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Lecture No.

1
(The Electronic Structure of Atoms)
Lecturer: Prof. Allan N. Soriano, Ph.D. Ch.E. Email: allannsoriano@yahoo.com

Content
Atomic Models Quantum Mechanics Electronic Configuration Periodic Relations of Elements

Atomic Models
Democritus (400 BC)

He theorized that matter could not be divided into smaller and smaller pieces, and eventually the smallest possible piece would be obtained. He named the smallest piece of matter atomos meaning not to be cut.

Atomic Models (Cont.)

Aristotle (350 BC)

He modified an earlier theory that matter was made of four elements: earth, fire, water and air. He also rejected the idea of atomism of matter.

Fire Earth Water Air

Atomic Models (Cont.)

John Dalton (1800)

He proposed a modern model based on experimentation.

Daltons Atomic Theory:


1. Elements are composed of extremely small particles called atoms. All atoms of the same element are alike, and atoms of different elements are different. 2. The separation of atoms and the union of atoms occur in chemical reactions. In these reactions, no atom is created or destroyed, and no atoms of one element are converted into an atom of another element. 3. A chemical compound is the result of the combination of atoms of two or more elements. A given compound always contains the same kinds of atoms combined in the same proportions.

Atomic Models (Cont.)

Daltons Billiard Ball Model:

Atoms are solids and indivisible.

Atomic Models (Cont.)

J. J. Thomson (1900)

He discovered electron and proposed a model of the atom called Plum Pudding Model.

Atoms were made from a positively charged substance with negatively charged electrons scattered about.

Atomic Models (Cont.)

Ernest Rutherford (1910)

He proposed that atoms are mostly empty space and negative electrons orbit a positive nucleus using the Gold Foil Experiment.

The Gold Foil Experiment.

Atomic Models (Cont.)

Rutherfords Model:

A nucleus exists in the center of the atom. The nucleus contains protons and neutrons which together account for the mass. Electrons, which occupy most of the total volume of the atom, are outside the nucleus and move rapidly around it.

Atomic Models (Cont.)

Neils Bohr (1913)

He proposed an improved atomic model.


Electrons move in definite orbits around the nucleus. These orbits, or energy levels are located at certain distances from the nucleus. The Bohrs Model.

Atomic Models (Cont.)

Nuclear Bohr Model of Hydrogen Atom:

Electrons normally exist in the lower energy state (ground state). When an electron jumps into higher energy state it is said to be in an exited state.

Atomic Models (Cont.)

Werner Heisenberg (1925)


Theorized

that it is impossible to know simultaneously both the velocity and position of a particles (Heisenberg Uncertainty Principle). The probable location of an electron is based on how much energy the electron has.

Atomic Models (Cont.)

Electron Cloud Model: Electron cloud is a space in which electron are likely to be found. Electrons whirl about the nucleus billion of times in 1 second. They are not moving around in random pattern.

Quantum Mechanics
THE WAVE NATURE OF LIGHT
Electromagnetic Radiation

Light travels through space in a wave motion.

Quantum Mechanics (Cont.)

Definitions

Speed of light (c) equivalent to 2.998 x 108 m/sec.

c =
Wavelength () the distance between two similar points on two successive waves. It should be expressed in meters. (1nm = 10-9 m). Frequency () is the number of waves that pass a given spot in a second, this is the reciprocal of second (1/s = hertz).

Amplitude (a) height of a crest or depth of a trough.


Intensity (brightness) of Radiation is proportional to the square of amplitude (a2).

Quantum Mechanics (Cont.)

Colors of Visible Spectrum: Color Violet Blue Green Yellow Orange Red Wavelength, nm 400 450 450 500 500 570 570 590 590 620 620 750

Sample Problem: What is the frequency of red light with a wavelength of 700nm and violet light with a wavelength of 400nm?

Quantum Mechanics (Cont.)

Heinrich Hertz

Generated electromagnetic waves with long wavelengths larger than those of visible light and who demonstrated that long wavelength radiation exhibits the same phenomena as light does.

Electromagnetic Radiation (Spectra).

Quantum Mechanics (Cont.)

THE PARTICLE NATURE OF LIGHT


Max Plank

Proposed the quantum theory of radiant energy.

Suggested that radiant energy could be absorbed or given off only in definite quantities called quanta.

E = hv = hc / h Planks constant (6.626 x 10-34 J-s)


Albert Einstein

Proposed that Planks quanta were discontinuous bits of energy called photons.

Quantum Mechanics (Cont.)

Sample Problem: Consider a violet light with a wavelength of 400nm. (a) Calculate the energy, in joules, of one photon of this light. (b) Calculate the energy in kilojoules of one mole of such photons.

Quantum Mechanics (Cont.)

ATOMIC SPECTRA
Isaac Newton

Showed that visible (white light) from the sun can be broken down into its various component by a prism.

Definitions
Continuous Spectrum spreading out into a wide range band of the white light. Emission Spectrum When an element absorbs sufficient energy (from a flame or electric arc), it emits radiant energy in the form of light. When this radiation is passed through a prism, it separates into a component wave length.

Absorption Spectrum when continuous radiation (white light) passes through a substance, certain wavelengths of radiation may be absorbed. These wavelengths are characteristics of a substance that absorbs the radiation and pattern of these lines are referred to as an absorption spectrum.

Quantum Mechanics (Cont.)

Every element has its own unique line spectrum, therefore these spectra are characteristics of an atoms electronic structure .

Quantum Mechanics (Cont.)

Bohrs Theory:
1. The electron of the hydrogen atom can exist only in certain circular orbits (energy levels or shell). 2. The electron has a definite energy characteristic of the orbit in which it is moving. 3. When an electron of an atom is as close to the nucleus, it is in the condition of the lowest energy called the ground state. When an atoms are heated in an electric arc or Bunsen burner, electron absorbs energy and jump to outer levels, which are higher energy states (excited state). 4. When an electron falls back to a lower level, it emits a definite amount of energy. The energy difference between the high-energy state and low-energy state is emitted in the form of a quantum of light.

Quantum Mechanics (Cont.)

E = -RH / n2
Where: E energy of the electron RH Rydberg Constant (2.180 x 10-18 J) n energy level

E = h = Ehi Elo hv = -RH[(1/nhi2) (1/nlo2)] v = [RH/h] [(1/nlo2) (1/nhi2)] Sample Problem: What are the frequency and wavelength of the line in the hydrogen spectrum that corresponds to an electron transition from n=3 level to n=2 level?

Quantum Mechanics (Cont.)

The Relationship between Electron Transitions of a Hydrogen Atom and the Spectral Lines.

Quantum Mechanics (Cont.)

The Relationship between Electron Transitions of a Hydrogen Atom and the Spectral Lines:

Since electron transitions to n=1 level (Lyman series) release more energy than those to the n=2 level (Balmer series), the wavelength s of the lines in Lyman series are shorter than those of the Balmer series.
Balmer series occur in visible region. The lines in the Lyman series occur in the ultraviolet region. The lines of the Paschen series (n=3) occur at wavelengths longer than Balmer series. It appears in the infrared region.

Quantum Mechanics (Cont.)

QUANTUM MECHANICAL MODEL


Louis De Broglie

He reasoned that if light could show the behavior of particles (photons) as well as waves, then perhaps an electron, which Bohr had treated as particle, could behave like a wave. (Dualistic Nature of Light).

Erwin Schrdinger

Formulated wave equation that relates the energy of the electron to its position in the atom. Solutions of these equations give rise to quantum numbers.

Quantum Mechanics (Cont.)

QUANTUM NUMBERS set of numbers that describes an electron orbital

1. First Quantum Number (Principal) (n) indicates the main energy level by the electron. It defines the total energy of the electrons and has values from (1 to 7).
2. Second Quantum Number (Azimuthal) (l) it describes the way the electron moves around the nucleus or the shape of the probability distribution. The values range from 0 to (n1).

Quantum Mechanics (Cont.)

n
1 2 3

l
0 0 1 0 1 2 0 1 2 3

Spectral Lines
s type (sharp) s p type (principal) s p d type (diffuse) s p d f type (fundamental)

Quantum Mechanics (Cont.)

Quantum Mechanics (Cont.)

3. Third Quantum Number (Magnetic) (ml) it defines the possible orientation of the electrons in space. The values are from l through 0 to +l. l
0 1 2

ml
0 -1, 0, +1 -2, -1, 0, +1, +2

Number of orbitals (2l + 1)


1 3 5

4. Fourth Quantum Number (Spin) (ms) it takes into account the spinning of the electron around its own axis as it moves about the nucleus. The spin is either clockwise or counterclockwise. The values are +1/2 (clockwise) and -1/2 (counterclockwise).

Quantum Mechanics (Cont.)

Concepts:

Hunds Rule

When filling a set of degenerate energy levels, the electron enter the orbitals singly, with spins in the same direction (same as s number), until the set is half filled, before they pair up with opposite spins.

Paulis Exclusion Principle

Each electron within a given atom must have a unique set of the four quantum numbers.

Quantum Mechanics (Cont.)

Aufbaus Principle

Electrons will successively occupy the available orbitals on order of increasing energy.

Quantum Mechanics (Cont.)

Example: Write the possible set of quantum numbers for the electrons in: (a) 3s (b) 3d (c) 4f

Quantum Mechanics (Cont.)

Atomic Orbital Shapes:

s and p Orbitals

d Orbitals

Electronic Configuration
Electronic Configuration

Refers to the arrangement of electrons in energy levels.

Methods of Writing

1. Orbital method 2. Shell method 3. Arrow Rectangular method 4. Core Method

Electronic Configuration (Cont.)

Example (neutral atom): Write the electronic configuration using the four methods of the following elements: (a) Br (b) Ca

Example (monoatomic ions):


Give the electronic configuration of: (a) V4+ (b) Cl

Quantum Mechanics (Cont.)

Related Concepts:

Magnetism

Paramagnetic substances that contain net unpaired electrons and are attracted by a magnet. Ex. Li

Diamagnetic substances that do not contain net unpaired electrons and are slightly repelled by a magnet. Ex. Mg

Periodic Relations of Elements


Periodic Classifications of Elements

Elements may be classified according to their electronic configurations.

1. The Noble Gases They are also known as Inert Gases or Group O elements. They are colorless monoatomic gases, which are chemically unreactive and diamagnetic. They have outer configurations of ns2np6 (except for Helium). 2. The Representative Elements These elements are found in the A families of the periodic table. They exhibit a wide range of chemical behavior and physical characteristics. The chemistry of these elements depends upon the valence electrons.

Periodic Relations of Elements (Cont.)

3. The Transition Elements They are found in the B families of the periodic table. All of these elements are metals and most of them are paramagnetic and form highly colored, paramagnetic compounds. 4. The Inner-Transition Elements These elements are found at the bottom of the periodic table, but they belong to the 6th and 7th periods after the elements of group IIIB. All innertransition elements are metal and are paramagnetic. Their compounds are also paramagnetic and colored.

Periodic Relations of Elements (Cont.)

Periodic Variation in Physical Properties

1. Atomic Radius one-half the distance between the nuclei of the two atoms in an elemental substance.
TREND:

LEFT RIGHT TOP BOTTOM

decreases increases

Periodic Relations of Elements (Cont.)

2. Ionic Radius one-half the distance between the nuclei of a metal and a non-metal. positive ions are smaller than
the metal atoms from which they are formed negative ions are larger than the nonmetal atoms from which they are formed
TREND:

LEFT RIGHT
* this happens when comparing both TOP metals and non-metals but by comparing the metals and non-metals, nonmetals have larger ionic radius than metals.

decreases* increases

BOTTOM

Periodic Relations of Elements (Cont.)

3. Ionization Energy the minimum energy required to remove an electron from a gaseous atom in its ground state. LEFT RIGHT
TREND:

increases

TOP BOTTOM

decreases

4. Electron Affinity measure of the energy change when electron is added to a neutral atom to form a negative ion. LEFT RIGHT
TREND:

increases

TOP BOTTOM

decreases

END of Lecture No. 1

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