Chapter 1 Basic Concepts: Atoms

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1 Chapter 1 Basic Concepts: Atoms CHEM 511 chapter 1 page 1 of 12 What is inorganic chemistry? The periodic table is made of elements, which are made of...? Particle Symbol Mass in amu Charge e e Define: atomic number (Z): Define: mass number (A): From general chemistry we recall that atoms of the same element all contain the same number of protons, but may or may not contain the same number of neutrons. Isotopes: Isotopes of hydrogen: Isobars: Isotones: How can you roughly tell, by looking at the periodic table, if an element has just one isotope (i.e., the element is a monotope)?

2 CHEM 511 chapter 1 page 2 of 12 Distinction of isotope with allotrope. Examples of allotropes with oxygen? sulfur (below) carbon? Inside the atom Early quantum mechanics (~1900-~1925) treated the electron as a particle. Why? Note that this equation works well for hydrogen and hydrogen-like atoms ONLY!! Limitations? Later quantum mechanics (~1925 and on) Think of the electron NOT as a particle, but as a wave. What else has this wave-particle duality? What is the wavelength of a 68 kg person walking at 4.0 mph (1.8 m/s)?

3 CHEM 511 chapter 1 page 3 of 12 Heisenberg s Uncertainty Principle HUP: It is impossible to know precisely the momentum and location of an electron simultaneously. Schrodinger s Wave Equation (Ψ) Ψ represents the wave function (as opposed to a particle function) of the electron it is based on x, y, z coordinates and time (for convenience, it may be better to use polar coordinates (r, θ, Φ)) Ψ describes the behavior of an electron in a specific region of space (i.e., an orbital); it is a mathematical function and can have positive or negative values a negative value doesn t mean the electron isn t present! Atomic Orbitals To define any orbital we need three quantum numbers: n, l,ml 1. Principal Quantum Number (n) Numerical values for n? 2. Orbital Quantum Number (l) aka orbital angular momentum Q. N. aka azimuthal Q. N. Numerical values for l? 3. Magnetic Quantum Number (ml) Numerical values for ml? To plot Ψ versus distance from the nucleus results in graphs like this:

4 4πr 2 R(r) 2 4πr 2 R(r) 2 CHEM 511 chapter 1 page 4 of 12 Another useful feature is to look at the squared function of the wavefunction (Ψ 2 ) (note, it isn t actually squared, Ψ is multiplied by a factor such that when integrated over all space, you are guaranteed to find the electron somewhere in that space). Your book actually applies an additional factor 4πr 2 (surface area of a sphere), as shown below. What can we infer about the shape (and size) of the s orbitals from these graphs? Radial distribution plot for 2p & 3p Probability plots for other orbitals

5 A note on radial nodes: to determine the number of radial nodes use the formula n-l-1. (This does not include nodal planes.) # of nodes for 1s: # of nodes for 2s: # of nodes for 3s: # of nodes for 2p: # of nodes for 3p: CHEM 511 chapter 1 page 5 of 12 p-orbitals d-orbitals The Orbitron shows informative pictures:

6 CHEM 511 chapter 1 page 6 of 12 One more quantum number: the magnetic spin quantum number (m s ) aka spin quantum number) Moving charges generate magnetic fields thus two electrons close to each other must have opposite spins Pauli Exclusion Principle: Result of the PEP? Many Electron Atoms In a hydrogen atom (1 electron), all orbitals of the same n have the same energy Introduction of just one additional electron changes this and "splits" the energy of the orbitals. Why?

7 CHEM 511 chapter 1 page 7 of 12 Effective nuclear charge (Z eff ): That portion of the total nuclear charge that is experienced by a given electron. Z eff = Z actual S (Shielding factor) Slater s Rules for determining effective nuclear charge (empirically derived): Write the electron configuration in the following groupings: (1s), (2s, 2p), (3s, 3p), (3d), (4s, 4p), (4d), (4f), (5s, 5p), etc. Electrons higher than the electron of interest do not contribute to the shielding factor Electrons in s- and p-orbitals: o Each electron in (ns, np) contribute S = 0.35 o Each electron in the n-1 shell contribute S = 0.85 o Each electron in the n-2 or lower shells contribute S = 1.00 Electrons in d- or f-orbitals o Each of the other electrons in the other d- or f-orbitals contributes S = 0.35 o Each of the electrons in a lower group contributes S = 1.00 Why useful? It helps to determine electron configuration! EX. Determine the Z eff for the outermost electron in the following electron configurations: (a) 1s 2 2s 2 2p 6 (b) 1s 2 2s 2 2p 5 3s 1

8 The Classification of the Elements 1 What are the three main categories of elements according to the periodic table? CHEM 511 chapter 1 page 8 of 12 Important sections of the periodic table: main group elements transition metal elements rare earth elements aka inner transition elements Important families (aka groups) Group 1 (or 1A) Group 2 (or 2A) Group 15 (or 5A) Group 16 (or 6A) Group 17 (or 7A) Group 18 (or 8A) Group 11 (or 1B) 1 Other representations of the elements can be found here: Dangerous potential time-sink!

9 CHEM 511 chapter 1 page 9 of 12 Brief review of electron configuration The ground state (lowest energy) electron configuration is determined by the Aufbau principle Filling orbitals is straight forward until the d-block elements Determine the electron configuration of: B P Ti Cr Ni Cu Se Bi

10 CHEM 511 chapter 1 page 10 of 12 Core vs. valence electrons? How are cations created? How are anions created? Determine the electron configuration of: Na + P 3- Mn 4+ Xe - Fe 3+ Fe 2+ Ag + Periodic Trends Atomic radius: a measurement of the unionized form of an atom. metallic radius: Usual method for metals is to measure the distance between nuclei in the solid and divide by 2 covalent radius: For nonmetals, measure the distance between nuclei of a binary molecule and divide by 2 ionic radius: a measurement of an ion's size, usually derived from the distance between an oxygen nucleus and a metal ion. (an approximation only)!!

11 CHEM 511 chapter 1 page 11 of 12 Size trends within the periodic table? Down a group? Across a period? Note: transition metals in the 5th and 6th periods are nearly the same size!! The period 6 atoms have 32 MORE electrons than the period 5 atoms. How can they be the same size? Atomic Radii (pm) Period 5 Zr Nb Mo Tc Ru Rh Pd Ag Period 6 Hf Ta W Re Os Ir Pt Au What do we know about the relative size of cations to parent atoms? anions to parent atoms? Cations are smaller than the parent (neutral) atoms Anions are larger than the parent (neutral) atoms Ionization energy: Energy needed to remove an electron from an isolated atom in the gas phase

12 CHEM 511 chapter 1 page 12 of 12 Based on this figure, what are the periodic trends for E i1? Down a group? Across a period? What about the dips at Be-B and N-O? Electron Affinity: The energy gained or released when an electron is added to the valence shell of an isolated atom in the gas phase.

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