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Chemistry · Ch 4 — Structure of Atom

Results of Bohr's Theory

4.6.2

Results of Bohr's Theory

Solving out Bohr's postulates for the hydrogen atom gives several concrete, testable results. The allowed stationary states are labelled by the positive integers n=1,2,3,…n = 1,2,3,\ldots, called principal quantum numbers. Their radii follow rn=n2a0r_n = n^2 a_0, where a0=52.9a_0 = 52.9 pm; the smallest orbit (n=1n=1), called the Bohr radius, therefore has radius 52.9 pm. The energy of the stationary state of principal quantum number n is En=−RH(1n2)E_n = -R_H\left(\frac{1}{n^2}\right), where RHR_H, the Rydberg constant expressed in energy units, equals 2.18×10−182.18\times10^{-18} J; working this out for the lowest state (the ground state, n=1n=1) gives E1=−2.18×10−18 JE_1 = -2.18\times10^{-18}\ \text{J}, and for n=2n=2 gives E2=−2.18×10−18×14=−0.545×10−18E_2 = -2.18\times10^{-18}\times\frac{1}{4} = -0.545\times10^{-18} J — a smaller magnitude, i.e. a less negative, higher energy, exactly as expected for an orbit farther from the nucleus. The negative sign itself is a convention: a free electron at rest infinitely far from the nucleus (n → ∞) is assigned zero energy, and since the electron in an atom is bound MORE tightly than that free, zero-energy state, its energy is lower, i.e. negative — the smaller the value of n, the closer the electron sits to the nucleus and the more negative (lower) its energy becomes. Bohr's theory extends directly to hydrogen-LIKE species — ions such as He⁺, Li²⁺, Be³⁺ that, like hydrogen, have only one electron outside the nucleus — simply by including the nuclear charge Z: En=−2.18×10−18(Z2n2)E_n = -2.18\times10^{-18}\left(\frac{Z^2}{n^2}\right) J and rn=52.9(n2Z)r_n = 52.9\left(\frac{n^2}{Z}\right) pm. As Z increases (for the same n …

Misc Negative-energy asideWhat the negative sign of electron energy means

Worked out. An explanatory aside: a free electron at rest, infinitely far from the nucleus, is assigned zero energy (this corresponds to n = ∞ in the energy expression, giving E∞ = 0). As the electron is pulled closer to the nucleus (smaller n), its energy becomes increasingly negative, meaning it is at a LOWER energy than a free electron at rest — the negative sign reflects the attractive electrostatic force between electron and nucleus, and stationary states with smaller n have larger, more neg …

Misc Problem 4.6Identifying hydrogen-like species

Worked out. Worked example: how many electrons are present in 12H^2_1H, ₂He and He⁺, and which of these are hydrogen-like species (species with only one electron)? 12H^2_1H (deuterium) has 1 proton and therefore 1 electron. Neutral ₂He has 2 protons and therefore 2 electrons. He⁺ has one electron fewer than neutral He, i.e. 2 − 1 = 1 electron. So both 12H^2_1H and He⁺ are hydrogen-like species, since each has exactly one electron; neutral …

Misc Problem 4.7Radius and energy of the first orbit of He⁺

Worked out. Worked example: He⁺ is a hydrogen-like species with nuclear charge Z = 2; for its first orbit n = 1. Radius r1=52.9×n2Z=52.9×12=26.45r_1 = 52.9 \times \frac{n^2}{Z} = 52.9 \times \frac{1}{2} = 26.45 pm. Energy En=−2.18×10−18×Z2n2=−2.18×10−18×41=−8.72×10−18E_n = -2.18\times10^{-18}\times\frac{Z^2}{n^2} = -2.18\times10^{-18}\times\frac{4}{1} = -8.72\times10^{-18} J. Both the smaller radius and the more negative energy, compared with a hydrogen atom's first orbit, follow from He⁺'s double …