41

A. Basic Concepts
Atomic Weight
The mass of a particular atom relative
to the mass of an atom or carbon-12
(12C), which is arbitrarily assigned a
mass of exactly 12.
Average Atomic Weight
Average weight of an element based
on the naturally occurring isotopes
and the relative abundance of these
isotopes on Earth.

Ave. At. Wt. = ∑ (weight of isotope )(fractional abundance)

http://www.sci.tamucc.edu/pals/morvant/genchem/atomic/page9.htm
http://www.sci.tamucc.edu/pals/morvant/genchem/atomic/page8.htm

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A. Basic Concepts
Isotopes
Different forms of an element having the same number of protons
but different numbers of neutrons (and therefore different atomic
weights).

http://www.sci.tamucc.edu/pals/morvant/genchem/atomic/page9.htm

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A. Basic Concepts
Isotones
Two nuclides that have the
same number of neutron but
different proton number

The largest number of

observationally stable
nuclides exist for
Isotones 50
(Kr-86, Sr-88, Y-89, Zr-90
and Mo-92)
Isotone 82
(Ba-138, La-139, Ce-140,
Pr-141, Nd-142 and Sm-144)
http://upload.wikimedia.org/wikipedia/commons/8/80/Isotopes_and_half-life.svg

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Review Questions and Problems
1. Arrange the proton, neutron and electron in increasing mass.
a. proton < electron < neutron c. electron < neutron < proton
b. electron < proton < neutron d. neutron < electron < proton
3. In Rutherford’s experiment, which of the following is true?
a. the proton is evenly distributed in the nucleus of an atom
b. the atom is almost an empty space
c. the nucleus contains proton, neutron and electron
d. all of the these
4. The sum of the number of protons, neutrons and electrons of a zinc ion, Zn+2
is
a. 94 b. 92 c. 95 d. 93
8. Atoms with the same atomic number but different mass number is called
a. isobars b. isotopes c. isotherms d. isoelectronic
15. The atomic weight of chlorine is 35.45 and its naturally occurring isotopes
are Cl–35 and Cl–37. What is the percentage abundance of Cl–35?
a. 95.8% b. 98.7% c. 77.5% d. 75.0%
Part 3: Electronic Structure of Atoms
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Review Questions and Problems
19. Which of the following pairs are isoelectronic?
a. Mn+2 and Ar c. S-2 and Cl-1
b. Zn+2 and Cu+2 d. Na+ and Cl-1

Atomic Mass
No. Symbol Proton Electron Neutron
Number Number
1 N 7 14 7 7 7
2 Ga+3 31 70 31 28 39
3 S–2 16 32 16 18 16
4 V 23 50 23 23 27
5 K+ 19 39 19 18 20
6 C 6 14 6 6 8
7 Br-1 35 80 35 36 45

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B. Electromagnetic Theory
• Michael Faraday (1791-1867)
discovered that the plane of
polarization of a linearly polarized
light is rotated (Faraday rotation)
when it travels along the magnetic
field direction in the presence of an
optically transparent dielectric material
• James Clerk Maxwell (1831-1879)
proposed that visible light consists of
electromagnetic waves that comprises
both electric field and magnetic field
components; these components have
the same wavelength, frequency, speed
and travels in mutually perpendicular
planes
Part 3: Electronic Structure of Atoms
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B. Electromagnetic Theory
• Electromagnetic radiation is the emission of energy in the
form of electromagnetic waves

http://en.wikipedia.org/wiki/File:Electromagneticwave3D.gif

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C. Limitation to the Theory of Light
1. Black-body Radiation
• Max Karl Ernst Ludwig Planck (1858-1947) proposed that
atoms and molecules could emit or absorb energy in discrete
amount and gave the name quantum which denotes the
smallest amount of energy that can be emitted or absorbed
in the form of electromagnetic radiation
• The energy of a single quantum of energy (E) emitted is
proportional to the frequency (v) of the radiation
E = hv
• Where h = Planck’s constant and v = frequency

CONST 06
h = 6.62606896 × 10-34 J⋅s

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C. Limitation to the Theory of Light
2. Atomic Spectra
• Robert Wilhelm Eberhard Bunsen (1811-1899) and Gustav
Robert Kirchhoff (1824-1887) invented the spectroscope
where white light is separated using a prism into its
component colors and passed to sample
• Each element was found to have a characteristic spectrum
whether light was passed to the gaseous state of the sample
(absorption) or sample was stimulated energetically producing
light (emission)

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C. Limitation to the Theory of Light
2. Atomic Spectra
• Johann Jakob Balmer (1825-1898) showed that the positions
of the lines of light in the visible portion of the hydrogen
spectrum could be predicted by the expression:

1 Bm 2 Bm 2
λ=~ = 2 = 2
v m −n 2
m −4
where λ = wavelength, ṽ = wavenumber , B = Balmer
constant, n = 2 and m = any integer greater than n

4 ÷ CONST 16
B = 3.645068202 × 10-7 m

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C. Limitation to the Theory of Light
2. Atomic Spectra
• Johannes Robert Rydberg (1854-1919) generalized the
Balmer equation for all transitions of hydrogen and
proposed a generalized equation to describe the wavelengths
of spectral lines of many elements:

~ 1 4 1 1   1 1 
v = =  − 2  = RH 2 − 2 
λ B4 m  n m 

where RH = Rydberg constant

CONST 16
R∞ = 10.97373157 × 106 m-1

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C. Limitation to the Theory of Light
2. Hydrogen Spectral Series
• involves emission spectrum of atomic hydrogen with
wavelengths given by the Rydberg formula and is due to the
electrons moving between energy levels in the atom

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C. Limitation to the Theory of Light
2. Hydrogen Spectral Series
Spectral series n n∞
Lyman Series 1 91.2
Theodore Lyman (1874-1954)

Balmer Series 2 365

Johann Balmer (1825-1898)

Paschen Series 3 820

Friedrich Paschen (1865-1947)

Brackett Series 4 1460

Frederick Brackett (1896-1988)

Pfund Series 5 2280

August Pfund (1879–1949)

Humphreys Series 6 3280

Curtis Humphreys (1898 - 1986)

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C. Limitation to the Theory of Light
3. Photoelectric Effect
• Phenomenon in which electrons are ejected from the
surface of metals upon illumination beyond the
threshold frequency
• Albert Einstein (1879-1955) made the
following conclusions about the photoelectric
effect:

Light is absorbed by the electrons in the
metal which increases the energy of the
electron

When light is absorbed by the electron, the
binding energy or the work function (φ)
must be overcome before the electron can be
ejected from the metal

An excess energy after overcoming the work
function will be converted to kinetic energy
Part 3: Electronic Structure of Atoms
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C. Limitation to the Theory of Light
3. Photoelectric Effect

hc 1 2
E = hv = = BE + KE = φ + mv
λ 2
where c = speed of light in vacuum, φ = work function, m =
mass of electron and v = velocity of electron
The electron volt (eV) is the amount of energy gained by the charge of a single electron
moved across an electric potential difference of one volt

CONST 28 Co = 2.99792458 × 108 m⋅s-1

CONST 23 1 eV = 1.602176487 × 10-19 J

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D. Emission Spectra
Bohr Model of the Hydrogen Atom
Niels Henrik David Bohr (1885-1962) proposed that not
only the energy is quantized and made the following
assumptions:
1. In the hydrogen atom, the electron moves in a circular orbit about the
nucleus where the centripetal force that keeps the electron in such path
is provided by the coulombic force of attraction between the electron
and the proton in the nucleus
me v2 e2
Fcent = Fcoul r
=
4πε 0 r 2
where r = radius of circular orbit, me = mass of electron, v = velocity of
electron, e = charge of electron, ε0 = permittivity of free space

CONST 32
ε0 = 8.854187817 × 10-12 C2 ⋅ J-1⋅m-1
Part 3: Electronic Structure of Atoms
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D. Emission Spectra
Bohr Model of the Hydrogen Atom
2. The energy of the electron remains constant as it remains in its orbit
about the nucleus

Total energy of the system E T = KE + PE

2
1 e
ET = me v2 −
2 4πε 0 r
1 e2
From Fcent = Fcoul expression ET = −
2 4πε 0 r

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D. Emission Spectra
Bohr Model of the Hydrogen Atom
2. Only certain orbits with a quantized value of angular momentum are
allowed
Definition of angular momentum, L L = m e vr
nh
Proposed quantization of momentum L = m e vr =
2π
Bohr assumed that the quantized values of the angular momentum were multiples of h, where n is
some integer and n ≠ 0 (electron would have no momentum and would not be orbiting the nucleus).
He assumed that the orbits of the electron were circular.

nh
In terms of velocity v=
2πme r

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D. Emission Spectra
Bohr Model of the Hydrogen Atom
2. Only certain orbits with a quantized value of angular momentum are
allowed
n 2h 2ε 0
Using Fcent = Fcoul expression r= = a 0n 2
πm e e 2
where a0 = Bohr radius and n = positive integer referred to as quantum
number
Bohr showed that the radius of the orbits is quantized

CONST 05
a0 = 5.2911772086 × 10-11 m = 0.529 Å
Part 3: Electronic Structure of Atoms
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D. Emission Spectra
Bohr Radius
• approximately equal to the most probable distance between hydrogen’s
electron and proton in its ground state

h 2ε 0 h
a0 = 2
=
πm e e m e cα
where h = reduced/rationalized Planck’s constant (다이락) = h/2π and α =
fine-structure constant
Fine-structure constant, α is a coupling constant characterizing electromagnetic interaction
strength introduced by Arnold Johannes Wilhelm Sommerfeld (1868- 1951)

CONST 09
h = 1.054571628 × 10-34 J⋅s
CONST 10
α = 7.297352538 × 10-3 ≈ 1/137
Part 3: Electronic Structure of Atoms
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D. Emission Spectra
Bohr Model of the Hydrogen Atom
3. Allowable orbital transitions occurs when an electron absorbs or
emits a photon whose energy is exactly equal to the difference
between the energy of the orbits
Recall…
n 2 h 2ε 0 1 e2 1 e 2 πm e e 2
r= = a 0n 2 ET = − =−
πm e e 2 2 4πε 0 r 2 4πε 0 n 2 h 2ε 0

hc mee4  1 1 
∆E = hv = = hcv = E f − E i = 2 2  2 − 2 
λ 8ε 0 h  ni nf 
m e e 4  1 1   1
 1 

v= 2 3 − = R −
8ε 0 h c  n i2 n f2   n2 n2 
H
 i f 

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E. Dual Nature of Particles
• Louis-Victor-Pierre-Raymond de Broglie (1892-
1987) proposed that all moving particles have
wave properties according to the following
relation:
h h
λ= =
P mv
Visible massive particles have very short wavelengths while electrons possess wave properties
due to their small mass (로레즈 왁터)

• Clint J. Davisson (1881-1958), Lester H. Germer (1896-1972)

and George P. Thomson (1892-1975) demonstrated that
electrons possess wave-like properties (니켈)

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F. Heisenberg Uncertainty Principle
• Limitations of Bohr’s theory include its inability to account the
emission spectra of atoms containing more than one electron and
the presence of additional lines in hydrogen emission spectrum
in the presence of a magnetic field
• The wave-like property of an electron does not account for the
exact position of the electron
• Werner Karl Heisenberg (1901-1976) proposed
that it is impossible to determine simultaneously
both the momentum (P) and position (x) of a
particle with certainty

h h
∆P∆x ≥ m ∆ v∆ x ≥
4π 4π

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G. Quantum or Wave Mechanics
• Erwin Schrodinger (1887-1961) formulated an
equation that encompasses both particle and
wave-like behavior which can specify possible
energy states an electron can occupy in a
hydrogen atom and corresponding wave
functions
• Solution to Schrodinger equation can describe
subatomic, atomic, molecular and even
macroscopic systems

 h ∂2 
− 2
+ V̂(x ) Ψ = EΨ
 2m ∂x 
where Ψ = wave function, E = sum of kinetic and potential energy and V̂ = potential
energy

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Review Questions and Problems
2. The constant known as the fundamental number of hydrogen is the ______.
a. Rydberg constant c. Fine-structure constant
b. Planck’s constant d. Balmer constant
For numbers 6 and 7…
Calculate the series limits for the following:
6. Balmer series (m = 2)
a. 4389 cm–1 b. 27434 cm–1 c. 12193 cm–1 d. 6859 cm–1
7. Brackett series (m = 4)
a. 4389 cm–1 b. 27434 cm–1 c. 12193 cm–1 d. 6859 cm–1
From numbers 10 and 11…
Calculate the minimum wavelength of light necessary to overcome the work
functions for the following metals:
10. Li (φ = 2.90 eV)
a. 248 nm b. 428 nm c. 575 nm d. 581 nm
11. Ge (φ = 5.00 eV)
a. 248 nm b. 428 nm c. 575 nm d. 581 nm
Part 3: Electronic Structure of Atoms
 66
Review Questions and Problems

13. What is the speed of an electron being emitted by Rb (φ = 2.16 eV) when
350 nm of light shined on the metal in the vacuum?
a. 1.87 × 105 m/s b. 4.60 × 105 m/s c. 7.00 × 105 m/s d. 9.94 × 105 m/s

For Q5 and Q6…

For an electron in the fifth energy level of the Bohr hydrogen atom, calculate
the following:
Q5. radius in Å
a. 8.5Å b. 13.3 Å c. 17.4 Å d. 19.1 Å

Q6. angular momentum of the electron in J-s

a. 2.1 × 10–34 b. 3.2 × 10–34 c. 4.2 × 10–34 d. 5.3 × 10–34

Q7. What velocity must an electron have in order to have a de Broglie

wavelength of 1.00 Å?
a. 7.28 × 106 m/s b. 3.96 × 106 m/s c. 2.84 × 106 m/s d. 1.27 × 106 m/s

Part 3: Electronic Structure of Atoms

 67
Review Questions and Problems
Q8. For an atom of mercury, an electron in the 1s shell has a velocity of about
58% of the speed of light. At such speeds, the mass of the electron is about
1.23 me and the uncertainty in velocity is 10,000 m/s, what is the uncertainty
in the position of this electron?
a. 4.7 nm b. 3.6 nm c. 2.4 nm d. 1.5 nm

Part 3: Electronic Structure of Atoms

 68
H. Quantum Numbers
1. Principal Quantum Number (n) VALUE DESIGNATION

1 1st or K-shell
• a positive integer (1, 2, 3, and so on)
2 2nd or L-shell
• indicates the relative size of the orbital 3 3rd or M-shell
and relative distance from the nucleus 4 4th or N-shell
• specifies the energy level 5 5th or O-shell
6 6th or P-shell
7 7th or Q-shell

2. Angular Momentum or Azimuthal Quantum Number (l)

• integer from 0 to n-1
• indicates the shape of the orbital
n l NAME OF ORBITAL SHAPE

0 s (sharp) spherical
1 p (principal) dumbbell
4
2 d (diffuse) rosette
3 f (fundamental) very hard to illustrate

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H. Quantum Numbers
3. Magnetic Quantum Number (ml)
• integer from –l through 0 to +l
• describes the orientation of the orbitals in space
• the number of possible ml values equals 2l+1
l = 0 (s-orbital) l = 1 (p-orbital) l = 2 (d-orbital)

0 -1 0 +1 -2 -1 0 +1 +2

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H. Quantum Numbers
Shapes of the Orbitals
s-orbital
• all s-orbitals are spherical
• as n increases, the s-orbitals get larger

www.javierdelucas.es
http://www.neutron.rmutphysics.com

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H. Quantum Numbers
Shapes of the Orbitals
p-orbital
• there are three p-orbitals - px, py, and pz.
• these three p-orbitals lie along the x-, y- and z- axes of a
Cartesian system
• the letters correspond to allowed values of ml of -1, 0,
and +1.)
• orbitals are dumbbell shaped
• as n increases, the p-orbitals get larger.

http://chem-guide.blogspot.kr/2010/04/shape-of-atomic-orbital-s-and-p.html

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H. Quantum Numbers
Shapes of the Orbitals
d-orbital
• three (3) of the d-orbitals lie in a
plane bisecting the x-, y and z-
axes and two (2) of the d-
orbitals lie in a plane aligned
along the x-, y- and z-axes
• four (4) of the d-orbitals have
four lobes each and one (1) d-
orbital has two lobes and a
collar

Part 3: Electronic Structure of Atoms

 73
H. Quantum Numbers
Shapes of the Orbitals
f-orbital
• there are seven (7) each with a complex, multi-lobed shape

Part 3: Electronic Structure of Atoms

 74
H. Quantum Numbers
4. Spin Quantum Number (ms)
• has values of either +½ or -½
Thus, each electron in an atom is described completely by a set of
four (4) quantum numbers: the first three (3) describe its orbital and
the fourth its spin

• Stern and Gerlach designed an

experiment where a beam of atoms
was passed through a slit and into a
magnetic field and the atoms were
then detected
• Two spots were found: one with the
electrons spinning in one direction
and one with the electrons spinning
in the opposite direction

Part 3: Electronic Structure of Atoms

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I. Electronic Configuration
1. Rules in Writing Electronic Configurations
• Aufbau principle

From German word, aufbau meaning
building up

The orbitals of an atom must be filled with
a maximum of two electrons in the order of
increasing orbital energy

Works well for the atoms in their ground
states
• Madelung-Klechkovsky rule

From German word, aufbau meaning
building up

Proposed by Erwin Madelung (1881-1972)
and Vsevolod Klechkovsky (1900-1972)

Orbitals are filled in the order of increasing
(n + l) and if two orbitals have the same
value of (n + l), they are filled in order of
increasing n
Part 3: Electronic Structure of Atoms
 76
I. Electronic Configuration
1. Rules in Writing Electronic Configurations
• Pauli’s Exclusion Principle

Proposed by Wolfgang Ernst Pauli (1900-1958)

No two electrons in an atom can have the same
set of quantum numbers and an atomic orbital
must contain a maximum of two electrons with
opposite spins
• Hund’s rule of multiplicity

Proposed by Friedrich Hermann Hund (1896-
1997)

The most stable arrangement of electrons in
subshells is the one with more parallel spins

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 77
I. Electronic Configuration
2. Methods of Writing Electronic Configurations
• Orbital method

• Rectangular-arrow Method

• Shell Method

• Core Method

Part 3: Electronic Structure of Atoms

 78
Review Questions and Problems
5. The region in space where an electron is most likely to be found is called
a. orbital b. energy level c. shell d. nucleus
9. The quantum number that has an allowable value of 0, 1, 2, etc. is the
a. Magnetic c. Angular Momentum
b. Spin d. Principal
12. It states that no two atoms will have the same set of quantum numbers.
a. Heisenberg Uncertainty Principle c. Aufbau Building Up Principle
b. Pauli’s Exclusion Principle d. Hund’s Rule of Multiplicity
14. What is the maximum number of electrons in an atom that can have the
quantum number: n= 2, ms= –½ ?
a. 8 b. 6 c. 1 d. 4
16. Which of the following properties do not depend on the electronic
configuration of the atoms?
a. physical c. nuclear
b. chemical d. none of these

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 79
Review Questions and Problems
17. Which of the following sets of quantum numbers is incorrect?
a. n=1, l=0, ml= –1, ms= –½ c. n=3, l=1, ml=0, ms= –½
b. n=1, l=0, ml=0, ms= +½ d. n=4, l=2, ml= –1, ms= +½
18. In what group of the periodic table is the element with the following
electron configuration? [Ar] 4s2 3d10 4p3
a. 1A b. 2A c. 3A d. 4A

Given four sets of quantum numbers, identify the element

n l ml ms Element
2 0 0 -½
3 2 +1 +½
4 1 +1 +½
4 3 +1 -½
3 1 0 -½
5 2 -1 +½
Part 3: Electronic Structure of Atoms
 80

PART 4

Periodic Table
of Elements
and Periodic
Law