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(Text from Chemistry and Chemical Reactivity, by Kotz, Treichel, and Weaver
Atomic Electron Configurations and Chemical Periodicity (Chapter Eight)
8.1 Electron Spin Electron spin must be represented by the four quantum number, the electron spin magnetic quantum number, ms. Most substances are slightly repelled by a strong magnet; that is, they are diamagnetic Some metals and diamagnetic. compounds are attracted to a magnetic field—they are paramagnetic Electron spin is either +½or -½. Two paramagnetic. electrons have opposite spin orientations. Their spins are paired. Paramagnetism is the attraction to a magnetic field of substances in which the constituent ions or atoms contain unpaired electrons. In summary, substances where all the electrons are paired are diamagnetic and repel magnets, while substances with unpaired electrons are paramagnetic and attracted to magnetic fields. 8.2 The Pauli Exclusion Principle The Pauli Exclusion Principle states that no two electrons in an atom can have the same set of four quantum numbers (n, l, ml, and ms), thus, no atomic orbital can contain more than two electrons. Orbital box diagrams represent electrons by arrows. By understanding that an orbital can accommodate no more than two electrons, it is possible to know the maximum number of electrons that can occupy each electron shell or subshell. The maximum number of electrons possible in any shell is 2n2. 8.3 Atomic Subshell Energies and Electron Assignments Electrons are assigned to shells of increasingly higher energy. Within a given shell, electrons are assigned to subshells of successively higher energy. Electrons are assigned in such a way that the total energy of the atom is as low as possible. Electrons are assigned to subshells in order of increasing “n + l” value. For two subshells with the same value of value of “n + l”, electrons are assigned fir sto the subshell of lower n. The order in which electrons are assigned to subshells in an atom, and many atomic properties, can be rationalized by the concept of effective nuclear charge (Z* This is the nuclear charge experienced by a Z*). Z* particular electron in a multi-electron atom, as modified by the presence of other electrons. Electron shielding is the phenomenon of core electrons causing valence electrons to “feel” a charge or attraction to the nucleus that is less than the actual charge on the nucleus. As a result, shielding reduces Z*. 8.4 Atomic Electron Configurations The electron configuration of elements show where electrons are found in the shells, subshells, and configurations orbitals that result in the lowest energy for the atom. An alternative to orbital box notation that is more compact is spdf notation Using this notation, H is 1s1. The first 1 represents the electron shell, n, with the notation. letter showing the orbital type, and the superscript showing how many electrons are assigned to the designated orbital.
2 PART TWO: THE STRUCTURE OF ATOMS AND MOLECULES Chapter Eight: Atomic Electron Configurations and Chemical Periodicity (Text from Chemistry and Chemical Reactivity, by Kotz, Treichel, and Weaver Electron configurations are often written in abbreviated form by combining the noble gas notation with the spdf or orbital box notation. The electrons included in the noble gas notation are often referred to as the core electrons, electrons of the atom. The electrons beyond the core electrons are the valence electrons which determine the chemical properties of an element. The elements of Group 1 and 2 are s-block elements Group 13-18 elements are referred to as the p -block elements. elements, elements which have the general configuration ns2px, where x varies between 1 and 6 and n is equal to the period number. Hund’s rule states that the most stable arrangement of electrons is that with the maximum number of unpaired electrons, all with the same spin direction. As a result, when using orbital box notation, pair up electrons in the same set of orbitals only when all of the orbitals have one electron. For example, with nitrogen, the last three electrons in the 2p orbitals are all unpaired. Transition elements use d or f subshells in addition to s and p subshells. A general note is that the energy level of d orbitals equivalent to the (period # - 1) and the energy level of f orbitals is equivalent to the (period # - 2). For example, scandium is in the 4th period and has an electron configuration of [Ar]4s23d4. There are minor differences in the configuration of transition elements for maximum stability: Cu: [Ar]4s13d10 – one electron is taken from the 4s to fill the 3d. Au: [Xe]6s14f145d10 – one electron is taken from the 6s to fill the 5d. Ag: [Kr]5s14d10 – one electron is taken from the 5s to fill the 4d. Cr: [Ar]4s13d5 – one electron is taken from the 4s to half-fill the 3d. Mo: [Kr]5s14d5 – one electron is taken from the 5s to half-fill the 3d. Full shells and half-filled shells are more stable. The elements which require f subshells are called the lanthanides (4f) and the actinides (5f). 8.5 Electron Configuration of Ions To form a cation (positive ion) from a neutral atom, one or more of the valence electrons is removed; that is, electrons are removed from the electron shell of highest n. If several subshells are present within the nth shell, the electron or electrons of maximum l are removed. All common transition metal cations have electron configurations of the general type [noble gas core](n – 1)dx. In the process of ionization, the ns electrons are lost before (n – 1)d electrons. 8.6 Atomic Properties and Periodic Trends Similarities in properties of the elements are the result of similar valence shell electron configurations.
Atomic radii generally decreases going across a period and increases going down a group. As one progresses across a period, more protons are being attracted, which allow electrons to become more strongly attracted to the nucleus. Additionally, electrons are being added in the same shells, so the atom is not growing larger. Down a group, size increases because the orbital size increases and the addition of more shells leads to shielding effects.
3 PART TWO: THE STRUCTURE OF ATOMS AND MOLECULES Chapter Eight: Atomic Electron Configurations and Chemical Periodicity (Text from Chemistry and Chemical Reactivity, by Kotz, Treichel, and Weaver Generally, cations (the removal of electrons), decreases atomic size, while anions (addition of electrons), increases atomic size.
Ionization energy is the energy required to remove an electron from an atom in the gas phase. To separate an electron from an atom, energy must be supplied to overcome the attraction of the nuclear charge. Ionization energy generally increases across the period and decreases down a group. As one progresses across a period, atomic radius decreases and allows atoms to have a stronger hold on their electrons. Down a group, size increases and the nucleus-electron attractive force decreases, making it easier to pull an electron away. Removing each subsequent electron requires more energy, and there is a large jump in the amount of energy required when a shell is depleted.
The electron affinity of an atom is defined as the energy of a process in which an electron is acquired by the atom in the gas phase. This is a measure of how much the atom wants electrons. Greater affinity means a more negative value of electron affinity, since EA is measured with negative numbers. The trends follow that of ionization energy. Elements with high ionization energy generally have a high affinity for an electron. Electron affinity increases (becomes more negative) across a period and decreases down a group (less negative).
The electronegativity of an atom is defined as a measure of the ability of an atom in a molecule to attract electrons to itself. It increases across a period and decreases down a group. 8.7 Periodic Trends and Chemical Properties Main group metals generally form cations with an electron configuration equivalent to that of the nearest noble gas. Nonmetals generally acquire enough electrons to form an anion with the electron of the next, higher noble gas.
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