chapter-1-1 chemistry 281, winter 2014, la tech cth 277 10:00-11:15 am instructor: dr. upali...
TRANSCRIPT
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Chapter-1-1Chemistry 281, Winter 2014, LA Tech
CTH 277 10:00-11:15 am
Instructor: Dr. Upali Siriwardane
E-mail: [email protected]
Office: 311 Carson Taylor Hall ; Phone: 318-257-4941;
Office Hours: MTW 8:00 am - 10:00 am;
TR 8:30 - 9:30 am & 1:00-2:00 pm.
January 14, 2014 Test 1 (Chapters 1&,2),
February 6, 2014 Test 2 (Chapters 3 &4)
February 25, 2014, Test 3 (Chapters 5 & 6),
Comprehensive Final Make Up Exam: February 27, 2012
9:30-10:45 AM, CTH 311.
Chemistry 281(01) Winter 2014
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Chapter-1-2Chemistry 281, Winter 2014, LA Tech
Chapter 1. Atomic Sturcture
Chapter 1. Atomic structure 3
The origin of the elements 3
1.1 The nucleosynthesis of light elements 5
1.2 The nucleosynthesis of heavy elements 6
1.3 The classification of the elements 8
The structures of hydrogenic atoms 10
1.4 Spectroscopic information 10
1.5 Some principles of quantum mechanics 11
1.6 Atomic orbitals 12
Many-electron atoms 18
1.7 Penetration and shielding 18
1.8 The building-up principle 20
1.9 Atomic parameters
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Chapter-1-3Chemistry 281, Winter 2014, LA Tech
Origin of Elements in the Universe Scientists have long based the origin of our Universe on the Big Bang Theory. According
to this theory, our universe was simply an expanding fairly cold entity consisting of only
Hydrogen and Helium during it's incipient stages. Over the expanse of many years, and
through a continuing process of fusion and fission, our universe has come to consist of
numerous chemical elements, four terrestrial planets (Earth, Mars, Venus, and Mercury),
and five giant gas planets (Saturn, Jupiter, Neptune, Pluto, and Uranus).
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Chapter-1-4Chemistry 281, Winter 2014, LA Tech
Eight Steps in the History of the Earth
1. The Big Bang
2. Star Formation
3. Supernova Explosion
4. Solar Nebula Condenses
5. Sun & Planetary Rings Form
6. Earth Forms
7. Earth's Core Forms
8. Oceans & Atmosphere Forms
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Chapter-1-5Chemistry 281, Winter 2014, LA Tech
Nuclear Chemistry• Fusion is lighter nuclei coming together to form
heavier.• Fission is heavier nuclei breaking in to lighter
nuclei.• Mass is not conserved E=mc2
• Nuclear reactions are balanced by A (mass) and Z (atomic) number.
• Energy released is E=mc2, m is mass defect in amu mutiplied by the conversion factor (931.5 MeV/amu)
• Binding energy of nuclei expressed in Mev/nucleons
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Chapter-1-6Chemistry 281, Winter 2014, LA Tech
Balancing Nuclear Equations
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Chapter-1-7Chemistry 281, Winter 2014, LA Tech
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Chapter-1-8Chemistry 281, Winter 2014, LA Tech
Nuclear Binding EnergyThe binding energy of a nucleus is a measure of how
tightly its protons and neutrons are held
together by the nuclear forces. The binding energy per nucleon, the energy required to remove
one neutron or proton from a nucleus, is a function of the mass number A. (Dm) –mass defect
(Dm) = Mass of Nuclide - mass of (p + n +e )
Proton mass: 1.00728 amu
Neutron mass: 1.00867 amu 931.5 MeV/amu
Electron mass: 0.00055 amu
Mass defect (Dm), then multiply by
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Chapter-1-9Chemistry 281, Winter 2014, LA Tech
Bonding Energy Curve
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Chapter-1-10Chemistry 281, Winter 2014, LA Tech
Nuclear Fusion Reactions• Nuclear energy, measured in millions of electron
volts (MeV), is released by the fusion of two light nuclei, as when two heavy hydrogen nuclei, deuterons (2H), combine in the reaction
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Chapter-1-11Chemistry 281, Winter 2014, LA Tech
Nuclear Fission Reactions• Nuclear energy is also released when the fission
(breaking up of ) of a heavy nucleus such as U is induced by the absorption of a neutron as in
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Chapter-1-12Chemistry 281, Winter 2014, LA Tech
Origin of the Elements: Nucleosynthesis
•Elements formed in the universe's original stars
were made from hydrogen gas condensing due to gravity. These young stars "burned" hydrogen in fusion reactions to produce helium and the hydrogen was depleted. Reactions such as those below built up all the heavier elements up to mass number 56 in the periodic table.•When the stars got old they exploded in a super
nova, spreading the new elements into space with high flux of neutrons to produce heavy elements by neutron capture.
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Chapter-1-13Chemistry 281, Winter 2014, LA Tech
Nuclear Burning
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Chapter-1-14Chemistry 281, Winter 2014, LA Tech
Supernova Explosion
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Chapter-1-15Chemistry 281, Winter 2014, LA Tech
The nucleo-synthesis of light elements • Stellar nucleo-synthesis
Elements carbon to Iron is form by nuclear fusion in stars after all H is converted to He.
• Double star SupernovaWhite dwarf (dense ball of carbon/oxygen) steals material from another star and get heated releasing huge energy. It goes to nuclear overload and carbon/oxygen suddenly
fuses to iron and it explodes known as type 1a supernova.
Most of the elements up to iron in the universe
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Chapter-1-16Chemistry 281, Winter 2014, LA Tech
The nucleosynthesis of heavy elements Havier elements are formed during Supernova explosion.
Giant one star supernova explosionsA heavier star buns all its H and nuclear burning goes faster and forms layer after layers of new elements with increasing mass number up to iron. Core collapses and become denser and the star explodes. Iron capture neutrons and all heavier elements beyond iron.
Corpse of supernova explosion leaves a core neutrons. Rotating neutron produces EM pluses creating a pulsar
Hypernova explosions: g-ray bursts
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Chapter-1-17Chemistry 281, Winter 2014, LA Tech
Cosmic Abundances
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Chapter-1-18Chemistry 281, Winter 2014, LA Tech
Terrestrial Abundances
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Chapter-1-19Chemistry 281, Winter 2014, LA Tech
Stability of the Elements and Their Isotopes
P/N Ratio
Why are elements
With Z > 82 are
Unstable?
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Chapter-1-20Chemistry 281, Winter 2014, LA Tech
Terrestrial Abundances
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Chapter-1-21Chemistry 281, Winter 2014, LA Tech
Magic Numbers• Nuclei with either numbers of protons or
neutrons equal to Z, N =2 (He), 8(O), 20 (Ca), 28(Si), 50(Sn, 82(Pb), or 126(?)(I)
• exhibit certain properties which are analogous to closed shell properties in atoms, including
• anomalously low masses, high natural abundances and high energy first excited states.
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Chapter-1-22Chemistry 281, Winter 2014, LA Tech
The classification of the elements• Dobereiner Triads• Newlands called the Law of Octaves• Mendeleyev’s periodic table• Lothar Meyer’s atomic volume curves• Glen Seaborg atomic number and long form
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Chapter-1-23Chemistry 281, Winter 2014, LA Tech
Dobereiner Triads
Cl 35.5 Li 7 S 32
Br 79 Na 23 Se 79
I 127 K 39 Te 128
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Chapter-1-24Chemistry 281, Winter 2014, LA Tech
Newlands’ Law of octaves
Octaves 1 Li Be B C N O F
Octaves 2 Na Mg Al Si P S Cl
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Chapter-1-25Chemistry 281, Winter 2014, LA Tech
Lothar Mayer’s atomic volume curves
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Chapter-1-26Chemistry 281, Winter 2014, LA Tech
Mendeleyev’s Periodic Table
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Chapter-1-27Chemistry 281, Winter 2014, LA Tech
Long Form of Periodic Table
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Chapter-1-28Chemistry 281, Winter 2014, LA Tech
What is periodic table? Describe its use in chemistry?
All elements in a group have similar chemical properties
Group I- alkali metal:Li, Na, K Rb, Cs, Fr
Common ele.n conn: ns1
Group II- alkaline earth metals:Be, Mg, Ca, Sr, Ba, Ra: Common ele.n conn: ns2
Group VII- Halogens: Cl, Br, I, At:
Common ele.n conn:ns2 np5
Group VIII- Noble gases:He, Ne, Ar, Kr, Xe, Rn:
Common ele.n conn ns2 np6
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Chapter-1-29Chemistry 281, Winter 2014, LA Tech
Chemical properties and the periodic tableElectron configurations help us understand changes in atomic radii, ionization energies, and electron affinities.
Various trends in reactivity can be observed.
• Main group metals become more reactive as you go down a group.
• Reactivity of nonmetals decreases as you go down a group.
• Transition metals become less reactive as you go down a group.
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Chapter-1-30Chemistry 281, Winter 2014, LA Tech
Other ways of numbering groups in the periodic table• Several methods are used for numbering periodic table
groups• American chemists preferred method.
• The IUPAC old system.
• The IUPAC current system.• The American Chemical Society (ACS) has also
adopted the current IUPAC system.
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Chapter-1-31Chemistry 281, Winter 2014, LA Tech
Other numbering systems
H
Li
Na
K
He
Be
Mg
Ca ZnCuTiSc NiCoFeMnCrV Ga KrBrSeAsGe
Al ArClSPSi
B NeFONC
IA IIA IIIA IIIA IVA VA VIA VIIA 0
IIIB IVB V B VIB VIIB VIII B IB
IIB
1
2
3
4
1 2 13 14 15 16
17 18
IA IIA III B IVB VB VIB VIIB
VIIIB
3 4 5 6 7 8 9 10
11 12
IIIA IVA VA VIA VIIA VIIIA IB IIB
Previous IUPAC
Current IUPAC and ACS
Preferred US
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Chapter-1-32Chemistry 281, Winter 2014, LA Tech
The structures of hydrogenic atoms :Bohr Theory
• The Bohr model is a ‘planetary’ type model.
• Each principal quantum represents a new ‘orbit’ or layer.
• The nucleus is at the center of the model.
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Chapter-1-33Chemistry 281, Winter 2014, LA Tech
Emission Spectrum of Hydrogen•
Bohr studied the spectra produced when atoms were excited in a gas discharge tube.
He observed that each element produced its
own set of characteristic lines.
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Chapter-1-34Chemistry 281, Winter 2014, LA Tech
Emission Spectrum of Hydrogen
• Line Spectrum• Energy is absorbed when an electron goes from a
lower(n) to a higher(n) • Energy is emitted when an electron goes from a
higher(n) to a lower(n) level
• Energy changed is given by:DE = Ef - Ei
• or DE = -2.178 x 10-18 [1/n2f - 1/n2
i] J
• DE is negative for an emission and positive for an absorption
• DE can be converted to l or 1/ l by l = hc/E.
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Chapter-1-35Chemistry 281, Winter 2014, LA Tech
Bohr model of the atom
• The Bohr model is a ‘planetary’ type model.
• Each principal quantum represents a new ‘orbit’ or layer.
• The nucleus is at the center of the model.
• RH = 2.178 x 10-18 JEn = -
En = RH
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Chapter-1-36Chemistry 281, Winter 2014, LA Tech
What is Bohr’s Atomic model?
• explain emission spectrum of hydrogen atom• applied the idea of Quantization to electrons to orbits• energies of these orbits increase with the distance
from nucleus.
• Energy of the electron in orbit n (En):
• En = -2.178 x 10-18 J (Z2/n2)
• En = -2.178 x 10-18 J 1/n2; Z=1 for H
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Chapter-1-37Chemistry 281, Winter 2014, LA Tech
Bohr model of the atom
Balmer later determined an empirical relationship that described the spectral lines for hydrogen.
DE = - 2.178 x 10-18
J ( )1
nf2
1
ni2-
nf = 2 ni = 3,4, 5, . . . Blamer series
Spectra of many other atoms can be described by
similar relationships.
En = -
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Chapter-1-38Chemistry 281, Winter 2014, LA Tech
Paschen, Blamer and Lyman Series
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Chapter-1-39Chemistry 281, Winter 2014, LA Tech
Calculation using the equation: E = -2.178 x 10-18 (1/nf
2 - 1/ni2 ) J, Calculate
the wavelength of light that can excite the electron in a ground state hydrogen atom to n = 7 energy level.
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Chapter-1-40Chemistry 281, Winter 2014, LA Tech
The energy for the transition from n = 1 to n = 7:
DE = -2.178 x 10-18 J [1/n2f - 1/n2
i]; nf = 7, ni = 1
DE = -2.178 x 10-18 [1/72 - 1/12] J
DE = -2.178 x 10-18 [1/49 - 1/1] J
DE = -2.178 x 10-18 [0.02041 - 1] J
DE = -2.178 x 10-18 [-0.97959] J
= 2.134 x 10-18 J (+, absorption)
calculate the l using l = hc/E 6.626 x 10-34 Js x 3.00 x 108 m/s
l = ---------------------- 2.13 x 10-18 J l = 9.31 x 10-8 m
Calculation using Bohr eqaution
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Chapter-1-41Chemistry 281, Winter 2014, LA Tech
Wave- Particle Duality of Matter and Energy• Wave theory applies to electromagnetic radiation• EMR can also be described as particles• quanta :A particles of light energy. • Quantum: One particle of light with a certain energy. • Photon: A stream of Quanta• Wave theory could be applied to electrons
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Chapter-1-42Chemistry 281, Winter 2014, LA Tech
Wave theory of the electron• 1924: De Broglie suggested that electrons have
wave properties to account for why their energy was quantized.
• He reasoned that the electron in the hydrogen atom was fixed in the space around the nucleus.
• He felt that the electron would best be represented as a standing wave.
• As a standing wave, each electron’s path must equal a whole number times the wavelength.
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Chapter-1-43Chemistry 281, Winter 2014, LA Tech
De Broglie proposed that all particles have a wavelength as related by:
l = wavelength, meters
h = Plank’s constant
m = mass, kg
v = frequency, m/s
De Broglie waves
l =h
mv
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Chapter-1-44Chemistry 281, Winter 2014, LA Tech
Wave Character of Electrons
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Chapter-1-45Chemistry 281, Winter 2014, LA Tech
What is a wave-mechanical model?• motions of a vibrating string shows one dimensional motion.• Energy of the vibrating string is quantized• Energy of the waves increased with the nodes. • Nodes are places were string is stationary. • Number of nodes gives the quantum number. One
dimensional motion gives one quantum number.
Vibrating String : y = sin(npx/l)
d2y/dx2 = -(n2p2/l2)sin(npx/l) = -(n2p2/l2)y
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Chapter-1-46Chemistry 281, Winter 2014, LA Tech
Constructively Interfered 2D-Wave
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Chapter-1-47Chemistry 281, Winter 2014, LA Tech
destructively Interfered 2D-Wave
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Chapter-1-48Chemistry 281, Winter 2014, LA Tech
Two-dimensional wave - Vibrations on a Drumskin One circular node
(at the drumskin's edge)
Two circular nodes
(one at the drumskin's edge plus
one more)
Three circular nodes
(one at the drumskin's edge plus
two more)
One transverse node
(plus a circular one at the
drumskin's edge)
Two transverse nodes
(plus one at the drumskin's
edge)
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Chapter-1-49Chemistry 281, Winter 2014, LA Tech
How did Schrodinger come up with a equation
started with The “Vibrating String” and the "Particle in a One-dimensional Box“ solutions
Vibrating String : y = sin(npx/l)
d2y/dx2 = -(n2p2/l2)sin(npx/l) = -(n2p2/l2)ySince l = 2l/n; d2y/dx2 = -(4m2v2/h2)y 1/l2= 4/ l2n2; l = h/mv; 1/l2 = 4/ l2n2 = 4m2v2/ h2
Particle in an One-dimensional Box:
d2y/dx2 = -(4m2v2p2/h2)y E = ½mv2 + V or v2 = (2/m)(E-V)
d2y/dx2 = -(8mp2/h2)(E - V)y
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Chapter-1-50Chemistry 281, Winter 2014, LA Tech
Schrödinger Equation
= wave function E = total energy V = potential energy
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Chapter-1-51Chemistry 281, Winter 2014, LA Tech
Polar Coordinates
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Chapter-1-52Chemistry 281, Winter 2014, LA Tech
Schrödinger Equation in Polar Coordinates
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Chapter-1-53Chemistry 281, Winter 2014, LA Tech
Solutions to Shrődinger Equation
Series of allowed discrete values:
n, l, ml, ms
n = 1,2,3,4,5,6,7..etc.
En = -
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Chapter-1-54Chemistry 281, Winter 2014, LA Tech
Components of Mathematical expression of hydrogen like orbitals
in polar coordinates:
n, l, ml, ms (r,,) = R n, l, (r) Y l, ml, (,)
R n, l, (r ) = Radial Wave Function
Y l, ml, (,) =Angular Wave Function
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Chapter-1-55Chemistry 281, Winter 2014, LA Tech
Quantum model of the atom• Schrödinger developed an equation to
describe the behavior and energies of electrons in atoms.
• His equation ( Wave function ) is similar to one used to describe electromagnetic waves. Each electron can be described in terms of Wave function its quantum numbers. n, l, ml, ms),
• 2 is proportional probablity of finding the electron in a given volume. Max Born Interpretation: 2 = atomic orbital
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Chapter-1-56Chemistry 281, Winter 2014, LA Tech
Quantum Model of atom• Electrons travel in three dimensions• Four quantum numbers are needed• three to describe, x, y, z, and four for the spin• four quantum numbers describe an orbital
currently used to explain the arrangement, bonding and spectra of atoms.
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Chapter-1-57Chemistry 281, Winter 2014, LA Tech
Quantum numbers
• Principal quantum number, n• Tells the size of an orbital and largely
determines its energy.• n = 1, 2, 3, ……• Angular momentum, l• The number of subshells (s, p, d, f) that a
principal level contains. It tells the shape of the orbitals.
• l = 0 to n - 1
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Chapter-1-58Chemistry 281, Winter 2014, LA Tech
Quantum numbers
• Magnetic quantum number, ml
• Describes the direction that the orbital projects in space.
• ml = l to +l (all integers, including zero)
• For example, if l = 2, then ml would have values of -2, -1, 0, 1 and 2.
• Knowing all three ml numbers provide us with a picture of all of the orbitals.
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Chapter-1-59Chemistry 281, Winter 2014, LA Tech
Four Quantum Numbers of the Atom• n value could be 1, 2, 3, 4, 5, 6. 7. . . etc.
• l values depend on n value: can have 0 . . . (n - 1) values
• ml values depends on l value: can have
-l . , 0 . . . +l values of ml
• ms values should always be -1/2 or +1/2
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Chapter-1-60Chemistry 281, Winter 2014, LA Tech
Radial Distribution Function, Pnl(r).This is defined as the probability that an electron in
the orbital with quantum numbers n and l will be found at a distance r from the nucleus. It is related to the radial wave function by the following relationship:
R n, l, (r ) = Radial Wave Function
Y l, ml, (,) =Angular Wave Function
; normalized by
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Chapter-1-61Chemistry 281, Winter 2014, LA Tech
s orbitals
R n, l, (r) only no Y l, ml, (,)
s-Atomic orbitals
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Chapter-1-62Chemistry 281, Winter 2014, LA Tech
2s
3s
s-Atomic orbitals
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Chapter-1-63Chemistry 281, Winter 2014, LA Tech
p-Atomic orbitals
2p
3p
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Chapter-1-64Chemistry 281, Winter 2014, LA Tech
Nodes in the Total nodes = n -1
Radial nodes = n -1- l
Angular nodes = l
Eg 4d orbital:
Total nodes = 4 -1 = 3
Radial nodes = n -1- l = 4-1-2 = 1
Angular nodes = l = 2
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Chapter-1-65Chemistry 281, Winter 2014, LA Tech
.
Rnl(r) Pnl(r) n l
1s
1s
1 0
2s
2s
2 0
2p
2p
2 1
3s
3s
3 0
3p
3p
3 1
3d
3d
3 2
Radial wavefunctions, Rnl(r), and the radial distribution functions, Pnl(r)
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Chapter-1-66Chemistry 281, Winter 2014, LA Tech
d-orbitals
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Chapter-1-67Chemistry 281, Winter 2014, LA Tech
Representative d orbitals
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Chapter-1-68Chemistry 281, Winter 2014, LA Tech
f-orbitals
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Chapter-1-69Chemistry 281, Winter 2014, LA Tech
Classification by sublevels
H
Li
Na
Cs
Rb
K
TlHgAuLuBa
Fr
PtIrOsReWTa
He
RnAtPoBiPb
Be
Mg
Sr
Ca
CdAgY PdRhRuTcMoNb
LrRa
ZnCu
Hf
Zr
TiSc NiCoFeMnCrV
In XeITeSbSn
Ga KrBrSeAsGe
Al ArClSPSi
B NeFONC
Gd
Cm
Tb
Bk
Sm
Pu
Eu
Am
Nd
U
Pm
Np
Ce
Th
Pr
Pa
Yb
No
La
Ac
Er
Fm
Tm
Md
Dy
Cf
Ho
Es f f
ss
dd
pp
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Chapter-1-70Chemistry 281, Winter 2014, LA Tech
Atomic Orbitals of Multi-Electrnon Atoms
• Unlike a hydrogen-like atom multi-electron atoms there are electron-electron repulsions.
• Schrodinger equation cannot be solved analytically for multi-electron atoms.
• However, it is possible to obtain a crude solution for a multi-electron atom by employing a relatively simple construct.
• The "effective" nuclear charge for each electron is used in place of nuclear charge in the equations for a hydrogen-like atom
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Chapter-1-71Chemistry 281, Winter 2014, LA Tech
Screening (shielding) constant (σ)
a) Screening (shielding) constant (σ) for each electron is calculated based on:
b) the principle quantum number
c) orbital type and penetration and of all other electrons in an atom.
d) σ gives Zeff . Zeff = Z - σ; Z is the atomic number. σ is the screening constant calculated by Slater Rules
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Chapter-1-72Chemistry 281, Winter 2014, LA Tech
Effective nuclear charge (Zeff)
Zeff is the nuclear charge felt by an electron in a multielectron atom:
a) Each electron in an atom has different Zeff.
b) Each Zeff is less than atomic number (Z) since electrons screen each other from the nucleus.
c) Zeff depends on the n and l quantum number of an electron.
d) Zeff Depends on orbital type the electron is in: Zeff of 4s > 4p > 4d > 4f.
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Chapter-1-73Chemistry 281, Winter 2014, LA Tech
Radial Distribution Functions, Penetration and Shielding
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Chapter-1-74Chemistry 281, Winter 2014, LA Tech
Penetration & Shielding of an Electron in Multi-electron AtomPenetration of an electron:
• Greater the penetration there is more chance of electrons being located close to the nucleus.
• Comparing s, p, d, or f orbitals within same shell (or principle QN), penetration of an electrons are in the order: s > p> d > f
Shielding power of an electron:• Shields of other electrons depends penetration and the
orbital type. Shielding power of electrons in orbitals of that same shell are: s > p > d > f
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Chapter-1-75Chemistry 281, Winter 2014, LA Tech
Slater Rules of Obtaining Zeff
Group electron configuration in the following form:
[1s][2s 2p][3s 3p][3d][4s 4p][4d][4f][5s 5p][5d][5f] etc
Orbitals within a bracket are said to belong to the same group.
• [1s] group where they contribute .30.
• [ns np] group, other electrons in the same group contribute .35
• [ns np] group, each electron in the n-2 or lower group
contributes 1.0.
• [nd] or [nf] group, rules 1 and 2 remain the same and all
electrons in groups to the left contribute 1.0
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Chapter-1-76Chemistry 281, Winter 2014, LA Tech
Slater Rules of Obtaining Zeff
Consider the outer electron in K. Assume the configuration is [1s2]
[2s2 2p6][3s2 3p6)[3d1] s is then (18 x 1) since the outer electron is in
a [nd] group. Thus Zeff is (19-18)= 1
If we assume that the configuration is [1s2][2s2 2p6][3s2 3p6][3d°][4s1],
the value of s is (8 x 0.85) + (10 x 1)= 16.8 and Zeff is 2.2.
Therefore Zeff is greater and the outer electron experiences more
nuclear attraction when it is in the 4s orbital.
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Chapter-1-77Chemistry 281, Winter 2014, LA Tech
Slater Rules of Obtaining Zeff
Slater's rule states S = 0.35*x + 0.85*y +z
x,y and z refer to the electron configuration of the atom.
This is for Cl: 1s²2s²2p⁶3s²3p⁵ and for
K: 1s²2s²2p⁶3s²3p⁶4s¹
x is the number of valence electrons, the electrons in the highest energy level, 7 for Cl and 1 for K.y is the number of electrons in the energy level below the valence level, 8 for Cl and 8 for K.z is the remaining number of electrons, 2 for Cl and 10 for K.
So we get for Cl S = 0,35*7 + 0,85*8 +2 = 11,25 and for K S =
0,35*1 +0,85*8 + 10 = 17,15
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Chapter-1-78Chemistry 281, Winter 2014, LA Tech
Effective nuclear charge (Zeff) of Atomic Orbitals vs. Z (atomic number)
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Chapter-1-79Chemistry 281, Winter 2014, LA Tech
How do you get the electronic configuration of an atom?
• Use periodic table• Periodic table is divided into orbital blocks• Each period:• represents a shell or n • Start writing electron configuration• Using following order1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4f 5d 6p 7s 5f 6d…
(building up (Auf Bau) principle:)
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Chapter-1-80Chemistry 281, Winter 2014, LA Tech
What is Building Up (Auf Bau) Principle• Scheme used by chemist to obtain
electronic configuration of a multi-electron atom in the ground state by filling hydrogen like atomic orbital starting with lowest energy.
• 1s 2s 2p3s 3p 4s 3d 4p 5s 4d 5p 6s 4f 5d 6p 7s
• 5f 6d… (building up principle)
• If two or more orbitals exist at the same energy level, they are degenerate. Do not pair the electrons until you have to.
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Chapter-1-81Chemistry 281, Winter 2014, LA Tech
What is Pauli Exclusion Principle:
Electrons in an atom cannot have all four of their quantum numbers equal.
Eg. He: 1s2
electron orbital n l ml ms
________________________________
1s1 1 0 0 +½()
1s2 1 0 0 -½()
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Chapter-1-82Chemistry 281, Winter 2014, LA Tech
Filling order of orbitals
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Chapter-1-83Chemistry 281, Winter 2014, LA Tech
Filling order of orbitals
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Chapter-1-84Chemistry 281, Winter 2014, LA Tech
Tl
5d10
6s2
6p1
Hg
4f14
5d10
6s2
Au
4f14
5d10
6s1
Hf
4f14
5d2
6s2
Lu
4f14
5d1
6s2
Li
2s1
Na
3s1
Cs
6s1
Rb
5s1
K
4s1
Fr
7s1
Pt
4f14
5d9
6s1
Ir
4f14
5d7
6s2
Os
4f14
5d6
6s2
Re
4f14
5d5
6s2
W
4f14
5d4
6s2
Ta
4f14
5d3
6s2
H
1s1
He
1s2
Rn
5d10
6s2
6p6
At
5d10
6s2
6p5
Po
5d10
6s2
6p4
Bi
5d10
6s2
6p3
Pb
5d10
6s2
6p2
Cd
4d10
5s2
Ag
4d10
5s1
Zr
4d2
5s2
Y
4d1
5s2
Pd
4d10
Rh
4d8
5s1
Ru
4d7
5s1
Tc
4d5
5s2
Mo
4d5
5s1
Nb
4d3
5s2
Lr
6d1
7s2
Ba
6s2
Be
2s2
Mg
3s2
Sr
5s2
Ca
4s2
Ra
7s2
Zn
3d10
4s2
Cu
3d10
4s1
Ti
3d2
4s2
Sc
3d1
4s2
Ni
3d8
4s2
Co
3d7
4s2
Fe
3d6
4s2
Mn
3d5
4s2
Cr
3d5
4s1
V
3d3
4s2
In
4d10
5s2
5p1
Xe
4d10
5s2
5p6
I
4d10
5s2
5p5
Te
4d10
5s2
5p4
Sb
4d10
5s2
5p3
Sn
4d10
5s2
5p2
Ga
3d10
4s2
4p1
Kr
3d10
4s2
4p6
Br
3d10
4s2
4p5
Se
3d10
4s2
4p4
As
3d10
4s2
4p3
Ge
3d10
4s2
4p2
Al
3s2
3p1
Ar
3s2
3p6
Cl
3s2
3p5
S
3s2
3p4
P
3s2
3p3
Si
3s2
3p2
B
2s2
2p1
Ne
2s2
2p6
F
2s2
2p5
O
2s2
2p4
N
2s2
2p3
C
2s2
2p2
Gd
4f7
5d1
6s2Cm
5f7
6d1
7s2
Tb
4f9
6s2
Bk
5f9
7s2
Sm
4f6
6s2
Pu
5f6
7s2
Eu
4f7
6s2
Am
5f7
7s2
Nd
4f4
6s2
U
5f3
6d1
7s2
Pm
4f5
6s2
Np
5f4
6d1
7s2
Ce
4f1
5d1
6s2
Th
6f2
7s2
Pr
4f3
6s2
Pa
5f2
6d1
7s2
Yb
4f14
6s2
No
5f14
7s2
La
5d1
6s2
Ac
6d1
7s2
Er
4f12
6s2
Fm
5f12
7s2
Tm
4f13
6s2
Md
5f13
7s2
Dy
4f10
6s2
Cf
5f10
7s2
Ho
4f11
6s2
Es
5f11
7s2
Electronic Configuration of elements (core format)
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Chapter-1-85Chemistry 281, Winter 2014, LA Tech
Using the periodic tableTo write the ground-state electron configuration of an element:
Starting with hydrogen, go through the elements in order of increasing atomic number
As you move across a period
• Add electrons to the ns orbital as you pass through groups IA (1) and IIA (2).
• Add electrons to the np orbital as you pass through Groups IIIA (13) to 0 (18).
• Add electrons to (n-1) d orbitals as you pass through IIIB (3) to IIB(12) and add electrons to (n-2) f orbitals as you pass through the f -block.
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Chapter-1-86Chemistry 281, Winter 2014, LA Tech
Writing electron configurations
• Examples
• O 1s2 2s2 2p4 • Ti 1s2 2s2 2p6 3s2 3p6 3d2 4s2 • Br 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p5 • Core format
• O [He] 2s2 2p4 • Ti [Ar] 3d2 4s2 • Br [Ar] 3d10 4s2 4p5
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Chapter-1-87Chemistry 281, Winter 2014, LA Tech
Writing electron configurationsExample - Cl-
• First, write the electron configuration for chlorine:• Cl [Ne] 3s2 3p5
• Because the charge is 1-, add one electron. Cl-
[Ne] 3s2 3p6 or [Ar]
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Chapter-1-88Chemistry 281, Winter 2014, LA Tech
Writing electron configurations
• Electron configurations can also be written for ions.
• Start with the ground-state configuration for the atom.
• For cations, remove a number of the outermost electrons equal to the charge.
• For anions, add a number of outermost electrons equal to the charge.
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Chapter-1-89Chemistry 281, Winter 2014, LA Tech
Writing electron configurationsExample - Ba2+
• First, write the electron configuration for barium.
Ba [Xe] 6s2
• Because the charge is 2+, remove two electrons.
Ba2+ [Xe] or [Kr] 3d10 4s2 4p6
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Chapter-1-90Chemistry 281, Winter 2014, LA Tech
Hund’s Rule• Rule to fill electrons into p,d,f orbitals containing
more than one sublevel of the same energy. • filling p, d, f orbitals: Put electrons into separate
orbitals of the subshell with parallel spins before pairing electrons.
• The existence of unpaired electrons can be tested for since each acts like a tiny electromagnet.
• Paramagnetic - attracted to magnetic field. Indicates the presence of unpaired electrons.
• Diamagnetic - pushed out of a magnetic field. Indicates that all electrons are paired.
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Chapter-1-91Chemistry 281, Winter 2014, LA Tech
Orbital Box DiagramsValence Shell Electron configuration shown in
box or circle form.
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Chapter-1-92Chemistry 281, Winter 2014, LA Tech
Exception to Building Up Principle
a) Electronic Configuration of d-block and f-block elements
d5 or d10 and f7 or f14 are stable Cr :[Ar] 3d4 4s2 wrong
Cr :[Ar] 3d5 4s1 correct
Cu :[Ar] 3d9 4s2 wrong
Cu :[Ar] 3d10 4s1 correct
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Chapter-1-93Chemistry 281, Winter 2014, LA Tech
Lanthanoids
Gd
4f7
5d1
6s2
Tb
4f9
6s2
Sm
4f6
6s2
Eu
4f7
6s2
Nd
4f4
6s2
Pm
4f5
6s2
Ce
4f1
5d1
6s2
Pr
4f3
6s2
Yb
4f14
6s2
La
5d1
6s2
Er
4f12
6s2
Tm
4f13
6s2
Dy
4f10
6s2
Ho
4f11
6s2
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Chapter-1-94Chemistry 281, Winter 2014, LA Tech
Actinoids
Cm
5f7
6d1
7s2
Bk
5f9
7s2
Pu
5f6
7s2
Am
5f7
7s2
U
5f3
6d1
7s2
Np
5f4
6d1
7s2
Th
6f2
7s2
Pa
5f2
6d1
7s2
No
5f14
7s2
Ac
6d1
7s2
Fm
5f12
7s2
Md
5f13
7s2
Cf
5f10
7s2
Es
5f11
7s2
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Chapter-1-95Chemistry 281, Winter 2014, LA Tech
Electronic Configuration of Transition Metal cations
d-block and f-block elements
d orbitals are lower in energy than s orbitals
f orbitals are lower in energy than d orbitals
E.g. Neutral atom Fe :[Ar] 3d6
4s2
Cation, Fe3+
:[Ar] 3d5
Exception to Building Up Principle
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Chapter-1-96Chemistry 281, Winter 2014, LA Tech
Magnetic Properties of Atoms a) Paramagnetism? attracted to magnetic field due to un-paired
electrons.
b) Ferromagnetism? attracted very strongly to magnetic field due to
un-paired electrons. c) Diamagnetism? Repelled by a magnetic field due to paired
electrons.
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Chapter-1-97Chemistry 281, Winter 2014, LA Tech
Periodic trends• Many trends in physical and chemical properties
can be explained by electron configuration.• We’ll look at some of the more important
examples.
Atomic radii
Ionic radii
First ionization energies
Electron affinities
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Chapter-1-98Chemistry 281, Winter 2014, LA Tech
How does Zeff vary across a period and down a group?
•Zeff increase going across a period
•Zeff decrease going down a group
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Chapter-1-99Chemistry 281, Winter 2014, LA Tech
Types of Atomic Radii
1 Covalent Radii: Radii based on covalently liked atoms in covalently bonded molecules.
2 Van der Waals Radii: Radii based on non bonded atoms in solids.
3 Metallic Radii (12-coordinate):Radii based on metallic solids.
4 Ionic Radii: Radii based on bond distances in ionic solids.
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Chapter-1-100Chemistry 281, Winter 2014, LA Tech
•Atomic radii depend on the distance from the nucleus to the
outermost electron in the valence shell.
•Going across protons are added to nucleus This increase the
Zeff decreasing radii
•Atomic radii decrease going across a period
How does Atomic radii of atoms vary going across a period?
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Chapter-1-101Chemistry 281, Winter 2014, LA Tech
•Atomic radii depend on the distance from the nucleus to the
outermost electron in the valence shell.
•Going down the group outer most shell increases radii hence
the distance from the nucleus
•The atomic radii increase going down a group
How does Atomic radii of elements vary going down a group?
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Chapter-1-102Chemistry 281, Winter 2014, LA Tech
•Cations have smaller radii than neutral atoms.
•Anions have larger radii than neutral atoms
•The more charge on the ion more effect on the
radii.
How does Ionic radii of elements vary?
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Chapter-1-103Chemistry 281, Winter 2014, LA Tech
Atomic radii of elements going down a group?
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Chapter-1-104Chemistry 281, Winter 2014, LA Tech
Atomic radii for the main group (s,p block) elements
Ba
Sr
Ca
Mg
Be
Tl
In
Ga
Al
B
Pb
Sn
Ge
Si
C
Cs
Rb
K
Na
Li
Bi
Sb
As
P
N
Te
Se
S
O
I
Br
Cl
F
H
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Chapter-1-105Chemistry 281, Winter 2014, LA Tech
Atomic radii of the representative- main group elements• Atoms get larger as you go down a group.
A new shell is being added.
• Atoms get smaller as you go across a period.
The nucleus contains more protons.
The higher charge attracts the electrons more strongly, making the atom smaller.
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Chapter-1-106Chemistry 281, Winter 2014, LA Tech
Lanthanoide Contration
• Filling of the 4f orbitals in the lanthanides, which occur within the third series of transition elements, causes these transition metals to be smaller than expected because the 4f orbitals are very poor nuclear shielders and Zeff of 6s2
obitals increase and the atomic radii decrease.• 3rd-series elements have nearly the same
effective nuclear charge as the 2nd-series elements, and thus, nearly the same size
Ce [Xe] 4f1
5d16s
2
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Chapter-1-107Chemistry 281, Winter 2014, LA Tech
Ionic radii
• Cations• These are smaller than the atoms from
which they are formed.
• For main group elements, the outer shell of electrons is removed.
• The positively charged ion can also do a better job of holding on to the electrons that remain.
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Chapter-1-108Chemistry 281, Winter 2014, LA Tech
Ionic radii
• Anions• These are larger than the atoms from which
there are formed..
• Adding electrons increases the repulsion between electrons.
• The ion has a harder time holding on to the electrons.
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Chapter-1-109Chemistry 281, Winter 2014, LA Tech
Ionic radii (pm)
Li Li+ Be Be2+ O O2- F F-
152 74 111 35 74 140 71 133
Na Na+ Mg Mg2+ S S2- Cl Cl-
186 102 160 72 103 184 99 181
K K+ Ca Ca2+ Br Br-
227 138 197 100 114 195
Rb Rb+ Sr Sr2+ I I-
248 149 215 116 133 216
Cs Cs+ Ba Ba2+
265 170 217 136
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Chapter-1-110Chemistry 281, Winter 2014, LA Tech
Isoelectronic configurations
Species that have the same electron configurations.
Example
Each of the following has an electron configuration of 1s2 2s2 2p6
O2- F- Ne
Na+ Mg2+ Al3+
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Chapter-1-111Chemistry 281, Winter 2014, LA Tech
The energy required to remove an electron from an atom.
First Ionization Energy (DH1 ):
Ca ----> Ca+
+ e-; DH1 = positive
Second Ionization Energy (DH2)
Ca+ ----> Ca2+
+ e-; DH2 = positive
DH2 > DH1
What is Ionization Potential?
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Chapter-1-112Chemistry 281, Winter 2014, LA Tech
•Ionization Potential depend on Zeff of the nucleus to the outermost electron
in the valence shell.
•Going down the group Zeff for the outer most shell decrease hence the
Ionization Potential also decrease
•Going across the period Zeff for the outer most shell increase hence the
Ionization Potential also increase
How does Ionization Potential vary going down a group?
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Chapter-1-113Chemistry 281, Winter 2014, LA Tech
Ionization energy
• First ionization energy
The energy to remove one electron from a neutral atom in the gas phase.
• A(g) + first ionization energy A+(g) + e-
• This indicates how easy it is to form a cation.
Metals tend to have lower first ionization energies than nonmetals.
• They prefer to become cations.
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Chapter-1-114Chemistry 281, Winter 2014, LA Tech
0
500
1000
1500
2000
2500
0 20 40 60 80 100
First ionization energyHe
Ne
Ar
Kr
Xe
Rn
Fir
st
ion
izati
on
en
erg
y (
kJ/
mol)
Atomic number
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Chapter-1-115Chemistry 281, Winter 2014, LA Tech
Changes of I.E. Across a period
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Chapter-1-116Chemistry 281, Winter 2014, LA Tech
Electron affinity
• A measure of an atom’s tendency to gain electrons in the gas phase.
• A(g) + e- A-(g) + thermal energy
• Electron affinity is an irregular periodic function of atomic number. In general, it increases from left to right.
• Noble gases are not included since they have little or no tendency to gain electrons.
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Chapter-1-117Chemistry 281, Winter 2014, LA Tech
•Electron Affinity depends on Zeff of the nucleus to the outermost electron in the
valence shell.
•Going down the group Zeff for the outer most shell decrease hence the Electron
Affinity also increase
•Going across the period Zeff for the outer most shell increase hence the Electron
Affinity also decrease
How does Electron Affinity vary in the periodic table?
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Chapter-1-118Chemistry 281, Winter 2014, LA Tech
Electron affinity
Atomic number
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Chapter-1-119Chemistry 281, Winter 2014, LA Tech
ElectronegativityPauling Electronegativity, cP
The ability of an atom that is bonded to another atom or atoms to attract electrons to itself.
It is related to ionization energy and electron affinity.
It cannot be directly measured.
The values are unitless since they are relative to each other.
The values vary slightly from compound to compound but still provide useful qualitative predictions.
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Chapter-1-120Chemistry 281, Winter 2014, LA Tech
Electronegativities
0.5
1
1.5
2
2.5
3
3.5
4
0 20 40 60 80 100
Ele
ctr
on
eg
ati
vit
y
Atomic number
Electronegativity is a
periodic property.
Electronegativity is a
periodic property.
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Chapter-1-121Chemistry 281, Winter 2014, LA Tech
Electronegativity Scales• Pauling Electronegativity, cP
• Mulliken Electronegativity, cM
• The Allred-Rochow, cAR
• Sanderson electronegativity
• Allen electronegativity
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Chapter-1-122Chemistry 281, Winter 2014, LA Tech
Pauling Electronegativity, cP
EA-A and EB-B bond-energy of homonuclear A-A & B-B diatomic molecules
EA-B bond-energy of heteronuclear A-B diatomic molecule
cA cB are electronegativity values of A and B
Pauling comments that it is more accurate to use the geometric mean rather than the arithmetic mean
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Chapter-1-123Chemistry 281, Winter 2014, LA Tech
Mulliken Electronegativity, cM
The Mulliken electronegativity can only be calculated for an element for which the electron affinity is known• For ionization energies and electron affinities in
electronvolts
• For energies in kilojoules per mole
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Chapter-1-124Chemistry 281, Winter 2014, LA Tech
The Allred-Rochow, cAR
The effective nuclear charge, Zeff experienced by valence electrons can be estimated using Slater's rules, while the surface area of an atom in a molecule can be taken to be proportional to the square of the covalent radius, rcov. When rcov is expressed in ångströms,
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Chapter-1-125Chemistry 281, Winter 2014, LA Tech
Sanderson, cs
Sanderson has also noted the relationship between electronegativity and atomic size, and has proposed a method of calculation based on the reciprocal of the atomic volume.
The simplest definition of electronegativity is that of Allen, bases on average energy of the valence electrons in a free atom
Allen, cA
where εs,p are the one-electron energies of s-
and p-electrons in the free atom and ns,p are
the number of s- and p-electrons in the valence
shell.