CHAPTER 23

THE TRANSITION ELEMENTS

PRACTICE EXAMPLES
1A (a) Cu 2 O should form. 2 Cu 2S  s  + 3 O 2  g   2 Cu 2 O  s  + 2 SO 2  g 
(b) W(s) is the reduction product. WO3  s  + 3 H 2  g   W  s  + 3 H 2 O  g 
(c) Hg(l) forms. 2 HgO  s  

 2 Hg  l  + O 2  g 

1B (a) SiO 2  s  is the oxidation product of Si. 3 Si  s  + 2 Cr2 O3  s  


 3 SiO 2  s  + 4 Cr  s 
(b) Roasting is simply heating in air. 2 Co  OH 3  s  
 , Air
 Co 2 O3  s  + 3H 2 O  g 
(c) MnO 2  s  forms; (acidic solution). Mn 2+  aq  + 2H 2 O(l)  MnO 2  s  + 4H +  aq  + 2e 

2A We write and combine the half-equations for oxidation and reduction. If E o  0 , the
reaction is spontaneous.
Oxidation: {V 3+  aq  + H 2 O(l)  VO 2+  aq  + 2H +  aq  + e  }  3 E o = 0.337V
Reduction: NO3  aq  + 4H +  aq  + 3e  NO  g  + 2H 2 O

E o = +0.956V
Net: NO3-  aq  + 3V 3+  aq  + H 2 O(l)  NO  g  + 3VO 2+  aq  + 2H +  aq  Ecell o = +0.619V
Because the cell potential is positive, nitric acid can be used to oxidize V 3+  aq  to VO 2+  aq 
under standard conditions.

2B The reducing couple must have a half-cell potential of such a size and sign that a positive sum
results when this half-cell potential is combined with E o {VO 2 (aq)|V 2 (aq)}  0.041V (this is
the weighted average of the VO2+ | V3+ and V3+ | V2+ reduction potentials) and a negative sum
must be produced when this half-cell potential is combined with E o {V 2 (aq)|V(s)}=  1.13V .
So, -Eo for the couple must be > –0.041 V and < + 1.13 V (i.e., it cannot be more positive than
1.13V, nor more negative than –0.041 V). Some possible reducing couples from Table 20-1 are:
 E o {Cr 3 (aq)|Cr 2+ (aq)}  0.42 V ;  E o {Fe 2+ (aq)|Fe(s)}  0.440 V
 E o {Zn 2+ (aq)|Zn(s)}  0.763 V . Thus Fe(s), Cr2+(aq), and Zn(s) will do the job.

INTEGRATIVE EXAMPLE
3A Because the reduction potential for PtCl62− is more positive than that of V3+, the
following half-reactions occur spontaneously in the cell:
Oxidation: [ V2+ + e− → V3+ ] × 2 E° = +0.255 V
Reduction: PtCl62− + 2 e− → PtCl42− + 2 Cl− E° = +0.68 V
2+ 2− 3+ 2− −
Overall: 2 V + PtCl6 → 2 V + PtCl4 + 2 Cl E° = 0.94 V

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 Chapter 23: The Transition Elements

2(0.94)
The equilibrium constant for the overall reaction is K  10 0.0592  5.7 1031 . For the
reverse reaction to be spontaneous, we need Q > 5.7 × 1031. Because Q = [V3+]2 [PtCl42−]
[Cl−]2/[V2+] [PtCl62−], the formation of PtCl62− is favored by using a very low
concentration of V2+ and very high concentrations of V3+, PtCl42−, and Cl−. In practical
terms, though, the amount of PtCl62− that could be formed spontaneously would be small.
A quick calculation shows that starting from [V3+]o = [PtCl42−]o = [Cl−]o = 1. M and [V2+]
= [PtCl62−]o = 0, the equilibrium concentration of PtC62− would be about 1.6 × 10−11 M.
So, in practical terms, an external voltage source would be required to make a significant
amount of PtCl62− from V3+, PtCl42−, and Cl−.

3B The disproportionation reaction is 3 Ti2+ → 2 Ti3+ + Ti and E° = −1.261 V. Because E° <

0, the reaction is not spontaneous under standard conditions.

EXERCISES
Properties of the Transition Elements

1. (a) Ti [Ar] 3d 4s (b) V 3+ [Ar] 3d 4s

(c) Cr 2+ [Ar] 3d 4s (d) Mn 4+ [Ar] 3d 4s

(e) Mn 2+ [Ar] 3d 4s (f) Fe 3+ [Ar] 3d 4s

3. A given main-group metal typically displays just one oxidation state, usually equal to its
family number in the periodic table. Exceptions are elements such as Tl ( +1 and +3 ), Pb
( +2 and +4 ), and Sn ( +2 and +4 ), for which the lower oxidation state represents a pair of s
electrons not being ionized (a so-called “inert pair”).
Main group metals do not form a wide variety of complex ions, with Al3+ , Sn 2+ , Sn 4+ , and
Pb 2+ being major exceptions. On the other hand, most transition metal ions form an extensive
variety of complex ions. Most compounds of main group metals are colorless; exceptions
occur when the anion is colored. On the other hand, many of the compounds of transition
metal cations are colored, due to d-d electron transitions. Virtually every main-group metal
cation has no unpaired electrons and hence is diamagnetic. On the other hand, many transition
metals cations have one or more unpaired electrons and therefore are paramagnetic.

5. When an electron and a proton are added to a main group element to create the element of next
highest atomic number, it is the electron that influences the radius. The electron is added to the
outermost shell (n value), which is farthest from the nucleus. Moreover, the added electron is
well shielded from the nucleus and hence it is only weakly attracted to the nucleus. Thus, this
electron billows out and, as a result, has a major influence on the size of the atom. However,
when an electron and a proton are added to a transition metal atom to create the atom of next

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Chapter 23: The Transition Elements

highest atomic number, the electron it is not added to the outermost shell. The electron is added
to the d-orbitals, which are one principal quantum number lower than the outermost shell. Also,
the electron in the same subshell as the added electron offers little shielding. Thus it has small
effect on the size of the atom.

7. Of the first transition series, manganese exhibits the greatest number of different oxidation
states in its compounds, namely, every state from +1 to +7 . One possible explanation might
be its 3d 5 4 s2 electron configuration. Removing one electron produces an electron
configuration ( 3d 5 4 s1 ) with two half-filled subshells, removing two produces one with a
half-filled and an empty subshell. Then there is no point of semistability until the remaining
five d electrons are removed. These higher oxidation states all are stabilized by being present
-
in oxides ( MnO 2 ) or oxoanions (e.g., MnO4 ).

9. The greater ease of forming lanthanide cations compared to forming transition metal cations,
is due to the larger size of lanthanide atoms. The valence (outer shell) electrons of these
larger atoms are further from the nucleus, less strongly attracted to the positive charge of the
nucleus in diffuse f-orbitals that are do not penetrate effectively and are very effectively
shielded by the core electrons. As a result, they are removed much more readily.

Reactions of Transition Metals and Their Compounds

11. (a) TiCl4  g  + 4 Na  l  


 Ti  s  + 4NaCl  l 

(b) Cr2 O3  s  + 2Al  s  


 2 Cr  l  + Al2 O3  s 

(c) Ag  s  + HCl  aq   no reaction

(d) K 2 Cr2 O7  aq  + 2KOH  aq   2 K 2CrO 4  aq  + H 2 O(l)

(e) MnO 2  s  + 2 C  s  

 Mn  l  + 2CO  g 

13. (a) Sc  OH 3  s  + 3H +  aq   Sc3+  aq  + 3 H 2 O(l)

(b) 3 Fe 2+  aq  + MnO 4   aq  + 2 H 2 O  l   3 Fe3+  aq  + MnO 2  s  + 4 OH  (aq)
(c) 2 KOH  l  + TiO 2  s  

 K 2 TiO3  s  + H 2 O  g 
(d) Cu  s  + 2 H 2SO 4  conc, aq   CuSO 4  aq  + SO 2  g  + 2 H 2 O(l)

15. We write some of the following reactions as total equations rather than as net ionic
equations so that the reagents used are indicated.
(a) FeS  s  + 2 HCl  aq   FeCl2  aq  + H 2S  g 
4 Fe 2+  aq  + O 2  g  + 4H +  aq   4Fe3+  aq  + 2 H 2 O(l)
Fe3+  aq  + 3 OH   aq   Fe  OH 3  s 

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 Chapter 23: The Transition Elements

(b) BaCO3  s  + 2 HCl  aq   BaCl2  aq  + H 2 O(l) + CO 2  g 

2 BaCl 2  aq  + K 2 Cr2 O 7  aq  + 2 NaOH  aq   2 BaCrO 4  s  + 2 KCl  aq  + 2 NaCl  aq  + H 2 O(l)

Extractive Metallurgy

17. HgS(s) + O2(g)   Hg(l) + SO2(g)

4 HgS(s) + 4 CaO(s)   4 Hg(l) + 3 CaS(s) + CaSO4(s)

19. The plot of Go versus T will consist of three lines of increasing positive slope.
The first line is joined to the second line at the melting point for Ca(s), while the second
line is joined to the third at the boiling point for Ca(l).
2 Ca(s) + O2(g)  2 CaO(s) Hf = -1270.2 kJ
S = 2(39.75 J K-1) – [2(41.42 J K-1) + 205.1 J K-1] = -208.4 J K-1

The graph should be similar to that for 2 Mg(s) + O2(g)  2 MgO(s). We expect a
positive slope with slight changes in the slope after the melting point (839 C) and boiling
point (1484 C) , mainly owing to changes in entropy. The plot will be below the
G line for 2 Mg(s) + O2(g)  2 MgO(s) at all temperatures.

Oxidation-Reduction
21. (a) Reduction: VO 2+ aq  + 2H + aq  + e   V3+ aq  + H 2O (l)
(b) Oxidation: Cr 2+ aq   Cr 3+ aq  + e 

23. (a) First we need the reduction potential for the couple VO+2 aq  / V2 + aq . We will use
the half-cell addition method learned in Chapter 20.
VO 2  aq  + 2 H +  aq  + e  VO 2+  aq  + H 2 O(l) G o = 1 F  +1.000 V 
+

VO 2+  aq  + 2 H +  aq  + e   V 3+  aq  + H 2 O(l) G o = 1 F  +0.337 V 

V 3+  aq  + e   V 2+  aq  G o = 1 F  0.255 V 

VO 2  aq  + 4 H +  aq  + 3 e   V 2+  aq  + 2 H 2 O
+
G o = 3 FE o

1.000 V + 0.337 V  0.255 V

Eo = = + 0.361 V
3

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Chapter 23: The Transition Elements

We next analyze the oxidation-reduction reaction.

Oxidation: {2 Br   aq   Br2  l  + 2e  }  3  E o = 1.065 V
Reduction: {VO 2 +  aq  + 4H +  aq  + 3e   V 2+  aq  + 2H 2 O(l)}  2 E o = +0.361V

Net: 6 Br   aq  + 2 VO 2  aq  + 8 H +  aq   3 Br2  l  + 2 V 2+  aq  + 4 H 2 O
+

o
Ecell = 0.704V
Thus, this reaction does not occur to a significant extent as written under standard
conditions.

(b) Oxidation: Fe 2+  aq   Fe3+  aq  + e  E o = 0.771V

Reduction: VO 2  aq  + 2 H +  aq  + e   VO 2+  aq  + H 2 O(l)
+
E o = +1.000V

Fe2+  aq  + VO 2  aq  + 2 H +  aq   Fe3+  aq  + VO 2+  aq  + H 2 O(l)

+
Net:
o
Ecell = +0.229V
This reaction does occur to a significant extent under standard conditions.

(c) Oxidation: H 2 O 2  2 H +  aq  + 2 e + O 2  g   E o = 0.695 V

Reduction: MnO 2  s  + 4 H +  aq  + 2 e   Mn 2+  aq  + 2 H 2O(l) E o = +1.23V

Net: H 2 O 2 + MnO 2  s  + 2 H +  aq   O 2  g  + Mn 2+  aq  + 2 H 2 O(l)

o
Ecell = +0.54V
Thus, this reaction does occur to a significant extent under standard conditions.

25. The reducing couple that we seek must have a half-cell potential of such a size and sign
that a positive sum results when this half-cell potential is combined
with E o {VO 2 (aq)|V 3 (aq)}  0.337 V and a negative sum must be produced when this
+
half-cell potential is combined with E o {V 3 (aq)|V 2 (aq)}=  0.255V .
So, -Eo for the couple must be> –0.337 V and <+ 0.255 V (i.e. it cannot be more
positive than 0.255V, or more negative than –0.337 V)
Some possible reducing couples from Table 20.1 are:
 E o {Sn 2 (aq)|Sn(s)}  0.137 V ;  E o {H + (aq)|H 2 (g)]  0.000 V
 E o {Pb 2+ (aq)|Pb(s)]  0.125 V ; thus Pb(s), Sn(s), H2(g) , to name but a few, will do the job.

27. Table D-4 contains the following data: Cr 3+ /Cr 2+ reduction potential = -0.424 V,
Cr2 O 7 2- /Cr 3+ reduction potential = 1.33 V and Cr 2+ /Cr reduction potential = -0.90 V.
By using the additive nature of free energies and the fact that G = -nFE, we can
determine the two unknown potentials and complete the diagram.
3(1.33V) - 0.424 V
(i) Cr2 O7 2- /Cr 2+ : E = = 0.892 V
4

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 Chapter 23: The Transition Elements

0.424 V + 2(-0.90 )V
(ii) Cr 3+ /Cr : E = =  0.74 V
3

Chromium and Chromium Compounds

29. Orange dichromate ion is in equilibrium with yellow chromate ion in aqueous solution.
Cr2 O7 2  aq  + H 2 O(l) 
 2CrO 4 2  aq  + 2H +  aq 

The chromate ion in solution then reacts with lead(II) ion to form a precipitate of yellow
lead(II) dichromate. Pb 2+  aq  + CrO 4 2  aq  
 PbCrO 4  s 

PbCrO 4 s will form until H + from the first equilibrium increases to the appropriate
level and both equilibria are simultaneously satisfied.

31.   
Oxidation: {Zn s  Zn 2+ aq + 2e  }  3
Reduction: Cr2 O7
2
 aq, orange  +14H +  aq  + 6e  2 Cr 3+  aq, green  + 7 H 2O(l)
3 Zn  s  + Cr2 O7  aq  +14 H +  aq   3 Zn 2+  aq  + 2 Cr 3+  aq  + 7 H 2O(l)
2
Net:

Oxidation: Zn s   Zn 2 + aq  + 2e 
Reduction: {Cr 3+ aq,green  + e   Cr 2 + aq, blue } 2
Net: Zn  s  + 2 Cr 3+  aq   Zn 2+  aq  + 2 Cr 2+  aq 

The green color is most likely due to a chloro complex of Cr3+, such as Cr  H 2 O 4 Cl2  .
+

Oxidation: {Cr 2 + aq, blue   Cr 3+ aq,green  + e  } 4

Reduction: O 2  g  + 4 H +  aq  + 4e   2 H 2 O(l)

Net: 4 Cr 2+  aq  + O 2  g  + 4 H +  aq   4 Cr 3+  aq  + 2 H 2 O(l)

Simple substitution into Equation (23.19) yields Cr2 O 7  in each case. In fact, the
2
33.
expression is readily solved for the desired concentration as follows:
2 2
 Cr2 O 7 2  = 3.2  1014  H +   CrO 4 2  . In each case, we use the value of pH to determine
     
 H  = 10 .
+  pH

(a) Cr2O7 2  = 3.2 1014 (106.62 ) 2 (0.20) 2  0.74 M

 
 Cr2O 7  = 3.2 1014 108.85   0.20 2 = 2.6  105 M
2 2
(b)  

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Chapter 23: The Transition Elements

35. Each mole of chromium metal plated out from a chrome plating bath (i.e., CrO3 and
H2SO4) requires six moles of electrons.
3600 s 3.4 C 1 mol e  1 mol Cr 52.00 g Cr
mass Cr =1.00 h      = 1.10 g Cr
1 hr 1s 96485 C 6 mol e 1mol Cr

37. Dichromate ion is the prevalent species in acidic solution. Oxoanions are better oxidizing
agents in acidic solution because increasing the concentration of hydrogen ion favors
formation of product. The half-equation is:
Cr2 O72-(aq)  14 H  (aq)  6 e 
 2 Cr 3 (aq)  7H 2O(l) Note that precipitation occurs
most effectively in alkaline solution. In fact, adding an acid to a compound is often an
effective way of dissolving a water-insoluble compound. Thus, we expect to see the form
that predominates in alkaline solution to be the most effective precipitating agent. Notice
2 2
also that CrO 4 is smaller than is Cr2 O7 , giving it a higher lattice energy in its
compounds, which makes these compounds harder to dissolve.

The Iron Triad

39. 4 Fe2+(aq) + O2(g) + 4 H+  4 Fe3+(aq) + 2 H2O(l) E = 0.44 V

[Fe2+] = [Fe3+]; pH = 3.25 or [H+] = 5.6  10-4 and PO2 = 0.20 atm

0.0592  [Fe3+ ]4  0.0592  [Fe3+ ]4 

E = E - log  2+ 4 + 4  = 0.44 V - log  
n  [Fe ] [H ] PO 4  [Fe 2+ 4
] [10 -3.25 4
] 0.20 
 2   
E = 0.24 V (spontaneous under these conditions)
[II] [III] [II]
41. Fe3+(aq) + K4[F e(CN)6](aq)  K F e [F e(CN)6](s) + 3 K+(aq)
[II]
- [II]
Alternate formulation: 4Fe3+ + 3[F e(CN)6]4 (aq) + Fe4[F e(CN)6]3

Group 11 Metals
43. (a) Cu 2 + aq  + H 2 g   Cu s  + 2H + aq 
(b) Au + aq  + Fe 2 + aq   Au s  + Fe 3+ aq 
2Cu 2+  aq  + SO 2  g  + 2 H 2 O(l)  2 Cu +  aq  + SO 4  aq  + 4 H +  aq 
2
(c)

Cu 2+  2
45. The Integrative Example showed K c = 1.2 10 = 2
or Cu 2+  = 1.2  106 Cu + 
6

Cu + 
When Cu +  = 0.20 M,  Cu 2+  = 1.2 106  0.20  = 4.8 104 M. This is an
2
(a)
impossibly high concentration. Thus  Cu +  = 0.20 M can never be achieved.

638
 Chapter 23: The Transition Elements

(b) When  Cu +  = 1.0 1010 M,  Cu 2+  = 1.2 106 1.0 1010  = 1.2  1014 M . This is
2

an entirely reasonable (even though small) concentration;  Cu +  = 1.0 1010 M can

be maintained in solution.

Group 12 Metals
47. Given: Hg2+/Hg reduction potential = 0.854 V and Hg22+/Hg reduction potential = 0.796 V
Using the additive nature of free energies and the fact that G = -nFE, we can determine the
2(0.854V) - 0.796V
Hg2+/Hg22+ potential as = 0.912 V
1

49. (a) Estimate Kp for ZnO(s) + C(s)  Zn(l) + CO(g) at 800 C (Note: Zn(l) boils at 907 C)

{2 C(s) + O2(g)  2 CO(g)} 1/2 G = (  415 kJ) × (1/2) 

{2 ZnO(s)  2 Zn(l) + O2(g)}1/2 G = (+485 kJ) × (1/2) 

ZnO(s) + C(s)  Zn(l) + CO(g) G = 35 kJ

Use G = -RTlnKeq where T = 800 C, Keq = Kp

35 kJ mol-1 = -(8.3145  10-3 kJ K-1 mol-1)((273.15 + 800) K)(ln Kp)
lnKp = -3.9 or Kp = 0.02

(b) Kp = PCO = 0.02 Hence, PCO = 0.02 atm

51. We must calculate the wavelength of light absorbed in order to promote an electron across
each band gap.
First, a few relationships. Emole = N A Ephoton Ephoton = hv c = v or v = c/

Then, some algebra. Emole = N A Ephoton = N A hv = N A hc/ or  = N A hc/Emole

6.022 1023 mol1  6.626  1034 J s  2.998 108 m s 1 109 nm
For ZnO,  = 
290  103 J mol1 1m
1.196 108 J mol1 nm
= = 413 nm violet light
290  103 J mol1

1.196 108 J mol1 nm

For CdS,  = = 479 nm blue light
250  103 J mol1

The blue light absorbed by CdS is subtracted from the white light incident on the surface
of the solid. The remaining reflected light is yellow in this case. When the violet light is

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Chapter 23: The Transition Elements

subtracted from the white light incident on the ZnO surface, the reflected light appears
white.

INTEGRATIVE AND ADVANCED EXERCISES

53. There are two reasons why Au is soluble in aqua regia while Ag is not. First, Ag+, the
oxidation product, forms a very insoluble chloride, AgCl, which probably adheres to the
surface of the metal and prevents further reaction. AuCl3 is not noted as being an insoluble
chloride. Second, gold(III) forms a very stable complex ion with chloride ion, [AuCl4]–. This
complex ion is much more stable than the corresponding dichloroargentate ion, [AgCl2]–.

57. The noble gas formalism requires that the number of valence electrons possessed by the
metal atom plus the number of sigma electrons be equal to the number of electrons in the
succeeding noble gas atom.
(a) Mo(CO)6 ; Mo has 42 electrons, 6 CO contribute another 12 for 54, which is the number
of electrons in Xe
(b) Os(CO)5 ; Os has 76 electrons, 5 CO contribute another 10 for 86, which is the number
of electrons in Rn
(c) Re(CO)5-; Re anion has 76 electrons, 5 CO contribute another 10 for 86, which is the
number of electrons in Rn
(d) The trigonal bipyramidal shape of nickel and iron carbonyls does not fit well in
crystalline lattices, either because of its symmetry or repulsions with its neighbors and,
consequently, these five-coordinate carbonyls are liquids at room temperature.
Compare this to octahedral complexes (Cr(CO)6 and others), which are solids because
they fit well into these lattices. Weak intermolecular attractions in the low molecular
mass, symmetrical nickel and iron carbonyls result in the liquid state at room
temperature. Because of the two metal atoms in the higher molecular mass, less
symmetrical cobalt carbonyl molecules, stronger intermolecular attractions lead to the
solid state.
(e) This compound would be an ionic, salt-like material consisting of Na+ and V(CO)6- ions.

61. (a) Dissolution: AgO(s)  2 H  (aq) 

 Ag 2 (aq)  H 2 O(l)

Oxidation :  O 2 (g)  4 H  (aq)  4 e 

2 H 2 O(l)   E   1.229 V
Reduction : {Ag 2 (aq)  e  
 Ag  (aq)} 4 E   1.98 V
Net : 2 H 2 O(l)  4 Ag 2 (aq) 
 O 2 (g)  4 H  (aq)  4 Ag  (aq)

(b) E ocell   1.229 V  1.98 V   0.75 V  spontaneous since E ocell > 0.

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64. The equations are balanced with the ion-electron method. Oxalic acid is oxidized in each case.
 2 H  (aq)  2 CO 2 (g)  2 e 
Oxidation: H 2 C 2 O 4 (aq) 
Reduction:MnO 2 (s)  4 H  (aq)  2 e  
 Mn 2 (aq)  2 H 2 O(l)
Net: H 2 C2 O 4 (aq)  MnO 2 (s)  2 H  (aq) 
 Mn 2 (aq)  2 CO 2 (g)  2 H 2 O(l )

 2 H  (aq)  2
Oxidation:{H 2 C 2 O 4 (aq)  CO 2 (g)  2 e } 5
Reduction: {MnO 4  (aq)  8 H  (aq)  5 e  
 Mn 2 (aq)  4 H 2 O(l) }  2
Net: 5 H 2 C 2 O 4 (aq)  2 MnO 4  (aq)  6 H  (aq) 
 2 Mn 2 (aq)  10 CO 2 (g)  8 H 2 O(l)
We then determine the mass of the excess oxalic acid.

0.1000 mol MnO 4 5 mol H 2 C 2 O 4
mass H 2 C 2 O 4  2H 2 O  0.03006 L   
1 L soln 2 mol MnO 4
126.07 g H 2 C 2 O 4  2H 2 O
  0.9474 g H 2 C 2 O 4  2H 2 O
1 mol H 2 C 2 O 4  2H 2 O
Thus, the mass of oxalic acid that reacted with MnO2 is 1.651 g – 0.9474 g = 0.704 g
H2C2O42H2O. Now we can determine the mass of MnO2 in the ore.
1 mol H 2 C 2 O 4 .2H 2 O 1 mol MnO 2
mass MnO 2  0.704 g H 2 C2 O 4  2H 2 O  
126.07 g H 2 C2 O 4  2H 2 O 1 mol H 2 C2 O 4
86.94 g MnO 2 0.485 g MnO 2
  0.485 g MnO 2 %MnO 2   100%  82.3%
1 mol MnO 2 0.589 g ore

65. (a) We consider reaction with 1.00 millimoles of Fe2+. In each case, we need the balanced
chemical equation of the redox reaction.
2
Cr2 O 7 (aq)  14 H  (aq)  6 Fe 2 (aq) 
 2 Cr 3 (aq)  7 H 2 O(l)  6 Fe 3 (aq)
2
titrant 2 1 mmol Cr2 O 7 1 mL solution
volume  1.00 mmol Fe  2
 2
 1.67 mL soln
6 mmol Fe 0.1000 mmol Cr2 O 7

MnO 4 (aq)  8 H  (aq)  5 Fe 2 (aq) 
 Mn 2 (aq)  4 H 2 O  5 Fe 3 (aq)

titrant 3 1 mmol MnO 4 1 mL solution
volume  1.00 mmol Fe  5 mmol Fe 2  0.1000 mmol MnO   2.00 mL soln
4

More of the 0.1000 M MnO4– solution would be required.

(b) We use the reaction of each with Fe2+ to find the equivalence between them.
0.1000 mmol Cr2 O7 2 6 mmol Fe 2 1 mmol MnO 4 
VMnO   24.50 mL   
4
1 mL soln 1 mmol Cr2 O7 2 5 mmol Fe 2
1 mL soln
 
 29.40 mL of 0.1000 mmol MnO 4 
0.1000 mmol MnO 4

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Chapter 23: The Transition Elements

67. The precipitation reaction of dichromate ion permits us to determine from the formula of
barium chromate the amount of chromium present, while the redox reaction of
permanganate ion permits us to determine the amount of manganese present in the 250.0 mL
solution. The 15.95 ml volume of Fe2+ titrant assumes (contrary to what the problem
implies) that the chromate has been removed by precipitation. Ba(MnO4)2 is quite water

soluble, so [ MnO 4 ] should not be affected.

Equation: MnO 4 (aq)  8 H  (aq)  5 Fe 2 (aq) 

 Mn 2 (aq)  4 H 2O  5 Fe3 (aq)
0.549 g BaCrO 4 1 mol BaCrO 4 1 mol Cr 52.00 g Cr
mass of Cr  250.0 mL soln    
10.00 mL sample 253.3 g BaCrO4 1 mol BaCrO4 1 mol Cr
mass of Cr  2.82 g Cr
equation: Cr2 O7 2-  14 H   6 Fe 2  2Cr 3  7 H 2 O  6 Fe3
10 ml 1 mol Cr 3 6 mol Fe 2
volume of titrant to reduce Cr2 O 7 2-  2.82 g Cr   
250 ml 52.00 g Cr 1 mol Cr2 O7 2-
1 mol Cr2 O7 2- 1 L titrant 1000 mL
 3
 2
  86.78 ml Fe2 titrant
2 mol Cr 0.0750 mol Fe 1L
Now the volume of titrant to reduce both MnO 4 - and Cr2 O 7 2- must be (15.95  86.78) mL
Volume of titrant  102.73 mL.
Not just 15.95 mL, which must be the volume of titrant required for MnO 4  alone.
15.95 mL titrant 0.0750 mmol Fe2 1 mmol MnO 4 
mass Mn  250.0 mL soln   
10.00 mL sample 1 mL titrant 5 mmol Fe 2
1 mmol Mn 54.94 mg Mn 1 g Mn
 
   0.3286 Mn
1 mmol MnO 4 1 mmol Mn 1000 mg Mn
0.3286 g Mn 2.82 g Cr
%Mn   100%  3.286% Mn %Cr   100%  28.2% Cr
10.000 g steel 10.000 g steel

68. (a) We use the technique of Chapter 3 to determine the empirical formula of nickel
dimethylglyoximate.
1 mol Ni
20.31 g Ni   0.3461 mol Ni  0.3461 
1.000 mol Ni
58.69 g Ni
1 mol C
33.26 g C   2.769 mol C  0.3461 
 8.001 mol C
12.011 g C
1 mol H
4.88 g H   4.84 mol H  0.3461 
14.0 mol H
1.008 g H

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 Chapter 23: The Transition Elements

1 mol O
22.15 g O   1.384 mol O  0.3461 
 3.999 mol O
15.999 g O
1 mol N
19.39 g N   1.384 mol N  0.3461 
 3.999 mol N
14.007 g N
The empirical formula of nickel dimethylglyoximate (NiDMG) is NiC8H14O4N4, with
an empirical molar mass of 288.91 g/mol
0.104 g NiDMG 1 mol NiDMG 1 mol Ni 58.69 g Ni
(b) mass of Ni  250.0 mL    
10.00 mL 288.91 g NiDMG 1 mol NiDMG 1 mol Ni
 0.528 g Ni
0.528 g Ni
% Ni in steel   100%  3.52%
15.020 g steel
71.
(a) (b) (c)
O
O O
O
Mn Mn Os
Hg Hg O
O O
O O
O O

1
73. ? Ti per unit cell = Ti per corner × 8 corners per cell = 1 Ti
8
? Ni per unit cell = 1

The empirical formula is NiTi. The % Ti by mass is 100 × 47.88/(47.88 + 63.55) = 45%

FEATURE PROBLEMS
74. (a) If ngas = 0, then S ~ 0 and G is essentially independent of temperature
(C(s) + O2(g)  CO2(g))
If ngas > 0, then S > 0 and G will become more negative with increasing
temperature, hence the graph has a negative slope (2 C(s) + O2(g)  2 CO (g)).
If ngas < 0, then S < 0 and G will become more positive with increasing
temperature, hence the graph has a positive slope (2 CO(g) + O2(g)  2 CO2 (g).

(b) The additional blast furnace reaction, C(s) + CO2(g)  2 CO(g)), has
H = [2   110.5 kJ]  [  393.5 kJ + 0 kJ] = 172.5 kJ and

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Chapter 23: The Transition Elements

S = [2  197.7 J K-1]  [1  5.74 J K-1 + 213.7 J K-1] = 176.0 J K-1

It can be obtained by adding reaction (b) to the reverse of reaction (c) (both appear
in the provided figure)
C(s) + O2(g)  CO2(g) Reaction (b)
2CO2(s)  2CO(g) + O2(g) Reverse of Reaction (c)
Net: C(s) + CO2(g)  2 CO(g) (Additional Blast Furnace Reaction)
Consequently, the plot of G for the net reaction as a function of temperature will
be a straight line with a slope of  [{S (Rxn b)}  {S (Rxn c)}] (in kJ/K) and a
y-intercept of [{H (Rxn b)}  {H (Rxn c)}] (in kJ).
Since Ho (Rxn b) =  393.5 kJ, Ho (Rxn c) =  566 kJ, So (Rxn b) = 2.9 J/K and
So (Rxn c) =  173.1 J/K, the plot of G vs. T for the reaction
C(s) + CO2(g)  2 CO(g) will follow the equation y  0.176 x  172.5
From the graph, we can see that the difference in G (line b – line c at 1000 C) is
~  40 kJ/mol. Kp is readily calculated using this value of G.
G = -RTlnKp = -40 kJ =  (8.3145  10-3 kJ K-1 mol-1)( 1273 K)(ln Kp)
lnKp = 3.8 Hence, Kp = 44
The equilibrium partial pressure for CO(g) is then determined by using the
Kp expression:

P   PCO 
2 2

K  CO
p 44  Hence, (PCO)2 = 11 and PCO = 3.3 atm or 3 atm.
(PCO2 ) (0.25 atm)

Alternatively, we can determine the partial pressure for CO2 at 1000 C via the calculated
H and S values for the reaction C(s) + CO2(g)  2 CO(g) to find G at 1000 C ,
and ultimately Kp with the relationship G = -RTlnKp (here we are making the
assumption that H and S are relatively constant over the temperature range 298 K to
1273 K). The calculated values of H and S (using Appendix D) are given below:
H = [2   110.5 kJ]  [  393.5 kJ + 0 kJ] = 172.5 kJ
S = [2  197.7 J K-1]  [1  5.74 J K-1 + 213.7 J K-1] = 176.0 J K-1
To find G at 1000oC, we simply plug x =1273 K into the straight-line equation we
developed above and solve for y (G).
So, y  0.176(1273K)  172.5 ; y  51.5 kJ
Next we need to calculate the Kp for the reaction at 1000oC.
 G = -RTlnKp = -51.5 kJ = -(8.3145  10-3 kJ K-1 mol-1)( 1273 K)(ln Kp)
lnKp = 4.87 Hence, Kp = 1.3  102
The equilibrium PCO(g) is then determined by using the Kp expression:

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 Chapter 23: The Transition Elements

P   PCO 
2 2

K  CO
p   Hence, (PCO)2 = 32.5 atm and PCO = 5.7 atm
(PCO2 ) (0.25 atm)

SELF-ASSESSMENT EXERCISES
79. (a) Pig iron is impure iron (95% Fe) formed in the reduction of iron ore in a blast
furnace.
(b) Ferromanganese is an iron-manganese alloy formed by the reduction of a
mixture of iron and manganese oxides.
(c) Chromite ore, Fe(CrO2)2 is the principal chromium ore.
(d) Brass is an allow of Zn and Cu with small amounts of Sn, Pb, and Fe.
(e) Aqua regia is a mixture of HCl(aq) and HNO3(aq) that dissolves inactive metals by a
combination of oxidation and complex ion formation.
(f) Blister copper, formed in the reduction of a mixture of Cu2O(s) and Cu2S(s), is
impure Cu(s) containing SO2(g).
(g) Stainless steel is an iron alloy with varying quantities of metals such as Cr, Mn,
and Ni, and a small and carefully controlled percentage of carbon.

80. (c), (f), and (g).

81. (b)

82. (d)

83. (a)

84. (d)

85. (c) and (e)

86. CrO3(s), (b) potassium manganate, (c) chromium carbonyl, (d) BaCr2O7, (e)
lanthanum(III) sulfate nonahydrate, (f) Au(CN)33H2O.

87. (a) 2Fe 2S3 (s)+3O 2 (g)+6H 2O(l)  4Fe(OH)3 (s)+6S(s)

(b) 2Mn 2+ (aq)+8H 2 O(l)+5S2 O 2-8 (aq)  2MnO-4 (aq)+16H + (aq)+10SO 2-4 (aq)
(c) 4Ag(s)+8CN - (aq)+O 2 (g)+2H 2O(l)  4[Ag(CN 2 ]- (aq)+4OH - (aq)

88. Atoms of Zn, Cd and Hg have configurations of 4s 2 3d 10 , 5s 2 4d 10 , and 6s 2 4 f 14 5d 10 ,

respectively. One the ns 2 electrons participate in bonding, and in this regard Zn, Cd, and
Hg resemble the group 2 elements.

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89. HNO3 is the oxidizing agent for oxidizing the metal to Au3+ but Au3+ must be
stabilized in solution. In aqua regia, Cl- ions combine with Au3+ to form [AuCl4]-, which
is stable in solution.

90. The Fe3+ ion forms a complex ion, Fe(H2O)63+, in aqueous solution. The complex
behaves as a weak monoprotic acid in solution. See Equation (23.36).

646