Faculty of Chemical Engineering

Department of Inorganic Technology

General Chemistry

Chapter 1
Atomic Structure

PhD. Đặng Văn Hân

Office: 112B2 or 804H3 Building
Email: [email protected]
Outline
1. Theory of atomic structure:
1.1. Classic
1.2. Bohr’s model
1.3. Quantum mechanical model
2. Schrodinger wave equation
3. Quantum numbers for electron states in atoms
4. Atomic orbitals & shapes
5. Electron state in multi-electron atoms:
5.1. Shielding and Penetration effect
5.2. Electron distribution law
5.3. Electron configuration
2
Dalton’s Atomic Theory
 John Dalton: Dalto
Tho Ruth
Bohr
Schro
mpso erfor dinge
n
n d r
1983 1913
1904 1911 1926

In 1803, Dalton proposed the atomic theory based on two laws

of conservation of mass and constant composition as follows:
1. All elements are composed of tiny indivisible particles called atoms.
They cannot be created or destroyed during chemical reactions.
2. In chemical reactions, atoms are combined, separated, or rearranged
– but never changed into atoms of another element.
3. Compounds are formed when different atoms combine in definite
proportions; Ex: H2O
3
Discovery of Electron
J.J, Thompson’s Exp. Dalto
Tho Ruth
Bohr
Schro
mpso erfor dinge
n
n d r
1983 1913
1904 1911 1926

Experiments: When the power supply connects 2

electrodes in the vacuum tube:

1. The cathode ray flows from the cathode to the

anode and hits the fluorescent screen in a straight
line.
R. Millikan’s Exp.
2. The cathode rays will be deflected in the same
Mass of the direction as negatively charged particles in an
electron is
9.11 x 10-28 g electric or magnetic field.
The oil drop apparatus 4
Thompson’s Atomic Theory
 Thompson’s Atomic Theory Dalto
n
Tho
mpso
Ruth
erfor
Bohr
Schro
dinge
n d r
1983 1913
1904 1911 1926

Thomson believed that the electrons were like

plums embedded in a positively charged “pudding,”

 “Plum pudding” model:

1. All atoms are electrically neutral. Total positive

charge (+) = Total negative charge (-).

2. The charge (+) is evenly distributed throughout

the volume of the atom, and electrons move
around those (+) charges.

5
Alpha (α), beta (β) Particles, and gamma () ray
Rutherford and Vilard Exp.: When radiation interacts with an electrical
or magnetic field, three types are
identified:
- Alpha (α) Particle: two positive
charged electrons with the same mass
and energy as the He nucleus.
- Beta (β) Particle: negative charges
which is similar to an electron.
- Gamma (γ) Ray: NOT affected by
electromagnetic field. It’s form in high
energy radiation.
6
Discovery of Proton & Neutron
 Based on their epx., E. Goldstein and E.

Rutherford claimed that the nucleus has a small

volume, with positively charged particles called
“protons” located at the center of the atom. Its
mass is 1.67x10-24 g (relative mass = 1)

1932 – J. Chadwick confirmed the

existence of the “neutron” – a particle

with no charge, but a mass nearly
equal to a proton.
7
Subatomic Particles
Particles Charge Mass (g) Location
Electron -1 9.11 x 10-28 Electron
(e-) (-1.6 x 10-19 C) 5.5e-4 amu cloud
Proton +1 1.67 x 10-24
Nucleus
(p+) (-1.6 x 10-19 C) 1amu
Neutron 1.67 x 10-24
0 Nucleus
(no) 1amu

 Instead of grams, the unit we use is the Atomic Mass Unit (amu),

1 amu = 1.67 × 10-24 grams.

8
Rutherford’s Atomic Model
Tho Ruth Schro
Dalto Bohr
mpso erfor dinge
n
Rutherford: 1803
n
1904
d
1911
1913
r
1926

Based on his experimental evidence ⇢ Atomic

model:
 The atom is mostly empty space.
 All the positive charges, and almost all the mass is
concentrated in a small area in the center. He called this a
“nuclear”.
 The nucleus is composed of protons and neutrons bound
together by nuclear forces.
 The electrons distributed around the nucleus, and occupy
most of the volume.
9
Atomic Number
ELECTRONS
Please remember that specific
PROTONS
atoms are composed of identical:
NEUTRONS

 The “atomic number (Z)” of an element is the number of protons in the nucleus

 # protons = # electrons

The symbol of the element: Mass

𝐴
𝑋
number
X: element

Atomic
𝑍
Atomic number (Z)= ne = np number 1
Atomic Number

Example:
MCl = 35 amu
A = 35 ⇢ nn = 35-17=18
Element: Chlorine

35
17 Cl
Z = ne = np = 17 Cell location in periodic table: 17

11
Isotopes
Frederick Soddy (1877-1956) proposed the idea of isotopes in 1912.
Isotopes are atoms of the same element having different masses,
due to varying numbers of neutrons. (different neutron numbers)

Naming Isotopes: Element-Mass number

12 13 14
6 𝐶 6 𝐶 6 𝐶
Cacbon-12 Cacbon-13 Cacbon-14

Stable Radioisotope Stable Radioisotope

Isotopes Isotopes 12
The Electromagnetic Wave (EW)
EW is the oscillations of the electric and magnetic fields are
perpendicular to each other and propagate in a vacuum with the
velocity = speed of light (c ~ 3x108 m.s-1)
 Specifications:
 Wavelength (λ): distance between two adjacent peaks;
 Frequency (ν): period of oscillation per unit of time:

ν = c/λ; (1 s-1 = 1 Hz);

 Energy (E): E = hν = hc/λ
Natural light has Where: h is Planck’s constant (6.626  10-34 J.s)
electromagnetic wave
and 1 eV = 1.6 x 10-19 J
13
The Electromagnetic Wave (EW)

A continuous spectrum of all wavelengths

Note that wavelength increases as frequency decreases
14
The Electromagnetic Spectrum
 Continuous Spectrum

Continuous spectrum is the rainbow of colors, containing all wavelengths of

light, no dark spots in spectrum
15
The Electromagnetic Spectrum
 Line Spectrum

Line spectra is a phenomenon which occurs

when excited atoms emit light of certain
wavelengths which correspond to different colors.
16
Line Spectrum

Atomic emission: an emission spectrum, is a line spectrum.

This technique is applied to qualify chemical elements

17
Bohr’s Model Dalto
n
Tho
mpso
Ruth
erfor
Bohr
Schro
dinge
n d r
1803 1913
1904 1911 1926

In 1913, Bohr proposed a new atomic theory based on the merger

of Rutherford's atomic model and Planck's quantity theory of light,
which included three main topics:

1. Electrons revolve around the nucleus with certain concentric

orbits are called stationary orbits;

2. When rotating in orbits, electrons are quantified and do not

emit electricity;
Bohr’s Model
3. Energy is absorbed and emitted only when the electron
moves from one stationary orbit to another orbit. E= 18
Limitations of Bohr’s Model
1. Cannot explain why electrons can only locate positions when moving in
orbits

2. Can only explain the line spectrum of hydrogen or one-electron ions

(He+, Li2+) adequately.

3. Cannot determine clearly the line-spectrum intensity of specific

elements.

4. It’s not suitable to calculate electron energy for multi-electron atoms.

19
SModern Atomic Theory

1. The movement of microscopic particle:

 Wave-particle duality properties;
 The uncertainty principle;
 Schrodinger wave equation.

2. Four quantum numbers

3. Electron State in Single-electron Atoms

Based on Quantum
4. Electron State in Multi-electron Atoms
Mechanics
Wave-Particle Duality Properties

Using Einstein’s and Planck’s equations, de Broglie showed that all

matters having mass (m), velocity (v) will propagate with wavelength
(λ) by the formula: h
 Particle Property
Louis de Broglie
(1892 – 1987)
m
Wave Property
Example:
- Electron has me = 9.1 x 10-28 g, v 6 x 105 m/s → λ 100 nm → Wave properties

- A ball has m = 200 g, v = 30 m/s → λ ( 10-39 nm) → No wave properties.

Microscopic objects such as electrons exhibit simultaneously

wave and particle properties. 21
The Uncertainty Principle
It is impossible to determine accurately both the momentum and
the position of an electron (or any other very small particle)
simultaneously.
h
Δ 𝑥 . Δ 𝑚𝑣 𝑥 ≥
Werner Heisenberg 4𝜋
(1901 – 1976)

Where: x is the uncertain position and mvx is the uncertainty in momentum

Example: Electron has me = 9.1 x 10-28 g, Δx 10-10 m → Δvx 6.6 x 106 m/s

Conclusion: Cannot determine the exact position of an electron, only

know the probability of its presence at a given point in space
22
Quantum Mechanics
Electrons in atom are clouds surrounding their nucleus and has
wave-particle properties.

So, why can we use Schrodinger Equation to describe atomic

structure?

1. Schrödinger Eq. contains both wave and particle terms.

2. Solving his equation leads to wave functions:

 The wave function gives the shape of the electronic orbital.

 The square of the wave function (2) gives the probability of finding the

electron. That is, gives the electron density for the atom.
23
The Schrodinger Wave Equation
Where:
 : wave function corresponding
      8 m
2 2 2 2
 2  2  2 E  V   0 to 3-dimensional wave amplitude.
x 2
y z h  V: potential energy of particle.
 x, y, z : coordinates of particle.

Describe the motion of microparticles in a stationary state

For Hydro with V = -e2/r, then:

      8 m
2 2

2
e 22

 2  2   E    0
x 2
y z 2
h  r 
2: always positive to show the probability presence of e.
2 unit: probability density of e in a volume unit dV. 24
The Schrodinger Wave Equation
Solve this Eq. for Hydrogen

 n ,,m (r ,  ,  )  Rn , (r ).Y,m ( ,  )
 

AO Size AO Shapes
The motion of electron in space of the Hydrogen atom
determined 3 quantum numbers:
n = 1, 2, ...;
ℓ = 0,1,..(n-1);
mℓ = - ℓ,…,0,.,+ ℓ 25
The Atomic Orbital (AO)
1. Electron State:
Electrons can be present in anywhere with varying probability forming a
region of space surrounding the nucleus known as an electron cloud.

2. Atomic Orbital (AO):

The region of space around the nucleus in which the
probability of an electron’s presence is lager 90%,
characterized by 3 quantum numbers: n, l, ml

AO describes size, shape and orientation in space

Probability of finding an
through three quantum numbers (n, l, ms). electron in a hydrogen atom
in its ground state 26
The Atomic Orbital (AO)
Review:
Choose the correct statement(s). An atomic orbital (AO) is:
1) The region in which there is maximum probability (> 90%) of finding an electron.
2) The surface with equal electron density cloud.
3) The orbital motion of electrons in an atom.
4) The energy state of an electron in an atom.
5) An AO is a wave function that describes the state of an electron in an atom defined by 4
quantum numbers: n, ℓ, mℓ, ms.
A. 1 and 5 B. only 1 C. 1, 2 and 3 D. 1, 2, 3, 4 and 5.
27
Three Quantum Numbers

Schrödinger’s equation requires 3 quantum numbers:

1. Principal Quantum Number, n
(lượng tử chính)

2. Azimuthal (Angular) Quantum Number, l

(lượng tử phụ)

3. Magnetic Quantum Number, ml

(lượng tử từ)

28
1. Principal Quantum Number, n

 The same as Bohr’s n.

 n, describes the main energy level, or shell, electron occupies.

 As n becomes larger, the atom & energy becomes larger

 n is positive integer = 1, 2, 3…

n 1 2 3 4 5 6 7
Electron
K L M N O P Q
Shell

29
2. Azimuthal Quantum Number, l
 Depends on the value of n (l < n and l = 0, 1, 2, …, n-1)

 l, describes the name & shape of the orbitals.

 We usually give a letter notation to each value of l:

n 1 2 3 4 5 6
l 0 1 2 3 4 5
Subshell s p d f g h

Maximum number of electrons in subshell = 2(2l+1)

Note: Electrons with the same n and l values ​will form a quantum subshell
Ex: 1s, 2s, 2p, 3s, 3p, 3d, 4s, 4p, 4d, 4f, …. 30
3. Magnetic Quantum Number, ml
 Depends on the value of l

 Has integral values from –l to +l (l = -l …0…+l)

 ml , describes the 3D orientation of each orbital in space.

Example:

ℓ = 0  ml = 0  1 s-orbital 

ℓ = 1  ml = -1,0,+1  3 p orbital 
-1 0 +1

ℓ = 2  ml = -2, -1, 0, +1, +2  5 orbital d 

+1 +2 31
3. Magnetic Quantum Number, ml
 In the nth shell
 Number of AO = n2  Max e- number = 2n2

 In the lth subshell

 Number of AO = (2l+1)  Max e- number = 2(2l+1)

Example. Determine the maximum number of electrons and the principal quantum
number n of L and N -shells:

a) L-shell:18 e, n = 3; N-shell: 32 e, n = 4 b) L-shell: 8 e, n = 2; N-shell: 32 e, n = 4

c) L-shell: 8 e, n = 2; N-shell: 18 e, n = 3. d) L-shell: 18 e, n = 3; N-shell: 32 e, n = 5

4. Spin Quantum Number, ms
Apart from 3 quantum numbers (n, l, ms), Using ms to describe the rotation
around electron axis by itself.
↑ ↓
 Refers to the spin of an electron and the orientation

of the magnetic field produced by this spin.

 Not affect the AO motion;

 For every set of n, l and ml values, ms = + ½ or - ½.

 Convention:
ms = +1/2: Clockwise rotation; ms = -1/2: Counter clockwise rotation of
electron 33
Short Summary
The 4 quantum numbers (n, l, ml and ms) completely determine the state of an
electron in an atom including size, energy, shape and motion.
Note:
 n = positive integer 1, 2, 3, …
 l < n and l = 0, 1, 2, …, n-1
 ml < n and ml = -l….0….+l
 ms = +1/2 or -1/2
 Number of Orbitals Max. Electrons
Convention: e- no. in this
 In Shell = n2 2n2
orbital

Shell
3p 6
Subshell
 In Subshell = 2l+1 2(2l+1)
34
Some Examples
Ex. 1: Which sets of the three quantum numbers are acceptable?
1) n = 4, ℓ = 3, mℓ = -3 2) n = 4, ℓ = 2, mℓ = +3
3) n = 4, ℓ = 1, mℓ = 0 4) n = 4, ℓ = 0, mℓ = 0
a) 1, 3, 4 b) 1, 4 c) 2, 3, 4 d) 3, 4

Ex. 2: Names of the orbitals correspond to n = 5, ℓ = 2; n = 4, ℓ = 3; n = 3, ℓ = 0:

a) 5d, 4f, 3s b) 5p, 4d, 3s c) 5s, 4d, 3p d) 5d, 4p, 3s

Ex. 3: Orbital 3px is defined by the following quantum numbers:

a) only n, ℓ, and mℓ b) only n and mℓ
c) only ℓ and mℓ d) n, ℓ, mℓ, ms 35
Atomic Orbital Shapes

ℓ = 0  s-orbital: sphere

s: sharp
ℓ = 1  p-orbital: dumbbell
p: principal
d: diffuse
ℓ = 2  d-orbital: clover
f: fundamental

ℓ = 3  f-orbital: complex 36
The s-Orbitals

 l = 0 → ml = 0 → No. AO = (2l+1) = 1
 All s-orbitals are spherical.

 As n increases, the s-orbitals get larger.

 As n increases, the number of nodes increase.

 A node is a region in space where the

probability of finding an electron is zero.

 At a node, 2 = 0

37
The d-Orbitals
 l = 1 → ml = 0, ±1; → No. AO = (2l+1) = 3
 There are three p-orbitals px , py, and pz.

 The orbitals are dumbbell shaped.

 The three p-orbitals lie along the x-, y- and z- axes of a Cartesian system.

 As n increases, the p-orbitals get larger.

 All p-orbitals have a node at the nucleus.

Electron
distribution of a
2p orbital.
38
The d-Orbitals

 l = 2 → ml = 0, ±1; ±2 → No. AO = (2l+1) = 5

 There are five d-orbitals.

39
The d-Orbitals
 Three of the d-orbitals lie in a plane bisecting the x-, y- and z-axes.

 Two of the d-orbitals lie in a plane aligned along the x-, y- and z-axes.

40
The f-Orbitals
 l = 3 → ml = 0, ±1; ±2; ±3 → No. AO = (2l+1) = 7

41
Electron State in Multi-electron Atoms

For Multi-electron Atoms:

Appear the attraction & repulsion between

electrons and nucleus.
→ Formation of shielding and penetration
effects in the atom;
→ The energy state of electrons depends on
both quantum number n & l.

 Similar with H, the e- state is also defined by 4 quantum number: n, l, m l, ms.

 AO shapes are similar with that of Hydrogen

42
Shielding (S) and Penetration (P) Effect

The shielding effect (S) describes the

repulsive interaction of the e- layers creates a
shielding screen → the decrease in attraction Z

between an electron and the nucleus.

The penetration effect (P): In contrast to (S) - the penetration ability

of electron from the outer layer to the nucleus.

Note: As (n+l) ↑, the shielding effect ↑ and penetration effect ↓

Electron-nuclear attraction ↓ En,l ↑ Aufbau Principle En,l (n + ℓ) 43

Aufbau Diagram

Orbitals and Their Energies

1. The largest energy gap is between
the 1s and 2s orbital

2. The gap between np and (n+1)s is

fairly large.

3. The gap between (n-1)d and ns is

quite small.
4. The gap between (n-2)f and ns is
even smaller.

44
Electron Distribution Law

Electron configurations tells us in which orbitals the electrons

for an element are located.
 4 quantum number: n, l, ml, ms
Electron
Arrangement
 Three rules:
 Aufbau principle (German aufbauen, "to build up")

 Pauli’s Exclusions Principle

 Hund’s rule.

45
Aufbau Principle

Stabilization Principle: the most stable state of electrons in an

atom has the lowest energy.

Electrons fill orbitals starting with lowest n and moving upwards

Two general rules help us to predict electron configurations:

 Electrons are assigned to orbitals in order of increasing value of (n+l).

For subshells with the same value of (n+l), electrons are assigned

first to the subshell with lower n.

46
Aufbau Principle (Kleshkovski Principle)

Example:

 Oxygen (O) has Z = 8

⇢ 1s2 2s2 2p4

 Titanium (Ti) has Z = 22

⇢ 1s2 2s2 2p6 3s2 3p6 4s23d2

Subshell: 1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4f 5d 6p 7s 5f 6d
(n + ℓ) 1 2 3 4 5 6 7 8 E
47
Pauli Exclusion Principle
Pauli’s Exclusions Principle: no two electrons can have the same
set of 4 quantum numbers.
 Therefore, two electrons in the same orbital must have opposite spins


 Paired Electron  Un-paired Electron

Example: n=3 n=3

ℓ=0  ℓ=0
mℓ = 0 mℓ = 0
3s2
ms = +1/2 ms = -1/2
48
Hund’s Rule
Hund’s Rule: electrons in the same subshell must be
distributed so that the absolute value of the total spin or unpair
electrons is maximized
Electrons fill each orbital singly before any orbital gets a second electron
[Trong phân lớp, điền spin dương (↑) đủ các obitals sau đó điền spin âm (↓)]

2p2
Example:
1s2 2s2 ↑↓
12
6 C→ Z = 6 → 1s 2s 2p2 2 2
→ ↑↓ ↑↓ -1 0 +1

↑ ↑
-1 0 +1

Nitrogen (N) has Z = 7 ➡

1s 2s 2p 49
Hund’s Rule
Example: The Orbital diagram for the ground state of the Oxygen
atom (Z=8 )

50
Determination of Electron Configuration
Step 1: Write Electron Distribution based on Energy (Aufbau Principle);

Step 2: ⇢ Write Electron Configuration with ascending n↑;

Step 3: Fill electrons in AOs based on the rules of electron arrangement

Example:
2s2 2p3
1s 2
14
1. 7 𝑁 → Z = 7 → En: 1s22s22p3 → ↑↓ ↑↓ ↑
-1
↑
0
↑
+1

48
2.
22 𝑇𝑖 → Z = 22 → E : 1s 2s 2p 3s 3p 4s 3d
n
2 2 6 2 6 2 2

⇢ E-: 1s22s22p63s23p63d24s2
4s2 3d2
↑↓ ↑ ↑
51
Unstable-Electron Configuration

Semi-saturated Configuration: ns2(n-1)d4 → ns1(n-1)d5

Full-saturated Configuration: ns2(n-1)d9 → ns1(n-1)d10

52
1. 24 𝐶𝑟 → Z = 24 → E : 1s22s22p63s23p64s23d4 (unstable)
n

→ En: 1s22s22p63s23p64s13d5 (stable)

E-: 1s22s22p63s23p63d54s1
64
2. 29 𝐶𝑢 → Z = 29 → En: 1s22s22p63s23p64s23d9 (unstable)
→ En: 1s22s22p63s23p64s13d10 (stable)
E-: 1s22s22p63s23p63d104s1
52
Electron Configuration of Ions
Last shell: 3d
Outermost shell: shell with maximum n
(lớp ngoài cùng) 3d24s2
Final shell: shell with the highest energy Outermost
shell: 4s
(lớp cuối cùng)

 Cation Mn+: M Mn+  Anion Xm-: X Xm-

Example:
1. Fe (Z = 26) → En: 1s22s22p63s23p64s23d6 2. Cl (Z = 17) → En: 1s22s22p63s23p5

Fe2+ (24) → En: 1s22s22p63s23p63d6 Cl1- (18)→ En: 1s22s22p63s23p6

Fe3+ (23) → En: 1s22s22p63s23p63d5
53
Valence Electron (VE)
Definition: are electrons in the outer shell associated with an atom

 In Group A (nsanpb): VE = ∑e- in nmax shell = a + b

Example: 15P: 1s 2
2s 2
2p6
3s 2
3p3
→ 5 VEs (3s 2
3p3
)

 In transition metals nse(n-1)df:

VE = ∑e- in (ns) subshell + ∑e- in (n-1)d subshell = e + f

Example: 25Mn: 1s 2
2s 2
2p6
3s 2
3p6
4s 2
3d5

→ 7 VEs (4s23d5)
54
Practices

Problem 1: Which of the following atom or ion does the outermost

electron configuration 3s23p6 represent:

a) X (Z = 17) b) X (Z = 19) c) X- (Z = 17) d) X+ (Z = 20)

Problem 2: The electron configuration of Cu2+ ion (Z = 29) in the ground

state is:
a) 1s22s22p63s23p63d94s0 b) 1s22s22p63s23p63d74s2
c) 1s22s22p63s23p63d84s1 d) 1s22s22p63s23p63d104s0

55
Practices

Problem 3: The valence electron configuration of Fe 3+ ion (Z= 26) in

the ground state is:
a) 3d44s1 b) 3d34s2 c) 3d6 d) 3d5

Problem 4: The valence electron configuration of Co 3+ ion (Z = 27) in

the ground state is:
a) 3d6 (no single electrons) b) 3d 44s2 (exist single electrons)
c) 3d6 (exist single electrons) d) 3d44s2 (no single electron)

56
Practices

Problem 5: Determine 4 quantum number from electron

configuration of atoms and ions:
electrons 2p5 ml = 0
1. 2p 5 Last (n,l,ml,ms) = (2,1,0,-1/2)
↑↓ ↑↓ ↑ electron ms = -1/2
Shell (n) Orbital (l)
-1 0 +1
3d4
2. 3d4 → ↑ ↑ ↑ ↑ (n,l,ml,ms) = (3,2,+1,+1/2)
-2 -1 0 +1 +2

L=2 OB=2l+1=5
3d 7

3. 3d7 → ↑↓ ↑↓ ↑ ↑ ↑ (n,l,ml,ms) = (3,2,-1,-1/2)

-2 -1 0 +1 +2 57