Transition Metals Colours

TRANSITION METAL CHEMISTRY
The term transition elements originally was coined to denote elements in the middle of the
periodic table that provided a transition between the base formers on the left (Groups 1A and
2A) and the acid formers on the right (Groups 5A through 7A).
Recall that metal oxides typically form basic aqueous solutions whereas non metal oxides
typically form acidic aqueous solutions.
The term transition elements actually applies to both d and f transition elements, all of which
are metals, but commonly is used to denote only d-transition metals. The f-transition metals
are usually called rare earths or inner transition metals.
Transition metals are located between Groups 2A and 3A. Strictly speaking, d-transition metals
must have partially filled d-orbitals. Zn, Cd, and Hg (Group 2B) have completely filled d-orbitals
and are actually post transition metals but they are often referred to as transition metals
because of similar properties.
Cu, Ag, and Au (Group 1B) and Pb (Group 8B) also have filled d-orbitals however their cations
(except Ag+) have partially filled d-orbitals.
General Properties of Transition Metals:
All are metals

Most are harder, more brittle, have higher mp and bp and Hvap than non transition
metals.
Their ions and compounds are often colored.
They form many coordination complexes
Most have multiple oxidation states
Many of the metals and their compounds are good catalysts.
Electron Configuration:
Period 4
21
Sc [Ar] 3d 4s
40
V [Ar] 3d3 4s2
41
Cr [Ar] 3d5 4s1
42
23
Y [Kr] 4d 5s
Period 6
2
57
72
Hf [Xe] 4f14 5d2 6s2
Nb [Kr] 4d4 5s1
73
Mo [Kr] 4d5 5s1
74
Tc [Kr] 4d5 5s2
75
Re [Xe] 4f14 5d5 6s2
76
Os [Xe] 4f14 5d6 6s2
Ta [Xe] 4f14 5d3 6s2

W [Xe] 4f14 5d4 6s2
43
Fe [Ar] 3d6 4s2
44
Ru [Kr] 4d7 5s1
Co [Ar] 3d7 4s2
45
Rh [Kr] 4d8 5s1
77
Ni [Ar] 3d8 4s2
46
Pd [Kr] 4d10 5s0
78
Cu [Ar] 3d10 4s1
47
Ag [Kr] 4d10 5s1
79
Zn [Ar] 3d10 4s2
48
Cd [Kr] 4d10 5s2
80
26
27
28
30
bb/CH306/Transitionmetals.doc
La [Xe] 5d1 6s2
Zr [Kr] 4d2 5s2
Mn [Ar] 3d5 4s2
25
29
39
Ti [Ar] 3d2 4s2
22
24
Period 5
2
Ir [Xe] 4f14 5d7 6s2
Pt [Xe] 4f14 5d9 6s1
Au [Xe] 4f14 5d10 6s1
Hg [Xe] 4f14 5d10 6s2
Energies of 3d and 4s orbitals are nearly equal. Generally the 3d orbitals fill after the 4s-orbital
is filled. Cr and Cu are exceptions to the filling order in the first transition series. They have
only one electron in their 4s orbital and one extra electron in their 3d orbital. This gives a more
favorable configuration in accordance with Hunds rule.
The 4d and 5s, and 5d and 6s orbitals are even closer in energy than the 3d and 4s orbtitals
making electron configurations difficult to predict for the 2nd and 3rd transition series.
The properties of the transition metals can be correlated roughly with either the total number of
d-electrons or the number of unpaired electrons.
Melting Points:
Alkali metals melt below 200 C. Several post transition metals are low melting (Ga = 30 C).
Transition metals typically melt above 1000 C. Tungsten is highest melting, above 3400 C. Of
all the elements, carbon has the highest melting point, i.e., ca. 3800 C. Hg is the exception to
the rule. Hg, a liquid at room temperature, has the lowest mp of all metals (-39C).
METALS mp vs. Group Number

4000
Period 6
3500
3000
mp (C)
2000
Zr
Sc
1500
Ti
Ca
500
Cs
0
0
Pt
Pd
Co
Mn
Au
Ni
Cu
Ag
La
Cd
Rb
2A
3B
4B
5B
Ge
Zn
Period 4
K
1A
Rh
Fe
Y
Sr
Ir
Cr
Ba
1000
Ru
Tc
Hf
Period 5
Os
Mo
Nb
2500
-500
Re
Ta
6B
7B
8B
8B
10
8B
La
Ga
Hg
1B
12
2B
Pb
Sn
In
3A
14
4A
16
Group Number
Atomic Size:
Atomic size decreases left to right across each transition metal series as net core charge
increases but size then increases at the far right (Group 1B and 2B) as valence electrons
repulsion increases as d-orbitals fill.
Atomic size, as expected, increases down all Groups in the periodic table as additional shells of
electrons are added with increasing atomic mass. This holds for the 1st and 2nd row transition
metals but the 3rd row transition metals are the same size as the 2nd row. This unexpected
shrinkage is called the lanthanide contraction.
The lanthanide contraction of period 6 (the 3rd transition series) occurs because these elements
contain an additional 14 electrons in the 4f orbitals. The effective nuclear charge increases by
15 between La and Hf (the 1st and 2nd elements in the 3rd transition series).
Results of the Lanthanide Contraction:
1. 3rd transition series metals have the highest densities of all elements, for example:
(g/mL)
22.6
22.4
21.5
20.8
Os
Ir
Pt
Re
Fe = 7.9 g/mL
(g/mL)
19.3
19.3
13.5
11.3
W
Au
Hg
Pb
2. 3rd transition series metals have unusually high ionization energies, i.e., are rather
unreactive.
3. 3rd transition series metals have much higher oxidation resistance. The platinum metals,
i.e., Ru, Os, Rh, Ir, Pd and Pt (plus Au) do not form simple cations or even oxyanions.
Au and Pt are especially useful in low voltage circuits where trace oxidation is
problematic.
METALS Density vs. Group Number

25
Os
Re
Density (g/mL)
20
15
Period 5
Ta
Hf
10
Nb
5
Rb
Cs
Ba
2A
3B
Tc
Mn
Cr
Ru
Rh
Co
Fe
4B
5B
Hg
Pd
Ni
Ag
La
Cd
Cu
7B
8B
8B
8B
10
1B
2B
3A
Pb
Sn
Ge
Ga
Period 4
6B
In
Zn
Ti
Sr Sc
Ca
1A
Mo
Zr
La
Pt
Au
Period 6
Ir
4A
15
Group Number
Acidity and Basicity of Transition Metals:

Recall that nonmetal hydroxides and oxyacids increase in acidity as the oxidation number of the
central nonmetal increases. For example HClO4 (Cl = +7) is more acidic than HClO3 (Cl = +5).
Similarly, the acidity of the hydroxides and oxyacids of transition metals increases as the
oxidation number of the central transition metal increases.
Oxid. #
+1
Mn
+2
+3
+4
MnO
Mn2O3
H2 O
Mn(OH)2
manganese(II
) hydroxide
Basic
+5
+6
+7
MnO2
MnO3
Mn2O7
H2 O
H2 O
H2 O
H2 O
Mn(OH)3
manganese(III
) hydroxide
MnO(OH)2
(H2MnO3)
manganous
acid
MnO2(OH)2
(H2MnO4)
manganic
acid
MnO3(OH)
(HMnO4)
permanganic
acid
Amphoteric
Acidic
Note: The oxyacids of Cl are all acidic. They are shown here only to see an analogous oxidation pattern.
Oxid. #
+1
Cl
HClO
[ClOH]
hypochlorou
s acid
+2
+3
HClO2
[ClO(OH)]
chlorous acid
+4
+5
+6
HClO3
[ClO2(OH)]
chloric
acid
HClO4
[ClO3(OH)]
perchloric
acid
CrO
Cr2O3
CrO3
H2 O
H2 O
H2 O
Cr(OH)2
chromium(II)
hydroxide
Cr(OH)3
chromium(III)
hydroxide
CrO2(OH)2
(H2CrO4)
(H2Cr2O7)
chromic
acid
Cr
+7
General Trends in Acidity:
The more electronegative (EN) the central atom in an oxyacid, the greater the acidity.
The following sequence of decreasing acidity (from left to right) with decreasing EN
illustrates. Get the pKa values from the unit on The Atom and compare EN values.
H2SO4 > H2SeO4 > H3PO4 H3AsO4 > H4GeO4
For a given central atom, the acid strength increases with the number of oxygens it
holds.
H2SO4 > H2SO3
and
HNO3 > HNO2
Problem 1: Write the formulas of all four oxyacids of bromine. Name them and number them
in order of acidity where 1 is most acidic and 4 is least acidic. Explain why this trend in acidity
occurs. Hint: Consider the oxidation state of bromine and consider the stability of the conjugate
base that forms when the acid gives up an acidic hydrogen atom.
Transition Metals as Catalysts:

Transition metals and their compounds function as effective catalysts in both homogeneous
(single phase) and heterogeneous (multiple phase) reactions.
Unreactive metals such as Pt, Pd, Ni and Au are sometimes used in a finely divided state to
provide surfaces upon which heterogeneous reactions occur, e.g., hydrogenation of unsaturated
organics.
Other transition metals act as homogeneous catalysts having d-orbital vacancies that can
accept electrons from reactants to form intermediates that subsequently decompose.
Some typical reactions catalyzed by transition metals follow.
1.
Haber Process:
[Fe2O3, 500 C, 400 atm]

N2 + 3 H2
2.
2 NH3
Contact Process:
[V2O5, 400 C]
2 SO2 + O2
3.
2 SO3
[H2 /Ni @ 25 C, 1 atm]
Hydrogenation:
CH2=CH-CH2CH3
4.
CH3CH2CH2CH3
[Pt, 850 C]
4 NO + 6 H2O
Ostwalt Process:
4 NH3 + 5 O2
2 NO + O2
2 NO2
NO2 + H2O HNO3
5.
Catalytic Converters:
[Pd or Rh]
CO + HCs + O2
CO2 + H2O
NO and NO2 N2 + O2
6.
Linear Polyethylene:
[TiCl4 or MoO3]
CH2=CH2
7.
Redox Reactions:
[Mon(PO4)m]
AsF3 + H2O2
(CH2CH2) n
AsF5
Classification into Subgroups:
Group 8B
The transition metals including Zn, Cd and Hg (Group 2B) are divided into
eight Groups designated as B-Group elements. The number designates the maximum oxidation
number of the Group members. No simple ion of these elements possesses a charge greater
than +3.
Elements in corresponding A and B-Groups form many compounds of identical stoichiometry as
illustrated by the following examples.
1A
2A
3A
4A
5A
6A
7A
-2
NaCl
MgBr2
Al(NO3)3
CCl4
POCl3
SO4
Cl2O7
KNO3
CaCl2
Ga(OH)3
PbO2
PO4-3
H2 S 2 O 7
HClO4
1B
2B
3B
4B
5B
6B
7B
-2
CuCl
ZnBr2
Sc(NO3)3
TiCl4
VOCl3
CrO4
AgNO3
CdCl2
Y(OH)3
ZrO2
VO4-3
H2Cr2O7
Mn2O7
HMnO4
Despite similar stoichiometry in compounds, the chemical properties of A-Group and B-Group
elements are dissimilar.
Group 1B and 2B metals have filled d-orbitals, and d- and s-orbitals, respectively (pseudo-noble
gas configurations) are unusually stable. In contrast, Groups 1A and 2A metals are very
reactive and are never found unreacted in the native state.
Group 8B consists of three columns of three metals each. Each
horizontal row is called triad and is named after the best known
metal of the row, i.e., the iron triad, the palladium triad, and the
platinum triad. Greater horizontal similarities than vertical
similarities are found in Group 8B.
Fe
Co
Ni
Ru
Rh
Pd
Os
Ir
Pt
The iron triad metals (Fe, Co, and Ni) are the only elements in the
periodic table that exhibit ferromagnetism in the uncombined
state.
Problem 2: Without looking this up, write the formula of
a) a common oxide of tungsten
b) a naturally occuring oxide of osmium
Oxidation States:
Characteristically, transition metals can exhibit more than one oxidation state. In most cases,
the maximum oxidation state found in a group is the same as the group number, but this is
usually not the most common oxidation state. The tables below list common oxidation states.
1st Transition Series
3B
Sc
4B
Ti
+4
+3
+2
+3
5B
V
+5
+4
+3
+2
6B
Cr
7B
Mn
+6
+7
+6
+3
+2
+4
+3
+2
Fe
8B
Co
Ni
+3
+2
+3
+2
+3
+2
1B
Cu
2B
Zn
+2
+1
+2
1B
Ag
2B
Cd
The most common oxidation states are in bold. Not all oxidation states are shown.
2nd Transition Series

3B
Y
4B
Zr
5B
Nb
6B
Mo
7B
Tc
Ru
+8
8B
Rh
Pd
+7
+6
+5
+4
+3
+2
+5
+4
+3
+3
+6
+4
+3
+2
+4
+3
+2
+4
+2
+2
+1
s-electrons are outside the d-electrons and are removed first.

Grp. 2B & 3B elements have fixed oxidation states, +2 and +3, respectively (except Hg)
1st transition series metals form ionic compounds which dissolve in water giving solvated
cations (Cr+3, Fe+3, Co+2) whereas 2nd and 3rd transition series metals form only water
soluble oxyanions, e.g., MoO4-2, WO4-2, etc.
Higher oxidation states are more common in the 2nd and 3rd transition series
Element
Sc
Half-Reaction
Sc+3 + 3e- Sc
Reduction Potential, E, (V)

-2.08
Ti
Ti+2 + 2e- Ti
-2.00
+ 2e
-0.26
+ 2e
Cr
-0.56
+ 2e
Mn
-1.02
+ 2e
Fe
-0.41
+ 2e
Co
-0.28
+ 2e
Ni
-0.23
+ 2e
Cu
+0.52
+ 2e
Zn
-0.76
V
Cr
Mn
Fe
Co
Ni
Cu
Zn
+2
Cr
+2
Mn
+2
Fe
+2
Co
+2
Ni
+2
Cu
+2
Zn
+2
These metals (except Cu) are

stronger reducing agents
than H2.
Elements with oxidation states below the most common for a particular metal usually act as
reducing agents. Elements with oxidation states above the most common for a particular
metal usually act as oxidizing agents.
Most transition metals are moderately strong reducing agents that react with dilute mineral
acids (HCl, H2SO4, HNO3) liberating H2 gas. The previous table shows that the reduction
potential of most transition metal ions is unfavorable (negative values, i.e., not
spontaneous). Rather the metals are readily oxidized to their ions. For this reason, few
are found as pure metals in the native state. Most are readily oxidized and thus occur
naturally as oxides. Examples include TiO2 (rutile), MoS2 (molybdenite), WO3 (wolframite),
Fe2O3 (hematite and rust), FeOCr2O3 (chromite), Mn2O3H2O (manganite), etc.
Cu and the noble metals ( Hg, Ag, Pt, Au, Pd, Ir, Ru, Re and Os) are the exceptions. They
are not readily oxidized and can only be dissolved in strong mineral acids or mixtures of
these acids. A number of these metals occur naturally in the elemental state, e.g., Ag, Au,
Cu, etc.
Study the Electrochemical Series table on the next page and memorize the mnemonic
LiKe CaBaNa MAZICNTL H. CHAPA. This is not a complete list but it is useful to the
chemist and is easily remembered.
Problem 3: On a periodic table, mark all the noble metals to learn where they are located.
Problem 4: Write the formula of
a) the most common chloride salt of lanthanum
b) the only sulfide of zinc
c) the most common phosphate of mercury.
Problem 5: Write out the electrochemical series in order of decreasing reactivity as metals.
Problem 6: State whether the following reactions will occur spontaneously at room
temperature. If the reaction does occur, write a balanced equation for the reaction. If the
reaction is not spontaneous, state no reaction.
a)
Zn reacts with water to evolve H2 gas.
b)
Hg reacts with cold dilute HNO3
c)
Ba reacts with water
d)
Ca reacts with concentrated HCl
e)
Cd reacts with dilute H2SO4
f)
Sc reacts with Cr+2 in solution
g)
Ti+2 reacts with V in solution
h)
Cu+2 reacts with Ni in solution
ACITIVITY SERIES OF METALS

The reduction potentials of various metals ions vs. the H 2 half cell are listed. The order of this series can
be easily remembered using the mnemonic LiKe CaBaNa MAZICNTL H. CHAPA
Ion
Li (s)
- 3.0
K (s)
-2.92
Ca (s)
-2.90
Ba (s)
-2.87
Na (s)
-2.71
Mg (s)
-2.37
Al (s)
-1.66
Zn (s)
-0.763
Fe (s)
-0.440
Cd (s)
-0.403
Ni (s)
-0.28
Sn (s)
-0.136
Pb (s)
-0.126
H2 (g)
0.00
Cu (s)
+0.337
Hg (s)
+0.778
Ag (s)
+0.799
Pt (s)
+1.2
Au (s)
+1.68
1e
1e
K (aq)
+2
(aq)
2e
+2
(aq)
2e
Na (aq)
1e
(aq)
2e
+3
(aq)
3e
Zn
+2
(aq)
2e
Fe
+2
(aq)
2e
+2
(aq)
2e
+2
(aq)
2e
Sn
+2
(aq)
2e
Pb
+2
(aq)
2e
2 H (aq)
2e
Ca
Ba
Mg
+2
Al
Cd
Ni
Cu
+2
(aq)
2e
Hg
+2
(aq)
2e
+1
(aq)
1e
+2
(aq)
2e
+1
(aq)
1e
Ag
Pt
Au
Reduction
Potential (V)
Li (aq)
Metal
These metals are powerful

reducing agents which
react even with HOH to
liberate H2 gas
These metals are

moderate reducing
reagents which react with
dilute mineral acids (HCl,
H2SO4, HNO3, etc.) and
liberate H2 gas.
These noble metals are

poor reducing agents and
do not react with dilute
mineral acids. They are
weaker reducing agents
than H2 (g)
A + voltage indicates that a reaction is favorable (compared to hydrogen) in the direction shown.
A - voltage indicates that a reaction is unfavorable but its reverse reaction is favorable.
o
The voltages are standard potentials (E ) which would be measured at standard conditions, i.e.,
25 C, 1 M concentration for aq. ions, and 1 atm. pressure for gases (as per the Nernst equation).
These reactions are referred to as half-cells because each is only half of a reaction. Two half cells
must be combined in order for a chemical reaction to occur. As reduction occurs, oxidation must also
be occurring simultaneously. As one chemical gains electrons, another must be providing (losing)
them.
Add two half cell potentials (one for oxidation and one for reduction). If the combined voltage is a +
value, we can expect the reaction to proceed as written.
Ammine Complexes:
Most representative metal hydroxides and transition metal hydroxides are insoluble in water.
e.g.,
Mg+2 + 2 OH-
Mg(OH)2
Exceptions are the Group 1A metals and Sr(OH)2 and Ba(OH)2.

Some insoluble metal hydroxides are amphoteric; i.e., in addition to acting as bases, they can
act as acids dissolving in an excess of strong base.
e.g.,
Al(OH)3 + NaOH [Al(OH)4]- (a soluble hydroxo complex).
Ammonia is a weak base (pKb = 4.8) and would not be expected to be able to produce a high
enough OH- concentration to dissolve insoluble amphoteric metal hydroxides and form soluble
hydroxo complexes. However, several metal hydroxides do dissolve in an excess of aqueous
ammonia to form ammine complexes.
e.g.,
Cu(OH)2 + 4 NH3 [Cu(NH3)4]+2 + 2 OH-
e.g.,
Co(OH)2 + 6 NH3 [Cu(NH3)6]+2 + 2 OH-
Interestingly, all metal hydroxides that exhibit this behavior are derived from the 12 metals of the
Co, Ni, Cu, and Zn groups. All common cations of these metals form soluble complexes in the
presence of aqueous ammonia.
Co(OH)2 + 6 NH3 [Co(NH3)6]+2 + 2 OHCo(OH)3 + 6 NH3 [Co(NH3)6]+3 + 3 OHNi(OH)2 + 6 NH3 [Ni(NH3)6]+2 + 2 OHCuOH
+ 2 NH3 [Cu(NH3)2]+1 +
OH-
Cu(OH)2 + 4 NH3 [Cu(NH3)4]+2 + 2 OHAgOH
+ 2 NH3 [Ag(NH3)2]+1 +
OH-
Zn(OH)2 + 4 NH3 [Zn(NH3)4]+2 + 2 OHCd(OH)2 + 4 NH3 [Cd(NH3)4]+2 + 2 OHHg(OH)2 + 4 NH3 [Hg(NH3)4]+2 + 2 OHCuOH and AgOH are unstable compounds and decompose to Cu2O and Ag2O, but in the
presence of aqueous NH3 they dissolve as shown above.
Problem 7: Write a balanced equation for the reaction of 6 moles NH3 with each of the
following
a) Au(OH)3
b) Pt(OH)4
10
Colors of Transition Metal Complexes:

Unlike compounds of the representative elements, compounds of transition metals are colored.
Why?
Colors of transition metal complexes arise from absorption of visible light as electrons undergo
transitions from one d-orbital to another. In their elemental forms, all five of the d-orbitals of
transition metals are degenerate (of the same energy) but in their complexes this changes.
Review the shapes and orientations of the five d-orbitals. In octahedral complexes, for example,
electrons in the dZ2 and dX2-Y2 orbitals are repelled by the donor electrons of the six ligands. d-orbital
electrons resist occupying the same region of space as the ligands donor electrons. As a result, the d Z2
and dX2-Y2 orbitals are higher in energy than the dXY, dXZ and dYZ orbitals.
eg
dX2-Y2
dXY
dXZ
dYZ
dX2-Y2
Field
Splitting
Energy
(Oct)
dZ2
dZ2
Free metal ion orbital energies
t2g
dXY
dXZ
dYZ
Metal ion orbital energies in an

octahedral field.
The d-orbitals are split into sets of orbitals separated by energies corresponding to wavelengths of
electromagnetic radiation in the visible region (400 to 800 m).
d-orbitals are split in other ways in other complexes such as tetrahedral, square planar complexes.
The magnitude of the field splitting energy depends upon the electron donating ability (field
strength) of the ligands. The frequency and wavelength of light absorbed (i.e., the color) are
related to the size of the field splitting energy, which in turn depends upon the electron donating
ability (field strength) of the ligands. Recall the relative field strength of various ligands.
I- < Br- <
WEAK
LIGANDS
Cl- < F- < OH- < C2O4-2 < H2O < SCN- <
NH3 < en < NO2- < CN- < CO
Increasing ability to donate an electron pair to a metal ion
STRONG
LIGANDS
A Cu+1 ion has a d10 electron configuration and all d-orbitals are filled. In order for absorption of
electromagnetic radiation to occur, a d-electron must be promoted to a 4p orbital (the next
highest orbital with room). Because the energy level of the 4p orbitals is much higher that of the
3d orbitals, photons of a very high energy are needed, i.e., ultraviolet radiation. No visible light
is absorbed so Cu+1 complexes, such as Cu(CN)2-, are colorless.
A Cu+2 ion has a d9 configuration with a vacancy in one of its eg orbitals. Visible light has
sufficient energy to excite a t2g electron to the vacant position in the eg orbitals. Many Cu+2
complexes are colored. Some examples of colored Cu+2 complexes follow.
11
Complex
of Light
Absorbed
Color of Light
Absorbed
Color of Light
Transmitted
[Cu(H2O)4]+2
610 m
orange
blue
430 m
purple
green
530 m
green
purple
[Cu(en)2]
+2
[CuBr4]-2
When certain visible wavelengths are absorbed from incoming white light, the light not absorbed
is transmitted or reflected and has the complementary color of the light absorbed. The
complementary color is the color seen by an observer.
Complementary Colors:
Very simply, blue and yellow are complementary; red and cyan (blue-green) are complementary;
green and magenta (blue-red) are complementary. A more complete list follows.
(m)
Spectral
Color
Complementary
Color
410
violet
lemon yellow
430
indigo
yellow
480
blue
orange
500
blue-green
red
530
green
purple
560
lemon yellow
violet
580
yellow
indigo
610
orange
blue
680
red
blue-green
The color of aqueous solutions of some transition metal nitrates compared to those of representative
metal nitrates are listed.
Representative Metal
Nitrates
Color of Aqueous
Solution
Transition Metal Nitrates
Color of Aqueous
Solution
Na+
colorless
Cr+3
deep blue
colorless
+2
pale pink
Fe
+2
pale green
+3
orchid (rust)
+2
Ca
+2
Mg
colorless
Mn
+3
colorless
Fe
Sn+2
colorless
Co+2
colorless
+2
green
+2
blue
Al
Sn
+4
Pb
+2
colorless
Ni
Cu
pink
12
Absorption Spectrum:
The amount of light absorbed by a sample as a function of wavelength is known as its
absorption spectrum. The visible absorption spectrum of clear (not colorless) samples can be
determined by scanning with a visible spectrophotometer. This is useful in the analysis of
transition metal complexes. The wavelength of maximum absorption max is related to the field
splitting energy of a complex.
In the example below, the absorption spectrum of [Ti(H2O)6]+3 shows a max in the visible region
at 530 m (green) and so the complex appears purple to the eye.
Abs.
max = 530 m
300
400
500
600
700
800
(m)
Problem 8: The presence of partially filled d-orbitals is usually necessary for color.
Explain why K+ and Sr+2 ions are usually colorless
Explain why Al+3 and Sn+4 ions are usually colorless.

Problem 9: Aqueous solutions of CrCl2 are blue, CrCl3 are green, K2CrO4 are yellow and
K2Cr2O7 are orange. Explain why these solutions are different colors.
Problem 10: In the discussion of colorless Cu+1 ion complexes on page 9, no mention was
made of the fact that these complexes have empty 4s orbitals that could accommodate excited
electrons from the 3d orbitals. This being the case, propose a reason for that fact that such
transitions do not give rise to absorption in the visible spectrum. What type of the
electromagnetic radiation would you expect to be absorbed in such a transition?
Problem 11: Answer the following questions with respect to the three transition metal
complexes:
[Co(H2O)6]+3, [CoF6]-3, [Co(NH3)6]+3
a) List the complexes in order of increasing field splitting energy (Oct).
b) The wavelengths of light absorbed by these are 475, 600, and 900 m. Predict which
wavelength corresponds to each compound.
c) Predict the apparent (observed) color of each complex.
13
Ferromagnetism:
All electrons spin and since all moving electric charges produce magnetic fields, electrons behave
as tiny magnets. When electrons are paired in orbitals, their spins are opposite (lowest energy
state) and so their magnetic fields cancel. Substances with only paired electrons are either
nonmagnetic or diamagnetic. Diamagnetic objects, when placed in a magnetic field, are not
attracted, in fact they are weakly repelled. Examples of diamagnetic elements include Zn and Cd.
When an atom possesses one or more unpaired electrons, the substance is said to be
paramagnetic. Paramagnetic substances contain many weak atomic magnets, but in the solid
phase, the magnetic fields are not aligned; instead they are randomly oriented. When placed in
a magnetic field, alignment of electron spins with the external magnetic field occurs to some
extent throughout the various regions (domains) in the solid. As a result, such paramagnetic
materials are weakly attracted to external magnetic fields. Examples of paramagnetic
substances include Al and O2.
Some metals exhibit strong magnetic properties. These materials are called ferromagnetic.
They are typically 106 times stronger than paramagnetic materials. Fe, Co, and Ni are the only
three elements that are ferromagnetic. They have 4, 3, and 2 unpaired d-electrons,
respectively. In ferromagnetic materials, after the external magnetic field is removed, the
ferromagnetic material may remain magnetized as its electron spins remain aligned. It becomes
a permanent magnet. Permanent magnets can become demagnetized by heating, pounding, or
melting.
One might ask, Why is Mn, with 5 unpaired electrons, not ferromagnetic?
Ferromagnetism is a solid state property. When individual paramagnetic atoms are correctly
spaced their magnetic fields readily align. In Mn, interatomic distance is incorrect to allow
optimal magnetic field alignment. Adding proper amounts of Cu to Mn adjusts the interatomic
spacing such that this alloy becomes ferromagnetic. Some naturally occurring metal oxides are
ferromagnetic, e.g., Fe3O4 (magnetite) and CrO2 are both used in magnetic recording tapes.
3d0
3d1
3d2
3d3
3d5
3d5
3d6
3d7
3d8
3d9
3d
unpaired
electrons
10
5
4
1
0
K+
Ca+2
Ti+4
Ti+3
V+4
V+3
V+2
Cr+3
Cr+2
Mn+3
Mn+2
Fe+3
Fe+2
Co+2
Ni+2
Cu+2
Cu+1
Zn+2
Ga+3
14
The Inner Transition Metals (f-Transition Metals):

All inner transition elements, are metals in which f-orbitals are being filled. These f-orbitals are
two shells inside the outermost occupied shell being filled.
In the Lanthanides (58Ce
In the Actinides (90Th
Lu), the 4f orbitals being filled are within the 6s and 5d orbitals.
71
Lr), the 5f orbitals being filled are within the 7s and 6d orbitals.
103
Note that the lanthanides do not include lanthanum and the actinides do not include actinium.
The chemical properties of these elements are governed by their valence electrons (in their
outermost shells). Each rare earth element has two s-electrons in its outermost shell and either
eight or nine electrons in the next shell inward (two s, six p, and zero or one d-electron). This
accounts for the chemical similarity of these elements. Most form M+3 ions by loss of the two
outer s-electrons and either the d-electron one shell inward or one of the f-electrons two shells
inwards.
Electron Configuration of the Lanthanides:
Atomic
Number
Name
Symbol
Electron
Configuration
Formula of
Chloride
Ox. State of
Lanthanide
57*
lanthanum*
La
[Xe] 5d1 6s2
LaCl3
+3
58
cerium
Ce
[Xe] 4f1 5d1 6s2
CeCl3, CeCl4
+3, +4
PrCl3, PrCl4
+3, +4
59
praseodymium
Pr
[Xe] 4f 6s
60
neodymium
Nd
[Xe] 4f4 6s2
NdCl3
+3
61
promethium
Pm
[Xe] 4f5 6s2
PmCl3
+3
62
samarium
Sm
[Xe] 4f6 6s2
SmCl2, SmCl3
+2, +3
63
europium
Eu
[Xe] 4f7 6s2
EuCl2, EuCl3
+2, +3
64
gadolinium
Gd
[Xe] 4f7 5d1 6s2
GdCl3
+3
65
terbium
Tb
[Xe] 4f9 6s2
TbCl3, TbCl4
+3, +4
66
dysprosium
Dy
[Xe] 4f10 6s2
DyCl3
+3
67
holmium
Ho
[Xe] 4f11 6s2
HoCl3
+3
68
erbium
Er
[Xe] 4f12 6s2
ErCl3
+3
69
thulium
Tm
[Xe] 4f13 6s2
TmCl3
+3
70
ytterbium
Yb
[Xe] 4f14 6s2
YbCl2, YbCl3
+2, +3
LuCl3
+3
[Xe] 4f14 5d1 6s2
* La is not an f-transition element and is only shown here to emphasize the filling order
71
lutetium
Lu
Empty (f0), half (f7) and full (f14) orbitals are favored electron configurations of the metals and
their ions, e.g., Ce+4, Gd+3, Lu+3.
Whereas the d-transition metals show a strong tendency to form coordination compounds, the
f-transition metals form few such compounds.
15
The Lanthanides (Rare Earths):

The lanthanides are not as rare as the name rare earths implies. Ce and Nd are more
abundant than Pb. Tm is about as prevalent as iodine. Mixtures of lanthanides and actinides
occur in minerals such as monazite and gadolinite. However, these elements are difficult to
obtain in pure form because of their chemical similarities. They are usually separated
chromatographically based on differences in attraction of these similar compounds in solution
for ionic sites on insoluble resins.
The standard reduction potentials (E values) of the lanthanides for M+3 (aq) + 3e- M (s) all
fall between 2.52 V (La) and 2.25 V (Lu). Thus they are all active metals liberating H2 from
hot water and dilute acids while undergoing oxidation to M+3 ions.
M(s) + 3H2O(l) M(OH)3(s) + 3/2 H2(g)
M(s) + 3HCl MCl3 + 3/2 H2(g)
The lanthanides react with chlorine forming salts of the general formula MCl3.
2M(s) + 3Cl2 2MCl3(s)
All lanthanides are silvery, high melting (800 to 1600C) metals. They oxidize readily forming
M2O3 oxides and MX3 halides. Their hydroxides are not very soluble and are basic. Their
carbonates, phosphates and fluorides are only slightly soluble. In all these properties (except
oxidation state) they resemble the alkaline earth metals (Group 2A).
Actinides:
The actinides are all radioactive. Uranium (Z = 92) is the upper limit of naturally occurring
elements. Of the 14 actinides, only U and Th are found in appreciable quantities in nature. All
elements of higher atomic mass (the transuranium elements) have only been synthesized in
small amounts in particle accelerators. Macroscopic samples of mendelevium (Md), nobelium
(No) and lawrencium (Lr) have never been seen.
Actinides are silvery and chemically reactive. Like the lanthanides, they form highly colored
compounds.
Some Applications of Lanthanides and Actinides:
A cerium salt, e.g., Ce(SO4)3, is a common oxidizing titrant in titrimetric analysis.
Several of the rare earths have some commercial importance. Praseodymium and neodymium
are used to tint sunglasses and welding/glassblowers goggles. Eu2O3, Y2O3, and Gd2O3 are
phosphors used in the fluorescent screens of color televisions. Thorium nitrate has been used
for over a century in gas mantles of lanterns and street lamps.
Uranium and Plutonium are used as fuel elements in nuclear reactors and nuclear weapons.
To extract uranium, its oxide ores are treated with nitric acid. The nitrate that forms is reduced
to metal with Ca. To enrich uranium in its fissionable 235U isotope for use in nuclear power
plants, the oxide is converted to UF4 with HF. The UF4 is oxidized to the volatile UF6 by F2. The
vapor of UF6, which contains both 238U and 235U, is then subjected to repeated diffusion through
porous barriers to concentrate the 235UF6 (Grahams Law).
SmCo5 alloy is the strongest known permanent magnet.
16
SELF STUDY QUESTIONS FOR TRANSITION METALS

1. Describe each of the following types of compounds as acidic, basic, or amphoteric
a) metal oxides
b) non metal oxides
c) oxides of metalloids
2. Collectively, the f-transition metals are also referred to by two other names. List both
and .
3. List 5 general (characteristic) properties of transition metals (aside from the fact that they are metals):
a) ..
b) ..
c) ..
d) ..
e) ..
4. The melting point of transition metals is usually not below .. C.
5. The highest melting transition metal is .
6. The highest melting elements of all is .. and its melting point is
. C.
7. The highest melting element in all transition metal series occurs in Group . (see the graph on
page 2).
8. The lowest melting transition metal is .
9. Circle the correct answer. Atomic size increases or decreases left to right from Groups 3B to Group
8B across each transition metal series.
10. Rank 1st transition metal series, 2nd transition metal series and 3rd transition metal series in order of
a) increasing melting point (1= lowest) (see graph on page 2)
b) increasing density (1 = lowest) (see graph on page 3)
11. Explain what is meant by the Lanthanide contraction.
12. List 3 results of the Lanthanide contraction.
13. List the following densities to the nearest whole number (g/mL): Os .. , Hg ,
Pb .., Fe ., Li (to 1 decimal point) .. . (Check a periodic table for the values not
listed in the notes.)
14. Given the formulas of a series of oxides of transition metals, rank the oxides in order of increasing
acidity, where 1 = least acidic. For example, rank the following in order of increasing acidity:
MnO2
Mn2O7 Mn2O3
MnO
MnO3
15. What is the principle behind the trend in question 14? Make a general statement that describes the
trend and that could be applied to other series of oxides of a transition metal.
16. Given a group of analogous oxyacids, circle the most acidic and draw a square around the least
acidic, e.g.,
a)
H3PO4
H2SeO4
H2SO4
b) H3PO4 H3PO2 H3PO3

c) HClO
HClO4
H4GeO4
(different number of oxygens)
HClO2 HClO3
(same number of oxygens)
(different number of oxygens)
17
17. What are the two principles behind the trends in question 16? Make two general statements, one for
each of the two trends. These trends should be applicable to other groups of analogous oxyacids.
18. Transition metals are catalysts in many diverse types of chemical reactions (see page 5). What
characteristic of transition metals makes this possible? (Hint: read page 7).
19. Distinguish between homogenous and heterogeneous catalysis and give an example of each.
20. List 4 transition metals that are often used as catalysts for hydrogenation of unsaturated organics.
21. State the relationship between B-Group number and oxidation state of metals in the group.
22. No simple (uncomplexed) transition metal possess a charge greater than . .
23. Predict the formulas of transition metal compounds. (Hint: use group numbers and oxidation
numbers, see page 6). For example, give the formula of:
a) the chloride of cadmium
b) the phosphate of silver
c) the sulfate of scandium
d) the carbonate of zirconium
e) permanganic acid (you will note the similarity to Grp 7A oxyacids)
f)
chromic acid (you will note the similarity to Grp 6A oxyacids)
24. Name the 3 horizontal triads of Group 8B metals

25. List 3 elements that are ferromagnetic.
26. State the difference between the water soluble ions of the 1st transition series metals compared to
those of the 2nd and 3rd transition series and give one example of each to illustrate. (see page 7).
27. Circle the correct answer. Most transition metals are readily oxidized, readily reduced, or unreactive
in dilute mineral acids such as HCl, H2SO4, etc.
28. List the formula of 4 mineral acids. (These are not listed in these notes, however, mineral refers to
the fact that they are derived from minerals, i.e., the earth, not organic)
29. List the chemical symbols of 5 noble metals.
30. Describe the chemical reactivity of noble metals.
31. You will need to memorize the mnemonic on the top of page 9, i.e., LiKe CaBaNa, MAZINCTL H.
CHAPA and then answer questions like those in problem 6 on page 8.
32. Circle the correct answer: A negative or positive reduction potential (voltage) indicates that a reaction
is spontaneous as written, compared to hydrogen.
33. Most A-group elements hydroxides are insoluble. List the formulas of all A-group element hydroxides
that are water soluble.
34. Write the formula of an amphoteric hydroxide of an A-group element.
35. All transition metal hydroxides from four of the B-groups dissolve in aqueous ammonia. List the
symbols of the metals at the top of each of the four groups.
36. Write an balanced equation for the reaction of
a) zinc hydroxide with 4 moles NH3
b) cobalt(III) hydroxide with 6 moles of NH 3
c) etc. (see page 10).
37. The five degenerate d-orbitals are split into two energy levels in octahedral complexes. Draw a
diagram showing this splitting and indicate which orbitals are each level.
18
38. Explain what is meant by the term field splitting energy in an octahedral complex.
39. Draw the electron configuration of Cu+ and Cu+2 in an octahedral complex and explain why Cu+2 is
more strongly colored than Cu+. The same rationale applies to other transition metal ions so you
should be able to do this for other transition metal ions as well.
40. The magnitude of the field splitting energy in a transition metal complex depends upon what
characteristic of the ligands?
41. Write the formula of one ligand that is a weak donor (.), one that is a strong donor (..)
42. CuSO45H2O is bright blue in appearance. What color of light is absorbed by this compound?
43. K2Cr2O7 is a dark orange crystalline solid. What color of light is absorbed by this compound?
44. KMnO4 forms dark purple solutions. What color of light is absorbed by this compound?
You are not expected to memorize all the complementary colors. These three should be enough to
illustrate the concept.
45. Explain what is meant by the term max in an absorption spectrum.
46. Explain why K+ and Sr+2 are usually colorless.
47. Explain why Al+3 and Sn+4 are usually colorless.
48. Answer question 11 on page 13. From our previous study of Coordination Complexes, it is assumed
that you recall that NH3 is a strong donor ligand, followed by H2O. F is a weak donor ligand. It is also
assumed that you recall the visible spectrum runs from 400 to 800 m, 400 being higher energy
(violet light) and 800+ being lower energy (red light).
49. Describe how the following materials behave when placed in a magnetic field
a) diamagnetic
b) paramagnetic
c) ferromagnetic
50. Write the formulas of 3 ferromagnetic elements and 2 ferromagnetic metal oxides
51. For the f-transition metals, list the most common oxidation state .. (see table p. 15)
52. How many actinides are there?
53. The standard reduction potential of all lanthanides fall between .. and . V (answer to 1
decimal place and include the sign, + or -)
54. Write a balanced chemical equation for the reaction of a lanthanide in hot water. (hint recall the most
common oxidation state of lanthanides).
55. How many actinides are there?
56. How many of the actinides are radioactive?
57. Give the symbol and atomic number of the heaviest (largest) naturally occurring element.
58. Uranium and plutonium are used primarily for what purposes?
19
CHEMISTRY AND APPLICATIONS OF SELECTED TRANSITION METALS

Group 6B: Chromium, Molybdenum and Tungsten:
Chromium: [Ar] 3d5 4s1
The chief ore is chromite, FeCr2O3. The element is industrially produced by reduction of this
oxide with Al. Chromium is a silvery, hard, brittle metal (mp = 1860C). It is extremely resistant
to ordinary corrosive agents, which accounts for its extensive use as an electroplated protective
coating. The metal dissolves in nonoxidizing mineral acids such as hydrochloric or sulfuric, but
not in aqua regia (a 3:1 mixture of HCl:HNO3) or concentrated or dilute cold nitric acid. These
later reagents passivate the metal making it more resistant to corrosion.
Chromium is mixed with iron to make various stainless steels (10 to 25% Cr). Nickel is
sometimes also used. Stainless steels are hard, dense, corrosion resistant steels.
Chromiums most common oxidation states are +2, +3 and +6. The +3 state is most stable.
Cr+2 + 2e- Cr
E = -0.56
Cr+3 + e- Cr+2
E = -0.41
Chromium dissolves slowly in dilute HCl or dilute H2SO4 liberating H2 and forming a blue
solution of chromous ion.
Cr(s) + 2H+(aq) Cr+2(aq) + H2(g)
Normally, the blue color is not observed because the Cr+2 ion is rapidly oxidized to violet Cr+3.
4Cr+2(aq) + O2(g) + 4H+(aq) 4Cr+3(aq) + 2H2O(l)
When HCl solution is used, the solution appears green as a result of the formation of complex
ions containing chloride coordinated to chromium, such as Cr(H2O)4Cl2+. Note that all Cr+3
complexes are hexacoordinate.
Chromium(III) hydroxide is amphoteric.
Cr(OH)3(s) + 3H+ Cr+3 + 3H2O
Cr(OH)3(s) + OH- Cr(OH)4Chromium is also encountered in aqueous solution in the +6 oxidation state. In basic solution,
the yellow chromate ion, CrO4-2, is the most stable form. In acidic solution, the dichromate ion,
Cr2O7-2 is formed.
CrO4-2(aq) + H+(aq) HCrO4-(aq)
2HCrO4-(aq) Cr2O7-2(aq) + H2O(l)
The equilibrium between these ions is easily observable because CrO4-2 is bright yellow and
Cr2O7-2 is deep orange.
The dichromate ion in acidic solution is a strong oxidant but chromate ion in basic solution is a
weak oxidant.
Cr2O7-2 + 14H+ + 6e- 2Cr+3 + 7H2O
E = +1.33 V
CrO4- + 4H2O + 3e- Cr(OH)3 + 5OH- E = -0.12 V
20
Dehydration of chromate or dichromate salts with concentrated H2SO4 produces chromium

trioxide (CrO3), also called chromia. Chromium(VI) oxide is a strong oxidant. A powerful
cleaning solution used for removing greasy stains and coatings from laboratory glassware is
made by adding concentrated H2SO4 to a solution of K2Cr2O7. The active ingredients are CrO3,
an oxidant, and H2SO4, an excellent solvent. This cleaning solution should be handled with
caution because it is corrosive and chromium(VI) compounds are toxic and carcinogenic.
Chromium(VI) is commonly used in electroplating operations. Removal of chromium from
industrial wastewater is required by law. A common method is reduction of Cr+6 with Na2SO3
(sodium sulfite) or NaHSO3 (sodium bisulfite) in acidic solution. The Cr+3 is then precipitated as
the insoluble hydroxide [Cr(OH)3], (Ksp = 6.7 10-31) by raising the pH to the point where the
hydroxide is least soluble (pH 8 to 9). Recall that Cr(OH)3 is amphoteric and its solubility
increases in strongly basic solution.
Problem: Draw the Lewis structures of chromate and dichromate ions. Note that Lewis
structures show all valence (outer shell) electrons. For Lewis structures of B Group elements
the outermost s-electrons and d-electrons are considered as valence electrons and are shown
in Lewis structures.
Problem: Calculate the residual concentration of Cr+3 (mg/L as Cr) remaining after an acidic 2.0
M solution of Cr+3 is neutralized with NaOH. Cr(OH)3 Ksp = 6.7 10-31.
Molybdenum and Tungsten:
Other members of Group 6B are Mo ([Kr] 4d5 5s1) and W ([Xe] 4f14 5d4 6s2).
Molybdenum occurs chiefly as molybdenite, MoS2 but also as molybdates such as PbMoO4 and
MgMoO4.
Tungsten is found almost exclusively as tungstates, i.e., wolframite (FeWO4+ MnWO4), scheelite
(CaWO4) and stozite (PbWO4).
The elemental forms of both are silvery and extremely refractory (high melting); Mo melts at
2620C and W melts at 3420C. Neither metal is attacked even by concentrated acids.
Concentrated nitric acid passivates the surface of Mo.
The chief uses of both metals are in the production of alloy steels; even small amounts cause
tremendous increases in hardness and strength. High speed steels, containing W and Cr, are
used to make cutting tools that remain hard even at high heat. Tungsten is also extensively
used as filaments for incandescent light bulbs.
Both Mo and W exist in multiple oxidation states (+2, +3, +4, +5, and +6). The +6 state is most
stable.
MoO3 and WO3 are more thermally stable, less acidic and weaker oxidants than CrO3.
Both Mo+6 and W+6 give tetrahedral oxo anions, MO4-2, whose alkali metal salts are water
soluble, e.g., Na2MoO4 and (NH4)2WO4. These anions polymerize on acidification giving rise to
a very complicated series of isopolyanions and in the presence of other elements
heteropolyanions. Some examples follow.
21
Isopolymolybdates:
When a basic solution of MoO4-2 is acidified, the molybdate ions condense in definite steps to
form a series of polymolybdate ions.
7MoO4-2 + 8H+ 4H2O + Mo7O24-6 (paramolybdate ion)
In more acidic solution octamolybdate ion [Mo8O26]-4 is formed.
Isopolytungstates:
Like Mo, as the pH is lowered, tungstate (WO4-2) in solution polymerizes to various
polytungstates, the most important being paratungstate, W12O41-10.
These isopolyanions combine with other oxo anions, particularly those of orthophosphate
(PO4-3) and orthosilicate (SiO4-4) forming brightly colored heteropolyanions.
Heteropolymolybdates
One important use of heteropolymolybdates is in the spectrophotometric determination of
phosphates and silicates in waste water and in industrial cleaning and electroplating solutions.
Phosphorus (as orthophosphate) can be quantitatively measured at concentrations below 1ppm.
Ammonium molybdate, (NH4)6Mo7O244H2O is added to a sample containing phosphate. When
the pH is lowered to ca. 0.7, yellow 12-molybdophosphoric acid polymer forms (H3PMo12O40).
This is reduced with SnCl2, for example, to a blue complex called molybdenum blue and read
on a spectrophotometer at 660 m.
Silica (as orthosilicate) can be quantitatively measured at concentrations near 1ppm.
Ammonium molybdate, (NH4)6Mo7O244H2O is added to a sample containing silicate.
When the pH is lowered to ca. 1.2, yellow 12-molybdosilicic acid polymer forms (H4SiMo12O40).
This is read spectrophotometrically at ca. 300 m.
Alternately, the yellow 12-molybdosilicic acid can be reduced to a molybdenum blue complex
and measured down to 0.2ppm at 815m.
22
Group 7B (Mn, Tc and Re)

Manganese:
Mn [Ar] 3d5 4s2
Manganese is relatively abundant, constituting about 0.085% of the earths crust. Among the
heavy metals, only Fe is more abundant. It occurs naturally as oxides or carbonates. It also
occurs over wide expanses of the Pacific seabed as nodules (combined with Ni, Cu and Co)
ranging in size from a few millimeters to a few meters in diameter. Billions of tons are present
but mining them presents a major technical and political challenge.
The metal is obtained from the oxide by reduction with Al.
Elemental manganese is hard and shiny and, like vanadium and chromium, is used mostly to
make steel alloys. A small amount of Mn (< 1%) makes steel easier to roll, forge, and weld.
Steel blades made with 12% Mn is tough enough to be used for naval armor and bulldozer
blades. Small amounts of Mn are added to aluminum beverage cans and bronze alloys to make
them stiffer and tougher.
The chemistry of Mn resembles that of Cr in some respects. The free metal is reactive and
readily displaces H2 from acids to form pale-pink Mn+2 ion:
Mn(s) + 2H+(aq) Mn+2(aq) + H2(g)
E = + 1.1.8 V
Like Cr, Mn can use all its valence electrons in its compounds and exhibits all oxidation states
from +1 through +7, with +2, +4. The +7 state is most common but only occurs in oxo
compounds.
As the oxidation state of Mn rises, its electronegativity rises and its oxides change from basic to
acidic. Manganese(II) oxide (MnO) is basic, manganese (III) oxide (Mn2O3) is amphoteric.
Manganese(IV) oxide (MnO2) is insoluble, so it shows no acid-base properties; it is used in drycell and alkaline batteries as the oxidizing agent in a redox reaction with Zn. Manganese(VII)
oxide (Mn2O7) reacts with water to form permanganic acid (HMnO4), which is as strong as
perchloric acid (HClO4).
All manganese species with oxidation states greater than +2 act as oxidants, but the purple
permanganate ion is particularly powerful. As with Cr in its highest oxidation state, MnO4- is a
much stronger oxidant in acidic than in basic solution.
MnO4- (aq) + 2H2O (aq) + 3e- MnO2(s) + 4OH-
E = + 0.58 V
MnO4- (aq) + 4H+(aq) + 3e- MnO2(s) + 2H2O
E = + 1.68 V
MnO4- (aq) + 8H+(aq) + 5e- Mn+2(aq) + 4H2OE = + 1.49 V

KMnO4 is useful in the laboratory as a strong oxidant, which in strongly acidic media is reduced
to colorless Mn+2 ion and in moderately acidic or basic solution is reduced to a brown
precipitate (MnO2). The color change and formation of the precipitate are good indicators of the
occurrence of a chemical reaction in qualitative testing.
Unlike Cr+2 and Fe+2, the Mn+2 ion resists oxidation in air. Removing an electron from the Mn+2
ion is difficult because it disrupts the stable d5 configuration.
Problem: Draw Lewis structures of MnO4- and dimanganese heptoxide (Mn2O7).
23
Technetium (Tc) and Rhenium (Re):

Tc [Kr] 4d5 5s2 and Re [Xe] 4f145d5 6s2 resemble each other closely in chemistry but differ
noticeably from manganese, although there are similarities in stoichiometries, e.g., MnO 4- and
ReO4-.
There are no stable isotopes of Tc. It occurs naturally in trace quantities as short-lived products
of radioactive decay of uranium. Most of the Tc in use is produced synthetically in fission
reactors.
Rhenium is in low abundance in the earths crust (ca. 10-90%). It is recovered in flue dusts (soot)
during the refining of molybdenum sulfide ores. Pt-Re thermocouples (electric thermometers)
and rhenium catalysts for hydrogenation are two of the few commercial uses of rhenium. Owing
to its scarcity Re is five times more expensive than gold.
24

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TRANSITION METAL CHEMISTRY

All are metals

V [Ar] 3d3 4s2

Cr [Ar] 3d5 4s1

Hf [Xe] 4f14 5d2 6s2

Nb [Kr] 4d4 5s1

Mo [Kr] 4d5 5s1

Tc [Kr] 4d5 5s2

Re [Xe] 4f14 5d5 6s2

Os [Xe] 4f14 5d6 6s2

Ta [Xe] 4f14 5d3 6s2

Fe [Ar] 3d6 4s2

Ru [Kr] 4d7 5s1

Co [Ar] 3d7 4s2

Rh [Kr] 4d8 5s1

Ni [Ar] 3d8 4s2

Pd [Kr] 4d10 5s0

Cu [Ar] 3d10 4s1

Ag [Kr] 4d10 5s1

Zn [Ar] 3d10 4s2

Cd [Kr] 4d10 5s2

La [Xe] 5d1 6s2

Zr [Kr] 4d2 5s2

Mn [Ar] 3d5 4s2

Ti [Ar] 3d2 4s2

Ir [Xe] 4f14 5d7 6s2

Pt [Xe] 4f14 5d9 6s1

Au [Xe] 4f14 5d10 6s1

Hg [Xe] 4f14 5d10 6s2

METALS mp vs. Group Number

METALS Density vs. Group Number

Acidity and Basicity of Transition Metals:

General Trends in Acidity:

Transition Metals as Catalysts:

[Fe2O3, 500 C, 400 atm]

Classification into Subgroups:

2nd Transition Series

s-electrons are outside the d-electrons and are removed first.

Reduction Potential, E, (V)

These metals (except Cu) are

Zn reacts with water to evolve H2 gas.

Hg reacts with cold dilute HNO3

Ba reacts with water

Ca reacts with concentrated HCl

Cd reacts with dilute H2SO4

Sc reacts with Cr+2 in solution

Ti+2 reacts with V in solution

Cu+2 reacts with Ni in solution

ACITIVITY SERIES OF METALS

These metals are powerful

These metals are

These noble metals are

Exceptions are the Group 1A metals and Sr(OH)2 and Ba(OH)2.

Al(OH)3 + NaOH [Al(OH)4]- (a soluble hydroxo complex).

Cu(OH)2 + 4 NH3 [Cu(NH3)4]+2 + 2 OH-

Co(OH)2 + 6 NH3 [Cu(NH3)6]+2 + 2 OH-

Cu(OH)2 + 4 NH3 [Cu(NH3)4]+2 + 2 OHAgOH

Colors of Transition Metal Complexes:

Free metal ion orbital energies

Metal ion orbital energies in an

NH3 < en < NO2- < CN- < CO

Increasing ability to donate an electron pair to a metal ion

Transition Metal Nitrates

Explain why K+ and Sr+2 ions are usually colorless