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OXIDATION AND REDUCTION

A large num ber of reactions can be regarded as occuring by the tran sfer of electrons from one species to another. Electron gain is called reduction and electron loss is oxidation; the jo in t process is called a redox reaction. The species th a t supplies electrons is the reducing agent (or reductant) and species th a t removes electrons is the oxidizing agent (or oxidant). The transfer of electrons is often accompanied by the transfer of atom, and it is some times difficult to keep track of where electrons have come from and gone to. It is therefore safest and sim plest-to analyze redox reactions according to a set of formal rules expressed in term s of oxidation num bers and not to think in term s of actual electron transfers. Oxidation then corresponds to the increase in oxidation num ber of an elem ent and reduction corresponds to decrease in oxidation number. A redox reaction is a chemical reaction in which there are changes in oxidation num ber of a t least one of th e elem ents involved. USE OF R^DOX POTENTIAL DATA Redox potential can be used to great advantage in explaining oxidation-reduction reac tions in aqueous solution. The reduction potential is related to energy by the equation; AG = -raEF where AG is change in Gibbs free energy n is the valency of ion F, F araday constant E = S tandard electrode potential This is really an application of thermodynamics. Ultim ately w hether a reaction occurs or not depends on energy. If the free energy change AG is positive, the reaction will not proceed, and therefore, therm odynamics saves' us the trouble of trying the reaction. If the value of AG is negative, then the reaction is thermodynamically possible and reaction will necessarily occur. Thermodynamics does not give any information on the rate of reaction, which may be fast, slow or infinitely slow, nor does it indicate if another reaction is even more favourable. Let us consider the corrosion th a t may occur when a sheet of galvanized (iron which is coated with Zn to prevent rusting) iron is scratched. H alf reactions and the corresponding reduction potential are given below. Fe2+ + 2e~ ------> Fe Zn2+ + 2e* ------Zn
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E = -0 .4 4 volts E = - 0.76 volts

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When in contact w ith w ater, either metal might be oxidized and lose m etal ions, so we require the reverse reactions, and the potential for these are called oxidation potentials, and have the same m agnitude bu t the opposite sign to the reduction potentials Fe ------ > Fe2* + 2e E = +0.44 volts Z n ------ > Zn2* + 2eE = +0.76 volts Zn -> Zn2* produced the largest positive E, therefore the value of AG will be most negative. T hat is why it is energetically more favourable for the Zn to dissolve, and hence the Zn will corrode away in preference to the Fe. It is possible th a t w hen the galvanized steel is scratched, the air may oxidize some iron. The Fe2+ so produced is immediately reduced to iron by Zinc, and ru stin g does not occur. Zn + Fe2* ------Fe + Zn2+ Similar applications in w hilh one m etal is sacrified to protect another are the attaching of sacrificial blocks of magnesium to underground steel pipelines and the hulls of ships to prevent the rusting of iron. Therefore, the coating of Zn serves two purposes (i) It covers the iron and prevents the oxidation and (ii) it provides anodic protection. The values of reduction potential (Table 3.1) can be used to predict th e possibility of a reaction and w hat equilibrium constant will be ? For example oxidation of As (III) to As (V) by tri-iodide in H A s02. HAs02 + Ii + 2 H2O ------H3A s04 + 3 r + 2H+ By using the table 3.1 we can w rite down the half reaction for H 3A s0 4 + 2e" -+ Products and I3" + 2e" -> Products H 3A s0 4 + 2e" + 2H+ ------ > H A s0 2 + 21^0 E = + 0.56 volts ------ 31" E = + 0.54 volts I3" + 2e~ The reaction we are investigating requires the first half reaction in the reverse direc tion, added to the second half reaction. HAs0 2 + 2HaO ------ H 3A s0 4 + 2e" + 2H+ I 3 + 2e ------ 31" E0 = + 0.54 volts E0 = -0 .5 6 volts AG = - 2 x 0.54 x F AG = +0.04 F
Table 3.1 Som e standard reduction potentials in acid solu tion a t 25C (volts) Group I Li* + e -+ Li K* + e - K Rb* + e -> Rb Cs* + e -> Cs Na* + e -> Na E -3.05 -2.93 -2.93 -2.92 -2.71 Group V As + 3e -> AsH 3 Sb + 3e -> SbH3 H3P 0 2 + e -> P H3P 0 3 + 2e - H3P 0 2 H3P 0 4 + 2e - H 3P 0 3 | n 2 + 3e -> NH4* Group II ^ N 2 + 2 e -> | n 2H6* E -0.60 -0.51 -0.51 -0.50 -0.28 -0.27 -0.23 Group VIII I3" + 2 e - i r Br3" + 2e - 3Br~ 2IC12 + 2 e I2 Br2 + 2e -> 2Br" 2 IO3 + lOe I2 Cl2 + 2 e -+ 2C12HOI + 2e -> I 2 vE +0.54 +1.05 +1.06 +1.07 + 1.20 +1.36 +1.45

AG = 2 x 0.56 x F

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Ba2* + 2e -> Ba Sr2* + 2e -> Sr Ca2* + 2e Ca Mg2* + 2e - Mg Be2* + 2e -> Be Group III Al3* + 3e -+ A 1 Ga3* + 3e > Ga In3* + 3e -> In Tl* e -> T1 Tl3* + 2e -> Tl* Group IV Si0 2 + 4e - Si PbS04 + 2e -> Pb CO2 + 4e >C Ge02 + 4e -> Ge Sn2* + 2e -> Sn Pb2* + 2e -> Pb Si + 4e > SiH4 C + 4e > CH4 Sn4* + 2e -> Sn2* Pb0 2 + 2e -* PbS0 4

-2.90 -2.89 -2.87 -2.37 -1.85

P + 3e -> PH3
2 Sb20 3 + 3e > Sb

+0.06 +0.15 +0.25 +0.56 +0.69 +0.96 +1.00 +1.03 +1.28 +1.35

H5I0 6 + 2e -> I0 32HOCI + 2e -+ Cl2 F2 + 2e -+ 2F~ Transition Metals La3* + 3e -> La Sc3* + 3e - Sc Mn2* + 2e -* Mn Zn2* + 2e - Zn Cr3* + 3e - Cr Fe2* + 2e -+ Fe Cr3* + e - Cr2* Cd2* + 2e -> Cd Ni2* + 2e -> Ni Cu2* + e - Cu* Hg2Cl2 + 2e -+ 2Hg Cu2+ + 2e -> Cu [Fe(CN)6]3~ + e -* [FeCCNJg]4Cu* + e Cu Cu2* + e - CuCl Mn04 + e >Mn042 Fe3* + e -> Fe2* Hg22* + 2e -+ 2Hg 2Hg2* + 2e -> Hg22* Mn0 2 + 2e - Mn2*

+1.60 +1.63 +2.65

HAs02 + 3e -> As H3As04 + 2e - HAs02 HN3 + 8e -> 3NH4* N03- + 3e -> NO HN0 2 + e -+ NO ^ N 20 4 + 2e - NO - N 2H5* + 2e -> NH4* NH3OH + 2e -> NH4* Group VI Te + 2e -> H2Te Se + 2e - H2Se S4Oe2 + 2e >2S20 32~ S + 2e ) H2S HS04- + 2e - H2S0 3 H2S0 3 + 2e > ~ S20 32' H2S0 3 + 4e >S 4H2S0 3 + 6e > S40 62S20 62- + 2e > 2H2S0 4 0 2 + 2e H2Oz H2Se0 3 + 4e -> Se Se042" + 2e - H2SeOy t 0 2 + 2e > H20

-2.52 -2.08 -1.18 -0.76 -0.74 -0.44 -0.41 -0.40 -0.25 +0.15 +0.27 +0.35

- 1.66 -0.53 -0.34 -0.34 +1.25

- 0.86 -0.36 - 0.20 -0.15 -0.14 -0.13 +0.10 +0.13 +0.15 +1.69

-0.72 -0.40 +0.08 +0.14 +0.17 +0.40 +0.45 +0.51 +0.57 +0.68 +0.74 +1.15 +1.23 +1.77 +2.01 +2.07

+0.36 +0.50 +0.54 +0.56 +0.77 +0.79 +0.92 +1.23

4 6

H20 2 + 2e -> 2H20 SjOg2- + 2e -> 2SO<2' 0 3 + 2e -> 0 2

Cr20 1z~ + 3e -+ Cr3* +1.33 Mn04 + 5e -+ Mn2* Ni0 2 + 2e -* Ni2* Mn04 + 3e -+ Mn0 2 +1.54 +1.68 +1.70

The free energy change is found to be positive. It indicates th a t the reaction will not go spontaneously in forward directional energetically feasible th a t the reaction proceed in backward direction. However, the value of AG is very small therefore, it is unwise to draw very firm condusions AG is very small, a change in concentration or pH or a tem perature,
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could change the potentials and hence change AG sufficiently to make the reaction go in either direction. Volumetric methods are known where reducing arsenic acid with iodide ion in 5M acid, and for oxidizing arsenions acid by tri-iodide at pH 7. A number of other uses of Redox potential are known. For example, it is possible to explain which species will oxidize or reduce. What will be the products of reaction and which oxidation states are stable with respect to solvent and also with respect to disproportionation. It will be explained in the following paragraphs. REDOX STABILITY IN WATER An ion or molecule in solution can be destroyed by oxidation or by reduction caused by any of the other species present. Therefore, when assessing the stability of a species in solution, we m ust keep in mind all possible reactants, the solvent, other solute, solute itself and dissolved oxygen. In the following paragraphs we will concentrated on the types of reactions th a t result from the thermodynamic instability of a solute. We will also discuss on rates, but the trends they show are generally less systematic than those shown by stabilities. When a substance is added to water, it may be unstable for one of the following reasons (1) It may react with w ater to evolve H 2 (2) It may react with water to evolve 0 2 (3). It may undergo disproportionation (auto-oxidation-reduction) in which species of higher and lower oxidation states are produced. 1. A reducing agent th at can reduce water to H2 rapidily. The reaction of metal with water or aqueous acid is actually the oxidation of metal by w ater or hydrogen ions, because the overall reaction is one of the following processes. M(s) + HjO ---- Mna9) + i H 2 + OH-(a9) (g ) z These reactions are thermodynamically favourable when M is an s-block element except Be or a first d-series metal. 2Sc + 6 H \a q ) ---- 2Scz\a q ) + M(s) + H*(aqO ---- > M*(aq) +

When the standard potential for the reduction of a metal ion to the metal is negative, the metal should undergo oxidation in 1M acid with evolution of H2. Although the reactions of Mg and A1 with moist air are spontaneous, both metals can be used for years in the presence of water and oxygen. They survive because they are passivated or protected against reaction due to formation of oxide film. A similar passivation occurs with iron, copper and zinc. The process of anodizing a metal, in which the metal is made an anode (the site of oxidation) in an electrolyte cell, is one which partial oxidation produces a smooth hard passivating film on its surface. Anodizing is especially effective for the protection of aluminium. 2. The strongly positive potential in equation given below. 2H +(aq) + 2e" ------ E = - (0.059V) pH

shows th a t acidified water is a poor reducing agent except toward strong oxidizing
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agents. .For example Co3+(a<|) for which E(Co3+, C 0 2+) = 1.92 V. It is reduced by w ater w ith evolution of 0 2. 4Co3+ (aq) + 21^0 (/) ------ > 4Co2+(aq) + 0 2 + 4H* (aq ) E = 0.69 V

Ag2+ is another example which can oxidize w ater rapidly and evolve 0 2. 3. Disproportionation, a redox reaction in which the oxidation num ber of an element is sim ultaneously raised and lowered. In other words, tjie elem ent undergoing disproportionation serves as its own oxidizing and reducing agent. 2Cu+(aq) ------ > Cu2+(aq) + Cu (s) This reaction is the difference of the following two half-reactions: Cu+(aq) + e" ------- Cu (s) E = + 0.52 V

Cu2* (aq) + e" ------ * Cu+ (aq) E = + 0.16 V Disproportionation is spontaneous because E = (0.52 V) - (0.16 V) = + 0.36 V. THE DIAGRAMMATIC PRESENTATION OF POTENTIAL DATA There are several useful diagram m atic sum m aries of th e relative therm odynam ic stabilities of a series of species in which one elem ent exists w ith a series of different oxidation numbers. We will discuss some diagrams here. Latimer Diagrams In a Latim er diagram s for an elem ent the numerical value of the standard potential (in volts\ is w ritten over a horizontal line connecting species w ith the elem ent in different oxidation states. The most highly oxidized form of the elements is on the left, and in species to the right the elem ent is in successively lower oxidation states. ALatim er diagram summ arizes a great deal of information in a compact form and shows the relationship between the various species in a particularly clear and compact manner. The Latim er diagram for chlorine an acidic solution is CIO4 +7 It may w ritten as CIO4 + 2H+ + 2e" ------ CIO3 + H20 Similarly It may also be w ritten as 2HC10 + 2H+ + 2e~ ------ Cl2 + 2 1 ^ 0 E = 1.63 V As in this example, the conversion of a Latim er diagram to a half-reaction often in volves balancing elem ents by including the predom inant species present in acidic aqueous solution. Change in then balanced by the inclusion of the appropriate num ber of electrons (pH = 0).
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D ispropotionates
+136

ClOj

<U8 > HC10 2

*165 > HC10

----- 7775-------

^
-1

+3 do-

+1
C 10-

E = +1.20 V

HCIO *167 > Cl^

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In basic aqueous solution (pH = 14) the Latimer diagram for chlorine is
d o 0.37 > C104 0-30 y C 1 0 2 . . -0.68 y c ,0 _

J
+0.33 V

{ 2 |_________ + 0.89_________ |

__+0.42

The incom plete d ata also suggest th a t OC1" should be stable w ith regard to disproportionation, but this is not true. The species which disproportionate are ignored and a single potential calculated for the change C103~OC1" to replace the value + 0.30 't and +0.68 V. Similarly a single potential is calculated for OC1 Cl. CIO; When the complete diagram is examined, it is apparent th a t the potential around OC1" do not decrease from left to right, and hence OC1" is unstable with respect to disproportionation into C103" and Cl". CIO< > > OC1- Cl

Change from C103" OCl*"(2e" transfer) Change from OC1" Cl"(2z - e transfer)

2a + 2 b \ - ----Therefore Electropotential from C103"OCl can be calculated as

= 2 x 0 .3 0 + 2 x 0 .6 8 _ 4 1 x 0 .4 2 + 1x1.36
2

Similarly we can calculate E for OC1"Cl". In the same way potential round C103~ do not decrease from left to right.
p in - _ 0.37 . r > \r \-

.cio3 +0.49

ocr

Similarly C103 should disproportionate into C104" and OC1 and OC1" should dispropor tionate to give Cl" and more C103". It is observed th a t the value for the Cl^Cl couple is the same as in acidic solution because its half-reaction does not involve the transfer of proton. Under basic conditions, the predominant species present in solution are OH" and H 20 , so these species are used to balance the equations for the half-reactions. For example, the half-reaction for the C10"/C12 couple in basic solution is 2C10' (aq) + 211*0 (I) + 2e' ------ Cl2(*) + 40H" (aq) E = + 0.42 V It is convenient to set out electrode potentials diagrammatically when a number of different oxidation states are being considered; Fig. 3.1 given diagram for manganese. I ------------------------------------------II------------------------------------- 1
M nO;
+7
+056 > MnO*~^26 > M nQ,

-t0# - > Mn3+

*L51 > Mn2* +2

> M n

+6 1.51

+4 +3

Fig. 3.1 Latimer diagram for Manganese (acidic medium).

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Reduction potential are shown for the relevant half reactions in acid solution. For example Mn2+ + 4H20 MnO (aq) + 8 H+ (aq) + 5e ------ E = +1.51 V, AG = - 5 x 1.51 F This is equivalent to MnO; (aq) + 8 H*(a<7) + ^ which when simplified is MnO; (aq) + 3H+(aq) + | n - Mn2+(aq) + 41^0 (/) ------ M n^(a^) + 41^0 (I) + 5H* (aq)

+ 1.69 + 1.51V Only the middle line values are strictly necessary, the others can be calculated. For example consider the calculation of the M n047M n02 reduction potential. We have : 1. MnO4-(aq) + e~ -> M n O ^ o g ); E = +0.56 V, AG = -n E F = -0.56 F 2. M n O ^ (aq) + 4H* (aq) + 2e~-> MnO 2(s) + 2H20 (I) E = +2.26 V, AG = -n E F = -4.52F Adding (1) and (2) we obtain MnOa (s) + 2H20 (I) AG = -5 .0 8 F MnO' (aq) + 4H+(aq) + 3e~ ------ From this diagram it is possible to tell which states are: () Powerfully oxidizing agent (relative lower oxidation states); these have large posi tive E value e.g., Mn04". () powerfully reducing; these have large negative E value e.g., Mn2+ /Mn. (c) Thermodynamically unstable in regard to disproportionation, we have 1. MnOj" (aq) + 4H+(aq) + 2e ------> M n0 2 (s) + 21^0 (/) E = +2.26 V, AG = -4.52 F 2. MnC> 4 (aq) + e~ ------>MnO2- (aq)

E = +0.56 V, AG = -0.56 F Taking (1) and substracting (2) x 2 gives 3. MnOj" (aq) + 4H+(aq) ------>2Mn0 4 (aq) + M n0 2(s) + 21^0 (I)

AG = [-4.52 - (2 x -0.56)] F = -3.40 F, E = 1.70 V AG is found to be negative for the disproportionation reaction, so the reaction is expected to go in the direction written. This conclusion could be equally will be reached by considering simply the electrode potentials. Inspection shows th a t w hat has been does above is to multiply each electrode potential by two, then add them algebraically reactions. The free energy change is negative if the sum of the potential is positive. In brief, if the algebraic sum of the electrode potentials is positive the state is unstable w.r.t. disproportionation. Alternatively, one can look at this in the following way. Drawing out the relevent piece of
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the diagram and remembering an oxidation potential is ju st the negative of the reduction potential, we can write. MnQ; MnO2- +226 > MnOi
Oxidation 0.56 Reduction

If the sum of the reduction and oxidation potential is positive, then the standard free energy change for the disproportionation will have a negative value and spontaneous dispreportionation is possible. In this case we have 2.26 - 0.56 = +1.7 and disproportionation is possible. This maybe summarized as a simple rule. Disproportionation of an intermediate oxidation state is possible (thermodynamically) if the reduction potential of the couple link ing the intermediate to the lower oxidation state is greater (more positive, than linking the intermediate to higher oxidation state (here +2.26 > +0.56). Manganese redox reactions in alkaline solution. The diagram discuss as above refer to the reaction of manganese compounds at pH = 0. For alkaline solutions (pH 14) the reactions are different so the Latimer diagram Fig. 3.2 is also different. MnO;
*058 > MnO2' 060 > MnOj - -2 - >Mn(OH)3 - - 1 > Mn(OH)2

*1MV- > Mn

I ______________I I ______________ I +0.59 -0.0 5


Fig. 3.2 Latimer diagram for manganese (basic medium). Discussion of relative stabilities of oxidation states usually involves considerations of reduction potentials. However, many people find data easier to understand if presented in diagrammatic rather than tabular form. Diagrams Fig. 3.3 (Ebsworth) can be constructed to display information about different oxidation states. The conventions used are listed below. 1. Free energy is plotted in electron volts (ev) along the vertical axis. The free energy differences between oxidation states are readily calculated from reduction potential; the procedure is illustrated in the example in Fig. 3.2. Consider Mn2* + 2e~ ------ Mn,E = -1.18 V; ^ - = - n E e =2.36

The difference in free energy between the +2 and 0 states of manganese is given by AG0 = -n E 0F = -2 x (-1.18) x 96,484 J. The multiplication by 96484 is to convert electrovolts into SI units (Joules) so this is not done and instead of calculating AGg we calculate AGg /F = -n E G electron volts. On justification for this is th a t we are concerned only with the relative positions of oxidation states on the diagram, and these are unaltered by multiplying all ordinate positions by the same constant. To show th a t this is unimportant on this diagram the ordinate is also given in kilojoules. In our example, therefore, the diagram m ust convey the information that the free energy difference between Mn2*(aq) and Mn (1 mole) is = - nEe = - 2 x (-1.18) = +2.36 eV. F 2. The horizontal axis represents the oxidation state of the element, in this case Mn. To change from left to right is represented as a reduction to conform to previous conventions.
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3. The element in zero oxidation state is considered to be zero free energy. 4. Usually lines are drawn connecting adjacent oxidation states through these have ho more (or less) theoretical significance than those lines connecting nonadjacent states. 5. The lower on the diagram an oxidation state is, the more stable it is; for example Mn3+ is a stable oxidation state relative to M n04 etc., but not to Mn2+.

F ig. 3.3(a) Free energies of the oxidation states of manganese relative to the metal in aqueous

solution at pH 0.
Oxidation state

F ig. 3.3(b) Free energies of the oxidation states of manganese relative to the metal in aqueous

solution a t pH 14.

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1. The lowerin the diagram, the morestable the state is relative to thosestates above it.Thus change from Mn3* - Mn2* is favourable thermodynamically. Only adjacent states are linked by lines, this is significant only in th a t more lines would complicate the figure beyond comprehension. 2. A particular state may be represented by a point which is: () A minimum e.g., Mn2*. This is stable oxidation state relative to its neighbour ing states. ( ) A maximum-unstable relative to its two neighbouring states and will dispropor tionate unless kinetically controlled. (c) On a convex curve e.g., Mn3*. Such sta te s are relatively unstable to disproportionation. Mn3*(a<j)------ M n0 2(s) Mn3*(aqO------ Mn2*(a^) Hence by addition 2Mn3*(a<?)------> M n0 2(s) + Mn2*(a^); Aq 9 is negative; the reaction goes. (d ) On a concave curve; e.g., M n0 2 relative to M n042~ and Mn3*. This dispropor tion does not tend to occur since AGe is positive. (e) On a straight line; when the line connecting three points is a straight line then assuming thermodynamic control an equilibrium mixture containing about equal amounts of product and relevants will be obtained. Frost Diagram The frost diagram of an element M is a plot of nEQ for the couple M(ZVM(0) against its oxidation state Z Fig. 3.4. The qualitative feature of Frost diagrams to remember is that the steeper the line joining two points in a diagram, the higher the potential of the corre sponding couple. It follows th at we can make thermodynamic predictions about the reaction between any two couples by comparing the slopes of the corresponding lines. The oxidizing agent in the couple with the more positive slope (the more positive E) is liable to undergo reduction. The reducing of the couple with the less positive slope (less positive E) is liable to undergo oxidation. The utility of Frost diagrams is best appreciated by using them. For example, the steep slope connecting H N 0 3 to lower oxidation states in Fig. 3.4 shows that HN0 3 is a good oxidizing agent under standard conditions. By comparing the slope of the Cu2*/Cu couple in the upper left comer of Fig. 3.4 with nitrogen couples, we see th at HNO^ NO has a more positive slope than Cu2*/Cu; hence, H N 0 3 can oxidize Cu to Cu2*. This diagram indicates th at the slope remains steep all the way to N2, implying th at N 2 should be the product of excess Cu is present. However, we must not forget th a t there may be Kinetic limits to these thermodynamic predictions. In this case, N 2 is not formed rapidily, and NO is commonly the gas evolved when Cu is heated with dil. H N 03.
F AG

F
AGe

=+0.95 eV s -1 .5 eV

= - 0.55 eV.

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Oxidation number

Fig. 3.4 The Frost diagram for nitrogen; the steeper the slope of the line, the higher the standard
reduction potential for the couple. The solid line refers to standard conditions (pH = 0), the dotted line to pH = 1 4 . The insert on the upper left emphasizes the zero slope for the H+ /H2 couple.

An ion or molecule in a Frost diagram is unstable w ith respect to disproportionation if it lies above the line connecting two adjacent species. It is shown in Fig. 3.5, where it has been observed th a t the average free energy of two term inal species liis below th a t for a substance of interm ediate oxidation number, implying th a t the la tte r in unstable w ith re spect to disproportionation. A specific example is NH2OH Fig. 3.5 (a) which is unstable with respect to disproportionation into NH 3 and N2. However, it is one of the intrecaceis of nitrogen chem istry th a t show formation of N 2 often prevents its production, in practic, NH2OH is resistan t to disproportionation.

A substance th a t lies below the line connecting its neighbours in a Frost diagram is more stable th an they are because its average free energy is lower. Accordingly, the comproportionation reaction is thermodynamically favourable. The N in NH 4N 0 3, for in stance, has two ions with oxidation numbers -3 to +5. Since N 20 , in which the oxidation
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of N has th e interm ediate value +1, lies below th e line joining NH4+ to N 0 3", their comproportionation is possible. NHJ + N 0 3 ------> NO + 21^0 When the points for three substances tie approximately on a straig h t line, no one species will be exclusive product. The three reactions are examples of this behaviour. They are NO (g ) + N 0 2() + HaO (/) ----- > 2H N 0 2 (rapid)
3 HN 0 3 (a<7) ------> H N 0 3 (a^) + 2 N 0 (g ) + H^O (V) rapid

2 N 0 2(#) + HaO (/) ------ HN 0 3(o<7) + H N 0 2 (aq) all useful for synthesis of H N 03. Frost diagram give a quick impression of the chemical properties of an element. How ever, for numerical calculations, Latim er diagram are more convenient. POURBAIX DIAGRAMS This diagram Fig. 3.6 is used to explain the general relation between redox activity and Bronstad acidity. The regions in the diagram indicate the conditions of pH and potential under which each species is stable. (Fig. 3.6).

Fig. 3.6 A simplified Pourbaix diagram for some important naturally occurring compounds of iron. The broken vertical lines represent the normal pH, range in natural waters. We can describe how the diagrams are constructed by considering some of the reactions involved. The reduction half-reaction does not involved H+ ions, and so Fe 3+(aq) + e~ ------ Fe 2*(ag) E = +0.77V

Its potential is independent of pH, giving a horizontal line on the diagram. If the environm ent contains a couple with reduction potential above the line i.e., more positive more oxidizing potential, then Fe3+ will be more stable species. Hence, the horizontal line is a type of phase boundary th a t separates the regions where Fe3+ and Fe2+ are stable. We can consider another reaction 2Fe3+(a<?) + 31^0 (I) ------> Fe20 3(s) + 6 H+ (aq)

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This is not a redox reaction therefore, the regions of stability of Fe 3+(ag) and Fe 20 3(s) are independent of any redox couples that may also be present. However, it does not depend on pH, with the Fe3+(a^) ion stable at low pH and the Fe 20 3 stable a t high pH. Hence, the regions where each species is stable are separated by a vertical line at some pH th at depends on the strength of Fe 20 3 as a base. A third reaction we can also consider is Fe*03(s) + 6 H+ (aq) + 2e~ ------> 2Fe2+(a?) + 3 ^ 0 (/) This reaction depends on the pH, as shown simply by writing the N em st equation for the potential E = E E - 0.059Vlog [Fe2+] - 0.177 V x pH This shows that the potential falls linearly as the pH increases Fig. 3.6. The region of potential and pH that lie above this line corresponds to conditions in which the oxidized species (Fe20 3) is stable: those below if correspond to conditions in which the reduced species (Fe2+) is stable. It is observed th a t a stronger oxidizing agent is required to oxidize and precipitate Fe2+ (aq) in acidic media than in basic media. The vertical line at pH = 9 divides the regions at which either the reactants or the products are stable in the reaction Fe2*(aq) + H20 (I) ------> 2FeO (s) + H20 (I) This is not a redox reaction, and the vertical line shows th at FeO (s) is favoured when the pH exceeds 9. Another line separates the regions in which FeO and Fe 20 3 are stable. F e ^ 3(s) + 2H+(aq) + 2e" ------ 2FeO (s) + R^O (I) The potential of this reduction depends on the pH, but when we write the Nemst equation. - 1 2F [H*]2 = Ee - 0.136 V It has been observed th at it has a less steep slope than for the Fe2O^Fe2* couple (small number of H* are involved). Two sloping line drawn on diagram acts as boundaries for the stability field of water. Any couples present with potential more positive than the upper line will oxidize water to 0 2 and any with potential more negative than lower line will reduce it to H2. POURBAIX DIAGRAM FOR MANGANESE Fig. 3.7, shows the potential of some manganese couples as a function of pH. The activity of all solution species containing manganese, and involved in the couples whose potentials are plotted. Fig. 3.7 represent the almost same data except th at only the solid lines are shown for Mn couples and several vertical lines have been added to represent acid base equilibria not involving electron transfer. In addition, the potentials for H 20/H 2 and 0 ^ 2^ at * atm pressure are shown by dotted lines; outside this area, oxidizing agents produce 0 2 and
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H+ J,6

E = E

OXIDATION AND REDUCTION

141

reducing agents produce H2, allowing for overvoltage. This type of figure is known as Pourbaix diagram or potential-pH diagram. The oxidation state always increases with in creasing E on crossing a boundary. For solution species, the boundaries are concentrationdependent in accordance with the N em st equation. Lowering the concentration of solution species has the effect of increasing predominance area of the solution species at the expense of solid species.

pH

Fig. 3.7 A section of the Pourbaix diagram for manganese. The broken vertical lines represent

the normal pH range in natural waters.

Mn 1 1 is stable over an extremely wide range of E values. On increasing the pH of a deacrated lm solution of Mn1 1 ion, white Mn(OH)2 begins to precipitate a t pH = 8 . If air is allowed to contact the solution, the E gradient varies from about 600 mV a t the air interface to about O at the solution precipitate interface and in several hours the precipitate develops th at are cream coloured on the bottom, through reddish brown, dark brown, or black where the surface is in contact with the solution. After standing several days, only the black M n0 2 will be present. The raddish-brown Mn30 4 a mixed valence oxide containing both Mn2+ and Mn3+ ions may be made directly by roasting any oxide of manganese in air at 1000C. On addition of I 2 crystals to an Mn1 1 solution is buffered a t an E around 600 mV, very slowly adding base precipitate Mn(OH)3. Its changes to brown colour hydrated Mn20 3 in the absence of air. The Mn2+ /Mn3+ couple may be added to the Pourbaix diagram to give a horizontal line at 1.51 V. In the usual pH range of 0-14, and with concentration of solution species set at one, the Mn 27Mn3+ couple has a higher potential than the Mn27M n0 2 couple thus Mn3+ is not stable under the condition depicted in Fig. 14 and gets disproportionates. If the acidity increases the Mn2+ /Mn3+ the eventually falls below the Mn2+ /M n0 2 line and the Mn3+ species exist. Mn1 does not appear in the diagram and the Mn+I/Mn couple m ust have a potential less than th at of Mn/Mn2+, but if free manganese solution concentration are low enough, the Mn*1 species has domain between Mn and Mn2+. This happened with Cyano complexes, and reduction of Mn2+ in the presence of cyanide gives Mn+1 complex. Mn(OH )2 get oxidized to M n0 2 in the presence of air. M n0 2 can coexist with M n04" except in very basic solution. Because the coexistance boundary lies above H 20 /0 2 boundary over the entire pH range of coexistance, M n04_ can be produced by air oxidation of M n0 2 however it can be produced indirect an oxidation route. At high pH, M n0 2 coexistance with M n042" acidifying M n O ^ results in disproportionation to M n0 2 and M n04. M n04" ion is strong oxidizing agent that is thermodynamically unstable in water at all pH values.
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Extraction of Elements The m ust abundant elements in the earth s crust are given in Table 3.2. Metal source may be classified broadly into five m ain types. 1. Type 1 metals: Electropositive and exist as chlorides carbonates, sulphate. 2. Electropositive alkaline earth metals. 3. Main source of these m etals are oxides and mixed oxides. 4. These are found as sulphide and less frequently as oxides. 5. These are unreactive m etals occur in free state. Some elements are vary abundant but most of the elem ents are very scare. The type of process used commercially for any particular elem ent depends on a num ber of factors such as () Is the elem ents is so unreactive th a t exist in native state ? ( ) Are any compounds of the elem ent unstable to h ea t ? (c) Does the elem ent exist as an ionic compound, and is th e elem ent stable in water? If both are true, is there a cheap element above it in electrochemical series which can be sacrificed to displace it from solution ? (d) Does the elem ent occur as sulphide ores which can be roasted or oxide ores which can be reduced. Using carbon is the cheapest w hilst the use of Mg, A1 and N a as reducing agents is more expensive. (e) If all other method faults, electrolysis usually works for ionic m aterials, but is expensive. If the elem ent is stable in w ater, electrolysing aqueous solutions is cheaper than using fused melts. Summary for the extraction of m etals is given in Fig. 3.8. Different m ethods are used for separating and extracting elem ents may be divided into five classes-separation of 1. Elem ents exist in native form. 2. Therm al decomposition method. 3. Displacement of one elem ent by another 4. Chemical reduction 5. Chemical oxidation. Separation of Elements In Native Form The elements which one unreactive are found in native form. For example gold and platinum m etals exist in significant am ounts as native elements. 1. Gold has a density of 19.3 g cm-3, which is very much higher th an th a t of rocks or slit it is mixed with. Gold can be separated by am algating with mercury. 2. Platinum m etals are found in native form. Platinum m etals are Ru, Rh, Pd, Os, Ir, Pt. 3. Liquid droplets of Hg and some non m etals such as C and S are also found as native elements. The atm osphere is made up about 78% nitrogen and 22% oxygen.
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T a b le 3.2 A b u n d a n c e o f th e e le m e n ts in th e e a r th c r u s t

Nam e 1. Oxygen 2 . Silicon 3. A luminium Iron Calcium 6 . M agnesium 7. Sodium 8 . Potassium 9.


10 .

Sym bol O Si A1 Fe Ca Mg Na K Ti H P Mn F Ba Sr S C Zr V Cl Cr Ni Rb Zn Cu Ce Nd La Y Co Sc Nb N Ga Li Pb Pr B

Abundance* 455000 272000 83000 62000 46600 27640 22700 18400


6 320

40. 41. 42. 43. 44. 45. 46. 47. 48. 49. 50. 51. 52. 53. 54. 55. 56. 56. 56. 59. 60. 61. 62. 63. 64. 65.
66.

Name Sam arium Gadolinium Dysprosium Erbium Y tterbium H afnium C aesium Bromine U ranium Tin Europium Beryllium Arsenic T antalum Germ anium Holmium Molybdenum Tungsten Terbium L utetium T hallium Thulium Iodine Indium Antimony Cadm ium Silver Mercury Selenium Palladium P latinum B ism uth Osmium Gold Iridium Tellurium Rhenium Ruthenium

Sym bol Sm Gd Dy Er Yb Hf Cs Br U Sn Eu Be As Ta Ge Ho Mo W Tb Lu Tl Tm I In Sb Cd Ag Hg Se Pd Pt Bi Os Au Ir Te Re Ru Rh

Abundance 7.0
6.1

4. 5.

4.5 3.5 3.1


2.8 2.6

2.5 2.3
2.1

T itanium

Hydrogen Phosphorus 11 . 12 . Manganese 13. 14. 15. 16. 17. 18. 19. Fluorine Barium S trontium Sulphur Carbon Zirconium V anadium

1 520
1 120 1 060

2 .1
2.0 1.8

544 390 384 340 180 162 136 126


122

1.7 1.5 1.3


1.2 1.2 1.2 0.8

20 . Chlorine 21 . Chromium 22 . Nickel

23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 33. 35. 36. 37.

Rubidium Zinc Copper Cerium Neodymium L anthanum Y ttrium Cobalt Scandium Niobium Nitrogen G allium L ithium Lead Praseodymium

99 78 76
68 66

0.7 0.5 0.46 0.24


0.20

0.16 0.08 0.08 0.05 0.015


0.01

40 35 31 29 25
20

67. 68. 69. 70. 71. 72. 73. 74 75 76 77

0.008 0.005 0.004


0.001 0.001

19 19 18 13 9.1 9.0

0.0007
0.0001 0.0001

38. Boron 78 Rhodium Th 8.1 39. Thorium U nits are ppm of th e e a rth s crust, which is the sam e as g/tonne.

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The Principal Sources of Metals Metal sources may be classified broadly into five m ain types as shown in the shortened version of the Periodic Table shown in Table 12A.
T a b le 3.3 C la s s ific a tio n o f m e ta l s o u r c e s in to fiv e m a in ty p e s

Li Na K Rb Cs Ft
1

B Mg A1 Ca Sc Sr Y Ba La Ra Ac
2

Be

L
Si Ti Zr Hf Th V Nb Ta Pa 3 Cr Mo W U Mn Tc Re Fe Ru
08

Co Rh Ir

Ni Pd Pt

Cu

V Au

Zn Ga Ge As Cd In Sn Sb Hg Tl Pb Bi 4

Se Te Po

Boron, silicon, arsenic, tellurium and polonium are generally considered to be nonmetallic. Type 1 metals These are very electropositive m etals found as soluble salts, e.g., chlorides, carbonates, sulphates, etc., in the S tassfurt deposits in N orth Germany, and as constituents of aluminosilicate rocks. The m etals are extracted by electrolytic techniques. Type 2 metals These are the electropositive alkaline-earth metals, found principally as insoluble car bonates and sulphates (magnesium sulphate is soluble). They are extracted by electrolysis.
T a b le 4.4 E x tr a c tio n o f m e ta ls

Electrode Process Li, Li

Standard Electrode Main Occurrence Potential V -3.04

Main Method of Extraction

Equation for Extraction


4.

K, K*

-2.92

Ba, Ba2* Sr, Sr2*

-2.90 -2.89

Spodumene LiAl(Si03)2 Electrolysis of fused LiCl with KC1 added Camallite Reduction of fused KC1 with KCl.MgCl2.6H20 Na vapour Electrolysis of Witherite BaC03 Barytes BaS04 fused BaCl2 Strontianite SrC03 Electrolysis of Celestine SrS0 4 fused SrCl2 Limestone CaC03 Gypsum CaS04 Rock salt NaCl Chile saltpetre NaN0 3 Electrolysis of fused CaCl2 and CaF2 Electrolysis of fused NaCl with CaCl2 added

Ca, Ca2* Na, Na*

-2.87 -2.71

Most invol ve electrolytic reduction: Mn* + ne~ -> M

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Mg, Mg2*

-2.37

C am allite KC1, MgCl2. Electrolysis of 6H20 Magnesite MgC0 3 fused MgCl2 with KC1 added Beryl 3Be0.Al 20 3. 6S i0 2 Bauxite A120 3.2H20 Silicate rocks Pyrolusite M n0 2 H ausm annite Mn 30 4 Ilm enite T i0 2.F e0 Rutile T i0 2 Zinc blende ZnS C alam ine ZnC 0 3 Chromite F e0.C r 20 3 M agnetite Fe 30 4 H aem atite Fe 20 3 S m altite CoAs2 M illerite NiS C assiterite S n 0 2 G alena PbS Bism uth glance Bi2S3 B ism uthite Bi20 3 Electrolysis of fused BeF 2 w ith N aF added Electrolysis of A120 3 in molten N a 3AlF 6

Be, Be2*

-1.7 0

AI, Al3*

- 1.66

Mn, M n2* -1.1 8 Ti, Ti4* Zn, Zn2* -0.95 -0.7 6

< Reduction of oxide 3Mn30 4 + 8A1 > 9Mn + 4A120 3 with Al or C

Reduction of TiCl4 TiCl4 + 2Mg - Ti + 2MgCl2 w ith Mg or N a Reduction of ZnO w ith C or electro lysis of Z nS0 4 Reduction of Cr 20 3 with Al Reduction of oxides w ith CO Reduction of C 0 30 4 with Al Reduction of NiO w ith CO Reduction of S n 0 2 with C Reduction of PbO w ith C Reduction of Bi20 3 w ith C ZnO + C > Zn + CO

Cr, Cr3* Fe, Fe2*

-0.74 -0.44

Cr 20 3 + 2A1 -+ 2Cr + A120 3 Fe 20 3 + 3CO * 2Fe + 3 C 0 2 3C0 30 4 + 8A1 -+ 9Co + 4A120 3 NiO + 5CO -+ Ni(CO)4 + C 0 2 Ni(CO )4 -> Ni + 4CO S n 0 2 + 2C -> Sn + 2CO PbO + C -> Pb + CO Bi20 3 + 3C > 2Bi + 3CO 2Cu20 + Cu2S - 6 Cu + S 0 2 Ag2S + 4NaCN > 2NaAg(CN )2 + Na2S 2NaAg(CN )2 + Zn -> 2Ag + N a 2Zn(CN )4

CO, CO2* -0.28 Ni, Ni2* Sn, Sn2* Pb, Pb2* Bi, Bi3* Cu, Cu2* Ag, Ag* -0.25 -0.14 -0.13 +0.32 +0.34 +0.80

Copper pyrites CuFeS 2 P artial oxidation C uprite Cu20 of sulphide ore A rgentite Ag2S Occurs as metal Special methods involving use of sodium cyanide

Hg, Hg2* Pt, P t2*

+0.85 + 1.20

C innabar HgS Occurs as metal Sperrylite PtAs2 Occurs as metal

Direct reduction of HgS + 0 2 -> Hg + S 0 2 HgS by h ea t alone Therm al decom position of (N H ^PtC le Special methods involving use of sodium cyanide (NH 4)2PtCl 6 -+ P t + 2NH 4C1 + 2C12 Sim ilar to th a t for silver 2NaAu(CN )2 + Zn -* 2Au + N a 2 Zn(Cn )4
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Au, Au3*

+1.50

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CHEMISTRY

2. THERMAL DECOMPOSITION METHOD A number of compounds decomposes into elements for examples 1. The hydrides of As and Sb are decomposed to give a silvery metal. ) 2. Sodium azide NaN 3 to give decomposes to give Na, and pure nitrogen on gentle heating. 2NaN 3 ------> 2Na + 3N 2 3. Ni is obtained by heating Ni(CO)4. Monds process is used for purifying nichel. Ni + 4CO 50-0 > Ni(CO)4 Ni + 4CO 4. Van Arkel method is used for the separation of Zr, Ti or B. The O iodides of these metals are least stable. These are decomposed by passing a gas over an electrically heated filament of tungston or tantalum. Til4 - -5e?t_>T i+ 2 I 2 Zrl4 ------>Zr + 2I2 5. The oxides of some metals are also thermally unstable. For example oxides of Hg or Ag decompose on heating. 2HgO ------ 2Hg + 0 2 Ag2C 0 3 ------> Ag20 + C0 2

-"H U Ag + Io 2
6 . Oxygen may be obtained by heating H20 2, KC103 or Ag20.

H20 2 ------> 21^0 + 0 2 2KC103 ------>2KC1 + 3 02 2Ag20 ------>2Ag + 0 2 3. DISPLACEMENT OF ONE ELEMENT BY ANOTHER In principle any element may be displaced from the solution by another element which is higher in the electrochemical series. This method can not be used for those elements which reacts with water. The few elements separated by this methods are given below. 1. Cu2+ ions are displaced as Cu metal by the scrap of iron which changes to Fe2+ because iron is above copper in the spectrochemical series. Cu2+ + Fe ------ >Cu + Fe2+ Similarly Cd can be obtained by using Zn. Zn + Cd2+ ------> Cd + Zn2+ and bromine by using chlorine Cl2 + Br~ ------ 2C1" + Br2

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4. EXTRACTION OF ELEMENTS BY CHEMICAL REDUCTION METHODS A variety of reducing agents are employed e.g., carbon, carbon monoxide and reactive metals such is Na, A1 and Mg. One to low cost and availability of coke, carbon is mainly used for reduction. The disadvantages are th a t of high tem perature is needed. Reduction by carbon
b last

mace "> Fe20 3 + C ---fu~ + ^ 2273k' '* ZnO + C

+ + (Pidgeon Process)

ji.- Zn + CO

PbO + C ------> Pb + CO Reduction by other metals. As already mentioned when C is used as a reducing agent, a high tem perature is required. If the tem perature required of C to reduce an oxide is two high for economic or practical purposes highly electropositive m etal such as A1 or Mg may be used for reduction purpose. A large am ount of energy (i.e., 1675 k J mol"1) is liberated when A120 3 is formed. It is known therm ite process. B20 3 + 2A1 ------- 2B + A120 3 Cr20 3 + 2A1 ------- 2Cr + A^Og 3Mn30 4 + 8A1 ------- 9Mn + 4A120 3 Similarly Mg may also be used to reduce oxides. If oxide is two stable to reduce then, electropositive m etals are used to reduce halides. 2MgCL2 + Ti TiCl4 + 2Mg ------- TiCl4 + 4N a ------- 4NaCl + Ti (a) Self Reduction Pbs, CuS and Sb2S3 ores first roasted in air. They get converted into oxides and then further roasted in the absence of air, causing self reduction. CuS roastair > CuO CuO + CuS (b) Reduction with H2 This method is not used widely. It is because at elevated tem perature some metals react with H2 to form hydrides and a risk of explosion. Some examples are given below where H2 is used as reducing agent. NH4 Mo0 4 + 2H2 ------ Mo + 4H20 + NH3 NH4 W 04 + 2H2 ------ W + 41^0 + Co3 0 4 + 41^ ------ 3Co + 41^0
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in th e absence of a ir

-K roag ------ > Cu + S 0 2 6

NH3

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CHEMISTRY

Therefore, only those m etals m etal oxide line above the hydrogen will be reduced. The main problem arises by the reduction of hydrogen is th a t the hydrogen reacts metal to produce hydrides. ELEMENT EXTRACTED BY OXIDATION The halogens are the most im portant elements extracted by oxidation. The standard reaction Gibbs energy for the oxidation of Cl" ions in w ater is strongly positive, which suggests th a t 2C1-(aq) + 2 ^ 0 (/) ------> 20H -(aq) + f y ig ) + Cl2(^) AG = +422 j J mol"1 electrolysis is required. The minimum potential difference th a t can achieve the oxidation of Cl is about 2.2 V. It may appear th a t there is a problem w ith competing reaction.
2 H2O (/) ------> 2 H2 (g) + 0 2(g) AG = + 414 k J mol-1 which can be driven forward by a potential difference of only 1.7V. However, the rate of oxidation of w ater is very slow at potential a t which it first becomes favourable thermody namically. The slowness is expressed by saying th at the reduction requires a high overpotential.

The only im portant m etals obtained by oxidation are ones th a t occur native. Gold is an example, because it is difficult to separate the granules of m etal in low grade ores by simple panning. The dissolution of gold depends on oxidation, which is favored by complexation with CNT ion to form [Au(CN)]~. This complex then reduced to m etal by reaction with Zinc. 2 [Au(CN)2]~ (aq) + Zn (s) ------ 2Au (s) + [Zn(CN)4f " (aq) SOLVED QUESTIONS Q. 1. Is Mn2* is stable in aqueous solution ? A ns. Referring to the em f diagram, we are obtain a sum for half-reaction as follows. Mn2* + 2e~ ------ Mn 2Mn2* ------> Mn3* + e ' Ee = -1.18 V E= -1.51 V

3Mn2* ------ Mn + 2Mn3* E 0 = -2 .6 9 V Because Ee is negative, the reaction does not occur and Mn2* will not disproportionate. Q. 2. Calculate Ee for M n3* + 3e~ -> Mn from diagram. A ns. Reaction Ee AG = -nFg Mn2+ + 2e~ ------ Mn Mn3 + e~ ------> Mn2+ 1.18 -2 x F x ( 1.18) 1-51 2 x F x (+1.51) ng (volts equation) 2.36 +1.51 -0.85

Mn3 + 3 e~ ------ > Mn 0-85 f From a q 9 we have g = -(0.85)/3/ = -0.28V. A ns. For the reaction

Q. 3. Will permagnate ion oxidize H20 to evolve 0 2 in acidic solution ?

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2MnO; + H20 ------ 2M n0j- + | o 2 + 2H* we have E = +0.564 - 1.229 = -0.665 V Hence the reaction does not occur, however, the reaction. 2MnO; + 2H *------> 2 Mn 02 + | o 2 + H20 This value 0.47 is barely in excess of the expected over voltage needed for 0 2 evolution and we find th a t 0 2 evolution in acidic perm agnate solution takes place very slowly.
Q. 4. Is the permagnate M n 0 4~ which is used in redox titration o f iron ? Which o f the following Fe (Fe3*IF<?*, 0.77 V), C f (Cl2 tCJr, 1.36 V) and Ce3* (Ce<*/Ce3\ 1.76 V) can permagnate oxidize in acidic solution ? A n s. The standard potential of M n04" to Mn2+ in acidic solution is +1.51 V. It indicates th a t K M n0 4 is strong oxidizing agents in acidic solution (pH = 0) to oxidize the first two ions, which have less positive standard electrode potential. Perm agnate ion can not oxidize Ce3*, which has a more positive standard potential. Q. 5. Another common analytical oxidizing agent is an acidic solution o f dichromate ion Cr20 7 2~ for which g = +1.38 V. Is the solution useful for titration o f Fe2* ? Could there be a side reaction when Ct~ is present ? A n s. Yes; E for reaction w ith Cl only slightly favourable (reaction is very slow). Q. 6. Show that m agnate (VI) ions are unstable with respect to disproportionation into Mn(VII) and M n(II) in acidic solution. A n s. The overall reaction m ust involve reduction of one Mn(VI) to Mn(II) balanced by four Mn(VI) oxidizing to Mn(VII). The equation is therefore,

t (aq) + Mn2*(a?) + 4 ^ 0 (I) 5 HMn 0 4 (a<7) + 3H*(a9) ------> 4MnO ~ The reaction can be expressed as the difference of the reduction of half-reactions HM 11O4 (aq) + 7H *(aq) + 4e~ ------> Mn2" (aq) + 4 1 ^ 0
4 MnC> 4 (aq)+ 4H*(a<?) + 4e ------> 4HM nO; (aq)

Ee = +1.63 V

E =+0.90 V The difference of the standard potentials is +0.73 V, so the disproportionation is essen tially complete.
Q. 7. Use the Latim er diagram to calculate the value o f Ee for reduction o f HCIO to Ct~ in aqueous acidic solution. A n s. The oxidation num ber of chlorine changes from +1 to 0 in one step (n = 1) and from 0 to -1 (n = 1) in the subsequent step. From the Latim er diagram given in the text.

HCIO (aq) + H* (aq) + e ' ------> ^ C l 2(g) + HjO (I) i c i a (g) + e ' ------C l' (aq)
2

Ee = +1.63 V Ee = +1.36 V

We see n = 1 and n" = 1 so n = 2. So standard potential of HCIO/CI- couple is e


E

E9 ' + E e "
= --------2--------

_ 1.63 V + l ._36_V _ + 1 5 0 v
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CHEMISTRY

Q. 8 . Construct a Frost diagram for oxygen from the Latim er diagram. n +0.70 ^ 1.76 ^ O2 ------- H2O2+------ H 2O I 1.23 I A ns. The oxidation num bers of O are O, -1 and -2 in the th ree species. For the change of oxidation num ber from 0 to - 1 ( 0 2 to H 20 2), E 0 = +*70 V and N = 1. So NE 0 = -0.70. Because the oxidation num ber of O to H20 is -2 , N = - 2 and E 0 for the formation of H 2O is +1.23 V, NE 0 = -2.46 V Fig. 11.

Oxidation number, N

Fig. 3.10 The Fros*. diagram for O in acidic solution (full line) and basic solution (broken line). Q. 9. Using a Frost diagram for manganese in acidic solution to judge the stability o f A ns. Because Mn3+ lies above the line joining Mn2+ to M n 0 2 it should disproportionate. It involves one electron transfer and therefore likely to be reasonably rapid. Q. 10 . Identify the environment in which the solid MnOz or its corresponding hydrous oxides are im portant by using Pourbaix diagram. A ns. M n0 2 is thermodynamically favoured only if E > +0.6V under mildly reducing condition, the stable species is Mn2+. Thus, M n0 2 is im portant in well aerated w aters where E approaches the value for the O JH 2^ couple. Q. 11. Using Pourbaix diagram evaluate the possibility o f fin d in g Fe(OH)3 (s) in a waterlogged soil. A ns. Fe(II) favoured. Q. 12. What is the lowest temperature at which ZnO can be reduced to Zn metal by carbon ? What is the overall reaction. A ns. The C, Co line in Ellingham diagram lies below the ZnO line a t approximately 950C, above this tem perature reduction of metal oxide is spontaneous. The contributing reactions are reaction.

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Zn (g ) + 0 2 (g ) ------ ZnO (s) (Physical state gas is given because it boils at 907C) So overall reaction is the difference C (s) + ZnO ( s ) ------ CO + Zn (g)
Q. 13. What is the m inim um temperature for reduction of MgO by carbon ? A ns. Above 1750C. Q. 14. In the region o f about 2000C carbon is 'thermodynamically capable o f reducing most metallic oxides to metals but at lower temperatures this is certainly not true. What explanation can you offer ? A ns. At tem peratures for which the C, CO lines lies above the metal oxide lines as shown in Ellingham diagram AG9 (M, MxO) is more negative than AG0 (C, CO). At these temperatures, AG0 (C, CO -AG0 ) (M, MxO) is positive, so reaction is not spontaneous. However, for tem peratures for which the C, CO lines lies below the metal oxide line, the reduction of metal oxide by carbon is spontaneous. Q. 15. Carbon monoxide is more effective reducing agent for metallic oxides than carbon below a temperature o f about 710X! but above this temperature the reverse is true. How do

you account for this ? In the reaction C + ^ 0 2 ------>CO, two volume o f CO for every one mole o f oxygen is used. Thus AS is positive, and hence AG become increasingly negative as T increases. Consequently the line on the Ellingham diagram slopes downwards Fig. The two lines for C -* C 0 2 and CCO cross at about 710C. Below this temperature the reaction to form C 0 2 is energetically more favourable, but above 710C the formation o f CO is preferred,. Q. 16. Generally sulphides are converted to oxides before reduction by C why ? A ns. Carbon is a good reducing agent for oxides but it is poor reducing agent for sulphides. The reason why carbon reduces so many oxides at elevated temperatures is that the AG0/T line for CO has negative slope. There are no compound CS analogous to CO with a steep negative AG0/T line. Thus sulphides are normally roasted in air to form oxides before reducing with carbon. Q. 17. What type o f metals are extracted by electrolysis ?
A ns. The metals with high negative electrode potential are extracted by this method. For example Na, Al, F etc. Q. 18. Look up the reduction potential data for iron. Explain the following acid FeOA Fe 3,0*77 >Fe 2*- > Fe, A lkali Fe0 4 -2 - 709 > Fe(OH~ )3 Fe(OH )2 M L -, Fe (a) is the oxidation state o f iron (II) to iron (III) easier in acid or alkaline solution ?

(b) Calculate the equilibrium constant for reaction Fe (s) + 2Fe3+ ------> 3Fe3+ (aq) (c) Is iron (VI) is more stable in acidic or alkaline solution. (d) W ill Fe 2*(aq) oxidize hydrogen peroxide to oxygen H 2Oz (a q ) ------>0 2 (g ) + 2H* ( aq) + 2e~, F? = 0 .7 V

in acid so lu tio n

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A ns. (a) alkaline.


(6) lO41

E (1) Fe2* 2c- ^ (2) Fe3* + e ^ 2 x (2) - 1 Fe Fe2* -0.44 +0.77 2Fe3* + Fe ____> 3Fe2*

AG = -n E F -2 F (-0.44) - F (0.77) -2F(0.77 + 0.44) = -2 (1.21) F

By subtracting (1) from two term equation (2) Now AGe = - n E F = 5.7 log K k J therefore , - 2 x 1.21 x 96.5 = -5.7 log K and log K = (2 x 1.21 x 96.5)/5.7 (c) alkaline
(d ) No.

= 41

so for 2 Fe3* + Fe ^ 3Fe2*,K = 1041

UNSOLVED QUESTIONS
1. C haracterize the condition of acidity or basicity which would m u st favour th e following transform ation in aqueous solution. (a) Mn2+------> MnO" (c) H 20 2 ------- 02

(6) C IO ;------ C103


W) h ------- > 21-

2. By using th e Ellingham diagram determ ine th e condition (if any) u nder which alum inium m ight be expected to reduce MgO. Comment on these condition. 3. Draw a F rost diagram for mercury in acid solution given th e following Latim er diagram .

Hg2* 02

- 91?- > Hg2*

*0796 > Hg 2H02 ------- > 0 2 + H202

4. From the following Latim er diagram , calculate the n et E value for th e following reaction

-01-2 -6 > H20

*1510 > H20 2

Given your value of E, com ment on the term odyanam ic tendency of H 0 2 to undergo disproportionation. 5. M etal source can be classified broadly into five m ain types. Give one exam ple of each type, including the m ain method of extraction of each. 6 . Carbon monoxide is a more effective reducing agent for m etallic oxides th a n carbon below a tem perature of about 710C b u t above this tem perature th e reverse is true. How do you account for this. 7. The stan d ard free energies of formation of MgO and CO a t a tem p eratu re of 1000C and 2000C are given below. Calculate the free energy change for th e reaction.

2MgO + C ------ > 2Mg + 2CO


C + 0 2 ------- 2 CO

AG0 1000 C = - 941 k J mol"1


AG 2000C = -3 1 4 k J mol' 1

AG 1000C = -4 3 9 k J mol-1 AG 2000C = -6 2 8 k J mol-1 8 . Mg and A1 are frequently used for the extraction of m etals such as Mn, Cr an d CO from their respective oxides. W hat is the principal reason why these two m etals are used as reducing agents ?
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CHEMISTRY

entities both in the solid and in solution. Complex ions are shown by use of square brackets. Compounds containing these ions are called coordination compounds. Coordination compounds, as the term is usually used in inorganic chemistry, include compounds composed of a metal atom or ion and one or more ligands (atoms, ions or molecules). DEFINITION OF SOME IMPORTANT TERMS Coordination number The coordination number in coordination compounds is defined as the number of ligand (donor) atoms (ligand will be defined later) surrounding the central m etal atom in a complex ion. For example, the coordination number of cobalt in [Co(NH3)6]3+ and [Co(en)3]3* is six. Coordination number Similarly the coordination number of Ag+in [Ag(NH3)2]+is 2, th at of Cu2+ in [Cu(NHg)4]2+ is 4, and th at of Fe3+ in [Fe(CN)6]3" is 6 . Coordination Sphere The central metal atom and ligands which are directly attached to it are enclosed in a square bracket and are collectively termed as coordination sphere. The ligands and the metal atom inside the square brakets behave as single constituent unit.
[(M N H 3)4Cla)Cl Coordination sphere

Ligand The molecule or ions th a t attached the metal in a complex ion are called ligands. The ligand has a lone pair of electron, hence behaves as a Lewis base. The interaction between a metal atom and the ligands can be thought of as Lewis acid-base reaction. As you know a Lewis base is a substance capable of donating one or more electron pairs. Every ligand has at least one unshared pair of valence electron. Few example, O H

.K i.
|^ H $t

The atom in ligand th a t is bound directly to the metal atom is known as the donor atom. For example, nitrogen is the donor atom and Cu2+ is the acceptor atom in the [Cu(NH3)4]2+ complex ion. Type of ligands (1) On the basis of presence of lone pair of electron. Ligand

(1) With one or more free pair(s) of electrons

(2) Without a free pair of electrons but with 7 i-bonding electrons, e.g., ethylene, cyclopentadienyl ion, benzene. (Contd.)

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