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The Hydrogen Spectrum and the Bohr Model In formulating his quantum theory, Planck was influenced by the

results of investigations of the emission spectra produced by free (gas-phase) atoms, results that led him to question whether any spectrum, even that of an incandescent lightbulb, was truly continuous. Among these earlier results was a discovery made in 1885 by a Swiss mathematician and schoolteacher named Johann Balmer (18251898). The Hydrogen Emission Spectrum Balmer determined that the frequencies of the four brightest lines in the visible region of the emission spectrum of hydrogen (Figure 7.9a) fit the simple equation (7.6) n=A3.2881*10 15 s -1 Ba 1 2 2 -1 n 2 b CONCEPT TEST 322| Chapter 7| Electrons in Atoms and Periodic Properties where nis a whole number greater than 2specifically, 3 for the red line, 4 for the green, 5 for the blue, and 6 for the violet. Without having seen any other lines in the hydrogen emission spectrum, Balmer predicted there should be at least one more (n 7) at the edge of the violet region, and indeed such a line was later

discovered. Balmer also predicted that hydrogen emission lines should exist in regions outside the visible range, lines corresponding to frequencies calculated by replacing 1/2 2 in Equation 7.6 with 1/1 2 , 1/3 2 , 1/4 2 , and so forth. He was right. In 1908 German physicist Friedrich Paschen (18651947) discovered hydrogen emission lines in the infrared region, corresponding to 1/3 2 instead of 1/2 2 in Balmers equation. A few years later, Theodore Lyman (18741954) at Harvard University discovered hydrogen emission lines in the UV region corresponding to 1/1 2 . By the 1920s the 1/4 2 and 1/5 2 series of emission lines had been discovered. Like the 1/3 2 lines, they are in the infrared region.

Later, Swedish physicist Johannes Robert Rydberg (18541919) revised Balmers equation by changing frequency to wave number(1/l), which is the number of wavelengths per unit of distance. Rydbergs equation is (7.7) where n1is a whole number that remains fixed for a series of emission lines and where n2 is a whole number equal to n1 1,n1 2,...,for successive bright lines in the spectrum. When Balmer and Rydberg derived their equations describing the hydrogen spectrum, they didnt know why the equations worked.The discrete frequencies of hydrogens emission lines indicated that only certain levels of internal energy were available in hydrogen atoms. However, classical (macroscale) physics could not explain the existence of these internal energy levels. A new model was needed that works at the atomic level. 1 l =C1.097*10 -2 (nm) -1 Da 1 n1 2 -1 n2 2 b

SAMPLE EXERCISE 7.4 Calculating the Wavelength of a Line in the Hydrogen Emission Spectrum In the visible portion of the hydrogen emission spectrum (Figure 7.9a), what is the wavelength of the bright line corresponding to n 3 in Equation 7.6? Collect and OrganizeWe are to calculate the wavelength of a line in hydrogen emission spectrum given the nvalues of its initial and final energy levels. Equation 7.7 relates what we know (nvalues) to what we seek (wavelength of light). AnalyzeWe know that the emission line is in the visible region, so we should obtain a wavelength between 400 and 750 nanometeres. In Equation 7.7,n2 must be greater than n1 . Fitting this requirement to the given nvalues, we let n2 3 and n1 2. Solve l=656 nm =C1.097*10 -2 (nm) -1 D(0.1389) =1.524*10 -3 (nm) -1 1 l =C1.097*10 -2 (nm) -1

Da 1 2 2 -1 3 2 b =C1.097*10 -2 (nm) -1 Da 1 4 -1 9 b 7.4 | The Hydrogen Spectrum and the Bohr Model | 323 Think about ItThe calculated wavelength is in the visible region of the electromagnetic spectrum, so the answer is reasonable. Practice ExerciseWhat is the wavelength, in nanometers, of the line in the hydrogen spectrum corresponding to n 4 in Equation 7.6? The Bohr Model of Hydrogen Scientists in the early 20th century faced yet another dilemma. Ernest Rutherford had established a model of the atom that was mostly empty space occupied by negatively charged electrons with a tiny nucleus containing virtually all the mass and all the positive charge. What kept the electrons from falling into the nucleus? Rutherford had suggested that the electrons had to be in motion and hypothesized

that they might orbit the nucleus the way planets orbit the sun. However, classical physics predicted that negative electrons orbiting a positive nucleus would emit energy in the form of electromagnetic radiation and eventually spiral into the nucleus. This does not happen! The problem of explaining why a hydrogen atoms electron is not pulled into its nucleus was addressed by Danish physicist Niels Bohr (18851962), who was well acquainted with the issue because he had studied with Rutherford. Bohr designed a theoretical model based on the electron in a hydrogen atom traveling around the nucleus in one of an array of concentric orbits. Each orbit represents an allowed energy level and is designated by the value of nas shown in Equation 7.8: (7.8) where n 1,2,3,...,q. In the Bohr model an electron in the orbit closest to the nucleus (n 1) has the lowest energy: The next closest orbit has an nvalue of 2 and an electron in it has an energy of Note that this value is less negative than the value for the electron in the n 1 orbit. As the value of nincreases, the radius of the orbit increases and so, too, does the energy of an electron in the orbit; its value becomes less negative. As n approaches q,Eapproaches zero: Zero energy means that the electron is no longer part of the atom. In other words, the H atom has become a H

ion and a free electron. An important feature of the Bohr model is that it provides a theoretical framework for explaining the experimental observations of Balmer, Rydberg, and others. To see the connection, consider what happens when an electron moves between two allowed energy levels in Bohrs model. If we label the initial energy level (the level where the electron starts) ninitial, and we label the second E=-2.178*10

-18 Ja 1 q2 b =0 E=-2.178*10 -18 Ja 1 2 2 b =-5.445*10 -19 J E=-2.178*10 -18 Ja 1 1 2 b =-2.178*10 -18 J E=-2.178*10 -18 Ja 1

n 2 b CHEMTOUR Bohr Model of the Atom CONNECTION We discussed Rutherfords gold-foil experiment and the development of the idea of the nuclear atom in Section 2.1. 324| Chapter 7| Electrons in Atoms and Periodic Properties level (the level where the electron ends up) nfinal, then the change in energy of the electron is (7.9) If the electron moves to an orbit farther from the nucleus, then nfinal ninitial, and the value of the terms inside the parentheses in Equation 7.9 is negative because . This negative value multiplied by the negative coefficient gives us a positive Eand represents an increase in electron energy. On the other hand, if an electron moves from an outer orbit to one closer to the nucleus, then nfinal ninitial , and the sign of Eis negative. This means the electron loses energy. When the electron in a hydrogen atom is in the lowest (n 1) energy level, the atom is said to be in its ground state. If the electron in a hydrogen atom is in an energy level above n 1, then the atom is said to be in an excited state. According to the Bohr model the hydrogen electron can move from the n 1 (ground state) energy level to a higher level (for example,n 3) by absorbing a quantity of energy ( E) that exactly matches the energy difference between the two states. Similarly, an electron in an excited state can move to an even higher energy level by absorbing a quantity of energythat exactly matches the energy difference between the

two excited states. An electron in an excited state can also move to a lower-energy excited state, or to the ground state, by emitting a quantity of energy that exactly matches the energy difference between those two states. This type of electron movement is called an electron transition. Energy-level diagrams show the transitions from one energy level to another that electrons in atoms can make. Figure 7.16 is such a diagram for the hydrogen atom. The black arrow pointing upward represents absorption of sufficient energy to completely remove the electron from a hydrogen atom (ionization).The downward-pointing colored arrows represent decreases in the internal energy of the hydrogen atom that occur when photons are emitted as the electron moves from a higher-energy level to a lower-energy level. If the colored arrows pointed up, they would represent absorptionof photons leading to increases in the internal energy of the atom. In every case the energy of the photon matches the absolute value of E. If you compare Equation 7.9 with Equation 7.7, you will see that they are much alike. The coefficients differ only because of the different units used to express wave number and energy.The key point is that the equation developed to fit the absorption and emission spectra of hydrogen has the same form as the theoretical equation developed by Bohr to explain the internal structure of the hydrogen atom. Thus, atomic emission and absorption spectra reveal the energies of electrons inside atoms. Based on the lengths of the arrows in Figure 7.16, rank the following transitions in order of greatest change in electron energy to the smallest change: a. n 4 n 2b.n 3 n 2 c. n2 n1d.n4 n3 CONCEPT TEST 1

nfinal 26 1 ninitial 2 E=-2.178*10 -18 Ja 1 nfinal 2 -1 ninitial 2 b ground statethe most stable, lowest energy state available to an atom or ion. excited state any energy state in an atom or ion above the ground state. electron transitionmovement of an electron between energy levels. Lyman (ultraviolet wavelengths) n= 1 n= 2 n= 3 n= 4

n= 5 n= 6 n= Balmer (visible wavelengths) Paschen (infrared wavelengths) Ionization FIGURE 7.16An energy-level diagram showing electron transitions for the electron in the hydrogen atom. The arrow pointing up represents ionization. Arrows pointing down represent the electron emitting energy and falling to a lower energy level. This diagram shows several possible transitions for the single electron in hydrogen; each arrow does not represent a different electron in the atom. 7.4 | The Hydrogen Spectrum and the Bohr Model | 325 SAMPLE EXERCISE 7.5 Calculating the Energy Needed for an Electron Transition How much energy is required to ionize a ground-state hydrogen atom? Collect and OrganizeWe are asked to determine the energy required to remove the electron from a hydrogen atom in its ground state. Equation 7.9 enables us to calculate the energy change associated with any electron transition.

AnalyzeTo use Equation 7.9, we need to identify the initial (ninitial ) and final (nfinal) energy levels of the electron. The ground state of a H atom corresponds to the n 1 energy level. If the atom is ionized,n qand the electron is no longer associated with the nucleus. Solve Dividing by q2 yields zero, so the difference in parentheses simplifies to 1, which gives E 2.178 10 18 J Think about ItThis is a small amount of energy, but it is comparable to the work function values (see Sample Exercise 7.3) which involved removing an electron from a metal surface. The sign of Eis positive because energy must be added to remove an electron from the atom and away from its positive nucleus. Practice ExerciseCalculate the energy, in joules, required to ionize a hydrogen atom when its electron is initially in the n 3 energy level. Before doing the calculation, predict whether this energy is greater than or less than the 2.178 10 18 J needed to ionize a ground-state hydrogen atom. =-2.178*10 -18 Ja 1 q2

-1 1 2 b E=-2.178*10 -18 Ja 1 nfinal 2 -1 ninitial 2 b One of the strengths of the Bohr model of the hydrogen atom is that it accurately predicts the energy needed to remove the electron. This energy is called the ionization energy of the hydrogen atom. We examine the ionization energies of other elements in Section 7.11. However, the Bohr model applies only to hydrogen atoms and to ions that have only a single elect

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