Chem

1 1A03

Chemistry 1A03
Introductory Chemistry I
Chemistry in the context of health,
energy and the environment

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Unit 3
Atomic Structure & Theory –
part 1
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Learning outcomes – Atomic structure part 1
1. Apply the relationship between wavelength, frequency, and
energy for light.

2. Describe the photoelectric effect experiment and apply the

relationship between photon energy, threshold energy (work

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function) of a metal, and kinetic energy or speed of the
ejected electron.
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Electromagnetic Spectrum
ν,

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λ,

Helpful conversion
1 nm = 10-9 m
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What do we know about atoms?
(2 min brainstorming session)
• Mostly empty space
• Neutron: 0 charge; proton: +1 charge;
electron: -1 charge
• Nucleus is very small but contains
almost all the mass of the atom
• Quantum mechanics describes electrons

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• Electrons behave as particles and waves
• Electrons are not actually at a fixed
location or distance from the nucleus
• Orbitals define regions of space where
- electrons are likely to be found
• Quantum numbers describe orbitals
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Quantum Theory
• Energy is quantized (discontinuous)
• A photon is a discrete packet
(a quantum) of energy
• E = hν
• E = energy (J)
• ν = frequency (s-1)

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• h = 6.626 x 10-34 Js
(Planck’s constant)
• Helped in the discovery of
the Photoelectric Effect
Bradley D. Fahlman et al.; Chemistry in Context; McGraw Hill Education: New York, 2018
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Sample question
Excited sodium ions emit photons with a wavelength of 589.0 nm.
What is the energy of this transition (in Joules)?
A. 3.373 x10−19 J E=hv = hc/λ
B. 8.941 x10−2 J E = (6.626 x10−34Js x 2.9979 x108m/s) /
5.890 x10−7m
C. 2.711 x10−7 J E= 3.373 x10−19 J

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D. 3.929 x10−19 J
• Planck’s constant: h = 6.626 x 10-34 Js
• Speed of light: c = 2.9979 x 108 m/s Emission of yellow light
• 1 nm = 10-9 m from Na (sodium) lamp
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The photoelectric effect

0 AA(x(x>>0)0)
I = 2x
x

700 nm
550 nm

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400 nm
Nobel Prize in Physics,
1921, for the
photoelectric effect

Ered light < Ethreshold

Egreen light > Ethreshold
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Sample question
• The wavelength of light needed to eject electrons from a
metal is 85.8 nm. Are electrons ejected if light of 90.0 nm
shines on the metal sample?
A. Yes • light at 90.0nm has lower energy than the
B. No threshold energy of the metal, which is at

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85.8nm
• light at a wavelength of 90.0nm does not
have enough energy to eject electrons
from the metal
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Photoelectric effect – key concepts
• Shining light on metal surface causes electrons to be ejected
(called “photoelectrons”), but only if the light is “energetic
enough”:
• Ephoton > Ethreshold
• Ethreshold = work function of the metal, symbol 
•  changes with different metals
• Exactly one electron is ejected from the metal surface for every

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one photon of light (provided it is energetic enough).
• If Ephoton > , then the excess energy goes towards the kinetic
energy of the ejected electron:
• Ephoton =  + KEelectron =  + ½ mu2
• u = velocity of ejected electron
• m = mass of ejected electron (9.109 x 10 -31 kg)
• Energy is quantized.
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Gizmos demo
http://www.explorelearning.com/index.cfm?method=cResource.dspVie
w&ResourceID=491&ClassID=1838684

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• What happens if we change λ of
light?
• What happens if we change intensity
of light?
• How do we measure the kinetic
energy of the ejected electrons?
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Sample question
• The wavelength of light needed to eject electrons from a
metal is 85.8 nm. What happens to the number of
electrons ejected when light of 80.0 nm or light of 70.0 nm
with the same intensity shines on the metal sample?

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80.0 nm light 70.0 nm light
A. Same # of e– ejected Same # e– ejected
B. Fewer e– ejected More e– ejected
C. More e– ejected Fewer e– ejected
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Sample question
• The wavelength of light needed to eject electrons from a
metal is 85.8 nm. What happens to the kinetic energy of
the ejected electrons when light of 80.0 nm or light of 70.0
nm with the same intensity shines on the metal sample?

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80.0 nm light 70.0 nm light
A. e– have same KE e– have same KE
B. e– have less KE e– have greater KE
C. e– have greater KE e– have less KE
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Summary of key concepts

• Energy is quantized (discontinuous)

• E = hν
• Light is quantized explains the photoelectric effect

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• Ephoton > Ethreshold
• Ethreshold = work function of the metal, symbol 
• Ephoton =  + KEelectron =  + ½ mu2
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Chemistry 1A03
Introductory Chemistry I
Chemistry in the context of health,
energy and the environment

©2008 – 2020 McMaster University

Unit 3
Atomic Structure & Theory –
part 2
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Learning outcomes – Atomic structure part 2
3. Qualitatively and quantitively describe energy transitions in
the hydrogen atom, including absorption and emission.
4. Discuss how atomic absorption spectroscopy can be used to
identify and quantify the amounts of heavy metals (e.g. lead)
present in our environment.
5. Understand the emission

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spectrum of the sun and explain
how ultraviolet radiation is
absorbed by sunscreens
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Electronic transitions in hydrogen: absorption
n=∞ …

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Electronic transitions in hydrogen: emission
n=∞
Spectrum
…
Series nf ni
region
Lyman 1 2, 3, 4… UV
Balmer 2 3, 4, 5… Visible, UV
Paschen 3 4, 5, 6… IR

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Brackett 4 5, 6, 7… IR

6→2 5→2 4→2 3→2

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Bowls of flame

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We are observing electronic transitions.
The emitted light consists of certain discrete wavelengths.
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Emission & absorption spectra
→ →

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 Chem
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Pb Flint, Michigan
• Flint, Michigan (2014-2017): Pb seeped into drinking
water source, affected 100 000 residents
• Environmental Protection Agency guideline for lead in
drinking water is 15 μg/L or 15 ppb
• Pb is a toxin: accumulates in soft tissues and bones,
damages nervous system, interferes with enzymes

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• We measure the presence and quantity of heavy metals
using atomic absorption spectroscopy
• Each metal gives rise to a unique set of bands
• Absorbance is proportional to [metal]
• Calibration curve (Lab 3): determine [metal] in sample
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Electronic transitions in hydrogen
absorption emission
n=∞ 𝑅
𝐸𝑛 = − 𝑛𝐻2
…

RH = 2.179 x 10-18 J

∆𝐸 = 𝐸𝑓 − 𝐸𝑖

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E > 0: absorption
E < 0: emission
Ephoton = h =│E│, always positive
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Sample question
n=∞

…
Which of the following electronic
transitions in a H atom will lead to A B C D
emission of a photon with the longest
wavelength?

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A. n = 1 to n = 4
B. n = 4 to n = 2
C. n = 3 to n = 2
D. n = 2 to n = 4
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Sample question
n=∞
• Calculate the wavelength of light

…
required to ionize an electron in a
hydrogen atom from the n = 2 state.
• RH = 2.179 x 10-18 J, h = 6.626 x 10-34 Js
• Strategy: What does ionize mean?
Use the Rydberg equation

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−18 1 1
• ∆𝐸 = −(2.179 × 10 J) −
∞2 22
• ∆𝐸 = 5.448 × 10−19 J
ℎ𝑐 ℎ𝑐
• 𝐸𝑝ℎ𝑜𝑡𝑜𝑛 = ∆𝐸 = ⇒=
 ∆𝐸
•  = 3.646 × 10−7m = 364.6 nm
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Sun’s Emission Spectrum
UVA
UVB
UVC

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 Chem
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Exposure to UV Radiation
• Shortwave radiation is largely screened by small molecules
(e.g. N2, O2, O3) in the atmosphere.
• Some UVA, UVB radiation reaches the earth’s surface; harmful
to biological molecules.

Tryptophan, Adenine,
amino acid in nucleoside

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proteins in DNA

• Chronic exposure => chance of skin cancer, cataracts & genetic

mutations
• Body’s response: produce melanin (dark pigment) to filter
UVB radiation.
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Electronic transitions in atoms and molecules

E2

UV Light

E1

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Electronic transitions in a
molecule: absorption of
Atomic orbitals Molecular orbitals light
for one atom for a molecule
(e.g. Li) (e.g. N2)
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Chemistry of sunscreen
• Physical sunscreens (ZnO and TiO2): remain on skin surface,
reflect UV rays.
• Chemical sunscreens: molecules absorb UV radiation before
radiation reaches dermis O

UVB UVA O

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C H 3 O
2 - e t h y lh e x y l p - m e t h o x y c in n a m a t e

O OH

OMe
 oxybenzone
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Sample question
• Which statement is false?
A. Transitions between energy levels in sunscreen occur in
the ultraviolet region of the spectrum.
B. Absorption and emission of energy between the same two
energy levels are equal in magnitude.

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C. When a molecule of sunscreen absorbs radiation, the
molecule is ionized.
D. An electronic transition in a molecule of sunscreen occurs
between two molecular orbitals.
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Luminol

E2

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E1

Electronic transitions in a
molecule: emission of light
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Summary of key concepts
• Atomic emission spectra and atomic absorption spectra share
lines at the same wavelength.
• Atomic absorption spectroscopy uses the distinct set of lines in
the atomic spectra to determine the identity of a substance.
• Atomic absorption spectroscopy can be used quantitatively to
determine the concentration of a substance, by plotting a

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calibration curve.
• Sunscreens protects our skin from absorbing UVA and UVB
radiations as the electronic transitions between energy levels in
sunscreen occur in the UV region of the spectrum.
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Chemistry 1A03
Introductory Chemistry I
Chemistry in the context of health,
energy and the environment

©2008 – 2020 McMaster University

Unit 3
Atomic Structure & Theory –
part 3
 Chem
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Learning outcomes – Atomic structure part 3
6. Describe the wave-particle duality of light and of the
electron, including the experimental evidence and theoretical
basis.
7. Use the four quantum numbers to describe atomic orbitals,
electrons in orbitals, and electron configurations.

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 Chem
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Wave-particle duality
• Waves (e.g. light) display particle-like properties.
• Particles (e.g. electrons) display wave-like properties.

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Nobel Prize in physics, 1906 Nobel Prize in physics, 1937 (shared)
Showed that the electron is a particle Showed that the electron is a wave
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Wave-particle duality
Units
• h=Js
• m = kg
• u = m s-1
1 Joule = 1 kg m2 s-2

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 Chem
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Thomson’s electron diffraction experiment
• Diffraction occurs when radiation and object spacing are
similar (e.g. X-rays,  = 100 pm, array of Al atoms 200 pm
spacing)

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(a) X-ray diffraction by metal foil
(b) Electron diffraction by metal foil
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Sample question
• In a photoelectric effect experiment, photons with a
wavelength of 40.0 nm strike a gold metal surface
(Ethreshold = 8.15 x 10-19 J), causing photoelectrons to be
ejected with a speed of 3.02 x 106 m/s.
• What is the de Broglie wavelength (in nm) of the emitted
photoelectrons? Mass of electron = 9.11 x 10-31 kg

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A. 0.241 nm
B. 2.46 nm
C. 4.15 nm
D. 338 nm
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Sample problem – solution
ℎ 6.626×10 −34 J∙s
•  = 𝑚𝑢 = (9.11×10−31 kg)(3.02×106 m/s)

•  = 2.41 × 10−10 m = 0.241 nm

• Notice there are two different formulae for wavelength:

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𝑐
• = applies to light (any electromagnetic radiation)

ℎ
• = applies to particles
𝑚𝑢
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Quantum Mechanics
• Schrödinger equation: combines ideas of particle (mass) and
wave behavior(wavefunction) to describe the state of e − in
atom
• Atomic orbitals:
• Wavefunctions, , solutions to the Schrödinger equation
• Defined by 3 quantum numbers

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• Describe regions of high probability of finding an electron
(high charge density)
• Please review quantum numbers, atomic orbitals, and
electron configurations: p. 334-337, 353-358 (11th ed) or
p. 324-326, 339-343 (10th ed)
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Review: n, ℓ, mℓ
• Principal quantum number, n
𝑅
• 𝐸𝑛 = − 𝑛𝐻2 RH = 2.179 x 10-18 J
• For an atom with one electron, n describes orbital
energy and distance from nucleus
• Larger n value = orbital is further from nucleus, e- in

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orbital is at higher energy
• n = 1, 2, 3, 4….
• n describes a principal shell
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Review: n, ℓ, mℓ
• Orbital angular momentum quantum number, ℓ
• ℓ describes orbital shape (angular distribution)
• ℓ = 0, 1, 2, 3…n-1
ℓ 0 1 2 3 4 5
Name of s p d f g h

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orbital

• Number of ℓ values = number of subshells in a given n

shell
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Review: n, ℓ, mℓ
• Magnetic quantum number, ml
• ml describes orbital orientation
• ml = - ℓ ,..,0,..,+ℓ
• ml has (2ℓ +1) values
• Number of ml values = number of orbitals in a given ℓ
subshell.

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Sample question
• How many orbitals are described by the following quantum
numbers when n = 5 and ℓ = 2?

A. 4 orbitals
B. 25 orbitals

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C. 11 orbitals
D. 5 orbitals ml = −2, −1, 0, +1, +2
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Example: hydrogen atom, n = 3
For n = 3 shell, For ℓ = 0, mℓ = 0 For ℓ = 1, mℓ = -1, 0, 1
ℓ = 0, 1, 2 (3 subshells) one 3s orbital three 3p orbitals

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For ℓ = 2, mℓ = -2, -1, 0, 1, 2
five 3d orbitals
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Sample question
• Which of the following set of quantum numbers represents
a 4d orbital?
n ℓ mℓ
ℓ=2
A 4 3 -2
n=4
B 3 1 1

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C 3 2 0
D 4 1 2
E 4 2 -1
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Orbital pictures
s orbitals are spherical
• 1s, 2s, 3s at 95% probability:
1s
p orbitals (px, py, pz) 2s
• Possible in n ≥ 2 3s
• 1 angular node (0 probability of finding electron)

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px py pz
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Orbital pictures
d orbitals:
• Possible in n ≥ 3
• 2 angular nodes
You should know

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the number &
shapes of each
type of orbital,
but not the c
mathematical
derivations.
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Summary of key concepts
• De Broglie equation
• The solution to the Schrödinger equation provides the
possible energy states of the electron in an atom
• Principle quantum numbers, n, orbital energy (shell of the
orbital)
• Orbital angular momentum

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quantum number, ℓ, orbital
shape (subshell in a given n
shell)
• Magnetic quantum number,
ml , orbital orientation
(orbital in a given ℓ subshell)
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Chemistry 1A03
Introductory Chemistry I
Chemistry in the context of health,
energy and the environment

©2008 – 2020 McMaster University

Unit 3
Atomic Structure & Theory –
part 4
 Chem
52 1A03
Learning outcomes – Atomic structure part 4
7. Use the four quantum numbers to describe atomic orbitals,
electrons in orbitals, and electron configurations. Define and
apply the three basic principles governing electron
configuration: the Aufbau Principle, Hund’s Rule, and the Pauli
Exclusion Principle.
8. Describe how orbital energies are modified when more

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than one electron is present in an atom.
9. Determine the number of unpaired electrons in a main
group (s- or p-block) atom or ion from its electron
configuration; use the terms “paramagnetic” or “diamagnetic”
to describe the atom or ion.
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Hydrogen vs multi-electron atoms

Energy only Energy depends

depends on n on n and ℓ

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Hydrogen: subshell energies Multi-electron atoms: subshell
are the same (degenerate) energies differ (electron screening,
effective nuclear charge)
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Electron spin quantum number, ms

• Electrons have spin, generating a magnetic field:

• Values of ms = +½ or -½
• Pair of e− with opposite spins has no magnetic field
• Atoms or ions with
• All spins paired are diamagnetic

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• 1 or more unpaired spins are paramagnetic
• We can identify any electron with the 4 quantum
numbers: n, ℓ, ml , and ms
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Sample question
• Which of the following is an allowed set of quantum
numbers for a valence shell electron of silicon in the
ground state?

n ℓ mℓ ms
A. 3 1 -1 -½

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B. 2 1 1 -½
C. 3 0 1 +½
D. 2 1 2 0
E. 3 2 2 +½
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Sample problem – solution
• Ground state Si electron configuration

1s2 2s2 2p6 3s2 3p2 Valence shell

ℓ=1
ℓ=0

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• When ℓ = 0, the allowed mℓ value is 0, the allowed ms
values are +½ and -½
• When ℓ = 1, the allowed mℓ values are -1, 0, and +1, the
allowed ms values are +½ and -½
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Review: electron configuration
1. Aufbau principle: occupy orbitals so that
the atom’s energy is minimized.
2. Pauli exclusion principle: every e- has
unique set of 4 quantum numbers.
3. Hund’s rule: orbitals of the same energy
are occupied singly, before pairing e -.

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Example: oxygen (ground state) 2p
2s
1s22s22p4 OR [He] 2s22p4
1s
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Sample question
• Identify the ground state electron configuration of a
fluorine atom.
• Which one is an excited state electron configuration of a
fluorine atom.

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A. 1s22s22p6
B. 1s22s22p5
C. 1s22s22p53s1
D. 1s22s12p43s2
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Building the periodic table

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Summary of key concepts
• The energy of the electron in a H atom is determined only
by n. The energy of an electron in a multi-electron atom,
both n and ℓ determine the energy of an electron.
• Pauli exclusion principle, Hund’s rule, and the Aufbau
principle provide the guidelines for building up electron
configuration for elements. The periodic table classifies the

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elements according to the electronic configurations of their
atoms.