Chemistry 1A03

Introductory Chemistry I

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Unit 3
Atomic Structure and Theory

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Electromagnetic Spectrum

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Helpful conversion: 1 nm = 10-9 m 2 Chem
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 iClicker #1

• Choose the false statement:

A. The frequency of red light is larger than that of
blue light.
B. The wavelength of red light is longer than that of

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blue light.
C. The energy of red light is lower than that of blue
light.

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What do we know about atoms?
(2 min brainstorming session)

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-

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 Quantum theory
• Energy is quantized (discontinuous)
• A photon is a discrete packet
(a quantum) of energy
• E = hν
• E = energy

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• ν = frequency
• h = 6.626 x 10-34 Js
(Planck’s constant) Nobel Prize in Physics, 1918

• Helped in the discovery of the Photoelectric Effect

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 iClicker #2
• 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
B. 8.941 x10−2 J

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C. 2.711 x10−7 J
D. 3.929 x10−19 J

Emission of yellow light

• Planck’s constant: h = 6.626 x 10-34 Js from Na (sodium) lamp

• Speed of light: c = 2.9979 x 108 m/s

• 1 nm = 10-9 m Chem
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 Chem
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Photoelectric effect

Red light ____________eject

I=0 electrons and ______ current
flow:

Ered light < Ethreshold

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700 nm

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Photoelectric effect

Increasing intensity of the red

I=0 light _______________change
the outcome:

Ered light < Ethreshold

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700 nm

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Photoelectric effect

Green light ejects electrons and

current flows:
I>0
Egreen light > Ethreshold

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550 nm

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Photoelectric effect

Purple light ejects electrons

I>0 and current flows:

Epurple light > Ethreshold

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400 nm

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Photoelectric effect

Doubling intensity of the purple

light _______________ the
I>0
number of ejected electrons
and current:
Epurple light > Ethreshold

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400 nm

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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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 iClicker #3
• 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
B. No

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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 Φ
• Φ 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 > Φ, then the excess energy goes towards the kinetic
energy of the ejected electron:
• Ephoton = Φ + KEelectron = Φ + ½ mu2
• u = velocity of ejected photoelectron
• m = mass of ejected photoelectron (9.109 x 10-31 kg)
• Energy is quantized.
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 iClicker #4
• 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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 iClicker #5
• The wavelength of light needed to eject electrons from a
metal is 85.8 nm. What happens to the kinetic energy (KE)
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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 Sample problem
• In a photoelectric effect experiment, the wavelength of the
incident photons is 40.0 nm. They strike a gold metal
surface, which has a threshold energy of 8.15 x 10-19 J.
• Identify whether the following statements are true or
false:

1. The light is not energetic enough to eject a photoelectron.

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2. The ejected photoelectrons have kinetic energy of
4.97 x 10-18 J.

3. The ejected photoelectrons have a speed of

3.02 x 106 m/s.

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 Sample problem – solution
• Given: λphoton = 40.0 nm = 4.00 x 10-8 m; ΦAu = 8.15 x 10-19 J
• Strategy: If Ephoton > Φmetal, then a photoelectron will be
ejected, and Ephoton = Φmetal + KEelectron, where KE = ½ mu2.
• Calculate Ephoton from λphoton;
• Determine whether Ephoton > Φmetal; and (if so)
• Plug into equation, solve for u.

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• Ephoton =

• KEelectron =

• KEelectron =

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 Sample problem – answer
• In a photoelectric effect experiment, the wavelength of the
incident photons is 40.0 nm. They strike a gold metal
surface, which has a threshold energy of 8.15 x 10-19 J.
• Identify whether the following statements are true or false:
1. The light is not energetic enough to eject a photoelectron.

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2. The ejected photoelectrons have kinetic energy of
4.97 x 10-18 J.

3. The ejected photoelectrons have a speed of

3.02 x 106 m/s.
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Electronic transitions in hydrogen: absorption

n=∞
…

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Electronic transitions in hydrogen: emission

n=∞
…

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Emission & absorption spectra

→ →

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 Pb Flint, Michigan

• Flint, Michigan (2014-2017): Pb seeped into drinking water

source, affected 100 000 residents.

• 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.
• Each photon is absorbed by one metal ion.

• Calibration curve (like Lab 3): determine [metal] in sample.

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 Electronic transitions in hydrogen

absorption emission
n=∞ 𝑅𝑅𝐻𝐻
𝐸𝐸𝑛𝑛 = − 2
𝑛𝑛
…

RH = 2.179 x 10-18 J

∆𝐸𝐸 = 𝐸𝐸𝑓𝑓 − 𝐸𝐸𝑖𝑖

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1 1
∆𝐸𝐸 = −𝑅𝑅𝐻𝐻 2 −
𝑛𝑛𝑓𝑓 𝑛𝑛𝑖𝑖2

∆E > 0: absorption
∆E < 0: emission
Ephoton = hν =│∆E│, always positive

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 iClicker #6
• Which of the following electronic transitions in an H atom
will lead to emission of a photon with the longest
wavelength? n=∞

…
A. n = 1 to n = 4

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B. n = 4 to n = 2
C. n = 3 to n = 2
D. n = 2 to n = 4

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 Sample problem
• 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 n=∞
• Strategy: What does ionize mean?

…
Use the Rydberg equation
1 1

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• ∆𝐸𝐸 = −(2.179 × 10−18 J) −
∞2 22
• ∆𝐸𝐸 =

• 𝐸𝐸𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 =

• λ=
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 Sun’s Emission Spectrum

UVA
UVB
UVC 6000K

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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. NH2
O N
H N
H2N C C OH

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CH2 N N
HO
O
H H
HN H H
OH H
Tryptophan, amino acid in proteins Adenine, nucleoside in DNA
• Body’s response: produce melanin (dark pigment) to filter
UVB radiation.
• Chronic exposure => chance of skin cancer, cataracts &
genetic mutations Chem
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Electronic transitions in atoms and molecules

E2

UV Light

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E1

Electronic transitions in a
molecule: absorption of light

Atomic orbitals Molecular orbitals

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
UVB UVA
O

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O

CH3O
2-ethylhexyl p-methoxycinnamate

O OH

OMe
oxybenzone
λ 30 Chem
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 iClicker #7
• 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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 Absorption and solar cells
Solar Cells

-
Conduction band

Eg = band gap e-
current flow

Valence Band
+

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• Semiconductors  electrons must be excited from low energy
valence band to higher energy conduction band
• Solar cells  silicon semiconductors
• Incoming light must have energy ≥ the “band gap” (Eg)
• The promoted electron can then do work through an external system
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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
• Waves (e.g. light) display particle-like properties.
• Particles display wave-like properties.
• Small particles (e.g. electrons) have long λ.

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

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A B
(a) X-ray diffraction by metal foil
(b) Electron diffraction by metal foil
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 iClicker #8
• 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?

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A. 0.241 nm
B. 2.46 nm
C. 4.15 nm
D. 338 nm
(Mass of electron = 9.11 x 10-31 kg)
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 Solution

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Chem

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 Quantum numbers and orbitals
• Schrödinger equation: combines ideas of particle & wave
behaviour to describe the state of e− in atom

• Orbitals:
• Wavefunctions, ψ, solutions to the Schrödinger equation

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• Defined by 3 quantum numbers
• Describe regions of high probability of finding an electron
(high charge density)

• Please review: quantum numbers, atomic orbitals, electron

configurations

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 Review: n, ℓ, mℓ
• Principal quantum number, n
• n describes orbital energy and distance from nucleus
• Larger n value = orbital is further from nucleus, e- in 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 (s orbital), ℓ = 1 (p), ℓ = 2 (d), ℓ = 3 (f)
• Number of ℓ values = number of subshells in a given n

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shell

• Magnetic quantum number, ml

• ml describes orbital orientation
• ml = - ℓ ,..,0,..,+ℓ
• ml has (2ℓ +1) values

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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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 iClicker #9
• Which of the following set of quantum numbers represents
a 4d orbital?

n ℓ mℓ
A 4 3 -2

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B 3 1 1
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
2s
p orbitals (px, py, pz) 3s

• 1 angular node (0 probability of finding electron)

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• Possible in n ≥ 2

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 Orbital pictures

d orbitals:

• 2 angular nodes

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• Possible in n ≥ 3

You should know the number &

shapes of each type of orbital, but
not the mathematical derivations.
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 Hydrogen vs multi-electron atoms

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• Hydrogen: subshell • Multi-electron atoms:
energies are the same subshell energies differ
(degenerate) (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

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all spins paired are diamagnetic
1 or more unpaired electrons are paramagnetic

• We can identify any electron with the 4 quantum

numbers

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 iClicker #10
• 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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 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

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same energy are occupied
singly, before pairing e-.

Example: oxygen (ground state) 2p

2s
1s22s22p4 OR [He] 2s22p4

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 iClicker #11, #12
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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Chem

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 Demo: bowls of flame

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Chem

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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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