CHAPTER 5 PERIODICITY AND ATOMIC STRUCTURE
Chapter Learning Goals
A. Electromagnetic Radiation Characterization
1. Interconvert wavelength, frequency, and energy of electromagnetic radiation. 2. Using the BalmerRydberg equation, calculate the wavelength and energy of a photon absorbed or released when an electron changes orbitals. 3. Interconvert the amount of energy associated with a quantum of radiant energy, frequency, and wavelength. 4. Using the de Broglie equation, calculate the mass of an object knowing its wavelength and vice versa.
B. Wave Functions and Quantum Numbers
1. Relate a set of quantum numbers to a particular orbital. 2. Sketch and name each of the s, p, and d orbitals.
C. Electron Configurations 1. State the Pauli Exclusion Principle, Hunds Rule and the Aufbau Principle. 2. Predict groundstate electron configurations for elements; use orbitalfilling diagrams to determine the number of unpaired electrons in these species.
D. Valence Electrons and the Periodic Table
1. Explain what is meant by effective nuclear charge, Zeff. 2. Write the general valenceshell electron configuration for each group of the periodic table, and identify the blocks in which the elements are located. 3. Given a set of atoms, determine which atom is expected to have the largest radius.
Chapter in Brief The periodic table is the most important organizing principle in chemistry. This chapter explains why the elements, when placed in order of increasing atomic weight, have a periodic occurrence of chemical and physical properties. This periodicity can be understood by examining the theory used to describe the electronic structure of atoms. Chapter 5 begins the examination of this theory by introducing electromagnetic radiation and the properties of waves. You will discover how both light and matter can have dual (both wave and particle) properties. With this information, you are introduced to quantum mechanics and quantum numbers, a mathematical theory used to describe the probability of finding an electron in an atom. You are then shown how to use quantum mechanics to determine the electronic configuration of the elements. Finally, you will apply this knowledge to learn how atoms in the same group in the periodic table have similar electronic configurations and how these electronic configurations affects periodic properties such as atomic radii.
Chapter 5Periodicity and Atomic Structure
LECTURE OUTLINE
Development of the Periodic Table A. Creation of the Periodic Table. 1. Ideal example of how scientific theory comes into being. a. random observations b. organization of data in ways that make sense c. consistent hypothesis emerges i. explains known facts ii. makes predictions about unknown phenomena B. Mendeleev's hypothesis about organizing known chemical information. 1. Met criteria for a good hypothesis. a. listed the known elements by atomic weight b. grouped them together according to their chemical reactivity b. was able to predict the properties of unknown elements ekaaluminum, eka silicon Light and the Electromagnetic Spectrum A. Electromagnetic radiation forms of radiant energy (light in all its varied forms). 1. Electromagnetic spectrum a continuous range of wavelengths and frequencies of all forms of electromagnetic radiation.
A.1.
B. Radiant energy has wavelike properties. 1. Frequency () the number of peaks (maxima) that pass by a fixed point per unit time (s or Hz). 2. Wavelength () the length from one wave maximum to the next. 3. Amplitude the height measured from the middle point between peak and trough (maximum and minimum). 2 a. Intensity of radiant energy is proportional to the amplitude . C. Speed of light (c) rate of travel of all electromagnetic radiation in a vacuum. 8 1. c = 3.00 10 m/s. 2. Wavelength Frequency = Speed. 1 (m) (s ) = c (m/s) c c 3. Frequency and wavelength are inversely related: = or = . a. long ; low b. short ; high
1
EXAMPLE: 14 1 Calculate the wavelength, in meters, of radiation with a frequency of 1.18 10 s . What region of the electromagnetic spectrum is this? SOLUTION: We can solve this problem by using the equation = c, where c = 3.00 10 m/s.
8
3.00 108 m/s 1.18 1014 s -1
= 2.54 10 6 m
This particular wavelength is found in the infrared region of the electromagnetic spectrum (see Figure 5.3, page 162 in your textbook.)
Chapter 5Periodicity and Atomic Structure
Electromagnetic Radiation and Atomic Spectra A. Individual atoms give off light when heated or otherwise excited energetically. 1. Provides clue to atomic makeup. 2. Consists of only a few . 3. Line spectrum series of discrete lines (or wavelengths) separated by blank areas. 4. Each element has its own unique line spectrum. B. Balmer discovered a pattern in atomic line spectra for the hydrogen atom. 1. All four lines in the hydrogen spectrum are expressed by
2 1
1 1 1 = R 2 2 . 2 n
a. R (Rydberg constant) = 1.097 10 nm 2. Rydberg every line in the entire hydrogen spectrum fits the generalized BalmerRydberg equation. 1 1 1 = R 2 2 ; ( n > m) m n
A.2.
EXAMPLE: Calculate the wavelength of light emitted when an electron falls from the n = 6 to n = 4 levels in the hydrogen atom. SOLUTION: We solve this problem by using the Rydberg equation. 1 1 1 = 1.097 10 2 nm 1 2 2 = 3.809 10 4 nm 1 4 6
= 2.625 103 nm
Workbook Problem 5.1
Determine the shortest wavelength and the two longest wavelength (in nm) lines in the Brackett series (m = 4) for hydrogen. Strategy: Determine the values of n that will make the longest and shortest. Remember that the value of is greatest when the value of m is smallest and the value is smallest when the value of m is greatest. Also remember that n > m. Step 1: Determine the value of n that will make the shortest. Step 2: Use the BalmerRydberg equation with m = 4 and solve for . Step 3: Solve for using the BalmerRydberg equation and the values of n that make the longest.
What key concept did you use?
Chapter 5Periodicity and Atomic Structure
Particlelike Properties of Electromagnetic Radiation: The Planck Equation A. Blackbody radiation the visible glow that solid objects give off when heated. 1. Intensity does not continue to rise indefinitely as decreases.
A.3.
2. Planck energy radiated by a heated object is quantized. a. radiant energy emitted in discrete units or quanta hc 34 b. E = h ; E = ; h = 6.626 x 10 Js (Planck's constant) c. highenergy radiation higher , shorter d. lowenergy radiation lower , longer EXAMPLE: What energy is emitted in the example on page 3 of these chapter notes ? SOLUTION: We need to use the equation E =
hc to calculate the energy. However, we first need to convert the wavelength we calculated from nanometers to meters, since the units for the speed of light is in m/s. 2.625 103 nm = 2.625 10 6 m 9 1 10 nm 6.626 10 34 J s 3.00 108 m/s E= = 7.573 1020 J 6 2.625 10 m 1m
)(
Workbook Problem 5.2
Determine the energy of the wavelengths calculated in Workbook Problem 5.1 Strategy: Use Plancks equation to solve for the energy.
What key concept did you use?
B. Photoelectric effect irradiating a clean metal surface with light causes electrons to be ejected from the metal. 1. Einstein beam of light behaves as if it were composed of photons (stream of small particles). 2. Energy of photons: E = h . a. energy depends only on frequency of photon b. intensity of light beam measure of number of photons, not energy C. Light energy can behave as both waves and small particles. 1. Both matter and energy occur only in discrete units. D. Atoms emit light quanta (photons) of a few specific energies. 1. Give rise to a line spectrum.
Chapter 5Periodicity and Atomic Structure
Wavelike Properties of Matter: The de Broglie Equation A. Einstein relationship between mass and . E hc/ h m= 2 = 2 = c c c B. de Broglie matter can behave in some respects like light. 1. Both light and matter are wavelike as well as particlelike.
A.4.
2. Relationship between of an electron or of any other particle or object of mass m moving at velocity v. h h m= ; = v mv C. Dual wave/particle description of light and matter is a mathematical model that accounts for atomic properties and behavior. EXAMPLE: -31 What velocity would an electron (mass = 9.11 10 kg) need for its de Broglie wavelength to be 590 nm? SOLUTION: Using the de Broglie equation, we can solve for velocity.
?=
(9.11 10
6.626 10 34 J sec
31
kg 5.90 10
2 2
)(
= 1.23 103
J sec kg m
Substituting 1 (kg m )/s for the unit J gives
kg m 2 s s 1.23 103 = 1.23 103 m/s kg m
Quantum Mechanics and the Heisenberg Uncertainty Principle A. Bohr described the structure of the hydrogen atom as containing an electron circling the nucleus. 1. Specific orbits of the electron correspond to specific energy levels. B. Schrdinger quantum mechanical model of the atom. 1. Abandon idea of an electron as a small particle moving around the nucleus in a defined path. 2. Concentrate on the electrons wavelike properties. C. Heisenberg Uncertainty Principle both the position (x) and the momentum (mv) of an electron cannot be known beyond a certain level of precision. h 1. ( x)( m v) 4 2. Cannot know both the position and the momentum of an electron with a high degree of certainty. 3. If the momentum is known with a high degree of certainty a. mv is small. b. x (position of the electron) is small. 4. If the exact position of the electron is known a. x is small. b. mv is large. 5
Chapter 5Periodicity and Atomic Structure
Wave Functions and Quantum Numbers A. Quantum mechanical model of atomic structure. 1. Mathematical form is a wave equation. 2. Wave function () or orbital solutions to wave equation. a. has a specific energy b. contains information about an electron's position in 3D space c. gives the probability of finding an electron within a given region in space d. defines a volume of space around the nucleus where there is a high probability of finding an electron e. says nothing about the electrons path or movement Wave function contains a set of three variables, quantum numbers. 1. Describes the energy level of an orbital. 2. Defines the shape and orientation of the region in space where the electron is most likely to be found. Principal quantum number (n ) describes the size and energy level of the orbital. 1. A positive integer (n = 1,2,3,4,..). 2. As the value of n increases, a. the number of allowed orbitals increases. b. size of the orbitals increases. c. the energy of the electron in the orbital increases. 3. Shell grouping of orbitals according to the principal quantum number. Angularmomentum quantum number (l) defines the 3D shape of the orbital. 1. Integral value from 0 to n 1. 2. Within each shell, there are n different shapes for orbitals. 3. Subshells grouping of orbitals according to the angularmomentum quantum number. 4. Referred to by letter rather than by number. quantum number l : 0 1 2 3 4 ... subshell notation: s p d f g ... Magnetic quantum number (ml )defines the spatial orientation of the orbital along a standard
2
B.
C.
D.
E.
set of coordinate axes. 1. Integral value from l to +l . 2. Within each subshell (same n and same l ) there are 2l + 1 different spatial orientations. F. Energy level of various orbitals (see Figure 5.9, page 174 in your textbook), 1. Hydrogen energy levels depend only on n . 2. Multielectron atoms energy levels depend on both n and l .
B.1.
EXAMPLE: Give the values of all possible quantum numbers of a 3d subshell. SOLUTION: For a 3d subshell, n = 3, l = 2; and ml = 2, 1, 0, 1, 2.
Workbook Problem 5.3
Determine the subshell for an electron having n = 4, l = 3. Strategy: Determine the subshell associated with a value of l = 3. Step 1: Identify the subshell with the value of n and the letter designation for l = 3. What key concept did you use? 6
Chapter 5Periodicity and Atomic Structure
B.2.
The Shapes of Orbitals A. s orbitals (see Figure 5.10, page 176 in your textbook). 1. Spherical. 2. Probability of finding an electron depends only on the distance of the electron from the nucleus. 3. Differences among s orbitals in different shells. a. Size increases in successively higher shells. b. Electron distribution in outer s orbitals has several different regions of maximum probability separated by a node. 4. Node a surface of zero probability. a. intrinsic property of a wave zero amplitude at node (see Figure 5.11, page 176 in textbook). B. p orbitals (see Figure 5.12, page 177 in your textbook). 1. Dumbbell shaped. 2. Electron distribution concentrated in identical lobes on either side of the nucleus. 3. Nodal plane cuts through the nucleus. a. Probability of finding a p electron near the nucleus is zero. 4. Have different phases (mathematical signs) a. crucial for bonding b. Only lobes with same phase can interact to form covalent bonds. 5. Three p orbitals oriented along the x, y, and z axes. (p x, p y, p z). C. d and f orbitals 1. d orbitals (see Figure 5.13, page 178 in your textbook). a. 4 d xy, d xz, d yz, d x2 y2 are cloverleaf shaped. i. four lobes of maximum electron probability separated by two nodal planes through the nucleus b. d z2 similar in shape to a p z orbital with an additional donutshaped region of electron probability in the xy plane c. Alternating lobes have different phases. 2. f orbitals eight lobes of maximum electron probability. a. three nodal planes through the nucleus Quantum Mechanics and Atomic Spectra A. Electron in an atom. 1. Occupies an orbital. 2. Each orbital has a specific energy. 3. The energies available to electrons are quantized. a. have only the specific energy values associated with the orbital B. Addition of energy to an atom causes 1. An electron to jump from a lowerenergy orbital to a higherenergy orbital. a. The atom becomes excited. 2. Excited atom is unstable. a. Electron returns to a lowerenergy level by emission of amount of energy equal to the energy difference between the higher and lowerenergy orbitals. b. since the energies of the orbitals are quantized, the amount of energy emitted is quantized 3. Calculate energy differences between orbitals by measuring the frequencies emitted. C. BalmerRydberg equation variables m and n corresponds to the principal quantum numbers of the two orbitals involved in the transition. 1. n principal quantum number of the outer shell (orbital the transition is from) 7
Chapter 5Periodicity and Atomic Structure
2. m principal quantum number of the inner shell (orbital the transition is to). Electron Spin and the Pauli Exclusion Principle A. Fourth quantum number ms. 1. Related to a property called electron spin. 2. Behave as if they were spinning around an axis. a. gives rise to a tiny magnetic field 3. Has two values: +1/2 ( ) or 1/2 ( ). 4. Independent of other quantum numbers.
C.1.
B. Pauli Exclusion Principle: No two electrons in an atom can have the same four quantum numbers. 1. Only two electrons with opposite spins per orbital. Orbital Energy Levels in Multielectron Atoms A. Energy level of an orbital in multielectron atoms depends on both n and l.. 1. Energy difference due to electronelectron repulsions. a. Outershell electrons are pushed farther away from the nucleus and are held less tightly. b. partially cancels the electronnucleus attractions c. Electrons are shielded from the nucleus by the other electrons.
D.1.
B. Effective nuclear charge, Zeff net nuclear charge actually felt by an electron. 1. Zeff = Zactual electron shielding. 2. Lower than the actual nuclear charge. 3. For the same shell, the lower value of l corresponds to a higher value of Zeff. a. corresponds to lower energy for the orbital 4. Useful for explaining various chemical phenomena.
C.2.
Electron Configurations of Multielectron Atoms A. Electron configuration describes the orbitals that are occupied by the electrons in an atom. B. Aufbau principle. 1. Fill the lowestenergy orbitals first. 2. Only two electrons with opposite spin per orbital. 3. Follow Hunds rule. a. If two or more orbitals with the same energy are available, put one electron with parallel spin in each until all are half full. C. Groundstate configuration - lowestenergy electron configuration. D. Degenerate orbitals orbitals with the same energy level. E. Orbitalfilling diagrams electrons are represented by arrows. EXAMPLE: Give the electron configuration for phosphorus. SOLUTION: Using the orbitalfilling diagram given in Figure 5.9 on page 174 in the textbook, we find 2 2 6 2 3 that the electron configuration for phosphorus is 1s 2s 2p 3s 3p .
Chapter 5Periodicity and Atomic Structure
EXAMPLE: Give the orbitalfilling diagram for phosphorus. SOLUTION: The orbitalfilling diagram for phosphorus would be: 1s 2s 2p x 2p y 2p z 3s _ 3p x 3p y 3p z
F. Shorthand version give the symbol of the noble gas in the previous row to indicate electrons in filled shells, and then specify only those electrons in unfilled shells. EXAMPLE: Give the shorthand electron configuration for phosphorus. SOLUTION: The shorthand electron configuration for phosphorus would be [Ne] 3s 3p .
2 3
Workbook Problem 5.4
Give the groundstate electronic configuration (both the complete and shorthand version) for vanadium. Give the orbitalfilling, diagram using the shorthand version of the electronic configuration. Strategy: Use Figure 5.9, page 174 in your textbook, to determine the order of the orbitals. Step 1: Determine the number of electrons in vanadium.
Step 2: Use the Aufbau principle to determine the groundstate electronic configuration.
Step 3: Determine the noble gas in the previous row. Specify only those electrons in the unfilled subshells.
Step 4: Draw the orbitalfilling diagram.
What key concept did you use? Electron Configurations and the Periodic Table A. Valenceshell electrons outermost shell of electrons. 1. Elements in each group of the periodic table have similar valenceshell electron configurations. 2. Most loosely held. 3. Determine an elements properties. B. Similar electron configurations explain why the elements in a given group have similar chemical behavior. C. Blocks of elements in the periodic table depends upon the valence orbitals being filled. 1. sblock elements Groups 1A and 2A (filling of an s orbital). 2. p block elements Groups 3A through 8A (filling of p orbitals; ns orbitals are filled). 3. d block elements transition metals (filling of (n 1)d orbitals). 4. fblock elements lanthanide and actinide elements (filling of (n 2) f orbitals). 9
Chapter 5Periodicity and Atomic Structure
EXAMPLE: Give the general electron configuration for the elements in Group 5A. SOLUTION: The elements in group 5A are p block elements. The p orbitals begin filling with the 3A elements; therefore, we know that the group 5A elements contain 3 p electrons. The electron configuration 2 3 for these elements is ns np .
Workbook Problem 5.5
Determine the general electronic configuration for elements in groups 7A and 4B. Strategy: Determine if the elements are sblock, p block, or d block elements. Step 1: Determine if other outer subshells need to be taken into consideration. Step 2: Determine the number of electrons in the outer block. What key concept did you use?
Some Anomalous Electron Configurations A. Halffilled and filled subshells have an unusual stability. 1. Leads to anomalies in electron configurations. B. Anomalies occur where the energy differences between subshells are small. 1. Transfer of an electron from one subshell to another lowers the total energy of the atom. a. due to decrease in electronelectron repulsions b. Z > 40 EXAMPLE: Give the electron configuration of Ag. SOLUTION: Silver is one of the elements that will transfer an electron from one subshell to another in order to lower the total energy of the atom. Therefore, the electron configuration of Ag is 1 10 [Kr]5s 4d .
Electron Configurations and Periodic Properties: Atomic Radii A. Radius of an atom half the distance between the nuclei of two identical atoms when they are covalently bonded together. B. Atomic radius increases down a group. 1. Successively larger valenceshell orbitals are occupied. C. Atomic radius decreases across a period. 1. Due to increase in Zeff for valenceshell electrons across a period. 2. The value of Zeff is dependent upon the amount of shielding felt by an electron. a. Amount of shielding depends on both the shell and subshell of the other electrons. 3. Valenceshell electron a. strongly shielded by electrons in inner shells. b. less strongly shielded by electrons in same shell i. order: s > p > d > f c. weakly shielded by electrons in same subshell. 10
Chapter 5Periodicity and Atomic Structure
Putting It Together The ionization energy is the energy required to remove an electron from a gaseous atom or ion in the groundstate. A particular metal, M, has an ionization energy of 19 7.0924 eV (1 eV = 1.602 10 J). A 0.500 g sample of the metal was oxidized to produce MO. 2+ This oxide was dissolved in hot concentrated hydrochloric acid producing both the M and 3+ 3+ 2+ M ions. The M ion is converted to M according to the reaction M
3+
+ Sn
2+
M
2+
2+
+ Sn
4+
Any excess Sn chloride. Sn
2+
that is left over from this reaction is eliminated by the addition of mercury (II)
+ HgCl2 Hg 2Cl2 + Sn
2+
4+
+ 2 Cl
The solution of M reaction M
2+
ions is then titrated with potassium permanganate according to the
+ MnO4 M
3+
+ Mn .
2+
a. Balance all of the chemical equations. b. 35.7 mL of 0.50 M potassium permanganate were required for the titration. How many moles of M are present, and what is the identity of M? c. Write the groundstate electron configuration for M. d. Determine the wavelength of the ionization energy.
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