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1. Every e − in an atom has a set of four quantum numbers (n, l, ml, ms) that describe
its spatial distribution and spin state.
2. Every e − dwells in an atomic orbital with a characteristic size, shape and energy
and has a spin (up or down).
3. In many-electron atoms the energies of the orbitals do not depend solely on n as
in the one-electron atoms, but they depend on both n and l, but not on ml)
Electrons with parallel spins ( ↑ ↑ ) tend to stay apart better than those with paired
spins ( ↑↓ ),
When e − - e − interactions become large the orbital approximation tends to break down.
Pauli Exclusion Principle : No two e − in an atom may have the same set of the four
quantum numbers (n, l, ml, ms).
Electron Configuration: list of the occupied orbitals and the number of e − in each.
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Additional electrons in inner orbitals (shield outer electrons more effectively than do
electrons in the same sublevel. Shielding by inner electrons greatly lowers the Zeff felt
by outer electrons.)
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Filling order of the Periodic Table
• Example: Hydrogen
1s1
1s 2s 2p
• Example: Helium (Z = 2)
1s2
1s 2s 2p
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• Lithium (Z = 3)
1s22s1
1s 2s 2p
• Berillium (Z = 4)
1s22s2
1s 2s 2p
• Boron (Z = 5)
1s22s22p1
1s 2s 2p
• Carbon (Z = 6)
1s22s22p2
1s 2s 2p
Hund’s Rule: Lowest energy configuration is
the one in which the maximum number of unpaired electrons
are distributed amongst a set of degenerate orbitals.
• Nitrogen (Z = 7)
1s22s22p3
1s 2s 2p
4
A vertical orbital diagram for the Li ground state
PLAN: Use the orbital diagram to find the third and eighth electrons.
9F
1s 2s 2p
SOLUTION: The third electron is in the 2s orbital. Its quantum numbers are:
1
n= 2 l= 0 ml = 0 ms= + or -
2
The eighth electron is in a 2p orbital. Its quantum numbers are:
1
n= 2 l= 1 ml = -1, 0, or +1 ms= + or -
2
• Oxygen (Z = 8)
1s22s22p4
1s 2s 2p
• Fluorine (Z = 9)
1s22s22p5
1s 2s 2p
• Neon (Z = 10)
1s22s22p6
1s 2s 2p full
5
• Sodium (Z = 11)
Ne 1s22s22p63s1 [Ne]3s1
3s
• Argon (Z = 18)
Ne [Ne] 3s23p6
3s 3p
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Condensed ground-state electron configurations in the first three periods
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A periodic table of partial ground-state electron configurations
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Keep in mind: Elements in a group have similar chemical properties because they have
similar outer electron configurations.
Categories of electrons
1. Inner (core) electrons are those seen in the previous noble gas and any
completed transition series. They fill all the lower energy levels of an atom.
2. Outer electrons are those in the highest energy level (hi ghest n value). They
spend more of their time farthest from the nucleus.
3. Valence electrons are those involved in forming compounds. Among the main-
group elements, the valence electrons are the outer electrons. For the transition
elements, all the (n -1)d electrons are counted among the valence electrons also,
even though the elements Fe (Z = 26 through Zn (Z = 30) use only a few of them
in bonding as we will see later towards the last weeks of the course.
1. Among the main-group elements (A groups), the group number equals the
number of outer electrons (those with the highest n). Chlorine (Group 7A) has 7
outer electrons; Tellurium (Group 6A) has 6 outer electrons.
2. The period number is the n value of the highest energy level.
3. The n value squared (n2) gives the total number of orbitals and 2n2 gives the
maximum number of electrons in the energy level.
Periods 4,5, 6 and 7 incorporate the d – block transition elements. The general trend is
to fill the (n -1)d orbitals between the ns and np orbitals. Period 5 follows the same
general pattern as Period 4. In Period 6, the 6s sublevel is filled in Cs and Ba and then
La (Z = 57), the first member of the 5d transition series, occurs. (Inner transistion
elements). For these elements filling of the f orbitals intervenes.
f orbitals: l = 3 ml = -3,-2,-1,0,+1,+2,+3 (7 orbitals).
The Period 6 inner transition series fills the 4f orbitals and consists of the lanthanides
(or rare earths) because they occur after and are similar to La. The other inner transition
series holds the actinides which fill the 5f orbitals that appear in Period 7.
In both series the (n – 2)f orbitals are filled after which the (n -1)d orbitals proceeds.
Period 6 ends proceeds with filling the 6p orbitals but Period 7 is incomplete because
only four elements with 7p electrons have been synthesized so far,
Anomalies Cr: 4s13d5 Mo: 5s14d2 Cu: 4s13d10 Ag: 5s13d10 Au: 6s13d10
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Determining Electron Configuration
PROBLEM: Using the periodic table on the inside cover of the text give the full
and condensed electron configurations, partial orbital diagrams
showing valence electrons, and number of inner electrons for the
following elements:
(a) Potassium (K; Z = 19) (b) Molybdenum (Mo; Z = 42) (c) Lead (Pb; Z = 82)
PLAN: Use the atomic number for the number of electrons and the periodic
table for the order of filling for electron orbitals. Condensed
configurations consist of the preceding noble gas and outer electrons.
SOLUTION:
(a) for K (Z = 19)
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Trends in three key atomic properties
All physical and chemical behavior of the elements is based ultimately on the
electron configurations of their atoms.
Atomic size: how closely one atoms lies next to another.
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Atomic radii of the main-group and transition elements
The ionization energy (IE) is the energy in kJ required for the complete removal of 1
mol of electrons from 1 mol of gaseous atoms or ions.
Many-electron atoms can lose more than one electron. The first ionization energy (IE1)
removes an outermost electron (highest sub-level) from the gaseous atom:
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Periodicity of first ionization energy (IE1)
The lowest values occur for the alkali metals and the highest for the noble gases.
In general, IE
a) Decreases down a group
b) Increases across a
period (since Zeff increases
and atomic size decreases)
However there are several
small dips as shown in the
adjacent figure
For Be:
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EXAMPLE
Identifying an Element from Successive
Ionization Energies
PROBLEM: Name the Period 3 element with the following ionization energies
(in kJ/mol) and write its electron configuration:
IE1 IE2 IE3 IE4 IE5 IE6
1012 1903 2910 4956 6278 22,230
PLAN: Look for a large increase in energy which indicates that all of the
valence electrons have been removed.
SOLUTION:
The largest increase occurs after IE5, that is, after the 5th valence
electron has been removed. Five electrons would mean that the
valence configuration is 3s23p3 and the element must be
phosphorous, P (Z = 15).
The complete electron configuration is 1s22s22p63s23p3.
The electron affinity (EA) is the energy change in kJ accompanying the addition of 1
mol of electrons to 1 mol of gaseous atoms or ions.
The first EA refers to the formation of 1 mol of monovalent (1 –) gaseous anions:
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Example
PROBLEM: Using the periodic table only, rank the elements in each of the
following sets in order of decreasing IE1:
(a) Kr, He, Ar (b) Sb, Te, Sn (c) K, Ca, Rb (d) I, Xe, Cs
SOLUTION:
(a) He > Ar > Kr These three elements are all in Group 8A(18), IE
decreases down a group.
(d) Xe > I > Cs I is to the left of Xe; Cs is furtther to the left and
down one period.
• Most main-group metals transfer e − to oxygen, so their oxides are ionic. In water
the oxides act as bases producing OH − ions from O 2− and reacting with acids.
• Non-metals share e − with oxygen, so non-metal oxides are covalent. In water
they act as acids producing H+ ions and reacting with bases.
• Some metals and many metalloids form oxides that can act as acids or as bases in
water. They are called amphoteric (Al2O3)
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Writing Electron Configurations of Main-Group
Ions
PROBLEM: Using condensed electron configurations, write reactions for the
formation of the common ions of the following elements:
(a) Iodine (Z = 53) (b) Potassium (Z =19) (c) Indium (Z = 49)
PLAN: Ions of elements in Groups 1A(1), 2A(2), 6A(16), and 7A(17) are
usually isoelectronic with the nearest noble gas.
Metals in Groups 3A(13) to 5A(15) lose the np and ns or just the np
electrons.
SOLUTION:
(a) Iodine (Z = 53) is in Group 7A(17) and will gain one electron to be
isoelectronic with Xe: I ([Kr]5s24d105p5) + e- I- ([Kr]5s24d105p6)
(b) Potassium (Z = 19) is in Group 1A(1) and will lose one electron to be isoelectronic
with Ar: K ([Ar]4s1) K+ ([Ar]) + e-
(c) Indium (Z = 49) is in Group 3A(13) and can lose either one electron or three
electrons: In ([Kr]5s24d105p1) In+ ([Kr]5s24d10) + e-
2 10 1
In ([Kr]5s 4d 5p ) In3+([Kr] 4d10) + 3e-
Magnetic Properties
17
Writing Electron Configurations and Predicting
Magnetic Behavior of Transition Metal Ions
PROBLEM: Use condensed electron configurations to write the reaction for the
formation of each transition metal ion, and predict whether the ion is
paramagnetic.
(a) Mn2+ (Z = 25) (b) Cr3+ (Z = 24) (c) Hg2+ (Z = 80)
PLAN: Write the electron configuration and remove electrons starting with
ns to match the charge on the ion. If the remaining configuration has
unpaired electrons, it is paramagnetic.
SOLUTION:
(a) Mn2+(Z = 25) Mn ([Ar] 4s23d5) Mn2+ ([Ar] 3d5) + 2e- paramagnetic
(b) Cr3+(Z = 24) Cr ([Ar] 4s13d5) Cr3+ ([Ar] 3d3) + 3e- paramagnetic
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Ionic radius Ionic vs. atomic radius
Example
Rank each set of ions in order of decreasing size, and explain your ranking:
(a) Ca2+, Sr2+, Mg2+ (b) K+, S2-,, Cl- (c) Au+, Au3+
(a) Sr2+ > Ca2+ > Mg2+ These are members of the same Group 2A(2), and decrease in
size going up the group.
(b) S2- > Cl- > K+ The ions are isoelectronic; S2- has the smallest Zeff and therefore, is
the largest while K+ is a cation with a large Zeff and is the smallest.
(c) Au+ > Au3+ The greater the + charge, the smaller the ion
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The Periodic Table
20
Lewis Electron-Dot Symbols
Example
Use partial orbital diagrams and Lewis symbols to depict the formation of Na+ and O2-
ions from the atoms, and determine the formula of the compound the ions form.
21
The Ionic Bonding Model
Central idea: transfer of e − from metal atoms to nonmetal atoms to form ions that come
together in a solid ionic compound.
Three ways to represent the formation of Li+ and F − through electron transfer
The total number of e − lost by the metal atoms equal the total number of e − gained by
the nonmetal atoms.
Consider,
The total energy needed is even greater than this because metallic Li and diatomic
fluorine must be first converted to separate gaseous atoms, which also requires energy.
The ∆H f of LiF (s) is – 617 kJ/mol, which means that 617 kJ of energy is released
o
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when 1 mol of ionic solid separates into gaseous ions. It indicates the strength of ionic
interactions that influence melting point, solubility and other properties.
1. Effect of ionic size: as we move down a group in the periodic table, the ionic
radius increases and the electrostatic energy between cations and anions
decreases.
2. Effect of ionic charge:
LiF : 1050 kJ/mol, (1 x1 charge), (Li is +1, F is -1)
MgO: 3923 kJ/mol (2 x 2 charge) (Mg is +2, O is -2)
Lattice energy of MgO is about 4 times as of LiF.
23
Covalent Bond (sharing of e − between atoms)
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Electronegativity – Linus Pauling (the greatest American chemist!)
dipole moment, µ
µ = (eδ) R
To denote polarity,
the arrow should point
toward the negative
end.
25
The ionic character of chemical bonds
PROBLEM: (a) Use a polar arrow to indicate the polarity of each bond:
N—H , F—N, I—Cl.
(b) Rank the following bonds in order of increasing polarity:
H—N, H—O, H—C.
PLAN: (a) Use above figure to find EN values; the arrow should point
toward the negative end.
(b) Polarity increases across a period.
N-H F-N I - Cl
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Oxoacids and their strength
Oxoacids of the same structure show increasing acid strength as the electronegativity of
the central atom increases. Their strength with a given central element increases with
the oxidation state of the central atom, or equivalently, with the number of lone oxygen
atoms attached to the central atom.
Example
HIO3 or HIO?
HIO3 = IO2(OH) - 2 more O
HIO =I(OH)
Example
Write the electron configuration of the first excited state of F-, O2-
F: 1s22s22p5
F-: 1s22s22p6
Excited state F-: 1s22s22p53s1
O: 1s22s22p4
O2-: 1s22s22p6
Excited state O2-: 1s22s22p53s1
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