BASIC CHEMISTRY

UDBB1114
I. ATOMIC STRUCTURE

II. CHEMICAL BONDS &

BONDING THEORIES

III. THERMOCHEMISTRY
ENERGY & PHYSICAL
PROPERTIES
The Wave Nature of Electrons
Attempting to explain why an atom has fixed energy levels,
Louis de Broglie, a French physicist proposed:

 if energy is a particle-like, perhaps matter is wavelike.

He reasoned that if electrons have wavelike motion in orbits of fixed

radii, they would have only certain allowable frequencies and
energies.

mass-energy equivalence: E = mc2

energy of a photon: E = h = hc/
 mc2 = hc/

h
de Broglie wavelength equation: λ=
𝑚𝑣

m- mass, 𝒗 – moving at speed (velocity)

 The de Broglie Wavelengths of Several Objects

Substance Mass (g) Speed (m/s)  (m)

slow electron 9x10-28 1.0 7x10-4

fast electron 9x10-28 5.9x106 1x10-10

alpha particle 6.6x10-24 1.5x107 7x10-15

one-gram mass 1.0 0.01 7x10-29

baseball 142 25.0 2x10-34

Earth 6.0x1027 3.0x104 4x10-63

𝒉
𝝀=
𝒎𝒗
The Wave Nature of Electrons
Example 1

Find the de Broglie wavelength of an electron with a speed of 1.00 x

106 m/s (electron mass = 9.11 x 10-31 kg); h = 6.626 x 10-34 kg.m2/s)

Example 2

What is the speed of an electron that has a de Broglie wavelength of

100. nm?
Summary of the major observations and theories leading from
classical theory to quantum theory.
Since energy is wavelike perhaps matter is wavelike

Observation Theory

Davisson/Germer: deBroglie: All matter travels in waves; energy of

electron diffraction atom is quantized due to wave motion of
by metal crystal electrons

Since matter has mass perhaps energy has mass

Observation Theory

Compton: photon Einstein/deBroglie: Mass and energy are

wavelength increases equivalent; particles have
(momentum decreases) wavelength and photons have
after colliding with momentum. 𝒉
electron 𝝀=
QUANTUM THEORY 𝒎𝒗
Energy same as Matter
particulate, massive, wavelike
The Heisenberg Uncertainty Principle
Stated that it is not possible to know both the position and
momentum of a moving particle at the same time:

h
Dx * mDν ≥
4p

• where Δx is the uncertainty in the position, Δν is the uncertainty

in the velocity.

• the more accurately we know the speed, the less accurately we

know the position, vice versa.
Applying the Uncertainty Principle

Example: An electron moving near an atomic nucleus has a speed 6x106 ± 1%.
What is the uncertainty in its position (Dx)?
The Quantum-Mechanical Model of the Atom
• Quantum mechanics take into account the dual nature (wave and
particle) of matter.

• In quantum mechanics model, the behavior of electron in atoms

is described by an equation known as Schrӧdinger equation:
 = 

• Where  is mathematical operation known as Hamiltonian

operator,  is the actual energy of the atom.
> Each solution has a  which is characterized by a specific E value.

• The symbol  is the wave function, a mathematical description of

the wavelike nature of the electron in three dimensions (x, y, z).
 The Schrödinger Equation

HY = EY

potential energy at x,y,z

wave function mass of electron

d2Y d2Y d2Y 8p2mQ

2
+ 2
+ 2
+ 2
(E-V(x,y,z)Y(x,y,z) = 0
dx dy dz h

how  changes in space total quantized energy of

the atomic system
The Quantum-Mechanical Model of the Atom
• The solution of the Schrӧdinger equation are called wave
functions.

• Even though ѱ has no physical meaning, ѱ2 – the square of the

wave function gives the probability density, a measure of the
probability of finding an electron of a particular energy in a
particular region of the atom.

[ѱ(x1, y1, z1)]2 = N1 N1/N2 is ratio of the probability of

[ѱ(x2, y2, z2)]2 N2 finding electrons at position 1 and 2.

• Electron density is another way of expressing probability.

• A region of high electron density is one where there is high

probability of finding an electron.

• For a given energy level, we depict this probability with an

electron probability density diagram.
Applications of the Schrӧdinger equation

 This equation has been used to calculate to energy and wave

function of a particle (e.g. electron) in one-dimensional box.

 This equation can be used to calculate energy and wave function

of a particle in three-dimensional box.

 This equation has been used to derive an expression for the

energy of an electron in H-atom.

 This equation introduces the concept of atomic orbital.

Learning Objectives:
Quantum mechanics: the theory that explains our current picture of
atomic structure

Wave properties of energy; quantized or particulate, model of light

Atomic spectrum – light emitted by excited hydrogen (H) atoms,

suggests an atom with distinct energy levels.

 Wave-particle duality – reveals two faces of matter and energy

which leads to the current model of the H atom and quantum
numbers that identify the regions of space an electron occupies in
an atom.

 Quantum-mechanical model of the atom – features of atomic

orbitals
Atomic Orbital

 An atomic orbital is defined as a three-dimensional region or

space (volume) around the nucleus of an atom whereby the
probability of finding an electron with a certain energy is
maximum

or

 An atomic orbital represents the space around the nucleus in an

atom where the electron spends most of its time.
Electron density diagram

Electron probability density in

the ground-state H atom.
 Quantum Numbers and Atomic Orbitals

An atomic orbital is specified by three quantum numbers.

n the principal quantum number - a positive integer

l the angular momentum quantum number - an integer from 0 to n-1

ml the magnetic moment quantum number - an integer from -l to +l

Quantum Numbers and Atomic Orbitals
• An atomic orbital is specified by three quantum numbers that are
part of the solution of the Schrӧdinger equation which indicate the
size, shape, and orientation in space of the orbital.

1. Principle quantum number (n)

- positive integer (1,2,3,…)
- indicates relative size of the orbital, and
- relative distance from the nucleus of the peak in the radial
probability distribution plot
- energy level: the higher the n value, the higher the energy level
- n = 1, H atom is in its ground state, lowest energy
- atom has more energy when occupies an orbital with n = 2.
Quantum Numbers and Atomic Orbitals

2. Angular momentum quantum number (l)

- integer from 0 to n-1
- related to shape of the orbital
- principle quantum number sets a limit on the angular momentum
number; n limits l
- n = 1, l can have only one value, 0
- n = 2, l can have two values, 0 to 1
- n = 3, l can have three values, 0, 1, or 2
Quantum Numbers and Atomic Orbitals

3. Magnetic quantum number (ml)

- integer from -l through 0 to +l
- prescribes the three-dimensional orientation of the orbital in the
space round the nucleus, relative to other orbitals in the atom
- The angular momentum quantum number sets as a limit on the
magnetic quantum number; l limits ml
- l = 0 can have only ml = 0
- l = 1 can have ml = -1, 0, +1
- l = 2 can have only ml = -2, -1, 0, +1, +2
 The Hierarchy of Quantum Numbers for Atomic Orbitals

Name, Symbol
(Property) Allowed Values Quantum Numbers

Principal, n Positive integer

1 2 3
(size, energy) (1, 2, 3, ...)

Angular
momentum, l 0 to n-1 0 0 1 0 1 2
(shape)

0 0 0
Magnetic, ml
-l,…,0,…,+l -1 0 +1 -1 0 +1
(orientation)

-2 -1 0 +1 +2
Determining Quantum Numbers for an Energy Level

Example: What values of the angular momentum (l) and magnetic (ml)
quantum numbers are allowed for a principal quantum number (n) of
3? How many orbitals are allowed for n = 3?
Determining Quantum Numbers for an Energy Level

Question: What are the angular momentum (l) and magnetic (ml) values for
for n = 4?
Quantum Numbers and Energy Levels
The energy states and orbitals of the atoms are defined with specific
terms and are associated with one or more quantum numbers:

1. Level
- shells, are given by the n value

2. Sublevel (subshell, l )

Value of l Letter Designation

0 s
1 p
2 d
3 f
Quantum Numbers and Energy Levels

3. Orbital
- each combination of n, l and ml specifies the size (energy),
shape, and spatial orientation of one of the atom’s orbital
- orbital in the 2s sublevel: n = 2 and l = 0, and given that l value, it
can have only ml = 0; thus 2s sublevel has only one orbital
- orbital in the 3p sublevel: n = 3 and l = 1, and given that l value, it
can have ml = -1, 0, and +1; thus the 3p sublevel has three
orbitals
Determining Sublevel Names and Orbital Quantum Numbers

Example: Give the name, magnetic quantum numbers, and number of orbitals
for each sublevel with the following quantum numbers:
(a) n = 3, l = 2 (b) n = 2, l = 0 (c) n = 5, l = 1 (d) n = 4, l = 3
Determining Sublevel Names and Orbital Quantum Numbers

Question: What are the n, l, and possible ml values for:

(a) 2p (b) 5f sublevels?

Review: Sublevel Names and Orbital Quantum Numbers
For n = 4 principal energy level,
a) State the number of subshells in this level
b) Identify each of the subshell by giving its l value and its letter designation.
c) Use the 2l + 1 rule to calculate how many orbitals each subshell has and identify
the ml value for each orbital.
d) What is the total number of orbital in the n = 4 level?
Shapes of Atomic Orbitals
Each sublevel of the H atom consists of a set of orbitals with characteristic
shapes.
The shape of an atomic orbital is determined primarily by l, the
angular momentum quantum number.

1. s orbital
- l = 0, has a spherical shape with the nucleus at its center
- Sphere has only one orientation, thus s orbital has only one ml
- 1s holds the electron in the H atom’s ground state, electron probability
density is highest at the nucleus
- 2s has two regions of high electron density, and between the two
regions is a spherical node where the probability of finding electron
drops to zero
- 3s has three regions of high electron density and two nodes
The s orbitals
Shapes of Atomic Orbitals

2. p orbital
- l = 1, has two regions (lobes) of high electron density, one on
either side of the nucleus
- Nucleus lies at the nodal plane of the dumbbell-shaped orbital
- The maximum value of l is n – 1, thus only levels with n ≥ 2 have
a p orbital.
- Similar to s orbital, 3p orbital is larger than a 2p orbital
- p orbitals have possible spatial orientation, ml values of -1, 0, +1
(3 mutually perpendicular orientation)
- x, y, z axes; px orbital lies along the x-axis, and so on
The 2p orbitals
Shapes of Atomic Orbitals

3. d orbital
- l = 2, has a five possible ml values; -2, -1, 0, +1, +2
- Has five possible orientations
- Four of the five d orbitals have 4 lobes (clover leaf shape) with 2
mutually perpendicular nodal planes between them and the
nucleus is at the conjunction of the lobes
- Three lie in the dxy, dxz, and dyz orbitals, one dx2-y2 orbital
- The fifth d orbital dz2 has two major lobes only along the z axis
and a donut-shape region surrounding the center
The 3d orbitals

Composite of all five

3p orbitals
Orbitals with higher l values
- Orbitals with l = 3 are f orbitals and must have a principal
quantum number of at least n = 4.
- There are seven f orbitals, each with a complex, multilobed
shape.

One of the seven possible 4f orbitals.

 Summary
 Cannot know precisely where the electron is at any moment
 The electron’s wave function (ψ) is a mathematical description of the
electron’s wavelike motion in an atom. The wave function, ψ, itself has
no direct physical meaning. However, the quantity ψ2 expresses the
probability that the electron is at a particular point within the atom.
 The probability is depicted with an electron probability density diagram.
 The value of ψ2 for a given volume is represented by a certain density
of dots: the greater the density of dots, the higher the probability of
finding the electron within that volume. ψ2 is also called the probability
density.
 Three features of the atomic orbital are described by quantum
numbers: size(n), shape(l) and orientation (ml).