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.

--+--+--~~--I B o 2 3 4 5 6 • Inner 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_:. crosses show the less common ones. . VIA. and UH). 17 16 Figure 10-1 OXidation numbers of atoms of the representative elements. Eu2+. and with minimum negative values equal to -(8 . Note the periodicity of oxidation numbers. The most common values are indicated by filled circles.I--+. with maximum positive values equal to the group numbers. 15 14 13 12 11 10 9 8 7 6 5 4 3 F s.g. Lanthanide and actinide elements compose another type of transition series.gn) for Groups VA. gn. and VilA..--+--r~~1 I. The next most common positive oxidation number is usually gn . in which adjacent elements have very similar properties.l metals 20 19 18 Ca K I Arr-~_'--+-?f--r--L_. Ce4+. Other oxidation numbers are possible and in some cases more commonly encountered (e.2. N r + I! It I 0 N C B Be Li 2 Ber-~_'--+-_'~r-~_. The oxidation number + 3 is common to all lanthanides and actinides in their compounds.

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

Thus. and oxygen oxidizes (the origin of the term) iron: 4Fe I 12e- + 302 ~ r 4Fe3+ + 602- (in the form of2Fe203) By donating electrons. The acceptance of electrons by a substance must cause a decrease in oxidation number. iron reduces oxygen. it is reduced. or it can act as a reducing agent and be oxidized to MnH. encountered under ordinary conditions in solids and in aqueous numbers have been observed only in rare complex ions or reduction (redox) reactions. in the intermediate oxidation states it can be either an oxidizing or a reducing agent.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. The asterisk indicates that oxidation unstable compounds. copper reduces silver ions. 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. in rusting. The ion Mn3+ can act as an oxidizing agent and be reduced to MnH.10. Mn3+ in solution is unstable and spontaneously disproportionates with self-oxidationreduction to give the + 2 and + 4 oxidation states: 2Mn3+ + 2H20 ~ MnH + Mn02 + 4H+ . Some common oxidizing and reducing agents are listed in Table 10-3. those containing an atom or atoms whose oxidation numbers decrease are called oxidizing agents (or oxidants).. If an atom's oxidation number increases.2 Oxidation-Reduction Reactions 363 Oxidation Numbers of First-Row Transition Metalsa 7 6 5 MnO:. It follows that an oxidation-reduction reaction may be thought of as one in which the reducing agent gives electrons to the oxidizing agent. the atom is oxidized. if its oxidation number decreases. whereas the loss of electrons must involve an increase. In fact. Species containing an atom or atoms whose oxidation numbers increase are called reducing agents (or reductants).

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

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. With the ion-electron method we consider a redox reaction to be the formal sum of two half-reactions. and since K2Cr207 has two Cr atoms. Oxidation-Number Method 1. 10-3 BALANCING OXIDATION-REDUCTION EQUATIONS Let's look at a reaction involving K2Cr207 and HI. becomes a base. you will be able to make more and more predictions. This process is similar to that described by the Brzinsted=Lowry acid-base theory (Section 5-3). and every base. . by accepting a proton. especially in the laboratory. when each oxidizing agent reacts it becomes a potential reducing agent. 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. If we assume that the reactants and products are known.1 in HI to zero in 12 and loses one electron per atom in the process. in which every acid. Imagine that each Cr atom accepts three electrons to change its oxidation state from + 6 to + 3. chromium (Cr) goes from + 6 in K2Cr207 to + 3 in Cr3+(CI04)3. In equation 10-1. Write the oxidation numbers of these atoms above the appropriate symbols on both sides of the equation. * then the problem is how to find the mole ratios and balance the equation for the reaction. and vice versa. There must be three times as many I atoms involved as Cr. one that donates electrons and one that accepts them.10-3 Balancing Oxidation-Reduction Equations 365 Furthermore. becomes an acid. Iodine goes from . 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. by giving up a proton. 2. Now choose enough of the reductant and oxidant so the electrons lost by one are used completely by the other. Identify the elements that change oxidation number during the reaction. As you gain experience.

one involving Cr and one involving I. 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). Section 1-7) are examples of half-reactions that actually occur. and then to combine enough of each half-reaction to cancel all the free electrons. simplify the reaction by eliminating all spectator ions (those ions that do not really participate in the reaction). 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. Balance the hydrogens. For example. The sequence of balancing steps can be summarized as: oxidation numbers-cations-anions-hydrogensoxygens. a. Ion-Electron (Half-Reaction) Method It is often useful to pretend that oxidation and reduction are occurring separately.366 Oxidation-Reduction and Chemical Properties 3. Cr20~- + 1- + H+ ---7 CrH + 12 + H20 2. Balance the anions that do not change (CI04 in this case): ---7 + + + + 312 + H20 312 + 7H20 5. The unbalanced reactions are Cr20~21---7 ---7 2CrH 12 . First. and make sure that oxygen is also balanced: ---7 The balancing process is thus completed. In what follows we shall balance the same equation by another method. 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. Now construct two balanced half-reactions.~such as K+ or CI04. Chemical reactions occurring at electrodes in batteries or electrolysis cells (Chapter 1. The K2Cr207 reaction can be balanced by half-reactions as follows: 1.

Balance the charge by adding electrons: 6e- + Cr20~. let's balance the equation representing the reaction between potassium permanganate (KMn04) and ammonia (NH3) that produces potassium nitrate (KN03). III Oxidation-number method. However. Balance the atoms in each half-reaction by adding H+ and H20 if the reactions occur in an acid medium. and the two 1. make sure that the number if atoms on both sides is the same. The two Cr require six electrons.on either side. and water. The unbalanced reaction is . As a second example. manganese dioxide (Mn02). 3. and that there are no net electrons left.+ 14H+ 21- ---7 ---7 If the half-reaction is balanced properly. 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. 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.10-3 Balancing Oxidation-Reduction Equations 367 h. 0. no atoms needed) 2CrH + 7H20 12 + 2e- + 7H20 c. that the charges balance. or H20 and OH. 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.produce two electrons. and H atoms balanced) (no H+ or OH.if the reactions occur in a basic one: Cr20~- + 14H+ 21- ---7 2CrH 12 ---7 (Cr. the number of electrons will indicate exactly the change in oxidation number. potassium hydroxide (KOH). At this point the equation as it stands is balanced.

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

+ 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.are needed to balance the oxidation-number change for each CI03: CI03 + 3S0~.+ 2H+ + 2e+ 6H+ + CI03 ~ CI.+ £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§. CI03 Solution + SO~.+ 3H20 H20 + SO~.3H20 3S0§.+ 3H20 3H20 + 3S0~.~ CI- + 3S0~- Since 12 oxygens appear on each side.+ 6H+ + 6e+__ow + CI03 ~ CI. Use both oxidation-number and ionelectron methods. In a . In the ion-electron method the reaction is divided into halves: CI03 ~ SO~.~ SO~.~ 3S0~.~ 3S0~.~ CISO~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. gains 6e- +5 CI03 + +4 -1 + SO~.+ 3H20 SO~.~ CI- + SO~- By the oxidation-number method.~ I CI- loses 2e- + +6 SO~- t Three moles of SO~.+. the equation is balanced.10-4 Redox Titrations 369 Balance the following equation involving the oxidation of sulfite (SO~-) to sulfate (SO~-) by chlorate (CI03).

If a chloride ion is oxidized to C12.127 mole liter " = 0.0-ml solution containing 1.00_g__. As with neutralization reactions. we find the molarity: 1. What is the molarity of the solution? What is the normality? Solution First. In the oxidation of a Group IIA metal. and each mole of magnesium metal furnishes 2 equiv of reducing ability.0500 liter = 0. In the reaction Na __" Na+ + e: the sodium undergoes a change in oxidation number of one unit.K. 1 mole X 1 0. 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. for when all of an oxidizing agent in a sample has reacted with a solution's reducing agent from the burette.Mrr(J. the number of equivalents of oxidant and reductant is the same. so the equivalent weight of sodium in this reaction is equal to its atomic weight. In titrations using solutions of oxidants or reductants as reagents. it is convenient to use equivalents. During the reaction. But if the reaction is -1 Cl" + +5 3HzO __" CIO. Mn04 is reduced to MnH.127M . The equivalent weight ofHCI in an acid-base neutralization reaction is equal to its molecular weight.370 Oxidation-Reduction and Chemical Properties similar way.K. the equivalent weight of Mg in this reaction is half its atomic weight. X 4 158_g__. Therefore. + 6H+ + 6e- then each HCI furnishes 6 equiv of reducing power.00 g of KMn04 is used in titrating a reducing agent. Mg __" Mg2 + + 2r each atom of magnesium changes by two oxidation-number units. A 50. the normality of a solution is the number oj equivalents per liter oj solution.Mrr(J. The equivalent weight of HCI in a redox reaction depends on the change in oxidation number of chlorine during the reaction. . -1 0 Cl : __" tCl2 + e: then there is one redox equivalent per HCI. and the equivalent weight is one-sixth the molecular weight. and the equivalent weight and molecular weight of HCI are identical.

) Normality ofKMn04 · M oIanty 0 fKM n 0 = x = 0.38 ml of KMn04 solution of unknown strength. with two carbon atoms. so each Mn04 provides 5 equiv of oxidizing power.100M Na2C204 solution is 0. provides 2 equiv of reducing power.00 equiv mole= = 0.0720M 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: .25-ml solution ofO. [One milliequivalent (meq) is 10-3 equiv.38 ml X x meq 1 ml 1 ml (Note that 1 meq ml :' = 1 equiv Iiter=I.25 ml X 0.] So meq Na2C204 = meq KMn04 31. and the molarity of the KMn04? Solution The reaction is +7 2Mn04 +3 + 5C20~. and the normality is five times the molarity: 0.10-4 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. What is the normality of the Na2C204 and of the KMn04.100MNa2C204 (sodium oxalate) in acid is titrated with 17.635 equiv liter ? = 0. Another way of understanding this is to write the two half-reactions: Mn04 + 8H+ + 5eC20~---? ---? MnH + 4H20 2C02 + 2e- For this reaction the 0.+ 16H+ ---? +2 +4 2MnH + 10C02 + 8H20 Manganese goes from + 7 to + 2.635N A 31. The milliequivalents of oxidant and reductant are equal at neutralization. Carbon goes from +3 to +4. so each C20~-.360_eqlli-v-liter-1 = ---~---5_equivmole-1 = 0.200 meq = 17.127 mole Iiter ? X 5.360N 0.0720 mole liter-l = 0.200N. the equivalent weight of KMn04 is one-fifth the molecular weight.

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

10-6 CHEMICAL PROPERTIES: THE s-ORBITAL METALS Knowing the electronic structures of atoms. or other elements. Virtually any substance capable of being reduced . always in the + 1 oxidation state.76 V. These metals are the most reactive known. All their compounds are ionic. Na. Not every chemical property becomes absolutely clear once we know the electronic structure of an atom of an element. The electron is lost easily. Don't try to memorize all the facts given here. chlorine. and those that can be explained by electronic structure. try to pick out of the descriptive material those properties that show regular trends across the periodic table. K. Write an equation for the oxidation of calcium in aqueous solution. but much of what we observe does make sense now. the reduction potential for the reduction of a sodium ion to metallic sodium is -2.71 V. and Cs All the alkali metals have an Sl outer electronic configuration. Ionization energy and electronegativity decrease from Li to Cs as the distance between the outer shells and the nucleus increases.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. Group IA. we can interpret the chemical properties of the metals in a reasonable way.76 V) shows that Ca2+ is definitely not a good oxidizing agent. If the oxidation potential for the oxidation of metallic sodium to sodium ion is +2. and it is this sense that we shall look for in the mass of chemical data. Rb. these elements thus have low ionization energies and low electronegativities.76 V 80 = -2. instead. They occur in combination with oxygen. and never occur naturally in the metallic state. the accepted international convention is to use reduction potentials. The oxidation potential of metallic calcium is + 2.71 V. Although we find it convenient to work with oxidation potentials.76 V The reduction potential refers to the reverse reaction + 2e- -7 Ca(s) The very negative reduction potential (-2. even the hydrides. Alkali Metals: Li. 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.

A typical reaction is D. Because the alkali metals are the strongest reducing agents known. and ductile. With only one mobile electron per atom. and the reaction with all these metals is violent and exothermic. The oxides of the alkali metals are basic.. and are soft. Water attacks all the alkali metals. Na+ ___. from Li to Cs..92 V.H~98 = -167 kJ The hydrogen gas evolved is ignited by the heat of the reaction and burns spontaneously in air. Almost all the compounds of the alkali metals are soluble in water.2. the metals are usually prepared by the electrolysis of their molten compounds. metallic bonds are weak. The alkali metals ordinarily are stored in kerosene or some other unreactive hydrocarbon.92V + 2. The bonds become weaker with increasing atomic number as the valence electrons become more distant from the nucleus.. are Li(s) Na(s) K(s) Rb(s) Cs(s) ___.. Color is produced when an electron in an atom is excited from one energy level to another.. Lithium loses electrons in solution more readily than Cs. The easily lost valence electron is responsible for the metallic properties of the alkali metals. Li + oxidized substance Instead. The metals have low melting and boiling points. The alkali metal ions have no free electrons to be excited by energies in the visible region. The oxidation potentials of the alkali metals.374 Oxidation-Reduction and Chemical Properties will be reduced in the presence of an alkali metal. Li+ ___. and when the difference in energy of these levels is in the visible portion of the spectrum. because the small size of a Li+ ion permits water molecules to approach the center of the ion more closely.Cs+ + e: + e: + e: + e: + e: go go go go go = = = = = + 3.. in spite of the higher ionization energy of Li. In contrast. in which the optical image falling on cesium-coated cathodes is converted to electrical impulses. Cesium has the lowest ionization energy of any element. The alkali metal ions in solution are colorless. Lithium can be cut with a knife with difficulty.92V Each of these metals has a strong tendency to lose electrons and become oxidized in solution. malleable. and all react with water to form basic hydroxides that are soluble and completely dissociated.05 V +2. potassium ions have a reduction potential of . but Cs is as soft as cheese. + K ___. its valence electron can be ejected most easily by tight in a photoelectric cell. b+ R ___. it is difficult to reduce their ions. .71 V +2. The photoelectric effect is used in photo cells and in television cameras such as the iconoscope. this makes the hydrated ion quite stable.92 V +2. the free metals cannot be prepared conveniently by reduction of their compounds with another substance: Li+ + reducing substance ___.

This leads us to expect a strong tendency to oxidize in aqueous solution and a large positive oxidation potential. Alkaline Earth Metals: Be.37 V +2. Thus. for the same reason that it has a higher first ionization energy than other elements in the group. Ca. Sr. The intense color has been shown to arise from the solvated electrons and not from the metal ions. Beryllium has a lower oxidation potential.85V +2. The nuclear charge has increased by one from the alkali metals in a given period. nevertheless all their compounds. like Li. Mg. has a high hydration energy because of its small size. or lower tendency to lose an electron in solution. Group IIA. The hydration of the doubly charged cation gives it enough extra stability to overcome the energy required to remove the second electron.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. However. 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. we might expect + 1 ions to form and the + 1 oxidation state to exist in solution.76 V +2. and Ba The chemistry of the alkaline earth metals is the chemistry of atoms with two easily lost electrons. so the oxidation potential is somewhat lower than might be expected. All are typical metals and strong reducing agents (although not quite as strong as the alkali metals). the alkaline earth atoms are smaller and have higher first ionization energies than those of alkali metals in corresponding periods.90 V They are more electronegative than are the alkali metals. Any solution of Ca+ ions . and these two effects combine to dominate in the oxidation of Be to BeH. thus. 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. but the screening of the nucleus by electrons in inner orbitals is similar for both groups. and the electrons associate with the NH3 solvent molecules. Such electrons are known as solvated electrons. the same color can be produced by introducing electrons into ammonia from a platinum electrode.89 V +2. The second ionization energies of these metals are usually double their first ionization energies. The atoms dissociate into positive ions and electrons. with the exception of some Be compounds. But this is not the case. It is true that Be. This behavior is reflected in the greater electronegativities of the smaller atoms within a group (Table 10-4). so the net nuclear charge is greater. Be has an extraordinarily high ionization energy and energy of vaporization (Table 10-4). are ionic.

is found as chalk.086 1.0 0. and phosphates. calcium. Sr. usually from deposits of shells and skeletons of marine organisms. and marble. and barium occur as the relatively insoluble carbonates. CaC03. Calcium carbonate. Beryllium and magnesium are found in complex silicate minerals such as beryl (Be3A12Si601s)and asbestos (CaMg3Si4012) (Chapter 14).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.0 1. Alkaline earth compounds are generally less soluble in water than the compounds of the alkali metals.3 1. The free metals do not occur in nature because they are too reactive. The hydrides of Ca.91 769 1384 9.2 129 708 1412 29. and BaH2) are ionic and are white powders that release H2 gas upon reaction with water: . Like the alkali metals. For the same reason. and Ba (CaH2' SrH2. sulfates.36 651 1107 9. Beryllium and magnesium are the only elements in this group commonly used as structural metals. The pure metals have higher melting and boiling points than do alkali metals because they have two electrons per atom for forming metallic bonds.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. 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.6 0. limestone.95 1. Emerald is impure beryl.2 139 873 1250 0. Calcium and magnesium are much more common than the other elements in the group. colored with a trace of chromium.98 725 1140 7. they are harder.2 150 772 1600 52. although they still can be cut with a sharp steel knife.74 842 1487 9. strontium.0 1. because of their lightness they are used pure or in alloys for aircraft and spacecraft.89 1.89 1278 2970 11 .7 295 405 520 0. DC) Equivalent conductivity of MCI2 (ohm-1 mole-1) 1. DC) MCI2 (boiling point. Magnesium. in which weight is an important factor.

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

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

including the first transition-metal In sol ution from the solid of series. as does Al.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. Chemical Properties of Individual Groups: Sc and Ti Groups The Sc. d5 configuration is present instead of a filled dlO• The d electrons must be disturbed when a + 3 ion is produced. But SC203 is . Potentials are for the prod uction electronic IS of Simple cations structure +3 The potentials and for K.Y-Lu triad has the outer electronic configuration dls2. and shows only + 3 oxidation states. Ca. it is quite easy to remove the two s electrons in Zn and leave the stable. and Sc are given for the production Transition-metal electronic + 1. the representative elements following a transition series achieve their maximum oxidation number by losing all their electrons outside the filled dtO shells. 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. filled dlO orbitals untouched. so we do not have the local fluctuations observed in the + 2 curve. The properties of these elements are similar to those of Al in Group IlIA. All react with water. In contrast. in which a half-filled. This same effect is observed to a lesser extent in Cr and Mn.0 Figure 10-2 Oxidation metals potentials for the fourth-period metals. + 2. The elements preceding the transition series become cations by losing all their electrons outside the inner noble-gas shells.

+ 3. they are likely to lose all of them. If they lose some electrons. and yellow light (ca. the tetrachloride. whereas Hfhas only +4. because Sc3+is larger than AP+. and the + 4 state is more covalent and nonmetallic. consequently. VCl4 is a molecular liquid with a boiling point of 154°C. it has the NaCl crystal structure. In contrast. and + 5. At low temperatures an oxide coating protects them. In aqueous solution. Most electronic energy levels are so far apart that the radiation absorbed in an ° . Like Ti. which has the d2s2 electronic configuration. The chlorides provide a particularly good illustration of this progression of properties.380 Oxidation-Reduction and Chemical Properties a basic oxide rather than amphoteric. insoluble pigment that has both basic and acidic properties. TiCls. is a white. The difference in behavior resembles that between CaO and BeO. is a strong reducing agent and oxidizes spontaneously in air. Ti02. Zr. +3. V02+. like AI20s. the dioxide. In the Ti-Zr-Hf triad. In contrast. TiC12. Vanadium(V) as VO~. At the top of the group. It boils before TiCls melts (decomposes) because it is a molecular compound with covalent bonds. 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 only the +5 state is important in Nb and Ta (although some +3 and +4 compounds are known). The dichloride. there is no aqueous chemistry of TiH. red light (ca. and the VH ion is violet. and +4 oxidation states. 560 nm). VZ05 is amphoteric like TiOz. is another strong reducing agent and is an ionic solid that decomposes at 440°C. these metals react easily with N. 610 nrn). is deep blue. and it is difficult to prepare them by the high-temperature reduction processes used with Fe and other metals. respectively. and at high temperatures. The lower oxidation states of Ti are ionic. and Hf. is a stable liquid that freezes at . 680 nm). It dissolves in both acids and bases to form complex and poorly characterized polymers. the nucleus. The + 4 oxidation state of V is also on the borderline ~tween ionic and covalent character. In contrast. Ti and Zr shows +2. TiO. is basic and ionic. Vanadium has oxidation states of + 2. The Vanadium Group and the Colors of Ions and Complex Compounds The chemistry of the V -Nb. C. Titanium (II) oxide. the metals are more inert than their oxidation potentials would suggest. TiC14.is colorless. + 4. the vanadyl ion. The color'S we see are the complementary colors to those absorbed (Table 20-2).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. the V3+ ion is green. The vanadium ions provide good examples of the colors that are typical of transition-metal compounds. It is an ionic solid that decomposes at 475°C in a vacuum. Titanium trichloride.25°C and boils at + 136°C. Since it reduces water to H2. the V(IlI) compounds are ionic. Only these colors are seen from the entire visible spectrum because the three solutions absorb orange light (ca.

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

MnH shows little tendency to go to higher oxidation states. Mn is by far the most important. element 103 was named). tensile strength. and shock resistance. Chromium(II) is a good reducing agent. The oxidation states Mn(III) through Mn(VI) are rare. Rhenium was discovered in 1925. and tungsten (W) is used in steel cutting tools that remain hard even when red hot.. Cr203 is amphoteric. in 1937. Technetium was discovered by Perrier and Segre. MnH + 4H20 s» = + 1. Manganese(II) in water forms the pink Mn(H20)~+ octahedral complex. It is strongly resistant to oxidation and is not a good reducing agent.49 V . and that the reaction tends to go in the other direction: = -1.33 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.33 V Of the Mn. As we would expect. these three metals are used mainly as alloying agents in steels. except for the chief natural ore. Unlike TiH. A common anion is the yellow chromate ion. molybdenum acts as a toughening agent._.- + 8H+ + 5e. and the MnS04 and MnCl2 salts are also pink. with a reduction potential of + 1.382 Oxidation-Reduction and Chemical Properties protection for the more easily attacked metals such as iron. MnO:. and Tc was the first element produced artificially. Mn(VI) does exist as the manganate ion. which dimerizes in acid to form the orange dichromate ion: 2CrO~- + 2H+ _. It is one of the most powerful common oxidizing agents.-. Cr20~- + H20 The dichromate ion is a powerful oxidizing agent. VH. in a sample of Mo that had been irradiated by deuterons (iH particles) in the Berkeley cyclotron by Ernest Lawrence (for whom. CrO~-. Chromium makes stainless steels corrosion resistant. and Cr(VI) is a good oxidizing agent.Tc-Re triad. MnO~-. and CrO and Cr(OH)2 are basic.. "artificial. and CrH. The new element was named technetium from the Greek technetos. the acidity of the oxides varies with the oxidation state: Cr03 is acidic. Chromium(III) is the most prevalent oxidation state of chromium. Vanadium gives steels ductility. Oxidation states from + 2 to + 7 are known. 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. the two extremes are the most important. Along with V. The Mn(VII) state is chiefly important for the deep purple permanganate ion. Mn02. " The chief use ofMn metal is to make hardtand tough manganese steels. incidentally.49 V: MnO:.

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

Copper. The metals are excellent conductors of electricity and heat since their electronic arrangement makes the i electrons extremely mobile. They have lower melting and boiling points than the preceding transition metals and are moderately soft. shows a strong tendency to bind to sulfur in proteins. Copper shows mainly the +2 oxida- . and are found naturally as the pure metals. Copper artifacts have been unearthed in some of the earliest farming communities in the Middle East. Complex ions of Pt(IV) and Ir(III) are octahedral. +3.C. These three metals have been the source of more strife and trouble than any other elements. The tetrachloroplatinate (II) ion. they are much less scarce than the platinum metals. and +4 are most important. are green. PtCI~-. and gold have little resemblance to the alkali metals. with which they are associated in the short form of the periodic table derived from Mendeleev's table (Figure 7-1). Nickel forms octahedral and square planar complexes in the Ni(II) state. and much work remains to be done on their reactions. The Coinage Metals Copper. More recently. dating from 7000-6000 B. All are relatively unreactive. and has been useful in preparing heavy-atom derivatives of proteins for x-ray crystallographic analysis. Their relative abundance and their occurrence as uncombined metals made them the first metals to be collected and worked by man. 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. as well as the hydrated cation. Gold is now used for plating external surfaces of delicate components in satellites and space probes.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. silver. they were used mainly for their symbolic and decorative qualities. Until a century ago. which follows from the decreasing number of unpaired d electrons. Metallurgy began when it was discovered that an alloy of copper with tin (a naturally occurring impurity) produced the much harder bronze.. They are malleable and ductile. they are inert and can be found naturally in the metallic state. The square planar complexes are usually red or yellow. The oxidation states + 2. Many Ni(II) salts. Bronze was known in the Sumerian cities of Ur and Eridu from 3500 B. Metals in the light and heavy platinum triads are relatively rare. silver. Although rare enough to be prized. The first metal to be reduced from its ore was probably copper. These properties are part of a downward trend that began with Group VIB (Cr-Mo-W). Complexes of Pt(II) are square planar. and gold have the slightly irregular outer electronic configuration d10Sl. and the metals form octahedral or square planar complex ions in solution.C. during the era that also saw the invention of writing.

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

Again. and HgO are only slightly soluble in water but quite soluble in strong acids. . exposure to light renders the silver halide of the film more susceptible to reduction to silver by a reducing agent in the developer. The oxides ZnO.. Mercury also has a + 1 state in compounds such as Hg2C12• But mercury(I) always appears as the dimeric ion. " ~:""' .' ~ . and the more rapidly varying representative elements begin. Yet ZnO is also soluble in strong bases. . I Reduction by hydroquinone Solution of Na. 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 x-ray and magnetic measurements show that the two Hg atoms are held together by a covalent bond. CdO. hence it is amphoteric. . When the unreduced silver halide is dissolved away. The next electrons to be added must go into the higher-energy p orbitals. a negative image formed by the finely divided silver remains oxidation state.386 Oxidation-Reduction and Chemical Properties Sensitized AgBr ~ Unsensitized AgBr Exposed film '."'. With these elements. 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. . The chemistry of the + 2 state in this group is as expected. 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... Hg~+. H -O-O-H.S.

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

The Li halides are ionic. B. which are formed when the seven 5f orbitals are filled successively with electrons. nearly all compounds of these elements are ionic salts with discrete + 3 ions. and to a lesser extent for the actinides. there are irregularities in thej-orbital utilization. These metals are chemically reactive. Some of the trends are shown in Tables 10-5 and 10-6. lanthanide compounds are found together in nature and are difficult to separate from one another. as in the periodic table on the inside front cover. The actinides are distinguished from the lanthanides in that they all are radioactive. This similarity is due primarily to the successive electrons going into the low-Iyingf \j>rbitals. The most important characteristic of the lanthanides is their close similarity to one another. 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. The sharp variations occur at the transition between metallic and nonmetallic properties. although these variations are systematic and fall into a pattern that can be followed across the remainder of the periodic table. 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.) All the lanthanides and actinides are typical metals with high luster and conductivity.which results in small changes in atomic and ionic radii ("-'0. Table 10-5 gives the melting points of the halides of Li. with oxidation potentials in the range 2-3 V.388 Oxidation-Reduction and Chemical Properties barium in Period 6 the seven 4f orbitals can fill successively with electrons. it is sufficient now to know the trend and leave the irregularities until later. Likewise in Period 7 after Z = 89.01 A) from one element to the next. is + 3. Because of their great similarity. when the 5f and the 6d orbitals have virtually the same energy. The transition metals also vary gradually from one element to the next. But again. Their melting points decrease with the heavier anions because these large anions cannot approach the Li+ ion as closely . we see sharp variations within a group. there are 14 actinide metals. But beginning with Group IlIA. 10-9 THE p-ORBITAL OR REPRESENTATIVE ELEMENTS After the interruptions for the transition and inner transition metals. more so for the actinides than for the lanthanides. (Incidentally. Be. (Promethium. The alkali metals and alkaline earth metals are remarkable for their smooth gradation of properties within a group.) The transuranium actinides (Z = 93 to Z = 103) are man-made elements. The electronic configurations of these inner transition elements are shown in Figure 9-3. As with d orbitals in the transition metals. is the only radioactive lanthanide. and C. the filling of the outermost p orbitals begins again (as with B and Al in Periods 2 and 3) and goes to completion. thereby producing the 14 lanthanide metals. The predominant oxidation state for the lanthanides. Z = 61.

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

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

at least under terrestrial conditions.2 oxidation state. Polonium. and only Bi is metallic. For example. the + 3 state is the most important. Silicon. has the electrical conductivity of a metal. carbon has a + 4 oxidation state in CCl4. especially + 4 and + 6. all metallic properties have been lost. But F. except under extraordinary conditions. However. water repellent. Arsenic and antimony are semimetals with amphoteric oxides. . and CS2. + 3. and the chemistry of lead is almost wholly that of the + 2 state. except in OF 2 and the peroxides. Nitrogen and phosphorus most commonly have oxidation states . but the break between metals and nonmetals is lower in the group. Germanium is a semimetal. it does lose the three 6p electrons to produce BiH.2 state and several positive states as well. thus the halogens are nonmetals. a rare. Both oxygen and sulfur are nonmetals. all odd oxidation numbers between -1 and + 7 are known.09 V go = + 0. like 0. For As and Sb. With Group VIlA. is too electronegative to exhibit the positive states. electrically insulating.86 V go = + 1. and I. is not a suitable alternative to carbon for life forms. and tin and lead are metals. and are reduced easily to anions with the S2p6 electronic configuration. Selenium and tellurium are semimetals. The trend in Group VIA is similar to that in the N group. radioactive element. Carbon and silicon show the +4 oxidation state in combination with oxygen-family elements and the halogens. Nitrogen and phosphorus are nonmetals whose covalent chemistry and oxidation states are governed by the presence of five valence electrons: S2p3. or + 5. Bismuth cannot lose all five valence electrons. the energy required is too high. Oxygen is strongly electronegative and has only the . They are only one electron short of possessing a noble-gas electronic arrangement. For Bi it is the only state. Sulfur has the .54 V rflo = + 1.36 V For Cl. but have a chemistry that resembles that of sulfur.10-9 The p-Orbital or Representative Elements 391 These silicones are inert. Their reduction potentials are F2 + C12 + Br2 + 12 + 2e2e2e2e- -7 -7 -7 -7 2F2Cl2Bc 21- go = + 2.3. Germanium and tin have both +4 and + 2 states. it occurs only in the -1 state. CO2. The same behavior occurs in Group VA. despite the science fiction writers. and stable to heat. Br.

The oxidation potentials of the alkaline earth metals (Be. In the third period.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. The reduction potentials of the halogens to form halide ions are all large (F2 + 2e.76 V] are also large. and CI04(+7). MgH( +2). The oxidation potentials of the alkali metal elements (Li.05 V] are very large. Sr. SiC14 (+4). hardness. The normality therefore depends on the reaction that the redox agent undergoes. Reactions in which the oxidation states of atoms change are called oxidation-reduction (redox) reactions. IJ 0 = + 2. . all of which can be related to the number of unpaired d electrons.86 V). 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). 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. 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. A species that undergoes self-oxidationreduction is said to disproportionate. we have the following: Na+( + 1).~ 2F-. Because of the lanthanide contraction. and common oxidation number. Mg. IJ 0 = + 3. The normality of a redox agent is the number of equivalents in 1 liter of solution. 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 oxidation number of an atom is often called the oxidation state of that atom (or element) in a compound. Ca. The oxides of elements at or near the borderline often exhibit amphoteric (both acidic and basic) behavior. Na. 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. Ba. IJo == + 2. For example. The tendency of a substance to lose electrons in aqueous solution is known as its oxidation potential. boiling point. Balancing a redox equation is equivalent to requiring that electrons be neither created nor destroyed. In a redox reaction electrons are transferred from the reducing agent to the oxidizing agent. AP+( +3). PF5(+5). The tendency for a substance to gain electrons in aqueous solution is called its reduction potential. K. for example. BeO and A1203 are amphoteric. The maximum oxidation number exhibited by an atom of an element generally increases across a period. Rb. all Sl atoms) to form hydrated cations of + 1 charge [Li(s) ~ Li+ + e-. SF6(+6). Cs. all S2) to form + 2 hydrated cations [Ca(s) ~ CaH + 2r. The transition metals undergo a smooth variation in melting point.

What is the difference between oxidation potentials and reduction potentials? 12. the total oxidation number is conserved? 4. Oxidation numbers are a convenient bookkeeping device for keeping track of electrons. The principle of conservation behind balancing redox equations is this: In a chemical reaction. 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. How does this principle lead inevitably to Rule 8 (Section 10-1): In chemical reactions. 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. From which metal can electrons be ejected with light of a longer wavelength. What is the normality of a O. H2S04.00V 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. What pattern of maximum oxidation numbers can be seen across a period in the transition metals? 7. The imaginary element turbidium (Tu) has the following oxidation potential: 80 = -3. follow from what you learned in Chapter 9 about ionization energies and electron affinities? 5. How does Rule 5. How are the most common oxidation states of the representative elements related to their group numbers? 6. Na or Cs? Why? . 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. electrons are neither created nor destroyed.1M solution of sulfuric acid in each of the three processes of Question 8? 10. whereas Ag and Au are? 13. What is the oxidation number of Co in K3CoF6? In K2CoI4? 2.Self-Study Questions 393 1. Give the equivalent weight of sulfuric acid. which deals with the relative oxidation numbers of nonmetals. 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.

Sc to Zn? 20. Cu. Xenon forms several nonionic compounds with F and O. Ni. rather than 5s2 as in Sr? 19. AI. If the first electrons after those in the Kr noble-gas shells go into the 5s orbital for Rb and Sr. Why is calcium harder than potassium? 16. do the higher or lower oxidation states become more important? Can you give a reason for this behavior? 22. What are the principal oxidation states of nitrogen and phosphorus? Oxidation numbers 1.394 Oxidation-Reduction and Chemical Properties 14. What is the lanthanide contraction? Why does it occur? What detectable chemical effects does it produce? 18. Ge. Why do amphoteric oxides appear for those elements that lie on a diagonal across the periodic table (Be. As the principal quantum number of the element increases within a transition-metal group (vertical column). 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. and XeF6• 2. How do the oxides of Cr. why is the outer electronic configuration of ZrH 4d2. and Au? 30. What are the ions in each compound? What are the ionic charge and oxidation number of Xe in each ion containing Xe? . Why are transition-metal compounds more often colored than those of the representative elements? 24. Which element is more metallic. XeF2. Are the halogens good reducing agents or good oxidizing agents? 29. Cu. Give the oxidation number of the central Xe atom in each of the following compounds: Xe04. How does the maximum oxidation number change with atomic number in the first transition-metal series. Sb) rather than in one group separating the metals from the nonmetals? 27. Why is BeO amphoteric? What does this term mean In relation to chemical behavior? 17. including CsXeF7 and Cs2XeF s. In a transition metal with several oxidation states. Be or Ba? What evidence permits you to say this? How can you explain this in terms of electronic configuration? 15. What aspect of electronic structure explains the high electrical conductivities of the coinage metals. and W? 26. 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. which state is usually most metal-like in its compounds? Can you give an example? 21. AI. Xe03. Why do Zn. Ag. Cd. How is the color of a chemical related to electronic transitions between energy levels? 23. and Hg have such low melting points compared with Cr. XeF4. Mo. Xenon can also form a number of ionic compounds.

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

540M FeH solution. Reaction 3 gave MnH in acid solution. (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. 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 the normality of the solution? 17.10M in TiOH.40 g of gaseous S02 are absorbed in 95 ml of water. Find the equivalent weight of an oxidizing agent that oxidizes FeH to FeH if 0.396 Oxidation-Reduction and Chemical Properties Zn --7 NHt + ZnH (acidic solution) d) CI02 --7 CI02 + ClOg (basic solution) e) FeH + Cr20~. (d) reduction to elemental sulfur.+ 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. Calculate the molarity of the solution. K2Cr207. (b) dilute FeS04 to produce TiH.OlM in C12. (a) When H3P04 reacts with NaOH to produce NaH2P04.5 ml of 0.664 g of the compound requires 23. Reaction 2 was carried out in very strong base to give MnO~-. Balance the following equations by any method you choose: a) H3PO~ + CO~. thereby producing Mn02 as a product. The solution was divided into parts and used in four different reactions. is made by adding enough water to 3.--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. 16. When absorption is complete. and reaction 4 yielded MnH. normality. Twelve grams ofKMn04 were dissolved in sufficient water to make a liter of solution. An acidic solution is 0.with sodium hydroxide.+ 109 + H20 h) KMn04 + NH3 --7 KN03 + Mn02 + KOH + H20 vot Molarity. Calculate for each of the following reactions the volume of solution if this composition that contains 1 equiv ofH2S03: (a) neutralization to SO~.+ CO2 + H20 (neutral solution) b) Mn02 + SO~. how many equivalents of H3P04 are there per mole? 19. (c) reduction to S2-. 18.52 g of the salt to fill a 100-ml volumetric flask. 20. What is its normality when reacted with (a) dilute FeS04 to produce FeH. (c) concentrated H2S04 to produce Ti4+? 21. redox equivalents 15. (b) dilute H202 to produce HCIO? I 14. Reaction 1was carried out in basic solution. A slightly acidic solution is O.--7 MnO~. Calculate the .--7 POl.+ 1. Exactly 6.--7 Mn(OH)2 + SO~(basic solution) c) H+ + Cr20~. A solution of potassium dichromate. (b) oxidation to SO~-. What is its normality when reacted with (a) dilute NaOH to produce Ti02.

Given the equation H2S04 26. what volume of C12 gas is required to react completely with the KI? (KI normality is based on its reducing action. (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. J.00-ml sample of an unknown copper solution is treated with excess potassium iodide in acidic solution. In acidic aqueous solution. When H2S reacts with KMn04 in acidic solution. L. "The Solvated Electron." Scientific American) February 1967. Dye. If 12.~ 13 + S20§.0 ml of a solution containing 6. (a) What are the oxidation numbers of C and Mn in the reactants and products? (None of the substances is a peroxide. 103 is reduced to 12 in acidic solution. What is the normality of the original permanganate solution? What is the molarity? 25.0250M sodium thiosulfate. If a 0. In oxidizing H2S03 to SO~-. What volume of 0. the following reaction can be written: Mn04 + H2S + H+ ~ Mn2+ + S + H20 Balance the equation.10N solution of KI in aqueous KOH at STP. what is the molarity of the unknown copper solution? The unbalanced reactions are Cu 2+ + I. (Check first to see if the reaction is balanced. Mn2+. permanganate ion will oxidize oxalic acid (COOH)2 to carbon dioxide while being reduced to manganous ion. J. the following reaction occurs: KOH + C12 + KI ~ KCl + KI03 + H20 Balance the equation.) 23.01 mole of oxalic acid? (e) How many equivalents of oxalic acid can be oxidized by 0. A 25.25N KI03 is required for the complete oxidation to sulfate of 125 ml ofO. Write a balanced chemical equation for this redox reaction. M.l00NHI. If chlorine gas is bubbled through 25 ml of a 0.50 ml of the Representative Elements) Bogden and Quigley.00 ml ofO.8 g of potassium permanganate per liter? (g) What is the molarity of a solution that contains 4. 70 ml are required to reach the end point. The . 1970. If chlorine gas is bubbled through a basic solution of potassium iodide.+ S40~- 22.04 equiv of potassium permanganate? (f) What is the normality of a solution that contains 15. and the liberated iodine is titrated with 0.~ CuI + 13 1.05N solution of H2S is used to titrate 50 ml of permanganate solution.25 g of potassium permanganate per liter? + HI ~ H2S + 12 + H20 calculate the number of moles of sulfuric acid consumed by reaction with 25.l0NH2S03? 27.Suggested Reading 397 thiosulfate solution are required to reach the end point.) (b) Write a balanced equation for the reaction. Bigelow.5 g of oxalic acid per liter? (h) What weight of oxalic acid can be oxidized to carbon dioxide by 150.) 24. New York.

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

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