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Introductory Chemistry - 1st Canadian Edition: Organization of Electrons in Atoms

Introductory Chemistry - 1st Canadian Edition
Organization of Electrons in Atoms
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table of contents
  1. Cover
  2. Title Page
  3. Copyright
  4. Table Of Contents
  5. Acknowledgments
  6. Dedication
  7. About BCcampus Open Education
  8. Chapter 1. What is Chemistry
    1. Some Basic Definitions
    2. Chemistry as a Science
  9. Chapter 2. Measurements
    1. Expressing Numbers
    2. Significant Figures
    3. Converting Units
    4. Other Units: Temperature and Density
    5. Expressing Units
    6. End-of-Chapter Material
  10. Chapter 3. Atoms, Molecules, and Ions
    1. Acids
    2. Ions and Ionic Compounds
    3. Masses of Atoms and Molecules
    4. Molecules and Chemical Nomenclature
    5. Atomic Theory
    6. End-of-Chapter Material
  11. Chapter 4. Chemical Reactions and Equations
    1. The Chemical Equation
    2. Types of Chemical Reactions: Single- and Double-Displacement Reactions
    3. Ionic Equations: A Closer Look
    4. Composition, Decomposition, and Combustion Reactions
    5. Oxidation-Reduction Reactions
    6. Neutralization Reactions
    7. End-of-Chapter Material
  12. Chapter 5. Stoichiometry and the Mole
    1. Stoichiometry
    2. The Mole
    3. Mole-Mass and Mass-Mass Calculations
    4. Limiting Reagents
    5. The Mole in Chemical Reactions
    6. Yields
    7. End-of-Chapter Material
  13. Chapter 6. Gases
    1. Pressure
    2. Gas Laws
    3. Other Gas Laws
    4. The Ideal Gas Law and Some Applications
    5. Gas Mixtures
    6. Kinetic Molecular Theory of Gases
    7. Molecular Effusion and Diffusion
    8. Real Gases
    9. End-of-Chapter Material
  14. Chapter 7. Energy and Chemistry
    1. Formation Reactions
    2. Energy
    3. Stoichiometry Calculations Using Enthalpy
    4. Enthalpy and Chemical Reactions
    5. Work and Heat
    6. Hess’s Law
    7. End-of-Chapter Material
  15. Chapter 8. Electronic Structure
    1. Light
    2. Quantum Numbers for Electrons
    3. Organization of Electrons in Atoms
    4. Electronic Structure and the Periodic Table
    5. Periodic Trends
    6. End-of-Chapter Material
  16. Chapter 9. Chemical Bonds
    1. Lewis Electron Dot Diagrams
    2. Electron Transfer: Ionic Bonds
    3. Covalent Bonds
    4. Other Aspects of Covalent Bonds
    5. Violations of the Octet Rule
    6. Molecular Shapes and Polarity
    7. Valence Bond Theory and Hybrid Orbitals
    8. Molecular Orbitals
    9. End-of-Chapter Material
  17. Chapter 10. Solids and Liquids
    1. Properties of Liquids
    2. Solids
    3. Phase Transitions: Melting, Boiling, and Subliming
    4. Intermolecular Forces
    5. End-of-Chapter Material
  18. Chapter 11. Solutions
    1. Colligative Properties of Solutions
    2. Concentrations as Conversion Factors
    3. Quantitative Units of Concentration
    4. Colligative Properties of Ionic Solutes
    5. Some Definitions
    6. Dilutions and Concentrations
    7. End-of-Chapter Material
  19. Chapter 12. Acids and Bases
    1. Acid-Base Titrations
    2. Strong and Weak Acids and Bases and Their Salts
    3. Brønsted-Lowry Acids and Bases
    4. Arrhenius Acids and Bases
    5. Autoionization of Water
    6. Buffers
    7. The pH Scale
    8. End-of-Chapter Material
  20. Chapter 13. Chemical Equilibrium
    1. Chemical Equilibrium
    2. The Equilibrium Constant
    3. Shifting Equilibria: Le Chatelier’s Principle
    4. Calculating Equilibrium Constant Values
    5. Some Special Types of Equilibria
    6. End-of-Chapter Material
  21. Chapter 14. Oxidation and Reduction
    1. Oxidation-Reduction Reactions
    2. Balancing Redox Reactions
    3. Applications of Redox Reactions: Voltaic Cells
    4. Electrolysis
    5. End-of-Chapter Material
  22. Chapter 15. Nuclear Chemistry
    1. Units of Radioactivity
    2. Uses of Radioactive Isotopes
    3. Half-Life
    4. Radioactivity
    5. Nuclear Energy
    6. End-of-Chapter Material
  23. Chapter 16. Organic Chemistry
    1. Hydrocarbons
    2. Branched Hydrocarbons
    3. Alkyl Halides and Alcohols
    4. Other Oxygen-Containing Functional Groups
    5. Other Functional Groups
    6. Polymers
    7. End-of-Chapter Material
  24. Chapter 17. Kinetics
    1. Factors that Affect the Rate of Reactions
    2. Reaction Rates
    3. Rate Laws
    4. Concentration–Time Relationships: Integrated Rate Laws
    5. Activation Energy and the Arrhenius Equation
    6. Reaction Mechanisms
    7. Catalysis
    8. End-of-Chapter Material
  25. Chapter 18. Chemical Thermodynamics
    1. Spontaneous Change
    2. Entropy and the Second Law of Thermodynamics
    3. Measuring Entropy and Entropy Changes
    4. Gibbs Free Energy
    5. Spontaneity: Free Energy and Temperature
    6. Free Energy under Nonstandard Conditions
    7. End-of-Chapter Material
  26. Appendix A: Periodic Table of the Elements
  27. Appendix B: Selected Acid Dissociation Constants at 25°C
  28. Appendix C: Solubility Constants for Compounds at 25°C
  29. Appendix D: Standard Thermodynamic Quantities for Chemical Substances at 25°C
  30. Appendix E: Standard Reduction Potentials by Value
  31. Glossary
  32. About the Authors
  33. Versioning History

Organization of Electrons in Atoms

Learning Objectives

  1. Learn how electrons are organized in atoms.
  2. Represent the organization of electrons by an electron configuration.

Now that you know that electrons have quantum numbers, how are they arranged in atoms? The key to understanding electronic arrangement is summarized in the Pauli exclusion principle: no two electrons in an atom can have the same set of four quantum numbers. This dramatically limits the number of electrons that can exist in a shell or a subshell.

Electrons are typically organized around an atom by starting at the lowest possible quantum numbers first, which are the shells–subshells with lower energies. Consider H, an atom with a single electron only. Under normal conditions, the single electron would go into the n = 1 shell, which has only a single s subshell with one orbital (because mℓ can equal only 0). The convention is to label the shell–subshell combination with the number of the shell and the letter that represents the subshell. Thus, the electron goes in the 1s shell–subshell combination. It is usually not necessary to specify the mℓ or ms quantum numbers, but for the H atom, the electron has mℓ = 0 (the only possible value) and an ms of either +½ or −½.

The He atom has two electrons. The second electron can also go into the 1s shell–subshell combination but only if its spin quantum number is different from the first electron’s spin quantum number. Thus, the sets of quantum numbers for the two electrons are {1, 0, 0, +½} and {1, 0, 0, −½}. Notice that the overall set is different for the two electrons, as required by the Pauli exclusion principle.

The next atom is Li, with three electrons. However, now the Pauli exclusion principle implies that we cannot put that electron in the 1s shell–subshell because no matter how we try, this third electron would have the same set of four quantum numbers as one of the first two electrons. So this third electron must be assigned to a different shell–subshell combination. However, the n = 1 shell doesn’t have another subshell; it is restricted to having just ℓ = 0, or an s subshell. Therefore, this third electron has to be assigned to the n = 2 shell, which has an s (ℓ = 0) subshell and a p (ℓ = 1) subshell. Again, we usually start with the lowest quantum number, so this third electron is assigned to the 2s shell–subshell combination of quantum numbers.

The Pauli exclusion principle has the net effect of limiting the number of electrons that can be assigned a shell–subshell combination of quantum numbers. For example, in any s subshell, no matter what the shell number, there can be a maximum of only two electrons. Once the s subshell is filled up, any additional electrons must go to another subshell in the shell (if it exists) or to higher-numbered shell. A similar analysis shows that a p subshell can hold a maximum of six electrons. A d subshell can hold a maximum of 10 electrons, while an f subshell can have a maximum of 14 electrons. By limiting subshells to these maxima, we can distribute the available electrons to their shells and subshells.

Example 8.4

Problem

How would the six electrons for C be assigned to the n and ℓ quantum numbers?

Solution

The first two electrons go into the 1s shell–subshell combination. Two additional electrons can go into the 2s shell–subshell, but now this subshell is filled with the maximum number of electrons. The n = 2 shell also has a p subshell, so the remaining two electrons can go into the 2p subshell. The 2p subshell is not completely filled because it can hold a maximum of six electrons.

Test Yourself

How would the 11 electrons for Na be assigned to the n and ℓ quantum numbers?

Answer

Two 1s electrons, two 2s electrons, six 2p electrons, and one 3s electron.

Now that we see how electrons are partitioned among the shells and subshells, we need a more concise way of communicating this partitioning. Chemists use an electron configuration to represent the organization of electrons in shells and subshells in an atom. An electron configuration simply lists the shell and subshell labels, with a right superscript giving the number of electrons in that subshell. The shells and subshells are listed in the order of filling.

For example, an H atom has a single electron in the 1s subshell. Its electron configuration is:

\ce{H}\text{: }1s

He has two electrons in the 1s subshell. Its electron configuration is:

\ce{He}\text{: }1s^2

The three electrons for Li are arranged in the 1s subshell (two electrons) and the 2s subshell (one electron). The electron configuration of Li is:

\ce{Li}\text{: }1s^22s^1

Be has four electrons, two in the 1s subshell and two in the 2s subshell. Its electron configuration is:

\ce{Be}\text{: }1s^22s^2

Now that the 2s subshell is filled, electrons in larger atoms must go into the 2p subshell, which can hold a maximum of six electrons. The next six elements progressively fill up the 2p subshell:

\begin{array}{rl} \ce{B}\text{:}&1s^22s^22p^1 \\ \ce{C}\text{:}&1s^22s^22p^2 \\ \ce{N}\text{:}&1s^22s^22p^3 \\ \ce{O}\text{:}&1s^22s^22p^4 \\ \ce{F}\text{:}&1s^22s^22p^5 \\ \ce{Ne}\text{:}&1s^22s^22p^6 \end{array}

Now that the 2p subshell is filled (all possible subshells in the n = 2 shell), the next electron for the next-larger atom must go into the n = 3 shell, s subshell.

Example 8.5

Problem

What is the electron configuration for Na, which has 11 electrons?

Solution

The first two electrons occupy the 1s subshell. The next two occupy the 2s subshell, while the next six electrons occupy the 2p subshell. This gives us 10 electrons so far, with 1 electron left. This last electron goes into the n = 3 shell, s subshell. Thus, the electron configuration of Na is 1s22s22p63s1.

Test Yourself

What is the electron configuration for Mg, which has 12 electrons?

Answer

1s22s22p63s2

For larger atoms, the electron arrangement becomes more complicated. This is because after the 3p subshell is filled, filling the 4s subshell first actually leads to a lesser overall energy than filling the 3d subshell. Recall that while the principal quantum number largely dictates the energy of an electron, the angular momentum quantum number also has an impact on energy; by the time we get to the 3d and 4s subshells, we see overlap in the filling of the shells. Thus, after the 3p subshell is completely filled (which occurs for Ar), the next electron for K occupies the 4s subshell, not the 3d subshell:

\ce{K}\text{: }1s^22s^22p^63s^23p^64s^1\text{, \textbf{not} }1s^22s^22p^63s^23p^63d^1

For larger and larger atoms, the order of filling the shells and subshells seems to become even more complicated. There are some useful ways to remember the order, like that shown in Figure 8.08 “Electron Shell Filling Order.” If you follow the arrows in order, they pass through the subshells in the order that they are filled with electrons in larger atoms. Initially, the order is the same as the expected shell–subshell order, but for larger atoms, there is some shifting around of the principal quantum numbers. However, Figure 8.08 gives a valid ordering of filling subshells with electrons for most atoms.

Figure 8.08 “Electron Shell Filling Order.” Starting with the top arrow, follow each arrow. The subshells you reach along each arrow give the ordering of filling of subshells in larger atoms. The n = 5 and higher shells have more subshells, but only those subshells that are needed to accommodate the electrons of the known elements are given.

Example 8.6

Problem

What is the predicted electron configuration for Sn, which has 50 electrons?

Solution

We will follow the chart in Figure 8.08 “Electron Shell Filling Order” until we can accommodate 50 electrons in the subshells in the proper order:

\ce{Sn}\text{: }1s^22s^22p^63s^23p^64s^23d^{10}4p^65s^24d^{10}5p^2

Verify by adding the superscripts, which indicate the number of electrons:

2 + 2 + 6 + 2 + 6 + 2 + 10 + 6 + 2 + 10 + 2 = 50

Therefore, we have placed all 50 electrons in subshells in the proper order.

Test Yourself

What is the electron configuration for Ba, which has 56 electrons?

Answer

1s^22s^22p^63s^23p^64s^23d^{10}4p^65s^24d^{10}5p^66s^2

As the previous example demonstrated, electron configurations can get fairly long. An abbreviated electron configuration uses one of the elements from the last column of the periodic table, which contains what are called the noble gases, to represent the core of electrons up to that element. Then the remaining electrons are listed explicitly. For example, the abbreviated electron configuration for Li, which has three electrons, would be:

\ce{Li}\text{: }[\ce{He}]2s^1

Where [He] represents the two-electron core that is equivalent to He’s electron configuration. The square brackets represent the electron configuration of a noble gas. This is not much of an abbreviation. However, consider the abbreviated electron configuration for W, which has 74 electrons:

\ce{W}\text{: }[\ce{Xe}]6s^24f^{14}5d^4

This is a significant simplification over an explicit listing of all 74 electrons. So for larger elements, the abbreviated electron configuration can be a very useful shorthand.

Example 8.7

Problem

What is the abbreviated electron configuration for P, which has 15 electrons?

Solution

With 15 electrons, the electron configuration of P is:

\ce{P}\text{: }1s^22s^22p^63s^23p^3

The first immediate noble gas is Ne, which has an electron configuration of 1s22s22p6. Using the electron configuration of Ne to represent the first 10 electrons, the abbreviated electron configuration of P is:

\ce{P}\text{: }[\ce{Ne}]3s^23p^3

Test Yourself

What is the abbreviated electron configuration for Rb, which has 37 electrons?

Answer

[\ce{Kr}]5s^1

There are some exceptions to the rigorous filling of subshells by electrons. In many cases, an electron goes from a higher-numbered shell to a lower-numbered but later-filled subshell to fill the later-filled subshell. One example is Ag. With 47 electrons, its electron configuration is predicted to be:

\ce{Ag}\text{: }[\ce{Kr}]5s^24d^9

However, experiments have shown that the electron configuration is actually:

\ce{Ag}\text{: }[\ce{Kr}]5s^14d^{10}

This, then, qualifies as an exception to our expectations. At this point, you do not need to memorize the exceptions; but if you come across one, understand that it is an exception to the normal rules of filling subshells with electrons, which can happen.

Electron Configuration Energy Diagrams

We have just seen that electrons fill orbitals in shells and subshells in a regular pattern, but why does it follow this pattern? There are three principles which should be followed to properly fill electron orbital energy diagrams:

  1. The aufbau principle
  2. The Pauli exclusion principle
  3. Hund’s rule

The overall pattern of the electron shell filling order emerges from the aufbau principle (German for “building up”):  electrons fill the lowest energy orbitals first. Increasing the principle quantum number, n, increases orbital energy levels, as the electron density becomes more spread out away from the nucleus. In many-electron atoms (all atoms except hydrogen), the energy levels of subshells varies due to electron-electron repulsions. The trend that emerges is that energy levels increase with value of the angular momentum quantum number, l, for orbitals sharing the same principle quantum number, n. This is demonstrated in Figure 8.09, where each line represents an orbital, and each set of lines at the same energy represents a subshell of orbitals.

Diagram of atomic orbitals. Long description available.
Figure 8.09 “Generic Energy Diagram of Orbitals in a Multi-Electron Atom.” [Long Description]

As previously discussed, the Pauli exclusion principle states that we can only fill each orbital with a maximum of two electrons of opposite spin. But how should we fill multiple orbitals of the same energy level within a subshell (e.g., the three orbitals in the 2p subshell)? Orbitals of the same energy level are known as degenerate orbitals, and we fill them using Hund’s rule: place one electron into each degenerate orbital first, before pairing them in the same orbital. Let’s examine a few examples to demonstrate the use of the three principles.Boron is atomic number 5, and therefore has 5 electrons. First fill the lowest energy 1s orbital with two electrons of opposite spin, then the 2s orbital with 2 electrons of opposite spin and finally place the last electron into any of the three degenerate 2p orbitals (Figure 8.10).

1s and 2s are full. One electron in the first orbital of 2p.
Figure 810 “Boron Electron Configuration Energy Diagram.”

Moving across the periodic table, we follow Hund’s rule and add an additional electron to each degenerate 2p orbital for each subsequent element (Figure 8.11). At oxygen we can finally pair up and fill one of the degenerate 2p orbitals.

Electron configuration diagrams for carbon, nitrogen, and oxygen. Long description available.
Figure 8.11 “Electron Configuration Energy Diagrams for Carbon, Nitrogen, and Oxygen.” [Long Description]

Key Takeaways

  • The Pauli exclusion principle limits the number of electrons in the subshells and shells.
  • Electrons in larger atoms fill shells and subshells in a regular pattern that we can follow.
  • Electron configurations are a shorthand method of indicating what subshells electrons occupy in atoms.
  • Abbreviated electron configurations are a simpler way of representing electron configurations for larger atoms.
  • Exceptions to the strict filling of subshells with electrons occur.
  • Electron configurations are assigned from lowest to highest energy following the aufbau principle
  • One electron is placed in each degenerate orbital before pairing electrons following Hund’s rule.
  • Electron configuration energy diagrams follow three principles: the aufbau principle, the Pauli exclusion principle and Hund’s rule.

Exercises

Questions

  1. Give two possible sets of four quantum numbers for the electron in an H atom.
  2. Give the possible sets of four quantum numbers for the electrons in a Li atom.
  3. How many subshells are completely filled with electrons for Na? How many subshells are unfilled?
  4. How many subshells are completely filled with electrons for Mg? How many subshells are unfilled?
  5. What is the maximum number of electrons in the entire n = 2 shell?
  6. What is the maximum number of electrons in the entire n = 4 shell?
  7. Write the complete electron configuration for each atom.
    1. Si, 14 electrons
    2. Sc, 21 electrons
  8. Write the complete electron configuration for each atom.
    1. Br, 35 electrons
    2. Be, 4 electrons
  9. Write the complete electron configuration for each atom.
    1. Cd, 48 electrons
    2. Mg, 12 electrons
  10. Write the complete electron configuration for each atom.
    1. Cs, 55 electrons
    2. Ar, 18 electrons
  11. Write the abbreviated electron configuration for each atom in Exercise 7.
  12. Write the abbreviated electron configuration for each atom in Exercise 8.
  13. Write the abbreviated electron configuration for each atom in Exercise 9.
  14. Write the abbreviated electron configuration for each atom in Exercise 10.
  15. Draw electron configuration energy diagrams for potassium and bromine.

Answers

  1. {1, 0, 0, +½} and {1, 0, 0, −½}
  1. Three subshells (1s, 2s, 2p) are completely filled, and one shell (3s) is partially filled.
  1. 8 electrons
    1. 1s^22s^22p^63s^23p^2
    2. 1s^22s^22p^63s^23p^64s^23d^1
    1. 1s^22s^22p^63s^23p^64s^23d^{10}4p^65s^24d^{10}
    2. 1s^22s^22p^63s^2
    1. [\ce{Ne}]3s^23p^2
    2. [\ce{Ar}]4s^23d^1
    1. [\ce{Kr}]5s^24d^{10}
    2. [\ce{Ne}]3s^2
  1. Potassium:
    The 1s, 2s, 2p, 3s, and 3p subshells are full, and the 4s subshell has one electron.
    Figure 8.11a “Potassium Electron Configuration.”

    Bromine:

    The 1s, 2s, 2p, 3s, 3p, 4s, and 3d subshells are full. The 4p subshell has 5 electrons.
    Figure 8.11b “Bromine Electron Configuration.”

Long Descriptions

Figure 8.09 description: A blank diagram showing the different subshells of an atom and how many orbitals they contain. Remember that an orbital can hold two electrons. From lowest to highest energy, the subshells shown are:

  • 1s (one orbital)
  • 2s (one orbital)
  • 2p (three orbitals)
  • 3s (one orbital)
  • 3p (three orbitals)

[Return to Figure 8.09]

Figure 8.11 description: Electron configuration energy diagrams for carbon, nitrogen, and oxygen.

Carbon’s 1s and 2s subshells are full. In the 2p subshell, the first two orbitals have one electron each.

Nitrogen’s 1s and 2s subshells are full. In the 2p subshell, each of the three orbitals has one electron.

Oxygen’s 1s and 2s subshells are full. In the 2p subshell, the first orbital has two electrons, and the second and third orbitals have one electron each.

[Return to Figure 8.11]

Media Attributions

  • “Electron Shell Filling Order” by David W. Ball © CC BY-NC-SA (Attribution NonCommercial ShareAlike)
  • “Generic Energy Diagram of Orbitals in a Multi-Electron Atom” by David W. Ball and Jessie A. Key © CC BY (Attribution)
  • “Boron Electron Configuration Energy Diagram” by David W. Ball and Jessie A. Key © CC BY (Attribution)
  • “Potassium Electron Configuration” © Public Domain
  • “Bromine Electron Configuration” © Public Domain

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Copyright © 2014

                                by Jessie A. Key

            Introductory Chemistry - 1st Canadian Edition by Jessie A. Key is licensed under a Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International License, except where otherwise noted.
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