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Chapter 6 Electronic Structure of Atoms

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1 Chapter 6 Electronic Structure of Atoms
Chemistry, The Central Science, 11th edition Theodore L. Brown; H. Eugene LeMay, Jr.; and Bruce E. Bursten Chapter 6 Electronic Structure of Atoms John D. Bookstaver St. Charles Community College Cottleville, MO © 2009, Prentice-Hall, Inc.

2 Aim: How does light act as a wave?
Do Now: All light travels through a vacuum at what speed? © 2009, Prentice-Hall, Inc.

3 Waves To understand the electronic structure of atoms, one must understand the nature of electromagnetic radiation. The distance between corresponding points on adjacent waves is the wavelength (). © 2009, Prentice-Hall, Inc.

4 Waves The number of waves passing a given point per unit of time is the frequency (). For waves traveling at the same velocity, the longer the wavelength, the smaller the frequency. © 2009, Prentice-Hall, Inc.

5 Electromagnetic Radiation
All electromagnetic radiation travels at the same velocity: the speed of light (c), 3.00  108 m/s. Therefore, c =  © 2009, Prentice-Hall, Inc.

6 Example Two electromagnetic waves are represented above. A) Which wave has the higher frequency? B) If one wave represents visable light and the other represents infrared radiation, which wave is which? If one represented blue light, and the other red, which would be which? © 2009, Prentice-Hall, Inc.

7 Example What if wavelength is given in nm? What must we do with the speed of light c? (3.00 x 108 m/s) © 2009, Prentice-Hall, Inc.

8 Pg. 250 Ex. 6.21 A laser pointer used in a lecture hall emits light at 650 nm. What is the frequency of this radiation? Using Figure 6.4 predict the color associated with this wavelength. © 2009, Prentice-Hall, Inc.

9 The Nature of Energy The wave nature of light does not explain how an object can glow when its temperature increases. Max Planck explained it by assuming that energy comes in packets called quanta. © 2009, Prentice-Hall, Inc.

10 The Nature of Energy Einstein used this assumption to explain the photoelectric effect. He concluded that energy is proportional to frequency: E = h where h is Planck’s constant,  10−34 J-s. © 2009, Prentice-Hall, Inc.

11 The Nature of Energy Therefore, if one knows the wavelength of light, one can calculate the energy in one photon, or packet, of that light: c =  E = h © 2009, Prentice-Hall, Inc.

12 Example What is the frequency, the energy of single photon, and the energy of a mole of photons of light having a wavelength of 555nm? © 2009, Prentice-Hall, Inc.

13 The Nature of Energy Another mystery in the early 20th century involved the emission spectra observed from energy emitted by atoms and molecules. © 2009, Prentice-Hall, Inc.

14 The Nature of Energy For atoms and molecules one does not observe a continuous spectrum, as one gets from a white light source. Only a line spectrum of discrete wavelengths is observed. © 2009, Prentice-Hall, Inc.

15 The Nature of Energy Niels Bohr adopted Planck’s assumption and explained these phenomena in this way: Electrons in an atom can only occupy certain orbits (corresponding to certain energies). © 2009, Prentice-Hall, Inc.

16 The Nature of Energy Niels Bohr adopted Planck’s assumption and explained these phenomena in this way: Electrons in permitted orbits have specific, “allowed” energies; these energies will not be radiated from the atom. © 2009, Prentice-Hall, Inc.

17 The Nature of Energy Niels Bohr adopted Planck’s assumption and explained these phenomena in this way: Energy is only absorbed or emitted in such a way as to move an electron from one “allowed” energy state to another; the energy is defined by E = h © 2009, Prentice-Hall, Inc.

18 The Nature of Energy The energy absorbed or emitted from the process of electron promotion or demotion can be calculated by the equation: E = −RH ( ) 1 nf2 ni2 - where RH is the Rydberg constant, 2.18  10−18 J, and ni and nf are the initial and final energy levels of the electron. © 2009, Prentice-Hall, Inc.

19 6.37 Pg. 251 Is energy emitted or absorbed when the following electronic transitions occur in hydrogen? From n=4 to n=2 From an orbit of radius 2.12 Å to one of radius 8.46 Å An electron adds to the H+ ion and ends up in the n=3 shell © 2009, Prentice-Hall, Inc.

20 6.39 Pg. 251 Using Equation 6.5, calculate the energy of an electron in the hydrogen atom when n=2 and when n=6. Calculate the wavelength of the radiation released when an electron moves from n=6 to n=2. b) Is this line in the visible region of the electromagnetic spectrum? If so, what color is it? © 2009, Prentice-Hall, Inc.

21 Aim: What is the uncertainty principle of electrons?
Do Now: How is Energy related to frequency? © 2009, Prentice-Hall, Inc.

22 The Wave Nature of Matter
Louis de Broglie posited that if light can have material properties, matter should exhibit wave properties. He demonstrated that the relationship between mass and wavelength was  = h mv © 2009, Prentice-Hall, Inc.

23 Sample Exercise 6.5 Pg. 224 What is the wavelength of an electron moving with a speed of 5.97 x 106 m/s? The mass of the electron is 9.11 x 10-31kg. © 2009, Prentice-Hall, Inc.

24 The Uncertainty Principle
Heisenberg showed that the more precisely the momentum of a particle is known, the less precisely is its position known: In many cases, our uncertainty of the whereabouts of an electron is greater than the size of the atom itself! (x) (mv)  h 4 © 2009, Prentice-Hall, Inc.

25 Quantum Mechanics Erwin Schrödinger developed a mathematical treatment into which both the wave and particle nature of matter could be incorporated. It is known as quantum mechanics. © 2009, Prentice-Hall, Inc.

26 Quantum Mechanics The wave equation is designated with a lower case Greek psi (). The square of the wave equation, 2, gives a probability density map of where an electron has a certain statistical likelihood of being at any given instant in time. © 2009, Prentice-Hall, Inc.

27 Quantum Numbers Solving the wave equation gives a set of wave functions, or orbitals, and their corresponding energies. Each orbital describes a spatial distribution of electron density. An orbital is described by a set of three quantum numbers. © 2009, Prentice-Hall, Inc.

28 Principal Quantum Number (n)
The principal quantum number, n, describes the energy level on which the orbital resides. The values of n are integers ≥ 1. © 2009, Prentice-Hall, Inc.

29 Angular Momentum Quantum Number (l)
This quantum number defines the shape of the orbital. Allowed values of l are integers ranging from 0 to n − 1. We use letter designations to communicate the different values of l and, therefore, the shapes and types of orbitals. © 2009, Prentice-Hall, Inc.

30 Angular Momentum Quantum Number (l)
Value of l 1 2 3 Type of orbital s p d f © 2009, Prentice-Hall, Inc.

31 Magnetic Quantum Number (ml)
The magnetic quantum number describes the three-dimensional orientation of the orbital. Allowed values of ml are integers ranging from -l to l: −l ≤ ml ≤ l. Therefore, on any given energy level, there can be up to 1 s orbital, 3 p orbitals, 5 d orbitals, 7 f orbitals, etc. © 2009, Prentice-Hall, Inc.

32 Magnetic Quantum Number (ml)
Orbitals with the same value of n form a shell. Different orbital types within a shell are subshells. © 2009, Prentice-Hall, Inc.

33 s Orbitals The value of l for s orbitals is 0.
They are spherical in shape. The radius of the sphere increases with the value of n. © 2009, Prentice-Hall, Inc.

34 s Orbitals Observing a graph of probabilities of finding an electron versus distance from the nucleus, we see that s orbitals possess n−1 nodes, or regions where there is 0 probability of finding an electron. © 2009, Prentice-Hall, Inc.

35 p Orbitals The value of l for p orbitals is 1.
They have two lobes with a node between them. © 2009, Prentice-Hall, Inc.

36 d Orbitals The value of l for a d orbital is 2.
Four of the five d orbitals have 4 lobes; the other resembles a p orbital with a doughnut around the center. © 2009, Prentice-Hall, Inc.

37 Energies of Orbitals For a one-electron hydrogen atom, orbitals on the same energy level have the same energy. That is, they are degenerate. © 2009, Prentice-Hall, Inc.

38 Energies of Orbitals As the number of electrons increases, though, so does the repulsion between them. Therefore, in many-electron atoms, orbitals on the same energy level are no longer degenerate. © 2009, Prentice-Hall, Inc.

39 Spin Quantum Number, ms In the 1920s, it was discovered that two electrons in the same orbital do not have exactly the same energy. The “spin” of an electron describes its magnetic field, which affects its energy. © 2009, Prentice-Hall, Inc.

40 Spin Quantum Number, ms This led to a fourth quantum number, the spin quantum number, ms. The spin quantum number has only 2 allowed values: +1/2 and −1/2. © 2009, Prentice-Hall, Inc.

41 Pauli Exclusion Principle
No two electrons in the same atom can have exactly the same energy. Therefore, no two electrons in the same atom can have identical sets of quantum numbers. © 2009, Prentice-Hall, Inc.

42 Electron Configurations
This shows the distribution of all electrons in an atom. Each component consists of A number denoting the energy level, © 2009, Prentice-Hall, Inc.

43 Electron Configurations
This shows the distribution of all electrons in an atom Each component consists of A number denoting the energy level, A letter denoting the type of orbital, © 2009, Prentice-Hall, Inc.

44 Electron Configurations
This shows the distribution of all electrons in an atom. Each component consists of A number denoting the energy level, A letter denoting the type of orbital, A superscript denoting the number of electrons in those orbitals. © 2009, Prentice-Hall, Inc.

45 Orbital Diagrams Each box in the diagram represents one orbital.
Half-arrows represent the electrons. The direction of the arrow represents the relative spin of the electron. © 2009, Prentice-Hall, Inc.

46 Hund’s Rule “For degenerate orbitals, the lowest energy is attained when the number of electrons with the same spin is maximized.” © 2009, Prentice-Hall, Inc.

47 Periodic Table We fill orbitals in increasing order of energy.
Different blocks on the periodic table (shaded in different colors in this chart) correspond to different types of orbitals. © 2009, Prentice-Hall, Inc.

48 Some Anomalies Some irregularities occur when there are enough electrons to half-fill s and d orbitals on a given row. © 2009, Prentice-Hall, Inc.

49 Some Anomalies For instance, the electron configuration for copper is
[Ar] 4s1 3d5 rather than the expected [Ar] 4s2 3d4. © 2009, Prentice-Hall, Inc.

50 Some Anomalies This occurs because the 4s and 3d orbitals are very close in energy. These anomalies occur in f-block atoms, as well. © 2009, Prentice-Hall, Inc.


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