The electron has conquered physics, and many worship the new idol rather blindly. H. Poincare (1907)

n the preceding chapters we saw that the ionization energies, electron affinities, and electronegativities of atoms can be explained on the basis of atomic orbital electronic structures. Now we can proceed to relate electronic structure to the chemical properties of the elements and their compounds. We shall begin by discussing (and balancing equations for) reactions that involve loss and gain of electrons by reactants (oxidationreduction reactions). Then we shall systematically examine the properties of the elements and their compounds, with emphasis on the oxidationreduction chemistry of the metallic elements.

10-1 OXIDATION NUMBERS
To make it easier to discuss oxidation-reduction chemistry, we assign an oxidation number to each atom in a molecule or complex ion, according to the following rules:

1. The oxidation number for an atom of any free (uncombined) element is zero; thus, the atoms in H2, 02' Fe, C12, and Na have zero oxidation numbers.

10-1 Oxidation Numbers

359

2. The oxidation number for any simple one-atom ion is equal to its charge; thus the oxidation number of Na+ is + 1; of Ca2+, + 2; and of Cl=, -1. 3. The oxidation number of hydrogen in any nonionic compound is + 1. This rule applies to the great majority of hydrogen compounds, such as H20, NH3, HCl, and CH4• For the ionic metal hydrides, such as NaH, the oxidation number of hydrogen is - 1. 4. The oxidation number of oxygen is - 2 in all compounds in which oxygen does not form an 0-0 covalent bond. Thus, its oxidation number is - 2 in H20, H2S04, NO, CO2, and CH30H, but in hydrogen peroxide, H202, it is -1. (Another exception to the rule that oxygen has an oxidation number of -2 is OF2, in which is +2 and F is -1.) 5. In combinations of nonmetals not involving hydrogen or oxygen, the nonmetal that is more electronegative is considered negative. Its oxidation number is given the same value as the charge on its most commonly encountered negative ion. In CCl4, for instance, the oxidation number for chlorine is -1; for carbon it is + 4. In CH4, the oxidation number for hydrogen is + 1; for carbon, it is -4. In SF 6, the oxidation number for fluorine is -1, and for sulfur, it is + 6; but in CS2, it is - 2 for Sand +4 for C. In molecules such as N4S4 in which the bonds are covalent (the combining atoms have the same or almost the same electronegativity), the concept of oxidation number loses usefulness. 6. The algebraic sum of the oxidation numbers of all atoms in the formula for a neutral compound must be zero. Hence, in NH4Cl, the total oxidation number for the four hydrogen atoms is 4( + 1) = +4, and the oxidation number for Cl is -1, so the oxidation number for N must be -3. 7. The algebraic sum of oxidation numbers of all atoms in an ion must equal the charge on the ion. Thus, in NHt, the oxidation number of N must be -3, so -3 + 4 = + 1. In SO~-, since the four oxygen atoms have a total oxidation number of - 8, the oxidation number for sulfur must be + 6 if the overall charge on the ion is - 2. 8. In chemical reactions, the total oxidation number is conserved. It is this rule that makes oxidation numbers useful in modern chemistry. If the oxidation number of an atom increases during a chemical reaction, the atom is oxidized; if the number decreases, the atom is reduced. In a balanced chemical reaction, oxidations and reductions must exactly compensate one another.

°

What is the oxidation number of each atom in NF 3? Solution Fluorine lies to the right of nitrogen in the periodic table. Therefore, it is considered negative. Fluorine is assigned an oxidation number of - 1, corresponding to the F- ion. Since there are three fluorines, each with an

360

Oxidation-Reduction

and Chemical Properties

oxidation number of -1, nitrogen must have an oxidation number of +3 for the sum of all oxidation numbers to be zero.

What is the oxidation number of Mo in the molybdate ion, MoOi-? Solution Since the oxidation number of each oxygen is -2, Mo must have an oxidation number of +6 if the sum IMo(+6) + 40( -2) is to be equal to -2.

Calculating Oxidation Numbers
From the preceding rules, we can calculate the oxidation numbers of the atoms in most molecules and complex ions. Certain oxidation numbers are characteristic of a given element, and these can be related to the position of the element in the periodic table. Figure 10·1 shows how oxidation numbers vary with atomic number. The maximum oxidation number generally increases across a period from + 1 to + 7. • Representative metals. Metals in Groups I-III in the periodic table form ions with positive charges equal to the numbers of their respective groups; that is, their oxidation numbers are the same as their group numbers . • Nonmetals. Nonmetals often assume either of two characteristic oxidation numbers. Their minimum oxidation number is usually - (8 -gn), where gn is the number of the group in the periodic table; thus, each atom can combine with 8 - gn hydrogen atoms. For example, one sulfur atom (Group VI) combines with two hydrogen atoms, since sulfur has an oxidation number of - 2. The maximum oxidation number of nonmetals is commonly +gn, especially in oxygen compounds. Examples are S03 and H2S04, in which the oxidation number of sulfur is + 6. Most nonmetals also exhibit intermediate oxidation numbers (see Table 10.1) . .. Transition metals. Among transition metals oxidation numbers follow the trends illustrated in Table 10·2. Early members of the series of transition metals exhibit maximum oxidation numbers of increasing magnitude, up to + 7 for manganese in Mn04 -, which correspond to the group numbers. Thereafter, the maximum oxidation number usually falls again by one number for each step to the right across the second half of the transition metals.

10-1 Oxidation Numbers 85 At Po Bi Pb Tl Ba 361 Lanthanides and transition metals 56 53 51 50 37 35 33 32 84 83 82 Bl 55 Cs 54 Xer-~r---+-~~r-~_'--+--+-4'-~~ Te Sb Sn In 5'2 Transition 49 metals -38 Sr Rb Kr Br As Ge Ga 36 34 Se Transition_:. Ce4+. Eu2+.--+--r~~1 I. The oxidation number + 3 is common to all lanthanides and actinides in their compounds.--+--+--~~--I B o 2 3 4 5 6 • Inner transition metals. 15 14 13 12 11 10 9 8 7 6 5 4 3 F s.. The next most common positive oxidation number is usually gn . .2. Other oxidation numbers are possible and in some cases more commonly encountered (e. and VilA. with maximum positive values equal to the group numbers. and with minimum negative values equal to -(8 . Note the periodicity of oxidation numbers. gn.g. N r + I! It I 0 N C B Be Li 2 Ber-~_'--+-_'~r-~_. in which adjacent elements have very similar properties. 17 16 Figure 10-1 OXidation numbers of atoms of the representative elements. VIA.gn) for Groups VA. and UH). crosses show the less common ones.I--+. The most common values are indicated by filled circles. Lanthanide and actinide elements compose another type of transition series.l metals 20 19 18 Ca K I Arr-~_'--+-?f--r--L_.

o' HCI. S50~SO~SF6 C2H6O CI -1 +7 Intermediate S -2 +4 +6 Intermediate P -3 +5 Intermediate values PH3. S02 H202. PCI5 P40. SO~-. N3N205 N20. Peroxides: H F. N02. in H20. Te As. S2H2S03. P3PO~-. AsO~-. SbCI3 10-2 OXIDATION-REDUCTION REACTIONS An atom with a particular oxidation number is sometimes referred to as being "in the oxidation state" of that number. H104. H2Te Te(OH)6 SbH3 Sb(OH)6 As<!13.-. HN03. N02 O~- -3 +5 All intermediate N03. H2Se04.-.+1 +7 -2 +4 +6 -3 +3 +5 lei IF? H5106. thus. AsH3.362 Oxidation-Reduction and Chemical Properties Oxidation Numbers of Nonmetals F ° N -1 -2 1 Fluorides: H20. CIO-. Se02. C4H. NO.2 oxidation state. SI Br +4 -1 Si02. S02' S03' S20j-. Reactions in which the oxidation states of component atoms change are called oxidation- ° . CCI4. C +4 -4 Complicated formation CO2. CIO. values CIO. values N2H4. CIHC104. Sb +5. values S20~-. BrF 5 BrF. NH3. +3.-. H is in the + 1 oxidation state and is in the . values BrO. +5 Intermediate -1 Se. NHt. H3P04. CF 4 C2H6. CH4 by chain OH-. BrH Br03. SiO::HBr. C102.H2S. H3P03. NH20H.o' H3P02 HSO. BrF3 HI. Na+F02-. Te02 H2Se. H2S04.. PHt. C102.I10. ICI.

It follows that an oxidation-reduction reaction may be thought of as one in which the reducing agent gives electrons to the oxidizing agent. if its oxidation number decreases. whereas the loss of electrons must involve an increase. The ion Mn3+ can act as an oxidizing agent and be reduced to MnH. those containing an atom or atoms whose oxidation numbers decrease are called oxidizing agents (or oxidants).2 Oxidation-Reduction Reactions 363 Oxidation Numbers of First-Row Transition Metalsa 7 6 5 MnO:. it is reduced. and the silver ions oxidize the metallic copper in the reaction Cu I + 2e- 2Ag+ ~ j CuH + 2Ag If an atom can have several oxidation states. The acceptance of electrons by a substance must cause a decrease in oxidation number. copper reduces silver ions. Thus. In fact. Some common oxidizing and reducing agents are listed in Table 10-3. in rusting. and oxygen oxidizes (the origin of the term) iron: 4Fe I 12e- + 302 ~ r 4Fe3+ + 602- (in the form of2Fe203) By donating electrons. The asterisk indicates that oxidation unstable compounds.10. encountered under ordinary conditions in solids and in aqueous numbers have been observed only in rare complex ions or reduction (redox) reactions. the atom is oxidized. If an atom's oxidation number increases. Mn3+ in solution is unstable and spontaneously disproportionates with self-oxidationreduction to give the + 2 and + 4 oxidation states: 2Mn3+ + 2H20 ~ MnH + Mn02 + 4H+ ..CrO~Ti02 Ti3+ TIO VO~VOH V3+ V2+ V(CO)6 CrOCI~Cr3+ Cr2+ Cr(CO)6 MnO~MnO~Mn02 Mn3+ Mn2+ Mn(CN)~Mn2(CO)10 Fe3+ Fe2+ * FeO~Co02 C03+ C02+ * 4 3 2 1 0 NI02 NI203 NiH Ni2(CN)~Ni(CO)4 Sc3+ * Cu3+ Cu2+ Cu+ Zn2+ Fe(CO)5 CO2(CO)8 "Underlined species are those most commonly solutions. iron reduces oxygen. in the intermediate oxidation states it can be either an oxidizing or a reducing agent. Species containing an atom or atoms whose oxidation numbers increase are called reducing agents (or reductants). or it can act as a reducing agent and be oxidized to MnH.

etc. N20. Lower oxidation states become higher Fe2+ ~ Fe3+ + eSO~.~ H2 3.) CeHICe3+ Reducing agents 1 . which they take from compounds with metals: C + [02-] ~ CO + 2eHere [02-] represents oxygen in a . Higher oxidation states become lower 8H+ + MnO.364 Oxidation-Reduction and Chemical Properties Common Oxidizing and Reducing Agents Oxidizing agents 1. + 5e.+ H20 ~ SO~. 3C + Fe203 ~ 3CO + 2Fe (or Fe2+1Fe3+) (or SO~-ISO~-) (or NOIN03") 3. NO.2 oxidation state in combination with a metal such as Fe in the following total equation.+ 2H+ + 2eNO + 2H20 ~ N03" + 4H+ + 3e- . Positive (usually metal) ions become neutral: Ag+ + e: ~ Ag 2H+ + 2e. NHt. Metals yield ions plus electrons: Zn ~ Zn2+ + 2eNa ~ Na+ + e= All metals yielding their common ions may be Included here 2 Nonmetals combine with other nonmetals. such as 0 and F.--> MnH + 4H20 CuH + e: --> Cu+ (often written as CuHICu+) Fe3+ + e: ~ FeH (or Fe3+IFeH) Cr20~-ICr3+ CI03"ICIN03"I(N02. Free (elemental) nonmetals become negative Ions: Fluorine Oxygen Chlorine Bromine Iodine Sulfur F2 + O2 + CI2 + Br2 12 + S+ +- Ze: 4e2e2e2e2e- ~ ~ ~ ~ ~ ~ 2F2022C12Br21S2- 2.

and since K2Cr207 has two Cr atoms. There must be three times as many I atoms involved as Cr. This process is similar to that described by the Brzinsted=Lowry acid-base theory (Section 5-3). when each oxidizing agent reacts it becomes a potential reducing agent. With the ion-electron method we consider a redox reaction to be the formal sum of two half-reactions. 10-3 BALANCING OXIDATION-REDUCTION EQUATIONS Let's look at a reaction involving K2Cr207 and HI. you will be able to make more and more predictions. Oxidation-Number Method 1. one that donates electrons and one that accepts them. becomes a base. If we assume that the reactants and products are known. Now choose enough of the reductant and oxidant so the electrons lost by one are used completely by the other. chromium (Cr) goes from + 6 in K2Cr207 to + 3 in Cr3+(CI04)3. As you gain experience. becomes an acid. and every base. the reaction requires six HI molecules: +6 K2Cr207 + -1 6HI + HCI04 --? KCI04 + +3 2Cr(Cl04)3 + 0 312 + H20 * At this point you should not feel that you should be able to predict products of reactions.1 in HI to zero in 12 and loses one electron per atom in the process. by accepting a proton.10-3 Balancing Oxidation-Reduction Equations 365 Furthermore. In equation 10-1. Identify the elements that change oxidation number during the reaction. in which every acid. Iodine goes from . Write the oxidation numbers of these atoms above the appropriate symbols on both sides of the equation. We start with the equation K2Cr207 + HI + HCI04 --? KCI04 + Cr(CI04)g + 12 + H20 (10-1) Two methods have been developed for balancing redox equations systematically. . With the oxidation-number method we use the fact that the amount of oxidation must equal the amount of reduction in the total chemical reaction. especially in the laboratory. and vice versa. by giving up a proton. * then the problem is how to find the mole ratios and balance the equation for the reaction. Imagine that each Cr atom accepts three electrons to change its oxidation state from + 6 to + 3. 2.

CuH + 2e- ---7 ---7 2H20 Cu O2 + 4H+ + 4e- (cathode) (anode) Redox reactions that occur in solution can be considered as the sum of two such half-reactions that proceed without the addition of an external driving force (the battery). Chemical reactions occurring at electrodes in batteries or electrolysis cells (Chapter 1. First. and then to combine enough of each half-reaction to cancel all the free electrons.366 Oxidation-Reduction and Chemical Properties 3. Cr20~- + 1- + H+ ---7 CrH + 12 + H20 2.~such as K+ or CI04. Section 1-7) are examples of half-reactions that actually occur. The K2Cr207 reaction can be balanced by half-reactions as follows: 1. Now construct two balanced half-reactions. a. simplify the reaction by eliminating all spectator ions (those ions that do not really participate in the reaction). Balance the anions that do not change (CI04 in this case): ---7 + + + + 312 + H20 312 + 7H20 5. In what follows we shall balance the same equation by another method. and make sure that oxygen is also balanced: ---7 The balancing process is thus completed. For example. Balance the other metal ions that do not change oxidation number (K + in this case): +6 K2Cr207 K2Cr207 K2Cr207 + + + 1 6HI 6HI 6HI + + + HCI04 8HCI04 8HCI04 ---7 2KCI04 2KCI04 2KCI04 + +3 2Cr(CI04)3 2Cr(CI04)3 2Cr(CI04)3 + 0 312 + H20 4. In all electron-transfer reactions the number of electrons donated by the reducing agent must equal the number if electrons accepted by the oxidizing agent. The unbalanced reactions are Cr20~21---7 ---7 2CrH 12 . Balance the hydrogens. Ion-Electron (Half-Reaction) Method It is often useful to pretend that oxidation and reduction are occurring separately. one involving Cr and one involving I. The sequence of balancing steps can be summarized as: oxidation numbers-cations-anions-hydrogensoxygens.

However. 3. the number of electrons will indicate exactly the change in oxidation number. and the two 1.on either side. Balance the atoms in each half-reaction by adding H+ and H20 if the reactions occur in an acid medium. and H atoms balanced) (no H+ or OH. and water.if the reactions occur in a basic one: Cr20~- + 14H+ 21- ---7 2CrH 12 ---7 (Cr. As a second example. and that there are no net electrons left.produce two electrons. or H20 and OH. that the charges balance. manganese dioxide (Mn02). The unbalanced reaction is . Add the two half-reactions and cancel species that appear on both sides of the overall reaction: Cr20~- + 14H+ + 61- ---7 2CrH + 312 + 7H20 As a precaution.+ 14H+ 21- ---7 ---7 If the half-reaction is balanced properly.10-3 Balancing Oxidation-Reduction Equations 367 h. potassium hydroxide (KOH). make sure that the number if atoms on both sides is the same. The two Cr require six electrons. let's balance the equation representing the reaction between potassium permanganate (KMn04) and ammonia (NH3) that produces potassium nitrate (KN03). 0. Balance the charge by adding electrons: 6e- + Cr20~. Multiply the half-reactions by coefficients that make the number of electrons transferred in each half-reaction the same: Cr20~- + 14H+ + 6e- ---7 ---7 61- 2CrH + 7H20 312 + 6e- 4. At this point the equation as it stands is balanced. no atoms needed) 2CrH + 7H20 12 + 2e- + 7H20 c. for some applications it is useful to complete the equation by restoring the "uninvolved" species and by grouping ions to form known species: This process can be summarized as: half-reactions-whole reaction-uninvolved ions. III Oxidation-number method.

there are 32 on each side. III Half-reaction method.3N0S' + 18H20 + 24t""" . ~ NH3 ~ Mn02 NOS' NOS' + Mn02 + OH. + l-6H2O ~ 2 3NH3 + ~ ~ . and the process is complete. is reduced and NH3 is oxidized: Since OH. respectively.320H- Electrons are added to balance the charge for each half-reaction: 3r + MnO. it now must be balanced: +7 8KMn04 8KMn04 -3 + 3NH3 ~ +5 +4 3KN03 + 8Mn02 + 5KOH + H20 3KN03 + 8Mn02 + 5KOH + 2H20 The hydrogen atoms must be balanced: + 3NH3 ~ The oxygen atoms must balance.+ H20 In this reaction. + 2H20 NH3 + 90H- The half-reactions are multiplied by 8 and 3. we need eight manganese atoms for three nitrogen atoms: +7 8KMn04 -3 + 3NH3 ~ +5 +4 3KN03 + 8Mn02 + KOH + H20 Potassium (K+) is the cation that does not change oxidation number.3) (change of + 8) To conserve overall oxidation numbers. and then added: ~ + 8MnO. The K+ ion does not change. MnO. + NH3 ~ MnO. so it is omitted: MnO.368 Oxidation-Reduction and Chemical Properties In this reaction manganese and nitrogen change oxidation number: 7+ 4+ 'Mn~Mn 35+ N~N (change of .~ Mn02 + 40HNOS' + 6H20 ~ ~ Mn02 + 40HNOS' + 6H20 + 8e5 8Mn02 +. Begin by simplifying the reaction. + 2H20 ~ NH3 + 90H. H20 and OH.is involved in the reaction.are used to balance the atoms in each half-reaction: MnO.

+ 3H20 3H20 + 3S0~.+ 3H20 H20 + SO~.+ 2H+ Balance the oxygens by adding H + ions and H20: 6H+ H20 6e- + CI03 + SO~- ~ ~ Add electrons to each half-reaction to balance charge: + 6H+ + CI03 ~ CI.3H20 3S0§.are needed to balance the oxidation-number change for each CI03: CI03 + 3S0~. In a .+ 3H20 SO~.+. the equation is balanced.~ SO~.~ CISO~CI. Use both oxidation-number and ionelectron methods. gains 6e- +5 CI03 + +4 -1 + SO~.+ 2H+ + 2e+ 6H+ + CI03 ~ CI.~ CI- + SO~- By the oxidation-number method.~ 3S0~.~ CI- + 3S0~- Since 12 oxygens appear on each side. In the ion-electron method the reaction is divided into halves: CI03 ~ SO~.~ I CI- loses 2e- + +6 SO~- t Three moles of SO~. CI03 Solution + SO~.+ 6H+ + 6e+__ow + CI03 ~ CI.~ CI- + 3S0~- 10-4 REDOX TITRATIONS One equivalent (equiv) of an acid or base in a neutralization reaction is the quantity of acid or base that will release or take up 1 mole of protons.+ £H4 +~ CI03 Balance the electrons by multiplying the lower half-reaction by 3: 6e- Add the two half-reactions to give a balanced equation: --6e' 3HzCJ + + 3S0§.~ 3S0~.10-4 Redox Titrations 369 Balance the following equation involving the oxidation of sulfite (SO~-) to sulfate (SO~-) by chlorate (CI03).

K. the normality of a solution is the number oj equivalents per liter oj solution. so the equivalent weight of sodium in this reaction is equal to its atomic weight. In the reaction Na __" Na+ + e: the sodium undergoes a change in oxidation number of one unit. If a chloride ion is oxidized to C12. we find the molarity: 1.Mrr(J. it is convenient to use equivalents. But if the reaction is -1 Cl" + +5 3HzO __" CIO.00 g of KMn04 is used in titrating a reducing agent.370 Oxidation-Reduction and Chemical Properties similar way. Mg __" Mg2 + + 2r each atom of magnesium changes by two oxidation-number units.127 mole liter " = 0. and each mole of magnesium metal furnishes 2 equiv of reducing ability. and the equivalent weight and molecular weight of HCI are identical.0-ml solution containing 1. The equivalent weight of HCI in a redox reaction depends on the change in oxidation number of chlorine during the reaction. X 4 158_g__. What is the molarity of the solution? What is the normality? Solution First. the number of equivalents of oxidant and reductant is the same. + 6H+ + 6e- then each HCI furnishes 6 equiv of reducing power. -1 0 Cl : __" tCl2 + e: then there is one redox equivalent per HCI.127M . During the reaction.K. and the equivalent weight is one-sixth the molecular weight. 1 mole X 1 0. the equivalent weight of Mg in this reaction is half its atomic weight. . In the oxidation of a Group IIA metal. As with neutralization reactions. for when all of an oxidizing agent in a sample has reacted with a solution's reducing agent from the burette. A 50. 1 equiv of an oxidizing or reducing agent in a redox reaction is defined as the amount of compound that will produce 1 mole of oxidationnumber change.00_g__. In titrations using solutions of oxidants or reductants as reagents. The equivalent weight ofHCI in an acid-base neutralization reaction is equal to its molecular weight. Mn04 is reduced to MnH.0500 liter = 0.Mrr(J. Therefore.

0720 mole liter-l = 0.00 equiv mole= = 0.127 mole Iiter ? X 5.38 ml X x meq 1 ml 1 ml (Note that 1 meq ml :' = 1 equiv Iiter=I. so each C20~-.635 equiv liter ? = 0. What is the normality of the Na2C204 and of the KMn04.200N.25-ml solution ofO. [One milliequivalent (meq) is 10-3 equiv.200 meq = 17. and the molarity of the KMn04? Solution The reaction is +7 2Mn04 +3 + 5C20~. with two carbon atoms.] So meq Na2C204 = meq KMn04 31. so each Mn04 provides 5 equiv of oxidizing power.+ 16H+ ---? +2 +4 2MnH + 10C02 + 8H20 Manganese goes from + 7 to + 2. the equivalent weight of KMn04 is one-fifth the molecular weight.360N 0.25 ml X 0.) Normality ofKMn04 · M oIanty 0 fKM n 0 = x = 0.635N A 31. Another way of understanding this is to write the two half-reactions: Mn04 + 8H+ + 5eC20~---? ---? MnH + 4H20 2C02 + 2e- For this reaction the 0.38 ml of KMn04 solution of unknown strength.10-4 Redox Titrations 371 The reduction of Mn04 to MnH is +7 +2 Mn04 + 8H+ + 5e- ---? MnH + 4H20 Since Mn changes by five oxidation units in this reaction.100M Na2C204 solution is 0. Carbon goes from +3 to +4.0720M 4 The importance of writing the equations or half-reactions when dealing with equivalents is illustrated by the fact that Mn04 can be reduced in various circumstances in the following ways: .360_eqlli-v-liter-1 = ---~---5_equivmole-1 = 0.100MNa2C204 (sodium oxalate) in acid is titrated with 17. provides 2 equiv of reducing power. and the normality is five times the molarity: 0. The milliequivalents of oxidant and reductant are equal at neutralization.

Sometimes the result of oxidation of a metal in solution is not a hydrated cation but an oxide complex: s» = -0..71 volts (V) The drive toward the oxidized state of Na in water is so strong that water itself is decomposed. The normality of any KMn04 solution thus depends on how we use it.771 V . This is a much more useful quantity in most chemical applications.+ SH+ + 4eMnO. and 5. The qualification.+ 2HzO + 3eMnO." in the preceding sentence is an important one.372 Oxidation-Reduction and Chemical Properties --3> --3> --3> --3> MnO.SO V Thus the reverse of this reaction will occur. but the others also occur. At the moment/we want to use them only as measures of the relative tendency of elements to exist in different oxidation states in solution. In contrast. 10-5 OXIDATION AND REDUCTION POTENTIALS The oxidation potential.~o.. the reaction has a stronger tendency to occur than does the oxidation of Hz. its standard oxidation potential at'?~5~C. and hydrogen ions are reduced to Hz gas... We shall return to a systematic study of oxidation potentials in Chapter 19..+ SH+ + 5e- MnO~MnOz + 40HMn3+ + 4HzO MnH + 4HzO The number of equivalent weights per mole of KMn04 in these examples is 1. of a reaction is a measure of the tendency for a reaction of the type Reduced substance --3> oxidized substance + electrons to take place. where we will see how they are measured in electrolytic cells..+ e: MnO. the oxidation potential measures the tendency of solid Na to lose an electron and form a hydrated sodium ion in aqueous solution. The last reaction is the one most frequently encountered. If the oxidation potential of a reaction is positive. If the oxidation potential for a reaction is negative. '4. This is true for sodium metal. the favored drive is toward the reduced rather than the oxidized state: Ag(s) --3> Ag+ + e: ~o = -O.. is Na(s) --3> Na+ + e: ~o = +2. ~. "in solution.3. The first ionization energy of sodium measures the tendency of a gaseous atom ofNa to lose an electron and to form a gaseous ion.. in comparison with the reaction tHz(g) --3> H+ + e: which is assigned an oxidation potential of zero.

K. and those that can be explained by electronic structure. Not every chemical property becomes absolutely clear once we know the electronic structure of an atom of an element. try to pick out of the descriptive material those properties that show regular trends across the periodic table.71 V. the accepted international convention is to use reduction potentials. If the oxidation potential for the oxidation of metallic sodium to sodium ion is +2. What is the reduction potential of Ca2+? Is Ca2+ a good oxidizing agent? Solution The equation is Ca(s) Ca2+ -7 Ca2+ + 2e- 80 = +2. 10-6 CHEMICAL PROPERTIES: THE s-ORBITAL METALS Knowing the electronic structures of atoms. Rb. The oxidation potential of metallic calcium is + 2.10-6 Chemical Properties: The s-Orbitol Metals 373 The oxidation potential of Mn to Mn04 is much more meaningful in solution chemistry than is the energy required to strip seven electrons from a Mn atom in the gas phase.71 V. and Cs All the alkali metals have an Sl outer electronic configuration. These metals are the most reactive known. or other elements. these elements thus have low ionization energies and low electronegativities. always in the + 1 oxidation state. but much of what we observe does make sense now.76 V The reduction potential refers to the reverse reaction + 2e- -7 Ca(s) The very negative reduction potential (-2. Although we find it convenient to work with oxidation potentials. even the hydrides. we can interpret the chemical properties of the metals in a reasonable way. Write an equation for the oxidation of calcium in aqueous solution. Ionization energy and electronegativity decrease from Li to Cs as the distance between the outer shells and the nucleus increases. Na. Don't try to memorize all the facts given here. chlorine.76 V 80 = -2.76 V) shows that Ca2+ is definitely not a good oxidizing agent. and it is this sense that we shall look for in the mass of chemical data. and never occur naturally in the metallic state. Group IA.76 V. Virtually any substance capable of being reduced . They occur in combination with oxygen. The electron is lost easily. instead. All their compounds are ionic. the reduction potential for the reduction of a sodium ion to metallic sodium is -2. Alkali Metals: Li.

and the reaction with all these metals is violent and exothermic. because the small size of a Li+ ion permits water molecules to approach the center of the ion more closely. b+ R ___. . its valence electron can be ejected most easily by tight in a photoelectric cell.05 V +2. Water attacks all the alkali metals.92V + 2..2.374 Oxidation-Reduction and Chemical Properties will be reduced in the presence of an alkali metal. Lithium can be cut with a knife with difficulty. this makes the hydrated ion quite stable.92V Each of these metals has a strong tendency to lose electrons and become oxidized in solution. and all react with water to form basic hydroxides that are soluble and completely dissociated.Cs+ + e: + e: + e: + e: + e: go go go go go = = = = = + 3. The alkali metal ions have no free electrons to be excited by energies in the visible region. in which the optical image falling on cesium-coated cathodes is converted to electrical impulses. and when the difference in energy of these levels is in the visible portion of the spectrum. With only one mobile electron per atom. Na+ ___.71 V +2.92 V +2. and ductile. metallic bonds are weak. In contrast. + K ___.. the free metals cannot be prepared conveniently by reduction of their compounds with another substance: Li+ + reducing substance ___. in spite of the higher ionization energy of Li. from Li to Cs. The bonds become weaker with increasing atomic number as the valence electrons become more distant from the nucleus.. Li+ ___. Cesium has the lowest ionization energy of any element. The photoelectric effect is used in photo cells and in television cameras such as the iconoscope. the metals are usually prepared by the electrolysis of their molten compounds.. The alkali metals ordinarily are stored in kerosene or some other unreactive hydrocarbon. it is difficult to reduce their ions. Li + oxidized substance Instead.92 V. but Cs is as soft as cheese.. The oxidation potentials of the alkali metals. The oxides of the alkali metals are basic. The easily lost valence electron is responsible for the metallic properties of the alkali metals. Almost all the compounds of the alkali metals are soluble in water. Because the alkali metals are the strongest reducing agents known. Color is produced when an electron in an atom is excited from one energy level to another. are Li(s) Na(s) K(s) Rb(s) Cs(s) ___. The alkali metal ions in solution are colorless.. A typical reaction is D. potassium ions have a reduction potential of . Lithium loses electrons in solution more readily than Cs.H~98 = -167 kJ The hydrogen gas evolved is ignited by the heat of the reaction and burns spontaneously in air. and are soft. The metals have low melting and boiling points. malleable.

85V +2. Alkaline Earth Metals: Be. nevertheless all their compounds. Be has an extraordinarily high ionization energy and energy of vaporization (Table 10-4). The hydration of the doubly charged cation gives it enough extra stability to overcome the energy required to remove the second electron. has a high hydration energy because of its small size. It is true that Be. The intense color has been shown to arise from the solvated electrons and not from the metal ions. so the oxidation potential is somewhat lower than might be expected. This behavior is reflected in the greater electronegativities of the smaller atoms within a group (Table 10-4). Group IIA.37 V +2. and the electrons associate with the NH3 solvent molecules. so the net nuclear charge is greater. However.10-6 Chemical Properties: The s-Orbital Metals 375 Alkali metals have the interesting property of being soluble in liquid ammonia and forming intensely blue solutions that leave behind the original metal when the ammonia evaporates. The second ionization energies of these metals are usually double their first ionization energies. This leads us to expect a strong tendency to oxidize in aqueous solution and a large positive oxidation potential. but the screening of the nucleus by electrons in inner orbitals is similar for both groups. we might expect + 1 ions to form and the + 1 oxidation state to exist in solution. Sr. like Li. Such electrons are known as solvated electrons. But this is not the case. Mg. All are typical metals and strong reducing agents (although not quite as strong as the alkali metals). Beryllium is the first example of the general observation that within a group elements with lower principal quantum number will be less metallic because their outer electrons are closer to the nucleus and are held more tightly. the alkaline earth atoms are smaller and have higher first ionization energies than those of alkali metals in corresponding periods. for the same reason that it has a higher first ionization energy than other elements in the group.89 V +2.90 V They are more electronegative than are the alkali metals. the same color can be produced by introducing electrons into ammonia from a platinum electrode. Any solution of Ca+ ions . Their oxidation potentials in aqueous solution are Be(s) Mg(s) Ca(s) Sr(s) Ba(s) ~ ~ ~ ~ ~ BeH + 2eMg2+ + 2eCaH + 2eSrH + 2eBaH + 2e- Co Co Co Co = = = = s» = + 1. The atoms dissociate into positive ions and electrons. The nuclear charge has increased by one from the alkali metals in a given period. Thus. are ionic. and these two effects combine to dominate in the oxidation of Be to BeH. Beryllium has a lower oxidation potential. Ca. and Ba The chemistry of the alkaline earth metals is the chemistry of atoms with two easily lost electrons. with the exception of some Be compounds. thus.76 V +2. or lower tendency to lose an electron in solution.

colored with a trace of chromium.0 0. Like the alkali metals. limestone. The hydrides of Ca.3 1. Calcium carbonate. DC) MCI2 (boiling point. Emerald is impure beryl. sulfates. Calcium and magnesium are much more common than the other elements in the group.086 1. The pure metals have higher melting and boiling points than do alkali metals because they have two electrons per atom for forming metallic bonds. strontium. although they still can be cut with a sharp steel knife. Magnesium. the pure alkaline earth metals are commonly prepared from molten compounds by electrolysis because of the difficulty of finding anything with a higher oxidation potential with which to reduce them chemically. they are harder.0 1. and marble. DC) Equivalent conductivity of MCI2 (ohm-1 mole-1) 1. usually from deposits of shells and skeletons of marine organisms.0 1. Beryllium and magnesium are found in complex silicate minerals such as beryl (Be3A12Si601s)and asbestos (CaMg3Si4012) (Chapter 14). and Ba (CaH2' SrH2. is found as chalk.36 651 1107 9.2 129 708 1412 29.89 1278 2970 11 . and phosphates.74 842 1487 9. The free metals do not occur in nature because they are too reactive. and barium occur as the relatively insoluble carbonates.98 725 1140 7.376 Oxidation-Reduction and Chemical Properties Properties of the Alkaline Earth Metals Electronegativity D Metallic radius (A) Melting point (D C) Boiling point (DC) Heat of fusion (kJ mole-:") Heat of vaporization (kJ rnole <") MCI2 (melting point.5 151 963 1560 would disproportionate spontaneously to Ca metal and Ca2+ ions: 2Ca+ ~ Ca(s) + Ca2+ The solution chemistry of the alkaline earth metals is exclusively that of the + 2 oxidation state.7 295 405 520 0. calcium. CaC03. Sr. For the same reason. Beryllium and magnesium are the only elements in this group commonly used as structural metals. Alkaline earth compounds are generally less soluble in water than the compounds of the alkali metals.95 1.6 0. in which weight is an important factor.89 1.2 150 772 1600 52.2 139 873 1250 0. because of their lightness they are used pure or in alloys for aircraft and spacecraft. and BaH2) are ionic and are white powders that release H2 gas upon reaction with water: .91 769 1384 9.

Atoms in the second transition-metal series. Beryllium is definitely the odd man out in Group IIA. a fact that indicates the absence of ions. The coordinating groups are arranged tetrahedrally around Be. Y to Cd. is interposed after La. hafnium is not as large as it would have been had it followed directly after La. showing both acidic and basic properties. The atoms tend to become smaller with increasing atomic number across a period because of the increased nuclear charge. It is virtually insoluble in water. which produces the lanthanide contraction. The reason is that the first inner transition-metal series. liquid BeCl2 does not conduct electricity. which also are only slightly soluble: CaO(s) + H20 ~ CaH + 20H- ~ Ca(OHMs) Ba(OH)2 is strongly basic. like those in diamond. Solid BeCl2 is composed of covalently bonded chains that are held together only by weak intermolecular forces. Its oxide is amphoteric. and basic with the exception ofBeO. Therefore. These facts suggest that the covalent bonds in Be. are hard. Mg(OH)2 is weakly basic. all with the expected 1: 1 atomic ratio (BeO. Sc to Zn. 10-7 THE FILLING OF THE d ORBITALS: TRANSITION METALS The transition metals are hard metals with high melting and boiling points. persist in the liquid.10-7 The Filling ojthe d Orbitals: Transition Metals 377 The oxides. covalent compound instead of an ionic solid such as CaCI2• Finally. are not as much larger than the atoms in the second series as would be expected. the lanthanides. but in strong acid it acts as if it were basic: BeO BeO + 2H+ + + 20H- 3H20 ~ Be(H20)~+ Be(OH)~- and in strong base it acts as if it were acidic: + H20 ~ In both cases. Its melting and boiling points and heats of vaporization are unusually high. the cation is so small that only a coordination number of 4 is possible. relatively insoluble in water. The amphoteric behavior of BeO arises because Be is so small and electronegative. There is a steady decrease in size from La to Lu because of increasing nuclear charge. Lu to Hg. The nuclear charge in Zr is 18 greater than that in Ti. are larger than those in the first. BeH attracts electrons from neighboring water molecules and makes it easier for them to lose a proton to the surroundings: BeH + 4H20 ~ Be(OH)~- + 4H+ Beryllium shows many other signs of nonmetallic behavior in addition to the amphoterism of its oxide. the basic oxides form hydroxides. CaO. and so on). But atoms in the third transition-metal series. but that . In water. reversing the trends within the rest of Group IIA (Table 10-4). BeCl2 has the low melting point expected of a molecular.

Oxidation Potentials The oxidation potentials for the production of ions from neutral atoms are plotted in Figure 10-2 for the first transition series. The driving force for the production of ions decreases as the atomic number increases because the electrons are held more tightly. not in the 4s. the 3d orbital energy dips below the 4s. It is more important for you to know the behavior of the first transition series than to remember the exceptions in the heavier metals. in turn. up to a maximum equal to the number of unpaired electrons in the d orbitals. is + 2.and d-orbital energies occurs at the beginning of a transition-metal series. These generalizations are true for the first transition series. and it remains there for all higher atomic numbers.and third-series transition metals have not only the same outer electronic configurations in corresponding groups. In contrast. with the exception ofCu and a few rare compounds of other metals. Thus. Ti(lV). but almost the same size as well. and thereafter falls by one per group to + 2 in Zn (loss of only the two s electrons). Vanadium is distinct from Nb and Ta. at ScH. Although the s orbitals fill first in Groups IA and HA. Tantalum and niobium were discovered in 1801 and 1802. the second and third series are more similar in properties than either is to the first.378 Oxidation-Reduction and Chemical Properties in Hf is 32 greater than that in Zr. Other higher oxidation states occur with the loss of more electrons from the d orbitals. In the first half of the series. but the very names of Ta and Nb reflect how difficult it is to separate them. it is the d orbitals that are occupied in transition-metal ions. The + 2-ion curve represents the removal of the two s electrons and the retention of the original d configuration. The lone electron in ScH is in a 3d orbital. the daughter of Tantalus. The result is that the second. Because of the difficulty in isolating it. V(V). Niobium. There are some higher oxidation states observed in the second and third series. as in Ru04 and OS04. The crossover of s. but for nearly half a century many chemists thought that they were the same element. This is why the maximum oxidation number increases from + 3 in. was named for Niobe. and added electrons go into the 4s orbital. It is . CreVI). the Greek mythological figure who was doomed to an eternity of frustrating labor. The outer electronic configuration of Ti2+ is 3d2. The Structure of Transition-Metal Ions In the K+ and Ca2+ ions. not 4s2• The lowest oxidation state in all the 3d transition metals. Ta was named after Tantalus. with both s electrons lost. This behavior is typical of all transition metals. Sc to + 7 in Mn (five d plus two s). The most common oxidation states are + 2 and + 3. and Mn(VII)-is also common (Table 10-2). the maximum oxidation state for each element-Sc(III). the 4s orbital is slightly more stable than the 3d. Titanium resembles Zr and Hf less than Zr and Hf resemble one another.

In contrast. and Sc are given for the production Transition-metal electronic + 1. The elements preceding the transition series become cations by losing all their electrons outside the inner noble-gas shells. + 2. so we do not have the local fluctuations observed in the + 2 curve. All react with water. and for +2 ions With the Ar noble-gas potentials configuration are shown of the Ion +3 Ions By each pornt given the outer particularly difficult to remove two electrons in Cu because only one is in the s orbital and the second would have to come from the filled dlO orbitals. it is quite easy to remove the two s electrons in Zn and leave the stable. d5 configuration is present instead of a filled dlO• The d electrons must be disturbed when a + 3 ion is produced. filled dlO orbitals untouched. as does Al.Y-Lu triad has the outer electronic configuration dls2. Chemical Properties of Individual Groups: Sc and Ti Groups The Sc. and shows only + 3 oxidation states.10-7 The Filling Element Neutral atom K dDs! of the d Sc Ti d's' Orbitals: Transition Metals V d's' 379 Ca d+s? I Cr d's!) Mn d's' Fe dGs' Co d's' +~~o +2 d'' dO +3 +2 0. But SC203 is .0 Figure 10-2 Oxidation metals potentials for the fourth-period metals. in which a half-filled. the representative elements following a transition series achieve their maximum oxidation number by losing all their electrons outside the filled dtO shells. including the first transition-metal In sol ution from the solid of series. Ca. This same effect is observed to a lesser extent in Cr and Mn. Potentials are for the prod uction electronic IS of Simple cations structure +3 The potentials and for K. The properties of these elements are similar to those of Al in Group IlIA.

red light (ca. TiO. and Hf. Zr. consequently. Ti02. 560 nm). VCl4 is a molecular liquid with a boiling point of 154°C. V02+. Titanium trichloride. The color'S we see are the complementary colors to those absorbed (Table 20-2). It boils before TiCls melts (decomposes) because it is a molecular compound with covalent bonds. The vanadium ions provide good examples of the colors that are typical of transition-metal compounds. At the top of the group. and the + 4 state is more covalent and nonmetallic. Only these colors are seen from the entire visible spectrum because the three solutions absorb orange light (ca. there is no aqueous chemistry of TiH. In the Ti-Zr-Hf triad. the V3+ ion is green. the V(IlI) compounds are ionic. the nucleus. is a stable liquid that freezes at .is colorless.Ta elements is similar to that of the previous triad: V and Ta have the d3s2 electronic configuration and Nb has the d4 Sl configuration. and it is difficult to prepare them by the high-temperature reduction processes used with Fe and other metals. In contrast. This is an example of a general trend in the transition metals: The lower oxidation numbers are less important for the second and third transition series because the electrons are farther from. whereas Hfhas only +4.380 Oxidation-Reduction and Chemical Properties a basic oxide rather than amphoteric. is deep blue. The dichloride. If they lose some electrons. which has the d2s2 electronic configuration. Vanadium has oxidation states of + 2. Titanium (II) oxide. 610 nrn). insoluble pigment that has both basic and acidic properties. respectively. +3. VZ05 is amphoteric like TiOz. TiC14. the dioxide. + 4. The lower oxidation states of Ti are ionic. and the VH ion is violet. because Sc3+is larger than AP+. the tetrachloride. TiC12. is another strong reducing agent and is an ionic solid that decomposes at 440°C. and yellow light (ca. The Vanadium Group and the Colors of Ions and Complex Compounds The chemistry of the V -Nb. In contrast. whereas only the +5 state is important in Nb and Ta (although some +3 and +4 compounds are known). The + 4 oxidation state of V is also on the borderline ~tween ionic and covalent character. C. Vanadium(V) as VO~. is basic and ionic. is a white. At low temperatures an oxide coating protects them. Most electronic energy levels are so far apart that the radiation absorbed in an ° . the vanadyl ion. It is an ionic solid that decomposes at 475°C in a vacuum. is a strong reducing agent and oxidizes spontaneously in air.25°C and boils at + 136°C. Ti and Zr shows +2. Like Ti. and +4 oxidation states. + 3. TiCls. these metals react easily with N. In aqueous solution. like AI20s. Since it reduces water to H2. The difference in behavior resembles that between CaO and BeO. It dissolves in both acids and bases to form complex and poorly characterized polymers. they are likely to lose all of them. it has the NaCl crystal structure. The chlorides provide a particularly good illustration of this progression of properties. and at high temperatures. In contrast. 680 nm). the metals are more inert than their oxidation potentials would suggest. and + 5.

Yb.'0. colors are produced (the theory of d-orbital energy differences.0. SnO..CtO{lMn'@'.O. yellow. 1)1. or splittings. But in transition-metal complex ions and compounds. hence.().. Larger and larger energy absorptions produce blue-green. in the red region. in transition-metal complexes is given in Chapter 20). white Pa.::0. white white ycHow yeJlowJ' brow~ green~: black bfowjl yei10~. white white white Hb.+ red. Dy.0. blue.O.O. y.a. these are the colors complementary to red. and finally yellow. . blue.O. ~"". . The Chromium Group and the Chromate Ion The elements Cr. CeO.' white blue Ta.O.{0. white Y. electronic excitation is in the ultraviolet.O. orange. ». They are relatively inert to corrosion because films of oxides formed on the surface adhere and protect the metal beneath. Lu. PrO. Sm.Q. white white bO. e.O..Q.. black Nd.O.O.'c$uO.O.gr!:Cn em Bk CI Figure 10-3 Oxides of many transition and Inner transition metals are colored.o.D Rgo . Sb. green. white S"O. Mo. would leave unabsorbed the wavelengths that produce a complementary blue-green color in the solution or compound.10-7 The Filling of the d Orbitals: Transition Metals 381 - Sc. The colors of several metal oxides are given in Figure 10-3..~ 'Bu.-ted: r ~cen.. . and W have high melting and boiling points and are hard metals..ed green .O. white TiO. Re. red-orange.Q. white yellow. TeO.O.O. PdO Ag. white Nb.UO.own black < GeO. the d-orbital energy differences are so small that the frequencies of radiation required for transitions are in the visible region. ZnO Ga.orange gru:n Pu0. J'(pP> white .~t 'Cotl' . MoO.NiO Cu. white A"O. :T1n. HIO.+ .red white white "brown b. green. Clearly. The thin layer of Cr203 on chromium metal makes chrome plating an efficient .PbO. and violet.RhO.O. The smallest energy absorption.O.O. ):tlJow ~Je :t~ Gd.0~.O.yinle! Aq. T. purple. violet.violet blue ':black La. dark tedbrown' 'boown tedyeUow rb~n no.reNew ¥ellowydlow black.L. Tb~O. W. color is an approximate guide to the electronic energy differences in metal complex ions and compounds. white .d green· white white rwhite Es Fill Md No Lr ThO. white ZrO.. Pm tiJ-ue whitebrowl. white orange t. PtO Au.fe. Er.

with a reduction potential of + 1. Chromium(III) is the most prevalent oxidation state of chromium. Rhenium was discovered in 1925.-. MnO:. Along with V. Mn(VI) does exist as the manganate ion.33 V Of the Mn. Mn is by far the most important. incidentally. which dimerizes in acid to form the orange dichromate ion: 2CrO~- + 2H+ _. It is strongly resistant to oxidation and is not a good reducing agent. As we would expect. tensile strength. Mn02.382 Oxidation-Reduction and Chemical Properties protection for the more easily attacked metals such as iron. and CrH. and shock resistance.Tc-Re triad. The oxidation states Mn(III) through Mn(VI) are rare. in a sample of Mo that had been irradiated by deuterons (iH particles) in the Berkeley cyclotron by Ernest Lawrence (for whom. and the MnS04 and MnCl2 salts are also pink. and Tc was the first element produced artificially. Cr20~- + H20 The dichromate ion is a powerful oxidizing agent. the acidity of the oxides varies with the oxidation state: Cr03 is acidic. except for the chief natural ore. Oxidation states from + 2 to + 7 are known. MnH shows little tendency to go to higher oxidation states. the two extremes are the most important. The Mn(VII) state is chiefly important for the deep purple permanganate ion. CrO~-. The new element was named technetium from the Greek technetos. and tungsten (W) is used in steel cutting tools that remain hard even when red hot. Vanadium gives steels ductility. element 103 was named). and CrO and Cr(OH)2 are basic. and Cr(VI) is a good oxidizing agent.33 V We could express the same chemical fact by saying that the reaction by which CrH is oxidized to dichromate ion has a low negative oxidation potential. in 1937. and the reaction by which dichromate ion is reduced to CrH has a large positive reduction potential: co co The Manganese Group and the Permanganate Ion = + 1. It is one of the most powerful common oxidizing agents._. VH.. Chromium(II) is a good reducing agent.49 V . Unlike TiH.- + 8H+ + 5e. MnO~-. " The chief use ofMn metal is to make hardtand tough manganese steels. molybdenum acts as a toughening agent. MnH + 4H20 s» = + 1. Manganese(II) in water forms the pink Mn(H20)~+ octahedral complex. "artificial.. Chromium makes stainless steels corrosion resistant. Cr203 is amphoteric.49 V: MnO:. A common anion is the yellow chromate ion. and that the reaction tends to go in the other direction: = -1. Technetium was discovered by Perrier and Segre. these three metals are used mainly as alloying agents in steels.

) Manganese provides an excellent example of the dependence of chemical properties on oxidation state. and d8s2.84 V .1-1. and the hydrated ferric ion. (One of our black comedies on World War II has this bitter remark about the medical services available to enlisted men: "The first time you come in.) Iron is one of the most important structural metals. the second time they paint your gums purple. In the modern systematic nomenclature. and the light and heavy platinum triads. respectively.10-7 The Filling of the d Orbitals: Transition Metals 383 Note again that a compound with a high positive reduction potential or a low negative oxidation potential will be a good oxidizing agent because the compound itself will have a strong tendency to go to the reduced form. is KMn04. Manganese(II) exists in solution as a cation and has a basic oxide. Ferrous or iron(II) compounds are usually green. and the magnetic mixed oxide magnetite. Iron. Both + 2 and + 3 states form octahedral complexes with cyanide: Fe(CN)~and Fe(CN)~-.5% carbon. The traditional names for these anions areferrocyanide and ferricyanide. and Ni is greater than that between these and the corresponding elements in the second and third transition series. The result is cast iron with 3-4% carbon. or paint. Rust (iron oxide) flakes off as it is formed and exposes fresh metal to attack. but the customary protection is an added surface layer such as chromium. The nomenclature of complex ions is given in Chapter 20. of course. Fe203. These nine elements are usually separated into the iron triad. cobalt. and nickel have the electronic configurations d6s2." The purple. d7 s2. MnO~. Fe-Co-Ni. since CoH is an excellent oxidizing agent and has a strong tendency to be reduced to Co2+: 80 = +1. Cobalt in solution exists mainly as the + 2 cation. Fe304 or FeO . Iron is no more intrinsically reactive than the other transition metals that we have been discussing. Iron is found in three main oxide ores: FeO. nickel. they are hexacyanoferrate (II) and hexacyanoJerrate(III). The open hearth and Bessemer processes are means of burning out most of this carbon with streams of oxygen to obtain steels with 0. Mn(OH)2' At the other extreme. Fe203. the iron oxides do not adhere to the surface of metallic iron. Solutions of the permanganate ion are used as disinfectants. is a pale violet. they give you two aspirins. Co. and hydroxide. Fe(H20H+. tin. (The + 3 state is very rare for Ni. Iron is produced by high-temperature reduction with the CO from coke in a blast furnace. the horizontal similarity between Fe. All show chiefly the + 2 and + 3 oxidation states. MnO. they arrest you for impersonating an officer.and MnOi. the + 6 and + 7 states exist as anions. however. If you show up again. Many of the other transition metals are important chiefly as alloying agents with iron. Chrome steel or stainless steel is more corrosion resistant. corresponding to the acidic oxides Mn03 and Mn207• The Iron Triad and the Platinum Metals In Group VIII. Unfortunately. Ru-Rh-Pd and Os-Ir-Pt.

These properties are part of a downward trend that began with Group VIB (Cr-Mo-W). and +4 are most important. are green. The oxidation states + 2. They have lower melting and boiling points than the preceding transition metals and are moderately soft. Copper artifacts have been unearthed in some of the earliest farming communities in the Middle East. they were used mainly for their symbolic and decorative qualities. the physical properties of Ag and Au-electrical and thermal conductivity and corrosion resistancehave become so valuable that the metals no longer can be spared for their traditional coinage roles. with which they are associated in the short form of the periodic table derived from Mendeleev's table (Figure 7-1). which follows from the decreasing number of unpaired d electrons. Copper shows mainly the +2 oxida- . PtCI~-.384 Oxidation-Reduction and Chemical Properties But in many octahedral complexes of Co(III) the ligands (the ions or molecules attached to Co) stabilize it against reduction. as well as the hydrated cation. Metallurgy began when it was discovered that an alloy of copper with tin (a naturally occurring impurity) produced the much harder bronze. The first metal to be reduced from its ore was probably copper. More recently. and gold have little resemblance to the alkali metals. The Coinage Metals Copper. The square planar complexes are usually red or yellow. Gold is now used for plating external surfaces of delicate components in satellites and space probes. Until a century ago. they are inert and can be found naturally in the metallic state. These three metals have been the source of more strife and trouble than any other elements. shows a strong tendency to bind to sulfur in proteins. All are relatively unreactive. Although rare enough to be prized. Complexes of Pt(II) are square planar. Complex ions of Pt(IV) and Ir(III) are octahedral. dating from 7000-6000 B. and has been useful in preparing heavy-atom derivatives of proteins for x-ray crystallographic analysis. Nickel forms octahedral and square planar complexes in the Ni(II) state. during the era that also saw the invention of writing.C. they are much less scarce than the platinum metals.. The metals are excellent conductors of electricity and heat since their electronic arrangement makes the i electrons extremely mobile. Their relative abundance and their occurrence as uncombined metals made them the first metals to be collected and worked by man. They are malleable and ductile. and are found naturally as the pure metals. +3. Bronze was known in the Sumerian cities of Ur and Eridu from 3500 B. Copper. and the metals form octahedral or square planar complex ions in solution. and much work remains to be done on their reactions.C. The tetrachloroplatinate (II) ion. silver. silver. and gold have the slightly irregular outer electronic configuration d10Sl. Many Ni(II) salts. Metals in the light and heavy platinum triads are relatively rare.

one of the few solutions in which silver halides are soluble: AgBr + 2S20~. and Ag(S203)~-' and Au(III) forms the very stable AuC!. Light from the camera image interacts with the crystalline AgBr in a poorly understood process that appears to involve defects in the crystal structure. In making photographic film.34 V Ag ~ Ag+ + e: . The complex is square planar. They are soft and have low melting and boiling points. Mercury is more inert and resembles Cu. thereby indicating their inertness and reluctance to oxidize: Cu ~ Cu2+ + 2c= .~ Ag(S203)~- + Br" (The old name for sodium thiosulfate was sodium hyposulfite.) The Low-Melting Transition Metals The most distinguishing characteristic of Zn. However. hence.!"complex.1. Ag(NH3)t. All three elements have a + 2 . and tetraamminecopper(II). The hydrated Cu(II) ion has a characteristic blue color.42 V Au ~ AuH + 3c- s» Copper(I) is unstable in solution and disproportionates spontaneously to Cu and Cu2+. the reverse is true: The + 1 state is common. rflo = -0. and makes the grains. For Ag. Ag. or crystals. The metals have low negative oxidation potentials. and Hg is their weak coherence as metals. The Chemistry of Photography All silver halides except AgF are sensitive to light and are the basis of the photographic process (Figure 10-4). Gold occurs in the + 3 state and less frequently in the + 1. Cu(NH3)~+' is an intense blue. Mercury is the only metal that is liquid at room temperature. and the + 2 and + 3 can be obtained only under extreme oxidizing conditions. more sensitive to reduction. Cd. fine crystals of AgBr are spread in gelatin on a film backing. and Au.0. The sensitized AgBr is reduced in the developer by a mild organic reducing agent such as hydroquinone: AgBr + e" (reducing agent) ~ Ag + Br- Then the unsensitized AgBr grains are dissolved and washed away in a sodium thiosulfate solution. Silver(I) forms complexes such as AgClz. The chemistry of Cu(II) is similar to that-of other transition metals in the + 2 oxidation state. which are the principal ores of copper. Copper(I) exists as the solid and extremely insoluble Cu20 and Cu2S. and + 1 to a lesser extent. Zinc and Cd resemble the alkaline earth metals in their chemical behavior.80 V rflo = . the synonym "hypo" for fixer.10-7 The Filling ojthe d Orbitals: Transition Metals 385 tion state in solution. it can be stabilized by complexes such as CuClz.

. . Mercury also has a + 1 state in compounds such as Hg2C12• But mercury(I) always appears as the dimeric ion. The oxides ZnO. I Reduction by hydroquinone Solution of Na. exposure to light renders the silver halide of the film more susceptible to reduction to silver by a reducing agent in the developer.386 Oxidation-Reduction and Chemical Properties Sensitized AgBr ~ Unsensitized AgBr Exposed film '. a negative image formed by the finely divided silver remains oxidation state. as basic oxides should be.03 dissol ves any remaining AgBr but leaves silver Finely divided silver forms a black deposit in the "exposed" areas of the film Figure 10-4 In the photographic process. Therefore. and HgO are only slightly soluble in water but quite soluble in strong acids.. and the more rapidly varying representative elements begin. Yet ZnO is also soluble in strong bases. . CdO. The next electrons to be added must go into the higher-energy p orbitals.."'. mercury has a + 1 oxidation number in Hg2Cl2 only in the same formal sense that oxygen is -1 in hydrogen peroxide. the d orbitals are filled and the transition series are closed. Again. Hg~+. When the unreduced silver halide is dissolved away. . . H -O-O-H.S. this behavior arises because of the small size of the ZnH cation and the ease with which it can pull electrons from water molecules and cause them to release protons..' ~ . and x-ray and magnetic measurements show that the two Hg atoms are held together by a covalent bond. With these elements. hence it is amphoteric. " ~:""' . The chemistry of the + 2 state in this group is as expected.

CrO~-. Thus. thereby reflecting the greater difficulty in removing electrons from the atoms. and Cr03 is acidic. The only exception to this rule is the absence of oxidation number 5 for Co. show only the higher oxidation states. and especially the third series. the maximum oxidation number is 3 for Sc. the behavior of the lowest oxidation state will be the most metallic. Therefore. Among oxides ofCr. and increases by 1 per group to a maximum of 7 for Mn. 6. For a given element with a range of oxidation numbers. shows the full range of oxidation states. Certain physical properties of the transition metals (melting points. the energy of the 'if orbitals is sufficiently low to allow those orbitals to be utilized. Cr203 is amphoteric. ScH exists as a hydrated ion SC(H20)~+. 7. to 2 for Zn. the two s electrons and all unpaired d electrons in the outer shell. and Cu. The second. Cr(VI). CrO is basic. Oxidation potentials for the oxidation of transition metals to the + 2 or + 3 cation in aqueous solution generally decrease as the atomic number increases. compounds of V(IlI) are ionic. after . whereas V(V) has many compounds with covalent bonds. 1. whereas TiCl4 is a molecular liquid. Ni. even when coordinated to water molecules. and TiClg are ionic solids. Co. Consequently. + 2 and + 3 are especially common. 3. boiling points. and Mn(VIl) are coordinated to oxide ions in VOt. 2. In higher oxidation states. Titanium dichloride. 4. The transition metals can lose. For example. Oxidation states lower than this maximum are found. the isolated cation is not stable. and Mn04. at most. We shall explain this Co anomaly in Chapter 20 when we discuss transition-metal complexes. Sc to Zn. 10-8 THE FILLING OF fORBITALS: LANTHANIDES AND ACTINIDES After the atomic number reaches 57. Thereafter it falls by 1 per vertical column. Ti(IV) requires the stabilizing influence of coordinating groups such as hydroxide in Ti(OHMH20n+. The first transition-metal series. Oxidation states that are not stable in solution sometimes can be stabilized by the formation of complexes such as CuClz. through Fe. TiCI2. 5. and that of the highest oxidation state will be the least metallic. and V(V). . Ionization energies increase in a corresponding manner. Lu to Hg. and hardness) reflect the number of unpaired d electrons in the atoms. Such high oxidation states can be stabilized by coordination to oxide ions.10-8 The Filling off Orbitals: Lanthanides and Actinides 387 Trends in the Transition Metals What systematic trends in behavior of the transition metals can we see from the foregoing material? Some of the trends in properties are as follows. These properties increase to a maximum in the Mn group and then decrease with increasing atomic number.

Likewise in Period 7 after Z = 89. But beginning with Group IlIA. Be.) All the lanthanides and actinides are typical metals with high luster and conductivity. (Incidentally. The actinides are distinguished from the lanthanides in that they all are radioactive. it is sufficient now to know the trend and leave the irregularities until later.01 A) from one element to the next. 10-9 THE p-ORBITAL OR REPRESENTATIVE ELEMENTS After the interruptions for the transition and inner transition metals. thereby producing the 14 lanthanide metals. when the 5f and the 6d orbitals have virtually the same energy. The transition metals also vary gradually from one element to the next. Because of their high oxidation potentials (and also low first ionization energies) the metals tarnish readily in air and react vigorously with water to displace hydrogen. B. The electronic configurations of these inner transition elements are shown in Figure 9-3. as in the periodic table on the inside front cover. Some of the trends are shown in Tables 10-5 and 10-6. The most important characteristic of the lanthanides is their close similarity to one another. we see sharp variations within a group.) The transuranium actinides (Z = 93 to Z = 103) are man-made elements. is + 3. and to a lesser extent for the actinides. although these variations are systematic and fall into a pattern that can be followed across the remainder of the periodic table. nearly all compounds of these elements are ionic salts with discrete + 3 ions. Their melting points decrease with the heavier anions because these large anions cannot approach the Li+ ion as closely . Because of their great similarity. there are irregularities in thej-orbital utilization. there are 14 actinide metals. Z = 61. it is because the first element of each series=-La and Ac-have d1 configurations instead ofj1 that these series are sometimes shown to begin with Ce and Th.388 Oxidation-Reduction and Chemical Properties barium in Period 6 the seven 4f orbitals can fill successively with electrons. This similarity is due primarily to the successive electrons going into the low-Iyingf \j>rbitals. lanthanide compounds are found together in nature and are difficult to separate from one another. The Li halides are ionic. The alkali metals and alkaline earth metals are remarkable for their smooth gradation of properties within a group. with oxidation potentials in the range 2-3 V. (Promethium. But again. Table 10-5 gives the melting points of the halides of Li. more so for the actinides than for the lanthanides. which are formed when the seven 5f orbitals are filled successively with electrons.which results in small changes in atomic and ionic radii ("-'0. and C. is the only radioactive lanthanide. These metals are chemically reactive. As with d orbitals in the transition metals. The predominant oxidation state for the lanthanides. the filling of the outermost p orbitals begins again (as with B and Al in Periods 2 and 3) and goes to completion. The sharp variations occur at the transition between metallic and nonmetallic properties.

AI203. In. and are not bound as strongly by electrostatic forces. Gallium has only the + 3 oxidation state and a chemistry quite similar to AI. By this criterion. Except for boron. but + 1 is more common. They are covalent molecular compounds. Beryllium constitutes the borderline case mentioned previously. Group resemblances are even less apparent in Group IVA. It can form a limited number of hydrides. including a silvery sheen.10-9 The p-Orbital or Representative Elements 389 Melting Points of Halides of Second-Period Elements (0 C) LiX 842 800a -127 -184 614 547 490 450 Ionic -107 -23 -46 90 Covalent "Extended chains held together by ionic forces. and the heavier molecules have a higher melting point because more thermal energy is required to move them. is amphoteric. With the strongly electronegative F. and can construct multiple covalent bonds with the same atom.Note the diagonal character of the border area: The amphoteric properties of Be in Group IlA appear one period lower in the neighboring group. Aluminum also can make covalent bonds but is definitely metallic. Silicon is a nonmetal with several metallic properties. In exhibits both + 3 and + 1. With elements of similar electronegativity. TI shows both states. The acidic oxide B203 forms boric acid in water: tB203 + ~H20 ~ B(OH)3 + H20 ~ B(OH)4 + H+ Aluminum oxide. The carbon tetrahalides exhibit the opposite behavior. It can polymerize with itself in a chain to form what are classified as organic compounds. The covalently bonded chains are held together by ionic forces. and TI are basic. the boron trihalides are also covalent. called silanes. Be acquires a positive charge and F a negative charge. Carbon is a nonmetal that almost always makes four covalent bonds with other elements. it forms covalent compounds. The border between metallic and nonmetallic behavior is shown in Table 10-6. analogous to the hydrocarbons. Be forms long chains similar to those in BeCI2• But because F is so electronegative. the elements in Group IlIA are metals. in Al instead ofB. with the general formula SixH2x+2' . Boron is a nonmetal and makes covalent bonds in compounds in which it has a + 3 oxidation state. and the oxides ofGa.

bp 13°C. Inert in water CO2 Gaseous. SIF~complex in solution Si02 Solid acidic oxide. bp 1412 °C BCI3 Molecular gas. mp -90°(. acidic oxide SiCI4 Volatile molecular liquid.complex in solution AI(OH)3 Amphoteric hydroxide CF4 Molecular gas. Inert in water BF3 Molecular gas. BeF3. bp 57. in which the Si atoms are bridged with oxygen atoms: CH3 -Si-O-Si-O-Si-OCH3 I CH3 I CH3 I I CH3 I CH3 I . complex In solution B(OH)3 Boric acid. bp 520°(. Forms dimer.390 Oxidation-Reduction and Chemical Properties Properties of Elements on the Metal-Nonmetal Periodic Table BeCI2 Covalent molecular chams held together in solid and liquid by weak Intermolecular forces Narrow liquid range. mp -184°C. Forms polymeric Ions AICI3 Covalent network solid. Be2CI4 BeF2 Covalent molecular chains held together in solid by ionic forces. Forms a dimer. Hydrolyzes completely in water SiF 4 Molecular gas. Hydrolyzes completely in solution Border of the CCI4 Molecular gas above 76. Forms polymeric anions MgF2 Ionic solid. mp -12r(. mp 800 ° C. mp 400°(.complex in solution Be(OH)2 Amphoteric hydroxide MgCI2 Ionic solid. mp 1266 ° C. AI2CI6 AIF3 Ionic solid. mp -70°C. and even these low-molecular-weight silanes are explosively reactive with halogens and oxygen. BF. mp 708 ° C. mp 1040°C.8°C. the silicones. mp -10rC. Silicon can form another class of polymers.6°(. AIF~. bp 223goC Mg(OH)2 Basic hydroxide But the chains break beyond x = 6. sublimes 178°C.

54 V rflo = + 1. carbon has a + 4 oxidation state in CCl4. Bismuth cannot lose all five valence electrons. Germanium and tin have both +4 and + 2 states. and stable to heat. For Bi it is the only state. like 0. all odd oxidation numbers between -1 and + 7 are known. Silicon. Arsenic and antimony are semimetals with amphoteric oxides. except under extraordinary conditions. especially + 4 and + 6. But F. Nitrogen and phosphorus are nonmetals whose covalent chemistry and oxidation states are governed by the presence of five valence electrons: S2p3. Both oxygen and sulfur are nonmetals. or + 5. and CS2. except in OF 2 and the peroxides. is too electronegative to exhibit the positive states.10-9 The p-Orbital or Representative Elements 391 These silicones are inert.86 V go = + 1. electrically insulating. has the electrical conductivity of a metal. but have a chemistry that resembles that of sulfur.2 oxidation state. Sulfur has the . despite the science fiction writers. and only Bi is metallic. Nitrogen and phosphorus most commonly have oxidation states . and are reduced easily to anions with the S2p6 electronic configuration. and I. Br. all metallic properties have been lost. Oxygen is strongly electronegative and has only the . Carbon and silicon show the +4 oxidation state in combination with oxygen-family elements and the halogens. . The same behavior occurs in Group VA. However. and the chemistry of lead is almost wholly that of the + 2 state. + 3. radioactive element. the energy required is too high. They are only one electron short of possessing a noble-gas electronic arrangement.09 V go = + 0. a rare. at least under terrestrial conditions.36 V For Cl. but the break between metals and nonmetals is lower in the group. CO2.2 state and several positive states as well. water repellent.3. and tin and lead are metals. it does lose the three 6p electrons to produce BiH. The trend in Group VIA is similar to that in the N group. the + 3 state is the most important. is not a suitable alternative to carbon for life forms. it occurs only in the -1 state. For example. With Group VIlA. Germanium is a semimetal. For As and Sb. Polonium. Selenium and tellurium are semimetals. Their reduction potentials are F2 + C12 + Br2 + 12 + 2e2e2e2e- -7 -7 -7 -7 2F2Cl2Bc 21- go = + 2. thus the halogens are nonmetals.

A species that undergoes self-oxidationreduction is said to disproportionate. and common oxidation number. The border between metals and nonmetals sweeps diagonally across the periodic table in an ill-defined band that goes approximately from Be and B to Po and At. The maximum oxidation number exhibited by an atom of an element generally increases across a period.05 V] are very large. In a balanced redox equation the total number of electrons lost by the reducing agent is equal to the total number gained by the oxidizing agent. AP+( +3).392 Oxidation-Reduction and Chemical Properties Atoms in complex ions and compounds are assigned oxidation numbers as an aid in keeping track of electrons during chemical reactions. In a redox reaction electrons are transferred from the reducing agent to the oxidizing agent. BeO and A1203 are amphoteric. all of which can be related to the number of unpaired d electrons. Mg. K. The reduction potentials of the halogens to form halide ions are all large (F2 + 2e. The oxidation potentials of the alkaline earth metals (Be. Sr. IJ 0 = + 3. IJo == + 2. for example. and CI04(+7). all S2) to form + 2 hydrated cations [Ca(s) ~ CaH + 2r. In the third period. .86 V). boiling point. elements in the second and third transition series are more similar in size and in chemical properties than are those in the first and second periods. The tendency for a substance to gain electrons in aqueous solution is called its reduction potential. The oxidation number of an atom is often called the oxidation state of that atom (or element) in a compound. Na. Because of the lanthanide contraction. Ca. PF5(+5). IJ 0 = + 2. Balancing a redox equation is equivalent to requiring that electrons be neither created nor destroyed. The tendency of a substance to lose electrons in aqueous solution is known as its oxidation potential. The oxidation potentials of the alkali metal elements (Li. Rb. The normality therefore depends on the reaction that the redox agent undergoes. SF6(+6).76 V] are also large. we have the following: Na+( + 1). The equivalent weight of a redox agent is equal to its molecular weight divided by the oxidation-number change it undergoes in the reaction under consideration. The oxides of elements at or near the borderline often exhibit amphoteric (both acidic and basic) behavior. The normality of a redox agent is the number of equivalents in 1 liter of solution. SiC14 (+4). The transition metals undergo a smooth variation in melting point. Cs. all Sl atoms) to form hydrated cations of + 1 charge [Li(s) ~ Li+ + e-. MgH( +2). Reactions in which the oxidation states of atoms change are called oxidation-reduction (redox) reactions. Ba. In such reactions the species whose oxidation number increases is called the reducing agent (reductant) and the species whose oxidation number decreases is called the oxidizing agent (oxidant). For example.~ 2F-. hardness.

How are the suffixes -ic and -ous associated with oxidation state? Match the following formulas and names: a) Sulfuric and sulfurous acids: H2S03 and H2S04 b) Nitric and nitrous acids: HN02 and HN03 3.Self-Study Questions 393 1. electrons are neither created nor destroyed. Give the equivalent weight of sulfuric acid. What is the normality of a O. whereas Ag and Au are? 13. follow from what you learned in Chapter 9 about ionization energies and electron affinities? 5. the total oxidation number is conserved? 4.1M solution of sulfuric acid in each of the three processes of Question 8? 10. What is the difference between oxidation potentials and reduction potentials? 12. which deals with the relative oxidation numbers of nonmetals. How does this principle lead inevitably to Rule 8 (Section 10-1): In chemical reactions. What pattern of maximum oxidation numbers can be seen across a period in the transition metals? 7. Oxidation numbers are a convenient bookkeeping device for keeping track of electrons. What is the oxidation number of Co in K3CoF6? In K2CoI4? 2. Is a substance that gives up electrons in a reaction an oxidizing agent or a reducing agent? Is it oxidized or reduced? Does its oxidation number increase or decrease in the process? 8. The principle of conservation behind balancing redox equations is this: In a chemical reaction.00V Is the turbidium a good oxidizing agent? A good reducing agent? Or is it neither? Is the TuH ion a good oxidizing agent? A good reducing agent? Or is it neither? 11. How are the most common oxidation states of the representative elements related to their group numbers? 6. How does Rule 5. in each of the following processes: a) An acid-base titration b) A redox reaction in which the sulfate ion goes to sulfite c) A redox reaction in which the sulfate ion goes to sulfide 9. From which metal can electrons be ejected with light of a longer wavelength. Na or Cs? Why? . H2S04. The imaginary element turbidium (Tu) has the following oxidation potential: 80 = -3. they are useful even though in the actual reaction electrons are not totally removed from one atom and entirely given to another. Why are Li and Na not found free in nature.

rather than 5s2 as in Sr? 19. Why do Zn. and many other metals differ from iron oxide in a way that has great economic importance? Try to imagine a world in which iron oxide behaved the same way. Xenon forms several nonionic compounds with F and O. How is the color of a chemical related to electronic transitions between energy levels? 23. Cu. What is the lanthanide contraction? Why does it occur? What detectable chemical effects does it produce? 18. and W? 26. which state is usually most metal-like in its compounds? Can you give an example? 21. including CsXeF7 and Cs2XeF s. Why is BeO amphoteric? What does this term mean In relation to chemical behavior? 17. why is the outer electronic configuration of ZrH 4d2. Why is calcium harder than potassium? 16. What are the principal oxidation states of nitrogen and phosphorus? Oxidation numbers 1. How does the maximum oxidation number change with atomic number in the first transition-metal series. and Au? 30. and XeF6• 2. do the higher or lower oxidation states become more important? Can you give a reason for this behavior? 22. What aspect of electronic structure explains the high electrical conductivities of the coinage metals. In a transition metal with several oxidation states. Which element is more metallic. XeF2. Xe03. Sb) rather than in one group separating the metals from the nonmetals? 27. Mo. Ge. Sc to Zn? 20. What important chemical industry would be badly hurt if this were so? 25. How does metallic character change within one group of the table? 28. AI. Cu.394 Oxidation-Reduction and Chemical Properties 14. How do the oxides of Cr. Give the oxidation number of the central Xe atom in each of the following compounds: Xe04. Xenon can also form a number of ionic compounds. and Hg have such low melting points compared with Cr. Why are transition-metal compounds more often colored than those of the representative elements? 24. AI. As the principal quantum number of the element increases within a transition-metal group (vertical column). Why do amphoteric oxides appear for those elements that lie on a diagonal across the periodic table (Be. Ag. What are the ions in each compound? What are the ionic charge and oxidation number of Xe in each ion containing Xe? . Ni. Cd. Be or Ba? What evidence permits you to say this? How can you explain this in terms of electronic configuration? 15. If the first electrons after those in the Kr noble-gas shells go into the 5s orbital for Rb and Sr. XeF4. Are the halogens good reducing agents or good oxidizing agents? 29.

£_H3. What is the oxidation number of nitrogen in each of the following ions or molecules: NH3. SF4? 4. Phosphine. (c) barium chloride.-i> 5S0~. PH3. For each of the following reactions. Mg3N2' NF3. C2H6. 12.+ 3H20 10. Balance the following equations by the oxidation-number method: a) H2S + Cr209.-i> S + CrH (acidic solution) b) NH3 + 02 -i> NO + H20 c) N02 + MnO:) -i> . the reducing agent. Mg(OH)2. phosphine can be prepared by adding water to calcium phosphide. Cr20~-. P205. the substance oxidized. Traces of P 2H4 are produced simultaneously and cause the PH3 to ignite in air to give pale. What is the oxidation number of the central atom in each of the following ions or molecules: Co(CN)~-. (d) ethane. (h) phosphorus pentoxide. Write a balanced equation for the reaction. Balance the following equations by the half-reaction method: a) MrrO. Ag (NH3)t? b) SH+ c) 3Clz 395 + + Cr20~60H- + 6Hl -i> 2CrH + 312 + 7H20 -i> CI0s- + 5Cl. N02. + KOH + 02 -i> K2Mn04 + H20 b) CuCI~. LiH.+ Cu -i> CuCl2 (acidic solution) Redox equations 8. BaCI2. SnO. (i) magnesium hydroxide. what is the net charge on each side of the equation? What element is oxidized? What element is reduced? 9. Sn02. £_20~-.Problems 3. ICI5. N20. (m) perchloric acid. MnOz + 1- + H+ -i> MnH + 12 + H20 is balanced. (0) cyanide. list the substance reduced. highly toxic gas that smells like rotten fish and is produced in small amounts when animal and vegetable matter decay in moist situations such as damp graveyards. (1) hypochlorous acid. (n) dichromate. HClO. N0s-? 5. 11. PtCI~-. (b) iodine. Au. CO§-. When the equation .(basic solution) e) H2 + OF2 -i> H20 + HF f) MnOz + Al -i> Al203 + Mn 13. H2S03.+ Mn02 (basic solution) d) NH3 + CIO. N2H4. Balance the reaction MnO:) + H+ + H2S -i> MnH + H20 + S What is the oxidation number of Mn in MnO:)? What element is oxidized? What element is the oxidizing agent? Is this latter element oxidized or reduced? 12. H202. (f) stannic oxide. Assign oxidation numbers to the atoms in the following chemical species: (a) gold." In the laboratory. Assign oxidation numbers to each of the elements present. H6Te06. flickering lights commonly called "corpse candles" or "will-o'-the-wisps. What is the oxidation number ofthe underlined element in each ion or molecule: Vat. and the oxidizing agent. NO. (k) telluric acid. CN-. a) 6H+ + MnO:) + 5S0~. HCI04. NOs. 7. (g) nitrous oxide.+ 2MnH + 3H20 . (e) stannous oxide. N02. (j) sulfurous acid. is a colorless.KN02. What is the oxidation number of platinum in the complex ion PtCI~-? 6.-i> N2H! + CI.

396 Oxidation-Reduction and Chemical Properties Zn --7 NHt + ZnH (acidic solution) d) CI02 --7 CI02 + ClOg (basic solution) e) FeH + Cr20~. (a) When H3P04 reacts with NaOH to produce NaH2P04.540M FeH solution. Exactly 6.with sodium hydroxide. 16.+ H2S03 --7 CrH + HS04 (acidic solution) d) Mn04 + VH --7 + MnH (acidic solution) e) FeS04 + NaCI02 --7 Fe2(S04)3 + NaCI (in sulfuric acid solution) f) KN02 + KMn04 --7 KN03 + Mn02 (in KOH solution) g) Mn04 + OH. water is added so the final volume of solution is 100 ml. how many equivalents of H3P04 are there per mole? (b) When H3P04 is reduced to H3P02. What is its normality when reacted with (a) dilute FeS04 to produce FeH. and reaction 4 yielded MnH. (c) reduction to S2-.--7 POl.--7 FeH + CrH (acidic solution) f) Cu + NOg --7 CuH + NO (acidic solution) c) NOg + equivalent weight of KMn04 and the normality of the potassium permanganate solution for each reaction. Twelve grams ofKMn04 were dissolved in sufficient water to make a liter of solution. Balance the following equations by any method you choose: a) H3PO~ + CO~. normality. thereby producing Mn02 as a product. (b) oxidation to SO~-. Reaction 3 gave MnH in acid solution.10M in TiOH. (c) concentrated H2S04 to produce Ti4+? 21. 18.40 g of gaseous S02 are absorbed in 95 ml of water. (a) What is the molarity of the solution? (b) The solution will be used in a titration in which the dichromate ion is reduced to CrH. (b) dilute FeS04 to produce TiH.+ 109 + H20 h) KMn04 + NH3 --7 KN03 + Mn02 + KOH + H20 vot Molarity.+ 1. Calculate the . Calculate the molarity of the solution.--7 MnO~. (d) reduction to elemental sulfur.52 g of the salt to fill a 100-ml volumetric flask. An acidic solution is 0. Reaction 1was carried out in basic solution. K2Cr207. is made by adding enough water to 3. Reaction 2 was carried out in very strong base to give MnO~-. What is the normality of the solution? 17. The solution was divided into parts and used in four different reactions. When absorption is complete. redox equivalents 15. Find the equivalent weight of an oxidizing agent that oxidizes FeH to FeH if 0. Calculate for each of the following reactions the volume of solution if this composition that contains 1 equiv ofH2S03: (a) neutralization to SO~. What is its normality when reacted with (a) dilute NaOH to produce Ti02.OlM in C12. how many equivalents of H3P04 are there per mole? 19. 20. (b) dilute H202 to produce HCIO? I 14.--7 Mn(OH)2 + SO~(basic solution) c) H+ + Cr20~.664 g of the compound requires 23. A solution of potassium dichromate. A slightly acidic solution is O.5 ml of 0.+ CO2 + H20 (neutral solution) b) Mn02 + SO~.

J.l0NH2S03? 27. L. What volume of 0. 1970.10N solution of KI in aqueous KOH at STP. the following reaction can be written: Mn04 + H2S + H+ ~ Mn2+ + S + H20 Balance the equation.) 23.~ CuI + 13 1.~ 13 + S20§. J. what volume of C12 gas is required to react completely with the KI? (KI normality is based on its reducing action.0250M sodium thiosulfate.50 ml of the Representative Elements) Bogden and Quigley. If 12. A 25. what is the molarity of the unknown copper solution? The unbalanced reactions are Cu 2+ + I.) (b) Write a balanced equation for the reaction.8 g of potassium permanganate per liter? (g) What is the molarity of a solution that contains 4.25 g of potassium permanganate per liter? + HI ~ H2S + 12 + H20 calculate the number of moles of sulfuric acid consumed by reaction with 25. Dye.05N solution of H2S is used to titrate 50 ml of permanganate solution.00 ml ofO. "The Solvated Electron. When H2S reacts with KMn04 in acidic solution. Write a balanced chemical equation for this redox reaction. 70 ml are required to reach the end point.) 24. Bigelow.01 mole of oxalic acid? (e) How many equivalents of oxalic acid can be oxidized by 0. The .0 ml of a solution containing 6. and the liberated iodine is titrated with 0. Mn2+. (Check first to see if the reaction is balanced. (a) What are the oxidation numbers of C and Mn in the reactants and products? (None of the substances is a peroxide.25N KI03 is required for the complete oxidation to sulfate of 125 ml ofO. If chlorine gas is bubbled through a basic solution of potassium iodide. permanganate ion will oxidize oxalic acid (COOH)2 to carbon dioxide while being reduced to manganous ion. Given the equation H2S04 26." Scientific American) February 1967.l00NHI.00-ml sample of an unknown copper solution is treated with excess potassium iodide in acidic solution. the following reaction occurs: KOH + C12 + KI ~ KCl + KI03 + H20 Balance the equation. 103 is reduced to 12 in acidic solution. If a 0.04 equiv of potassium permanganate? (f) What is the normality of a solution that contains 15. If chlorine gas is bubbled through 25 ml of a 0.+ S40~- 22. In acidic aqueous solution. What is the normality of the original permanganate solution? What is the molarity? 25.Suggested Reading 397 thiosulfate solution are required to reach the end point. In oxidizing H2S03 to SO~-. (c) What are the molecular weights and equivalent weights of the reactants KMn04 and (COOH)2? (d) How many moles of permanganate can be reduced by 0. M. New York.5 g of oxalic acid per liter? (h) What weight of oxalic acid can be oxidized to carbon dioxide by 150.

Menlo Park. Calif. Benjamin. W. Reinhold. R. Reinhold. Calif. Keyworth. 1963. K. E. R. Benjamin.. Chemical Periodicity. The Chemical Elements. A. A. Menlo Park.398 Oxidation-Reduction and Chemical Properties J. M. Brief Chemistry of the Elements. Rich. W. 1965. Bogden and Quigley. 1960. J. T. Larsen. Transitional Elements. .. Properties and the Periodic Law. Ford-Smith.. Sisler. W. H. Periodic Correlations. Laidler and M. Electronic Structure. 1971. 1970. Benjamin. New York. 1965. H. Hall and D. H. Menlo Park. A. New York. New York. A. Sanderson. L. L. Calif.

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