Section 21.

1
The Transition Metals: A Survey
AP LEARNING OBJECTIVES, MARGIN NOTES AND
REFERENCES
• LEARNING OBJECTIVES
• LO 1.10 STUDENTS CAN JUSTIFY WITH EVIDENCE THE ARRANGEMENT OF THE PERIODIC TABLE AND CAN APPLY
PERIODIC PROPERTIES TO CHEMICAL REACTIVITY.

• LO 1.11 THE STUDENT CAN ANALYZE DATA, BASED ON PERIODICITY AND THE PROPERTIES OF BINARY COMPOUNDS,
TO IDENTIFY PATTERNS AND GENERATE HYPOTHESES RELATED TO THE MOLECULAR DESIGN OF COMPOUNDS FOR
WHICH DATA ARE NOT SUPPLIED.
Section 21.1
The Transition Metals: A Survey

TRANSITION METALS
• SHOW GREAT SIMILARITIES WITHIN A GIVEN PERIOD AS
WELL AS WITHIN A GIVEN VERTICAL GROUP.

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Section 21.1
The Transition Metals: A Survey
THE POSITION OF THE TRANSITION ELEMENTS ON THE PERIODIC
TABLE

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Section 21.1
The Transition Metals: A Survey

FORMING IONIC COMPOUNDS

• MORE THAN ONE OXIDATION STATE IS OFTEN FOUND.
• CATIONS ARE OFTEN COMPLEX IONS – SPECIES WHERE
THE TRANSITION METAL ION IS SURROUNDED BY A
CERTAIN NUMBER OF LIGANDS (LEWIS BASES).

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Section 21.1
The Transition Metals: A Survey

THE COMPLEX ION CO(NH3)63+

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Section 21.1
The Transition Metals: A Survey

IONIC COMPOUNDS WITH TRANSITION METALS

• MOST COMPOUNDS ARE COLORED BECAUSE THE
TRANSITION METAL ION IN THE COMPLEX ION CAN
ABSORB VISIBLE LIGHT OF SPECIFIC WAVELENGTHS.
• MANY COMPOUNDS ARE PARAMAGNETIC.

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Section 21.1
The Transition Metals: A Survey

ELECTRON CONFIGURATIONS
• EXAMPLE
• V: [AR]4S23D3

• EXCEPTIONS: CR AND CU
• CR: [AR]4S13D5
• CU: [AR]4S13D10

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Section 21.1
The Transition Metals: A Survey

ELECTRON CONFIGURATIONS
• FIRST-ROW TRANSITION METAL IONS DO NOT HAVE
4S ELECTRONS.
• ENERGY OF THE 3D ORBITALS IS SIGNIFICANTLY LESS THAN THAT OF THE 4S
ORBITAL.

TI: [AR]4S23D2
TI3+: [AR]3D1

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Section 21.1
The Transition Metals: A Survey

CONCEPT CHECK!

WHAT IS THE EXPECTED ELECTRON CONFIGURATION

OF SC+?

EXPLAIN.

[AR]3D2

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Section 21.1
The Transition Metals: A Survey
PLOTS OF THE FIRST (RED DOTS) AND THIRD (BLUE DOTS)
IONIZATION ENERGIES FOR THE FIRST-ROW TRANSITION METALS

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Section 21.1
The Transition Metals: A Survey
ATOMIC RADII OF THE 3D, 4D, AND 5D TRANSITION
SERIES

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Section 21.2
The First-Row Transition Metals

 3d transition metals
 Scandium – chemistry strongly resembles lanthanides
 Titanium – excellent structural material (light weight)
 Vanadium – mostly in alloys with other metals
 Chromium – important industrial material
 Manganese – production of hard steel
 Iron – most abundant heavy metal
 Cobalt – alloys with other metals
 Nickel – plating more active metals; alloys
 Copper – plumbing and electrical applications
 Zinc – galvanizing steel
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Section 21.2
The First-Row Transition Metals

Oxidation States and Species for Vanadium in Aqueous Solution

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Section 21.2
The First-Row Transition Metals

Typical Chromium Compounds

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Section 21.2
The First-Row Transition Metals
Some Compounds of Manganese in Its Most Common
Oxidation States

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Section 21.2
The First-Row Transition Metals

Typical Compounds
of Iron
Section 21.2
The First-Row Transition Metals

Typical Compounds
of Cobalt
Section 21.2
The First-Row Transition Metals

Typical Compounds
of Nickel

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Section 21.2
The First-Row Transition Metals

Typical Compounds of Copper

Section 21.2
The First-Row Transition Metals

Alloys Containing Copper

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Section 21.3
Coordination Compounds

A Coordination Compound
 Typically consists of a complex ion and counterions
(anions or cations as needed to produce a neutral
compound):

[Co(NH3)5Cl]Cl2
[Fe(en)2(NO2)2]2SO4
K3Fe(CN)6

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Section 21.3
Coordination Compounds

Coordination Number
 Number of bonds formed between the metal ion and the
ligands in the complex ion.
 6 and 4 (most common)
 2 and 8 (least common)

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Section 21.3
Coordination Compounds

Ligands
 Neutral molecule or ion having a lone electron pair that
can be used to form a bond to a metal ion.
 Monodentate ligand – one bond to a metal ion
 Bidentate ligand (chelate) – two bonds to a metal ion
 Polydentate ligand – more than two bonds to a metal
ion

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Section 21.3
Coordination Compounds

Coordinate Covalent Bond

 Bond resulting from the interaction between a Lewis
base (the ligand) and a Lewis acid (the metal ion).

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Section 21.3
Coordination Compounds

The Bidentate Ligand

Ethylenediamine and the
Monodentate Ligand
Ammonia
Section 21.3
Coordination Compounds

The Coordination of EDTA

with a 2+ Metal Ion

ethylenediaminetetraacetate

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Section 21.3
Coordination Compounds

Rules for Naming Coordination Compounds

[Co(NH3)5Cl]Cl2
1. Cation is named before the anion.
“chloride” goes last (the counterion)
2. Ligands are named before the metal ion.
ammonia (ammine) and chlorine
(chloro) named before cobalt
Section 21.3
Coordination Compounds

Rules for Naming Coordination Compounds

[Co(NH3)5Cl]Cl2
3. For negatively charged ligands, an “o” is added to the
root name of an anion (such as fluoro, bromo, chloro,
etc.).
4. The prefixes mono-, di-, tri-, etc., are used to denote the
number of simple ligands.
penta ammine

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Section 21.3
Coordination Compounds

Rules for Naming Coordination Compounds

[Co(NH3)5Cl]Cl2
5. The oxidation state of the central metal ion is designated
by a Roman numeral:
cobalt (III)
6. When more than one type of ligand is present, they are
named alphabetically:
pentaamminechloro

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Section 21.3
Coordination Compounds

Rules for Naming Coordination Compounds

[Co(NH3)5Cl]Cl2
7. If the complex ion has a negative charge, the suffix “ate”
is added to the name of the metal.

The correct name is:

pentaamminechlorocobalt(III) chloride

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Section 21.3
Coordination Compounds

EXERCISE!

Name the following coordination compounds.

a) [Co(H2O)6]Br3 hexaaquacobalt(III) bromide

b) Na2[PtCl4] sodiumtetrachloro-platinate(II)

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Section 21.4
Isomerism

Some Classes of Isomers

Section 21.4
Isomerism

Structural Isomerism
 Coordination Isomerism:
 Composition of the complex ion varies.
 [Cr(NH3)5SO4]Br and [Cr(NH3)5Br]SO4
 Linkage Isomerism:
 Composition of the complex ion is the same, but
the point of attachment of at least one of the
ligands differs.

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Section 21.4
Isomerism

Linkage Isomerism of NO2–

Section 21.4
Isomerism

Stereoisomerism
 Geometrical Isomerism (cis-trans):
 Atoms or groups of atoms can assume different
positions around a rigid ring or bond.
 Cis – same side (next to each other)
 Trans – opposite sides (across from each other)

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Section 21.4
Isomerism

Geometrical (cis-trans)
Isomerism for a Square
Planar Compound

a) cis isomer
b) trans isomer
Section 21.4
Isomerism
Geometrical (cis-trans) Isomerism for an Octahedral
Complex Ion

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Section 21.4
Isomerism

Stereoisomerism
 Optical Isomerism:
 Isomers have opposite effects on plane-polarized
light.

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Section 21.4
Isomerism
Unpolarized Light Consists of Waves Vibrating in Many
Different Planes

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Section 21.4
Isomerism
The Rotation of the Plane of Polarized Light by an Optically
Active Substance

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Section 21.4
Isomerism

Optical Activity
 Exhibited by molecules that have nonsuperimposable
mirror images (chiral molecules).
 Enantiomers – isomers of nonsuperimposable mirror
images.

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Section 21.4
Isomerism

A Human Hand Exhibits a Nonsuperimposable Mirror Image

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Section 21.4
Isomerism

CONCEPT CHECK!

Does [Co(en)2Cl2]Cl exhibit geometrical isomerism?

Yes

Does it exhibit optical isomerism?

Trans form – No
Cis form – Yes
Explain.

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Section 21.5
Bonding in Complex Ions:
The Localized Electron Model
Bonding in Complex Ions
1. The VSEPR model for predicting structure generally does
not work for complex ions.
 However, assume a complex ion with a coordination
number of 6 will have an octahedral arrangement of
ligands.
 And, assume complexes with two ligands will be
linear.
 But, complexes with a coordination number of 4 can
be either tetrahedral or square planar.
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Section 21.5
Bonding in Complex Ions:
The Localized Electron Model
Bonding in Complex Ions
2. The interaction between a metal ion and a ligand can be
viewed as a Lewis acid–base reaction with the ligand
donating a lone pair of electrons to an empty orbital of
the metal ion to form a coordinate covalent bond.

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Section 21.5
Bonding in Complex Ions:
The Localized Electron Model
The Interaction Between a Metal Ion and a Ligand Can Be
Viewed as a Lewis Acid-Base Reaction

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Section 21.5
Bonding in Complex Ions:
The Localized Electron Model
Hybrid Orbitals on Co3+ Can Accept an Electron Pair from
Each NH3 Ligand
Section 21.5
Bonding in Complex Ions:
The Localized Electron Model
The Hybrid Orbitals Required for
Tetrahedral, Square Planar, and Linear
Complex Ions
Section 21.6
The Crystal Field Model

 Focuses on the energies of the d orbitals.

Assumptions
1. Ligands are negative point charges.
2. Metal–ligand bonding is entirely ionic:
 strong-field (low–spin):
large splitting of d orbitals
 weak-field (high–spin):
small splitting of d orbitals
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Section 21.6
The Crystal Field Model

Octahedral Complexes
 d z and d x  y point their lobes directly at the point-
2 2 2

charge ligands.
 d xz , d yz ,and d xy point their lobes between the point
charges.

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Section 21.6
The Crystal Field Model
An Octahedral Arrangement of Point-Charge Ligands and
the Orientation of the 3d Orbitals

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Section 21.6
The Crystal Field Model

Which Type of Orbital is Lower in Energy?

 Because the negative point-charge ligands repel
negatively charged electrons, the electrons will first fill
the d orbitals farthest from the ligands to minimize
repulsions.
 The d xz , d yz ,and d xy orbitals are at a lower energy in the
octahedral complex than are the
d z and d x  y orbitals.
2 2 2

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Section 21.6
The Crystal Field Model
The Energies of the 3d Orbitals for a Metal Ion in an
Octahedral Complex

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Section 21.6
The Crystal Field Model

Possible Electron Arrangements in the Split 3d

Orbitals in an Octahedral Complex of Co3+
Section 21.6
The Crystal Field Model

Magnetic Properties
 Strong–field (low–spin):
 Yields the minimum number of unpaired electrons.
 Weak–field (high–spin):
 Gives the maximum number of unpaired electrons.
 Hund’s rule still applies.

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Section 21.6
The Crystal Field Model

Spectrochemical Series
 Strong–field ligands to weak–field ligands.

(large split) (small split)

CN– > NO2– > en > NH3 > H2O > OH– > F– > Cl– > Br– > I–

 Magnitude of split for a given ligand increases as the

charge on the metal ion increases.
Section 21.6
The Crystal Field Model

Complex Ion Colors

 When a substance absorbs certain wavelengths of light
in the visible region, the color of the substance is
determined by the wavelengths of visible light that
remain.
 Substance exhibits the color complementary to those
absorbed.

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Section 21.6
The Crystal Field Model

Complex Ion Colors

 The ligands coordinated to a given metal ion determine
the size of the d–orbital splitting, thus the color changes
as the ligands are changed.
 A change in splitting means a change in the wavelength
of light needed to transfer electrons between the t2g and
eg orbitals.

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Section 21.6
The Crystal Field Model

Absorbtion of Visible Light by the Complex Ion Ti(H2O)63+

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Section 21.6
The Crystal Field Model

CONCEPT CHECK!

Which of the following are expected to form colorless

octahedral compounds?

Zn2+ Fe2+ Mn2+

Cu+ Cr3+ Ti4+ Ag+
Fe3+ Cu2+ Ni2+
Section 21.6
The Crystal Field Model

Tetrahedral Arrangement
 None of the 3d orbitals “point at the ligands”.
 Difference in energy between the split d orbitals is
significantly less.
 d–orbital splitting will be opposite to that for the
octahedral arrangement.
 Weak–field case (high–spin) always applies.

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Section 21.6
The Crystal Field Model
The d Orbitals in a Tetrahedral Arrangement of Point
Charges

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Section 21.6
The Crystal Field Model
The Crystal Field Diagrams for Octahedral and Tetrahedral
Complexes

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Section 21.6
The Crystal Field Model

CONCEPT CHECK!

Consider the Crystal Field Model (CFM).

a) Which is lower in energy, d–orbital lobes

pointing toward ligands or between ? Why?
b) The electrons in the d–orbitals – are they
from the metal or the ligands?

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Section 21.6
The Crystal Field Model

CONCEPT CHECK!

Consider the Crystal Field Model (CFM).

c) Why would electrons choose to pair up in d–

orbitals instead of being in separate orbitals?
d) Why is the predicted splitting in tetrahedral
complexes smaller than in octahedral complexes?

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Section 21.6
The Crystal Field Model

CONCEPT CHECK!

Using the Crystal Field Model, sketch possible

electron arrangements for the following. Label one
sketch as strong field and one sketch as weak field.
a) Ni(NH3)62+
b) Fe(CN)63–
c) Co(NH3)63+

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Section 21.6
The Crystal Field Model

CONCEPT CHECK!

A metal ion in a high–spin octahedral complex has 2

more unpaired electrons than the same ion does in a
low–spin octahedral complex.

What are some possible metal ions for which this

would be true?
Metal ions would need to be d4 or d7
ions. Examples include Mn3+, Co2+, and Cr2+.

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Section 21.6
The Crystal Field Model

CONCEPT CHECK!

Between [Mn(CN)6]3– and [Mn(CN)6]4– which is more

likely to be high spin? Why?

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Section 21.6
The Crystal Field Model

The d Energy Diagrams

for Square Planar
Complexes

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Section 21.6
The Crystal Field Model

The d Energy
Diagrams for Linear
Complexes Where the
Ligands Lie Along the z
Axis

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Section 21.7
The Biological Importance
of Coordination Complexes

 Metal ion complexes are used in humans for the

transport and storage of oxygen, as electron-transfer
agents, as catalysts, and as drugs.

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Section 21.7
The Biological Importance
of Coordination Complexes
First-Row Transition Metals and Their Biological Significance

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Section 21.7
The Biological Importance
of Coordination Complexes
Biological Importance of Iron
 Plays a central role in almost all living cells.
 Component of hemoglobin and myoglobin.
 Involved in the electron-transport chain.

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Section 21.7
The Biological Importance
of Coordination Complexes

The Heme Complex

Section 21.7
The Biological Importance
of Coordination Complexes
Myoglobin
 The Fe2+ ion is coordinated
to four nitrogen atoms in
the porphyrin of the heme
(the disk in the figure) and
on nitrogen from the
protein chain.
 This leaves a 6th
coordination position (the
W) available for an oxygen
molecule.
Section 21.7
The Biological Importance
of Coordination Complexes
Hemoglobin
 Each hemoglobin has two
α chains and two β
chains, each with a heme
complex near the center.
 Each hemoglobin
molecule can complex
with four O2 molecules.

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Section 21.8
Metallurgy and Iron and Steel Production

Metallurgy
 Process of separating a metal from its ore and
preparing it for use.
 Steps:
 Mining
 Pretreatment of the ore
 Reduction to the free metal
 Purification of the metal (refining)
 Alloying

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Section 21.8
Metallurgy and Iron and Steel Production

The Blast Furnace Used

In the Production of Iron

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Section 21.8
Metallurgy and Iron and Steel Production

A Schematic of the Open Hearth Process for Steelmaking

Heat
CaCO3 
 CaO + CO2
4Al + 3O 2 
 2Al2O3

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Section 21.8
Metallurgy and Iron and Steel Production

The Basic Oxygen Process for Steelmaking

 Much faster.
 Exothermic oxidation
reactions proceed so
rapidly that they produce
enough heat to raise the
temperature nearly to the
boiling point of iron
without an external heat
source.