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the First Two Electrons in the Third Shell
The Bohr model of a hydrogen-like ion predicts that the total energy E of an electron is given by
where Z is the net charge experienced by the electron, n is the principal quantum number and R is a constant equal to approximately 13.6 electron volts (eV). This formula is the result of the total energy being equal to
where e is the charge of the electron and rn is the orbit radius when the principal quantum number is n. The orbit radius is given by
h is Planck's constant divided by 2π and me is the mass of the electron.
Electrons in atoms are organized in shells whose capacities are equal to 2m², where m is an integer. Thus there can be at most 2 electrons in the first shell, 8 in the second shell, 8 in the third shell and 18 in the fourth and fifth shells. Here only the third shell is being considered. Here are all the ionization potentials for such ions. The values are for the elements for which the data is available in the CRC Handbook of Physics and Chemistry 82nd Edition (2001-2002). For elements above magnesium all of the electrons in the third shell have been removed except two.
|The Ionization Potentials for the
First Two Electrons in the Third Shell
for the Elements Magnesium through Zinc
An ion with only one electron in a shell is equivalent to the hydrogen atom but having a positive charge of Z instead of one, where Z is the proton number #p of the nucleus less the amount of shielding by the electrons in the inner shells. The Bohr theory applies to such system. According to the Bohr theory the ionization potential should be
R is constant and n, the quantum number, is equal to 1. Thus the ionization potential should be proportional to Z²; where Z=(#p−ε). For the first electron in the third shell it is usually presumed that the ten electrons in the first and second shells shield exactly ten units of charge. Here is the plot of the relationship.
This appears to be a quadratic relationship but shifted; i.e. something proportional to (#p−ε)². Thus equation is then
where R is the Rydberg constant, 13.6 eV.
The appropriate regression equation would be
The regression results are
The numbers in the square brackets are the t-ratios for the regression coefficients. For a regression coefficient to be statistically significantly different its magnitude must be greater than 2.0. As can be seen the regression coefficients for are highly significant.
The value of ε can be found as
Thus the shielding of the first electron in the third shell by the ten electrons in the first and second shells is not 10. Instead it is 0.815 of that value. This could be due to the distributions of the charges of the two inner electrons, either their radial dispersion or their asymmetry.
The ionization potentials for the first and second electrons in the third shell are shown below. The pattern is the same but the values for the second electron are slightly below those of the first electron.
When the same procedures are applied to the data for the second electron in the third shell the regression results are
The shielding ε that these coefficients imply is
Thus the additional shielding created by the second electron is (8.814100665−8.14917098)=0.664929685, different from but of the same order of magnitude as the value of 0.5 that the simple theory of shielding by electrons in the same shell suggests.
(To be continued.)
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