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General Chemistry

Dr. Rabih O. Al-Kaysi

Ext: 47247

Email: kaysir@ksau-hs.edu.sa

Lectures 5 & 6

Electronic Structure of

Atoms

1 - Electronic Structure

• Our goal:

• Understand why some substances behave as they do.

• For example: Why are K and Na reactive metals? Why do H and

Cl combine to make HCl? Why are some compounds molecular

rather than ionic?

• Atom interact through their outer parts, their electrons.

• The arrangement of electrons in atoms are referred to as

their electronic structure.

• Electron structure relates to:

• Number of electrons an atom possess.

• Where they are located.

• What energies they possess.

**2 - The Wave Nature of Light
**

• Study of light emitted or absorbed by substances has lead

to the understanding of the electronic structure of atoms.

• Characteristics of light:

• All waves have a characteristic wavelength, λ , and

amplitude, A.

• The frequency, ν , of a wave is the number of cycles

which pass a point in one second.

• The speed of a wave, v, is given by its frequency

multiplied by its wavelength:

c=λ ν

• For light, speed = c.

Identifying λ and ν

3 - Electromagnetic Radiation

• Modern atomic theory arose out of studies of the

interaction of radiation with matter.

• Electromagnetic radiation moves through a vacuum with

a speed of 2.99792458 × 10-8 m/s.

• Electromagnetic waves have characteristic wavelengths

and frequencies.

• Example: visible radiation has wavelengths between 400

nm (violet) and 750 nm (red).

4 - The Electromagnetic Spectrum

Class Guided Practice Problem

• The yellow light given off by a sodium vapor lamp used for public

lighting has a wavelength of 589 nm. What is the frequency of this

radiation?

c=λ ν

Class Practice Problem

• A laser used to weld detached retinas produces radiation with a

frequency of 4.69 x 1014 s-1 . What is the wavelength of this

radiation?

**5 - Quantized Energy and Photons
**

• Planck: energy can only be absorbed or released from

atoms in certain amounts “chunks” called quanta.

• The relationship between energy and frequency is

E = hν

where h is Planck’s constant (6.626 × 10-34 J.s).

• To understand quantization consider walking up a ramp

versus walking up stairs:

• For the ramp, there is a continuous change in height whereas up

stairs there is a quantized change in height.

6 - The Photoelectric Effect

• Planck’s theory revolutionized experimental

observations.

• Einstein:

• Used planck’s theory to explain the photoelectric effect.

• Assumed that light traveled in energy packets called

photons.

• The energy of one photon:

E = hν

7 - Line Spectra and the Bohr Model

Line Spectra

• Radiation composed of only one wavelength is called

monochromatic.

• Most common radiation sources that produce radiation

containing many different wavelengths components, a

spectrum.

• This rainbow of colors, containing light of all

wavelengths, is called a continuous spectrum.

• Note that there are no dark spots on the continuous

spectrum that would correspond to different lines.

Specific Wavelength “Line Spectra”

**When gases are placed under reduced pressure in a tube and a high
**

voltage is applied, radiation at different wavelengths (colors) will be

emitted.

Line Spectra

• Balmer: discovered that the lines in the visible line

spectrum of hydrogen fit a simple equation.

• Later Rydberg generalized Balmer’s equation to:

1 RH 1 1

= 2 − 2

λ h n1 n2

**where RH is the Rydberg constant (1.096776 × 107 m-1 ), h
**

is Planck’s constant (6.626 × 10-34 J·s), n1 and n2 are

integers (n2 > n1).

8 - Bohr Model

• Rutherford assumed the electrons orbited the nucleus

analogous to planets around the sun.

• However, a charged particle moving in a circular path

should lose energy.

• This means that the atom should be unstable according to

Rutherford’s theory.

• Bohr noted the line spectra of certain elements and

assumed the electrons were confined to specific energy

states. These were called orbits.

9 - Line Spectra (Colors)

• Colors from excited gases arise because electrons move

between energy states in the atom. Neon lamps

**Line Spectra (Energy)
**

• Since the energy states are quantized, the light emitted

from excited atoms must be quantized and appear as line

spectra.

• After lots of math, Bohr showed that

( )

−18 1

E = − 2.18 ×10 J 2

n

where n is the principal quantum number (i.e., n = 1, 2, 3,

… and nothing else).

10 - Limitations of the Bohr Model

• Can only explain the line spectrum of hydrogen

adequately.

• Electrons are not completely described as small particles.

**11 - The Wave Behavior of Matter
**

• Knowing that light has a particle nature, it seems

reasonable to ask if matter has a wave nature.

• Using Einstein’s and Planck’s equations, de Broglie

showed: h

λ=

mν

• The momentum, mv, is a particle property, whereas λ is

a wave property.

• de Broglie summarized the concepts of waves and

particles, with noticeable effects if the objects are small.

The Wave Behavior of Matter

The Uncertainty Principle

• Heisenberg’s Uncertainty Principle: on the mass scale

of atomic particles, we cannot determine exactly the

position, direction of motion, and speed simultaneously.

• For electrons: we cannot determine their momentum and

position simultaneously.

• If ∆ x is the uncertainty in position and ∆ mv is the

uncertainty in momentum, then

h

∆x ⋅ ∆mν ≥

4π

**12 - Quantum Mechanics and Atomic
**

Orbitals

• Schrödinger proposed an equation that contains both

wave and particle terms.

• Solving the equation leads to wave functions.

• The wave function gives the shape of the electronic

orbital.

• The square of the wave function, gives the probability of

finding the electron,

• that is, gives the electron density for the atom.

Electron Density Distribution

**Probability of finding an electron in a hydrogen
**

atom in its ground state.

13 - The Three Quantum Numbers

1. Schrödinger’s equation requires 3 quantum numbers:

2. Principal Quantum Number, n. This is the same as Bohr’s

n. As n becomes larger, the atom becomes larger and the

electron is further from the nucleus. (n = 1, 2, 3…)

2. Azimuthal Quantum Number, l. This quantum number

depends on the value of n. The values of l begin at 0 and

increase to (n - 1). We usually use letters for l (s, p, d and f

for l = 0, 1, 2, and 3). Usually we refer to the s, p, d and f-

orbitals. (l = 0, 1, 2…n-1). Defines the shape of the

orbitals.

3. Magnetic Quantum Number, ml. This quantum number

depends on l. The magnetic quantum number has integral

values between -l and +l. Magnetic quantum numbers give

the 3D orientation of each orbital in space. (m = -l…0…+1)

**14 - Orbitals and Quantum Numbers
**

Class Guided Practice Problem

• (a) For n = 4, what are the possible values of l? (b) For l

= 2. What are the possible values of ml? What are the

representative orbital for the value of l in (a)?

**Class Practice Problem
**

• (c) How many possible values for l and ml are there when

(d) n = 3; (b) n = 5?

15 - Representations of Orbitals

The s-Orbitals

• 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, Ψ 2 = 0

• For an s-orbital, the number of nodes is (n - 1).

The s-Orbitals

The p-Orbitals

**• There are three p-orbitals px, py, and pz.
**

• The three p-orbitals lie along the x-, y- and z- axes of a

Cartesian system.

• The letters correspond to allowed values of ml of -1, 0,

and +1.

• The orbitals are dumbbell shaped.

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

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

The p-Orbitals

Electron-distribution

of a 2p orbital.

The d and f-Orbitals

**• There are five d and seven f-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.

• Four of the d-orbitals have four lobes each.

• One d-orbital has two lobes and a collar.

16 - Orbitals and Quantum Numbers

**• Orbitals can be ranked in terms of energy to yield an
**

Aufbau diagram.

• As n increases, note that the spacing between energy

levels becomes smaller.

• Orbitals of the same energy are said to be degenerate.

**Orbitals and Their Energies
**

17 - Electron Spin and the Pauli

Exclusion Principle

• Line spectra of many electron atoms show each line as a

closely spaced pair of lines.

• Stern and Gerlach designed an experiment to

determine why. At MIT

• A beam of atoms was passed through a slit and into a

magnetic field and the atoms were then detected.

• Two spots were found: one with the electrons

spinning in one direction and one with the electrons

spinning in the opposite direction.

Electron Spin and the Pauli Exclusion

Principle

Electron Spin and the Pauli Exclusion

Principle

**• Since electron spin is quantized, we define ms = spin
**

quantum number = ± ½.

• 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.

18 - Electron Configurations:

Hund’s Rule

• Electron configurations tells us in which orbitals the

electrons for an element are located.

• Three rules:

• electrons fill orbitals starting with lowest n and moving

upwards;

• no two electrons can fill one orbital with the same spin

(Pauli);

• for degenerate orbitals, electrons fill each orbital singly before

any orbital gets a second electron (Hund’s rule).

Electron Configurations and the

Periodic Table

**• The periodic table can be used as a guide for electron
**

configurations.

• The period number is the value of n.

• Groups 1A and 2A (1 & 2) have the s-orbital filled.

• Groups 3A - 8A (13 - 18) have the p-orbital filled.

• Groups 3B - 2B (3 - 12) have the d-orbital filled.

• The lanthanides and actinides have the f-orbital filled.

Class Guided Practice Problem

• Write the electron configurations for the following

atoms: (a) Cs and (b) Ni

**Class Practice Problem
**

• Write the electron configurations for the following

atoms: (a) Se and (b) Pb

Condensed Electron Configurations

• Neon completes the 2p subshell.

• Sodium marks the beginning of a new row.

• So, we write the condensed electron configuration for

sodium as

Na: [Ne] 3s1

• [Ne] represents the electron configuration of neon.

• Core electrons: electrons in [Noble Gas].

• Valence electrons: electrons outside of [Noble Gas].

Transition Metals

• After Ar the d orbitals begin to fill.

• After the 3d orbitals are full, the 4p orbitals begins to fill.

• Transition metals: elements in which the d electrons are

the valence electrons.

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