1.

4 Balancing Redox Equations using Oxidation Numbers

In previous chemistry classes you learned how to balance equations. Following the Law of Conservation of Mass you learned that the number of atoms of each element must be the same on both the reactant and product side of the equation. Many redox reactions cannot easily be balanced just by counting atoms. Consider the following net ionic equation: Cu(s) + Ag+(aq) Cu2+(aq) + Ag(s) If you simply count atoms, the equation appears to be balanced - 1 copper atom or ion on each side of the equation, and one silver. But do you see what isn't balanced - the charges! If you total the electrical charge on the reactant side of the equation you find a total charge of +1, versus +2 on the product side. Charges represent gain or loss of electrons, and, like atoms, electrons are conserved during chemical reactions. There are two common techniques we can use to help us balance redox reactions - the oxidation number method and the half-reaction method. We'll look at the oxidation number method first. Balancing Equations using Oxidation Numbers You may have already guessed how we will balance equations using the oxidation number method. Let's create our summary table for the copper-silver reaction: Cu(s) + Ag+(aq) Cu2+(aq) + Ag(s)

element

initial ox no

final ox no

change in e-

Cu Ag

0 +1

+2 0

lost 2 gain 1

We can see that the number of electrons lost by copper does not equal the number gained by silver. We need to correct that, so we will multiply Ag by 2, giving us a total of two silvers. (We'll multiply copper by one - it won't change anything but will help keep us organized): initial ox no final ox no

element

change in e-

balance for electrons

Cu

+2

lost 2

Ag

+1

gain 1

We now are balanced for electrons - two electrons will transfer, from copper to silver. The highlighted values - our multipliers to balance electrons - will become our balancing coefficients in the equation. Our chart helps us to keep organized and see that we should put a "1" in front of copper and a "2" in front of silver. Our balanced equation: 1 Cu(s) + 2Ag+(aq) 1 Cu2+(aq) + 2Ag(s) It is not necessary to put the "1" in front of copper.

Let's work through several more examples. As we go we'll learn several tricks that we'll need to use. Balance the following reaction using the oxidation number method: MnO41- + Fe2+ + H1+ Mn2+ + Fe3+ + H2O The next step is to determine oxidation numbers. In the summary table below I will only include items whose oxidation numbers change. Since the number of electrons lost must equal the number of electrons gained, we will multiply by values that give us equal numbers of electrons: initial ox no final ox no

element

change in e-

balance for electrons

Mn Fe

+7 +2

+2 +3

5 1

1 5

= =

5 5

Balancing our equation for electrons we get: 1 MnO41- + 5 Fe2+ + H1+ 1 Mn2+ + 5 Fe3+ + H2O But wait - the equation is not balanced for hydrogen and oxygen atoms! After balancing for electrons, it is still necessary to balance for all other atoms in the equation. Using inspection 1we see that there are 4 oxygen on the reactant side of the equation ( 1 MnO4 ), but only 1 on the product side. Put a 4 in front of H2O to correct this: 1 MnO41- + 5 Fe2+ + H1+ 1 Mn2+ + 5 Fe3+ + 4 H2O We now have 8 hydrogen on the product side (4 H2O), so we will need 8 on the reactant side as well. This gives us our final balanced equation:

1 MnO41- + 5 Fe2+ + 8 H1+ 1 Mn2+ + 5 Fe3+ + 4 H2O

This example will show us another very important trick. Balance the following equation: NH3 + O2 NO2 + H2O Determine oxidation numbers and set up a summary table - but don't finish it just yet: initial ox no final ox no change in e-

element

balance for electrons

N O

-3 0

+4 -2

7 2

Before using a multiplier to get the electrons to match, notice the subscript with oxygen - O2. In our summary chart we base our oxidation number changes on a single atom, but our formula tells us that we must have at least two oxygen. You will save some time and frustration if we take this into account now. So in our summary table we will add some columns to change our minimum number of atoms and electrons involved. Then we complete the chart: initial ox no final No. change in ox no atoms eNo. ebalance for electrons

element

N O

-3 0

+4 -2

7 2

= 2 =

7 4

4 = 28 7 = 28

We now have our multipliers for the balanced equation "4" for nitrogen and "7" for oxygen but which oxygen??? The one on the reactant side or the two different compounds that contain oxygen on the product side??? Here's where our trick becomes more useful, but will require some trial and error. Since were were counting oxygen atoms in the O2 molecule on the reactant side of the equation, that's where we'll use the "7". (You could make the same argument about NO2 , but since nitrogen's oxidation number also changed we will use nitrogen's balancing coefficient there). 4 NH3 + 7 O2 4 NO2 + H2O The last step is to balance for hydrogen atoms (and finishing oxygen), which will mean placing a 6 in front of H2O:

4 NH3 + 7 O2 4 NO2 + 6 H2O

A fairly easy but long one. Use the trick given in the last example to help solve it. You may want to try it on your own before looking at the solution. Balance: K2Cr2O7 + NaI + H2SO4 Cr2(SO4)3 + I2 + H2O + Na2SO4 + K2SO4 Your first concern is to make sure you correctly determine all oxidation numbers. You can simply your work for those tricky polyatomic ions such as SO42- if you realize that the S in SO42- will always be the same as long as the SO42- remains intact. Since the only place you see sulfur in this reaction is inSO42-, sulfur's oxidation number is not going to change. Similarly, hydrogen and oxygen are always in compounds, so their oxidation numbers also won't change during the reaction. That narrows down the list of elements to check. initial ox no final ox no No. change in atoms e No. ebalance for electrons

element

Cr I

+6 +1

+3 0

3 1

Next, check for any subscripts associated with either of these two elements - we see that Cr always has a subscript of "2" (in both K2Cr2O7 and Cr2(SO4)3), and I has a subscript in I2. So we'll add that to our summary chart to get a total number of electrons transferred, and then balance. initial ox no final ox no No. change in atoms eNo. ebalance for electrons

element

Cr I

+6 +1

+3 0

3 1

2 = 2 =

6 2

1 = 6 3 = 6

Our table now tells us to use a balancing coefficient of "1" for Cr on both sides of the equation and "3" for iodine. Since we counted the atoms in I2 (and not HI), the "3" will go in front of I2: 1 K2Cr2O7 + NaI + H2SO4 1 Cr2(SO4)3 + 3 I2 + H2O + Na2SO4 + K2SO4 With these numbers in place, we now balance for atoms in the remainder of the equation to get our final answer: 1 K2Cr2O7 + 6 NaI + 7 H2SO4 1 Cr2(SO4)3 + 3 I2 + 7 H2O + 3 Na2SO4 + 1 K2SO4

One more tricky one. Balance Zn + HNO3 Zn(NO3)2 + NO2 + H2O Determine oxidation numbers and create your summary chart: initial ox no final ox no No. change in atoms eNo. ebalance for electrons

element

Zn N

0 +5

+2 +4

2 1

The main thing to notice is that N appears in two separate products - Zn(NO3)2 and NO2. Should we consider the subscript for nitrogen from Zn(NO3)2? In this case no, because this compound also contains Zn, the oxidized element. Also, the oxidation number for nitrogen does not change from HNO3to Zn(NO3)2 . initial ox no final ox no

element

change in e-

balance for electrons

Zn N

0 +5

+2 +4

2 1

1 2

= =

2 2

We now get our balancing coefficients from our summary table. A "1" will be placed in front of Zn, but which N should we use for the "2"? If you put it in front of both HNO3 and NO2 you'll find you cannot balance for nitrogen atoms. Since the oxidation number for nitrogen changed in becoming NO2, we will try it there first. Some trial-and-error may be required: 1 Zn + HNO3 1 Zn(NO3)2 + 2 NO2 + H2O With the 2 in place in front of NO2, we can now balance the rest of the equation for atoms. Doing so gives us the final answer: 1 Zn + 4 HNO3 1 Zn(NO3)2 + 2 NO2 + 2 H2O

Balancing by oxidation number can be easy or difficult, depending on the equation you are given to balance. If you sometimes struggle with the more difficult examples, don't worry you do get better with practice. Focus first on solving the simpler equations.

1. Balance the following redox reactions using the oxidation number method. a. SnCl2 + HgCl2 SnCl4 + HgCl

balance for electrons initial Sn Hg +2 +2 final +4 +1 change 2 1 Coefficient 1 2 = = Total e2 2

Place a 1 in front of compounds containing Sn, and a 2 in front of compounds with Hg: Answer: 1 SnCl2 + 2 HgCl2 1 SnCl4 + 2 HgCl Double check to make sure all other atoms in the equation are balanced.

b. HNO3 + H2S NO + S + H2O

balance for electrons initial N S +5 -2 final +2 0 change 3 2 Coefficient 2 3 = = Total e6 6

Place a 2 in front of compounds containing N, and a 3 in front of compounds with S. Then balance for hydrogen and oxygen. Answer: 2 HNO3 + 3 H2S 2 NO + 3 S + 4 H2O

c. NaClO + H2S NaCl + H2SO4

balance for electrons

initial Cl S +1 -2

final -1 +6

change 2 8

Coefficient 4 1 = =

Total e8 8

Answer: 4 NaClO + 1 H2S 4 NaCl + 1 H2SO4

d. CdS + I2 + HCl CdCl2 + HI + S Because one of the atoms undergoing oxidation or reduction has a subscript (I 2) we will account for the number of atoms of each element when preparing our summary chart:

balance for electrons no. atoms No. e2 2 (in I2) = 2 Total e= = 2 2

initial S I -2 0

final 0 -1

change 2 1

Coefficient 1 1

Place the balancing coefficients into the equation in front of the elements undergoing oxidation and reduction. For iodine, the 1 will go in front of the diatomic I 2 because these were the atoms being counted. 1 CdS + 1 I2 + HCl CdCl2 + HI + 1 S Then balance the rest of the equation. First balance for iodine atoms, then for Cd and H: Answer: 1 CdS + 1 I2 + 2 HCl 1 CdCl2 + 2 HI + 1 S

e. I2 + HNO3 HIO3 + NO2 + H2O Once again, because one of the atoms undergoing oxidation or reduction has a subscript (I2) we will account for the number of atoms of each element when preparing our summary chart:

balance for electrons no. atoms 2 (in I2) = No. e10 1 Total e= = 10 10

initial I N 0 +5

final +5 +4

change 5 1

Coefficient 1 10

The 1 for iodine is placed in front of the diatomic iodine; the 10 goes in front of both nitrogens. Then balance for iodine on both sides of the equation, then for all other atoms. Answer: 1 I2 + 10 HNO3 2 HIO3 + 10 NO2 + 4 H2O

f. MnO4- + H+ + Cl- Mn2+ + Cl2 + H2O

balance for electrons no. atoms No. e5 2 (Cl2) = 2 Total e= = 10 10

initial Mn Cl +7 -1

final +2 0

change 5 1

Coefficient 2 5

Because of the diatomic chlorine (Cl2) we multiply the change in oxidation number for chlorine by 2. We then determine what coefficients are needed to balance for electrons. The 5 for chlorine will be placed in front of the diatomic chlorine. Then balance both sides of the equation for chlorine, then for all other atoms. Answer: 2 MnO4- + 16 H+ + 10 Cl- 2 Mn2+ + 5 Cl2 + 8 H2O

2. Balance the following half-reactions for both atoms and electrons by adding the appropriate number of electrons to the correct side of the equation. Also identify each as either an oxidation or reduction.

a. b. c. d.

Pb2+ Pb Cl2 ClFe3+ Fe2+ N2O + H2O NO + H+

Pb2+ + 2e- Pb Cl2 + 2 e- 2 ClFe3+ + e- Fe2+

reduction reduction reduction

N2O + H2O 2NO + 2 H+ + 2e-

oxidation

3. Break each equation into two half-reactions. Identify each half-reaction as oxidation or reduction.

a.

Cu + 2 H+ Cu2+ + H2 Cu Cu2+ + 2 e2 H+ + 2 e- H2 oxidation reduction

b.

2 Al + 3 S Al2S3 2 Al 2Al3+ + 6 e3S + 6e- 3 S2oxidation reduction

4. Balance the following equations using the half-reaction method. a. Na + Br2 NaBr

Step 1 Write the two balanced half-reactions, removing any spectator ions: Na Na+ + eBr2 + 2 e 2 Br
-

Step 2 Balance for electrons 2

Step 3 Add the half-reactions, replacing any spectator ions that were removed and/or recombining compounds 2 Na 2 Na+ + 2eBr2 + 2 e- 2 Br-

add together:

2 Na + Br2 2 Na+ + 2 Br-

reform compound:

2 Na + Br2 2 NaBr

b. Zn + S ZnS

Step 1 Write the two balanced half-reactions, removing any spectator ions: Zn Zn2+ + 2 eS + 2 e- S2-

Step 2 Balance for electrons

Step 3 Add the half-reactions, replacing any spectator ions that were removed and/or recombining compounds Zn Zn2+ + 2 eS + 2 e- S2-

added together: reform compound:

Zn + S Zn2+ + S2Zn + S ZnS

c. Ag + Cr2O72- + H+ Ag+ + Cr3+ + H2O For each half-reaction, remember to balance for atoms first, then add electrons to balance for charge.

Step 1 Write the two balanced halfreactions, removing any spectator ions: Ag Ag+ + e-

Step 2

Step 3

Balance electrons

Add the half-reactions, replacing any spectator ions that were removed and/or recombining compounds

6 Ag 6 Ag+ + 6 eCr2O72- + 14 H+ + 6 e- 2 Cr3+ + 7 H2O

added together: 6Ag + Cr2O72- + 14 H+ 6Ag+ 2Cr3+ + 7H2O

1.5 Balancing Redox Equations using Half-reactions

Another way to balance redox reactions is by the half-reaction method. This technique involves breaking an equation into its two separate components - the oxidation reaction and the reduction reaction. Since neither oxidation nor reduction can actually occur without the other, we refer to the separate equations as half-reactions. The general technique involves the following: The overall equation is broken down into two half-reactions. If there are any spectator ions, they are removed from the equations. Each half-reaction is balanced separately - first for atoms and then for charge. Electrons are added to one side of the equation or the other in order to balance charge. For example, if the reactant side of the equation has a total charge of +3, the product side must also equal +3. Next the two equations are compared to make sure electrons lost equal electrons gained. One of the half reactions will be an oxidation reaction, the other will be a reduction reaction. Finally the two half-reactions are added together, and any spectator ions that were removed are placed back into the equation Mg(s) + Cl2 (g) MgCl2 (s)

Consider the following reaction:

In this reaction, Mg is oxidized and Cl is reduced. You may find it useful to use oxidation numbers to help you determine this. Mg changes from 0 to +2; Cl changes from 0 to -1. When we write the half-reactions,we break apart compounds that contain either of the key elements (elements undergoing oxidation or reduction). Oxidation numbers are written as if they were ion charges. Notice that the chlorine from MgCl2 is written as two separate ions, not combined as is Cl2. Balance the two reactions for atoms. Mg Mg+2 Cl2 2 Cl-

Next balance the equations for charge by adding electrons. Remember - one half-reaction will be an oxidation reaction (electrons on the product side) and the other will be reduction (electrons will be on the reactant side) Mg Mg+2 + 2 eoxidation Cl2 + 2 e- 2 Clreduction

In this example, balancing for charge results in both sides, of both equations, having net charges of 0. That won't always be the case. Be sure you see in this example how charges are balanced. We then compare the two equations for numbers of electrons. We see that both equations have 2 electrons so we do not need to make any adjustments for that. Finally, add the two equations together: Mg + Cl2 Mg+2 + 2 Cland reform any compounds broken apart in the earlier steps: Mg + Cl2 MgCl2 We see that the original equation was already balanced, not just for atoms but for electrons as well.

Next example:

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

Identify the elements undergoing oxidation (Cu) and reduction (Ag). The nitrate group (NO3) is a spectator ion which we will not include in our half-reactions. Cu Cu+2 + 2 eoxidation Ag+ + 1 e- Ag reduction

After balancing for atoms and for charge, we see that the two equations do not have the same number of electrons - there are 2 in the copper reaction but only one in the silver reaction. Multiply everything in the silver reaction by 2, then we will add the equations together: Step 1 Step 2 Step 3

Write the balanced half-reactions Cu Cu+2 + 2 eAg + 1 e- Ag-

Balance electrons

Add half-reactions Cu Cu+2 + 2 e-

2 Ag+ + 2e- 2 Ag

Add equations together Reform compound/return spectator ions

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

Here is a reaction occurring in an acid solution, which accounts for the presence of the H+ions. This example adds a little more complexity to our problem. MnO4- + Fe2+ + H+ Mn2+ + Fe3+ + H2O

In this example, spectator ions have already been removed. Even though hydrogen and oxygen do not undergo changes in oxidation number they are not spectators and we need to work with them in our half-reactions. We determine that Mn undergoes reduction (+7 to +2) while Fe undergoes oxidation (+2 to +3). The iron half-reaction is straight forward, but the manganese reaction is more complex - we must include hydrogen and oxygen in its half-reaction: Fe2+ Fe +3 + 1eoxidation MnO4- + 8 H+ + 5 e- Mn2+ + 4 H2O reduction

To balance the manganese half-reaction - first balance for Mn and O atoms. Next balance the H atoms, and finally add enough electrons to balance the charge on both sides of the equation. Be sure you see what has been done so you can do it on your own. Step 2

Step 1

Step 3

Write the balanced half-reactions Fe2+ Fe +3 + 1eMnO4- + 8H+ + 5e- Mn2+ + 4H2O 5

Add half-reactions 5Fe2+ 5Fe +3 + 5eMnO4- + 8 H+ + 5e- Mn2+ + 4 H2O

Add equations together

MnO4- + 5 Fe2+ + 8 H+ Mn2+ + 5 Fe3+ + 4H2O

Last example:

HNO3 + Cu + H NO2 + Cu

2+

+ H2O

1. Determine what is oxidized, what is reduced, and write the two balanced half-reactions (Step 1) 2. Balance for electrons lost = electrons gained (Step 2) 3. Add equations together Step 1 Step 2 Step 3

Write the balanced half-reactions Cu Cu+2 + 2eHNO3 + H+ + 1 e- NO2 + H2O 2

Add half-reactions Cu Cu+2 + 2e2HNO3 + 2H+ + 2e- 2NO2 + 2H2O

Add equations together

2HNO3 + Cu + 2H+ 2NO2 + Cu2+ + 2H2O

When balancing redox reactions, either the oxidation number method or the half-reaction method may be used. Often you'll find that one method works best for some equations, while the other method is more suited for other reactions. Or you may find one method just easier to use. The practice exercises and assignments tell you which method to use for a reaction, but as you get get more experience you'll be able to make your own decision as to which method to use. Writing half-reactions, however, is a skill you will need for our final topic in this course Electrochemistry - so be sure you can write balanced half-reactions.