Chapter 5

Perodicity and Atomic Structure

Mendeleevs Periodic Table

In the 1869, Dmitri Mendeleev proposed that the properties of the chemical elements repeat at regular intervals when arranged in order of increasing atomic mass. Mendeleev is the architect of the modern periodic table.

Chapter 5

Prediction of New Elements

Mendeleev noticed that there appeared to be some elements missing from the periodic table so he left spots for undiscovered elements. Based on his periodic table, he accurately predicted the properties of some of these the unknown elements before their discovery.

Chapter 5

Periodic Trends
The arrangement of the periodic table means that the physical properties of the elements follow a regular pattern. Some trends include:
Atomic Radius (end of Chapter 5) Ionization Energy (Chapter 6) Electron Affinity (Chapter 6) Electronegativity (Chapter 7)
Chapter 5 4

The Structure of Atoms

Plum Pudding Model

Chapter 5

Tootsie Pop Model

5

The Dual Nature of Light: The Particle and The Wave

From the time of the ancient Greeks, people have thought of light as a stream of tiny particles - like marbles or billiard balls Thomas Young (in 1807) performed the now classic double slit experiment to test this theory.

Chapter 5

A great animation of the idea of light as waves and particles can be found here: http://video.google.com/videoplay?docid=-4237751840526284618&q=quantum

The Dual Nature of Light: The Wave

As evidenced by the double slit experiment, light travels through space as a wave, similar to an ocean wave. Wavelength () is the distance light travels in one cycle. Frequency () is the number of wave cycles completed each second. Amplitude is the height measured from the center of the wave. The square of this value gives the Intensity.

Velocity (c) =
Light has a constant velocity (c) of 3.00 108 m/s.
Chapter 5 7

Frequency - Wavelength
The red light in a laser pointer comes from a diode laser that has a wavelength of about 632 nm. What is the frequency of the light?

Chapter 5

The Dual Nature of Light: The Particle

In 1900, Max Planck proposed that radiant energy is not continuous, but is emitted as small bundles of energy
This is the quantum concept.

Planck determined that the energy of an emitted bundle is directly proportional to the frequency of the emitted light times a constant (h)

E = h =

hc

h = 6.626 10 34 J s

Chapter 5

The Photoelectric Effect

The Photoelectric Effect shows that when light is shined on the surface of a metal, electrons are ejected and a current can be detected. Albert Einstein used Plancks idea of quanta to explain this phenomona.
If the light were waves only, then the energy of that radiation would depend only on the intensity of the light. Einstein hypothesized that electrons are only ejected if the frequency of the light exceeds a threshold value specific to the metal, regardless of light intensity Even at low light intensities, electrons are ejected immediately if the frequency exceeds the threshold

Millikan tested Einsteins hypothesis in 1914 and proved that is was correct Einstein wins the Nobel Prize! Yea!
Chapter 5
Figure above from http://en.wikipedia.org/wiki/Photoelectric_Effect

10

Energy of Emission
For red light with a wavelength of about 632 nm, what is the energy of a single photon and one mole of photons?

Chapter 5

11

Wave Particle Duality

Louis de Broglie suggested that if light can behave like matter (particles) then matter can behave as light. This concept is called wave particle duality. For a Particle E = mc2 = h mv For Light E = h = h mc

h = 6.626 x 10-34 kg m2 / s
Chapter 5

h = 6.626 x 10-34 J s
12

Wave Particle Duality

How fast must an electron be moving if it has a de Broglie wavelength of 551 nm? How fast must an electron be moving if it has a de Broglie wavelength of 631 nm? me = 9.109 x 1031 kg
Chapter 5 13

The Electromagnetic Spectrum

The complete electromagnetic spectrum (all possible wavelengths and frequencies) is an un-interrupted band, or continuous spectrum. The radiant energy spectrum includes most types of radiation, most of which are invisible to the human eye.

ROY G BIV
Chapter 5 14

The Atomic Spectra

When a particular element is heated and the light emitted is focused and passed through a prism, the resulting breakdown results in a non-continuous spectrum or a discrete line spectrum
This spectrum is called the elements atomic spectrum The discrete lines indicate a light is emitted or absorbed in a series of discrete frequencies rather than continuously
Chapter 5

Each element has its own, 15 unique spectrum

The Bohr Model of the Atom

In 1913, Niels Bohr suggested a new model of the atom that explained why hydrogen had a discrete line spectrum rather than a continuous spectrum. Bohr's basic theory: electrons in atoms can only be at certain energy levels, and they can give off or absorb radiation only when they jump from one level to another. In his model that an atom consists of an extremely dense nucleus that is surrounded by electrons that travel in set orbits around the nucleus. He hypothesized that the energy possessed by these electrons and the radius of the orbits are quantized, meaning it is limited to specific values and is never between those values. These orbits were of varying energies, The dependent on their distance from the nucleus
Chapter 5

Gobstopper Model
16

Quantized versus Continuous

The quantum concept means that the energy of the electron and its radius of orbit around the nucleus is limited to specific values (and cannot be anywhere in between!). If these values were continuous, they would be free to have any value. Energy
E3
hv = E3 E2

E2
hv = E3 E1 hv = E2 E1
Chapter 5

E1

17

Atomic Spectra: The Balmer-Ryberg Equation

In 1885, Johann Balmer determined that the pattern of the atomic spectra of hydrogen could be predicted by a mathematical formula. Balmer determined that the wavelength or frequency of the lines in the spectrum could be expressed by the following equations:

E = RH

1 1 2 ni n f2

RH is the Ryberg constant (2.18 x 10-18 J) ni and nf are integers with nf > ni

In addition to the lines seen in the visible region (Balmer series), there are additional sets of lines found in the UV region (Lyman series) and the IR region (the Paschen series). All conform to the above equations.
Chapter 5 18

The Bohr Theory: Problems

Bohrs theory only works for hydrogen atoms. Once you have more than one electron, the calculations for the electron energy and the orbit radii breakdown. Therefore, a new theory needed to be developed for multi-electron elements. Bohrs theory did make two important contributions:
It suggested a reasonable explanation for the discrete line spectrum of the elements It introduced the idea of quantized electron energy levels (orbits!)
Chapter 5 19

The Quantum Mechanical Model of the Atom

In the 1920s Erwin Schrdinger applied the principles of wave mechanics to atoms and developed the Quantum Mechanical Model of the Atom
Basically, Schrdinger said to give up on the idea of literal orbits for the electrons and instead concentrate on the electron as a wave.

This theory builds on Bohrs idea of quantized energy levels (orbits) and adds additional requirements for electron location and energy.
Chapter 5 20

10

Quantum Mechanics
Werner Heisenberg (19011976): supported this idea by showing that it is impossible to know (or measure) precisely both the position and velocity (or the momentum) at the same time. The simple act of seeing an electron would change its energy and therefore its position.
Think about pinpointing a fly on the wall. What happens when you try to swat it?

Heisenberg Uncertainty Principle : (x)(m ) Uncertainty in electron' s position : (x)

Chapter 5

h 4

h (4 )(m )

21

Quantum Mechanics
Working with Heisenbergs Principle, Schrdinger developed a compromise which calculates both the energy of an electron and the probability of finding an electron at any point in the molecule. This is accomplished by solving the Schrdinger equation, resulting in the wave function, .
Wave Equation
solve

Wave Function or Orbital ()

Probability of finding an electron in a region of space (2)

These regions were termed orbitals

Chapter 5 22

11

Quantum Numbers
The wave function contains three variables known as the Quantum Numbers which describe the size, energy, shape and position of the orbitals.
n is the principal energy level (Bohrs Orbits!) l is the sublevel ml is the orbital

These numbers serve as an address of the probable location of the electron.

Chapter 5 23

Principal Quantum Number (n)

The Principal Quantum Number (n) provides info about the distance of the electron from the nucleus
As n increases, the number of allowed orbitals also increases as does the size of those orbitals. This increased size allows the electron to reside further from the nucleus As the electron moves away from the nucleus its energy increases, therefore n also indicates the energy of electrons

We often state that electrons and orbitals denoted by the same n value are in the same shell

Allowed Values: n = 1, 2, 3, ... never 0

Chapter 5 24

12

Angular-Momentum Quantum Number (l)

The angular momentum quantum number (l) defines the three dimensional shape of the orbitals found within a particular shell These discrete sets of orbitals are called sublevels The number of sublevels within a shell is equal to the principal quantum number (n)

Allowed Values: l = 0, 1, 2 ... n - 1 1 p 2 d 3 f

25

l Value: Letter Used:

Chapter 5

0 s

increasing energy

Magnetic Quantum Number (ml)

The Magnetic Quantum Number (ml) describes the orientation in 3D space of the sublevel, thereby denoting a specific orbital. The number of orientations (and therefore orbitals) per sublevel is determined by the equation:

2l + 1 Allowed Values: ml = - l, , + l
y axis

l
2l + 1

0 (s) 1 (p) 2 (d)

3 (f)
x axis

Chapter 5

z axis

26

13

Spin Quantum Number (ms)

The Pauli Exclusion Principle states that no two electrons can have the same four quantum numbers This results in no more than double occupancy in any one orbital only two electron per orbital and they must have opposite spins

Chapter 5

27

Electron Occupancy in Sublevels

The Pauli Exclusion Principle states that an orbital can hold up to two electrons The maximum number of electrons in each of the sublevels depends on the number of orbitals within that sublevel:
The s sublevel holds a maximum of 2 electrons (1 orbital). The p sublevel holds a maximum of 6 electrons (3 orbitals). The d sublevel holds a maximum of 10 electrons (5 orbitals). The f sublevel holds a maximum of 14 electrons (7 orbitals)

The maximum electrons per principle quantum level (n) is obtained by adding the maximum number of electrons in each sublevel.
Chapter 5 28

14

Quantum Number Combinations

Why cant an electron have the following quantum numbers? (a) n = 2, l = 2, ml = 1 (c) n = 5, l = 2, ml = 1 Give orbital notations for electrons with the following quantum numbers: (a) n = 2, l = 1, ml = 1 (c) n = 3, l = 2, ml = 1 (b) n = 4, l = 3, ml = 2 (b) n = 3, l = 0, ml = 3

Chapter 5

29

Shapes of the Orbitals

Each orbital has a specific shape determined by its angular momentum quantum number (l). As you increase the principle quantum number (n), the orbitals increase in size but not shape! Remember, these orbitals represent a region in space where there is a high probability of finding the electron.
These are not discrete locations! They are also not pictures of the path that an electron follows around a nucleus

Chapter 5

30

15

l = 0 : The s Orbitals
The s orbitals are spherical, meaning the probability of finding the electron depends only on distance from the nucleus, not direction. The value of 2 is greatest near the nucleus then drops off as you move away. It never reaches zero however so there is technically no definite boundary to the atom.

Chapter 5

31

l = 1 : The p Orbitals
The p orbitals are dumbbell shaped with their electron density concentrated in identical lobes residing on opposite sides of a nodal plane. This shape means that a p electron will never be found near the nucleus. The two lobes of a p orbital have different phases (are opposite in sign) which becomes important in bonding among atoms. The three orientations (ml = -1, 0, +1) are 90 differentials along the x, y and z axes. The orbitals are designated px (along the x axis), py (along the y axis), and pz (along the z axis)

Chapter 5

32

16

l = 2 : The d Orbitals

Chapter 5

33

Effective Nuclear Charge (Zeff)

The nuclear charge (Z) of an atom is determined by the number of protons found in the nucleus
It is felt by the electrons as an attraction

Multiple electrons in an atom lead to a shielding effect on the outer electrons. This electron shielding (S) leads to energy differences among orbitals within a shell. Net nuclear charge felt by an electron is called the effective nuclear charge (Zeff).

Zeff = Z + S

Chapter 5

34

17

Effective Nuclear Charge (Zeff)

Note that the 3d sublevel is actually higher in energy than the 4s sublevel.

WHY??

Chapter 5

35

The Modern Periodic Table

H.G.J. Moseley discovered that the nuclear charge increased by 1 for each element in the Mendeleevs table. He concluded that the changing atomic number rather than the changing mass explained the repeating trends of the elements The periodic law states that the properties of elements recur in a repeating pattern when arranged according to increasing atomic number. With the introduction of the concept of electron energy levels by Niels Bohr, the periodic table took its current arrangement.
Chapter 5

http://www.webelements.com/

36

18

Electron Configurations
Many of an elements chemical properties depend on its electron configuration The electron configuration of an atom is a shorthand method of writing the location of electrons by sublevel. The principal quantum level (n) is written first, followed by the letter designation of the sublevel (l) then a superscript with the number of electrons in the sublevel. There are rules for the order and manner that each sublevel is filled called the Aufbau Principle.
Chapter 5 37

Electron Configurations: Aufbau Principle

Pauli Exclusion Principle: No two electrons in an atom can have the same quantum numbers (n, l, ml, ms). Hunds Rule: When filling orbitals in the same sublevel, maximize the number of parallel spins (so fill then pair!). Rules of Aufbau Principle: 1. Lower n orbitals fill first. 2. Each orbital holds two electrons; each with different ms. 3. Half-fill degenerate orbitals before pairing electrons.
Chapter 5 38

19

Using the Periodic Table for Electron Configurations

The periodic table took on its current shape once the quantum model of the atom was developed. You can use it to fill up your sublevels and orbitals to build your electron configurations.

Chapter 5

39

Writing Electron Configurations

Step 1: Locate the element on the periodic table. Step 2: Determine the number of electrons the element Iron has 26 electrons has: Step 3: Starting at the beginning of the Periodic Table, move left to right across the periods, filling each sublevel with electrons until you reach the location of your element:

Fe: 1s2 2s2 2p6 3s2 3p6 4s2 3d 6

Step 4: Check that the sum of the superscripts equals the atomic number of iron (26).
Chapter 5 40

20

An Alternative Method

Increasing Energy
Chapter 5

Core [He] [Ne] [Ar] [Kr] [Xe] [Rn]

1s 2s 3s 4s 5s 6s 7s

2p 3p 4p 5p 6p 7p

3d 4d 4f 5d 5f 6d

41

Writing Electron Configurations

Li 1s 2s 2s 1s2 2s1

Be 1s B

1s2 2s2

1s 2s 2px 2py 2pz 1s 2s 2px 2py 2pz

1s2 2s2 2p1

C
Chapter 5

1s2 2s2 2p2

42

21

Writing Electron Configurations

N 1s 2s 2px 2py 2pz 1s 2s 2px 2py 2pz 1s2 2s2 2p3

1s2 2s2 2p4

Ne 1s 2s 2px 2py 2pz [Ne] 3s 3px 3py 3pz Chapter 5 S

1s2 2s2 2p5

[Ne] 3s2 3p4

43

Writing Electron Configurations

Give the ground-state electron configurations for: Ne (Z = 10) Eu (Z = 63) Mn (Z = 25) W (Z = 74) Zn (Z = 30) Lw (Z = 103)

Identify elements with ground-state configurations: 1s2 2s2 2p4 1s2 2s2 2p6 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d6 [Ar] 4s2 3d1 [Xe] 6s2 4f14 5d10 6p5

Chapter 5

44

22

Exceptions to the Filling Order

When filling the d sublevel, exceptions occur for the chromium (Cr) and copper (Cu) families:
4s 3d 3d 4p 4p

Cr

4s

4s

3d 3d

4p 4p

Cu
Chapter 5

4s

45

Periodic Trends
The arrangement of the periodic table means that the physical properties of the elements follow a regular pattern. Some trends include:
Atomic Radius (end of Chapter 5) Ionization Energy (Chapter 6) Electron Affinity (Chapter 6) Electronegativity (Chapter 7)
Chapter 5 46

23

Atomic Radius
An atoms atomic radius is the distance from the nucleus to the outermost electrons.

Why do you think the radius increases in this way?

Chapter 5 47

24