Chapter 6 Electronic Structure
Learning Objectives for this chapter:
Lecture 14 March 23, 2011
Explain the difference between a continuous spectrum and a line spectrum. Explain the difference between an emission and an absorption spectrum. Use the concept of quantized energy states to explain atomic line spectra. Given an energy level diagram, predict wavelengths in the line spectrum, and vice versa. Define and distinguish between shells, subshells, and orbitals. Explain the relationships between the quantum numbers. Use quantum numbers to label electrons in atoms. Describe and compare atomic orbitals given the n and quantum numbers. List a set of subshells in order of increasing energy. Write electron configurations for atoms in either the subshell or orbital box notations. Write electron configurations of ions. Use electron configurations to predict the magnetic properties of atoms.
Electromagnetic Radiation (Energy) travels in waves
wavelength () distance, units = m or nm or amplitude
lambda
Light (Energy) have particle like behavior Max Plank: for particles, En
magnetic vector
frequency (n) units = s-1 = Hz
nu
E=hn
h = Planks constant h = 6.626 10-34 Js
Einstein: light is massless particle photon
# of waves that pass a given point in some unit of time
E=hn=h c l
E n so if E, n E l so if E, l
1
nodes (amplitude = 0)
occur at interval /2
electric vector
direction of propagation
c=
speed of light 2.998 108 ms-1
Question 1: (a) Which type of radiation involves less energy x-ray or microwave? (b) Which type of radiation has the higher frequency, radar or red light? (c) Which type of radiation has the longer wavelength, ultraviolet or infrared light? Question 2: Carbon dioxide absorbs energy at a wavelength of 1498 nm (a) In what spectral range does the absorption occur? (b) Calculate the frequency of the absorption (c) What is the energy absorbed by one photon?
A Mystery in Chemistry that led to our Understanding of Electronic Structure in Atoms Mystery: Emission spectra of atoms
continuous spectrum all frequencies (color) of visible light (looks like a rainbow) photographic plate high voltage atomic spectrum Discrete frequencies (lines) of light (a fingerprint to identify atoms) photographic plate
SUN white light (all colors)
slit
prism
slit
prism
other sources: hot metal filament (e.g. W)
gas filled discharge tube (e.g. H, He, Hg) produces light
Atomic Emission Spectrum produced when an electron moves new model of electron configuration in atom, from a higher energy level to a lower energy level in an atom, which explained the atomic spectrum of the giving off light in the process Niels Bohr:
hydrogen atom electrons move about the nucleus in a circular orbit of fixed radius each orbital is described by the principle quantum number (n), which is an integer. n = 1 is called the ground state. It is the most stable energy state and the lowest energy state of the system. n = 2, 3, 4, are all excited states, which are higher energy than the ground state.
photon out An emission process in an excited hydrogen atom is when an electron originally in a higher-energy level (n = 3) falls back to a lower energy level (n = 2). The results is an emitted photon (photon out) of energy hn =E (in this case, E = En=2 En=3).
n=1 n=2 n=3
An absorption process is when an electron originally in a lowerphoton in energy level (n = 1) moves up to a higher energy level (n = 3). To do this the electron absorbs a photon (photon in) of energy hn, where hn=E (in this case, E = En=3 En=1)
absorption
requires energy
Bohr showed the energies that an electron in the hydrogen atom can possess are given by:
So, to determine energy from an emission process (E) it is the difference between the energies from the initial state (Ei) and the final state(Ef).
emission
stairs
produces energy
En = -RH
1 n2
RH = Rydberg constant RH = 2.1810-18J
E= Ef Ei = RH 1 2 - 1 2 nf ni
A mechanical analogy for the emission ( ) and absorption ( ) process. The ball can rest on any step but not between steps.
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Question 3: When an electron moves from n=3 to n=2 in a Hydrogen atom, what is the wavelength of the
Answer = 656.0 nm emitted photon (in nm)? Question 4: Upon emission of a photon, the final state of an electron in a Hydrogen atom is the ground state. If the emitted photon has an energy of 2.04410-18 J, what is the principle quantum number for the initial state Answer: n = 4 of the electron?
Quantum Mechanical Model
Bohrs model of an atom has some problems such as it only worked for atoms with one electron Erwin Schrdinger used complicated mathematics to describe the behavior of submicroscopic particles, now called Schrdingers equation (which led to the start of a new field called Quantum Mechanics). Schrdingers equation specifies the possible energy states the electron can occupy in a hydrogen atom and those states corresponding wavefunctions () - an Atomic Orbital can be thought of as a wavefunction of an electron.
1. The model can only refer to the probability of finding an electron in a region; it cannot specify its path or exact location. 1 2. The kinetic energy of the electron in an atom is inversely related to volume. KE V 3. Four quantum number are necessary to describe completely the energy of an electron in an atom.
A representation of the electron density distribution surrounding the nucleus in the hydrogen atom. It shows a high probability of finding the electron closer to the nucleus
Quantum Numbers
1) Principle Quantum Number (n) n = 1, 2, 3, The value of n is the main factor that determines the energy of an electron and its distance from the nucleus.
The maximum number of electrons per principal level is 2n 2.
2) Angular Momentum Quantum Number () = 0, 1, 2, , (n - 1) The Angular Momentum Quantum Number tells us the shape of the orbital. The value of depends on
n and ranges from 0 to (n - 1).
Name of orbital
0
s
1
p
2
d
3
f
4
g
5
h
3) Magnetic Quantum Number (m) m = -, (- + 1), , 0, (+ - 1), + The Magnetic Quantum Number describes the orientation of the orbital in space. For a 4) Electron Spin Quantum Number (ms) ms = + or - The Electron Spin Quantum Number describes the spinning motion of the electron. There are two possible
spinning motions. It is the electrons spin that accounts for its magnetic properties. certain value of there are (2 + 1) integer values of m.
Question 5: (a)
(b) (c) (d) (e) (f)
When n = 2, the values of can be ____ and ____. When = 1, the values of m can be ____, ____, and ____, and the subshell has the letter label ____. When = 2, the subshell is called a _____ subshell. When a subshell is labeled s, the value of is ____ and m have the value ______. When a subshell is labeled p, _____ orbitals occur within the subshell. When a subshell is labeled f, there are _____ values of m , and _____ orbitals occur within the subshell.
Electron Configuration
notation that describes the arrangement of electrons in an atom
4f 4d
4 Increasing Energy
4p 3d 4s and so on
For a Hydrogen atom, an electron in the ground state must be in the 1s, so its electron configuration is 1s1
3
2 1
3p 3s 2p 2s 1s
1s1
# electron in orbitals or subshell
fill third fill second fill first
Question 6: Write the electron configuration for the following atoms
Be, N, Ne, Na, Si, Cl
Electron energy sublevels in the order of increasing energy
The ground state electron configuration can be abbreviated using notions with a noble gas core, see below
Boron: 1s2 2s2 2p1
can be written as
[He] 2s2 2p1
can be written as
since [He] = 1s2
Sulfur: 1s2 2s2 2p6 3s2 3p4 can be written as Potassium: 1s2 2s2 2p6 3s2 3p6 4s1
[Ne] 3s2 3p4
since [Ne] = 1s2 2s2 2p6
[Ar] 4s1 since [Ar] = 1s2 2s2 2p6 3s2 3p6
Question 7: Write the electron abbreviated configuration using the noble gas core notation for Be, N, Ne, Na, Si, Cl
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