Chap 5: Periodicity & Atomic Structure

Chapter 5. Periodicity & Atomic Structure

Why do elements have periodic properties?

Wave Phenomena
Classical wave description of light explains refraction, interference, diffraction

Diffraction of light

Why do elements and compounds have characteristic colors? Demo (Q224): colored balloon explosions

When light passes through a large slit, the edges cast shadows and the light that goes through is a distinct replica of the slit. (A beam of classical particles would also behave this way.)

However, when the slit is small, (<100 l) the beam is diffracted , it spreads out.

Diffraction
Light passing through a narrow slit spreads out.

Photoelectric Effect
However, the color of the incident light affected the electron energy KE (electron)

frequency of incident light

Einstein proposed the energy of light is carried in packets (photons). The amount of energy in a photon depends on the frequency: E = hn = hc/ l where h = 6.63 x 10 -34 J-s (Plancks constant)

This is purely a wave phenomenon. A beam of classical particles would make a shadow pattern.

seat activity single slit diffraction

Photoelectric effect explanation: hn > W electron emitted hn < W no electron emitted (in this picture, intensity is related to the number of photons/s)

Photon Energy
E photon = hn = hc/l

Matter Waves
Matter classically considered to be composed of particles p, n, e Beams of these particles display wavelike phenomena (e.g. diffraction) deBroglie suggested a particle wavelength by analogy with light photon energy: E = h n = hc/ l (Planck) and E = pc (Relativity) where p is momentum gives

l = h/p

Ephoto
n

classical momentum of a particle: p = mv deBroglie wavelength of a particle l = h/p = h/mv Some phenomena are consistent with a particle picture. Other phenomena are consistent with a wave picture. But a theory is useful only if it is predictive, these pictures must be unified!

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Chap 5: Periodicity & Atomic Structure

Quantum Mechanics
Wave and particle descriptions are based on intuition developed from macroscopic observations. Inconsistency with experiments on light and elementary particles suggests that these pictures fail in the microscopic realm. A postulate of QM: An electron (or other system) is described by a wavefunction (y) like that used to describe light classically. The wavefunction is determined by solving a wave equation. The probability of finding the electron in a given location is equal to the square of the value of the wavefunction (y2) at that location. A wavefunction for an atom or molecule is also called an orbital .

Quantization
An important consequence of the postulate is that the possible measured values of many quantities (e.g. energy, momentum, angular momentum) are quantized , i.e. only certain discrete values can be measured. Consider an e confined within a 1-d box of length a. The probability of finding the electron outside the box is zero, so the wavefunction must vanish at both ends. Therefore, only certain discrete wavelengths are allowed (l = 2 a, a , 2a/3, a/2, etc.). Each possibility is called a state and designated by a quantum number (n ), i.e. ln=2a/n where n = 1, 2, 3, etc. The electron momentum and energy are related to the wavelength: p = h/ l E= h 2/2ml2 Energy Levels En = h 2n2/4ma 2

Wavefunction & probability distribution

P.I.B. wavefunction

Classical uncertainty uncertainty

Diffraction The uncertainty of the vertical position of a photon ( Dy) is the size of the slit. The uncertainty of the direction of flight is related to the angular spread of the diffracted beam ( Dq).

y3

high probability

Probability distribution

Dq ~ 1/ Dy or Dy Dq = const. (Dq is related to the uncertainty of the y-component of photon momentum)

y32
nodes zero probability

Heisenberg Uncertainty Principle

Consider an electron with a wavefunction and probability distribution like these Uncertainty principle: A wavefunction with a small Dx results in a large uncertainty in momentum, Dp , and vice versa.
Dx Dp h / 4p

Summarize QM

1. Possible states of a system are quantized; each discrete state is assigned a quantum number and each is associated with a particular value of a measurable quantity like energy. 2. States are related to a wavefunction (also called orbitals). The probability that a measurement of position will yield a specific result can be determined by the shape of the wavefunction squared.

Dx the electron will almost always be found within this range

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Chap 5: Periodicity & Atomic Structure

H-atom Energy Levels

En = hc n2 (n = 1, 2, 3, ) n=4 (3rd excited state) n=3 (2nd excited state) n=2 (1st excited state)

Atomic Emission Spectra

When an electron falls (decays) from a higher energy state to one of lower energy, the excess energy is emitted as a photon:

= 1.097 x 10 7 m-1 h = 6.626 x 10 -34 J s c = 2.998 x 10 8 m/s

IR visible

hc = 2.179 x 10 -18 J
= 1,312 kJ/mol UV

n=1 (ground state) visible part

Some atomic emission spectra

H He O N Fe Na m = -l, -l+1, , l-1, l Xe Fingerprints for elemental analysis. l = 0, 1, n-1 l=0= l=1= l=2= l=3= s subshell p subshell d subshell f subshell n = 1, 2, 3,

Quantum Numbers
principal quantum number H-atom energy depends only on n specifies electron shell determines size of orbital angular momentum quantum number specifies sub-shell n and l determine orbital shape

magnetic quantum number specifies direction (orientation) of orbital in space (i.e. x, y, z)

s Orbital Shapes
The s orbitals are spherical. Probability of finding s electron depends only on distance from nucleus, not on angular position.

p Orbital Shapes
The p orbitals are dumbbellshaped. This representation of orbital shapes simply draws a surface to show where the probability of finding the electron decreases beyond some arbitrarily small value (e.g. there is a 95% probability of finding the electron withing the dumbbell). It gives you a good feeling for the angular dependence of the orbital shape but not the radial-dependence (distance from the nucleus).

y1s = A e -r / a0

y2 s = A(2 - r / a0 ) e -r /2 a0

a0 = 0.53 (Bohr radius)

y2 p = A(r / a0 ) e -r /2 a0 cosq

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Chap 5: Periodicity & Atomic Structure

d Orbital Shapes
d orbitals have two different shapes. Most have 4 lobes (regions of high electron density).

Dot-density representations
In these cross-sectional views, the density of dots represents the probability of finding the electron in that location. They give a better feeling for how the wavefunction varies with distance from the nucleus.

This is an f orbital. It has 8 regions of electron density.

Multielectron Atoms
Approximation: Assume orbitals are similar to those in H-atom. More than one orbital will be occupied by electrons in a given atom.

Ground State Electron Configurations

Aufbau Principle: Lower energy orbitals fill first. Orbitals only hold two electrons, and each should have different spin. Degenerate orbitals are filled with electrons until all are half filled before pairing up of electrons can occur (Hunds Rule ).

Increasing Energy

Core [He] [Ne] [Ar] [Kr] [Xe] [Rn]

1s 2s 3s 4s 5s 6s 7s

2p 3p 4p 5p 6p 7p

3d 4d 4f 5d 5f 6d

n+l rule H-atom multi-electron atom (not on same energy scale) An atom or molecule with one or more unpaired electrons is paramagnetic and is attracted to a magnetic field.

Sub-shell energies are no longer exactly equal (degenerate) because of interactions between electrons ( shielding ).

electronconfig

Some Electron Configurations

1s
paramagnetic

Atomic Radii
2p Atomic radius determined by outermost orbital occupied

2s

H He

1s1 1s2 1s2 2 s1 = [He] 2 s 1 1s2 2 s2 = [He] 2 s 2 1s2 2 s2 2p1 = [He] 2 s2 2p1 1s2 2 s2 2p2 = [He] 2 s2 2p2 1s2 2 s2 2p3 = [He] 2 s2 2p3 1s2 2 s2 2p4 = [He] 2 s2 2p4 1s2 2 s2 2p5 = [He] 2 s2 2p5 1s2 2 s2 2p6 = [He] 2 s2 2p6

paramagnetic

Li Be

paramagnetic paramagnetic paramagnetic paramagnetic paramagnetic

B C N O F Ne

Increase down group due increasing n (additional outer shell). Decrease across row due to increasing nuclear charge.

A few elements have anomalous e configs

Chromium should be [Ar]4s23d4, but is [Ar]4 s13d5 Copper should be [Ar]4s23d9, but is [Ar]4 s13d10

Radii

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