Oxidation and Reduction

Oxidation and Reduction In the early days o f chemistry, a substance was said to be oxidized after it had reacted with oxygen. The reaction itself was called oxidation. A familiar example o f oxidation in this sense is the rusting o f iron. In this reaction, iron in the presence o f moisture reacts with oxygen from the air to produce ordinary rust, iron oxide. Another example o f oxidation is the burning o f fuels. When wood, natural gas, or coal burns, the oxygen in the air combines with the carbon and hydrogen in the fuel to produce water and the oxides o f carbon. Today, the term oxidation still is used in this sense, but it has a broader meaning, as well. Oxidation refers today to a category o f reactions with some characteristics similar to those o f the reactions o f oxygen just described. O rig in ally , reduction referred to a ch em ical reactio n in w h ich a compound lost oxygen: 2Fe20 3(5) + 3C (s) - 4Fe (/) + 3CO, (g) (Eq. 1)

In Equation 1, the iron (III) oxide is being reduced. This is because, during the reaction, oxygen is removed from the compound, leaving elemental iron. Today, the term reduction has been given a second, broader meaning. To describe reactions in which oxidation and reduction occur in the broader sense o f those terms, chemists use oxidation numbers. The next three sections explain their determination and use.

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118 Oxidation Numbers

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The oxid ation n u m b e r , or oxidation state, o f an atom is the

apparent charge assigned to an atom o f an element. The charge is called apparent because, while in some cases an oxidation number is the actual
charge on an ion, in other cases there is no evidence for the presence o f a true electric charge on an atom that has been assigned an oxidation number. Oxidation numbers, therefore, are merely a convenient device for analyzing types o f reactions discussed in this chapter.
The Rules fo r D etermining Oxidation Numbers 1. The oxidation num ber o f an atom in the uncom bined slate is zero. For example, the oxidation numbers o f the follow ing atom s are all 0 : An atom o f phosphorus in the P4 molecule. An atom o f chlorine in the C l2 molecule. An atom o f sodium. Na. when not part o f a compound. 2. The oxidation number o f a monatoinic ion is equal to the charge on the ion. ion: Mg2' in M gBr,; C l- ion in NH4C1; 0 : ~ ion in N a ,0 oxidation +2 -1 -2 n u m b er: 3. In most com pounds, the oxidation number o f hydrogen is +1. except in the case o f the hydride com pounds o f the metals from G roups 1 and 2. In hydrides, the oxidation number o f hydrogen i s - l . For example, compound: H2S 0 4 NH3 H ,0 NaH (sodium hydride) oxidation number o f hydrogen: +1 +1 +1 -1 4. In the vast majority o f compounds, the oxidation num ber o f oxygen is -2 . In peroxides the oxidation number o f oxygen is - 1 . In O F,, its oxidation number is +2. For example, compound: H 20 F e ,0 3 KClOj H20 2 O F, oxidation number o f oxygen: -2 -2 -2 -I +2 5. In binary com pounds o f nonmetals, the more electronegative element is assigned the negative oxidation number. For example, in PCI3, chlorine is more electronegative than phosphorus. Each chlorine atom partially gains one electron, giving each chlorine atom an oxidation number o f-1 and the phosphorus atom an oxidation number o f -3 . 6. The sum o f the oxidation numbers for all the atoms in a neutral molecule or formula is zero. The sum o f the oxidation numbers for nil atoms represented by a polvatoniic ion is equal to the charee on the ion. For example. 11,0: ' (2 x + 1) + (-2 ) = 0 oxidation number o f each o f 2 II atoms H C O j':( + ! ) + (+4) - (3 * - 2 ) = -1 oxidation number o f charge on ion each o f :3 oxygen atom

Figure 4.1 : How oxidation numbers should be determined.

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Oxidation numbers are assigned to atoms in chemical formulas. Rules have been developed for assigning oxidation numbers to atoms. These rules are given in Figure 4.1. Sample Problem 1 Using the rules for assigning oxidation numbers given in Figure 4.1, assign oxidation numbers to each element in the compound calcium chloride CaCl2. Solution Calcium fluoride is an ionic compound composed o f the calcium ion, Ca2\ and the chloride ion. C l'. The calcium ion is a monatomic ion with a charge o f 2+. Hence, by Rule 2, the oxidation number of the calcium atom in calcium chloride is +2. The chloride ion is a monatomic ion with a charge o f 1-. Hence by Rule 2, the oxidation number o f an atom o f chlorine in calcium chloride is - 1. An example o f oxidation-reduction. Oxidation is defined simply as a change in which the oxidation number o f an element increases. Such a change can take place only at the expense o f a decrease in the oxidation number o f some other element. The latter is termed reduction. For example, consider the following reaction 0 0+3-2 2 A1 + 3 S -> AI,S3 in which the oxidation number o f each element is written above the symbol. Aluminum and sulfur in the free state have, in accordance with our rules, an oxidation number of 0 ; whereas in the compound, aluminum sulfide, the oxidation number o f aluminum is +3 and that o f sulfur is -2 . In this reaction, aluminum gains in oxidation number from 0 to +3 and hence is oxidized; whereas sulfur loses in oxidation number from 0 to -2 and is reduced. Let us examine this reaction in another way. As it proceeds, each atom o f aluminium gives up 3 electrons and each atom o f sulfur takes up 2 electrons. In the reaction as a whole, 6 electrons given up by the 2 aluminum atoms are taken up by the 3 sulfur atoms. A transfer o f electrons has taken place, and the resultant compound A1,S3 is electrovalent; it is composed o f A P * and S ' ~ ions. In this particular case, Al gains in oxidation number or loses electrons;

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Inorganic Chemistry

likewise, sulfur loses in oxidation number or gains electrons. It is often convenient when dealing with electrovalent substances to discuss these changes in terms o f a gain or loss in electrons as well as in term s o f changes in oxidation number. To summarize: for reactions involving a transfer o f electrons,
Oxidation is gain in oxidation num ber or loss o f electrons Reduction is loss in oxidation num ber or gain o f electrons.

Oxidation and reduction are mutually dependent processes; if electrons are taken up by one substance, they must be given up by another. There can be no oxidation without reduction, nor reduction without oxidation. The union o f aluminum and sulfur may be written as taking place in two steps with e representing an electron: 2 AI -> 2 A I^ + + 6 e (oxidation) 6 e + 3 S - > 3 S (reduction) (1) (2)

By adding the two steps and cancelling the electrons, we obtain the net equation which was written above. O xidizing a n d r e d u c i n g ag e n ts. O xygen, sulfur, or other nonmetals, as they combine with metals, are recognized as oxidizing agents', therefore, the metals must be the reducing agents. In all oxidation-reduction chemical changes, the following relationship exists:
Oxidizing agent = electron receiver = loser in oxidation number Reducing agent = electron giver = gainer in oxidation number

The receiver-loser and giver-gainer relationship is somewhat confusing, but it is helpful to consider that a particle giving away negative charge must itself become more positive. If it receives a negative charge, it becomes less positive. In the combination 2 Fe + 3 Cl2 - 2 FeCl3 (2 Fei++, 6 Cl ) Cl2 is the oxidizing agent; each Cl receives 1 electron and loses 1 in oxidation number. Fe is the reducing agent: each Fe gives 3 electrons and gains 3 in oxidation number. In the replacement Zn + C u S 0 4 (solution) or Z n S 0 4 (solution) + Cu

Zn + Cu+^ + S 0 4~ -> Zn'~ + S 0 4~~ + Cu

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Cu " is the oxidizing agent: it receives 2 electrons and loses 2 in oxidation number. Zn is the reducing agent: it gives 2 electrons and gains 2 in oxidation number. Balancing oxidation-reduction equations. To balance these equations, we make use o f the rule that the total gain in oxidation

numbers must equal the total loss in oxidation numbers o f the elements.
Consider the reaction

+J -I

+ 1 -2
i

+2 -1

+ 1 -1

FeC lj + H,S -> FeC lj + HC1 + S

----------------

in which the oxidation number o f each element is placed above the symbol. Two o f the elements undergo a change in oxidation number; each iron atom loses 1 (from +3 to +2) and each sulfur atom gains 2 (from -2 to 0) in oxidation number. The loss o f 1 in oxidation number o f Fe is indicated by - I , and the gain o f 2 in oxidation number o f S is indicated by +2. To balance the gain and loss, 2 iron atoms will be required for each sulfur atom, and this will call for a ratio o f 2 FeCI3 to 1 H,S. This must be the ratio in which these two substances react: 2 FeClj + 1 H2S -> 2 FeCl2 + 2 HC1 + S Having obtained the ratio o f the oxidizing agent, FeCl3, to the reducing agent H2S, it is easy to complete the balancing o f the equation on the right side. In this equation, the change in oxidation number o f sulphur (2) is made the coefficient o f FeCl3, while the change in oxidation number o f iron ( 1) is the coefficient Of H,S. In general, we may employ the following steps in balancing oxidation-reduction equations: 1. Write the oxidation number o f each of the elements in each compound above the symbol of the element in the equation. 2. Determine which elements have changed in oxidation number and the amount o f change. Usually two elements only will have changed; one gains in oxidation number while the other loses.

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Inorganic Chemistry 3. Balance the gain and loss in oxidation numbers. This may be ac co m p lish e d a u to m a tic a lly by p la c in g th e n u m b er representing the change in the oxidizing agent in front o f the formula for the reducing agent, and vice versa. 4. Complete the balancing o f the two elements which have changed oxidation number on the right side o f the equation, keeping in mind that the ratio o f oxidizing agent to reducing agent as determined from the change in oxidation numbers must be maintained. Balance hydrogen and oxygen atoms after all other elements have been balanced. Let us illustrate the outlined steps by balancing an equation:
(1) 0 1 + 5 -2 + 1 + 5 -2 + 2 -2 + 1 -2

P + U N O , -> HPQj + NO + HjO

+5

+5

+2

(2)
(3)

P + H NO 3 - HPOj + NO + HjO

5
3 P + T H N 0 3 - HPOj
t

NO + 11 ,0

(4)

3 P + 5 MNOj

3 HPOj + 5 NO + H20

(balanced)

Oxidation-reduction equations are more difficult to balance by ordinary trial and error methods than those which involve no change in oxidation number. The change in oxidation number method for balancing oxidation-reduction equations, however, is rapid and accurate.
B A LA N C IN G
so lvent present.

E Q U A T IO N S

FOR

REDOX

R E A C T IO N S NO

In general when you are faced with balancing an equation for a nonaqueous redox reaction, you will be provided with form ulas for all reactants and products. The m ethod used, the oxidalion-number method is outlined below :
BALANCING REDOX EQUATIONS : OXIDATION-NUMBER METHOD

Step 1 Assign oxidation number to all atoms. Step 2 N otew hichatom sappeartoloseandw hichappeartogainelectrons, and determine how many electrons are lost and gained. Step 3 If there is more than one atom losing or gaining electrons in a formula unit, determine the total loss or gain o f electrons per formula unit.

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Step 4 Make the gain o f electrons by the oxidizing agent equal to the loss by the reducing agent by inserting the appropriate coefficient before the formula o f each on the left-hand side o f the equation. (See the following examples.) Step 5 Complete the balancing o f the equation by inspection. First balance atoms which have gained or lost electrons; second, atoms other than O or H; third, O atoms; and last, H atoms. Example 1 Problem : Balance the following equation MnO, + KCI06 + KOH -> K,M n04 + KCI + H20 Solution : Step 1: M n02 + K CIO- + K O H -> K,M n04 + K Cl + H, O
+ 4 -2 + 1 + 5 -2 + 1 -2 + 1 + 1 + 6 -2 + 1 1 + 1 2

Step 2: Manganese, Mn, changes oxidation number from +4 to +6 and so appears to lose two electrons. Cl changes from +5 to -1 and so a p p ^ r s to gain s,ix electrons. MnO, + KCIO, + KOH---- K2Mn02 + KCI + H2
+4 " +5 +6 -1

' Reduction: Each Cl atom :ains 6eEach KC103 formula unii gains 6eOxidation: Each Mn atom loses 2eEach MnO , formula unit loses 2e-

Step 3: As is shown above, since there is only one Mn atom in each MnO, formula unit, the electron loss per formula unit is two. Also, since there is but one Cl atom in each KCIO, formula unit, the electron gain per formula unit is six. Step 4: 3MnO, + K C I03 + KOH - K2M n 0 4 + KCI + H20 Just look at the left-hand side for now. By placing a 3 before M nO,, we are saying that if one M n02 form ula unit loses two electrons, then three will lose 3 * 2, or six, electrons. This will balance the electrons lost (six) against the electrons gained (six) by one KC103 form ula unit. Now that this 3 : 1 ratio (M nO ,/K C I3) has been established, it must not be changed. Step 5 : Add coefficient to the right-hand side to balance the Mn and Cl atoms, because they were involved in the electron transfer.

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Inorganic Chemistry 3 M n 0 2 + KCIOj + KOH -> 3K2M n 0 4 + KC1 + H20

Then, balance the K atoms (note : the coefficient before K C I03 must be changed) 3MnO, + KCIO, + 6KOH -> 3K2M n 0 4 + KC1 + 3H20 then, O atoms 3 M n 0 2 + KCIO3 + 6KOH -* 3K ,M n 0 4 + KC1 + 3H 20 and last, H atoms. But note that they are already balanced. Example 2 Problem: Balance the following equation H2C20 4 + K M n04 - C 0 2+ MnO + K20 + H20 S olution: Step 1 : H2C20 4 + K M n 0 4 -> C 0 2+ MnO + K ,0 + H ,0 +1 +3 - 2 Step 2 :
H 2C 20 4 +

+1 +7 - 2
C 02

+4 - 2 +2 - 2
+ M nO +

+1 - 2 +1 -2
K ,0 + H :0

K M n O , ->

-3
+3

*7
+7

O ----- C O ,
+4

H ,C ,0 4 + K M n04

MnO
+2

K ,0

HzO

Reduction: Each Mn jains 5e-

Oxidation: Hacli C' loses 1e-

S tep 3:
H ,C ,0 4 + K M n 0 4 -> CO, + -3 +7 +4 H2C 20 4 + K M n 0 4 ----- *
+3 -

M nO + K20 + H ,0 <-2 C 0 2 + MnO + K20 + /i i

+7+4+2

Each K M n 0 4 gains 5eSince there are two C atoms per formula unit, each H2C20 4 loses 2 X 1, or 26-

Step 4 : 5H,C2 0 4 + 2KM n04 -> C 02+ MnO + K ,0 + H, 0

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Oxidation and Reduction Step 5 : 5H,CjO< + 2K M nO, -* 10C02+ 2M nO + K,0 + 5H,0

125

BALANCING EQUATIONS FOR REDOX REACTIONS AQUEOUS

s o l u t io n s .

For reactions which occur in aqueous solution you may be given only a skeletal equation, one in which only the principal reactants and products are given. You must complete the equation, as well as balance it. There are two methods for doing this. These methods, the oxidation-number method and the half-reaction method, are different and should not be confused with each other. Each has its advantages and disadvantages.
B A L A N C IN G R ED O X E Q U A T IO N S (A Q U E O U S S O L U T IO N S ) :

OXIDATION-NUMBER METHOD Step 1 Assign oxidation numbers to all atoms. Step 2 Note which atoms appear to lose and which appear to gain electrons, and determine how many electrons are lost and gained. Step 3 If more than one atom in a formula unit loses or gains electrons, determine the total loss or gain per formula unit. Step 4 Make the gain o f electrons by the oxidizing agent equal to the loss by the reducing agent by inserting an appropriate coefficient before the formula o f each on the left-hand side o f the equation. (See the following examples.) Step 5 Balance the atoms which have gained or lost electrons by adding appropriate coefficients on the right. Step 6 Balance all other atoms except for O and H. Step 7 Balance the charge (the sum o f all the ionic charges) so
th a t it is th e sam e on both sid e s, by ad d in g e ith er H + o r

OH". (a) If the reaction takes place in acidic solution, add H+ ions to the side deficient in positive charges. (b) If the reaction takes place in basic solution, add O H ' ions to the side deficient in negative charges. Step 8 Balance O atoms by adding H ,0 to the appropriate side. Check to see that the H atoms are now balanced. (They will be, if you have made no mistakes.)

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Example 3 Problem : Complete and balance the following equation for a reaction which takes place in acidic solution : Cr20 72' + Fe2* - Cr34 + Fe3+ (acidic) Solution : Step 1: Cr20 72" + Fe2" -> Cr34 + Fe3+ +6 2 +2 +3 +3 Step 2 :
C r ,0 72+6

Fe2+ -------
+2

Cr3" +
+3

Fe3*
+3

ii

Oxidation: Loss o f i 5-pcrFe Reduction: Gain of 3e- per Cr

Step 3 :
Cr20 72+6

Fe2+
+2

----- *

Cr-3+ +
+3

Fe3*
+3

j\

Loss o f Ie per Fc^*

Total Gain of 2 X 3, or le per C r20 72'

Step 4: Step 5: Step 6 : Step 7:

C r,0 72" + 6 Fe2+ -> C r3 + + Fe3, Cr20 72' + 6Fe2+ ^ 2Cr34 + 6 Fe34 Done! Total charge on left = -2 + 6 (+2) = +10. Total charge on right = 2 (+3) + 6 (+3) = +24. Added positive charge needed on left = +14. 14H4 + C r,0 7 2 + 6Fe2" - 2Cr,+ + 6 Fe3

Step 8 :14 H + Cr20 72' + 6Fe2' - 2Crv + 6 Fe3* + 7H20 .

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Problem: Complete and balance the following equation for a reaction in basic solution : C r0 42 + Fe(OH), -> C r0 2 + Fe(OH)3 (basic) Solution: Cr042Step 1:
+6

Fe(OH)2

C r0 2+3 ii

+ F e(O H )3
+3

Oxidation: Loss ot le~ oerFe

Reduction Gain of 3e perCr

Step 4:
Step 5:

Gain of 3c pcrCr04- C r0 42" + 3Fe(OH)j - C r0 2~ + Fe(OH)3 C r0 42' + 3Fe(OH), C r 0 2" + 3Fe(OH)3

Step 6 : Done!

Step 7 : Total charge on left = - 2 + 3 (0) = -2 . Total charge on right = -1 + 3 (0) = - I . Added negative charge needed on right = - I. C r0 42" + 3Fe(OH), Step 8 : 2H20 + C r0 4- + 3Fe(OH), C r0 2 + Fe(OH)3+ OH C rO ,' + 3Fe(O H ),O H '

The second method for balancing redox equations for reactions which occur in aqueous solution is the half-reaction method, also known as the ion-electron method. Note that in it you do not assign any oxidation numbers.
BALANCING REDOX EQUATIONS (AQUEOUS S O L U T IO N S ):

11AI -F-ft KACTION METHOD Step I Separate the skeletal equation into two half-reactions, one an oxidation and the other a reduction. Step 2 Balance each half-reaction separately according to this sequence :

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a Balance all atoms other than H and O by inspection, b Balance O atoms by adding H20 to the appropriate side, c Balance the H atoms. The way this is done depends on whether the solution is acidic or basic. i In acidic solution, add the appropriate number o f H+ to the side deficient in H. n In basic solution, instead o f adding H4 ions, add one

H20 molecule to the side deficient in H plus one OH ion to the opposite side fo r each needed H atom. You
may wish to cancel out HzO molecules duplicated on each side at this point. d Balance the charge by adding electrons (e~) to the side deficient in negative charge. Step 3 Multiply each balanced half-reaction by an appropriate number in order to balance the electron loss against the electron gain Then add the two half-reactions. Step 4 Subtract out (cancel) anything which appears on both sides. (The electrons should all disappear in this step.) Exam ple 5 Problem : Using the half-reaction method complete and balance the following equation for a reaction occurring in acidic solution.
Cr20 72 ' + Fe2* -> Cr3* + Fe3* Solution : Step I : Cr20 72" -> Cr3* Step 2 : a Cr20 7 2- -> ICr3* b Cr2 0 72' -+ IC i3* + 7H2 0 c 14H* + Cr2 07 2" -> 2 0 * + 7H20 d be- + 14H' Cr20 7 2' -> ICt3* + 7H20
Step 3 :
6e-

(acidic) Fe2* -> Fe3 < (done!) (done!) (done!) Fe2*- Fe3* + e~ [Fe2* - Fe3* e ] x 6

I4H* + Cr20 , 2' - 2C r* + 7H20

be- I4H + Cr20 72 - -> 2Cr3* + 7H2 0

6 Fe2 + ^ 6 Fe3 * + 6e
be- I4H* + Cr2 0 , 2' + 6Fe2* -> 2Cru 6 Fe5* + 7H2 0 + be Step 4 : I4H* + Cr2 0 72 + 6Fe2< - 2Cr* 6 Fe3* + 7H,0

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129

Problem : Complete and balance the following equation for a reaction taking place in basic solution using the half-reaction method :
C r0 42' + Fe(O H)2 * C r0 2~+ Fe(O H )3 (basic)
S olution: Step I : C r 0 42 - > C r 0 2~ Step 2 : a (done)

Fe(OH), -> Fe(OH)j (done!) H20 + Fe(O H), -+ Fe(OH)3 OH + H20 + Fe(O H ), -> Fe(O H)3+ H .O O H ' + Fe(OH), -> Fe(OH)3 [ O i r + Fe(O H), -> Fe(OH)j + c) * 3

b C r 0 42" -> C r 0 2 + 2H :0
c 4 H 20 + C r 0 42 - C r 0 ,+ 2H 20 + 4 0 H 2 H ,0 + C r 0 42~ - C K V +40H ' Step 3 : 3 tf + 2H ;0 + C r 0 42~ C K V + 40H -

3<T + 2H,0 + Cr042 ' -> Cr02* + 401 r 30H" + 3Fe(0H), -* 3Fe(OH)3 + 3e '
3<T + 2H ,0 + 3 0 H + C r0 42' + 3Fe(0H), -* C K V + 3Fe(OH)3 + 4 0 H + 3e Step 4 : 2H20 + C r0 42' + 3Fe(0H ), - C K V + 3Fe(OH)3 + OH'.

At this point a comparison o f the oxidation-number and half reaction methods is in order. For nonsolution reactions the oxidationnumber is usually superior to the half-reaction method. Fro reactions in aqueous solution the half-reaction method is the slower o f the two, but for most people the surer. A major advantage o f the half reaction method is the lack o f necessity o f assigning oxidation numbers. Individual half-reactions are used in describing electrode reactions in electrochem ical cells. The biggest advantage o f the oxidation-number method is its potential speed! With practice you will find that you can do much o f it in your head. lon-electron m ethod o f balancing equations. This method is applicable-only to ionic reactions; however, since most reactions in solution are between ions, the method proves convenient and useful. The method takes into account only those ions in solution which actually enter into reaction; in other words, only the net reaction in

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Inorganic Chemistry

shown. Those ions which remain unaltered in the solution do not appear in'the equation. The oxidation-reduction equation is broken down into two partial equations or steps called half-reactions; one equation represents the oxidation step, the other the reduction step. The number o f electrons transferred in each step is indicated, and each equation is balanced both atomically .and electrically. The gain and loss o f electrons is then balanced by multiplying step by appropriate number. Example 1 : FeCl3 + SnCl2 -> FeCl2 + SnCl4 (not balanced) From an ionic standpoint, we should write down only the ions w hich enter into the chemical change namely Fe+++, which is reduced to Fe**, and Sn++, which is oxidized to Sn++'l"\ The two half reactions would be Sn++ - Sn++++ + 2 e (oxidation) Fe+++ + e -> Fe++ (reduction) Each step is now balanced electrically as well as atomically. Since 2 electrons appear in the first step, we may balance electrons by multiplying the second equation by 2 2 Fe+++ + 2 e -> 2Fe~ Now the two steps may be added (electrons are cancelled), and we obtain the net ionic reaction S n ^ - Sn+++++ 2e 2 Few + 2e -> 2 Fe++ S n ^ + 2 Fe+++ -> Sn++++ + 2 Fe+ + Note that the final step is also balanced electrically; the net charge on each side o f the equation is +8. Example 2 : Copper reacts with dilute nitric acid to form cupric ions, water, and nitric oxide. Applying the ion-electron method to this reaction, copper is oxidized from the free state to cupric ion : Cu -> Cu++ + 2 e (oxidation) (1) Meanwhile, nitric acid is reduced to NO and H ,0 , the latter two substances being un-ionized :

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Oxidation and Reduction H+ + NO," NO + H20

131

The latter equation is balanced atomically as follows : 4 H+ + N 0 3~ NO + 2 H20 This equation is now balanced atomically but not electrically, since the net charge on the left is +3, and the net charge on the right side is 0. The addition o f 3 e to the left side will balance the step electrically: 3 e + 4 H+ + N 0 3- -> NO + 2 H20 (2) To balance the gain and loss o f electrons, equation (1) may be multiplied by 3 and equation (2) by 2, then : 3Cu > 3 Cu++ + 6e 6e + &H* + 2 N Q 3~ - 2 NO + 4 H20 ___________ 3 Cu + 8 H* + 2 N 0 3- -* 3 C u++ + 2NO + 4 H20 Example 3 : It is further assumed in the ion-electron method that H+ ions and H20 molecules may be used to balance each half reaction atomically if the reaction is being carried out in acid solution, or OH~ ions and H20 molecules may be used if the reaction is in basic solution. To illustrate, permanganate ion will oxidize sulfide ion to free sulfur in acid solution S' " S+2e (1) and the permanganate ion is reduced to manganous ion M n 0 4~ -> Mn++ To balance the latter step atomically, we may add 8 hydrogen ions to the left side, in which case 4 molecules o f water will appear on the right side : 8 H+ + M n04- -> M n++ + 4 H ,0 5 electrons are then necessary on the left side to balance electrically: 5 e + 8 H* M n04 -> M nft + 4 H ,0 (2) Combining steps (1) and (2) and balancing gain and loss of electrons, 5 S " ' - 5 S + l Oe 10 e+ 16 H+ + 2 M n 0 4 > 2 MnT 4 + 8 H ,0 5 S + 16 H+ + 2 M n 0 4 5 S + 2 Mn+4 + 8 H20

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