Chapter One Atoms: The Quantum World

CHEM 1211K Fall 2013

Objectives
At the end of this chapter you will be able to:
Understand the structure of the atom and gain familiarity with subatomic particles. Characterize the wave and particle nature of light such as: Energy, frequency, wavelength and the work of Rydberg with atomic spectra. Correlate the duality of light to the dual nature of subatomic particles, the electron in particular. Combine the photoelectric effect, uncertainty principle, and the Schrdinger equation to develop an understanding of where electrons are located in the atom. Use quantum numbers to describe the most probably locations of electrons in atoms. Write electron configurations to describe the filling of electrons and correlate to the periodic table. Define periodic properties and explain their trends.

Key Ideas
Matter is composed of atoms The structures of atoms can be understood in terms of the theory of matter known as quantum mechanics, in which the properties of particles and waves merge.

Why is it important?
Atoms are the fundamental building blocks of matter. Almost all the explanations of chemical phenomena are expressed in terms of atoms. This chapter explores the periodic variation of atomic properties and shows how quantum mechanics is used to account for the structures and therefore the properties of atoms.

This material is the foundation for almost all explanations of chemistry.

4

Characteristics of Electromagnetic Radiation (1.2)

Light is a form of ______________________, which consists of oscillating (time-varying) electric and magnetic fields.

All forms of electromagnetic radiation transfer energy from one region of space to another.
5

Characteristics of Electromagnetic Radiation (1.2)

Important attributes of light:
Wavelength:

Amplitude:

Intensity:
6

Similar to Figure 1.7

Not in text

Characteristics of Electromagnetic Radiation (1.2)

The color of light (visible spectrum) depends on its _________ and __________:

Figure 1.9
8

Characteristics of Electromagnetic Radiation (1.2)

_________ is the number of cycles of a wave Not in text per second.
Measured in Hertz (Hz)

Atomic Spectra (1.3)

In this section, we will focus on the hydrogen atom since it is the simplest atom (only one electron). When electric current is passed through a sample of H2 gas, the sample emits light.

10

Atomic Spectra (1.3)

White light passed through a prism results in a continuous spectrum of light.

But when light emitted by excited hydrogen atoms passes through a prism, a number of _______________result.

11

Atomic Spectra (1.3)

Johann Balmer determined that the wavelengths of all spectral lines fit the expression:

Next, Johannes Rydberg determined:

12

Atomic Spectra (1.3)

Text Example 1.2: Calculate the wavelength (in nm) of the radiation emitted by a hydrogen atom for n1 = 2 and n2 = 3.

13

Atomic Spectra (1.3)

Passing white light through a vapor composed of the atoms of an element produces an _________________.
Figure 1.11

14

Atomic Spectra (1.3)

Section summary

15

Radiation, Quanta, and Photons (1.4)

Important clues about the nature of electromagnetic radiation came from observations of objects as they are heated. Max Planck proposed that the exchange of energy between matter and radiation occurs in ________ or packets of energy.

16

Radiation, Quanta, and Photons (1.4)

Experimental evidence to support Plancks theory was provided by the _____________________.

Figure 1.15
17

Radiation, Quanta, and Photons (1.4)

Albert Einstein explained the photoelectric effect.
Electromagnetic radiation consists of particles called _________.

http://www.nobelprize.org/nobel_prizes/physics/laureates/1921/einstein-bio.html

18

Radiation, Quanta, and Photons (1.4)

Text Example 1.4: What is the energy of a single photon of blue light of frequency 6.4 x 1014 Hz? What is the energy of a mole of photons of the same frequency?

19

Radiation, Quanta, and Photons (1.4)

Section Summary:

20

The Wave-Particle Duality of Matter (1.5)

There is ample evidence to show that electromagnetic radiation behaves like waves!
_________ is a pattern of high and low intensities generated by an object in the path of a ray of light. Peaks and troughs of waves traveling along one path interfere with the peaks and troughs of waves traveling along another path.

21

The Wave-Particle Duality of Matter (1.5)

Constructive interference

Figure 1.19

Destructive interference
22

The Wave-Particle Duality of Matter (1.5)

Photoelectric effect

X-ray diffraction

From Zumdahl, 5th ed.

23

The Wave-Particle Duality of Matter (1.5)

If light can be a wave and a particle, why cant other particles also act like waves?!?!
Louis de Broglie proposed that ALL particles (such as electrons) should be regarded as having wavelike properties.

24

The Wave-Particle Duality of Matter (1.5)

Section summary

25

The Uncertainty Principle (1.6)

A particle has a definite trajectorythe path on which location and linear momentum are specified at each instant. We cannot specify the precise location of a particle if it behaves like a wave.
The electrons in atoms CANNOT be described as orbiting the nucleus with a definite trajectory The solar system model of the atom is WRONG.
26

The Uncertainty Principle (1.6)

Location and momentum are complimentaryif one property is known then the other cannot be known simultaneously. The ____________________________ expresses the complementarity of location and momentum quantitatively:

1 h px > 2 2

27

The Uncertainty Principle (1.6)

Section summary
The location and momentum of a particle are complementary. The location and the momentum cannot both be known simultaneously with arbitrary precision. The quantitative relationship between the precision of each measurement is described by the Heisenberg uncertainty principle.

28

Wavefunctions and Energy Levels (1.7)

Erwin Schrodinger recognized that it would be beneficial to replace the precise trajectory of a particle (unrealistic due to the dual nature) with a ________________. Max Borns interpretation of the wavefunction is that the probability of finding the particle in a region is proportional to the square of the wavefunction.
29

Wavefunctions and Energy Levels (1.7)

When 2 is zero, the particle has zero probability density. A location where passes through zero is called a _______.

Figure 1.24

30

Wavefunctions and Energy Levels (1.7)

To calculate the wavefunction for any particle, we use the ___________________.
We dont need to know the equation. We will simply use the solutions to the equation. Solutions to the Schrodinger equation give us an address for the places we are most likely to find electrons.

31

Wavefunctions and Energy Levels (1.7)

Section summary
The probability density for a particle at a location is proportional to the square of the wavefunction at that point. The wavefunction is found by solving the Schrodinger equation for that particle.
When the equation is solved, it is found that the particle can posses only certain discrete energies.

32

The Hydrogen Atom

We are now ready to build a quantum mechanical model.
Technically, this model works only for the hydrogen atom, but we can use it to make very good approximations for other atoms.

33

The Principle Quantum Number (1.8)

There are many, many solutions to the Schrodinger equation.
Each solution consists of a wave function.

Each wave function results in specific values of the three quantum numbers.

34

The Principle Quantum Number (1.8)

The ________________________ (n) Describes the main __________ (shell) that the electron occupies.

n may be any positive integer.

35

The Principle Quantum Number (1.8)

The lowest energy possible for an electron (in a hydrogen atom) is obtained when n = 1.
This lowest energy state is called the _________ ________.

Figure 1.28
36

The Principle Quantum Number (1.8)

Section Summary
The energy levels of a hydrogen atom are defined by the principle quantum number, n = 1, 2, and form converging series as shown in Figure 1.28.

37

Atomic Orbitals (1.9)

The _______________________________ (l):

Designates the sublevel that the electron occupies. l may have any value from 0(n-1)

38

Atomic Orbitals (1.9)

Each value of l represents a _____________.
Value of l Orbital type Number of orbitals in subshell

39

Atomic Orbitals (1.9)

The _________________________ (ml): Designates the specific orbital within a subshell that the electron occupies.

To determine the allowed values of ml for a given set of quantum numbers, determine the largest possible value of l.

40

Atomic Orbitals (1.9)

Figure 1.30

41

Atomic Orbitals (1.9)

The _______________________ tells us the probability density for finding an electron at a given radius summed over all directions.

Figure 1.32

Figure 1.33

42

Atomic Orbitals (1.9)

The boundary surface for a p orbital has two lobes separated by a nodal plane.
Figure 1.35

43

Atomic Orbitals (1.9)

Remember that there are three p orbitals in a given energy level.

Figure 1.36

44

Atomic Orbitals (1.9)

Five d orbitals of in a given energy level
Figure 1.37

Seven f orbitals

Figure 1.38
45

Atomic Orbitals (1.9)

The total number of orbitals in a shell with principle quantum number n is n2.

How many electrons are in a shell with principle quantum number n?

46

Atomic Orbitals (1.9)

Section summary
The location of an electron in an atom is described by a wavefunction known as an atomic orbital. Atomic orbitals are designated by the quantum numbers n, l, and ml and fall into shells and subshells .

47

Electron Spin (1.10)

Electrons behave in some respects like a planet rotating on its axis. This property is called ____.
These two spin states are distinguished by a fourth quantum number, the ____________________.
Figure 1.40

48

Electron Spin (1.10)

Section Summary
An electron has a property of spin. The spin is described by the quantum number ms, which may have only one of two values.

49

The Electronic Structure of Hydrogen (1.11)

The ground state for the single electron of hydrogen is n = 1. What four quantum numbers can we use to describe its location?

50

The Electronic Structure of Hydrogen (1.11)

When the atom acquires energy by absorbing a photon of radiation, the electron can reach the n = 2 shell.

51

The Electronic Structure of Hydrogen (1.11)

Example: What type of orbital is described the set of quantum numbers?
n = 3, l = 2, ml = -2

n = 1, l = 0, ml = 0, ms = +1/2

52

The Electronic Structure of Hydrogen (1.11)

Example: What is the maximum amount of electrons that the n = 5 shell can hold? What is the maximum amount of electrons that can be found in the l = 3 subshell?

How many electrons in an atom with n = 4 can have ml = -2?

53

The Electronic Structure of Hydrogen (1.11)

Section Summary
The state of an electron in a hydrogen atom is defined by the four quantum numbers n, l, ml , and ms. As the value of n increases, the size of the atom increases.

54

Orbital Energies (1.12)

The energies of the orbitals in many-electron atoms are not the same as those in hydrogen.
Nuclei of many-electron atoms are more highly charged. Greater nuclear charge attracts electrons more, and lowers energies of orbitals.

55

Orbital Energies (1.12)

In addition to being more attracted to the nucleus, the multiple electrons in a manyelectron atoms repel one another.
Each electron is less tightly bound to the nucleus than it would be if the other electrons were not present.

56

Orbital Energies (1.12)

The shielding of other electrons effectively reduces the pull of the nucleus on the electron. The ___________________________ experienced by the electron is always less than the actual nuclear charge, Ze.

57

Orbital Energies (1.12)

Section summary
In a many-electron atom, because of the effects of penetration and shielding, the order of energies of orbitals in a give shell is

s<p<d<f

58

Orbital Energies (1.12)

s orbitals p orbitals

d orbitals

f orbitals

59

Orbital Energies (1.12)

Figure 1.44

60

The Building-Up Principle (1.13)

_____________________ is a list of all occupied orbitals with the number of electrons that each one contains for a specific atom.

61

The Building-Up Principle (1.13)

The ______________________ says that no more than two electrons may occupy any given orbital.
When two electrons do occupy one orbital, their spins must be paired.

62

The Building-Up Principle (1.13)

We can use an orbital diagram to show the distribution of orbitals in an atom.

63

The Building-Up Principle (1.13)

To predict ground-state electron configurations of a neutral atom with atomic number Z:
1. Add Z electrons, one after the other, to the orbitals in the order of lowest to highest energy, but with no more than two electrons in any one orbital. 2. If more than one orbital in a subshell is available, add electrons with parallel spins to different orbitals of that subshell rather than pairing two electrons in one of the orbitals.
64

The Building-Up Principle (1.13)

1 H: 1 s 1 22s1 Li: 1 s 3 5B: 22s22p 22p 12p 1 1 s O: 8 x y z
10Ne:

65

The Building-Up Principle (1.13)

______________________ is short hand based on the idea that any atom contains all of the same electrons possessed by the noble gas immediately preceding it.

66

The Building-Up Principle (1.13)

We can think of many-electron atoms as consisting of ______________ and _______ _________.

67

The Building-Up Principle (1.13)

Exceptions to electron configuration rules center around full or half full d subshells.

68

The Building-Up Principle (1.13)

Section summary:
We account for the ground-state electron configuration of an atom by using the building-up principle in conjunction with the energies of orbitals (see Figure 1.41), the Pauli exclusion principle, and Hunds rule. See Toolbox 1.1 on page 36 of your text.

69

Electronic Structure and the Periodic Table (1.14)

The periodic table was formulated long before the structures of atoms were known by noting trends in experimental data. (See Box 1.2 on page 38 for interesting details)
The reasons for the ___________ of the elements remained a mystery for many, many years.

70

Electronic Structure and the Periodic Table (1.14)

The s- and p-blocks form the ___________ of the periodic table. The d-block elements are known as ________ _______.

The f-block elements are the __________ and _________.

71

Electronic Structure and the Periodic Table (1.14)

Section Summary:
The blocks of the periodic table are names for the last orbital to be occupied according to the building up principle. The periods are numbered according to the principle quantum number of the valence shell.

72

The Periodicity of Atomic Properties

The periodic trends we will discuss are primarily the result of _________ or __________.
Inner (core) electrons shield the outer (valence) electrons from the effects of the positively charged nucleus. Electrostatic attraction decreases, so valence electrons are not pulled in as tightly.

73

The Periodicity of Atomic Properties

Trend from left to right across a period:
All elements in a period have the same number of core electrons.

Proceeding from left to right, elements have ____ valence electrons.

There are also more protons = more positive charge.

The core electrons can more effectively screen a smaller number of electrons.
Electrostatic attraction __________ across the period.

74

The Periodicity of Atomic Properties

Effective nuclear charge vs. atomic number

Figure 1.45

75

The Periodicity of Atomic Properties

All three elements have two core electrons.

Ne has more valence electrons (8) than O (6) or Li (1). Nes core electrons cannot effectively shield all 8 valence electrons. The attraction between the nucleus and valence electrons is very strong.
76

Atomic Radius (1.15)

The ____________ of an element is defined as half the distance between neighboring atoms.

From Zumdahl, 5th edition

77

Atomic Radius (1.15)

What is the general trend in atomic radii?

Figure 1.46

78

Atomic Radius (1.15)

Section Summary:
Atomic radii generally decrease fro left to right across a period as the atomic number increases, and they increase down a group of successive shells are occupied.

79

Ionic Radius (1.16)

The ___________ of an element is its share of the distance between neighboring ions in an ionic solid.

80

Ionic Radius (1.16)

Figure 1.49

81

Ionic Radius (1.16)

Figure 1.48
82

Ionic Radius (1.16)

Atoms and ions with the same number of electrons are called ______________. Na+ FMg2+

83

Ionic Radius (1.16)

Section summary:
Ionic radii generally increase down a group and decrease from left to right across a period. HOWEVER, cations are smaller than their parent atoms and anions are larger.

84

Ionization Energy (1.17)

The __________________ is the minimum energy needed to remove an electron from a neutral atom in the gas phase.

What is the ______________________?

85

Ionization Energy (1.17)

In general, first ionization energy _________ up a group and from left to right across a Figure 1.51 period.

86

Ionization Energy (1.17)

The general trend indicates that O should have a higher first ionization energy than N, but it does not. Why?

87

Ionization Energy (1.17)

Example: An element has the following set of ionization energies. To what group on the periodic table does the element belong?
IE1 = 578 kJ/mol IE2 = 1820 kJ/mol IE3 = 2750 kJ/mol IE4 = 11600 kJ/mol IE5 = 14500 kJ/mol

88

Ionization Energy (1.17)

Section Summary:
The first ionization energy is highest for elements close to helium and is lowest for elements close to cesium. Second ionization energies are higher than first ionization energies (for the same element) and very much higher if the electron is to be removed from a closed shell.

89

Electron Affinity (1.18)

______________ is the energy released when an electron is added to a gas-phase atom.

Positive electron affinity means that energy is ________ when an electron attaches to an atom.

Negative electron affinity means that energy must be _________ to push an electron onto an atom.
90

Electron Affinity (1.18)

Electron affinity values become __________________:
Up a group From left to right across a period

91 Figure 1.54

Electron Affinity (1.18)

Notice that the hiccups arent in the same place they were for ionization energy.
How are they different?

92

Electron Affinity (1.18)

Figure 1.55

93

Electron Affinity (1.18)

Section summary:
Elements with the highest (most positive) electron affinities are those in Group 16 (VIA).

94

The Periodicity of Atomic Properties

Example: Arrange these elements in order of increasing electron affinity, atomic radius and ionization energy. Al, Si, Na

95