General Chemistry I

Chemistry: The central science

Phong D. Tran
Department of Fundamental and Applied Sciences
University of Science and Technology of Hanoi
Email: [email protected]

Lectures 4-6: Electronic structure of atoms

1
2
Atom is composed of electron, neutron and proton

3
• Arrangement of electrons in space around the nucleus
• Electron energy
(thus related to its physical and chemical activity)

Given facts (Observations)

• Emission spectrum of atoms
• Periodic chemical properties of elements

4
Continous spectrum: a rainbow of colors, containing light of
all wavelengths
6
He, Ne, Ar are inert gases
Li, Na, K are soft, very active (violently reaction with water or O2)

Na Na is kept in Kerosene oil

He balloons
Xmas in Lab
(Ar balloons provide inert atmosphere for experiments)
• Arrangement of electrons in space around the nucleus
• Electron energy
(thus related to its physical and chemical activity)

Given facts (Observations)

• Emission spectrum of atoms
• Periodic chemical properties of elements

10
Spherical coordinates

Electron is dimensionless particle (equal to point in math)

Rydberg (1888) found an empirical equation to
calculate the wavelengths of the spectral lines of H

λ is the wavelength of a spectral line (m),

RH is the Rydberg constant (1 .096776 x 107 m -1),
n1 and n2 are positive integers, with n2 > n1
 The work of Planck and Einstein paved
the way for understanding how electrons
are arranged in atoms

Bohr assumed that the prevailing laws of physics were

inadequate to describe all aspects of atoms

To explain the line spectrum of hydrogen, Bohr relied

on several assumptions
1. the electron moves around the proton in circular
orbits

2. Only orbits of certain radii, corresponding to

certain definite energies, are permitted

3. An electron in a permitted orbit has a specific

energy and is in an "allowed“ energy state

4. An electron in an allowed energy state will not

radiate energy and therefore will not spiral into
the nucleus (as predicted by classical physics) 14
 5. Energy is emitted or absorbed by the electron
only as the electron changes from one allowed
energy state to another

Calculations by Bohr show that the energies of

the different allowed states are :

h - Planck's constant
c - the speed of light Energies are negative since these
RH – Rydberg’s are bound states: positive energy
constant must be given to extract the
electron
 Only the specific frequencies of light that have an
energy (hν) = energy difference between states
can be absorbed or emitted by the atom.

From Bohr’s model :

this equation corresponds to Rydberg’s equation, which

was obtained using experimental data
 ELECTRON CAN CHANGE FROM ONE ALLOWED STATE TO
ANOTHER ONE
- To increase energy : absorbs a photon
- When decreasing energy : emits a photon

Energy

Photon hν
Photon h E1 emitted
absorbed

E2
Electron is promoted (excited) Electron de-excites to a
to a higher energy state lower energy state

CONSERVATION OF ENERGY :
Photon energy is the difference between the 2 states
hν = E1-E2 (higher- lower)
If a compound X absorbs the photon λ1,
it will emit photon λ2 where:

A) λ1 = λ2
B) λ1 > λ2
C) λ1 < λ2

18
There are many possible
transitions between
allowed states but always
hν = E1-E2 (higher –lower)

Line spectrum

n is called quantum number

When n = ∞ , the energy is 0

Then the atom has lost its

electron : ionized state H+ 19
 BOHR’S MODEL : CONCLUSIONS

GREAT SUCCESS ! Bohr’s model explains the

line spectrum of the hydrogen atom

BUT : it cannot explain the spectra of other atoms

Two important useful ideas Bohr’s model:

(1) Electrons in atoms have only certain discrete
energy levels
(2) Energy is exchanged in moving an electron from
one level to another one
 5. QUANTUM PHYSICS.
THE WAVE BEHAVIOR OF MATTER

Bohr could not explain why electrons were restricted to

some fixed distances around the nucleus…

Louis de Broglie (1924) proposed that if light can behave

as a particle (photon) then

PARTICLES (electrons and others) MAY EXHIBIT

WAVE CHARACTERISTICS.

Another revolutionary idea !!

 De Broglie : PARTICLE MOVEMENT AND WAVE
PROPERTIES ARE RELATED BY

h

mu
where
λ = wavelength “associated” to the particle
m = mass (kg)
u = velocity (m/s) for an electron moving at 5.0×106 m/s
λ= 1.46×10 m (0.146 nm). Quite small
−10

! So not detected earlier…

The wave properties of matter are proved by a number of

experiments ! And are used every day in some electronic
devices (‘tunnel diodes’ in your mobile phone)
 h

mu

Calculate the wavelength associated to you movement

h = 6.62607004 × 10-34 m2 kg / s

23
 QUANTUM MECHANICS : THE PHYSICS OF
MATTER WAVES

De Broglies’s waves of matter brought some

justification to Bohr’s model but

Heisenberg, Schrödinger and others improved and

generalised these ideas and very fast developed
a new physics

Schrödinger’s equation allows calculating these

waves (wavefunctions) in systems like atoms
 MAIN FEATURES of QUANTUM MECHANICS

A wave cannot be precisely localized …

As electrons behave like waves they cannot be

precisely localized

More precisely we cannot know simultaneously

their speed and their position
( uncertainty principle)

There are described by wave functions which give

their probability of presence in some portion of space
and their energy
 JUST TO FRIGHTEN YOU !
Here is Schrödinger’s equation !

In some way this replaces Newton’s law F = ma

Solving Schrodinger's equation for an atom leads to a

series of functions called wave functions, Ψ (psi) that
describe the electron in an atom
 The wave function ψ(x,y,z) will give the probability
density or the electron density (ψ2) = probability that
the electron will be in a certain region of space

Example of an electron
density distribution

the density of dots represents

the probability of finding the
electron.
 6. ATOMIC ORBITALS

The wavefunctions are stationary waves around the

nucleus.

The solution to Schrodinger's equation for the

hydrogen atom yields a set of wave functions and
corresponding energies

There is a lowest-energy stationary wave, and higher

energy ones.

These wave functions are called ORBITALS

 Each orbital describes a specific distribution of
electron density in space

Each orbital has a characteristic energy and shape

Each atomic orbital in an atom is characterised by a

unique set of three quantum numbers (from
Schrödinger’s wave equation) :

n, ℓ, and mℓ
 Quantum numbers

n = principal quantum number

has positive integer values
n=1,2,3,…

If n increases,
- the orbital becomes larger
- the electron spends more time farther from the
nucleus
- the electron has a higher energy
- the electron is less tightly bound to the nucleus
 ℓ = angular momentum quantum number, has
integer values from 0 to (n - 1) for
each value of n
( for instance if n=1 ℓ =0 ; if n=3 ℓ can be 0, 1, 2 )
ℓ defines the shape of the orbital
Orbitals are named s, p, d, f depending on the
value of ℓ :
sharp
principal
diffuse
Orbital name fundamental
 mℓ = magnetic quantum number

describes the orientation of the orbital in space

has integer values between

-ℓ and ℓ, including 0

32
 How to manage these quantum numbers ?
n= 1, 2, 3… 0 ≤ ℓ ≤ n-1 - ℓ ≤ ml ≤ +ℓ

n=1 ℓ : only possibility ℓ=0

ℓ=0 so ml =0 . Just 1 orbital (1;0;0)
Orbital 1s because n=1 and s means l=0

n=2 then ℓ=0 or ℓ=1

if ℓ=0 ml =0 : 1 orbital (2;0;0) Orbital 2s (n=2 and l=0)

if ℓ=1 ml = -1 or 0 or +1 : 3 orbitals (2,1,-1), (2,1,0), (2,1,1)

3 Orbitals 2p (n=3 and p means l=1)
 n=3 then ℓ=0 or ℓ=1 or ℓ=2

if ℓ=0 ml =0 : 1 orbital Orbital 3s (n=3 and l=0)

if ℓ=1 ml = -1 or 0 or +1 3 Orbitals 3p (n=3 and p means l=1)

if ℓ=2 ml =-2 or -1 or 0 or +1 or +2
5 Orbitals 3d (n=3 and d means l=2)

n=4 then ℓ=0 or 1 or 2 or 3

1 orbital 4s (l=0)
3 orbitals 4p (l=1)
5 orbitals 4d (l=2)
7 orbitals 4f (l=3 so ml = -3…0 …+3 7 possible values)
 Summary table

- orbitals with the same value of n form a “shell”.

- orbitals that have n = 3, for example, are said to be in
the 3rd shell.
- orbitals with the same n and ℓ values form a “subshell”
- in shell number n there are n subshells
- the total number of orbitals in a shell is n2
Orbital energy levels
in the
H atom.

Energy depends only

on n.
All the orbitals in
one shell have the
same energy

36
REPRESENTATIONS OF ORBITALS
1) probability= f(distance to nucleus)
example : s orbitals
As n increases, the most likely
distance from the nucleus to
1s find the electron increases

2s 3s
 REPRESENTATIONS OF ORBITALS
2) volumes within which 90% chances to find the electron

90% is arbitrary. We can chose 80 or 92 or 95%.... But not 100 % !

s orbitals : spherical

1s 2s 3s
boundary surfaces for p orbitals (dumbbell-shaped)

p orbitals
have
preferential
orientations

pz px py
(m=0) (m=1) (m=-1)
 boundary surfaces for d orbitals

The shapes of the f orbitals are even more complicated …..

Experimental result

H2O
dry Co(NO3)2 [Co(H2O)6](NO3)2
Colorless powder Pink solution

NH3

[Co(NH3)6](NO3)2
Blue solution

Can can we explain this phenomenon?

41
42
 Color: Absorption versus Observation

The colors of the visible light spectrum

Wavelength Frequency
Color
interval interval
Red ~ 700–635 nm ~ 430–480 THz
Orange ~ 635–590 nm ~ 480–510 THz
Yellow ~ 590–560 nm ~ 510–540 THz
Green ~ 560–520 nm ~ 540–580 THz 43
1. Write electronic configuration of following species:

Mo (Z=42), Mo5+ and Mo6+

2. A compound of Mo shows green color. What could be the oxidation state of Mo

within this compound? Mo5+ or Mo6+? Give an explanation

44
1. Write down the electronic configuration of Fe (Z =26), Fe2+, Fe3+
2. A compound of Fe2+ (FeII) change color when it is heated up (see figure).
Give an explanation?

45
46
Spin crossover: Information storage

47
1. Write down electronic configuration of Li (Z=3), Na (Z=11), Mg (Z=12).
2. In which block these elements belong to?
3. Following is a schematic illustration of a Li battery design.
Why is Li preferred for battery design?

48
 7. MANY-ELECTRON ATOMS

Difference with H : in many-electron atoms,

for a given value of n, the energy of an orbital
increases with increasing value of ℓ.

2s < 2p
3s < 3p <3d

etc.
 Orbital energy levels Orbital energy levels
in H or one electron ions In many electron atoms

Note
that 3d
is above
4s

50
 A little more physics : electron Spin

Electrons (and other particles) have an intrinsic

property, called spin, that causes each electron to
behave as a tiny magnet.

People say : as if it were a

tiny sphere spinning around
one axis

BUT :
AN ELECTRON IS NOT A SPHERE (it is dimensionless)
and IT DOES NOT SPIN AROUND AN AXIS
 Spin is quantified : 2 possible values
4th quantum number ms = -1/2 or +1/2

No two electrons in an atom can have the same

set of four quantum numbers n, ℓ, mℓ and ms

One orbital ( defined by n,ℓ, mℓ ) can hold a maximum

of two electrons with opposite spins -1/2 and +1/2
Electron Paramagnetic Resonance: EPR

53
Only MoV species provide ERP signal.
MoIV and MoVI states are silent
55
56
 Spin is quantified : 2 possible values
4th quantum number ms = -1/2 or +1/2

No two electrons in an atom can have the same

set of four quantum numbers n, ℓ, mℓ, and ms

One orbital ( defined by n,ℓ, mℓ ) can hold a maximum

of two electrons with opposite spins -1/2 and +1/2
A convenient scheme for orbitals and electrons

1 Orbital = 1 box
Electrons =arrows representing spin (1/2 or -1/2 , up or down)

Orbital 1s with 1 electron unpaired electron

Orbital 1s with 2 electrons paired electrons

“full” orbitals 2s and 2p

The 3 orbitals 2p are grouped since

they have the same energy
Electron configuration: the way in which the
electrons are distributed among the various orbitals
of an atom

The most stable electron configuration of an atom is

the ground state = the lowest possible energy state

Orbitals are “filled“ in order of increasing energy,

with no more than two electrons per orbital
 Example of electron configuration
The lithium atom (Li) has 3 electrons.
The 1s orbital can accommodate 2 of the
electrons. The third one goes into the next lowest
energy orbital, the 2s.

Positive spin magnetic quantum number

ms= +1/2
Negative spin magnetic quantum number
ms= -1/2
Orbital diagram

We write it like this :

Lithium electron configuration is 1s22s1
 What about Nitrogen ? (N : 7 electrons)
1s 2s
2p

??? No !!!

HUND'S RULE: for degenerate orbitals (orbitals with

same energy), the lowest energy state is attained when
the number of electrons with the same spin is maximized

1s 2s 2p

1 electron
in each p
orbital
N: 1s2 2s2 2p3
 How to build electron
configuration of atoms ?
The diagonal rule to fill
orbitals with electrons

Remember 4s < 3d so
4s is filled before 3d
Same for 5s and 4d,4f etc.

Exceptions to the rule:

Cu (Z = 29) and Cr (Z = 24)

Cu = 4s13d10 instead of 4s23d 9
Cr = 4s13d5 instead of 4s23d 4
The electron configuration of 14Si is:

A)1s2 2s2 2p6 3s2 3p2

B)1s2 2s1 2p6 3s1 3p3

The electron configuration of 5B is:

A) 1s2 2s2 2p1
B) 1s2 2s1 2p2

What will happen if 01 atom inside the Si crystal

is replaced by 01 B atom? (p-type Si in Si solar cell)
64
Si Technology
Transition metals
The chemistry of Mo and that of W are “identical”

In Nature, Mo-containing enzymes can be replaced by W-enzymes

67
Transition metals
Hydrogenase Enzymes: Made of Fe, Ni
 Condensed Writing

Use noble gas electron configuration to shorten other

elements electron configuration

So we can write Na: [Ne]3s1

70
 8. THE PERIODIC TABLE

Mendeleev 1869

based on
« periodicity »
of chemical
properties

Elements having similar electronic configuration have

similar properties.
The cause of periodicity is the repetition of similar
electronic configuration.
 Elements with similar electronic structure of the outer
shell (valence shell) : in the same column

Z=1 H Hydrogen 1s1

Z= 3 Li Lithium 1s2 2s1
Z= 11 Na Sodium 1s2 2s2 2p6 3s1
Z= 19 K Potassium 1s2 2s2 2p6 3s2 3p6 4s1
Z= 37 Rb Rubidium 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s1
Z = 55 Cs Cesium [Xe]6s1

72
 Elements with similar electronic structure of the outer
shell (valence shell) : in the same column

Z= 4 Be Beryllium 1s2 2s2

Z= 12Mg Magnesium 1s2 2s2 2p6 3s2
Z= 20Ca Calcium 1s2 2s2 2p6 3s2 3p6 4s2
Z= 38Sr Strontium 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6
5s2
 Elements with similar electronic structure of the outer
shell (valence shell) : in the same column

Z= 2 He Helium 1s2
Z= 10Ne Neon 1s2 2s2 2p6
Z= 18Ar Argon 1s2 2s2 2p6 3s2 3p6
Z= 36Kr Krypton 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6

Their outer shell is full (this is why He is here). « Noble gases »

Very stable electron configuration
 Lines = progressive filling of subshells and
shells (1s, 2s, 2p, 3s, 3p, 4s, 3d,…
2nd line :
Li Be B C N O F Ne
1s22s1 1s22s2 1s22s22p1 1s22s22p2 1s22s22p3 1s22s22p4 1s22s22p5 1s22s22p6

These belong to These belong to

« block s » = « block p » =

Filling of the Filling of the 3

2s orbital 2p orbitals

2 electrons at 6 electrons at
most, 2 different most, 6 different
elements elements
 STRUCTURE OF THE PERIODIC CLASSIFICATION

d-block
5 orbitals d
He :
10 electrons at most
exception
10 columns for 10 different
elements on each line
s-block p-block
2
electrons 3 orbitals p
at most 6 electrons
at most
2 columns
for 2 6 columns
different for 6
elements different
on each elements on
line each line

f-block 7 orbitals f, 14 electrons at most14

columns for 14 different elements on each line
The electron configuration of 26Fe is:
A) [Ar] 3d6 4s2
B) [Ar] 4s2 3d6
C) [Ar] 3d8

The electron configuration of 26Fe2+ is:

A) [Ar] 3d6
B) [Ar] 4s2 3d4
C) [Ar] 4s1 3d5

The electron configuration of 26Fe3+ is:

A) [Ar] 3d5
B) [Ar] 4s2 3d3 77
The electron configuration of 27Co is:
A) [Ar] 3d7 4s2
B) [Ar] 4s2 3d7
C) [Ar] 3d9

The electron configuration of 27Co2+ is:

A) [Ar] 3d7
B) [Ar] 4s2 3d5
C) [Ar] 4s1 3d6

The electron configuration of 27Co3+ is:

A) [Ar] 3d6
B) [Ar] 4s1 3d5 78
The electron configuration of 27Co3+ is: [Ar] 3d6

d6

In a ligand field: [Co(H2O)6]3+

dx2-y2 dz2
ΔE

dxy dyz dxz

79
 Quick test (20 min.)
Name………………………………………………………….
Student ID…………………………………………………..
Class…………………………………………………………….

Question 1 (10 points).

Write down the electron configuration of following species:
Cu (Z =29), Cu+, Cu2+
Fe (Z = 26), Fe2+, Fe3+ and Fe4+
Question 2 (10 points).
Please suggest a strategy to purify graphene sheets from the following mixture

+ +

Naphthalene Graphene sheets

1-Pyreneacetic acid
 Quick test (20 min.)
Name………………………………………………………….
Student ID…………………………………………………..
Class…………………………………………………………….

Question 1 (10 points).

Please suggest a strategy to separate a mixture of: Cl2, Br2 and I2

Question 2 (10 points).

Please suggest a strategy to purify graphene sheets from the following mixture

+ +

Naphthalene Graphene sheets

1-Pyreneacetic acid
 1. The wave nature of light

The light that we can see with our eyes,

visible light, is an example of
electromagnetic radiation.
Other types of electromagnetic radiation:
- the radio waves,
- the infrared radiation from heated
matter,
-X-rays 82
 Electromagnetic radiation
All types of electromagnetic radiation
move through a vacuum at a speed of
3.00 108 m/s, the speed of light

Electromagnetic radiations have

wavelike characteristics similar to
waves on water

But what oscillate are electric and

magnetic fields
83
FOR ANY TYPE OF WAVE

Wavelength =distance
between 2 maxima
Amplitude = maximum
intensity
Period = time between 2
maxima (seconds)

Frequency = number of
periods per second
= 1/period

84
 λ = distance traveled during one period
So λ =speed x period = speed/frequency

Wavelength is inversely proportional to frequency

Longer wavelength =>lower frequency

Shorter wavelength =>higher frequency

For electromagnetic radiation speed =c

So : λ = c /ν

c = speed of light, 3.00 x 108 m/s

λ (lambda) = wavelength, (m)
ν (nu) is the frequency (1/s = Hertz)
 Electromagnetic spectrum

Different forms of electromagnetic radiation have

different properties because of different wavelengths
Electromagnetic wavelengths and
relevant units
 Unit of frequency: cycles per second or s-1, or
Hertz (Hz)

Electromagnetic frequencies range from 104 -109 (radio

waves) to 1020 Hz (gamma rays), visible light is around
1014 Hz

So we use kHz (kilo, 103) , MHz (mega, 106),

GHz (giga, 109), THz (tera, 1012)

Mobile phones frequencies are between 800 -

2400 MHz so wavelengths are between 12-37 cm.
 2. Quantized energy and photons
1900 : Physicists could not explain characteristics
of radiation emitted by hot objects

Max Planck proposed a quantum theory that

permitted to solve the problem

Radiant energy can only be emitted or

absorbed in discrete quantities called
quanta
Revolutionary way of thinking (energy is
quantified) ! 89
 Energy of a single quantum of
radiation
E  h
where

E = energy (J)
h = Planck’s constant 6.63 x 1034 J . s
ν = frequency of the radiation (Hz) 90
 Photons

Photoelectric effect : Electrons are ejected

from a metal’s surface when exposed to light of
certain frequencies

But if the frequency is not enough nothing

happens. Why ???

91
 Einstein 1905: a revolutionary theory

1) Electrons need certain amount of energy – called W

work function - to escape from the metal

2) LIGHT IS MADE OF PARTICLES

(PHOTONS) each of them with an energy E = hν

3) the metal will ABSORB PHOTONS AND THEIR

ENERGY if hν>W thus it is necessary that ν>W/h

4) then electrons are emitted with the excess energy as

kinetic energy = hν-W
 IS LIGHT (and any electromagnetic
radiation) A WAVE OR PARTICLES ?

BOTH !

Light possesses both wavelike and particle-

like characteristics and, depending on the
situation, will behave more like a wave or
more like particles.

93
 Line Spectra

Most common radiation sources, including

lightbulbs and stars, produce radiation
containing many different wavelengths

A spectrum is produced when radiation

from such sources is separated into its
different wavelength components.
94
Decomposition of light into wavelength components by
a prism

SPECTRUM

95
 General Chemistry I

Chemistry: The central science

Phong D. Tran
Department of Fundamental and Applied Sciences
University of Science and Technology of Hanoi
Email: [email protected]

Lectures 4-6: Electronic structure of atoms

96