline.
Question


    Can you identify the common chemical
      characteristic of all metal corrosion?
The transfer of electrons from metals to oxidizing
 agents.
Questions
Define oxidation and reduction in terms of the
 gain or loss of oxygen.
        Oxidation is the gain of oxygen
        Reduction is the loss of oxygen
Define oxidation and reduction in terms of the
 gain or loss of electrons.
           LEO the lion goes GER
        Loss of Electrons is Oxidation
        Gain of Electrons is Reduction
Questions
What happens to the atoms in an iron nail that
 corrodes?
   Iron atoms are oxidized when iron corrodes


How do you identify the oxidizing agent and
 the reducing agent in a redox reaction?
 The species reduced is the oxidizing agent.
  The species oxidized is the reducing agent.
Questions
Use electron transfer or electron shift to identify what
 is oxidized and what is reduced in each reaction.
 (use electronegativity values for molecular
 compounds)
             2Na(s) + Br2(l)     2NaBr(s)

              Na oxidized, Br2 reduced
              H2(g) + Cl2(g)     2HCl(g)

               H2 oxidized, Cl2 reduced
Questions
Use electron transfer or electron shift to identify what
 is oxidized and what is reduced in each reaction.
 (use electronegativity values for molecular
 compounds)
               2Li(s) + F2(g)    2LiF(s)

                Li oxidized, F2 reduced
               S(s) + Cl2(g)     SCl2(g)

               S oxidized, Cl2 reduced
Questions
Use electron transfer or electron shift to identify what
 is oxidized and what is reduced in each reaction.
 (use electronegativity values for molecular
 compounds)
              N2(g) + 2O2(g)      2NO2(s)

               N2 oxidized, O2 reduced
   Mg(s) + Cu(NO3)2(aq)        Mg(NO3)2(aq) + Cu(s)

              Mg oxidized, Cu reduced
Questions
Identify the reducing agent and the oxidizing agent
  for each reaction.

             2Na(s) + Br2(l)   2NaBr(s)

       Na reducing agent, Br2 oxidizing agent


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

       H2 reducing agent, Cl2 oxidizing agent
Questions
Identify the reducing agent and the oxidizing agent
  for each reaction.

              2Li(s) + F2(g)    2LiF(s)

        Li reducing agent, F2 oxidizing agent


               S(s) + Cl2(g)   SCl2(g)

        S reducing agent, Cl2 oxidizing agent
Questions
Identify the reducing agent and the oxidizing agent
  for each reaction.

             N2(g) + 2O2(g)     2NO2(s)

       N2 reducing agent, O2 oxidizing agent


  Mg(s) + Cu(NO3)2(aq)        Mg(NO3)2(aq) + Cu(s)

       Mg reducing agent, Cu oxidizing agent
End of Section 20.1
Oxidation Numbers
Oxidation number is a + or – number assigned to
 an atom to indicate its degree of oxidation or
 reduction.

General Rule
 A bonded atom’s oxidation # is the charge that it
 would have if the e- in the bond were assigned to
  the atom of the more electronegative element.
Rules for Assigning Oxidation Numbers

1. The oxidation number of a monatomic ion is = in
   magnitude and sign to its ionic charge.
      Bromide (Br1-) is -1    Iron III (Fe3+) is +3
2. The oxidation number of hydrogen in a
   compound is +1, except in metal hydrides, such
   as NaH, where it is -1
3. The oxidation number of oxygen in a compound
   is -2 except in peroxides, such as H2O2, where it
   is -1 and in compounds with the more
   electronegative fluorine, where it is positive.
Rules for Assigning Oxidation Numbers

4. The oxidation number of an atom in uncombined
   (elemental) form is 0.
  Potassium metal (K) is 0   Nitrogen Gas (N2) is 0

5. For any neutral compound, the sum of the
   oxidation numbers of the atoms in the compound
   must equal 0
6. For polyatomic ion, the sum of the oxidation
   numbers must equal the ionic charge of the ion.
Some Thought


Determining oxidation numbers of elements in
 compounds is a way for chemists to keep track
 of electron transfer during redox reactions
    What are other examples where items are
     numbered to keep track of movement?
     The numbers on a sports player’s jersey
The area codes assigned to telephone numbers in
  different regions
Binary Ionic Compounds
In binary ionic compounds, such as NaCl and
  CaCl2, the oxidation numbers of the atoms equal
  their ionic charges.
              Na1+ + Cl-1       NaCl
                    oxidation # +1 -1
                                  neutral

              Ca2+ + Cl-1      CaCl2
                    oxidation # +2 -1
                                 neutral

  Note the sign I put before the oxidation number
Molecular Compounds

No ionic charges are associated with atoms of
 molecular compounds.
However, oxygen is reduced in the formation of
 water for example.

In water the two shared e- in the H – O bond are
  shifted toward the O and away from the H.
Imagine the e- contributed by the two H atoms are
  completely transferred to the O.
Molecular Compounds

The charge that would result from the transfer are
  the oxidation numbers of the bonded elements.
The oxidation number of O is -2 and the oxidation
  number of each hydrogen is +1

Oxidation numbers are often written above the
 chemical symbols in a formula.

                       +1 -2
                       H2O
Multiple Oxidation Numbers

Many elements can have several different oxidation
 numbers.
          +1 +6 -2
          K2CrO4 – Potassium Chromate

         +1 +12 -2
         K2CrO7 – Potassium Dichromate
Sample Problems

What is the oxidation number of each kind of atom
 in the following ions and compounds?
    +4 -2
    SO2
             +4 -2
              CO32-
                        +1 +6 -2
                         Na2SO4

                                       -3 +1   -2
                                       (NH4)2S
Sample Problems

Determine the oxidation number of each element in
 the following.
    +3 -2
    S2O3
             +1   -1
              Na2O2
                        +5   -2
                         P2O5

                                     +5   -2
                                       NO3-
Sample Problems

Determine the oxidation number of chlorine in each
 of the following substances.
   +1 +5 -2
    KClO3
               0
               Cl2
                        +2   +7   -2
                         Ca(ClO4)2

                                       +1   -2
                                       Cl2O
Sample Problems

What are the oxidation numbers of iodine in the
 following?
   +1 +7 -2
    HIO4
           +1 +5 -2
              HIO3
                      +1 +1 -2
                         HIO
                                 0
                                 I2
                                      +1    -1
                                           HI
Oxidation Number Changes


When copper wire is placed in a solution of silver
 nitrate the following reaction occurs
    +1 +5 -3        0         +2   +5 -2      0
  2AgNO3(aq) + Cu(s)         Cu(NO3)2(aq) + 2Ag(s)

               Ag is reduced from +1 to 0

               Cu is oxidized from 0 to +2
Oxidation Number Changes

An increase in the oxidation number of an atom or
  ion indicates oxidation.
A decrease in the oxidation number of an atom or
  ion indicates reduction.
    +2 +6 -2         0           0           +2 +6 -2
    2CuSO4(aq) + Fe2(s)        2Cu(s) + 2FeSO4

               Cu is reduced from +2 to 0
               Fe is oxidized from 0 to +2
Sample Problem
Identify which atoms are oxidized and which are
  reduced in the following reaction. Also identify
  the oxidizing agent and the reducing agent.

        +1 -1        0          +1 -1        0
       2HBr(aq) + Cl2(g)       2HCl(aq) + Br2(l)

Cl is reduced from 0 to -1, so Cl2 is the oxidizing agent

Br is oxidized from -1 to 0, so Br1- is the reducing agent
Sample Problem

Identify which atoms are oxidized and which are
  reduced in each reaction

             0        0           +1 -2
            O2(g) + 2H2(g)      2H2O(l)

             O2 is reduced from 0 to -2

             H2 is oxidized from 0 to +1
Sample Problem


Identify which atoms are oxidized and which are
  reduced in each reaction
         +1 +5 -2          +1 +3 -2         0
        2KNO3(s)          2KNO2(s) + O2(g)

              N is reduced from +5 to +3

               O is oxidized from -2 to 0
Sample Problem

Identify the oxidizing agent and the reducing agent
  in each equation.

              0        0           +1 -2
             O2(g) + 2H2(g)      2H2O(l)

     O2 is reduced, thus O2 is the oxidizing agent

     H2 is oxidized, thus H2 is the reducing agent
Sample Problem


Identify the oxidizing agent and the reducing agent
  in each equation.
         +1 +5 -2         +1 +3 -2      0
        2KNO3(s)          2KNO2(s) + O2(g)

      N is reduced, thus N is the oxidizing agent

      O is oxidized, thus O is the reducing agent
Questions

What is the general rule for assigning oxidation
 numbers?

The oxidation number is the charge a bonded atom
    would have if the electrons in the bond were
  assigned to the more electronegative element
How is a change I oxidation number related to the
  process of oxidation and reduction?
An increase in oxidation number indicates oxidation; a
   decrease in oxidation number indicates reduction.
Sample Problem
Identify which atoms are oxidized and which are
  reduced in each reaction. Also identify the
  oxidizing agent and the reducing agent.
              0        0           +1 -2
           2Na(s) + Cl2(g)      2NaCl(s)

    Cl2 is reduced, thus Cl2 is the oxidizing agent

    Na is oxidized, thus Na is the reducing agent
Sample Problem
Identify which atoms are oxidized and which are
  reduced in each reaction. Also identify the
  oxidizing agent and the reducing agent.
              0        0           +1 -2
 2HNO3(aq) + 6HI(aq)        2NO(g) + 3I2(s) + 4H2O(l)

     O2 is reduced, thus O2 is the oxidizing agent

     H2 is oxidized, thus H2 is the reducing agent
End of section 20.2
Identifying Redox Reactions
  In general, all chemical reaction can be
       assigned to one of two classes
1. Redox reactions in which electrons are
   transferred from one reacting species to another.
    a. Many single-replacement reactions,
       combination reactions, decomposition
       reactions and combustion reactions are redox
       reactions.
2. All other reactions in which no electron transfer
   occurs.
    a. Double-replacement reactions and acid-base
       reactions are not redox reactions
What Kind of Reaction Is It?
        2Mg(s) + O2(g)        2MgO(s)

Combination reaction – two or more substances
  react to form a single new substance


        2HgO (s)         2Hg (l) + O2 (g)

Decomposition reaction – a single compound
  breaks down into two or more simpler products.

            Many are redox reactions
What Kind of Reaction Is It?
Zn(s) + Cu(NO3)2(aq)       Cu(s) + Zn(NO3)2 (aq)

 Single Replacement Reaction – one element
 replaces a second element in a compound.

   2C6H18(l) + 25O2 (g)    16CO2(g) + 18H2O(l)


 Combustion Reactions – an element or a compound
 reacts with oxygen often producing energy in the
 form of heat and light..

             Many are redox reactions
What Kind of Reaction Is It?
Na2S(aq) + Cd(NO3)2(aq)   CdS(s) + 2NaNO3(aq)


Double Replacement Reaction – involving an
exchange of positive ions between two compounds.

  2C6H18(l) + 25O2 (g)     16CO2(g) + 18H2O(l)


Combustion Reactions – an element or a compound
reacts with oxygen often producing energy in the
form of heat and light..

          Many are not redox reactions
Identifying Redox Reactions

If the oxidation number of an element in a reacting
    species change, then that element has undergone
    either oxidation or reduction.

   Many reactions in which color changes occur are
   redox reactions.
Balancing Redox Equations
 Many redox reaction are too complex to be
        balanced by trial and error.

Two systematic methods are available to
balance redox reactions
The two methods are based on the fact that the
total number of electrons gained in reduction
must equal the total number of electrons lost in
oxidation.
One method used oxidation number changes,
and the other used half reactions.
Using Oxidation Number Changes to
       Balance Redox Equations

              Oxidation Number Method
You balance by comparing the increases and the
  decreases in oxidation numbers.
         +3   -2   +2 -2       0      +4 -2
         Fe2O3(s) + CO(g)     Fe(S) + CO2(g)

Step 1 – assign oxidation numbers to all the atoms in
  the equation.
Using Oxidation Number Changes to
      Balance Redox Equations
              Oxidation Number Method
                               C oxidized (+2)

        +3   -2    +2 -2            0            +4 -2
         Fe2O3(s) + CO(g)           Fe(S) + CO2(g)
                  Fe reduced (-3)


Step 2 – Identify which atoms are oxidized and which
  are reduced
Using Oxidation Number Changes to
      Balance Redox Equations
              Oxidation Number Method
                                 (+2) oxidized

        +3   -2    +2 -2               0         +4 -2
         Fe2O3(s) + CO(g)             Fe(S) + CO2(g)

                  (-3) reduced


Step 3 – Use one bracketing line to connect the atoms
  that undergo oxidation and another such line to
  connect those that undergo reduction.
Using Oxidation Number Changes to
       Balance Redox Equations


In a balanced redox equation, the total increase in
   oxidation number of the species oxidized must be
   balance by the total decrease in the oxidation
   number of the species reduced.
Using Oxidation Number Changes to
      Balance Redox Equations
             Oxidation Number Method
                                  3 x (+2) = +6

        +3 -2           +2 -2           0         +4 -2
       Fe2O3(s)    +   3CO(g)         2Fe(S) + 3CO2(g)

                  2 x (-3) = -6


Step 4 – Make the total increase in oxidation number
  equal to the total decrease in oxidation number by
  using appropriate coefficients.
Using Oxidation Number Changes to
      Balance Redox Equations

             Oxidation Number Method

  Fe2O3(s) + 3CO(g)     2Fe(S) + 3CO2(g)

Step 5 – Make sure that the equation is balanced for
  both atoms and charge.
Sample Problem
                 Oxidation Number Method

                                   S oxidized (+4) x 3= +12

+1 +6 -2          +1 -2      0         +1 -2 +1     +3 -2    +4 -2
2K2Cr2O7(aq) + H2O(l) + 3S(s)             KOH(aq) +   2Cr2O3(s) + 3SO2 (g)

           Cr reduced (-3) x 4 = -12

   4 Cr atoms must be reduced for each 3 S atom that are
   oxidized
Sample Problem
             Oxidation Number Method

                             S oxidized (+4) x 3= +12

  +1 +6 -2         +1 -2    0        +1 -2 +1    +3 -2   +4 -2
 2K2Cr2O7) + 2H2O + 3S               4KOH + 2Cr2O3 + 3SO2

              Cr reduced (-3) x 4 = -12

Check the equation and balance by inspection
4 in front of KOH balances potassium
2 in front of H2O balances hydrogen and oxygen.
Sample Problems
Balance each redox equation using the oxidation
number change method

           KClO3(s)      KCl (s) + O2 (g)

          2KClO3(s)      2KCl (s) + 3O2 (g)

 HNO2 (aq) + HI (aq)        NO (g) + I2 (s) + H2O (l)

2HNO2 (aq) + 2HI (aq)      2NO (g) + I2 (s) + 2H2O (l)
Sample Problems
Balance each redox equation using the oxidation
number change method

     Bi2S3 + HNO3      Bi(NO3)3 + NO + S + H2O

  Bi2S3 + 8 HNO3      2Bi(NO3)3 + 2NO + 3S + 4H2O

         SbCl5 + KI       SbCl3 + KCl + I2

        SbCl5 + 2KI        SbCl3 + 2KCl + I2
Using Half Reactions to Balance
          Redox Equations
               Half Reaction Method

Half reaction is an equation showing just the oxidation
   or just the reduction that takes place

You write and balance the oxidation and reduction half
  reaction separately before combining them into a
  balanced redox equation

Then you balance the electrons gained in the reduction
  with the electrons lost in the oxidation.
Using Half Reactions to Balance
           Redox Equations
                Half Reaction Method

S + HNO3        SO2 + NO + H2O (unbalanced)


        S + H+ + NO3-        SO2 + NO + H2O

In this case only HNO3 is ionized. The products are
   covalent compounds
Step 1 – write the unbalanced equation in ionic form
Using Half Reactions to Balance
           Redox Equations
                Half Reaction Method

Oxidation Half Reaction
                      0       +2
                      S       SO2

Reduction Half Reaction
                     +5            +2
                     NO3-          NO

Step 2 – Write separate half reactions for the oxidation
  and reduction processes.
Using Half Reactions to Balance
           Redox Equations
Half Reaction Method
                       0       +2
                      S       SO2

Sulfur is already balanced, but oxygen is not.
The reaction takes place in acid solution, so H2O and
  H+ are present and can be used to balance oxygen
  and hydrogen as needed.
              2H2O + S         SO2 + 4H+

Step 3 – Balance the atoms in the half reactions.
Using Half Reactions to Balance
           Redox Equations

Half Reaction Method
                    +5         +2
                    NO3-       NO

Nitrogen is already balanced, but oxygen is not.

             4H+ + NO3-        NO + 2H2O
Using Half Reactions to Balance
           Redox Equations
Half Reaction Method
                     0        +4
           2H2O + S           SO2 + 4H+ + 4e -

S is oxidized going from 0 to +4, a loss of 4 e-

                         +5         +2
         3e- + 4H+ + NO3-           NO + 2H2O

N is reduced going from +5 to +2, a gain of 3 e-
Step 4 – Add enough electrons to one side of each half
  reaction to balance the charges.
Using Half Reactions to Balance
           Redox Equations
Half Reaction Method
                        0        +4
    (x 3)    6H2O + 3S           3SO2 + 12H+ + 12e -

S is oxidized going from 0 to +4, a loss of 4 e-

                            +5            +2
   (x 4)    12e- + 16H+ + 4NO3-
            12                           4NO + 8H2O

N is reduced going from +5 to +2, a gain of 3 e-
Step 5 – Multiply each half reaction by an appropriate
  number to make the numbers of electrons equal in
  both.
Using Half Reactions to Balance
           Redox Equations
Half Reaction Method
        6H2O + 3S         3SO2 + 12H+ + 12e -

      12e- + 16H+ + 4NO3-          4NO + 8H2O

6H2O + 3S + 16H+ + 4NO3- + 12e -     3SO2 + 12H+ +
  4NO + 8H2O + 12e –

     3S + 4H+ + 4NO3-      3SO2 + 4NO + 2H2O

Step 6 – Add the balanced half reactions to show an
  overall equation and then subtract the terms that
  appear in both sides of the equation
Using Half Reactions to Balance
           Redox Equations
Half Reaction Method

       3S + 4HNO3-        3SO2 + 4NO + 2H2O

Spectator ion – are present during a reaction, but do
  not participate in or change during a reaction.
Because none of the ions in the reactants appear in the
  products, there are no spectator ions in this
  particular example.
Step 7 – Add the spectator ions and balance the
  equation.
Sample Problem

                 Half Reaction Method

      KMnO4 + HCl         MnCl2 + Cl2 + H2O + KCl


K+ + MnO4- + H+ + Cl-    Mn2+ + 2Cl- + Cl2 + H2O + K+ + Cl-


Step 1 – write the unbalanced equation in ionic form
Sample Problem

                Half Reaction Method

Reduction Half Reaction
                    +7          +2
                   MnO4-        Mn2+

Oxidation Half Reaction
                      -1         0
                     2Cl-       Cl2

Step 2 – Write separate half reactions for the oxidation
  and reduction processes.
Sample Problem

Reduction Half Reaction
                   +7         +2
            8H+ + MnO4-        Mn2+ + 4H2O

Oxidation Half Reaction
                     -1         0
                     2Cl-      Cl2

Solution is acidic, so H2O and H+ ions are used to
  balance equation. (If solution is basic, H2O and OH-
  are used)

Step 3 – Balance the atoms in the half reactions.
Sample Problem

Half Reaction Method
                          +7        +2
         5e- + 8H+ + MnO4-          Mn2+ + 4H2O

Mn is reduced going from +7 to +2, a gain of 5 e-
                    -1          0
                   2Cl-        Cl2 + 2e-

Cl is oxidized going from -1 to 0, a loss of 2 e-
Step 4 – Add enough electrons to one side of each half
  reaction to balance the charges.
Sample Problem
Half Reaction Method

                            +7          +2
    (x 2) 10e- + 16H+ + 2MnO4-          2Mn2+ + 8H2O

Mn is reduced going from +7 to +2, a gain of 5 e-
                       -1         0
              (x5) 10Cl-         5Cl2 + 10e-

Cl is oxidized going from -1 to 0, a loss of 2 e-
Step 5 – Multiply each half reaction by an appropriate
  number to make the numbers of electrons equal in
  both.
Sample Problem
Half Reaction Method
      10e- + 16H+ + 2MnO4-       2Mn2+ + 8H2O
               10Cl-      5Cl2 + 10e-

10e- + 16H+ + 2MnO4- + 10Cl-     2Mn2+ + 8H2O + 5Cl2
  + 10e-

   16H+ + 2MnO4- + 10Cl-       2Mn2+ + 8H2O + 5Cl2

Step 6 – Add the balanced half reactions to show an
  overall equation and then subtract the terms that
  appear in both sides of the equation
Sample Problem
Half Reaction Method

          16H+ + 6Cl- + 2MnO4- + 2K+ + 10Cl-
        5Cl2 + 2Mn2+ + 4Cl- + 8H2O + 2K+ + 2Cl-

   16H+ = 6Cl- + 10Cl- (from the HCl in original equation)
    2MnO4- = 2K+ (from the KMnO4 in original equation)
     2Mn2+ = 4Cl- (from the MnCl2 in original equation)
        2K+ + 2Cl- (from the KCl in original equation)

Step 7 – Add the spectator ions and balance the
  equation.
Sample Problem
Half Reaction Method

            16H+ + 16Cl- + 2MnO4- + 2K+
           5Cl2 + 2Mn2+ + 6Cl- + 8H2O + 2K+

Adding spectator and non-spectator Cl- on each side gives

  16HCl + 2KMnO4        5Cl2 + 2MnCl2 + 8H2O + 2KCl

Step 7 – Add the spectator ions and balance the
  equation.
Sample Problem 2


The following takes place in basic solution. Balance the
  equation using the half reaction method


            Zn + NO3-      NH3 + Zn(OH4)2-

   4Zn + NO3- + 6H2O + 7OH-        4Zn(OH4)2- + NH3
Sample Problem 3


The following takes place in basic solution. Balance the
  equation using the half reaction method


             Zn + As2O3       AsH3 + Zn2+

   6Zn + As2O3 + 9H2O       6Zn2+ + 2AsH3 + 12OH-
Choosing a Balancing Method

In some redox reactions, the same element is both
   oxidized and reduced. (called a disproportional
   reaction)

       3Br2 + 6KOH       5KBr + KBrO3 + 3H2O

              Br is reduced from 0 to -1
              Br is oxidized from 0 to + 5

Equations like above and equation for reactions that
  take place in acidic or alkaline solution are best
  balanced by the half reaction method.
End of Chapter 20

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Measures of Dispersion and Variability: Range, QD, AD and SD
 

Chapter 20

  • 2. Some Common Reactions The combustion of gasoline in an automobile engine requires oxygen Burning of wood in a fireplace requires oxygen The reactions that break down food in your body and release energy use oxygen The oxide of hydrogen is water Charcoal oxidizes when it burn forming CO2 Bleaching stains in fabric is still oxidation even though it does not burn.
  • 3. Oxidation When methane burns in air, it oxidizes and forms oxides of carbon and hydrogen. CH4(g) + 2O2(g) CO2(g) + 2H2O(g) When elemental iron turns to rust, it slowly oxidizes to compounds such as iron (III) oxide. 4Fe(s) + 3O2(g) 2Fe2O3(s)
  • 4. Reduction Originally reduction meant a loss of oxygen from a compound 2Fe2O3(s) + 3C(s) 4Fe(s) + 3CO2(g) iron oxide carbon iron carbon dioxide Reduction of iron ore to metallic iron involves the removal of oxygen from iron (III) oxide. Involves heating the ore with carbon.
  • 5. Question What happens to magnesium and oxygen when they react to form magnesium oxide? +2 -2 2Mg + O2 2MgO magnesium oxygen magnesium oxide Magnesium loses electrons to form Mg2+ Oxygen gains electrons to form O2-
  • 6. Electron Shift in Redox Reactions The modern concept of oxidation and reduction have been extended to include many reactions that do not even involve oxygen. Oxygen is the most electronegative element (besides fluorine) When oxygen bonds with an atom of a different element (except fluorine), electrons from that atom shift toward oxygen.
  • 7. Redox Reactions Redox reactions are currently understood to involve any shift of electron between reactants. Oxidation – a process that involves a complete or partial loss of electrons or a gain of oxygen. • Results in an increase in the oxidation number of an atom Reduction – a process that involves a complete or partial gain of electrons or the loss of oxygen. • Results in a decrease in the oxidation number of an atom
  • 8. Redox Reactions Oxidation and reduction always occur simultaneously. The substance gaining oxygen or losing electrons is oxidized The substance losing oxygen or gaining electrons is reduced.
  • 9. Redox Reactions During a reaction between a metal and a nonmetal, electrons are transferred from atoms of the metal to atoms of the nonmetal. Mg + S Mg2+S2- magnesium sulfur magnesium sulfide 2 electrons are transferred from a magnesium atom to a sulfur atom. Magnesium atoms become more stable by the loss of electrons. Sulfur atoms become more stable by the gain of electrons
  • 10. Redox Reactions Mg + S Mg2+S2- magnesium sulfur magnesium sulfide Oxidation: Mg Mg2+ + 2e- (loss of electrons) Reduction: S + 2e- S2- (gain of electrons) Magnesium atom is said to be oxidized to a magnesium ion Sulfur atom is said to be reduced to a sulfide ion.
  • 11. Redox Reactions When a metal combines with oxygen, it loses electrons When oxygen is removed from the oxide of a metal, the metal gains electrons. This knowledge is what led to the broader definition of oxidation and reduction as an exchange of electrons.
  • 12. Redox Reactions Reducing agent – the substance that loses the electrons Mg + S MgS reducing agent oxidized Oxidizing agent – the substance that accepts electrons Mg + S MgS oxidizing agent reduced
  • 13. Sample Problem Silver nitrate reacts with copper to form copper nitrate and silver. From the equation below, determine what is oxidized and what is reduced. Identify the oxidizing agent and the reducing agent. 2AgNO3 + Cu Cu(NO3)2 + 2Ag Rewrite the equation in ionic form 2Ag+ + 2NO3- + Cu Cu2+ + 2NO3- + 2Ag
  • 14. Sample Problem 2Ag+ + 2NO3- + Cu Cu2+ + 2NO3- + 2Ag Oxidation: 2 e- are lost from copper when it becomes a Cu2+ Reduction: 2e- are gained by two silver ions which become neutral silver atoms. 2Ag+ + 2NO3- + Cu Cu2+ + 2NO3- + 2Ag oxidizing reducing Agent agent reduced oxidized
  • 15. Sample Problem 2Na + S 2Na+ + S2- oxidized reduced reducing agent oxidizing agent 4Al + 3O2 4Al3+ + 3O2- Oxidized reduced Reducing agent oxidizing agent 2I- I2 + 2e- oxidation Zn2+ + 2e- Zn reduction
  • 16. Redox with Covalent Compounds Some reactions involve covalent compounds. In these compounds complete electron transfer does not occur. 2H2 (g) + O2 (g) 2H2O (l) In each reactant hydrogen molecule, the bonding electrons are shared equally between the hydrogen atoms. In water, however, the bonding electrons are pulled toward oxygen because it is much more electronegative than hydrogen.
  • 17. Redox with Covalent Compounds 2H2 (g) + O2 (g) 2H2O (l) There is a shift of bonding electrons away from hydrogen, even though there is not a complete transfer. Hydrogen is oxidized because it undergoes a partial loss of electrons.
  • 18. Redox with Covalent Compounds 2H2 (g) + O2 (g) 2H2O (l) In oxygen, the bonding electrons are share equally between oxygen atoms in the reactant oxygen molecule. When oxygen bonds to hydrogen in the water molecule, there is a shift of electrons toward oxygen. Oxygen is thus reduced because it undergoes a partial gain of electrons.
  • 19. Redox with Covalent Compounds H H O O H O shift of bonding e- shared e- shared e- away from H equally equally H and toward O H is reducing O is oxidizing agent agent
  • 20. Redox with Covalent Compounds Some reactions involving covalent reactants or products, the partial electron shifts are less obvious. General guideline for covalent reactants or products: • for carbon compounds, the addition of oxygen or the removal of hydrogen is always oxidation
  • 21. Processes Leading to Oxidation & Reduction Processes Leading to Oxidation & Reduction Oxidation Reduction Complete loss of electrons Complete gain of electrons (ionic reactions) (ionic reactions) Shift of electrons away from Shift of electrons toward an an atom in a covalent bond atom in a covalent bond Gain of oxygen Loss of oxygen Loss of hydrogen by a Gain of hydrogen by a covalent compound covalent compound Increase in oxidation Decrease in oxidation number number
  • 22. Corrosion Iron, often used in the form of the alloy steel, corrodes by being oxidized to ions of iron by oxygen. 2Fe(s) + O2 (g) + 2H2O (l) 2Fe(OH)2 (s) 4Fe(OH)2(s) + O2 (g) + 2H2O (l) 4Fe(OH)3 (s) • Equations describe the corrosion of iron to iron hydroxides in moist conditions.
  • 23. Corrosion Water in the environment accelerates the rate of corrosion. Corrosion occurs more rapidly in the presence of salts and acids. Salts and acids produce electrically conducting solutions that make electron transfer easier.
  • 24. Resistance to Corrosion Not all metals corrode easily. Gold and platinum are called noble metals because they are very resistant to losing their e- by corrosion. Other metals lose electrons easily but are protected from extensive corrosion by the oxide coating formed on their surface. • Aluminum oxidizes quickly in air to form a coating of very tightly packed aluminum oxide particles.
  • 25. Resistance to Corrosion Iron also forms a coating when it corrodes But the coating of iron oxide that forms is not tightly packed. Water and air can penetrate the coating and attack the iron metal below it. Corrosion continues until the iron object becomes only a pile of rust.
  • 26. Controlling Corrosion To prevent corrosion, the metal surface can be coated with oil, paint, plastic or another metal. Coatings exclude air and water from the surface, preventing corrosion. If coating is scratched or worn away, however, the exposed metal will begin to corrode.
  • 27. Controlling Corrosion Another method of corrosion control One metal is “sacrificed” or allowed to corrode, in order to save a second metal. To protect an iron object, a piece of magnesium (or other active metal) may be placed in electrical contact with the iron. When oxygen and water attack the iron object, the iron atoms lose electrons as the iron being to be oxidized.
  • 28. Controlling Corrosion Because magnesium is a better reducing agent than iron and is more easily oxidized the magnesium immediately transfers electrons to the iron, preventing their oxidation to iron ions. Magnesium is “sacrificed” by oxidation and protects the iron in the process.
  • 29. Controlling Corrosion Sacrificial zinc and magnesium blocks are sometimes attached to piers and ship hulls to prevent corrosion damage in areas submerged in water. Underground pipelines and storage tanks may be connected to magnesium block for protection It is easier and cheaper to replace a block of magnesium or zinc than to replace a bride or a pipeline.
  • 30. Question Can you identify the common chemical characteristic of all metal corrosion? The transfer of electrons from metals to oxidizing agents.
  • 31. Questions Define oxidation and reduction in terms of the gain or loss of oxygen. Oxidation is the gain of oxygen Reduction is the loss of oxygen Define oxidation and reduction in terms of the gain or loss of electrons. LEO the lion goes GER Loss of Electrons is Oxidation Gain of Electrons is Reduction
  • 32. Questions What happens to the atoms in an iron nail that corrodes? Iron atoms are oxidized when iron corrodes How do you identify the oxidizing agent and the reducing agent in a redox reaction? The species reduced is the oxidizing agent. The species oxidized is the reducing agent.
  • 33. Questions Use electron transfer or electron shift to identify what is oxidized and what is reduced in each reaction. (use electronegativity values for molecular compounds) 2Na(s) + Br2(l) 2NaBr(s) Na oxidized, Br2 reduced H2(g) + Cl2(g) 2HCl(g) H2 oxidized, Cl2 reduced
  • 34. Questions Use electron transfer or electron shift to identify what is oxidized and what is reduced in each reaction. (use electronegativity values for molecular compounds) 2Li(s) + F2(g) 2LiF(s) Li oxidized, F2 reduced S(s) + Cl2(g) SCl2(g) S oxidized, Cl2 reduced
  • 35. Questions Use electron transfer or electron shift to identify what is oxidized and what is reduced in each reaction. (use electronegativity values for molecular compounds) N2(g) + 2O2(g) 2NO2(s) N2 oxidized, O2 reduced Mg(s) + Cu(NO3)2(aq) Mg(NO3)2(aq) + Cu(s) Mg oxidized, Cu reduced
  • 36. Questions Identify the reducing agent and the oxidizing agent for each reaction. 2Na(s) + Br2(l) 2NaBr(s) Na reducing agent, Br2 oxidizing agent H2(g) + Cl2(g) 2HCl(g) H2 reducing agent, Cl2 oxidizing agent
  • 37. Questions Identify the reducing agent and the oxidizing agent for each reaction. 2Li(s) + F2(g) 2LiF(s) Li reducing agent, F2 oxidizing agent S(s) + Cl2(g) SCl2(g) S reducing agent, Cl2 oxidizing agent
  • 38. Questions Identify the reducing agent and the oxidizing agent for each reaction. N2(g) + 2O2(g) 2NO2(s) N2 reducing agent, O2 oxidizing agent Mg(s) + Cu(NO3)2(aq) Mg(NO3)2(aq) + Cu(s) Mg reducing agent, Cu oxidizing agent
  • 40. Oxidation Numbers Oxidation number is a + or – number assigned to an atom to indicate its degree of oxidation or reduction. General Rule A bonded atom’s oxidation # is the charge that it would have if the e- in the bond were assigned to the atom of the more electronegative element.
  • 41. Rules for Assigning Oxidation Numbers 1. The oxidation number of a monatomic ion is = in magnitude and sign to its ionic charge. Bromide (Br1-) is -1 Iron III (Fe3+) is +3 2. The oxidation number of hydrogen in a compound is +1, except in metal hydrides, such as NaH, where it is -1 3. The oxidation number of oxygen in a compound is -2 except in peroxides, such as H2O2, where it is -1 and in compounds with the more electronegative fluorine, where it is positive.
  • 42. Rules for Assigning Oxidation Numbers 4. The oxidation number of an atom in uncombined (elemental) form is 0. Potassium metal (K) is 0 Nitrogen Gas (N2) is 0 5. For any neutral compound, the sum of the oxidation numbers of the atoms in the compound must equal 0 6. For polyatomic ion, the sum of the oxidation numbers must equal the ionic charge of the ion.
  • 43. Some Thought Determining oxidation numbers of elements in compounds is a way for chemists to keep track of electron transfer during redox reactions What are other examples where items are numbered to keep track of movement? The numbers on a sports player’s jersey The area codes assigned to telephone numbers in different regions
  • 44. Binary Ionic Compounds In binary ionic compounds, such as NaCl and CaCl2, the oxidation numbers of the atoms equal their ionic charges. Na1+ + Cl-1 NaCl oxidation # +1 -1 neutral Ca2+ + Cl-1 CaCl2 oxidation # +2 -1 neutral Note the sign I put before the oxidation number
  • 45. Molecular Compounds No ionic charges are associated with atoms of molecular compounds. However, oxygen is reduced in the formation of water for example. In water the two shared e- in the H – O bond are shifted toward the O and away from the H. Imagine the e- contributed by the two H atoms are completely transferred to the O.
  • 46. Molecular Compounds The charge that would result from the transfer are the oxidation numbers of the bonded elements. The oxidation number of O is -2 and the oxidation number of each hydrogen is +1 Oxidation numbers are often written above the chemical symbols in a formula. +1 -2 H2O
  • 47. Multiple Oxidation Numbers Many elements can have several different oxidation numbers. +1 +6 -2 K2CrO4 – Potassium Chromate +1 +12 -2 K2CrO7 – Potassium Dichromate
  • 48. Sample Problems What is the oxidation number of each kind of atom in the following ions and compounds? +4 -2 SO2 +4 -2 CO32- +1 +6 -2 Na2SO4 -3 +1 -2 (NH4)2S
  • 49. Sample Problems Determine the oxidation number of each element in the following. +3 -2 S2O3 +1 -1 Na2O2 +5 -2 P2O5 +5 -2 NO3-
  • 50. Sample Problems Determine the oxidation number of chlorine in each of the following substances. +1 +5 -2 KClO3 0 Cl2 +2 +7 -2 Ca(ClO4)2 +1 -2 Cl2O
  • 51. Sample Problems What are the oxidation numbers of iodine in the following? +1 +7 -2 HIO4 +1 +5 -2 HIO3 +1 +1 -2 HIO 0 I2 +1 -1 HI
  • 52. Oxidation Number Changes When copper wire is placed in a solution of silver nitrate the following reaction occurs +1 +5 -3 0 +2 +5 -2 0 2AgNO3(aq) + Cu(s) Cu(NO3)2(aq) + 2Ag(s) Ag is reduced from +1 to 0 Cu is oxidized from 0 to +2
  • 53. Oxidation Number Changes An increase in the oxidation number of an atom or ion indicates oxidation. A decrease in the oxidation number of an atom or ion indicates reduction. +2 +6 -2 0 0 +2 +6 -2 2CuSO4(aq) + Fe2(s) 2Cu(s) + 2FeSO4 Cu is reduced from +2 to 0 Fe is oxidized from 0 to +2
  • 54. Sample Problem Identify which atoms are oxidized and which are reduced in the following reaction. Also identify the oxidizing agent and the reducing agent. +1 -1 0 +1 -1 0 2HBr(aq) + Cl2(g) 2HCl(aq) + Br2(l) Cl is reduced from 0 to -1, so Cl2 is the oxidizing agent Br is oxidized from -1 to 0, so Br1- is the reducing agent
  • 55. Sample Problem Identify which atoms are oxidized and which are reduced in each reaction 0 0 +1 -2 O2(g) + 2H2(g) 2H2O(l) O2 is reduced from 0 to -2 H2 is oxidized from 0 to +1
  • 56. Sample Problem Identify which atoms are oxidized and which are reduced in each reaction +1 +5 -2 +1 +3 -2 0 2KNO3(s) 2KNO2(s) + O2(g) N is reduced from +5 to +3 O is oxidized from -2 to 0
  • 57. Sample Problem Identify the oxidizing agent and the reducing agent in each equation. 0 0 +1 -2 O2(g) + 2H2(g) 2H2O(l) O2 is reduced, thus O2 is the oxidizing agent H2 is oxidized, thus H2 is the reducing agent
  • 58. Sample Problem Identify the oxidizing agent and the reducing agent in each equation. +1 +5 -2 +1 +3 -2 0 2KNO3(s) 2KNO2(s) + O2(g) N is reduced, thus N is the oxidizing agent O is oxidized, thus O is the reducing agent
  • 59. Questions What is the general rule for assigning oxidation numbers? The oxidation number is the charge a bonded atom would have if the electrons in the bond were assigned to the more electronegative element How is a change I oxidation number related to the process of oxidation and reduction? An increase in oxidation number indicates oxidation; a decrease in oxidation number indicates reduction.
  • 60. Sample Problem Identify which atoms are oxidized and which are reduced in each reaction. Also identify the oxidizing agent and the reducing agent. 0 0 +1 -2 2Na(s) + Cl2(g) 2NaCl(s) Cl2 is reduced, thus Cl2 is the oxidizing agent Na is oxidized, thus Na is the reducing agent
  • 61. Sample Problem Identify which atoms are oxidized and which are reduced in each reaction. Also identify the oxidizing agent and the reducing agent. 0 0 +1 -2 2HNO3(aq) + 6HI(aq) 2NO(g) + 3I2(s) + 4H2O(l) O2 is reduced, thus O2 is the oxidizing agent H2 is oxidized, thus H2 is the reducing agent
  • 63. Identifying Redox Reactions In general, all chemical reaction can be assigned to one of two classes 1. Redox reactions in which electrons are transferred from one reacting species to another. a. Many single-replacement reactions, combination reactions, decomposition reactions and combustion reactions are redox reactions. 2. All other reactions in which no electron transfer occurs. a. Double-replacement reactions and acid-base reactions are not redox reactions
  • 64. What Kind of Reaction Is It? 2Mg(s) + O2(g) 2MgO(s) Combination reaction – two or more substances react to form a single new substance 2HgO (s) 2Hg (l) + O2 (g) Decomposition reaction – a single compound breaks down into two or more simpler products. Many are redox reactions
  • 65. What Kind of Reaction Is It? Zn(s) + Cu(NO3)2(aq) Cu(s) + Zn(NO3)2 (aq) Single Replacement Reaction – one element replaces a second element in a compound. 2C6H18(l) + 25O2 (g) 16CO2(g) + 18H2O(l) Combustion Reactions – an element or a compound reacts with oxygen often producing energy in the form of heat and light.. Many are redox reactions
  • 66. What Kind of Reaction Is It? Na2S(aq) + Cd(NO3)2(aq) CdS(s) + 2NaNO3(aq) Double Replacement Reaction – involving an exchange of positive ions between two compounds. 2C6H18(l) + 25O2 (g) 16CO2(g) + 18H2O(l) Combustion Reactions – an element or a compound reacts with oxygen often producing energy in the form of heat and light.. Many are not redox reactions
  • 67. Identifying Redox Reactions If the oxidation number of an element in a reacting species change, then that element has undergone either oxidation or reduction. Many reactions in which color changes occur are redox reactions.
  • 68. Balancing Redox Equations Many redox reaction are too complex to be balanced by trial and error. Two systematic methods are available to balance redox reactions The two methods are based on the fact that the total number of electrons gained in reduction must equal the total number of electrons lost in oxidation. One method used oxidation number changes, and the other used half reactions.
  • 69. Using Oxidation Number Changes to Balance Redox Equations Oxidation Number Method You balance by comparing the increases and the decreases in oxidation numbers. +3 -2 +2 -2 0 +4 -2 Fe2O3(s) + CO(g) Fe(S) + CO2(g) Step 1 – assign oxidation numbers to all the atoms in the equation.
  • 70. Using Oxidation Number Changes to Balance Redox Equations Oxidation Number Method C oxidized (+2) +3 -2 +2 -2 0 +4 -2 Fe2O3(s) + CO(g) Fe(S) + CO2(g) Fe reduced (-3) Step 2 – Identify which atoms are oxidized and which are reduced
  • 71. Using Oxidation Number Changes to Balance Redox Equations Oxidation Number Method (+2) oxidized +3 -2 +2 -2 0 +4 -2 Fe2O3(s) + CO(g) Fe(S) + CO2(g) (-3) reduced Step 3 – Use one bracketing line to connect the atoms that undergo oxidation and another such line to connect those that undergo reduction.
  • 72. Using Oxidation Number Changes to Balance Redox Equations In a balanced redox equation, the total increase in oxidation number of the species oxidized must be balance by the total decrease in the oxidation number of the species reduced.
  • 73. Using Oxidation Number Changes to Balance Redox Equations Oxidation Number Method 3 x (+2) = +6 +3 -2 +2 -2 0 +4 -2 Fe2O3(s) + 3CO(g) 2Fe(S) + 3CO2(g) 2 x (-3) = -6 Step 4 – Make the total increase in oxidation number equal to the total decrease in oxidation number by using appropriate coefficients.
  • 74. Using Oxidation Number Changes to Balance Redox Equations Oxidation Number Method Fe2O3(s) + 3CO(g) 2Fe(S) + 3CO2(g) Step 5 – Make sure that the equation is balanced for both atoms and charge.
  • 75. Sample Problem Oxidation Number Method S oxidized (+4) x 3= +12 +1 +6 -2 +1 -2 0 +1 -2 +1 +3 -2 +4 -2 2K2Cr2O7(aq) + H2O(l) + 3S(s) KOH(aq) + 2Cr2O3(s) + 3SO2 (g) Cr reduced (-3) x 4 = -12 4 Cr atoms must be reduced for each 3 S atom that are oxidized
  • 76. Sample Problem Oxidation Number Method S oxidized (+4) x 3= +12 +1 +6 -2 +1 -2 0 +1 -2 +1 +3 -2 +4 -2 2K2Cr2O7) + 2H2O + 3S 4KOH + 2Cr2O3 + 3SO2 Cr reduced (-3) x 4 = -12 Check the equation and balance by inspection 4 in front of KOH balances potassium 2 in front of H2O balances hydrogen and oxygen.
  • 77. Sample Problems Balance each redox equation using the oxidation number change method KClO3(s) KCl (s) + O2 (g) 2KClO3(s) 2KCl (s) + 3O2 (g) HNO2 (aq) + HI (aq) NO (g) + I2 (s) + H2O (l) 2HNO2 (aq) + 2HI (aq) 2NO (g) + I2 (s) + 2H2O (l)
  • 78. Sample Problems Balance each redox equation using the oxidation number change method Bi2S3 + HNO3 Bi(NO3)3 + NO + S + H2O Bi2S3 + 8 HNO3 2Bi(NO3)3 + 2NO + 3S + 4H2O SbCl5 + KI SbCl3 + KCl + I2 SbCl5 + 2KI SbCl3 + 2KCl + I2
  • 79. Using Half Reactions to Balance Redox Equations Half Reaction Method Half reaction is an equation showing just the oxidation or just the reduction that takes place You write and balance the oxidation and reduction half reaction separately before combining them into a balanced redox equation Then you balance the electrons gained in the reduction with the electrons lost in the oxidation.
  • 80. Using Half Reactions to Balance Redox Equations Half Reaction Method S + HNO3 SO2 + NO + H2O (unbalanced) S + H+ + NO3- SO2 + NO + H2O In this case only HNO3 is ionized. The products are covalent compounds Step 1 – write the unbalanced equation in ionic form
  • 81. Using Half Reactions to Balance Redox Equations Half Reaction Method Oxidation Half Reaction 0 +2 S SO2 Reduction Half Reaction +5 +2 NO3- NO Step 2 – Write separate half reactions for the oxidation and reduction processes.
  • 82. Using Half Reactions to Balance Redox Equations Half Reaction Method 0 +2 S SO2 Sulfur is already balanced, but oxygen is not. The reaction takes place in acid solution, so H2O and H+ are present and can be used to balance oxygen and hydrogen as needed. 2H2O + S SO2 + 4H+ Step 3 – Balance the atoms in the half reactions.
  • 83. Using Half Reactions to Balance Redox Equations Half Reaction Method +5 +2 NO3- NO Nitrogen is already balanced, but oxygen is not. 4H+ + NO3- NO + 2H2O
  • 84. Using Half Reactions to Balance Redox Equations Half Reaction Method 0 +4 2H2O + S SO2 + 4H+ + 4e - S is oxidized going from 0 to +4, a loss of 4 e- +5 +2 3e- + 4H+ + NO3- NO + 2H2O N is reduced going from +5 to +2, a gain of 3 e- Step 4 – Add enough electrons to one side of each half reaction to balance the charges.
  • 85. Using Half Reactions to Balance Redox Equations Half Reaction Method 0 +4 (x 3) 6H2O + 3S 3SO2 + 12H+ + 12e - S is oxidized going from 0 to +4, a loss of 4 e- +5 +2 (x 4) 12e- + 16H+ + 4NO3- 12 4NO + 8H2O N is reduced going from +5 to +2, a gain of 3 e- Step 5 – Multiply each half reaction by an appropriate number to make the numbers of electrons equal in both.
  • 86. Using Half Reactions to Balance Redox Equations Half Reaction Method 6H2O + 3S 3SO2 + 12H+ + 12e - 12e- + 16H+ + 4NO3- 4NO + 8H2O 6H2O + 3S + 16H+ + 4NO3- + 12e - 3SO2 + 12H+ + 4NO + 8H2O + 12e – 3S + 4H+ + 4NO3- 3SO2 + 4NO + 2H2O Step 6 – Add the balanced half reactions to show an overall equation and then subtract the terms that appear in both sides of the equation
  • 87. Using Half Reactions to Balance Redox Equations Half Reaction Method 3S + 4HNO3- 3SO2 + 4NO + 2H2O Spectator ion – are present during a reaction, but do not participate in or change during a reaction. Because none of the ions in the reactants appear in the products, there are no spectator ions in this particular example. Step 7 – Add the spectator ions and balance the equation.
  • 88. Sample Problem Half Reaction Method KMnO4 + HCl MnCl2 + Cl2 + H2O + KCl K+ + MnO4- + H+ + Cl- Mn2+ + 2Cl- + Cl2 + H2O + K+ + Cl- Step 1 – write the unbalanced equation in ionic form
  • 89. Sample Problem Half Reaction Method Reduction Half Reaction +7 +2 MnO4- Mn2+ Oxidation Half Reaction -1 0 2Cl- Cl2 Step 2 – Write separate half reactions for the oxidation and reduction processes.
  • 90. Sample Problem Reduction Half Reaction +7 +2 8H+ + MnO4- Mn2+ + 4H2O Oxidation Half Reaction -1 0 2Cl- Cl2 Solution is acidic, so H2O and H+ ions are used to balance equation. (If solution is basic, H2O and OH- are used) Step 3 – Balance the atoms in the half reactions.
  • 91. Sample Problem Half Reaction Method +7 +2 5e- + 8H+ + MnO4- Mn2+ + 4H2O Mn is reduced going from +7 to +2, a gain of 5 e- -1 0 2Cl- Cl2 + 2e- Cl is oxidized going from -1 to 0, a loss of 2 e- Step 4 – Add enough electrons to one side of each half reaction to balance the charges.
  • 92. Sample Problem Half Reaction Method +7 +2 (x 2) 10e- + 16H+ + 2MnO4- 2Mn2+ + 8H2O Mn is reduced going from +7 to +2, a gain of 5 e- -1 0 (x5) 10Cl- 5Cl2 + 10e- Cl is oxidized going from -1 to 0, a loss of 2 e- Step 5 – Multiply each half reaction by an appropriate number to make the numbers of electrons equal in both.
  • 93. Sample Problem Half Reaction Method 10e- + 16H+ + 2MnO4- 2Mn2+ + 8H2O 10Cl- 5Cl2 + 10e- 10e- + 16H+ + 2MnO4- + 10Cl- 2Mn2+ + 8H2O + 5Cl2 + 10e- 16H+ + 2MnO4- + 10Cl- 2Mn2+ + 8H2O + 5Cl2 Step 6 – Add the balanced half reactions to show an overall equation and then subtract the terms that appear in both sides of the equation
  • 94. Sample Problem Half Reaction Method 16H+ + 6Cl- + 2MnO4- + 2K+ + 10Cl- 5Cl2 + 2Mn2+ + 4Cl- + 8H2O + 2K+ + 2Cl- 16H+ = 6Cl- + 10Cl- (from the HCl in original equation) 2MnO4- = 2K+ (from the KMnO4 in original equation) 2Mn2+ = 4Cl- (from the MnCl2 in original equation) 2K+ + 2Cl- (from the KCl in original equation) Step 7 – Add the spectator ions and balance the equation.
  • 95. Sample Problem Half Reaction Method 16H+ + 16Cl- + 2MnO4- + 2K+ 5Cl2 + 2Mn2+ + 6Cl- + 8H2O + 2K+ Adding spectator and non-spectator Cl- on each side gives 16HCl + 2KMnO4 5Cl2 + 2MnCl2 + 8H2O + 2KCl Step 7 – Add the spectator ions and balance the equation.
  • 96. Sample Problem 2 The following takes place in basic solution. Balance the equation using the half reaction method Zn + NO3- NH3 + Zn(OH4)2- 4Zn + NO3- + 6H2O + 7OH- 4Zn(OH4)2- + NH3
  • 97. Sample Problem 3 The following takes place in basic solution. Balance the equation using the half reaction method Zn + As2O3 AsH3 + Zn2+ 6Zn + As2O3 + 9H2O 6Zn2+ + 2AsH3 + 12OH-
  • 98. Choosing a Balancing Method In some redox reactions, the same element is both oxidized and reduced. (called a disproportional reaction) 3Br2 + 6KOH 5KBr + KBrO3 + 3H2O Br is reduced from 0 to -1 Br is oxidized from 0 to + 5 Equations like above and equation for reactions that take place in acidic or alkaline solution are best balanced by the half reaction method.