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<strong>atom</strong>, (b) <strong>the</strong> <strong>volume</strong>- <strong>of</strong> <strong>the</strong> <strong>nucleus</strong>, <strong>and'</strong> (c) <strong>the</strong> <strong>percentage</strong> <strong>of</strong> <strong>the</strong><br />

<strong>volume</strong> <strong>of</strong> <strong>the</strong> <strong>atom</strong> that is occupied by <strong>the</strong> <strong>nucleus</strong>.<br />

2. In a Ru<strong>the</strong>rford scattering experiment a target <strong>nucleus</strong> has a diameter<br />

<strong>of</strong> lA X 10-14 m. The incoming Cl particle has a mass <strong>of</strong><br />

6.64 X 10-27 kg. What is <strong>the</strong> kinetic energy <strong>of</strong> an Cl particle that has<br />

a de Broglie wavelength equal to <strong>the</strong> diameter <strong>of</strong> <strong>the</strong> target <strong>nucleus</strong>?<br />

Ignore relativistic effects.<br />

3. The <strong>nucleus</strong> <strong>of</strong> a hydrogen <strong>atom</strong> is a single proton, which has a<br />

radius <strong>of</strong> about 1.0 X IO-IY m. The single electron in a hydrogen<br />

<strong>atom</strong> normally orbits <strong>the</strong> <strong>nucleus</strong> at a distance <strong>of</strong> 5.3 X 10-11 m.<br />

What is <strong>the</strong> ratio <strong>of</strong> <strong>the</strong> density <strong>of</strong> <strong>the</strong> hydrogen <strong>nucleus</strong> to <strong>the</strong> density<br />

<strong>of</strong> <strong>the</strong> complete hydrogen <strong>atom</strong>?<br />

4. Review Conceptual Example I and use <strong>the</strong> information <strong>the</strong>rein as<br />

an aid in working this problem. Suppose you're building a scale<br />

model <strong>of</strong> <strong>the</strong> hydrogen <strong>atom</strong>, and <strong>the</strong> <strong>nucleus</strong> is represented by a ball<br />

<strong>of</strong> radius 3.2 cm (somewhat smaller than a baseball). How many<br />

miles away (I mi = 1.61 X 105 cm) should <strong>the</strong> electron be placed?<br />

* 5. ssm The <strong>nucleus</strong> <strong>of</strong> a copper <strong>atom</strong> contains 29 protons and has a<br />

radius <strong>of</strong> 4.8 X 10-15 m. How much work (in electron volts) is done<br />

by <strong>the</strong> electric force as a proton is brought from infinity, where it is<br />

at rest, to <strong>the</strong> "surface" <strong>of</strong> a copper <strong>nucleus</strong>?<br />

* 6. There are Z protons in <strong>the</strong> <strong>nucleus</strong> <strong>of</strong> an <strong>atom</strong>, where Z is <strong>the</strong><br />

<strong>atom</strong>ic number <strong>of</strong> <strong>the</strong> element. An Cl particle carries a charge <strong>of</strong><br />

+2e. In a scattering experiment, an Cl particle, heading directly toward<br />

a <strong>nucleus</strong> in a metal foil, will come to a halt when all <strong>the</strong> particle's<br />

kinetic energy is converted to electric potential energy. In such<br />

a situation, how close will an Cl particle with a kinetic energy <strong>of</strong><br />

5.0 X 10-13 J come to a gold <strong>nucleus</strong> (Z = 79)?<br />

Section 30.2 Line Spectra<br />

Section 30.3 The Bohr Model <strong>of</strong> <strong>the</strong> Hydrogen Atom<br />

7. ssm www Concept Simulation 30.1 at www.wiley.comlcollege/<br />

cutnell reviews <strong>the</strong> concepts on which <strong>the</strong> solution to this problem<br />

depends. The electron in a hydrogen <strong>atom</strong> is in <strong>the</strong> first excited state,<br />

when <strong>the</strong> electron acquires an additional 2.86 eV <strong>of</strong> energy. What is<br />

<strong>the</strong> quantum number n <strong>of</strong> <strong>the</strong> state'into which <strong>the</strong> electron moves?<br />

8. Using <strong>the</strong> Bohr model, determine <strong>the</strong> ratio <strong>of</strong> <strong>the</strong> energy <strong>of</strong> <strong>the</strong> nth<br />

orbit <strong>of</strong> a triply ionized beryllium <strong>atom</strong> (BeH, Z = 4) to <strong>the</strong> energy<br />

<strong>of</strong> <strong>the</strong> nth orbit <strong>of</strong> a hydrogen <strong>atom</strong> (H).<br />

9. A singly ionized helium <strong>atom</strong> (He+) has only one electron in orbit<br />

about <strong>the</strong> <strong>nucleus</strong>. What is <strong>the</strong> radius <strong>of</strong> <strong>the</strong> ion when it is in <strong>the</strong><br />

~ond excited state?<br />

(!!J: (a) What is <strong>the</strong> minimum energy (in electron volts) that is required<br />

to remove <strong>the</strong> electron from <strong>the</strong> ground state <strong>of</strong> a singly ionized<br />

helium <strong>atom</strong> (He+, Z = 2)? (b) What is <strong>the</strong> ionization energy<br />

for He+?<br />

11. ssm Find <strong>the</strong> energy (in joules) <strong>of</strong> <strong>the</strong> photon that is emitted<br />

when <strong>the</strong> electron in a hydrogen <strong>atom</strong> undergoes a transition from<br />

<strong>the</strong> n = 7 energy level to produce a line in <strong>the</strong> Paschen series .<br />

.-@ A hydrogen <strong>atom</strong> is in <strong>the</strong> ground state. It absorbs energy and<br />

makes a transition to <strong>the</strong> n = 3 excited state. The <strong>atom</strong> returns to <strong>the</strong><br />

ground state by emitting two photons. What are <strong>the</strong>ir wavelengths?<br />

13. Consider <strong>the</strong> Bohr energy expression (Equation 30.13) as it applies<br />

to singly ionized helium He+ (Z = 2) and doubly ionized<br />

lithium Li2+ (Z = 3). This expression predicts equal electron ener­<br />

gies for <strong>the</strong>se two species for certain values <strong>of</strong> <strong>the</strong> quantum number<br />

n (<strong>the</strong> quantum number is different for each species). For quantum<br />

numbers less than or equal to 9, what are <strong>the</strong> lowest three energies<br />

(in electron volts) for which <strong>the</strong> helium energy level is equal to <strong>the</strong><br />

lithium energy level?<br />

PROBLEMS I 971<br />

rilf.)In <strong>the</strong> hydrogen <strong>atom</strong> <strong>the</strong> radius <strong>of</strong> orbit B is sixteen times greater<br />

~ <strong>the</strong> radius <strong>of</strong> orbit A. The total energy <strong>of</strong> <strong>the</strong> electron in orbit A is<br />

- 3AO eV. What is <strong>the</strong> total energy <strong>of</strong> <strong>the</strong> electron in orbit B?<br />

* 15. ssm A wavelength <strong>of</strong> 410.2 nm is emitted by <strong>the</strong> hydrogen<br />

<strong>atom</strong>s in a high-voltage discharge tube. What are <strong>the</strong> initial and final<br />

values <strong>of</strong> <strong>the</strong> quantum number n for <strong>the</strong> energy level transition that<br />

produces this wavelength?<br />

*@ The energy <strong>of</strong> <strong>the</strong> n = 2 Bohr orbit is - 30.6 eV for an unidentified<br />

ionized <strong>atom</strong> in which only one electron moves about <strong>the</strong> <strong>nucleus</strong>.<br />

What is <strong>the</strong> radius <strong>of</strong> <strong>the</strong> n = 5 orbit for this species?<br />

* 17. ssm For <strong>atom</strong>ic hydrogen, <strong>the</strong> Paschen series <strong>of</strong> lines occurs<br />

when nf = 3, whereas <strong>the</strong> Brackett series occurs when nf = 4 in<br />

Equation 30.14. Using this equation, show that <strong>the</strong> ranges <strong>of</strong> wavelengths<br />

in <strong>the</strong>se two series overlap.<br />

*@ Interactive LearningWare 30.1 at www.wiley.comlcolIege/cutnell<br />

reviews <strong>the</strong> concepts that play roles in this problem. A hydrogen<br />

<strong>atom</strong> emits a photon that has momentum with a magnitude <strong>of</strong><br />

5A52 X 10-27 kg' m/so This photon is emitted because <strong>the</strong> electron<br />

in <strong>the</strong> <strong>atom</strong> falls from a higher energy level into <strong>the</strong> n = I leveL<br />

What is <strong>the</strong> quantum number <strong>of</strong> <strong>the</strong> level from which <strong>the</strong> electron<br />

falls? Use a value <strong>of</strong> 6.626 X 10-34 J. s for Planck's constant.<br />

** 19. A diffraction grating is used in <strong>the</strong> first order to separate <strong>the</strong><br />

wavelengths in <strong>the</strong> Balmer series <strong>of</strong> <strong>atom</strong>ic hydrogen. (Section 27.7<br />

discusses diffraction gratings.) The grating and an observation<br />

screen (see Figure 27.32) are separated by a distance <strong>of</strong> 81.0 cm.<br />

You may assume that ()is small, so sin ()= ()when radian measure<br />

is used for (). How many lines per centimeter should <strong>the</strong> grating<br />

have so that <strong>the</strong> longest and <strong>the</strong> next-to-<strong>the</strong>-Iongest wavelengths in<br />

<strong>the</strong> series will be separated by 3.00 cm on <strong>the</strong> screen?<br />

** 20. A certain species <strong>of</strong> ionized <strong>atom</strong>s produces an emission line<br />

spectrum according to <strong>the</strong> Bohr model, but <strong>the</strong> number <strong>of</strong> protons Z<br />

in <strong>the</strong> <strong>nucleus</strong> is unknown. A group <strong>of</strong> lines in <strong>the</strong> spectrum forms a<br />

series in which <strong>the</strong> shortest wavelength is 22.79 nm and <strong>the</strong> longest<br />

wavelength is 41.02 nm. Find <strong>the</strong> next-to-<strong>the</strong>-Iongest wavelength in<br />

<strong>the</strong> series <strong>of</strong> lines.<br />

"@ The<br />

Section 30.5 The Quantum Mechanical Picture<br />

<strong>of</strong> <strong>the</strong> Hydrogen Atom<br />

orbital quantum number for <strong>the</strong> electron in a hydrogen <strong>atom</strong><br />

IS £ = 5. What is <strong>the</strong> smallest possible value (algebraically) for <strong>the</strong><br />

total energy <strong>of</strong> this electron? Give your answer in electron volts.<br />

22. A hydrogen <strong>atom</strong> is in its second excited state. Determine, according<br />

to quantum mechanics, (a) <strong>the</strong> total energy (in eV) <strong>of</strong> <strong>the</strong><br />

<strong>atom</strong>, (b) <strong>the</strong> magnitude <strong>of</strong> <strong>the</strong> maximum angular momentum <strong>the</strong><br />

electron can have in this state, and (c) <strong>the</strong> maximum value that <strong>the</strong> z<br />

, 23. ssm www The principal quantum number for an electron in an<br />

~mponent a om is n = Lz6, <strong>of</strong>and <strong>the</strong> <strong>the</strong> angular magnetic momentum quantumcannumber have. is me = 2. What<br />

possible values for <strong>the</strong> orbital quantum<br />

have?<br />

number £ could this electron<br />

24. The maximum value for <strong>the</strong> magnetic quantum number in state<br />

A is me = 2, while in state B it is me = I. What is <strong>the</strong> ratio LA/LB <strong>of</strong><br />

<strong>the</strong> magnitudes<br />

<strong>the</strong>se two states?<br />

<strong>of</strong> <strong>the</strong> orbital angular momenta <strong>of</strong> an electron in<br />

* 25. Interactive Solution 30.25 at www.wiley.comlcollege/cutnell<br />

<strong>of</strong>fers one approach to problems <strong>of</strong> this type. For an electron in a hydrogen<br />

<strong>atom</strong>, <strong>the</strong> z component <strong>of</strong> <strong>the</strong> angular momentum has a maximum<br />

value <strong>of</strong> L, = 4.22 X 10-34 J . s. Find <strong>the</strong> three smallest possible<br />

values (algebraically)<br />

this <strong>atom</strong> could have.<br />

for <strong>the</strong> total energy (in electron volts) that


972 I CHAPTER 30 I THE NATURE OF THE ATOM<br />

ff6J Review Conceptual Example 6 as backg;ound for this problem.<br />

~ <strong>the</strong> hydrogen <strong>atom</strong>, <strong>the</strong> Bohr model and quantum mechanics<br />

both give <strong>the</strong> same value for <strong>the</strong> energy <strong>of</strong> <strong>the</strong> nth state. However,<br />

<strong>the</strong>y do not give <strong>the</strong> same value for <strong>the</strong> orbital angular momentum L.<br />

(a) For n = I, determine <strong>the</strong> values <strong>of</strong> L [in units <strong>of</strong> h/(27T)] predicted<br />

by <strong>the</strong> Bohr model and quantum mechanics. (b) Repeat part<br />

(a) for n = 3, noting that quantum mechanics permits more than one<br />

value <strong>of</strong> £ when <strong>the</strong> electron is in <strong>the</strong> n = 3 state.<br />

** 27. ssm www An electron is in <strong>the</strong> n = 5 state. What is <strong>the</strong> small­<br />

est possible value for <strong>the</strong> angle between <strong>the</strong> z component <strong>of</strong> <strong>the</strong> orbital<br />

angular momentum and <strong>the</strong> orbital angular momentum?<br />

Section 30.6 The Pauli Exclusion Principle and <strong>the</strong> Periodic<br />

Table <strong>of</strong> <strong>the</strong> Elements<br />

28. Two <strong>of</strong> <strong>the</strong> three electrons in a lithium <strong>atom</strong> have quantum numbers<br />

<strong>of</strong> n = 1, £ = 0, me = 0, m, = +! and n = 1, £ = 0, me = 0,<br />

m, = -!. What quantum numbers can <strong>the</strong> third electron have if <strong>the</strong><br />

<strong>atom</strong> is in (a) its ground state and (b) its first excited state?<br />

29. In <strong>the</strong> style shown in Table 30.3, write down <strong>the</strong> ground-state<br />

electronic configuration for arsenic As (2 = 33). Refer to Figure<br />

30.17 for <strong>the</strong> order in which <strong>the</strong> sub shells fill.<br />

30. Figure 30.17 was constructed using <strong>the</strong> Pauli exclusion principle<br />

and indicates that <strong>the</strong> n = 1 shell holds 2 electrons, <strong>the</strong> n = 2 shell<br />

holds 8 electrons, and <strong>the</strong> n = 3 shell holds 18 electrons. These num­<br />

bers can be obtained by adding <strong>the</strong> numbers given in'<strong>the</strong> figure for<br />

<strong>the</strong> subshells contained within a given shell. How many electrons can<br />

be put into <strong>the</strong> n = 5 shell, which is only partly shown in <strong>the</strong> figure?<br />

31. Write down <strong>the</strong> fourteen sets <strong>of</strong> <strong>the</strong> four quantum numbers that<br />

correspond to <strong>the</strong> electrons in a completely filled 4f subshell.<br />

* 32. What is <strong>the</strong> <strong>atom</strong> with <strong>the</strong> smallest <strong>atom</strong>ic number that contains<br />

<strong>the</strong> same number <strong>of</strong> electrons in its s subshells as it does in its d sub­<br />

shell? Refer to Figure 30.17 for <strong>the</strong> order in which <strong>the</strong> subshells fill.<br />

Section 30.7 X-Rays<br />

33. ssm Molybdenum has an <strong>atom</strong>ic number <strong>of</strong> 2 = 42. Using <strong>the</strong><br />

Bohr model, estimate <strong>the</strong> wavelength <strong>of</strong> <strong>the</strong> Kcx X-ray.<br />

34. Interactive LearningWare 30.2 at www.wiley.comlcollege/cutnell<br />

reviews <strong>the</strong> concepts that are pertinent to this problem. By using <strong>the</strong><br />

Bohr model, decide which element is likely to emit a Kcx X-ray with<br />

a wavelength <strong>of</strong> 4.5 X 10-9 m.<br />

35. Interactive Solution 30.35 at www.wiley.comlcollege/cutnell<br />

provides one model for solving problems such as this one. An X-ray<br />

tube is being operated at a potential difference <strong>of</strong> 52.0 kV. What is<br />

<strong>the</strong> Bremsstrahlung wavelength that corresponds to 35.0% <strong>of</strong> <strong>the</strong> kinetic<br />

energy with which an electron collides with <strong>the</strong> metal target in<br />

<strong>the</strong> tube?<br />

IADDITIONAL PROBLEMS<br />

44. Referring to Figure 30.17 for <strong>the</strong> order in which <strong>the</strong> sub shells<br />

fill and following <strong>the</strong> style used in Table 30.3, determine <strong>the</strong> groundstate<br />

electronic configuration for cadmium Cd (2 = 48).<br />

45. ssm www In <strong>the</strong> line spectrum <strong>of</strong> <strong>atom</strong>ic hydrogen <strong>the</strong>re is<br />

also a group <strong>of</strong> lines known as <strong>the</strong> Pfund series. These lines are produced<br />

when electrons, excited to high energy levels, make transitions<br />

to <strong>the</strong> n = 5 level. Determine (a) <strong>the</strong> longest wavelength and<br />

36. What is <strong>the</strong> minimum potential difference that must be applied<br />

to an X-ray tube to knock a K-shell electron completely out <strong>of</strong> an<br />

<strong>atom</strong> in a copper (2 = 29) target? Use <strong>the</strong> Bohr model as needed.<br />

* 37. ssm An X-ray tube contains a silver (2 = 47) target. The high<br />

voltage in this tube is increased from zero. Using <strong>the</strong> Bohr model,<br />

find <strong>the</strong> value <strong>of</strong> <strong>the</strong> voltage at which <strong>the</strong> Kcx X-ray just appears in<br />

<strong>the</strong> X-ray spectrum.<br />

* 38. Multiple-Concept Example 9 reviews <strong>the</strong> concepts that are<br />

important in this problem. An electron, traveling at a speed <strong>of</strong><br />

6.00 X 107 m/s, strikes <strong>the</strong> target <strong>of</strong> an X-ray tube. Upon impact, <strong>the</strong><br />

electron decelerates to one-quarter <strong>of</strong> its original speed, emitting an<br />

X-ray in <strong>the</strong> process. What is <strong>the</strong> wavelength <strong>of</strong> <strong>the</strong> X-ray photon?<br />

39.r.'<br />

Section 30.8 The Laser<br />

R tached retina back into place. The wavelength <strong>of</strong> <strong>the</strong><br />

laser ssm wwwAlaserisusedineyesurgerytoweldade­<br />

beam is 514 nm, and <strong>the</strong> power is 1.5 W. During<br />

surgery, <strong>the</strong> laser beam is turned on for 0.050 s. During this time,<br />

how many photons are emitted by <strong>the</strong> laser?<br />

40. ~ The dye laser used in <strong>the</strong> treatment <strong>of</strong> <strong>the</strong> port-wine stain<br />

8~ in 585Figure nm. A30.30 carbon (seedioxide Sectionlaser 30.9) produces has a wavelength a wavelength<strong>of</strong><br />

<strong>of</strong> 1.06 X 10-5 m. What is <strong>the</strong> minimum number <strong>of</strong> photons that <strong>the</strong><br />

carbon dioxide laser must produce to deliver at least as much or<br />

more energy to a target as does a single photon from <strong>the</strong> dye laser?<br />

41. A pulsed laser emits light in a series <strong>of</strong> short pulses, each having<br />

a duration <strong>of</strong> 25.0 ms. The average power <strong>of</strong> each pulse is<br />

5.00 mW, and <strong>the</strong> wavelength <strong>of</strong> <strong>the</strong> light is 633 nm. Find (a) <strong>the</strong><br />

energy <strong>of</strong> each pulse and (b) <strong>the</strong> number <strong>of</strong> photons in each pulse.<br />

. an eye condition known as narrow-angle glaucoma, in<br />

42. T'A • which laserpressure peripheral buildup iridotomy in <strong>the</strong> is eye a procedure can lead t<strong>of</strong>or loss treating <strong>of</strong> vision.<br />

A neodymium YAG laser (wavelength = 1064 nm) is used in<br />

<strong>the</strong> procedure to punch a tiny hole in <strong>the</strong> peripheral iris, <strong>the</strong>reby<br />

relieving <strong>the</strong> pressure buildup. In one application <strong>the</strong> laser delivers<br />

4.1 X 10-3 J <strong>of</strong> energy to <strong>the</strong> iris in creating <strong>the</strong> hole. How many<br />

photons does <strong>the</strong> laser deliver?<br />

* 43. Fusion is <strong>the</strong> process by which <strong>the</strong> sun produces energy. One<br />

experimental technique for creating controlled fusion utilizes<br />

a solid-state laser that emits a wavelength <strong>of</strong> 1060 nm and can produce<br />

a power <strong>of</strong> 1.0 X 1014 W for a pulse duration <strong>of</strong> 1.1 X 10-11 s.<br />

In contrast, <strong>the</strong> helium/neon laser used at <strong>the</strong> checkout counter<br />

in a bar-code scanner emits a wavelength <strong>of</strong> 633 nm and produces<br />

a power <strong>of</strong> about 1.0 X 10-3 W. How long (in days)<br />

would <strong>the</strong> helium/neon laser have to operate to produce <strong>the</strong><br />

same number <strong>of</strong> photons that <strong>the</strong> solid-state laser produces in<br />

1.1 X 1O-11 s?<br />

(b) <strong>the</strong> shortest wavelength in this series. (c) Refer to Figure 24.10<br />

and identify <strong>the</strong> region <strong>of</strong> <strong>the</strong> electromagnetic spectrum in which<br />

<strong>the</strong>se lines are found.<br />

46. The <strong>atom</strong>ic number <strong>of</strong> lead is 2 = 82. According to <strong>the</strong> Bohr<br />

model, what is <strong>the</strong> energy (in joules) <strong>of</strong> a Kcx X-ray photon?<br />

47. ssm When an electron makes a transition between energy levels<br />

<strong>of</strong> an <strong>atom</strong>, <strong>the</strong>re are no restrictions on <strong>the</strong> initial and final values <strong>of</strong>


Chapter 30 Problems 1515<br />

8. REASONING According to <strong>the</strong> Bohr model, <strong>the</strong> energy (in joules) <strong>of</strong> <strong>the</strong> nth orbit <strong>of</strong> an<br />

<strong>atom</strong> containing a single electron is<br />

En = -(2.18x10-18 J) Z:<br />

n<br />

(30.12)<br />

where Z is <strong>the</strong> <strong>atom</strong>ic number <strong>of</strong> <strong>the</strong> <strong>atom</strong>. The ratio <strong>of</strong> <strong>the</strong> energies <strong>of</strong> <strong>the</strong> two <strong>atom</strong>s can be<br />

obtained directly by using this relation.<br />

SOLUTION Taking <strong>the</strong> ratio <strong>of</strong> <strong>the</strong> energy E B 3+ <strong>of</strong> <strong>the</strong> nth orbit <strong>of</strong> a beryllium <strong>atom</strong><br />

n, e<br />

(ZBe3+ = 4) to <strong>the</strong> energy En, H <strong>of</strong> <strong>the</strong> nth orbit <strong>of</strong> a hydrogen (ZH = I) <strong>atom</strong> gives<br />

En, B,;' -(2.18xlO-18 J) Z~,;.<br />

= 2 Z2<br />

En.H "2 =~= (4)2<br />

-(2.18x 10-18 J) ZH Z~ (1)2 =[lli<br />

n2<br />

9. REASONING The <strong>atom</strong>ic number for helium is Z = 2. The ground state is <strong>the</strong> n = 1 state,<br />

<strong>the</strong> first excited state is <strong>the</strong> n = 2 state, and <strong>the</strong> second excited state is <strong>the</strong> n = 3 state. With<br />

Z= 2 and n = 3, we can use Equation 30.10 to find <strong>the</strong> radius <strong>of</strong> <strong>the</strong> ion.<br />

SOLUTION The radius <strong>of</strong><strong>the</strong> second excited state is<br />

10. REASONING<br />

a. The total energy En for a single electron in <strong>the</strong> nth state is given by<br />

Z2<br />

En = -(13.6 eV)-2 n<br />

(30.10)<br />

(30.13)<br />

where Z = 2 for helium. The minimum amount <strong>of</strong> energy required to remove <strong>the</strong> electron<br />

from <strong>the</strong> ground state (n = 1) is that needed to move <strong>the</strong> electron into <strong>the</strong> state for which<br />

n = 2. This amount equals <strong>the</strong> difference between <strong>the</strong> two energy levels.<br />

b. The ionization energy defined as <strong>the</strong> minimum amount <strong>of</strong> energy required to remove <strong>the</strong><br />

electron from <strong>the</strong> n = 1 orbit to <strong>the</strong> highest possible excited state (n = 00) .


11,<br />

1516 THE NATURE OF THE ATOM<br />

SOLUTION<br />

a. The minimum amount <strong>of</strong> energy required to remove <strong>the</strong> electron from <strong>the</strong> ground state<br />

(n = 1) and move it into <strong>the</strong> state for which n = 2 is<br />

Minimum energy = E, _ El = -(13.6 22 eV)(2)' - [-(13.6 12 eV) (2)' ] = 140.8 eVI<br />

b. The ionization energy is <strong>the</strong> difference between <strong>the</strong> ground-state energy (n = 1) and <strong>the</strong><br />

energy in <strong>the</strong> highest possible excited state (n = 00) . Thus,<br />

Ionization energy ~ E__ El = -(13.6 e~) (2)' [-(13.6 eV)(2)']_<br />

(00) 12 -154.4 eVI<br />

11. I SSMI REASONING According to Equation 30.14, <strong>the</strong> wavelength A emitted by <strong>the</strong><br />

hydrogen <strong>atom</strong> when it makes a transition from <strong>the</strong> level with nj to <strong>the</strong> level with nf is given<br />

by<br />

-=---- (Z2) --- wIth nj,nf =1,2,3, ... and nj >nf<br />

A1 2tr2mk2e4 h3e ( nl 1 ni2 1 J .<br />

where 2tr2mk2e4 /(h3e) = 1.097 X107 m-I and Z= 1 for hydrogen. Once <strong>the</strong> wavelength<br />

for <strong>the</strong> particular transition in question is determined, Equation 29.2 (E = hf = he / A) can<br />

be used to find <strong>the</strong> energy <strong>of</strong> <strong>the</strong> emitted photon.<br />

SOLUTION In <strong>the</strong> Paschen series, nf= 3. Using <strong>the</strong> above expression with Z= 1, nj = 7<br />

and nf= 3, we find that<br />

~ = (1.097 X 107 m-I)(I') (3~- 71,) or A=1.005xlO-6 m<br />

The photon energy is<br />

he (6.63XlO-34 J.s)(3.00XI08 rnls) I I<br />

E=-=-----------= 1.98xl0-19 J<br />

A 1.005xl0-6 m '------


Chapter 30 Problems 1517<br />

12. REASONING Since <strong>the</strong> <strong>atom</strong> emits two photons as it returns to <strong>the</strong> ground state, one is<br />

emitted when <strong>the</strong> electron falls from n = 3 to n = 2, and <strong>the</strong> o<strong>the</strong>r is emitted when it<br />

subsequently drops from n = 2 to n = 1. The wavelengths <strong>of</strong> <strong>the</strong> photons emitted during<br />

<strong>the</strong>se transitions are given by Equation 30.14 with <strong>the</strong> appropriate values for <strong>the</strong> initial and<br />

final numbers, ni and ne<br />

SOLUTION The wavelengths <strong>of</strong> <strong>the</strong> photons are<br />

n =3 ton =2 ,.1,= 1 ( 1.097x10 7 m_1)()2(1 1 "22-"32 1) =1.524xlO 6 m-1<br />

n = 2 to n = 1<br />

,.1,= !6.56XlO-7ml<br />

~ =(1.097X107 m-1)(1)2(*_ 212)=8.228X106 m-I<br />

A=I1.22X10-7 m!<br />

(30.14)<br />

(30.14)<br />

13. REASONING The Bohr expression as it applies to anyone-electron species <strong>of</strong> <strong>atom</strong>ic<br />

number Z, is given by Equation 30.13: En = -(13.6 eV)(Z2 / n2). For certain values <strong>of</strong> <strong>the</strong><br />

quantum number n, this expression predicts equal electron energies for singly ionized<br />

helium He + (Z = 2) and doubly ionized lithium Li + (Z = 3). As stated in <strong>the</strong> problem, <strong>the</strong><br />

quantum number n is different for <strong>the</strong> equal energy states for each species.<br />

SOLUTION For, equal energies, we can write<br />

Simplifying, this becomes<br />

Thus,<br />

or<br />

Z2 Z2<br />

-(13.6 eV) ~e = -(13.6 eV) ii<br />

nHe nLi<br />

or<br />

4 9<br />

2 2<br />

nHe nLi<br />

Therefore, <strong>the</strong> value <strong>of</strong> <strong>the</strong> helium energy level is equal to <strong>the</strong> lithium energy level for any<br />

value <strong>of</strong> nHe that is two-thirds <strong>of</strong> nLi· For quantum numbers less than or equal to 9, an


I.<br />

-I' j.<br />

-3.40eV 9-1.S1eV<br />

3-13.6 6nLiEnergy<br />

eV<br />

--- --~- --- -- -- ----<br />

1518 THE NATURE OF THE ATOM<br />

equality in energy levels will occur for nHe = 2,4, 6 corresponding to nLi = 3, 6, 9. The<br />

results are summarized in <strong>the</strong> following table.<br />

24<br />

nHe<br />

14. REASONING In <strong>the</strong> Bohr model <strong>of</strong> <strong>the</strong> hydrogen <strong>atom</strong> <strong>the</strong> total energy En <strong>of</strong> <strong>the</strong> electron is<br />

given in electron volts by Equation 30.13 and <strong>the</strong> orbital radius rn is given in meters by<br />

Equation 30.10:<br />

Solving <strong>the</strong> radius equation for n2 and substituting <strong>the</strong> result into <strong>the</strong> energy equation gives<br />

En = -13.6 = (-13.6)(S.29X10-11)<br />

rnl(S.29X10-11) rn<br />

Thus, <strong>the</strong> energy is inversely proportional to <strong>the</strong> radius, and it is on this fact that we base our<br />

solution.<br />

SOLUTION We know that <strong>the</strong> radius <strong>of</strong> orbit B is sixteen times greater than <strong>the</strong> radius <strong>of</strong><br />

orbit A. Since <strong>the</strong> total energy is inversely proportional to <strong>the</strong> radius, it follows that <strong>the</strong> total<br />

energy <strong>of</strong> <strong>the</strong> electron in orbit B is one-sixteenth <strong>of</strong> <strong>the</strong> total energy in orbit A:<br />

EA _ -3.40 eV = 1-0.213 eVI<br />

EB=16.0- 16.0<br />

IS. I SSM I REASONING A wavelength <strong>of</strong> 410.2 nm is emitted by <strong>the</strong> hydrogen <strong>atom</strong>s in a<br />

high-voltage discharge tube. This transition lies in <strong>the</strong> visible region (380-7S0 nm) <strong>of</strong> <strong>the</strong><br />

hydrogen spectrum. Thus, we can conclude that <strong>the</strong> transition is in <strong>the</strong> Balmer series and,<br />

<strong>the</strong>refore, that nf = 2. The value <strong>of</strong> ni can be found using Equation 30.14, according to which<br />

<strong>the</strong> Ba1mer series transitions are given by<br />

11 = 3, 4, S, ...


Chapter 30 Problems 1519<br />

This expression may be solved for ni for <strong>the</strong> energy transition that produces <strong>the</strong> given<br />

wavelength.<br />

SOLUTION Solving for ni' we find that<br />

Therefore, <strong>the</strong> initial and final states are identified by I ni = 6 and nf = 2 I·<br />

16. REASONING The energy levels and radii <strong>of</strong> a hydrogenic species <strong>of</strong> <strong>atom</strong>ic number Z are<br />

given by Equations30.13 and 30.10, respectively: En=-(13.6eV)(Z2/n2) and<br />

rn = (5.29 x 10-11 m)( n2 /Z) . We can use Equation 30.13 to find <strong>the</strong> value <strong>of</strong> Z for <strong>the</strong><br />

unidentified ionized <strong>atom</strong> and <strong>the</strong>n calculate <strong>the</strong> radius <strong>of</strong> <strong>the</strong> n = 5 orbit using<br />

Equation 30.10.<br />

SOLUTION Solving Equation 30.13 for <strong>atom</strong>ic number Z <strong>of</strong> <strong>the</strong> unknown species, we have<br />

Z=<br />

Therefore, <strong>the</strong> radius <strong>of</strong> <strong>the</strong> n = 5 orbit is<br />

-13.6 Enn2 eV = ~ {(-30.6 -13.6eV)(2)2 eV = 3<br />

17. I SSMI REASONING AND SOLUTION For <strong>the</strong> Paschen series, nf = 3. The range <strong>of</strong><br />

wavelengths occurs for values <strong>of</strong> nj = 4 to ni= 00. Using Equation 30.14, we find that <strong>the</strong><br />

shortest wavelength occurs for nj = 00 and is given by<br />

/L=8.204x10-7 m<br />

~---~v~---~<br />

Shortest wavelength in<br />

Paschen series


1520 THE NATURE OF THE ATOM<br />

The longest wavelength in <strong>the</strong> Paschen series occurs for ni= 4 and is given by<br />

A = 1.875 X 10-6 m<br />

~---~v·~---~<br />

Longest wavelength in<br />

Paschen series<br />

For <strong>the</strong> Brackett series, nf= 4. The range <strong>of</strong> wavelengths occurs for values <strong>of</strong> ni= 5 to<br />

ni= 00, Using Equation 30.14, we find that <strong>the</strong> shortest wavelength occurs for ni= 00 and is<br />

given by<br />

~ =(l.097Xl07 m-I)( 41,- 5; J<br />

or<br />

or<br />

A = 4.051 X 10-6 m<br />

v<br />

Longest wavelength in<br />

Brackett series<br />

A=1.459x10-6 m<br />

v<br />

Shortest wavelength in<br />

Brackett series<br />

The longest wavelength in <strong>the</strong> Brackett series occurs for ni= 5 and is given by<br />

Since <strong>the</strong> longest wavelength in <strong>the</strong> Paschen series falls within <strong>the</strong> Brackett series, <strong>the</strong><br />

wavelengths <strong>of</strong> <strong>the</strong> two series overlap.<br />

18. REASONING· To obtain <strong>the</strong> quantum number <strong>of</strong> <strong>the</strong> higher level from which <strong>the</strong> electron<br />

falls, we will use Equation 30.14 for <strong>the</strong> reciprocal <strong>of</strong> <strong>the</strong> wavelength A <strong>of</strong> <strong>the</strong> photon:<br />

where R is <strong>the</strong> Rydberg constant and nf and ni' respectively, are <strong>the</strong> quantum numbers <strong>of</strong> <strong>the</strong><br />

final and initial levels. Although we are not directly given <strong>the</strong> wavelength, we do have a<br />

value for <strong>the</strong> magnitude p <strong>of</strong> <strong>the</strong> photon's momentum, and <strong>the</strong> momentum and <strong>the</strong><br />

wavelength are related according to Equation 29.6:<br />

j~.<br />

'~<br />

',[i<br />

o i where his Planck's constant.<br />

h<br />

p=- A<br />

Using Equation 30.14 to substitute for ~, we obtain<br />

A


SOLUTION Rearranging Equation (1) gives<br />

Thus, we find<br />

Chapter 30 Problems 1521<br />

p=-=hR --- (1)<br />

Ah (1nf nf 1 J<br />

_1 __ 1 _ P<br />

nf nf - hR<br />

_1 __ 1 _L<br />

nf - nf hR<br />

1 1 P _ 1 5.452x10-27 kg·m/s -0.2499 or n =!lI<br />

nj2 = ni - hR -12- (6.626X10-34 J.s)(1.097X107 m-l) 1<br />

or<br />

19. REASONING AND SOLUTION We need to use Equation 30.14 to find <strong>the</strong> spacing<br />

between <strong>the</strong> longest and next-to-<strong>the</strong> longest wavelengths in <strong>the</strong> Ba1mer series. In order to do<br />

this, we need to first find <strong>the</strong>se two wavelengths.<br />

Longest:<br />

-=R --- = 1.097x10 m ---<br />

/41 ( nf 1 ni2 1 J ( 7 -1)( 22 1 32 1 )<br />

Next-to-Iongest:<br />

_I ~ =R( ~_~ nf nj J~(1.097XI07 m-I)(_l 22 __1 42 )<br />

or /4 = 656.3 nm<br />

or ~ = 486.2 nm<br />

Equation 27.7 states that sin B= mAid. Using <strong>the</strong> small angle approximation, we have<br />

sin B"'" tan B"'" B = Y<br />

L<br />

so that y/L = mAid. The position <strong>of</strong> <strong>the</strong> fringe due to <strong>the</strong> longest wavelength is Yl = mAlL/d.<br />

For <strong>the</strong> next-to-Iongest, Y2 = m~L/d. The difference in <strong>the</strong> positions on <strong>the</strong> screen is,<br />

<strong>the</strong>refore, Yl - Y2 = (mL/d)(Al -~) which gives<br />

d= mL(/4 -~)<br />

Yj- Y2


Chapter 30 Problems 1523<br />

21. REASONING The orbital quantum number .e has values <strong>of</strong> 0, 1, 2, ....., (n -1), according<br />

to <strong>the</strong> discussion in Section 30.5. Since.e = 5, we can conclude, <strong>the</strong>refore, that n ;? 6. This<br />

knowledge about <strong>the</strong> principal quantum number n can be used with Equation 30.13,<br />

E = -(13.6 eV)Z2/n2, to determine <strong>the</strong> smallest value for <strong>the</strong> total energy E .<br />

n n<br />

SOLUTION The smallest value <strong>of</strong> E (i.e., <strong>the</strong> most negative) occurs when n = 6. Thus,<br />

n<br />

using Z = 1 for hydrogen, we find<br />

Z2 12<br />

En = -(13.6 eV)~ = -(13.6 eV)"62 = 1-0.378 eV I<br />

22. REASONING<br />

a. The ground state is <strong>the</strong> n = 1 state, <strong>the</strong> first excited state is <strong>the</strong> n = 2 state, and <strong>the</strong> second<br />

excited state is <strong>the</strong> n = 3 state. The total energy (in eV) <strong>of</strong> a hydrogen <strong>atom</strong> in <strong>the</strong> n = 3<br />

state is given by Equation 30.13.<br />

b. According to quantum mechanics, <strong>the</strong> magnitude L <strong>of</strong> <strong>the</strong> angular momentum is given by<br />

Equation 30.15 as L=~.e(.e+l)(h/21r), where .e is <strong>the</strong> orbital quantum number. The<br />

discussion in Section 30.5 indicates that <strong>the</strong> maximum value that .e can have is one less<br />

than <strong>the</strong> principal quantum number, so that .e max = n - 1.<br />

c. Equation 30.16 gives <strong>the</strong> z-component Lz <strong>of</strong> <strong>the</strong> angular momentum as Lz = m£ (h / 21r) ,<br />

where me is <strong>the</strong> magnetic quantum number. According to <strong>the</strong> discussion in Section 30.5,<br />

<strong>the</strong> maximum value that m£ can attain is when it is equal to <strong>the</strong> orbital quantum number,<br />

which is .e max'<br />

SOLUTION<br />

a. The total energy <strong>of</strong> <strong>the</strong> hydrogen <strong>atom</strong> is given by Equation 30.13. Using n = 3, we have<br />

(13.6 eV)(1)2 = 1-1.51 eVI<br />

E3 = 32<br />

b. The maximum orbital quantum number is .e max = n - 1 = 3 - 1 = 2. The maximum<br />

angular momentum Lmax has a magnitude given by Equation 30.15:


1524 THE NATURE OF THE ATOM<br />

c. The maximum value for <strong>the</strong> z-component Lz <strong>of</strong> <strong>the</strong> angular momentum is<br />

(withmf =J!max=2)<br />

L =m ~=(2)6.63XlO-34 ],s=12.11X10-34 J.sl<br />

z £ 2tr 2tr .------<br />

23. ISSMII wwwl REASONING The values that I can have depend on <strong>the</strong> value <strong>of</strong> n, and<br />

only <strong>the</strong> following integers are allowed: I = 0, 1, 2, ... (n -1). The values that ml can<br />

have depend on <strong>the</strong> value <strong>of</strong> I , with only <strong>the</strong> following positive and negative integers being<br />

permitted: mf = -J!, ... -2, -1,0, +1, +2, .. .+e.<br />

SOLUTION Thus, when n = 6, <strong>the</strong> possible values <strong>of</strong> I are 0, 1,2,3, 4,5. Now when<br />

mf = 2 , <strong>the</strong> possible values <strong>of</strong> I are 2, 3, 4, 5, ... These two series <strong>of</strong> integers overlap for<br />

<strong>the</strong> integers 2, 3, 4, and 5. Therefore, <strong>the</strong> possible values for <strong>the</strong> orbital quantum number I<br />

that this electron could have are 11 =<br />

2, 3, 4, 51.<br />

24. REASONING The maximum value for <strong>the</strong> magnetic quantum number is ml = I ; thus, in<br />

state A, I = 2, while in state B, I = 1. According to <strong>the</strong> quantum mechanical <strong>the</strong>ory <strong>of</strong><br />

angular momentum, <strong>the</strong> magnitude <strong>of</strong> <strong>the</strong> orbital angular momentum for a state <strong>of</strong> given I is<br />

L = -JJ!(J! + 1) (h / 2tr) (Equation 30.15). This expression can be used to form <strong>the</strong> ratio<br />

LA / ~ <strong>of</strong> <strong>the</strong> magnitudes <strong>of</strong> <strong>the</strong> orbital angular momenta for <strong>the</strong> two states.<br />

SOLUTION Using Equation 30.15, we find that<br />

h<br />

LA = .j2(2+ 1) 2& h ~ V2 @" ~v'3~11.7321<br />

LB -J1(1 + 1) 2tr<br />

25. REASONING The total energy En for a hydrogen <strong>atom</strong> in <strong>the</strong> quantum mechanical picture<br />

is <strong>the</strong> same as in <strong>the</strong> Bohr model and is given by Equation 30.13:<br />

E/1 = -(13.6 eV)2 n<br />

Thus, we need to determine values for <strong>the</strong> principal quantum number n if we are to calculate<br />

<strong>the</strong> three smallest possible values for E. Since <strong>the</strong> maximum value <strong>of</strong> <strong>the</strong> orbital quantum<br />

number J! is n - 1, we can obtain a minimum value for n as nmin = J! + 1. But how to obtain<br />

1<br />

(30.13)


Chapter 30 Problems 1525<br />

£? It can be obtained, because <strong>the</strong> problem statement gives <strong>the</strong> maximum value <strong>of</strong> Lz, <strong>the</strong> z<br />

component <strong>of</strong> <strong>the</strong> angular momentum. According to Equation 30.16, Lz is<br />

where mf is <strong>the</strong> magnetic quantum number and his Planck's constant. For a given value <strong>of</strong> £<br />

<strong>the</strong> allowed values for mf are as follows: -£, .. " -2, -1, 0, +1, +2, ... , +£. Thus, <strong>the</strong><br />

maximum value <strong>of</strong>mf is £, and we can use Equation 30.16 to calculate <strong>the</strong> maximum value <strong>of</strong><br />

mf from <strong>the</strong> maximum value given for Lz·<br />

h<br />

Lz = mf 21C<br />

SOLUTION Solving Equation 30.16 for mf gives<br />

rn, ~ 21fL, ~ 21f(4.22X10-34 J,s)_4<br />

h 6.63xl0-34 J. S -<br />

(30.16)<br />

As explained in <strong>the</strong> REASONING, this maximum value for mf indicates that £ = 4.<br />

Therefore, a minimum value for n is<br />

n . =£+1=4+1=5 or n>5<br />

mm -<br />

This means that <strong>the</strong> three energies we seek correspond to n = 5, n = 6, and n = 7. Using<br />

Equation 30.13, we find <strong>the</strong>m to be<br />

[n = 5] E5 = -(13.6 eV)~ = 1-0.544 eVj<br />

5<br />

[n = 6] E6 = -(13.6 eV)~ = 1-0.378 eV[<br />

6<br />

[n=7] E7 = -(13.6 eV)~ = 1-0.278 eV[<br />

7<br />

26. REASONING AND SOLUTION<br />

a. For <strong>the</strong> angular momentum, Bohr's value is given by Equation 30.8, with n = 1,<br />

According to quantum <strong>the</strong>ory, <strong>the</strong> angular momentum is given by Equation 30.15. For<br />

n=I,£=O


1526 THE NATURE OF THE ATOM<br />

b. For n = 3; Bohr <strong>the</strong>ory gives<br />

while quantum mechanics gives<br />

[n = 3, .e = 0]<br />

[n=3,.e=1]<br />

[n = 3, .e = 2]<br />

27. I SSMII wwwl REASONING Let e denote <strong>the</strong> angle between<br />

<strong>the</strong> angular momentum L and its z-component Lz· We can see<br />

from <strong>the</strong> figure at <strong>the</strong> right that Lz = L cos e . Using<br />

Equation 30.16 for Lz and Equation 30.15 for L, we have<br />

The smallest value for e corresponds to <strong>the</strong> largest value <strong>of</strong> cos e. For a given value <strong>of</strong> I ,<br />

<strong>the</strong> largest value for cos e corresponds to <strong>the</strong> largest value for rn,. But <strong>the</strong> largest possible<br />

value for rnl is rnl = I . Therefore, we find that<br />

cos e =.e re<br />

~.e(.e+l) ~£+1<br />

SOLUTION The smallest value for e corresponds to <strong>the</strong> largest value for I. When <strong>the</strong><br />

electron is in <strong>the</strong> n = 5 state, <strong>the</strong> largest allowed value <strong>of</strong> I is I = 4 ; <strong>the</strong>refore, we see that<br />

or<br />

e = cos-1 (J4i5) = I 26.6° I<br />

i<br />

"1<br />

,j<br />

i;<br />

1<br />

!<br />

"

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