3TermsWavelength () is the distance from crest to crest or trough to trough on a wave.The frequency () of a wave expresses the number times a wave passes a given point in some unit of time.Amplitude of a wave is the height of the crest or depth of the trough with respect to the center line of the wave.
4Visible light is a small portion of the entire spectrum of EM radiation Increasing Energy and Frequency(decreasing wavelength)
7Electromagnetic Radiation The mathematical relationship between wavelength and frequency for EM radiation is:c = l۰nc = 2.998E8 m/s (speed of light in a vacuum)l = wavelength (in meters) (Greek letter, lambda)n = frequency (in Hertz or s-1) (Greek letter, nu)
8Electromagnetic Radiation Using the mathematical relationship between wavelength and frequency:c = lnCalculate the wavelength associated with Montana Tech’s student radio station, KMSM-FM which broadcasts at a frequency of MHz.
10What is the frequency of light, in hertz, if it has a wavelength of 1 What is the frequency of light, in hertz, if it has a wavelength of 1.05 x 10-7 m and is traveling in vacuum? What portion of the electromagnetic spectrum does this “light” belong to?Electromagnetic radiation slows down as it travels through matter. What fraction and percentage of “c” is the velocity of 475 nm light, if its frequency is 6.00 x 1014 Hz?
11Behavior of WavesWaves refract or bend when they pass from one medium to another with different densities.Diffraction is the bending of electromagnetic radiation as it passes around the edge of an object or through narrow openings.Interference is the interaction of waves that results in either reinforcing their amplitudes or canceling them out.
12RefractionRefraction – the change in direction of a beam of Electromagnetic Radiation (light) as it passes from one medium into another.
16Missing lines of light (dark lines) are found in solar spectra Missing lines of light (dark lines) are found in solar spectra. In distant stars these lines are shifted towards longer wavelengths (red shift). These red shifts are caused by the “Doppler effect”.What other places in your regular life to do find examples of the Doppler effect?
17Fraunhofer Lines (dark) in the Solar Spectrum Shifts to lower energies (red-shift) of these lines suggested to Hubble et al. that more distance galaxies were moving away more rapidly. This would be the expected result assuming the universe began with a Big Bang
18Redshift calculations Using wavelength = v/cUsing frequency = v/c’ represents the longer wavelength and ’ represents the lower frequency
19Try this example problem: A spectral line for atomic hydrogen (H) is known to occur at 485 nm. Studying the stars in a distant galaxy, it is noted that the spectral line now appears at 558 nm ( a shift to longer wavelength). At what percentage of “c” is the galaxy moving away from earth? What is the velocity of the galaxy relative to earth?
22Types of SpectraAtomic emission spectra consist of bright lines on a dark background.Atomic absorption spectra consist of characteristic series of dark lines produced when free gaseous atoms are illuminated by external sources of radiation.
24Absorption SpectraHow do the spectra change in going from H to Ne? Why?
25Black Body Radiation and the end of classical physics…the UV catastrophe.
26Quantum TheoryFrom work on BB radiation, Max Planck proposed that light can have both wavelike and particle-like properties.A quantum is the smallest discrete quantity of a particular form of energy.Particles of radiant energy are known as Photon.Quantum theory is based on the idea that energy is absorbed and emitted in discrete quanta…at least in small (nm) spaces.
27Quantum TheorySomething that is quantized has values that are restricted to whole-number multiples of a specific base value.The energy of a quantum of radiation is:E = h where h is Planck’s constanth = x J•sOr E = hc/
28Particle Nature of Light Each packet of electromagnetic radiation energy is called a quantum.Einstein called the packets photons. A mole of photons is called an Einstein.
29What is the wavelength of a photon, in vacuum, with an energy of 1.25 x J? What portion of the electromagnetic spectrum does this photon belong to?E = hn = hc/ll = hc/E = (6.626E-34 J s)(2.998E8 m/s)/(1.25E-20 J)l = 1.59E-5 m
31Planck and Einstein (1929) in happier days. Plank was among the few that recognized the significance of Special Relativity. But did not accept that the “quantum” was a real phenomenon.
32A new scientific truth does not triumph by convincing its opponents and making them see the light, but rather because its opponents eventually die, and a new generation grows up that is familiar with it.Max Planck
33Photoelectric EffectThe photoelectric effect is the release of electrons from a metal as a result of electromagnetic radiation.The photoelectric effect can be explained if the electromagnetic radiation is treat as being composed of tiny particles (wave packets) called photons.
34Only electrons with sufficient energy will displace electrons Only electrons with sufficient energy will displace electrons. This energy (or threshold frequency) is known as the Work Function (F)
35F = hn0 = Ebound electronThe work function depends on the type of metal. If the element surface is irradiated with light of frequency greater than the threshold, the excess energy appears in the kinetic energy of the electron.KEelectron = hn – hn0 = hv - F
37ProblemWhen light of frequency 1.30E15 s-1 shines on the surface of cesium metal, electrons are ejected with a maximum kinetic energy of5.2E-19J.Calculate the wavelength of this light.b) Calculate the work function for cesium.c) Calculate the longest wavelength of light that will displace electrons.
42The Hydrogen SpectrumJohannes Rydberg revised Balmer’s equation to describe the complete hydrogen spectrum.N1 is a whole number that remains fixed for a series of calculations in which n2 is also a whole number with values of n1+1, n1+2,… for successive line in the spectrum.
43ProblemWhat is the wavelength of the line in the visible spectrum corresponding to n1 = 2 and n2 = 4?1/l = 1.097E-2 nm-1(1/22 – 1/42)= 1.097E-2 nm-1(3/16)= 2.057E-3 nm-1l = 486 nm
44The Bohr Model for Electrons in the Hydrogen Atom The electron in a hydrogen atom occupies a discrete energy level and may exist only in the available energy levels.The electron may move between energy levels by either absorbing or emitting specific amounts of energy.Each energy level is designated by a specific value for n, called the principal quantum number.
45The Bohr model of the hydrogen atom places electrons in concentric orbits with certain “allowed” orbital energies for the electrons in the field of the nucleus (~Ze).Z is the atomic number, and e is the fundamental charge (1.6E-19 C)
47Energy of Electronic Transitions Neil Bohr derived the following formula for the energy levels of hydrogen-like orbitalsEn = - Z2e4m8e0n2h2Z is the atomic number, is the vacuum electric permittivitym and e is the mass and charge of the electron.
48Hydrogen SpectrumAn energy level is an allowed state that an electron can occupy in an atom.Movements of electrons between energy levels are called electronic transitions.
49Mathematically in the Bohr model, the energy of each orbital is: En = (- 2.18E-18J) (1/n2)Where n= 1, 2, 3,…∞The constant in the equation equals: RhcWhere R = E7 m-1 (Rydberg constant)Note that the orbital energies are mathematically all negative (< 0) in energy ( corresponding to bound electronic states)
50The Bohr model of the hydrogen atom places electrons in concentric orbits with certain “allowed” orbital energies for the electrons in the field of the nucleus (~Ze).Note pattern of orbital spacings…
54Electronic StatesThe lowest energy level (n) available to an electron in an atom is its ground state.An excited state of an electron in an atom (or molecule) is any energy state above the ground state.
55Particle or Waves?If electromagnetic radiation behaves as a particle, de Broglie reasoned, why couldn’t a particle in motion, such as an electron, behave as a wave?de Broglie’s Equation = h/mu (m in kg and u in m/s)
59Wave EquationsWave equation for a standing wave:L = nl/2The wave equation for electrons is called the Schrödinger EquationĤY = EYWhere Y(psi) is a wave function, and Ĥ is the Hamiltonian operator:Ĥ = -iħ (t)
60Wave equations describe a “quantized” electron (sec 3.5 & 3.6) Mathematical equations known as wave equations are use to describe probabilities of finding electrons around the nucleus.The wave equations for electrons yield three quantum numbers (n, l, ml) that define the energy, shape, and orientation for the electron orbitals.A fourth quantum number (ms) gives the quantized (relativistic) spin of an electron in an orbital.
61l (ang. momentum) positive less than n 0, 1,..(n-1) Quantum Numbers (QN)QN Restrictions Rangen (principal) positive integers 1, 2, …, l (ang. momentum) positive less than n 0, 1,..(n-1)ml (magnetic) integers between –l and ls (spin) half-integers –½, ½ ; –½, ½
62Possible sets of quantum number for n = 1, 2, 3 As n increases the possible number of orbitals increases by n2. Only two electrons can occupy a single orbital, thus there are 2n2 electrons per n-shell
68ProblemFor the following sets of quantum numbers, determine which describe actual orbits, and list why others are non-existent.n l ml s(a)(b) ½(c) ½(d) ½
69Shape and Sizes of Orbitals Psi squared, 2, defines the probability of an electron in some region of space around the nucleus .A radial distribution plot is a graphical representation of the probability of finding an electron in a thin spherical layer near the nucleus of an atom.
70The shape of an atomic orbital is determine by “l” the angular momentum quantum number node+-l=1; p-orbitall=2; d-orbitall=0; s-orbital
71Probability Electron Density for 1s (l=0) Orbital
72rmp r90 Electron density in the 1s orbital of the hydrogen atom The probability of the electron density is a function of the square of the wave-function (Y2)
76Assigning Quantum Number for Electrons Pauli’s exclusion principle - no two electrons in an atom may have the same set of four quantum numbers.An orbital can only hold two electrons and they must have opposite spins.
78Aufbau PrincipleAs protons are added one by one to the nucleus to build up the elements, electrons are similarly added to these hydrogen-like orbitals.
79Orbital Energy Levels for Hydrogen-Like Atoms 3p3d2s2p1s
80Many Electron AtomsThe presence of more than one electron in an atom effect the relative orbital energies which only depend on n in the one-electron orbital (hydrogen-like atom).In the many electron atom, orbital energies depend on both n and l (n+l rule).In general, for a given value of n, the lower the value of l, the lower in energy the orbital subshell (4s < 3d
81The effective nuclear charge (Zeff) felt by the 2s electron in lithium is less than the effective nuclear charge in hydrogen or helium.The presence of electron density in the 1s orbital “screens” the outer electron in the 2s orbital from the nuclear charge. This results a lowering in the outer shell. orbital energy
82Orbital Energies in Multi-electron Atoms Note the spacing of the orbitals and that the ordering of the energies depends on n + l.
83The 2s orbital is lower in energy than the 2p orbital because there is some 2s density closer to the nucleus
84TerminologyOrbitals that have the exact same energy level are said to be degenerate (e.g 2px and 2py).Core electrons are those in the filled, inner shells in an atom and are not involved in chemical reactions.Valence electrons are those in the outermost shell of an atom and have the most influence on the atom’s chemical reactivity.
85Electron Configuration 1s s pH: 1s1He: 1s2Li: 1s22s1Be: 1s22s2B: 1s22s22p1
86Orbital diagrams and electron configurations describe how the electrons fill orbitals Hund’s rules state that the lowest energy electron configuration will have a maximum in unpaired electrons. Note the filling of the 2p orbitals in C, O and N.
87Electron Configuration 1s s pC: 1s22s22p2orC: 1s22s22p2Hund’s Rule tells us which configuration is correct.
88Hund’s RuleThe lowest energy configuration for an atom is the one having the maximum number of unpaired electrons allowed by the Pauli principle in a particular set of degenerate orbitals.
89Electron Configuration 1s s pC: 1s22s22p2N: 1s22s22p3O: 1s22s22p4F: 1s22s22p5Ne: 1s22s22p6
90Electron Configurations of the Fourth Period K 1s22s22p63s23p64s or [Ar]4s14sCa 1s22s22p63s23p64s or [Ar]4s2Sc 1s22s22p63s23p64s23d or [Ar]4s23d1Ti 1s22s22p63s23p64s23d or [Ar]4s23d2V 1s22s22p63s23p64s23d or [Ar]4s23d33dCr 1s22s22p63s23p64s13d or [Ar]4s13d5Mn 1s22s22p63s23p64s23d or [Ar]4s23d5•Cu 1s22s22p63s23p64s13d or [Ar]4s13d10
91Anomalies in Configurations Chromium and Copper do not follow the pattern of the other elements.You should remember these two families, because other elements in these families exhibit the same types of configurationsYou can use the Periodic Table to guide you in writing electron configurations.
92The energies of orbitals in multi-electron atoms are different than for hydrogen due to electron-electron interactions (repulsion and exchange).
93The organization of the periodic table is based on the chemical properties of the elements which is determined by their electron configurations.nZeff
94Mendeleev’s Periodic Table organized elements according to their chemical combining properties.
95Electron Configurations of Ions Start with the configuration for the neutral atom, then add or remove electrons from the valence shells to make the desired ion.Atoms or ions that are isoelectronic with each other have identical numbers and configurations of electrons.
96Write the electron configurations for the following: a) Cb) Sd) Tie) Ti4+
97How many unpaired electrons are in the following ScAg+Cd2+
100Orbital Penetration and Effective Nuclear Charge Orbital penetration occurs when an electron in an outer orbital has some probability of being close to the nucleusPenetration ability follows this order: s > p > d > f.Effective nuclear charge (Zeff) is the attractive force toward the nucleus experienced by an electron in an atom.
108The Uncertainty Principle Quantum mechanics allows us to predict the probabilities of where we can find an electron.We cannot map out on the path an electron travels.The Heisenberg’s uncertainty principle says that you cannot determine the position and momentum of an electron at the same time.
110ChemTour: Electromagnetic Radiation Click to launch animationPC | MacThis ChemTour explores the relationship of frequency, wavelength, and energy using animations, interactive graphs, and equations. The quantitative exercises include graph reading and calculations using Planck’s constant and the speed of light.
111ChemTour: Light Diffraction Click to launch animationPC | MacThis animation recreates Thomas Young’s double-slit experiment and demonstrates how constructive and destructive interference occur.
112ChemTour: Doppler Effect Click to launch animationPC | MacA boat moving with or against the direction of wave movement demonstrates the motion-induced shifts in wavelengths and frequency that are examples of the Doppler effect.
113ChemTour: Light Emission and Absorption Click to launch animationPC | MacThis ChemTour examines the emission and absorption spectra for sodium and hydrogen and relates them to energy level transitions.
114ChemTour: Bohr Model of the Atom Click to launch animationPC | MacThis ChemTour explores the idea that energies of electrons surrounding atomic nuclei are quantized. In Practice Exercises, students learn to calculate the energies of specific states of hydrogen, and the energies involved in electronic transitions.
115ChemTour: de Broglie Wavelength Click to launch animationPC | MacIn this ChemTour, students learn to apply the de Broglie equation to calculate the wavelength of moving objects ranging from baseballs to electrons. Includes Practice Exercises.
116ChemTour: Quantum Numbers Click to launch animationPC | MacIn this ChemTour, students explore the rules for designating quantum numbers. Includes Practice Exercises.
117ChemTour: Electron Configuration Click to launch animationPC | MacThis ChemTour explains how electrons are distributed within atomic orbitals. Students learn how to determine an element’s electron configuration and learn how to complete an orbital box diagram. Includes practice exercises.
119Please consider the following arguments for each answer and vote again: A green photon can only be produced by the combination of two other green photons of the same wavelength.The color green is the result of combining the colors blue and yellow, just as a green photon will result from the combination of blue and yellow photons.Only two infrared photons have the proper total energy needed to form a green photon.Answer: BCombining Two Photons
121Absorption and Fluorescence of Light Please consider the following arguments for each answer and vote again:The wavelength is inversely proportional to the energy, so for energy to be conserved the absorbed photon must have a wavelength of 400 nm.The wavelength of the absorbed photon is the difference of the wavelength of the two emitted photons, which is 600 nm. For the energy to be conserved, the sum of the wavelengths must be conserved. So the wavelength of the absorbed photon is 1800 nm.Answer: AAbsorption and Fluorescence of Light
123Two-Slit Diffraction and Interferometry Please consider the following arguments for each answer and vote again:The wavelength of blue light is shorter than that of green light, so constructive and destructive interference occurs at smaller intervals.The interference pattern is dependent only on the width of and distance between the two slits. Therefore, the interference pattern should not change.Blue light is higher in energy than green light and therefore would be less affected by the two slits.Answer: ATwo-Slit Diffraction and Interferometry
125Photoelectric effect: Red and Yellow Light Please consider the following arguments for each answer and vote again:Photons of yellow light possess more energy than photons of red light, so a yellow photon also must eject an electron.Each metal has a specific wavelength of light that will cause electrons to be ejected. If red light has the correct wavelength, yellow cannot.Whether a yellow photon will eject an electron from the metal will depend on how tightly the electron is bound to the metal.Answer: APhotoelectric effect: Red and Yellow Light
127Photoelectric effect: Blue and Green Light Please consider the following arguments for each answer and vote again:So long as enough photons of light hit the metal, an electron will always be ejected, regardless of the wavelength of the light.The energy of a blue photon is higher than the energy of a green photon so an electron removed with blue light will not be removed with green light.Whether a green photon will eject an electron from the metal will depend on how tightly the electron is bound to the metal.Answer: CPhotoelectric effect: Blue and Green Light
129Photoelectric Effect: Kinetic Energies of Electrons Please consider the following arguments for each answer and vote again:To eject an electron with twice the kinetic energy, twice the energy must be provided by the photon, so the photon wavelength must be halved.A photon with a wavelength of 200 nm will overcome the work function and provide twice the kinetic energy.To double the kinetic energy of the ejected electron, the wavelength of the impacting photon also must be doubled.Answer: BPhotoelectric Effect: Kinetic Energies of Electrons
131De Broglie Wavelengths of H2O Molecules Please consider the following arguments for each answer and vote again:The kinetic energy of the deuterium molecule is twice that of the hydrogen molecule. Therefore, the deuterium molecule will have a shorter de Broglie wavelength.Because the speed of the hydrogen molecule is greater than the speed of the deuterium molecule, the de Broglie wavelength of the hydrogen molecule will be shorter.The hydrogen molecule and the deuterium molecule have the same momentum and therefore will have the same de Broglie wavelength.Answer: CDe Broglie Wavelengths of H2O Molecules
133Laser Cooling of Sodium Atoms Please consider the following arguments for each answer and vote again:A photon travels ~105 times faster than a sodium atom. Therefore, only one photon is required.The kinetic energy of a sodium atom is ~100 times less than the kinetic energy of a red photon.The de Broglie wavelength of a sodium atom at 60 K is ~104 times shorter than the wavelength of a red photon, so it will take 104 photons to stop a single sodium atom.Answer: CLaser Cooling of Sodium Atoms
135Transmission of Light through a Color Filter Please consider the following arguments for each answer and vote again:The filter absorbs no yellow light, so the object will appear yellow.Blue light is absorbed by the filter, so an object seen through the filter will appear blue.No yellow light is absorbed by the filter, so the object will appear black.Answer: ATransmission of Light through a Color Filter
137Consider the following arguments for each answer and vote again: The photon wavelength depends only on the energy of the lowest state, so only 1 wavelength is possible.There are 2 possible transitions—one from each of the 2 upper levels. Thus, 2 wavelengths of light are emitted.The 3 energy levels lead to 2 high-energy transitions and 1 low-energy transition. Therefore, 3 different photon wavelengths are possible.Answer: CEmission Spectra
139Consider the following arguments for each answer and vote again: The arrangement of the energy levels reflects the arrangement of the lines in the emission spectrum.This energy level diagram allows only 1 low-energy transition, consistent with the emission spectrum.Only this energy level diagram allows 3 high-energy transitions and 1 low-energy transition.Answer: CEnergy Levels
141Consider the following arguments for each answer and vote again: He+ has the same electron configuration as H; therefore, the energy level diagram will be the same.The atomic number of He+ is twice that of H. Therefore, to produce the same energy splitting, the energy levels must be twice that of H.The energy of the electron is proportional to Z2, which is 4 for He+. Therefore, the two levels, 4 and 2, must be increased by a factor of 4 to 16 and 8, respectively.Answer: BTransition in H and He+
143Electron Configurations Consider the following arguments for each answer and vote again:The answer must be lithium because it is the first element in row 2 to possess only one unpaired electron.Beryllium in its ground state has the electron configuration 1s22s2, so Be- in its ground state will have the configuration 1s22s22p1.In its ground state, boron has the electron configuration 1s22s22p1, so B+ must also have this configuration.Answer: BElectron Configurations
145Consider the following arguments for each answer and vote again: Hydrogen has a lower nuclear charge than helium, so it always has a lower ionization energy than any helium atom or ion.He(1s13p1) has almost the same ionization energy as H(3p1), which has a lower ionization energy than either H(1s1) or He+(4p1).Because the electron in He+(4p1) is in the fourth shell, the ionization energy of He+(4p1) is the lowest.Answer: BIonization Energies
147Ionization Energies of He(1s2) Consider the following arguments for each answer and vote again:It is harder to remove an electron from a doubly occupied orbital than from a singly occupied orbital.Each electron offsets the charge of one of the protons, giving an effective nuclear charge of zero.Each electron partially shields the other, leading to an effective nuclear charge that is between 1 and 2.Answer: CIonization Energies of He(1s2)
149Consider the following arguments for each answer and vote again: K+ has the highest nuclear charge and so has the smallest atomic radius.Because it is a noble gas, Ar has the smallest atomic radius.Cl- has the nucleus with the lowest mass, so it has the smallest atomic radius.Answer: AAtomic and Ionic Radii
151Electron Affinity of Halogen Atoms Consider the following arguments for each answer and vote again:Chlorine has the greatest affinity for electrons and so would release the most energy when an electron is added.Electron donation is most favorable energetically when it occurs between atoms on the same row of the periodic table.Because of its massive nuclear charge and large electron cloud, an iodine atom can most easily accept an additional electron.Answer: AElectron Affinity of Halogen Atoms