Chapter 7: ELECTRONS IN ATOMS AND PERIODIC PROPERTIES Problems: 7.1-7.62, 7.66-7.74, 7.77-7.129, 7.131, 7.133, 7.135-7.138, 7.140-7.142, 7.144, 7.148 ELECTROMAGNETIC RADIATION Electromagnetic (EM) Spectrum: a continuum of the different forms of electromagnetic radiation or radiant energy (Fig. 7.1 on p. 318) – The substances below are about the size of the wavelength indicated in the EM spectrum. – e.g., an atom is about 10-10-10-9 m in size while a CD is about 10-3 m (or 1 mm) thick. visible region: the portion of the EM spectrum that we can perceive as color For example, a "red-hot" or "white-hot" iron bar freshly removed from a high-temperature source has forms of energy in different parts of the EM spectrum – red or white glow = radiation within the visible region – warmth = radiation within the infrared region 7.1 LIGHT WAVES English chemist and physicist Michael Faraday established the basis for electromagnetism, and Scottish scientist James Clerk Maxwell expanded our understanding of electromagnetism, explaining that radiant energy consists of waves with an oscillating electric field and an oscillating magnetic field, which are perpendicular to one another. CHEM 161: Chapter 7 Notes v1214 page 1 of 26 Electromagnetic Radiation – EM waves have the following properties: wavelength and frequency (see Fig. 7.3). wavelength (λ=Greek “lambda”): distance between successive peaks λ= distance ; generally in units of m, cm, or nm cycle frequency (ν=Greek “nu”): number of waves passing a given point in 1 s ν= 1 cycle cycle ; generally in hertz (Hz) = or s time s CHEM 161: Chapter 7 Notes v1214 page 2 of 26 speed of light – The product of wavelength and frequency is equal to the speed of light in a vacuum, c=2.99792458×108 m/s, which is usually rounded to 4 s.f. → c=2.998×108 m/s (to 4 s.f.). c = λ × length length = time cycle ν × cycle time Know how to convert between wavelength and frequency using the speed of light! Ex. 1 The frequency of solar rays ranges from 6.0×1013 Hz to 2.0×1015 Hz, a. What is the corresponding range of wavelengths (in m) for this solar radiation? b. In what part(s) of the EM spectrum does this radiation fall? ____________________ CHEM 161: Chapter 7 Notes v1214 page 3 of 26 Ex. 2 The least expensive type of red laser pointer has a wavelength of about 635 nm. What is the frequency of this light in Hz? THE NATURE OF MATTER CLASSICAL Descriptions of Matter John Dalton (1803) – atoms are hard, indivisible, billiard-like particles – atoms have distinct masses (what distinguishes on type of atom from another) – all atoms of same element are the same JJ Thomson (1890s) – discovered the charge-to-mass ratio of electrons → atoms are divisible because electrons are only one part of the atom Ernest Rutherford (1910) – shot positive alpha particles at a thin foil of gold → discovery of the atomic nucleus James Maxwell (1873), Scottish scientist – all forms of radiant energy consist of electromagnetic waves 7.3 PARTICLES OF LIGHT AND QUANTUM THEORY Transition between Classical and Quantum Theory Max Planck (1900); Blackbody Radiation – heated solids to red or white heat – noted matter did not emit energy in continuous bursts, but in whole-number multiples of certain well-defined quantities → matter absorbs/emits energy in bundles = "quanta" (single bundle of energy= "quantum") Albert Einstein (1905); Photoelectric Effect Photoelectric Effect: Light shining on a clean metal → emission of electrons only – occurs when the light has a minimum threshold frequency (ν ) – When ν < ν → no electrons are emitted – When ν > ν → electrons are emitted, more e– emitted with greater intensity of light – Einstein applied Planck's quantum theory to light → light exists as a stream of "particles" called photons. 0 0 0 CHEM 161: Chapter 7 Notes v1214 page 4 of 26 Energy is proportional to the frequency (ν) and wavelength (λ) of radiation, and the proportionality constant (h) is now called Planck's constant where h = 6.626×10–34 J·s Ex. 1. Green laser pointers emit light strongly at a wavelength of 532 nm. a. What is the energy (in J) for one photon of this light? b. What is the energy (in kJ/mol) for a mole of photons of this light? The Photoelectric Effect When ν < ν → no electrons are emitted 0 CHEM 161: Chapter 7 Notes v1214 When ν > ν → electrons are emitted and 0 page 5 of 26 The Photoelectric Effect and Work Function (Φ ) of a Metal – The work function of a metal (symbolized using the Greek letter Phi, Φ) is the minimum amount of energy required to emit an electron from the surface of a metal. Φ = hν Work function: where 0 h = 6.626×10–34 J·s Ex. 2 a. The work function for lithium is 4.65×10-19 J. Calculate the longest wavelength (in nm) of light that can cause an electron to be ejected from a lithium atom. b. Use the visible spectrum below to determine the color of the light. c. If excess energy absorbed by an emitted electron is converted into kinetic energy, calculate the velocity of an electron ejected from a lithium atom after it absorbs violet light with a wavelength of 402 nm. (K.E. = ½ mv2 and melectron=9.109×10-31 kg) CHEM 161: Chapter 7 Notes v1214 page 6 of 26 7.2 ATOMIC SPECTRA 7.4 THE HYDROGEN SPECTRUM AND THE BOHR MODEL Emission Spectra: continuous or line spectra of radiation emitted by substances – a heated solid (e.g. the filament in an incandescent light bulb) emits light that spreads out to give a continuous spectrum = spectrum of all wavelengths of light, like a rainbow Hydrogen Line Spectrum – In contrast, when a sample of hydrogen is electrified, the resulting hydrogen emission spectrum contains only a few discrete lines: These discrete lines correspond to specific wavelengths → specific energies → The hydrogen atoms’ electrons can only emit certain energies → The energy of the electrons in the atom must also be quantized. – Thus, Planck’s postulate that energy is quantized applies to the electrons within an atom as well. – Each element has a unique line spectrum → emission spectra can be used to identify unknown elements in chemical analysis → the element’s line spectrum is often called its "atomic fingerprint" CHEM 161: Chapter 7 Notes v1214 page 7 of 26 THE BOHR MODEL (Fabric of the Cosmos video: t=6:45) A Danish physicist named Niels Bohr used the results from the hydrogen emission spectrum to develop a quantum model for the hydrogen atom. Bohr Postulates: Bohr Model of the Atom 1. Energy-level Postulate – An electron in a hydrogen atom may only exist in discrete (quantized), circular orbits around the nucleus – "tennis ball and stairs" analogy for electrons and energy levels – a ball can bounce up to or drop from one stair to another, but it can never sit halfway between two levels – Each orbit has a specific energy associated with it, indicated as n=1, 2, 3,... – ground state or ground level (n = 1): lowest energy state for a one-electron atom – when the one electron is in the lowest energy orbit – excited state: when the electron is in a higher energy orbit (n = 2,3,4,...) 2. Transitions Between Energy Levels – When the atom absorbs energy, the electron can jump from a lower energy orbit to a higher energy orbit. – When an electron drops from a higher energy level to a lower energy level, the atom releases energy, sometimes in the form of visible light. – Note also that as n increases, the difference in energy between levels decreases. → Higher energy levels are closer to one another than the lower energy levels. CHEM 161: Chapter 7 Notes v1214 page 8 of 26 The energy absorbed or emitted by an electron when it moves from one energy level to another can be determined using the following formula: where nfinal and ninitial are the electron’s final and initial energy levels (or orbits) ⎛ 1 1 ⎞ ΔE = −2.178×10-18 J ⎜⎜ 2 − 2 ⎟⎟ ⎝ n final ninitial ⎠ Sign conventions: E > 0 when an atom gains energy; E < 0 when an atom loses energy. Ex. 1: Calculate the energy emitted by an electron when it drops from energy level 5 down to energy level 2. (Remember to indicate the correct sign for energy lost or gained.) Ex. 2: Calculate the wavelength (in nm) corresponding to the energy determined in Ex. 1, and indicate the color of the light emitted using the visible spectrum on page 6. wavelength = __________________ color = _______________________ Quantum Mechanical Model In 1920s, a new discipline, quantum mechanics, was developed to describe the motion of submicroscopic particles confined to tiny regions of space. – Quantum mechanics makes no attempt to specify the position of a submicroscopic particle at a given instant or to explain how the particle got there. – It only gives the probability of finding submicroscopic particles. – Just like video footage of a location (e.g. food court at the mall) may allow you to predict where people are likely to be but not the exact location for one person at a future time → Instead we “take a snapshot” of the atom at different times and determine where its electrons are likely to be found (See Fig. 7.24 on p. 343). → View Fabric of the Cosmos (Double-Slit Experiment): t=12:05 Werner Heisenberg (1927); Heisenberg Uncertainty Principle – For very small particles (e.g. an electron), it is impossible to know precisely the particle’s position and its momentum (= mass×velocity). → We cannot know the exact motion of an electron as it moves around the nucleus. – Heisenberg’s Uncertainty Principle is expressed mathematically as h 4π Δx · mΔv ≥ CHEM 161: Chapter 7 Notes v1214 where Δx=uncertainty in position, mΔv=uncertainty in momentum, page 9 of 26 and h is P Example: a. Calculate the uncertainly in position for a baseball given the baseball’s mass of 0.143 kg and an uncertainty in velocity of 0.45 m/s (~1 mph), then compare to the size of the baseball (diameter≈0.08 m). b. Calculate the uncertainly in position for an electron (mass=9.1095 ×10–31 kg) with the same uncertainty in velocity of 0.45 m/s, then compare to the size of the electron (diameter≈10-15 m). Thus, the Uncertainty Principle is only relevant for very small particles, like an electron. 7.5 ELECTRON WAVES Dual Nature of the Electron Louis de Broglie (1924) – If light can behave like a wave and a particle → matter (like an electron) can behave like waves. – If the electron behaves like a circular wave oscillating around the nucleus → an electron can only have specific wavelengths to form a continuous wave. → other wavelengths would cancel one another and not form a continuous wave. Topview of a standing wave Sideview of linear and circular standing waves (Images from http://dev.physicslab.org/Document.aspx?doctype=3&filename=AtomicNuclear_deBroglieMatterWaves.xml) CHEM 161: Chapter 7 Notes v1214 page 10 of 26 If an electron can only have specific wavelengths → that electron can only have specific corresponding frequencies and energies. Thus, setting the following equations equal to one another, for matter: E = mc2 for wave: E = hc λ and changing the c to any velocity, v, gives the de Broglie relation: λ= h mv This is used to determine the wavelength of any matter given its velocity and mass. Ex. 1 a. A baseball with mass 0.143 kg is thrown at a velocity of 42 m/s (~95 mph); calculate the wavelength (in m) associated with the baseball’s motion. b. How does the baseball’s λ compare in size to the baseball (diameter≈0.08 m)? Ex. 2 a. Calculate the wavelength (in m) of an electron also traveling at 42 m/s. (The mass of the electron is 9.1095 ×10–31 kg.) b. How does the electron’s λ compare in size to the electron (diameter ≈ 10–15 m)? Thus, although all matter can have wave properties, such properties are only significant for submicroscopic particles. The wavelength in these very small particles is about the same size or much larger than the particle, so the wave properties affect the behavior of the particle. CHEM 161: Chapter 7 Notes v1214 page 11 of 26 Limitations of the Bohr Model → Quantum Mechanical Model – Unfortunately, the Bohr Model failed for every other element with more than one proton or electron. (The multiple electron-nuclear attractions, electron-electron repulsions, and nuclear-nuclear repulsions make other atoms much more complicated than hydrogen.) → Most of the energy levels split into sublevels labeled s, p, d, and f. ORBITAL ENERGY LEVELS Orbital energy levels in the hydrogen atom 3s ___ 3p ___ ___ ___ 3d ___ ___ ___ ___ ___ Energy 2s ___ 2p ___ ___ ___ 1s ___ Note that for hydrogen, all of the orbitals within the same principal quantum number, n, have the same energy (are degenerate). In polyelectronic atoms, the presence of more than one electron causes electron-electron repulsions that result in a change in the energies of the various sublevels within the atom. Orbital energy levels in polyelectronic atoms (every atom but hydrogen) 3d ___ ___ ___ ___ ___ 3p ___ ___ ___ 3s ___ Energy 2p ___ ___ ___ 2s ___ 1s ___ Note that for in polyelectronic atoms (containing more than one electron), only the orbitals within the same sublevel are degenerate. CHEM 161: Chapter 7 Notes v1214 page 12 of 26 7.6 QUANTUM NUMBERS AND ELECTRON SPIN Erwin Schrödinger (1926) – developed a differential equation to find the electron's wave function (ψ), and the square of the wave function (ψ ) indicates the probability of finding the electron near a given point – probability density for an electron is called the "electron cloud" or orbital → each atomic orbital has a distinct “shape” – Each orbital is identified by a set of three integers called quantum numbers. 2 Quantum Numbers, Energy Levels, and Orbitals – FOUR quantum numbers describe the distribution and behavior of electrons in atoms. – Each wave function (ψ) corresponds to a set of 3 quantum numbers and refers to a specific atomic orbital. First (or Principal) Quantum Number (n): n=1,2,3,... – relates the average distance of the electron from the nucleus – The higher n is, the farther the electron is from the nucleus and the higher in energy (less stable) the orbital Second (or Angular Momentum) Quantum Number (ℓ ): ℓ =0,…, n-1 → Sublevels (s, p, d, f): gives "shape" of the electron clouds associated with each orbital – The limitations on n and ℓ → for n=1, ℓ =0 → the 1s sublevel → for n=4, ℓ =0 → the 4s sublevel n=4, ℓ =1 → the 4p sublevel → for n=2, ℓ =0 → the 2s sublevel n=4, ℓ =2 → the 4d sublevel n=2, ℓ =1 → the 2p sublevel n=4, ℓ =3 → the 4f sublevel → for n=3, ℓ =0 → the 3s sublevel n=3, ℓ =1 → the 3p sublevel n=3, ℓ =2 → the 3d sublevel Third (or Magnetic) Quantum Number (mℓ ): mℓ = -ℓ ,…,0,…,ℓ → indicates the number of orbitals in each sublevel → ℓ =0 (s orbital): → mℓ=0 → only one type of s orbital → ℓ =1 (p orbitals): → mℓ=-1, 0, 1 → 3 types of p orbitals: px, py, pz → ℓ =2 (d orbitals): → mℓ=-2, -1, 0, 1, 2 → 5 types of d orbitals: dxy, dyz, dxz, d z2 , dx2 − y2 → ℓ =3 (f orbitals): → mℓ=-3, -2, -1, 0, 1, 2, 3 → 7 types of f orbitals Fourth (or Electron Spin) Quantum Number (ms): ms= +½ and -½ – This will be discussed in more detail later in the chapter. Ex. 1: What are valid values for ℓ when n=4? ______________________________ CHEM 161: Chapter 7 Notes v1214 page 13 of 26 Ex. 2: What are valid values for mℓ when n=5 and ℓ =2? ______________________________ Ex. 3: Fill in the missing set(s) of quantum numbers given the quantum numbers provided: a. If n=2 and ℓ= 1, mℓ can be____________ given that ms= +½. b. If n=3, ℓ can be ____________ given that mℓ=+2 and ms= +½. c. If n=4, ℓ can be ____________ given that mℓ=-2 and ms can be ____________. Note that quantum numbers allow us to determine the number of each type of orbital in each principal energy level (n value) and sublevel (ℓ value). 7.7 THE SIZES AND SHAPES OF ATOMIC ORBITALS The images below are boundary surface representations within which there’s a 90% probability of finding the electron in a given orbital. – These representations show the relative size, shape, and orientation of the various orbitals. s orbitals: spherical (see Fig. 7.24 on p. 343) – size of the orbitals increase with n – since number of protons, neutron, and electrons increase with n Boundary surface representations of the 1s, 2s, and 3s orbitals showing the increase in size with n value. A cross section of the hydrogen 1s orbital probability distribution divided into thin spherical shells. p orbitals: dumbbell-shaped (see Fig. 7.26 on p. 345) – 3 types: px, py, pz (where x, y, and z indicates axis on which orbital aligns) – Figure (a) below shows the probability distribution for a pz orbital. – Figure (b) below shows the boundary surface representations of the p orbitals. CHEM 161: Chapter 7 Notes v1214 page 14 of 26 d orbitals: boundary surface representations of the d orbitals (see Fig. 7.27 on p. 345) – 5 types: dxy, dxz, dyz,, d x2 −y2 , dz2 f orbitals: You won’t be tested on f orbitals. Be able to identify a p or d orbital given its image. CHEM 161: Chapter 7 Notes v1214 page 15 of 26 The interesting part... – Consider the figure at the right showing the electron distribution for the 2px orbital. – Note that there is a “node” (zero probability) at and near the origin, so the electron is never there. → How can the electron be present in either of the two lobes without going through the origin? 7.8 THE PERIODIC TABLE AND FILLING THE ORBITALS OF MULTIELECTRON ATOMS Electron Configuration: Shorthand description of the arrangement of electrons by sublevel according to increasing energy Aufbau (Building-Up) Principle – Electrons are distributed in orbitals of increasing energy, where the lowest energy orbitals are filled first. – Once an orbital has the maximum number of electrons it can hold, it is considered “filled.” – Remaining electrons must then be placed into the next highest energy orbital, and so on. – Parking garage analogy Orbitals in order of increasing energy: 1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s < 5d < 6p REMEMBER! Each orbital can hold 2 electrons. – Each s orbital can hold 2 electrons. – A set of three p orbitals can hold 6 electrons. – A set of five d orbitals can hold 10 electrons. – A set of seven f orbitals can hold 14 electrons. Ex. 1 Li → atomic number=3 → 3 eelectron configuration for Li: ____________________________ Ex. 2 electron configuration for S: ___________________________________________ Ex. 3 electron configuration for Co: __________________________________________ CHEM 161: Chapter 7 Notes v1214 page 16 of 26 Electron configurations of atoms with many electrons can become cumbersome. → Abbreviated electron configurations (“noble-gas core” notation): – Since noble gases are at the end of each row in the Periodic Table, all of their electrons are in filled orbitals. – Such electrons are called “core” electrons since they are more stable (less reactive) when they belong to completely filled orbitals. valence electrons: electrons that are in the outermost shell (unfilled orbitals) Noble gas electron configurations are used to abbreviate the “core” electrons of all elements. [He] = 1s2 [Ne] = 1s2 2s2 2p6 [Ar] = 1s2 2s2 2p6 3s2 3p6 [Kr] [Xe] = 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 = 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 Writing Electron Configurations Using the Periodic Table – The Periodic Table's shape actually corresponds to the filling of energy sublevels. – See Fig. 7.32 (p. 350), to see how electrons for each element are distributed into the energy sublevels. CHEM 161: Chapter 7 Notes v1214 page 17 of 26 Example: Write the electron configurations for the following using Noble Gas core notation: [Co] = 1s2 2s2 2p6 3s2 3p6 4s2 3d7 = __________________________________________________________ [Cd] = 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 = __________________________________________________________ [Ni] = __________________________________________________________ [I] = __________________________________________________________ Exceptions to the Aufbau (Building-Up) Principle (for Cr, Mo, W, Cu, and Ag) Atoms gain extra stability with half-filled or completely filled d subshells. → If we can fill or half-fill a d subshell by promoting an electron from an s orbital to a d orbital, we do so to gain the extra stability. Example: Write the electron configurations for the following using Noble Gas core notation: Transition Metal expected electron configuration actual electron configuration chromium copper silver The Fourth (or Electron Spin) Quantum Number (ms = +½ or -½ ), indicates if the electron in a specific orbital (indicated by the first 3 quantum #’s) is spin ↑ or spin ↓. In 1925, two graduate students in the Netherlands, Goudsmit and Uhlenbeck, found two additional electron energy states not accounted for by Schrödinger’s equations. → Electrons have a quantum mechanical property called spin, with two orientations: spin ↑ or ↓. – Two other scientists, Otto Stern and Walther Gerlach, observed experimental evidence of spin when they shot a beam of Ag atoms through a non-uniform magnetic field, and the field split in two. CHEM 161: Chapter 7 Notes v1214 page 18 of 26 ATOMIC ORBITAL DIAGRAMS electron configuration: shorthand description of an atom’s electrons among sublevels atomic orbital diagram: shows the energy sublevels within an atom and the arrangement and spin (↑ or ↓) of electrons within each orbital in the sublevels Pauli Exclusion Principle: no 2 e-s in an atom can have same four quantum #s → Two electrons in the same orbital must have opposite spins – For example, with the helium atom, there are three ways to represent two electrons in 1s orbital (where spin is represented with the electron pointing up or down): for He: (a) (b) (c) ↑↑ 1s ↓↓ 1s ↑↓ 1s – but the Pauli exclusion principle rules out (a) and (b) since these show two electrons in the same orbital with the same spin. Hund's Rule: the most stable arrangement of electrons in subshells has the greatest number of parallel spins – i.e., distribute electrons with same spin (up or down) and do not pair electrons until each orbital in the subshell has an electron For example, if carbon’s electron configuration is: 1s2 2s2 2p2 → carbon’s orbital diagram can be shown with the sublevels further from the nucleus having higher energy and the electrons within each orbital: ↑↓ 2p ↑↓ (a) 2s ↑↓ 1s ↑ Energy (b) 2p ↑↓ 2s ↑↓ ↓ 1s ↑ 2p ↑↓ (c) ↑ 2s ↑↓ 1s – but using Hund's rule, we know (c) would be the most stable. CHEM 161: Chapter 7 Notes v1214 page 19 of 26 General Rules for Assigning Electrons in Atomic Orbital Diagrams 1. First, determine the electron configuration. 2. There is only one s orbital for each level: one 1s, one 2s, one 3s, etc. – There are 3 p orbitals for each p sublevel. – There are 5 d orbitals for each d sublevel. 3. Each orbital can only hold 2 electrons → Each s orbital can hold 2 e–, the 3 p orbitals can hold 6 e–, the 5 d orbitals can hold 10 e–. 4. Electrons in the same orbital must have opposite spins. 5. To fill sublevels, put one electron in each orbital (with same spin) before pairing. 6. Finally, write the quantum numbers for the outermost electrons in the atom. Orbital energy levels in atoms with more than one electron (every atom but hydrogen) 3d ___ ___ ___ ___ ___ 3p ___ ___ ___ 3s ___ Energy 2p ___ ___ ___ 2s ___ 1s ___ Ex. 1 Use full notation to write the electron configuration then draw the atomic orbital diagram for fluorine, then indicate the set of quantum numbers for each electron. Ex. 2 Use core notation to write the electron configuration, then draw the atomic orbital diagram for the valence electrons in phosphorus (electrons in the outermost shell) and indicate the quantum numbers for each valence electron. CHEM 161: Chapter 7 Notes v1214 page 20 of 26 Ex. 3 Use core notation to write the electron configuration, then draw the atomic orbital diagram for the valence electrons in cobalt (electrons in the outermost shell) then indicate the quantum numbers for the valence electrons in the highest energy orbitals. 7.9 ELECTRON CONFIGURATIONS OF IONS Ions of the Main Group (Representative) Elements – Representative elements generally form ions—ie. gain or lose electrons—to achieve a noble gas electron configuration → Ions from representative metals are usually isoelectronic with—i.e. have the same electron configuration as—one of the noble gases! Electron Configurations of Cations and Anions For IONS, one must account for the loss or gain of electrons: # electrons = atomic # – (charge = change in # of valence electrons) Or you can simply use the Periodic Table – Find out with which element the ion is isoelectronic – Move to the left for electrons lost or to the right for electrons gained → write the electron configuration for that element Example 1: Fill in the blanks for the following ions: Ion Isoelectronic with what element? Electron Config. using core notation Ion Na+ I– P–3 Ba+2 Al+3 Ti+4 CHEM 161: Chapter 7 Notes v1214 Isoelectronic with what element? Electron Config. using core notation page 21 of 26 Cations from Transition Metals, Sn, Pb – Transition metals lose s electrons before the d electrons when forming cations Atom Electron Configuration using core notation Electron Configuration using core notation Ion Zn Zn+2 Sn Sn+4 Cu Cu+ Cd Cd+2 Ex. Write the electron configurations for the following: Fe atom: _________________ Fe+2 ion: _______________ Fe+3 ion: _______________ Example: Given the electron configurations of Fe+2 and Fe+3, predict which ion is more stable, and explain your choice. 7.10 THE SIZES OF ATOMS AND IONS Atomic Radius (or Size): distance from the nucleus to the outermost electrons CHEM 161: Chapter 7 Notes v1214 page 22 of 26 Periodic Trend for Atomic Radius ATOMIC RADIUS – Increases down a group: More p+, n, and e– → bigger radius – Decreases from left to right along a period: – Electrons that lie between the nucleus and the outermost electrons shield or screen the outermost electrons, preventing them from experiencing the full charge of the nucleus. → Effective nuclear charge (Zeff) can be approximated by the following: Zeff = # of protons – # of core electrons – Number of p+ and e– increases, but electrons go into same subshell, and other valence electrons cannot shield each other from the attractive force of the nucleus. – The higher the effective nuclear charge (Zeff) → smaller radius Compare atoms of aluminum and chlorine: Trend from top to bottom → like a snowman Trend from left to right → like a snowman that fell to the right IONIC RADIUS: distance from the nucleus to the outermost electrons in an ion – An atom loses electrons to form a cation. → A cation has a smaller radius than its corresponding atom. – An atom gains electrons to form an anion. → An anion has a larger radius than its corresponding atom. 11 p+ 11 e– loses 1 e– Na atom 11 p+ 10 e– 17 p+ 17 e– Na+ ion Cl atom 17 p+ 18 e– gains 1 e– Cl– ion Example: Order the following in terms of increasing ionic radius: I , F , Cl , P , S . − − − 3− 2− _______ < _______ < _______ < _______ < _______ smallest radius CHEM 161: Chapter 7 Notes v1214 largest radius page 23 of 26 7.11 IONIZATION ENERGIES (IE) First Ionization Energy: Energy necessary to remove the first electron from a neutral atom in gaseous state to form the positively charged ion. → X+(g) + e X(g) − Consider the following ionization energies for magnesium: → Mg+(g) + e Mg+(g) → Mg2+(g) + e Mg(g) IE1 = 738 kJ/mol − IE2 = 1451 kJ/mol − Thus, to completely ionize a magnesium atom requires the following: Mg(g) kJ/mol → Mg2+(g) + 2 e total IE = 738 + 1451 − = 2189 kJ/mol Consider the following first ionization energies for various elements: Periodic Trend for First Ionization Energy – Decreases down a group: – The bigger the atom, the farther away electrons are from the positively charged nucleus. → Valence electrons are less strongly attracted and are more easily removed. – Increases from left to right along a period: – Effective nuclear charge increases from left to right across the periodic table. → As the attraction between a valence electron and the nucleus increases, more energy is required to remove a valence electron from the neutral atom. CHEM 161: Chapter 7 Notes v1214 page 24 of 26 Variations in Successive Ionization Energies (IE) – Recognize that it becomes more difficult to remove electrons from stable ions, so ionization energies increase with an increasing number of electrons removed. We can indicate first and successive ionization energies in the following way: First ionization energy = IE1 Second ionization energy = IE2 Third ionization energy = IE3 Consider the following ionization energies for aluminum: Al(g) → Al+(g) + e Al+(g) → Al2+(g) + e Al2+(g) → Al3+(g) + e Al3+(g) → Al4+(g) + e − − − − IE1 = 580 kJ/mol IE2 = 1815 kJ/mol IE3 = 2740 kJ/mol IE4 = 11,600 kJ/mol – Note the large jump between the 3rd and 4th IE’s for aluminum. – Note that removing an electron from an Al3+ ion requires much more energy than removing an electron from a neutral Al atom or the previous ions formed. – Note that Al3+ is a stable ion (with a positive charge AND a noble gas electron configuration), so an enormous amount of energy is required to remove an electron from a stable ion and make it unstable. Consider these Ionization Energies (in kJ/mol): Note that for the elements included in the table above that the largest jump in ionization energies occurs when an electron is being removed from a stable ion with a Noble gas electron configuration. CHEM 161: Chapter 7 Notes v1214 page 25 of 26 Ex. 1: Between which two ionization energies (e.g. IE1 & IE2, IE2 & IE3, etc.) would you expect there to be the largest jump for the following? a. Ba: Between _____ and _____ b. Ti: Between _____ and _____ Ex. 2: This 2nd period element has a large jump between IE5 and IE6: _____ 7.12 ELECTRON AFFINITIES electron affinity (EA): energy associated with 1 mole of gaseous atoms to gain 1 mole of electrons X(g) + e– → X–(g) – A quantitative measure of an atom’s ability to accept an electron – The more negative an atom’s electron affinity → the more likely an atom can gain an electron – Consider the electron affinities shown below. – Fluorine has the most negative electron affinity, but notice there is no clear trend for electron affinity, like there is with electronegativity or atomic radius. Example: Explain the difference between electronegativity and electron affinity. CHEM 161: Chapter 7 Notes v1214 page 26 of 26