# Chemistry, The Central Science, 11th edition Theodore L. Brown; H. Eugene LeMay, Jr.; and Bruce E.

Bursten

Chapter 4 Electronic Structure of Atoms
John D. Bookstaver St. Charles Community College Cottleville, MO

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 ().

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. – Wavelength: It is the distance between two consecutive peaks or troughs in a wave. – Frequency: It indicates how many waves pass a given point per second. – Speed: It indicates how fast a given peak is moving through the space. – Speed of light ,c= ,where =wave length and  =frequency

EMR
Electromagnetic Radiation: Electromagnetic radiation is one of the ways in which energy travels through space. All forms of EMR compose the electromagnetic radiation spectrum, which includes sun rays, microwaves, Xrays, visible spectrum, UV rays and IR rays.
• Some characteristics of EMR are: • All electromagnetic radiation moves at a constant speed of about 3.0 X 108 m/s. • All EMR exhibit wave like behavior. Waves have three primary characteristics:
– Wavelength: It is the distance between two consecutive peaks or troughs in a wave. – Frequency: It indicates how many waves pass a given point per second. – Speed: It indicates how fast a given peak is moving through the space. – Speed of light ,c= ,where =wave length and  =frequency

• All electromagnetic radiation travels at the same velocity: the speed of light (c), 3.00  108 m/s. • Therefore, c = 

(visible spectrum Roy G. Make a list of type of EMR you might see in your home. • What will happen if you change the red light in the dark room for photo processing with the yellow light and why? .Refer to the following EMR spectrum. BiV) • Imagine you have invented a machine that allows you to see all types of EMR.

html .acoustics.mind.salford.uk/feschools/waves/diffract3.net/~zona/mstm/physics/waves/interference/waveInterference1/WaveIn terference1.Wave Nature of Light • Before the concept of quantization of energy. Animation Diffraction: http://www. the wave like nature of light/energy was widely accepted.htm Animation for Interference: http://id. • Two properties that exhibit the wave like behavior of light are interference and diffraction.ac.

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

he introduced the concept of quantization of energy. E= hv.) So. but is done in small packets of energy called by him as quantum. Planck suggested that the energy transfer or exchange is not a continuous process.(Word quantum means fixed amount. the wave model of the light was widely accepted. • According to Planck’s theory. But it was unable to explain some phenomenon for example change in the radiation (wave length) emitted by an object with the change in temperature. where E= energy of radiation h= Planck’s constant v= frequency of radiation . • To explain this.Planck’s Theory of Quantization of Energy • Planck’s theory: Before Planck’s theory.

Quantization of Energy: Max Plank • www • Where else do you see quantization in real life? • www.physics.usceud .

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

6. Inc. © 2009.The Nature of Energy • Einstein used this assumption to explain the photoelectric effect. .626  10−34 J-s. • He concluded that energy is proportional to frequency: E = h where h is Planck’s constant. Prentice-Hall.

upscale. The photoelectric effect led scientists to think about the dual nature of light i. But the wave theory of light could not explain it. as a wave and a particle both.edu/chemistry-pankuch/Photoelectric/PE3. when the light shines on the metal.html .Photoelectric Effect: It refers to the emission of electrons from a metal. Animation 1: http://www.ca/GeneralInterest/Harrison/Flash/Nuclear/XRayIntera ct/XRayInteract. For each metal the frequency of light needed to release the electrons is different.e.ucc.html Animation 2: http://faculty.utoronto.

s wf .http://www. Einstein said electromagnetic radiation has a dual wave. • 1905.nobel.particle nature.astronomy.edu/%7Echm_tgc/sounds/flashfiles/pee.nz/events/monthly_meetings/Reviews/2001/gigant4. jpg • Photoelectric Effect Max Planck suggested that the hot object emits energy in small. http://www.gif http://www.se/physics/educational/tools/quantum/w-pimages/wp. specific amounts called quanta.shsu.tpub.gif http://www.com/doenuclearphys/nuclear%20physics%20and%20reactor%20theory_files/image003.org.

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.

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

utk.phys.utk.Continuous and Line Spectra (Absorption and Emission Spectrum.phys.com/imgres?imgurl=http://csep10.gif&imgrefurl=http://csep10.html&h=240&w=450&sz=33&hl=en&start=2&tbnid=TaN57QO8MhMG4M:&tbnh=66&tbnw=124&prev=/images%3Fq%3Dabsorption%2Band%2Bemission%2Bspectr um%26svnum%3D10%26hl%3Den%26lr%3D%26sa%3DN) .Line Spectra) (http://images.google.edu/astr162/lect/light/spectra.edu/astr162/lect/light/a bsorption.

. •The lowest possible energy state of an atom is called the ‘ground state’. Ex. A beam of red light has a lower energy photons than beam of blue light.Bohr Model Of the Hydrogen Atom • Ephoton=hv The energy levels of Hydrogen ( As explained by Bohr’s Model) : •An excited atom can release some or all of its excess energy by emitting a photon. •Different wavelengths of light carry different amount of energy per photon. thus moving to a lower energy state.

Animation : http://pokok.edu/~chuck/PRENHALL/Chapter%2031/AABXTEJ0.The Nature of Energy • Niels Bohr adopted Planck’s assumption and explained these phenomena in this way: 1.net/~chemistry/AL2. Prentice-Hall.gac. Inc. .htm#Animation Animation: http://physics. Electrons in an atom can only occupy certain orbits (corresponding to certain energies).mysch.html © 2009.

© 2009. these energies will not be radiated from the atom.The Nature of Energy • Niels Bohr adopted Planck’s assumption and explained these phenomena in this way: 2. Inc. Electrons in permitted orbits have specific. “allowed” energies. Prentice-Hall. .

Inc. Prentice-Hall. Energy is only absorbed or emitted in such a way as to move an electron from one “allowed” energy state to another.The Nature of Energy • Niels Bohr adopted Planck’s assumption and explained these phenomena in this way: 3. . the energy is defined by E = h © 2009.

edu/~rhangart/courses/b373/lecturenotes/photomorph/sinewave.gif .626 x 10-34J s) •  is frequency • E=h(c/ ) • http://sunflower.bio.com/light/s3.Light Equations • • • • c=   c is the speed of light (3. or nm)  represents the frequency (waves/s or hertz) http://www.astronomynot es.0 x 108 m/s) lambda is the wave length (in m.indiana.htm • E=h  • E is energy (in joules) • h is Planck’s Constant (h= 6. cm.

Heisenberg Uncertainty Principle: States that it is impossible to determine simultaneously both the position and velocity of an electron or any other particle.http://hackensackhigh. . • Dual Wave-Particle nature by De Broglie • Quantum Theory: Describes mathematically the wave properties of electrons or other very small particles treating e as waves and using Heisenberg’s and De Broglie’s principles.org/~rkc2/diffraction.jpg • .

The energy of electrons in atoms is quantized. 3.cartage. The region in which an electron with a specific energy will most probably be located is called an atomic orbital. 4.htm-) 1.Quantum Mechanical Model of Atom (Schrodinger’s Model) Erwin Schrödinger. . Electrons of different energies are likely to be found in different regions. The position and momentum of an electron cannot both be determined simultaneously. The important consequences of the quantum-mechanical view of atoms are the following: (http://www. in developing a quantum-mechanical model for the atom. The number of possible energy levels for electrons in atoms of different elements is a direct consequence of wave-like properties of electrons. began with a classical equation for the properties of waves. 2. The region in space around the nucleus in which an electron is most probably located is what can be predicted for each electron in an atom.org.lb/en/themes/sciences/chemistry/Generalchemistry/Atomic/Electronicstructure/Electronicstructures/Quantum/Quantum. He modified this equation to take into account the mass of a particle and the de Broglie relationship between mass and wavelength.

. Prentice-Hall. Inc.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.

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

© 2009. • Each orbital describes a spatial distribution of electron density. Inc. use(http://www. each corresponding to a property of atomic orbital. The fourth quantum number was later introduced to clarify the spin of electrons. Prentice-Hall.google.Quantum Numbers • Schrodinger arrived at three functions while solving the wave equation for electrons and came up with three quantum numbers. • An orbital is described by a set of three quantum numbers. .com/search?hl=en&q=wave+mechanical+model) • Solving the wave equation gives a set of wave functions. or orbitals. and their corresponding energies.

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

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

. Inc. Prentice-Hall.Angular Momentum Quantum Number (l) Value of l Type of orbital 0 s 1 p 2 d 3 f © 2009.

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

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

Orbitals and Electron Capacity of the First Four Principle Energy Levels Maximum Principle Number of Number of Type of number of energy level orbitals per orbitals per sublevel electrons (n) type level(n2) (2n2) 1 2 s s p s 3 p d s 4 p d f 1 1 3 1 3 5 1 3 5 7 16 32 9 18 1 4 2 8 .

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

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. © 2009. Prentice-Hall. or regions where there is 0 probability of finding an electron. Inc.

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

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

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

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

Aufbau’s Principle • Orbitals with lowest energy are filled first .

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

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

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

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

– A letter denoting the type of orbital. Animation: http://intro. Prentice-Hall.html © 2009.edu/WorkshopFolder/Electronconfnew.chem. .okstate. Inc.Electron Configurations • This shows the distribution of all electrons in an atom • Each component consists of – A number denoting the energy level.

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

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

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

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

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

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

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

• Angular Momentum Quantum Number: (l) Indicates the shape of the orbital. -1/2) Indicates the two fundamental spin states of an electron in an orbital . • Magnetic Quantum Number: (m) Indicates the orientation of an orbital around the nucleus. • Spin Quantum Number: (+1/2.Quantum Number Terms • Ground State: Lowest energy state of an atom • Excited State: A state in which an atom has a higher potential energy then it has in its ground state • Orbital: A 3D region around the nucleus that indicates the probable location of an electron • Quantum Numbers: Specify the properties of atomic orbitals and the properties of electrons in orbitals • Principle Quantum Number: (n) Indicates the main energy level occupied by the electron.

http://www. • Pauli’s Exclusion Principle: No two electrons in the same atom can have the same set of four quantum numbers.gif Electron Configuration Theories • Aufbau’s Principle: An electron occupies the lowest-energy orbital that can receive it.com/Quick_atom/hund.tannerm. . and all electrons in singly occupied orbitals must have the same spin. • Hund’s Rule: Orbitals of equal energy are each occupied by one electron before any orbital is occupied by a second electron.

Zinc ion and Cu ion.Ways to Represent Electron Configuration 1.Orbital Notation 4. .Electron Dot Structure Write the above four electron configurations for Zinc.Expanded Electron Configuration 2.Noble gas notation 3.