Energy and Wavelength of Emitted Hydrogen Spectra
The energy associated with a particular orbital of a hydrogen atom can be found using the equation
22.3En=−13.6eVn2(n=1,2,3,...),
where n corresponds to the orbital value from the atom’s nucleus. The negative value in the equation is based upon a baseline energy of zero when the electron is infinitely far from the atom. As a result, the negative value shows that energy is necessary to free the electron from its orbital state. The minimum energy to free the electron is also referred to as its binding energy. The equation is only valid for atoms with single electrons in their orbital shells (like hydrogen). For ionized atoms similar to hydrogen, the following formula may be used.
22.4En=Z2n2Eo(n=1,2,3,...)
Please note that Eo corresponds to –13.6 eV, as mentioned earlier. Additionally, Z refers to the atomic number of the element studied. The atomic number is the number of protons in the nucleus—it is different for each element. The above equation is derived from some basic physics principles, namely conservation of energy, conservation of angular momentum, Coulomb’s law, and centripetal force. There are three derivations that result in the orbital energy equations, and they are shown below. While you can use the energy equations without understanding the derivations, they will help to remind you of just how valuable those fundamental concepts are.
Derivation 1 (Finding the Radius of an Orbital)
One primary difference between the planetary model of the solar system and the planetary model of the atom is the cause of the circular motion. While gravitation causes the motion of orbiting planets around an interior star, the Coulomb force is responsible for the circular shape of the electron’s orbit. The magnitude of the centripetal force is mev2rn, while the magnitude of the Coulomb force is k(Zqe)(qe)re2. The assumption here is that the nucleus is more massive than the stationary electron, and the electron orbits about it. That is consistent with the planetary model of the atom. Equating the Coulomb force and the centripetal force,
22.5mev2rn=k(Zqe)(qe)re2,
which yields
22.6rn=k(Zqe2)mv2.
Derivation 2 (Finding the Velocity of the Orbiting Electron)
Bohr was clever enough to find a way to calculate the electron orbital energies in hydrogen. That was an important first step that has been improved upon, but it is well worth repeating here, because it does correctly describe many characteristics of hydrogen. Assuming circular orbits, Bohr proposed that the angular momentum L of an electron in its orbit is also quantized, that is, it has only specific, discrete values. The value for L is given by the formula
22.7L=mevrn=nh2π(n=1,2,3,...),
where L is the angular momentum, me is the electron’s mass, rn is the radius of the n th orbit, and h is Planck’s constant. Note that angular momentum is L=Iω. For a small object at a radius r,I=mr2 , and ω=vr , so that L=Iω=(mr2)(vr)=mvr. Quantization says that the value of mvr can only be equal to h / 2, 2h / 2, 3h / 2 , etc. At the time, Bohr himself did not know why angular momentum should be quantized, but by using that assumption, he was able to calculate the energies in the hydrogen spectrum, something no one else had done at the time.
Derivation 3 (Finding the Energy of the Orbiting Electron)
To get the electron orbital energies, we start by noting that the electron energy is the sum of its kinetic and potential energy.
22.8En=KE+PE
Kinetic energy is the familiar KE=12mv2, assuming the electron is not moving at a relativistic speed. Potential energy for the electron is electrical, or PE=qeV, where V is the potential due to the nucleus, which looks like a point charge. The nucleus has a positive charge Zqe; thus, V=kZqern, recalling an earlier equation for the potential due to a point charge from the chapter on Electricity and Magnetism. Since the electron’s charge is negative, we see that PE=−kZqe2rn.Substituting the expressions for KE and PE,
22.9En=12mev2−kZqe2rn.
Now we solve for rn and v using the equation for angular momentum L=mevrn=nh2π(n=1,2,3,...), giving
22.10v=nh2πmern(n=1,2,3,...)
and
22.11rn=nh2πmev(n=1,2,3,...).
Substituting the expression for rn and v into the above expressions for energy (KE and PE), and performing algebraic manipulation, yields
22.12En=−Z2n2Eo(n=1,2,3,...)
for the orbital energies of hydrogen-like atoms. Here, Eo is the ground-state energy (n = 1) for hydrogen (Z = 1) and is given by
22.13Eo=2π2qe4mek2h2=13.6eV.
Thus, for hydrogen,
22.14En=−13.6eVn2(n=1,2,3,...).
The relationship between orbital energies and orbital states for the hydrogen atom can be seen in Figure 22.12.
Worked Example
A hydrogen atom is struck by a photon. How much energy must be absorbed from the photon to raise the electron of the hydrogen atom from its ground state to its second orbital?
Strategy
The hydrogen atom has an atomic number of Z = 1. Raising the electron from the ground state to its second orbital will increase its orbital level from n = 1 to n = 2. The energy determined will be measured in electron-volts.
Solution
The amount of energy necessary to cause the change in electron state is the difference between the final and initial energies of the electron. The final energy state of the electron can be found using
22.15En=Z2n2Eo(n=1,2,3,...).
Knowing the n and Z values for the hydrogen atom, and knowing that Eo = –13.6 eV, the result is
22.16Ef=1222(−13.6eV)=−3.4eV.
The original amount of energy associated with the electron is equivalent to the ground state orbital, or
22.17EO=1212(−13.6eV)=−13.6eV.
The amount of energy necessary to change the orbital state of the electron can be found by determining the electron’s change in energy.
22.18ΔE=Ef−Eo=(−3.4eV)−(−13.6eV)=+10.2eV
Discussion
The energy required to change the orbital state of the electron is positive. That means that for the electron to move to a state with greater energy, energy must be added to the atom. Should the electron drop back down to its original energy state, a change of –10.2 eV would take place, and 10.2 eV of energy would be emitted from the atom. Just as only quantum amounts of energy may be absorbed by the atom, only quantum amounts of energy can be emitted from the atom. That helps to explain many of the quantum light effects that you have learned about previously.
Worked Example
Characteristic X-Ray Energy
Calculate the approximate energy of an X-ray emitted for an n = 2 to n = 1 transition in a tungsten anode in an X-ray tube.
Strategy
How do we calculate energies in a multiple-electron atom? In the case of characteristic X-rays, the following approximate calculation is reasonable. Characteristic X-rays are produced when an inner-shell vacancy is filled. Inner-shell electrons are nearer the nucleus than others in an atom and thus feel little net effect from the others. That is similar to what happens inside a charged conductor, where its excess charge is distributed over the surface so that it produces no electric field inside. It is reasonable to assume the inner-shell electrons have hydrogen-like energies, as given by
22.19En=Z2n2Eo(n=1,2,3,...)
For tungsten, Z = 74, so that the effective charge is 73.
Solution
The amount of energy given off as an X-ray is found using
22.20ΔE=hf=Ei−Ef,
where
22.21Ef=−Z212Eo=−7321(13.6eV)=−72.5keV
and
22.22Ei=−Z222Eo=−7324(13.6eV)=−18.1keV.
Thus,
22.23ΔE=Ei−Ef=(−18.1keV)−(−72.5keV)=54.4keV.
Discussion
This large photon energy is typical of characteristic X-rays from heavy elements. It is large compared with other atomic emissions because it is produced when an inner-shell vacancy is filled, and inner-shell electrons are tightly bound. Characteristic X-ray energies become progressively larger for heavier elements because their energy increases approximately as Z2. Significant accelerating voltage is needed to create such inner-shell vacancies, because other shells are filled and you cannot simply bump one electron to a higher filled shell. You must remove it from the atom completely. In the case of tungsten, at least 72.5 kV is needed. Tungsten is a common anode material in X-ray tubes; so much of the energy of the impinging electrons is absorbed, raising its temperature, that a high-melting-point material like tungsten is required.
The wavelength of light emitted by an atom can also be determined through basic derivations. Let us consider the energy of a photon emitted from a hydrogen atom in a downward transition, given by the equation
22.24ΔE=hf=Ei−Ef
Substituting En=(−13.6eVn2) , we get
22.25hf=(13.6eV)(1nf2−1ni2).
Dividing both sides of the equation by hc gives us an expression for 1λ,
22.26hfhc=fc=1λ=13.6eVhc(1nf2−1ni2).
It can be shown that
22.27(13.6eVhc)=(13.6eV)(1.602×10−19J/eV)(6.602×10−34J⋅s)(2.998×108m/s)=1.097×107m−1=R,
where R is the Rydberg constant.
Simplified, the formula for determining emitted wavelength can now be written as
22.281λ=R(1nf2−1ni2).
Worked Example
What wavelength of light is emitted by an electron dropping from the third orbital to the ground state of a hydrogen atom?
Strategy
The ground state of a hydrogen atom is considered the first orbital of the atom. As a result, nf = 1 and ni = 3. The Rydberg constant has already been determined and will be constant regardless of atom chosen.
Solution
22.29 1λ=R(1nf2−1ni2)
For the equation above, calculate wavelength based on the known energy states.
22.301λ=1.097×107(112−132)=9.751×106m−1
Rearranging the equation for wavelength yields
22.31λ=1.026×10−7m=102.6nm.
Discussion
This wavelength corresponds to light in the ultraviolet spectrum. As a result, we would not be able to see the photon of light emitted when an electron drops from its third to first energy state. However, it is worth noting that by supplying light of wavelength precisely 102.6 nm, we can cause the electron in hydrogen to move from its first to its third orbital state.