The Electron: History of Cathode Rays

Chapter Seven
Atomic Structure

1838: Michael Faraday

Electricity flows causes purple glow in a tube at near vacuum
Few molecules: minimal molecular interference
Glow from absorption of current by remaining air molecules

Numerical Values for Atomic Particles

Millikans Oil Drop Experiment

Atomize oil
Tiny, negative oil droplets
Measure of velocity under gravity

1897: J.J. Thomson

Ratio of cathode ray particles mass to charge

Turn on electric field

Velocity decreases
Attraction to (+) pole
Calculate particle charge
Multiples of same number
e- =- 1.602 X 10-19 C

me / e- = 5.686 X 10-12 kg\C

Negatively charged particle is called an electron

Robert Millikan
Value for the charge on an electron
e = -1.602 X 10-19 C

Calculate electron mass

Charge to mass ratio
Electron charge
Electron Mass
3

me / e- = 5.686 X 10-12 kg\C

e- =- 1.602 X 10-19 C
emass = 9.109 X 10-31 kg\ electron

Rutherfords Experiments

The Atom: J. J. Thomsons Model

Tested JJ Thomsons theory of electrons in center of atom

Bounced alpha particles (He2+) through gold foil
Most went through, some slightly deflected,
Some bounced back completely

Positively charged sphere with electrons imbedded inside

Raisin pudding model

Hydrogen atom
1 electron at the center of a sphere
Helium atom:
2 electrons along a straight line
Applied this analysis to atoms with up to 100 electrons
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Final Model

Rutherfords Conclusions
Determined Thomsons theory flawed and concluded new model

Positive charge carried by particles called protons

Proton charge: fundamental unit of positive charge
The nucleus of a hydrogen atom consisted of 1 proton

Nucleus
Heavy
Dense
(+) charged (He2+)

proton

neutron

Atomic number
# of protons in the nucleus

Electron Cloud
Light and fluffy
Surrounds nucleus
(- )charged

- electron

Neutrons

Experimental Results
particles that go all the way through hit nothing
particles deflected hit electrons in electron cloud
particles bouncing back hit nucleus

Hydrogen
Discovered by James Chadwick
(Deuterium)
Atomic particle with nearly the same mass as protons
No charge- accounts for extra mass of isotopes
Change in mass, no change in properties

Wavelength

Electromagnetic Radiation

Distance between 2 identical points in a cycle

Wave
Repeating disturbance spreading out from a defined origin

Electromagnetic waves
Originate from charge movement

Produce fluctuations in electric and magnetic fields

Require no medium

Symbolized by

Characterized by wavelength, frequency, and amplitude

Wavelength: Distance between 2 identical points in a cycle
Frequency: The number of times the repetition passes a
given point per second
Amplitude: Height of wave from center to peak

Units of length depend on range used

Nanometers (nm) = 10-9 m

Visible light: 390 nm to about 760 nm.

Angstrom (A) = 1010 m

Visible light is 3900 A to 7600 A.

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Frequency

Relationship of Wavelength and Frequency

The number of times the repetition passes a given point

per second

Wavelength x Frequency = Constant = Speed of light = c

c = x =3.0 x108 m/s

Long wavelength: Lower frequency
Short wavelength: Higher frequency

Symbolized by
Hertz (Hz) = 1 cycle per second = 1 cycle/s
Measurement of pitch of a sound wave
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Electromagnetic Spectrum

What is the wavelength of an FM-radiowave

with a 94.9 MHz frequency?

Complete range of wavelengths and frequencies

Extends continuously from shortest wavelengths to longest.

c = =3.00 x 108 m/s

= c/
94.9M Hz = 94.9 x 106 Hz = 94.9 x 106/s

3 . 00 x 10 8 m
1s
x
s
94
.
9
x 10

= 3 . 16 m

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Continuous and Line Spectra

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Emission Spectrum of Helium

Continuous spectrum:
Wavelengths merge
Electromagnetic spectrum is continuous
White light: Consists of all colors of the spectrum.

Line spectrum:
Occurs when light is produced through an element
Spectrum is discontinuous
A pattern of lines characteristic of that element
Used for Identification
Emission Spectroscopy is the analysis of light emitted from a
strongly heated or energized element
Emission Spectrum: A record of the emitted light
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Plancks Constant

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The Photoelectric Effect

Max Plancks Hypothesis

Energy is absorbed or emitted in discrete amounts.
May be in multiples of these discrete amounts
Quantum: The smallest amount of energy:
E = h
Plancks constant: h = 6.626 X 10-34 J s

A full spectrum beam of light hits a metal surface

Energy transferred to electrons in metal creating current
Electrons in metal break attraction to metal ions and escape
The energy leaves in discrete packets, not as a single beam
Einstein called these packets photons.

Einstein
Energy bundled into little packets
Energy of 1 packet= 1 photon= 1 quantum of energy
Ephoton = h
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Energy Calculations

Examples

Einstein: Energy is determined by its frequency

Energy of photon = E = h
Energy/mol = NA (photons/mol) X h ( J s/photon) X (s-1)
Use to compute energy of various wavelengths of light

What is the energy of a radiowave with a frequency of 94.9 MHz?

E photon = h =

6.626 x10 34 Js 94.0 x106

x
= 6.23x10 26 J
s
1

What is the energy per photon and per mole of photons of violet light, with
a wavelength of 415 nm?
E photon =

c = and E = h

hc

Emol

Ephoton = hc/

6.626 x10 34 Js 3.00 x108 m

1
x
x
= 4.79 x10 19 J
1
415 x10 9 m
s
4.79 x10 19 J 6.02 x10 23 photons 2.88 x105 J
x
=
photon
mol
1mol

What wavelength has an energy of E = 1.00 x 10-20J?

=
19

6.626 x10 34 Js 3.00 x108 m

1
x
= 1.99 x10 5 m
x
1
1.00 x10 20 J
s

What is the energy of an electron in a

n=4 energy level?

Energy Level Calculations

All calculations done by comparing energy levels
Initial level: Ei =- B/ ni2
Final level: Ef =- B/ nf2
Elevel = -B/nf2 - -B /nf2 = B (1/ni2 1/nf2)
Energy is emitted or absorbed when an electron
moves between energy levels.
High to low level
energy released: atom more stable
Low to high level
energy absorbed: atom less stable
= 0 at a level infinitely far from the nucleus
Ground state: The lowest possible energy level
Excited state: All other levels

E=

B 2.179 x10 18 J
=
= 1.362 x10 19 J
2
2
n
4

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What is the wavelength of the shift from n = 4 to n =2?

Is light emitted or absorbed?

Emission Spectra
Together, all the photons making the same change from one
energy level to another produce one spectral line

1
1
B B
E = 2 2 = B 2 2
n n
n f ni
f
i

The collection of lines is the emission spectrum

1
1
E = 2 . 179 x10 18 Jx 2 2 = 4 . 086 x10 19 J
2
4

E=
=

6 . 626 x 10

34

hc

so =

3 . 00 x 10
s

20

hc
E

1
4 . 086 x 10

19

= 4 . 86 x 10

Emission Spectrum for Mercury, Hg

= 486.2 nm Visible blue green light is emitted (higher to lower n)

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Bohrs Hydrogen Atom

Wave Mechanics: Matter as Waves

Niels Bohr (1913): Electron energy (En) was quantized

Light has both wave and particle properties

Only certain specified values allowed (stable orbits)

Wave- light dispersed into a continuous spectrum

Particle- Discrete photons displace electrons

A specified energy value is an energy level of the atom

The energy of each stable orbit En = B/n2

Louis de Broglie (1923)

Matter can behave as both particles & waves
A particle with a mass, m, moving at a speed, v, will have a
wavelength () = h/mv
Prediction of matter waves led to the development of the
electron microscope

n is the quantum number for the atom

integers only, 1,2 3..
B = 2.179 X 10-18 J

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Quantum Numbers and Atomic Orbitals

The Principal Quantum Number (n)

Atomic orbital
A region in space with a high probability of finding an electron.
Identified by 4 quantum numbers.

Four Quantum Numbers

1.
2.
3.
4.

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The principal quantum number (n)

The orbital quantum number (l)
The magnetic quantum number (ml)
The spin quantum number (ms)

Restricted to the positive integers: 1, 2, 3, 4, 5,

Indicates the shell or level of the orbital
Indicates the size of the orbital
Integers correspond to row numbers in periodic table
1
2
3
4
5
6
7

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The Orbital Quantum Number (l)

The Magnetic Quantum Number (ml):

Non-negative integers smaller than n

Designates the subshell
Indicates the shape of the orbital

Determines the orientation in space of the orbitals

Any integer from- lto +l
The number of possible values for ml = 2l + 1
Determines the number of orbitals in a subshell
Corresponds to Px,Py,Pz orbitals of the P subshell

I = 0 are called s orbitals

Spherical
l = 1 are called p orbitals
2 teardrops joined point- to- point
Referred to as Px,Py,Pz

l= 1
# values = 3
Range: -1 to 1
ml = -1,0,1

I= 2 are d orbitals
l= 3 are f orbitals.
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Electron Spin Quantum Number (ms)

Quantum Numbers Summary

Explains some of the finer features of atomic emission spectra

The number can have two values: +1/2 and 1/2
The spin refers to a magnetic field induced by the moving
electric charge of the electron as it spins
The magnetic fields of two electrons with opposite spins cancel
one another; there is no net magnetic field for the pair.

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