CHAPTER 30 THE NATURE OF THE ATOM Rutherford Scattering and the Nuclear Atom
Early Greek models of atoms described them as tiny indivisible spheres. In fact atomos, the Greek word for indivisible, is the origin of the word atom. The plum pudding model was an improvement proposed after electrons were discovered. The idea was that electrons were embedded in a sphere of positive matter like plums in a pudding. This model was replaced with the planetary model proposed by Ernest Rutherford. He directed a beam of alpha particles at a very thin sheet of gold foil. Most of the alpha particles passed through undeflected as expected. Some, however, were deflected up to 180 degrees. The only explanation was that the positive charge of each atom must be concentrated in a relatively small volume which was named the nucleus.
The amount of empty space in an atom is difficult to imagine. It may help to imagine an atom the size of our solar system. If the nucleus of an atom were about the size of the sun, the
A device that contains atoms in this state is called a gas discharge tube. In the case of a solid. it will emit only the wavelengths that are characteristic of that element. If high voltage is impressed across the gaseous element in the tube.67 x 10-27 kg and a radius of 1. Later in the chapter we will address the shortcomings of the planetary model. The electron.
.29 x 10-11 m. etc. Example The nucleus of a hydrogen atom is a proton with a mass of 1. they can be made to emit specific wavelengths characteristic of the atomic structure of that element. If atoms of an element can be separated from other atoms and each other. The Earth's orbit would be 10 times the current radius of Pluto's orbit.0 x 10-15 m. Line Spectra Electromagnetic waves are emitted by all phases of matter when energy is added to them by heating. a continuous spectrum is produced because of the interactions among the atoms and molecules that make up the solid. If we break the light up into individual wavelengths with a grating spectroscope. we can see the individual wavelengths as colors. electric current. with a mass of 9. Compare the density of the nucleus to the density of the atom.radius of the Earth's orbit (representing an electron) would be 400 times what it is now.11 x 10-31 kg orbits at a distance of 5.
and Paschen series. The simplest element is hydrogen and its spectrum has been studied extensively.When we see a series of bright fringes. The three groups of lines that are most famous are the Lyman series.
Each series is composed of the wavelengths emitted when the electron in a hydrogen atom falls from higher energy levels to a
. The spectra above include two line spectra and one continuous spectrum. we call this a line spectrum since each bright fringe has the appearance of a vertical line. Balmer series.
4. so we consider a jump from shell 3 to shell 2. … n = 4. 4. 5. R is called the Rydberg constant and has a value of 1. Example Find the longest and shortest wavelength in the Balmer series. 3. 5.1/n2) 1/λ = R(1/22 . the electron is falling to the first energy level. the electron is falling to the second energy level. In the case of the Lyman series. 6. In the case of the Balmer series. For the shortest wavelength we need the largest energy level jump. In the case of the Paschen series.1/n2) 1/λ = R(1/32 . so we consider a jump from infinity to shell 2. the electron is falling to the third energy level. The Bohr Model of the Hydrogen Atom
. They can be calculated as in the following example.097 x 107 m-1. The longest wavelength occurs when the energy level jump is the smallest.1/n2)
n = 2. … n = 3. Each series has a longest and shortest wavelength.…
In these equations.lower energy level. The equations used to calculate the wavelengths are:
Lyman series Balmer series Paschen series
1/λ = R(1/12 . The energy of a photon = hf where h is Planck's constant and f is the frequency of the photon.
This would prevent the electrons from radiating energy continuously and spiraling into the nucleus.In 1913. These orbits were called stationary orbits or stationary states. The total energy of an atom is:
E = KE + EPE
. When an electron changes from one orbit to another.Ef = hf
Since f = c/λ. Since only certain energies could be emitted by an atom (E = hf). Bohr's idea was to relate atomic structure to this quantization of energy in electromagnetic radiation. Neils Bohr presented a new model of atomic structure in an attempt to solve some of the problems associated with the planetary model. Planck and Einstein had already theorized that light consisted of discrete packets of energy called photons and that energy associated with photons was quantized (only certain values allowed). the energy difference is:
Ei .Ef = hc/λ
and the wavelengths associated with each energy level change could be calculated if the energies could be determined. The electron could only occupy one of these stationary orbits or be in transition between them. the electrons must only be able to occupy certain energy levels.
.E = ½mv2 + (-kZe2/r)
The electrical potential energy is negative since we are looking at the energy of an electron. a centripetal force exists due to the electric charge. the radius of the orbit. 3. 2. To determine r. This gives us the expression:
Ln = mvnrn = nh/2πn = 1. we get:
vn = nh/2πmrn
By substituting into the equation for centripetal force. . . so:
mv2/r = kZe2/r2 mv2 = kZe2/r E = ½ kZe2/r + (-kZe2/r) E = -kZe2/2r
This gives us Bohr's equation for the total energy of the atom due to the location and speed of the electron. Bohr had to assume that the angular momentum of the electron is quantized. Since we are considering a circular orbit.
Solving for vn. we get:
m(nh/2πmrn)2 = kZe2/rn
.29 x 10-11 m)(n2/Z)
For hydrogen. Example Find the radius of the He+ ion when it is in the second excited state. .6 eV.18 x 10-18 J)Z2/n2
n = 1. m. 2. 13.13.6 eV is called the ionization energy for hydrogen. . the equation is:
En = (. If energy is added to the electron. . when the electron has an energy of -13. k. it leaves the atom (n = ∞) and a hydrogen ion is formed. This is the lowest energy level possible in a hydrogen atom.29 x 10-11 m.
Using the accepted values for h.
In a hydrogen atom. 3. This is called the Bohr Radius. 2. we call this the ground state.6 eV)Z2/n2
n = 1. . Z = 1.
.rn = (h2/4π2mke2)n2/Z
n = 1. . Bohr energy levels in joules can be calculated with:
En = (-2. it can occupy a higher energy level until it emits a photon and falls back to a lower energy level. the expression reduces to:
rn = (5. 3. the smallest Bohr orbit (n = 1) has a radius of 5. If the electron is given 13. . 3.6 eV. and e. . .
If the energies are expressed in electron volts. 2.
If white light is passed through a sample of a gas. A gas can emit photons to form a bright line or emission spectrum when its electrons fall from higher energy levels to lower ones.The energy differences associated with the Lyman.
. Balmer. electrons can absorb photons and jump up to an excited state. The reverse process can also happen. The frequencies corresponding to the energies absorbed are absent from the normal continuous spectrum of white light and appear as dark lines called absorption lines. Bohr's equations only apply to an atom with one electron. and Paschen series are shown in the energy level diagram above. Absorption lines appear in the spectrum of the Sun and are called Fraunhofer lines in honor of their discoverer. Interactions among multiple electrons were not considered. Notice how the higher energy levels are very close together.
The DeBroglie wavelength of the electron would be:
λ = h/p = h/mv
If we substitute for λ and rearrange the equation. Quantum mechanics and the Schrödinger equation do a better job. DeBroglie's Explanation Bohr's assumption that angular momentum was quantized as an integral multiple of Planck's constant divided by 2π was explained by DeBroglie. n = 1. . This equation is:
2πr = nλ
n = 1. . DeBroglie felt that particles like electrons existed both as a particle and as a wave. the circumference of the orbit must be an integral multiple of the electron's wavelength. 3. . .The Bohr model provides a fairly good description of the hydrogen atom but it does not accurately describe any other atoms with multiple electrons. 2. 2. 3. 3. .
This is what Bohr assumed for the angular momentum of the electron. In order for an electron to remain in a stable state. . . 2. we get:
2πr = nh/mv mvr = nh/2π
n = 1. .
. The magnitude of the orbital momentum of the electron is:
L = [ℓ(ℓ + 1)]½h/2π
. the value 1 corresponds to p orbitals. 1. 2. The orbital quantum number. . etc.The Quantum Mechanical Picture of the Hydrogen Atom The Bohr model of the atom uses a single number to identify the state of an electron in the hydrogen atom. These states are specified with a total of four quantum numbers per electron. 3. The value 0 corresponds to s orbitals. ℓ can have the values 0. It is called a quantum number since it can only have certain discrete values such as 1. (n-1). 2 corresponds to d orbitals. ℓ determines the angular momentum of the electron due to its orbital motion. 3. It can have integral values beginning with 1(n = 1. . Electrons with slightly different states exist within those principal energy levels.). . . 2. etc. . 1. 2. The principal quantum number specifies the energy level (shell) where the electron is located. 2.
mℓ. The magnetic quantum number. Values of mℓ depend on ℓ and range from -ℓ to +ℓ. in the case of ℓ = 2. describes the effect of an externally applied magnetic field on the energy of the atom. In the case of ℓ = 1. The spin quantum number. and (c) the maximum value that Lz can have. there are three possible orientations. Pieter Zeeman. What are the possible values for the orbital quantum number? Another Example A hydrogen atom is in the second excited state. ms. Example The principal quantum number for an electron in an atom is n = 6. The magnetic quantum number is mℓ = 2. there is only one possible orbital orientation. In the case of ℓ = 0.opposite spins always pair up. mℓ plays no role in determining the energy.
.3. The component of the angular momentum in the Z direction is found with:
Lz = mℓh/2π
The magnetic quantum number describes the orientation of the orbital within the atom. etc. indicates the direction of rotation of the electron itself. The two possibilities are up and down or +½ and -½. 4. Determine (a) the total energy (in eV) of the atom. (b) the magnitude of the maximum angular momentum the electron can have. there are 5 possible orientations. This number becomes important as electrons pair up in orbitals since. If there is no magnetic field. This is called the Zeeman Effect for its discoverer. in stable orbitals .
Furthermore. Y. The lower diagram shows the p orbital oriented along the Z axis. when p. and f orbitals are considered. each energy state corresponds to a specific distance from the nucleus. Quantum mechanics changes this to a probability distribution with the distance r being the most probable distance. The Pauli Exclusion Principle and the Periodic Table
The upper diagram shows the s orbital in the second shell. d. their shapes are not spherical and orientations with respect to the X. and Z axes must be considered.In the Bohr model of the atom.
In the second shell there are eight sets so eight electrons can be found there.
. Since there are only two unique sets in the first energy level. however. only two electrons can be found there. the energy of the electron in that state increases.In a multiple-electron atom. where principal quantum number states (shells) overlap. the Bohr equation for the energy of an atom does not work. Most atoms spend most of their time in the ground state. As the principal quantum number and the orbital quantum number increase. There are some places. The Pauli Exclusion Principle states that no two electrons in an atom can have the same set of the four quantum numbers. When all the electrons in an atom are in their lowest possible energy states. The lowest energy level present in an atom is n = 1 but only two electrons can occupy that shell. The four quantum number approach still gives reasonably good results. this is called the ground state. etc.
An electron from the L shell (n =2) or the M shell (n = 3) will fall to the K shell and release characteristic X-
. This overlap occurs again with the 5s and 4d orbitals and in several other places. The 4s orbital has less energy than the 3d orbitals. This is called Bremsstrahlung (braking radiation). they release this energy when they collide with a metal target. When electrons are given large kinetic energies by moving through a large potential difference. This is what gives the Periodic Table its distinctive structure. usually molybdenum or platinum.On the Periodic Table the fourth energy level begins before the third energy level is complete.
Sometimes electrons in the K shell of the target are knocked out of the shell. The energy is released in a spectrum of wavelengths as the electrons are stopped. X-rays X-rays were discovered by Wilhelm Roentgen. a Dutch physicist.
we can write:
eV = hc/λ λ0 = hc/eV
Example Find the cutoff wavelength for a potential difference of 45.
. is a two dimensional picture and the depth at which absorption occurs is difficult to determine. More dense tissue such as bone absorbs X-rays better than muscle.ray radiation. is determined by the maximum kinetic energy an electron has when it strikes the target material. λ0. This. however. Conventional X-ray photographs have been used for many years as a diagnostic tool. and E = hf = hc/λ. It is called characteristic since the wavelength depends on the energy difference between the two shells.
The cutoff wavelength. Since the energy due to the voltage is eV.000 volts. fat or organ tissue.
P 970 Questions 1. 29. 35. 9.A CAT scan or CT scan (computerized axial tomography) takes multiple X-rays of a slice of the body from different angles. 7. 28. 10. 15. 6. 22. 38
. 12. 23. 7. 8. 11 P 971 Problems 3. The images are then combined into one more detailed image of that slice.