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7.7 (a)

λ = 3.00 × 108 m/s c = = 3.5 × 10−6 m = 3.5 × 103 nm ν 8.6 × 1013 /s 3.00 × 108 m/s c = = 5.30 × 1014 /s = 5.30 × 1014 Hz −9 λ 566 × 10 m

(b)

ν =

7.8

(a) Strategy: We are given the wavelength of an electromagnetic wave and asked to calculate the frequency. Rearranging Equation (7.1) of the text and replacing u with c (the speed of light) gives:

ν = c λ

Solution: Because the speed of light is given in meters per second, it is convenient to first convert −9 wavelength to units of meters. Recall that 1 nm = 1 × 10 m (see Table 1.3 of the text). We write:

456 nm × 1 × 10−9 m = 456 × 10−9 m = 4.56 × 10−7 m 1 nm

8

**Substituting in the wavelength and the speed of light (3.00 × 10 m/s), the frequency is:
**

m 3.00 × 108 c s = 6.58 × 1014 s −1 or 6.58 × 1014 Hz ν = = −7 λ 4.56 × 10 m

Check: The answer shows that 6.58 × 10 waves pass a fixed point every second. This very high frequency is in accordance with the very high speed of light. (b) Strategy: We are given the frequency of an electromagnetic wave and asked to calculate the wavelength. Rearranging Equation (7.1) of the text and replacing u with c (the speed of light) gives:

14

λ =

c ν

8

Solution: Substituting in the frequency and the speed of light (3.00 × 10 m/s) into the above equation, the wavelength is: m 3.00 × 108 c s = 0.122 m λ = = ν 91 2.45 × 10 s

CHAPTER 7: QUANTUM THEORY AND THE ELECTRONIC STRUCTURE OF ATOMS

195

**The problem asks for the wavelength in units of nanometers. Recall that 1 nm = 1 × 10
**

λ = 0.122 m × 1 nm 1 × 10−9 m

8

−9

m.

= 1.22 × 108 nm

7.9

**Since the speed of light is 3.00 × 10 m/s, we can write
**

(1.3 × 108 mi) × 1.61 km 1000 m 1s × × = 7.0 × 102 s 1 mi 1 km 3.00 × 108 m

Would the time be different for other types of electromagnetic radiation? 7.10 A radio wave is an electromagnetic wave, which travels at the speed of light. The speed of light is in units of 7 m/s, so let’s convert distance from units of miles to meters. (28 million mi = 2.8 × 10 mi)

? distance (m) = (2.8 × 107 mi) × 1.61 km 1000 m × = 4.5 × 1010 m 1 mi 1 km

**Now, we can use the speed of light as a conversion factor to convert from meters to seconds 8 (c = 3.00 × 10 m/s).
**

? min = (4.5 × 1010 m) × 1s 3.00 × 108 m = 1.5 × 102 s = 2.5 min

7.11

λ =

c 3.00 × 108 m/s = = 3.26 × 10−2 m = 3.26 × 107 nm ν 9192631770 s −1

This radiation falls in the microwave region of the spectrum. (See Figure 7.4 of the text.) 7.12 The wavelength is:

λ = 1m = 6.05780211 × 10−7 m 1, 650, 763.73 wavelengths

ν =

c 3.00 × 108 m/s = = 4.95 × 1014 s −1 −7 λ 6.05780211 × 10 m

7.15

E = hν =

hc (6.63 × 10−34 J ⋅ s)(3.00 × 108 m/s) = = 3.19 × 10−19 J −9 λ 624 × 10 m

7.16

(a) Strategy: We are given the frequency of an electromagnetic wave and asked to calculate the wavelength. Rearranging Equation (7.1) of the text and replacing u with c (the speed of light) gives:

λ =

c ν

8

Solution: Substituting in the frequency and the speed of light (3.00 × 10 m/s) into the above equation, the wavelength is:

2 × 102 nm −18 −9 1. 5.4 × 10−5 J/mol 1 photon 1 mol 7.63 × 10−34 J ⋅ s) ⎜ 7.29 × 10−15 J −9 λ (0.0 × 104 /s −19 J. To apply E = hν.196 CHAPTER 7: QUANTUM THEORY AND THE ELECTRONIC STRUCTURE OF ATOMS m s = 4. Ε = hc = λ = E m⎞ ⎛ (6.17 (a) λ = The radiation does not fall in the visible region.63 × 10 energy of a single photon associated with this frequency is: −34 J⋅s) into the above equation.) (b) (c) E = hν = (6.154 × 10 m) 7. 7.19 E = hν = . (b) Strategy: We are given the frequency of an electromagnetic wave and asked to calculate its energy.0 × 103 m = 5.2 × 10−7 m × = 1.0 × 10 /s) = 4.7 × 10−18 J/photon 23 1 mol 1 kJ 6.2) of the text relates the energy and frequency of an electromagnetic wave.0 × 10−7 m = 4. E = hν Solution: Substituting in the frequency and Planck's constant (6.18 The energy given in this problem is for 1 mole of photons.4 of the text). Equation (7.0 × 10−19 J s⎠ ⎝ Check: We expect the energy of a single photon to be a very small energy as calculated above. we must divide the energy by Avogadro’s number.5 × 1014 s 3.0 × 10 c 3.00 × 108 m/s) = = 1.63 × 10−34 J ⋅ s)(3.0 × 10 4 −29 J Converting to J/mol: E = 4.0 × 102 nm λ = 1 7.0 × 1012 nm ν 6.63 × 10−34 J ⋅ s) ⎜ 3.4 of the text.00 × 108 Check: The wavelength of 400 nm calculated is in the blue region of the visible spectrum as expected.00 × 108 ⎟ 1 nm s ⎠ ⎝ = 1.022 × 10 photons hc . hc (6.0 × 103 kJ 1 mol 1000 J × × = 1.63 × 10 −34 J⋅s)(6.00 × 108 m/s = = 5.022 × 1023 photons × = 2.7 × 10 J 1 × 10 m The radiation is in the ultraviolet region (see Figure 7. (See Figure 7. the 1⎞ ⎛ E = hν = (6.0 × 10−29 J 6.5 × 1014 ⎟ = 5. λ The wavelength of this photon can be found using the relationship. it is radio radiation. The energy of one photon is: E = 1.

38 × 10−19 J s⎠ ⎝ 7.63 × 10−34 J ⋅ s) ⎜ 8. Even the frequencies emitted by isotopes of the same element are very slightly different. Substitute the frequency (ν) into this equation to solve for the energy of one quantum associated with this frequency.25 The arrangement of energy levels for each element is unique.70 × 102 nm λ = 1 8.11 × 1014 ⎟ = 5.29 E4 − E1 = (−1.0 × 10−7 m = 2.0 × 102 nm ΔE 10 × 10−19 J .4 × 102 nm ΔE 14 × 10−19 J (b) The energy difference between the states E2 and E3 is: E3 − E2 = (−5. can make a white shirt look much whiter and brighter than a similar shirt washed in ordinary detergent. you should find that the visible region of the spectrum runs from 400 to 700 nm. (a) The energy difference between states E1 and E4 is: 7. E = hν.11 × 1014 s 3.63 × 10−34 J ⋅ s)(3.CHAPTER 7: QUANTUM THEORY AND THE ELECTRONIC STRUCTURE OF ATOMS 197 7. the wavelength is found as in part (a). λ = hc (6.28 Excited atoms of the chemical elements emit the same characteristic frequencies or lines in a terrestrial laboratory. Absorption of visible light could not give rise to emitted ultraviolet light because the latter has higher energy.00 × 108 (b) (c) Checking Figure 7. The emitted light could be analyzed by passing it through a prism.0 × 10 λ = −19 )J − (−15 × 10 −19 )J = 14 × 10 −19 J hc (6. for example. Certain brands of laundry detergents contain materials called “optical brighteners” which. or in a star many light-years distant from earth. is very common.0 × 10 −19 J) = 5 × 10 −19 J The energy difference between the states E1 and E3 is: E1 − E3 = (−15 × 10 −19 J) − (−5. 7. Light emitted by fluorescent materials always has lower energy than the light striking the fluorescent substance.4 × 10−7 m = 1. The frequencies of light emitted by an element are characteristic of that element.0 × 10 (c) −19 J) − (−10.20 (a) λ = c ν m s = 3. The reverse process.27 7.63 × 10−34 J ⋅ s)(3.0 × 10 −19 J) = −10 × 10 −19 J Ignoring the negative sign of ΔE. ultraviolet light producing visible light by fluorescence.26 7. in the sun. 1⎞ ⎛ E = hν = (6.00 × 108 m/s) = = 1.70 × 10−7 m = 3.00 × 108 m/s) = = 2.4 of the text. 370 nm is in the ultraviolet region of the spectrum.

17 × 10 s ⎟ ⎝ ⎠ Check: This wavelength is in the visible region of the electromagnetic region (see Figure 7.and endothermic processes? 7.18 × 10−18 J) ⎜ − = − 1. we can solve for the frequency of the photon.17 × 1014 s −1 or 6.4 of the text).09 × 10−19 J) = = 6. We know that ΔE = hν Rearranging the equation and substituting in the known values. ν = ΔE (4.998 × 108 m/s) = = 3.6) we write: ⎛ 1 1 ⎞ ⎟ ΔE = RH ⎜ − ⎜ n2 nf2 ⎟ ⎝ i ⎠ ⎛ 1 1 ⎞ ΔE = (2. Then.00 × 108 m/s) = = 1.63 × 10−34 J ⋅ s)(3.32 Strategy: We are given the initial and final states in the emission process. This is consistent with the fact that because ni = 4 and nf = 2. We can calculate the energy of the emitted photon using Equation (7.00 × 108 s = 4. we will omit the minus sign for ΔE because the frequency of the photon must be positive. this transition gives rise to a spectral line in the Balmer series (see Figure 7. Substituting the frequency calculated above into this equation gives: ν m 3.6 of the text).55 × 10−19 J Is the sign of the energy change consistent with the sign conventions for exo. Solution: From Equation (7. and from the frequency we can solve for the wavelength. To calculate the frequency.28 × 103 nm ΔE 1. .55 × 10−19 J 2 2⎟ ⎟ 3 ⎠ ⎝5 ⎠ The sign of ΔE means that this is energy associated with an emission process.3 × 10−9 m 7. The value of Rydberg's constant is −18 2.6) of the text.63 × 10−34 J ⋅ s) We also know that λ = c .17 × 1014 Hz h (6. λ = hc (6.18 × 10−18 J) ⎜ − ⎟ 2 22 ⎠ ⎝4 ΔE = −4. ⎛ 1 1 ΔE = RH ⎜ − ⎜n2 nf 2 ⎝ i ⎞ ⎛ 1 1 ⎞ ⎟ = (2.6256 × 10−34 J ⋅ s)(2.86 × 10−7 m = 486 nm λ = ⎛ 14 1 ⎞ ⎜ 6.28 × 10−6 m = 1.027 × 10−19 J λ 656.198 CHAPTER 7: QUANTUM THEORY AND THE ELECTRONIC STRUCTURE OF ATOMS 7.09 × 10 −19 J The negative sign for ΔE indicates that this is energy associated with an emission process.30 We use more accurate values of h and c for this problem.18 × 10 J. from this energy. E = hc (6.31 In this problem ni = 5 and nf = 3.

39 λ = h 6.372 × 10−19 J λ 589.250 = 0. which is Equation (7. We use 6.CHAPTER 7: QUANTUM THEORY AND THE ELECTRONIC STRUCTURE OF ATOMS 199 7.33 This problem must be worked to four significant figure accuracy. . Note that because the units of Planck's 2 2 constant are J⋅s.998 × 108 m/s) = = 3. but we need to calculate ΔE.65 × 10−10 m = 0. and solve for ni.022 × 1023 photons × = 2 × 102 J/mol 1 photon 1 mol 7. the energy change ΔE must be negative. We need the de Broglie equation.63 × 10−34 J ⋅ s)(3.40 Strategy: We are given the mass and the speed of the proton and asked to calculate the wavelength.565 nm −27 2 mu (1.34 ⎛ 1 1 ΔE = RH ⎜ − ⎜ n2 nf2 ⎝ i ⎞ ⎟ ⎟ ⎠ nf is given in the problem and RH is a constant. or −4.6256 × 10−34 J ⋅ s)(2.58 × 10 Substitute ΔE into the following equation. m must be in kg and u must be in m/s (1 J = 1 kg⋅m /s ).58 × 10−19 J λ 434 × 10−9 m −19 Since this is an emission process.18 × 10−18 J) ⎜ − ⎟ ⎜n2 22 ⎟ ⎝ i ⎠ 1 ni 2 ni = ⎛ −4.210 + 0.63 × 10−34 J ⋅ s = = 5.58 × 10−19 J ⎞ 1 = ⎜ = − 0.8) of the text.18 × 10−18 J ⎟ 22 ⎝ ⎠ 1 0.6256 × 10−34 J ⋅ s)(2. The photon energy is: E = hc (6.369 × 10−19 J λ 589.0 × 10−9 m hc (6.58 × 10−19 J = (2.6256 × 10 J⋅s for Planck’s 8 constant and 2.00 × 108 m/s) = = 4.040 = 5 7.6 × 10−9 m −34 E = For one photon the energy difference is: ΔE = (3.998 × 108 m/s) = = 3. ⎛ 1 1 ΔE = RH ⎜ − ⎜ n2 nf2 ⎝ i ⎞ ⎟ ⎟ ⎠ J.00 × 10 m/s) 7.369 × 10 −19 J) = 3 × 10 −22 J For one mole of photons the energy difference is: 3 × 10−22 J 6.998 × 10 m/s for the speed of light.675 × 10 kg)(7.372 × 10 −19 J) − (3.040 ⎟+ ⎜ 2. E = hc (6. ⎛ 1 1 ⎞ −4. First calculate the energy of each of the photons.

are there always 2l + 1 values? Why? 7.673 × 10 kg)(2. 1. p.63 × 10−34 ⎜ ⎟ s2 h ⎝ ⎠ = 1. l. n = 3. λ = (1. are 0 and 1.56 Strategy: What are the relationships among n.96 × 10−34 m = 9. l.41 Converting the velocity to units of m/s:: 1. Within a given subshell (label l) there are 2l + 1 allowed energy states (orbitals) each labeled by a different value of the magnetic quantum number. −1. ml. so the allowed values of the angular momentum quantum number. and d orbitals. 2 . Each allowed value of the angular momentum quantum number labels a subshell.63 × 10−34 ⎜ ⎟ s2 h ⎝ ⎠ λ = = = 1. 0.90 × 10 m/s) The problem asks to express the wavelength in nanometers. For the other subshell in this problem labeled by the angular momentum quantum number l = 0. The allowed values run from −l through 0 to +l (whole numbers only). If the allowed whole number values run from −1 to +1.20 × 102 mi 1.7 m/s 1 hr 1 mi 1 km 3600 s λ = h 6.37 × 10−15 m 8 −27 mu (1. 1. the allowed value of the magnetic quantum number is 0.61 km 1000 m 1 hr × × × = 53. The values of ml for each l value are: l = 0: ml = 0 l = 1: ml = −1.0124 kg)(53.61 km 1000 m 1h × × × = 16 m/s 1h 1 mi 1 km 3600 s ⎛ kg ⋅ m 2 ⎞ ⋅s⎟ ⎜ 6. In this case n = 2. the allowed values of the magnetic quantum number. we convert mph to m/s.5 × 10−3 kg)(16 m/s) 7. and 1.7 × 10−32 m = 1. 0.63 × 10−34 J ⋅ s = = 9.e. respectively.55 The angular momentum quantum number l can have integral (i. there are three possible values of l: 0.37 × 10−6 nm 7. whole number) values from 0 to n − 1.96 × 10−32 cm (0.7 m/s) mu 7.200 CHAPTER 7: QUANTUM THEORY AND THE ELECTRONIC STRUCTURE OF ATOMS Solution: Using Equation (7. and ml? Solution: We are given the principal quantum number. are −1. The possible l values range from 0 to (n − 1). 1 l = 2: ml = −2.37 × 10−15 m) × 1 nm 1 × 10−9 m = 1.7 × 10−23 nm = λ = mu (2.42 First. 0. and 2. 35 mi 1. Thus. For the subshell labeled by the angular momentum quantum number l = 1.8) we write: λ = h mu ⎛ kg ⋅ m 2 ⎞ ⋅s⎟ ⎜ 6. corresponding to the s. The values of ml can vary from −l to l.

The electron spin quantum number. and 11 orbitals. −1. −1/2 A 2s orbital is larger than a 1s orbital. seven. 9. five.CHAPTER 7: QUANTUM THEORY AND THE ELECTRONIC STRUCTURE OF ATOMS 201 7. They differ only in their orientation with respect to each other.64 n value 1 2 3 4 5 6 orbital sum 1 1+3=4 1+3+5=9 1 + 3 + 5 + 7 = 16 1 + 3 + 5 + 7 + 9 = 25 1 + 3 + 5 + 7 + 9 + 11 = 36 total number of electrons 2 8 18 32 50 72 2 In each case the total number of orbitals is just the square of the n value (n ). −1. 6f. l = 1. Can you assign a specific value of the magnetic quantum number to these orbitals? What are the allowed values of the magnetic quantum number for the 2p subshell? 7. 7. and energy. 0. can be either +1/2 or −1/2. ml = −2. 1. 6p. Following the same reasoning as part (a) (b) (c) 7. 5p. l = 2. ms = +1/2. There can be a maximum of two electrons occupying one orbital.57 (a) (b) (c) 2p: n = 2. These subshells each have 1. the allowed values of l are 0. l = 0. 3. and 5 [l = 0 to (n − 1). 0. 4.62 7. These subshells each have one. 5f. For n = 6. 6g.58 (a) The number given in the designation of the subshell is the principal quantum number. or −2 An orbital in a subshell can have any of the allowed values of the magnetic quantum number for that subshell. 3. 1. respectively.65 3s: two 3d: ten 4p: six 4f: fourteen 5f: fourteen . The total number of electrons 2 is 2n .59 4p: n = 4. 2.60 7. 5d. or −1 3s: n = 3. (a) 7. Both have the same spherical shape. These correspond to the 5s. For s orbitals. ml = −1. 1. 6d. ml = 2. 3. does the principal quantum number n affect the number of electrons in a given subshell? 7.61 The allowed values of l are 0. 2. The two orbitals are identical in size. 0. respectively (number of orbitals = 2l + 1). 1. ml = 0 (only allowed value) 5d: n = 5.63 two (b) six (c) ten (d) fourteen What rule of nature demands a maximum of two electrons per orbital? Do they have the same energy? How are they different? Would five 4d orbitals hold as many electrons as five 3d orbitals? In other words. 1. l = 1. 7. so in this case n = 3. The 1s orbital is lower in energy than the 2s. 5. ml can have integer values from −l to +l. and 4. and 5g subshells. ms. These l values correspond to the 6s. l = 0. 7. All the orbitals in a subshell have exactly the same energy. ms = +1/2. integer values]. −1/2 3d: n = 3. three. l = 2. shape. ml = 0. and 6h subshells. ml = 1. therefore. 0. and nine orbitals. 2.

is wrong because the electron spin quantum number ms can have only half-integral values.78 Ne: Sc: Se: Fe: I: (0 unpaired electrons. they have equal energy. If two orbitals in the hydrogen atom have the same value of n. an orbital diagram may be helpful. the 1s. (Fluorine only has nine electrons. there are not enough electrons in the 2p subshell.70 7. and 2p electrons) than the 3s electrons. You should write the electron configurations for each of these elements to answer this question. The element would be paramagnetic.202 CHAPTER 7: QUANTUM THEORY AND THE ELECTRONIC STRUCTURE OF ATOMS 7. The 3s orbital is said to be more “penetrating” than the 3p and 3d orbitals. There are no d-type electrons.22 in your textbook. 7. The configuration shown might be an excited state of an aluminum atom. 7.67 7.68 See Figure 7.69 2s > 1s (b) 3p > 2p (c) equal (d) equal (e) 5s > 4f 7. it is mathematically impossible for all the electrons to be paired. 3p.66 The electron configurations for the elements are (a) (b) (c) N: 1s 2s 2p 2 2 2 2 2 2 3 6 6 2 2 2 4 There are three p-type electrons. In some cases. Why?) 2 1 [Ar]4s 3d (1 unpaired electron) 2 10 4 [Ar]4s 3d 4p (2 unpaired electrons) 2 6 [Ar]4s 3d (4 unpaired electrons) 2 10 5 [Kr]5s 4d 5p (1 unpaired electron) . B: P: Mn: Kr: Cd: Pb: [He]2s 2p (1 unpaired electron) 2 3 [Ne]3s 3p (3 unpaired electrons) 2 5 [Ar]4s 3d (5 unpaired electrons) (0 unpaired electrons) 2 10 [Kr]5s 4d (0 unpaired electrons) 2 14 10 2 [Xe]6s 4f 5d 6p (2 unpaired electrons) 2 1 7.77 Since the atomic number is odd. is wrong because the maximum value of the angular momentum quantum number l is n − 1.) The 2 2 6 2 1 number of electrons (13) is correct. The correct electron configuration is 1s 2s 2p . there are also too many electrons. In the hydrogen atom there is only one electron. and 3d orbitals have the same energy. (a) 7. n. There must be at least one that is unpaired. Si: 1s 2s 2p 3s 3p S: 1s 2s 2p 3s 3p 7.) The configuration shown − 2 2 5 is that of the F ion. In the many-electron atom. 2s.76 For aluminum. There are six s-type electrons.75 (a) 2s < 2p (a) (c) (e) (b) 3p < 3d (c) 3s < 4s (d) 4d < 5f is wrong because the magnetic quantum number ml can have only whole number values. Equation (7. so the 3s. What would be the electric charge of a boron ion with the electron arrangement given in the problem? For fluorine. The energy does not depend on any of the other quantum numbers.5) of the text gives the orbital energy in terms of the principal quantum number. (The 2p subshell holds six electrons. there are too many electrons. the 3p orbital electrons are more effectively shielded by the inner electrons of the atom (that is. alone (for the hydrogen atom). (Boron only has five electrons. The electron configuration should be 1s 2s 2p 3s 3p .) The electron configuration should 2 2 1 be 1s 2s 2p . For boron.

89 [Ar]4s 3d 4p 2 10 4 The ground state electron configuration of Tc is: [Kr]5s 4d . 1. Fe: [Ar]4s 3d 2 14 4 W: [Xe]6s 4f 5d 7. The task is simplified if we use the noble gas core preceding Ge for the inner electrons.CHAPTER 7: QUANTUM THEORY AND THE ELECTRONIC STRUCTURE OF ATOMS 203 7. Remember that any given orbital can hold at most 2 electrons.91 2 6 Zn: [Ar]4s 3d 2 14 10 1 Tl: [Xe]6s 4f 5d 6p Orbital 1s 1s 2s 2s 2p 2p 2p 2p 2p n 1 1 2 2 2 2 2 2 2 2 10 Ni: [Ar]4s 3d 2 8 There are a total of twelve electrons: l 0 0 0 0 1 1 1 1 1 ml 0 0 0 0 1 1 0 0 ms +1 2 −1 2 +1 2 −1 2 +1 2 −1 2 +1 2 −1 2 −1 +1 2 . corresponding to ml = −2. B: V: 1s 2s 2p 2 2 2 2 1 3 8 2 5 As: [Ar]4s 3d 4p I: [Kr]5s 4d 5p 1 14 2 10 2 10 3 5 [Ar]4s 3d Ni: [Ar]4s 3d Au: [Xe]6s 4f 5d 10 What is the meaning of “[Ar]”? of “[Kr]”? of “[Xe]”? 7.23 of the text. 4p. Starting with n = 3. (Ar is the noble gas in the 2 2 6 2 6 period preceding germanium. The electrons configuration for Ge is: 2 10 2 [Ar]4s 3d 4p You should follow the same reasoning for the remaining atoms.) [Ar] represents 1s 2s 2p 3s 3p .87 7. This core accounts for 18 electrons. 2. −1. 3d. 0. This leaves two electrons to place in the 4p orbitals. which leaves 14 electrons to place. there are three p orbitals of equal energy. Solution: Germanium has 32 electrons.88 7. You should find that the order of filling is 4s. The noble gas core in this case is [Ar]. corresponding to ml = −1. However. Starting with n = 2.90 Strategy: How many electrons are in the Ge atom (Z = 32)? We start with n = 1 and proceed to fill orbitals in the order shown in Figure 7. We can place electrons in the orbitals according to the Pauli exclusion principle and Hund's rule. 0. don't forget about degenerate orbitals.23 of your text to check the order of filling subshells past the Ar noble gas core. The 4s orbital can hold two electrons. There are 14 remaining electrons to distribute among these orbitals. 1. See Figure 7. Each of the five 3d orbitals can hold two electrons for a total of 10 electrons. there are five d orbitals of equal energy.

there are n orbitals = 2 = 4.. This orbital can hold 2 electrons. etc.63 × 10−7 m = 463 nm. and 4f orbital). The two are connected through Equation (7. frequency.1) of the text.63 × 10−34 J ⋅ s)(3.2 of the text for a simple application of the relationship to a light wave. Parts (a) and (c) are artifacts of Bohr’s early planetary model of the hydrogen atom and are not considered to be valid today. characteristic wave speed (sound. (a) 7. light. continuous spectra). n = 4 and ml = +1. or 3 (i.94 Part (b) is correct in the view of contemporary quantum theory.4 of the text. or −2. Each of the three orbitals holds 2 electrons for a total of 6 electrons. which is blue.93 + S (6 valence electrons) 2 unpaired electrons S (7 valence electrons) 1 unpaired electron We first calculate the wavelength.92 n 2 3 3 l 1 0 0 ml −1 0 0 ms −1 2 +1 2 −1 2 ↑↓ 2 3s + ↑ ↑ ↑ 3 3p ↑↓ 2 3s ↑↓ ↑ ↑ 4 3p ↑↓ 2 3s − ↑↓ ↑↓ ↑ 5 3p S (5 valence electrons) 3 unpaired electrons S has the most unpaired electrons 7. 2 2 (b) (c) 7. for a total of 4 electrons. Continuous variation in energy means that all energy changes are allowed (e. momentum (mass × velocity). See Example 7. specifies one orbital in each subshell with l = 1. ms = +1/2.96 (a) (b) (c) (d) (e) . Bohr’s explanation of emission and absorption line spectra appears to have universal validity. l = 3 and ml = −2. n = 4.95 Wavelength and frequency are reciprocally related properties of any wave. atomic line spectra). ms = −1/2 specifies 1 electron in this orbital for a total of − 1 electron (one e in the 2s orbital). 2. Quantization of energy means that emission or absorption of only descrete energies is allowed (e. If n = 3 and l = 2. If n = 2 and l = 0. a 4p. Typical particle properties: mass. Each of the five orbitals can hold 2 electrons for − a total of 10 electrons (2 e in each of the five 3d orbitals).. −1. E 4.. then ml can only be zero.00 × 108 m/s) = = 4. ml has the values 2.g. With n = 2. then we find the color using Figure 7.). At the atomic level (microscopic world) objects can exhibit characteristic properties of both particles and waves.g.30 × 10−19 J 7. 7. λ = hc (6. 0. For phenomena that we normally perceive in everyday life (macroscopic world) these properties are mutually exclusive. speed or velocity. kinetic energy. 1. specifies one 4f orbital. specifies 1 electron per orbital. This is completely outside the realm of our everyday common sense experience and is extremely difficult to visualize. Typical wave properties: wavelength.e. 4d.204 CHAPTER 7: QUANTUM THEORY AND THE ELECTRONIC STRUCTURE OF ATOMS Orbital 2p 3s 3s The element is magnesium.

101 7.376 J × 1 photon 3.674 × 10−24 g/H atom = 1.05 × 10−25 nm λ = = mu (0. In the photoelectric effect. the positive surface charge becomes large enough to start attracting the ejected electrons back toward the metal with the result that the kinetic energy of the departing electrons becomes smaller.86 × 10−9 m = 8. we can calculate the energy of a single photon with a wavelength of 633 nm.141 kg)(44.76 × 108 J/s = 3.00 × 108 m/s) = = 3.97 7.376 J pulse is: 0.05 × 10−34 m = 1.674 × 10−27 kg 23 1 mol 6.376 J 1.00 × 10 0. E = hc (6.63 × 10−34 ⎜ ⎟ s2 h ⎝ ⎠ = 1.14 × 10 −19 J = 1.00 × 10 −9 s pulse is: s = 3.63 × 10−34 ⎜ ⎟ s2 h ⎝ ⎠ = 8. the metal surface becomes positively charged as more electrons are lost.674 × 10 kg)(44.76 × 108 W Compare this with the power delivered by a 100-W light bulb! .102 There are many more paramagnetic elements than diamagnetic elements because of Hund's rule. 100 mi 1h 1.CHAPTER 7: QUANTUM THEORY AND THE ELECTRONIC STRUCTURE OF ATOMS 205 7.20 × 1018 photons −9 (b) Since a 1 W = 1 J/s.63 × 10−34 J ⋅ s)(3.7 m/s) (b) The average mass of a hydrogen atom is: 1.14 × 10−19 J −9 λ 633 × 10 m The number of photons produced in a 0.609 km 1000 m × × × = 44.99 See the appropriate sections of the textbook in Chapter 7.008 g 1 mol × = 1. the power delivered per a 1. The wave properties of electrons are used in the operation of an electron microscope.022 × 10 atoms ⎛ kg ⋅ m 2 ⎞ ⋅s⎟ ⎜ 6.86 nm λ = = −27 mu (1.7 m/s) 7. (a) First. (a) 7.100 First convert 100 mph to units of m/s. After a long enough period of time.7 m/s 1h 3600 s 1 mi 1 km Using the de Broglie equation: ⎛ kg ⋅ m 2 ⎞ ⋅s⎟ ⎜ 6.98 7. Since the electrons are charged particles. light of sufficient energy shining on a metal surface causes electrons to be ejected (photoelectrons).

we can determine how many photons are needed to provide 11 J of energy. ⎛ 1 1 ΔE = RH ⎜ − ⎜n2 nf 2 ⎝ i λ = ⎞ ⎛ 1 1 ⎞ ⎟ = (2. Since water is continuously being struck by visible radiation without decomposition. 285. Using Equation (7.10 × 1023 photons 7.184 J/g⋅°C)(5.00 × 108 m/s) = = 4.70 × 103 J) × 1 photon 1.18 × 10−18 J) ⎜ − ⎟ = − 1. The actual energy converted to visible light is 15 percent of this value or 11 J.65 × 10−7 m = 365 nm ΔE 5. with ni = ∞ and nf = 2.105 For the Lyman series.00 × 108 m/s) = = 1. .8 kJ 1 mol × = 4.104 First.63 × 10−34 J ⋅ s)(3.63 × 10−34 J ⋅ s)(3. the energy output of the light bulb in 1 second is 75 J. we want the shortest wavelength (highest energy). 7.45 × 10−19 J Therefore the two series do not overlap.206 CHAPTER 7: QUANTUM THEORY AND THE ELECTRONIC STRUCTURE OF ATOMS 7. we want the longest wavelength (smallest energy). First.746 × 10−19 J This wavelength is in the visible region of the electromagnetic spectrum.00°C) = 7.45 × 10−19 J 2 2⎟ ⎟ 2 ⎠ ⎝∞ ⎠ hc (6.64 × 10−18 J For the Balmer series.64 × 10−18 J 2 ⎟ 12 ⎠ ⎝2 ⎠ hc (6.18 × 10−18 J) ⎜ − = − 5.63 × 10−34 J ⋅ s)(3.022 × 1023 molecules The maximum wavelength of a photon that would provide the above energy is: λ = hc (6.746 × 10−19 J/molecule 1 mol 6.06 × 10−5 m 4 3 The number of photons required is: (7. let’s find the energy needed to photodissociate one water molecule.63 × 10−34 J ⋅ s)(3.21 × 10−7 m = 121 nm ΔE 1.88 × 10−20 J = 4.70 × 10 J Energy of a photon with a wavelength = 1.746 × 10−22 kJ/molecule = 4.106 Since 1 W = 1 J/s. with ni = 2 and nf = 1.00 × 108 m/s) = = 1. 7. it seems unlikely that photodissociation of water by this method is feasible. Then.06 × 10 nm: E = hν = hc (6. we need to calculate the energy of one 550 nm photon.88 × 10−20 J/photon λ 1.6) of the text: ⎛ 1 1 ΔE = RH ⎜ − ⎜n2 nf 2 ⎝ i λ = ⎞ ⎛ 1 1⎞ ⎟ = (2.19 × 10−7 m = 419 nm E 4.103 The energy required to heat the water is: msΔt = (368 g)(4.00 × 108 m/s) = = 3.

n = 3 → 2.12 × 10−19 J/photon 23 1 mol 6.83 × 10−7 m = 483 nm −19 E (4.CHAPTER 7: QUANTUM THEORY AND THE ELECTRONIC STRUCTURE OF ATOMS 207 The energy of one 550 nm photon is: E = hc (6.21 × 10 −18 J = 1.84 × 10 + −19 −19 −19 −19 J.63 × 10−34 J ⋅ s)(3. n = 6 → 2.09 × 10 For the transition. . J J J J λ = 657 nm λ = 487 nm λ = 434 nm λ = 411 nm All the Balmer transitions for He are in the ultraviolet region. ΔE = −1.107 The energy needed per photon for the process is: 248 × 103 J 1 mol × = 4.63 × 10−34 J ⋅ s)(3. n = 6 → 2. For He : ⎛ 1 1 ⎞ ΔE = RHe+ ⎜ − ⎟ 2 ⎜ n2 nf ⎟ ⎝ i ⎠ λ = hc (6. ΔE = −1.12 × 10 J) Any wavelength shorter than 483 nm will also promote this reaction.21 × 10−18 J 2 2⎟ 2 ⎠ ⎝3 λ = 1. the calculations are identical to those above.64 × 10−7 m = 164 nm For the transition.99 × 10−25 J ⋅ m 1.00 × 108 m/s) = = 4. Note the negative sign for energy indicating that a photon has been emitted. n = 5 → 2.94 × 10 −18 −18 −18 J J J λ = 121 nm λ = 109 nm λ = 103 nm −18 For H.62 × 10−19 J/photon λ 550 × 10−9 m The number of photons needed to produce 11 J of energy is: 11 J × 1 photon 3. n = 3 → 2 ⎛ 1 1 ⎞ ΔE = (8. except the Rydberg constant for H is 2.0 × 1019 photons 7. ΔE = −3. n = 4 → 2. whereas.022 × 10 photons λ = hc (6.18 × 10 For the transition. the transitions for H are all in the visible region.63 × 10−34 J ⋅ s)(3. n = 4 → 2.00 × 108 m/s) = ΔE ΔE + For the transition. ΔE = −4.83 × 10 For the transition.03 × 10 For the transition.58 × 10 For the transition.00 × 108 m/s) = = 3.62 × 10 −19 J = 3. ΔE = −4.108 The Balmer series corresponds to transitions to the n = 2 level. Once a person goes indoors.64 × 10 For the transition. n = 5 → 2. 7.72 × 10−18 J) ⎜ − = − 1. ΔE = −1. the reverse reaction Ag + Cl → AgCl takes place. ΔE = −4.

7.00 × 108 m/s) = = 3.32 × 10−19 J/photon λ 600 × 10−9 m −17 The number of photons needed to produce 4. Thus.113 . Then. The energy of one photon is: E = 107.780 × 10 J 1 × 10 m 7.112 A “blue” photon (shorter wavelength) is higher energy than a “yellow” photon.2 × 102 photons 7.63 × 10−34 J ⋅ s)(3. then: λ hc hc hc = + λ1 λ2 λ3 Dividing by hc: 1 1 1 = + λ1 λ2 λ3 7. λ = hc (6.0 × 10 (4. we need to calculate the energy of one 600 nm photon.111 Since the energy corresponding to a photon of wavelength λ1 equals the energy of photon of wavelength λ2 plus the energy of photon of wavelength λ3.0 × 10−17 J) × 1 photon 3. we can determine how many photons are −17 needed to provide 4.022 × 10 photons The wavelength of this photon can be found using the relationship E = hc/λ. there must be fewer “blue” photons than “yellow” photons. To apply E = hν we must divide by Avogadro’s number.63 × 10−34 J ⋅ s)(3. blue light will eject electrons with greater kinetic energy.12 × 103 nm −19 −9 E 1. energy of photon 1 = (energy of photon 2 + energy of photon 3) Since E = hc . Refer to Figures 7.109 (a) (b) ΔH ° = ΔH fo (O) + ΔH fo (O2 ) − ΔH fo (O3 ) = 249.0 × 10 J of energy. For the same amount of energy delivered to the metal surface. The energy of one 600 nm photon is: E = hc (6.208 CHAPTER 7: QUANTUM THEORY AND THE ELECTRONIC STRUCTURE OF ATOMS 7.00 × 108 m/s) 1 nm = × = 1.4 kJ/mol + (0) − 142.110 First.2 kJ 1 mol 1000 J × × = 1.2 kJ/mol = 107. the yellow light would eject more electrons since there are more “yellow” photons.780 × 10−19 J/photon 23 1 mol 1 kJ 6.2 kJ/mol The energy in part (a) is for one mole of photons.20 and 7. then the equation must relate the wavelength to energy.32 × 10 −19 J of energy is: J = 1.21 in the textbook. Since the “blue” photons are of higher energy.

1s 2 2 3 N (7 electrons).314 (273 + 20)K K ⋅ mol ⎟ ⎝ ⎠ = 1.CHAPTER 7: QUANTUM THEORY AND THE ELECTRONIC STRUCTURE OF ATOMS 209 7. so the total number of electrons is the same as the atomic number of the element.39 × 10−2 nm mu (6. 4.4 of the text.) 7. we also need the mass of a He atom in kg. we need to calculate the root-mean-square speed using Equation (5.118 The wavelength of a He atom can be calculated using the de Broglie equation. (a) (b) (c) He (2 electrons).63 × 10−34 J ⋅ s) = = 7.003 × 10−3 kg He 1 mol He × = 6. J ⎞ ⎛ 3 ⎜ 8.00 × 108 m/s) = = 0.16) from the text. First.114 The excited atoms are still neutral.35 × 103 m/s −3 4. (See Figure 7. [Ne]3s 3p 2 10 3 7. ni = 236.18 × 10−18 J) ⎜ − = − 3. nf = 235 ⎛ 1 1 ⎞ ΔE = (2.115 Applying the Pauli exclusion principle and Hund’s rule: (a) ↑↓ 2 1s [Ne] ↑↓ 2 3s [Ar] ↑↓ 2 4s ↑↓ 2 2s ↑ ↑↓ ↑↓ ↑ 5 2p ↑ ↑ 3 3p ↑ (b) (c) ↑↓ ↑↓ ↑ ↑ 7 3d 7. 1s 2s 2p 2 2 6 1 Na (11 electrons).647 × 10−27 kg)(1. 1s 2s 2p 3s 2 (d) (e) As (33 electrons).022 × 10 He atoms Finally.003 × 10 kg/mol urms = To calculate the wavelength. the wavelength of a He atom is: λ = h (6.596 m ΔE 3.34 × 10−25 J 2 2⎟ 235 ⎠ ⎝ 236 λ = hc (6.647 × 10−27 kg/atom 23 1 mol He 6.39 × 10−11 m = 7.116 7.35 × 103 m/s) .63 × 10−34 J ⋅ s)(3. [Ar]4s 3d 4p 2 5 Cl (17 electrons).34 × 10−25 J This wavelength is in the microwave region.117 Rutherford and his coworkers might have discovered the wave properties of electrons.

True.28 × 105 J/mol = 328 kJ/mol 1 atom 1 mol It takes considerably less energy to remove the electron from an excited state.18 × 10−18 J 6. False.31 × 106 J/mol = 1. True.00 × 108 m/s) = = 4.45 × 10−19 J 6. The difference in ionization energy is: (412 − 126)kJ/mol = 286 kJ/mol.31 × 103 kJ/mol 1 atom 1 mol (b) ⎛ 1 1 ⎞ ΔE = (2. p = mu or Δp = mΔu .022 × 10 atoms λ = hc (6.75 × 10−19 J 7.022 × 1023 atoms × = 1. nf = ∞ ⎛ 1 1 ⎞ ΔE = (2. the electron is (on average) further from the nucleus and hence easier to remove.121 False.122 We use Heisenberg’s uncertainty principle with the equality sign to calculate the minimum uncertainty.19 × 10−7 m = 419 nm ΔE 4.18 × 10−18 J) ⎜ − = 5.119 (a) Treating this as an absorption process: ni = 1. ΔxΔp = h 4π The momentum (p) is equal to the mass times the velocity. In the n = 4 state. 7. In terms of one atom: 286 × 103 J 1 mol × = 4.18 × 10−18 J 2 2⎟ ∞ ⎠ ⎝1 For a mole of hydrogen atoms: Ionization energy = 2.022 × 1023 atoms × = 3. which corresponds to a shorter wavelength.18 × 10−18 J) ⎜ − = 2. The n = 4 to n = 1 transition is a higher energy transition.75 × 10−19 J/atom 23 1 mol 6.120 (a) (b) (c) (d) (e) 7. False.210 CHAPTER 7: QUANTUM THEORY AND THE ELECTRONIC STRUCTURE OF ATOMS 7.45 × 10−19 J 2 2⎟ ∞ ⎠ ⎝2 Ionization energy = 5.63 × 10−34 J ⋅ s)(3. n = 2 is the first excited state.

(a) and (f) violate the Pauli exclusion principle.67 × 105 J) × 1 photon 3. (d).67 × 105 J to melt 5. In other words.123 It takes: (5.63 × 10−34 J ⋅ s)(3.CHAPTER 7: QUANTUM THEORY AND THE ELECTRONIC STRUCTURE OF ATOMS 211 We can write: Δp = mΔu = h 4πΔx Finally.02 g H 2 O 1 mol H 2 O The number of water molecules converted from ice to water by one photon is: 1. and these electrons must have opposite spins.0 × 102 g of ice.01 × 10 −19 J = 5.0 × 10 g of ice: (1.7 × 1025 H 2 O molecules 5.00 × 108 m/s) = = 3.3 × 10 kg)(5.01 × 10−19 J −9 λ 660 × 10 m 2 Number of photons needed to melt 5.125 Energy of a photon at 360 nm: Ε = hν = hc (6. the uncertainty in the velocity of the oxygen molecule is: Δu = h (6.63 × 10−34 J ⋅ s)(3.5 × 1023 photons 7.5 × 1023 photons The number of water molecules is: (5. only two electrons may exist in the same atomic orbital. (b).0 × 102 g ice) × 334 J = 1. and (e) violate Hund’s rule.7 × 1025 H 2 O molecules 18.124 = 31 H 2 O molecules/photon The Pauli exclusion principle states that no two electrons in an atom can have the same four quantum numbers.53 × 10−19 J −9 λ 360 × 10 m 2 Area of exposed body in cm : ⎛ 1 cm ⎞ 0.63 × 10−34 J ⋅ s) = = 2.0 × 10 m) 7. 1 g ice Energy of a photon with a wavelength of 660 nm: E = hc (6.00 × 108 m/s) = = 5. Hund’s rule states that the most stable arrangement of electrons in subshells is the one with the greatest number of parallel spins. 7.0 × 10−5 m/s −26 −5 4πmΔx 4π(5.022 × 1023 H 2 O molecules × = 1.0 × 102 g H 2 O) × 1 mol H 2 O 6.5 × 103 cm 2 ⎜ 1 × 10−2 m ⎟ ⎝ ⎠ 2 .45 m 2 × ⎜ ⎟ = 4.

02 g/mol = 0.314 J / mol ⋅ K)T 2 The actual temperature can be. M(N2) = 28.128 h . 28. and most probably is.8 × 105 J 1 photon 13+ (3. 3. ) → Fe 14+ ) to the average kinetic energy 3.02 g N 2 1 mol N 2 1 kg × × = 4.8 × 10 K 6 3 (8. they would be annihilated and energy would be given off.02802 ⎜ mol ⎟ ⎝ ⎠ urms (N 2 ) = Second.653 × 10−26 kg/molecule 23 1 mol N 2 6.8 m/s kg ⎞ ⎛ 0.127 The anti-atom of hydrogen should show the same characteristics as a hydrogen atom.212 CHAPTER 7: QUANTUM THEORY AND THE ELECTRONIC STRUCTURE OF ATOMS The number of photons absorbed by the body in 2 hours is: 0. calculate the root-mean-square velocity of N2. we can equate the energy for ionization (Fe ( 3 2 RT of the ions. the mass of an N2 molecule (in kg) and the velocity of an N2 mu molecule (in m/s) is needed to calculate the de Broglie wavelength of N2.2 × 10 23 photons with a wavelength of 360 nm correspond to an energy of: 5.2 × 1023 photons/2 hr 2 hr The factor of 0.5 is used above because only 50% of the radiation is absorbed.5 × 107 J 1 mol 1 kJ IE = 3 RT 2 7 3. calculate the mass of one N2 molecule in kilograms.5 × 2.022 × 10 N 2 molecules 1000 g .5 × 104 kJ 1000 J × = 3.02802 kg/mol J ⎞ ⎛ (3) ⎜ 8. Should an anti-atom of hydrogen collide with a hydrogen atom.5 × 10 J/mol = T = 2.314 ( 300 K ) mol ⋅ K ⎟ ⎝ ⎠ = 516.2 × 1023 photons) × 7.126 As an estimate. higher than this. 7.5 × 103 cm 2 ) × 7200 s = 3. First.0 × 1016 photons cm ⋅ s 2 × (4.53 × 10−19 J = 1. Looking at the de Broglie equation λ = 7.

63 × 10−34 J ⋅ s) = = 2. The kinetic energy acquired by the electrons is equal to the voltage times the charge on the electron.920 4 The energy supplied by one photon with a wavelength of 1.602 × 10−19 J = 8.4 × 104 J) × 1 photon 1.131 The heat needed to raise the temperature of 150 mL of water from 20°C to 100°C is: q = msΔt = (150 g)(4. KE = 1 mu 2 2 1 (9. After 2 calculating the kinetic energy.4 × 104 J 0.74 × 10−11 m = 17.0 × 10 J The microwave will need to supply more energy than this because only 92. we can calculate the velocity of the electrons (KE = 1/2mu ).63 × 10−24 J = 3.122 m) 4 8 The number of photons needed to supply 5. λ = h (6.1094 × 10 −31 kg)(4.130 Based on the selection rule.4 × 10 J of energy is: (5. The energy that needs to be supplied by the microwave is: 5.19 × 10 m/s) 7 = 1. which states that Δl = ±1. KE = (5.3 × 1028 photons .653 × 10 kg)(516.63 × 10−34 J ⋅ s)(3.122 m) is: E = hc (6.22 × 10 nm (0. only (b) and (d) are allowed transitions.01 × 10−16 J = 7 u = 4.63 × 10−24 J λ (0.76 × 10−11 m −26 mu (4.CHAPTER 7: QUANTUM THEORY AND THE ELECTRONIC STRUCTURE OF ATOMS 213 Now.1094 × 10−31 kg)u 2 2 8.8 m/s) 7.00 × 108 m/s) = = 1.19 × 10 m/s Finally. λ = λ = h mu (6.0 × 104 J = 5. we can calculate the wavelength associated with the electrons using the de Broglie equation.0% of microwave energy is converted to thermal energy of water.4 pm 7. we can calculate the wavelength associated with the electrons using the de Broglie equation.63 × 10−34 J ⋅ s) (9.01 × 10−16 J 1V We can now calculate the velocity of the electrons.129 7. Finally.184 J/g⋅°C)(100 − 20)°C = 5.00 × 103 V) × 1. substitute the mass of an N2 molecule and the root-mean-square velocity into the de Broglie equation to solve for the de Broglie wavelength of an N2 molecule.

9 × 10−29 m This uncertainty in position of the baseball is such a small number as to be of no consequence. 1. which gives: Δx(mΔu ) = Δx = h 4π h 6. we can calculate the wavelength and frequency from this energy. E = hc λ hc (6.00 × 108 m/s) = = 9.01)(5 × 106 m/s)] Note that because of the unit Joule in Planck’s constant. then we can calculate the wavelength and frequency of this gamma ray.63 × 10 J ⋅s 7. Δp = mΔu.132 The energy given in the problem is the energy of 1 mole of gamma rays. Δx = h 4πΔp Δx = 6.022 × 10 gamma rays Now. Thus.7 kg ⋅ m/s) = 7.929 pm E 2.0 × 10−7 )(6.14 × 10−13 J/gamma ray 23 1 mol 6. (b) We again start with the Heisenberg Uncertainly Principle to calculate the uncertainty in the baseball’s position.1094 × 10−31 kg)[(0.23 × 1020 s −1 −34 h 6.214 CHAPTER 7: QUANTUM THEORY AND THE ELECTRONIC STRUCTURE OF ATOMS 7.133 (a) We use the Heisenberg Uncertainty Principle to determine the uncertainty in knowing the position of the electron. ΔxΔp = h 4π We use the equal sign in the uncertainty equation to calculate the minimum uncertainty values.14 × 10−13 J λ = and E = hν ν = E 2. We need to convert this to the energy of one gamma ray.14 × 10−13 J = = 3. The uncertainly in the position of the electron is much larger than that radius of the atom.63 × 10−34 J ⋅ s 4π(1.29 × 10−13 m = 0. we have no idea where the electron is in the atom. . mass must be in kilograms and velocity must be in m/s.63 × 10−34 J ⋅ s = = 1 × 10−9 m 4πmΔu 4π(9.29 × 1011 J 1 mol × = 2.63 × 10−34 J ⋅ s)(3.

For Line A (3 → 2) ⎛ 1 ⎛ 1 1 ⎞ 1 ⎞ ΔE = RH Z2 ⎜ − ⎟ = (2. line B corresponds to the 4 → 2 transition.00 × 108 m/s) = = 7.1 × 10 m) −18 For the 5 → 2 transition.134 (a) Line A corresponds to the longest wavelength or lowest energy transition. We can derive an equation for the energy change (ΔE) for an electronic transition. nf.34 × 10−18 J = (2.34 × 10 Z = 16.1 nm E (4.1 nm). We can now substitute these values into the equation above to solve for Z. we now know ΔE. knowing the value of Z. Since this transition −18 corresponds to an emission process.18 × 10−18 J)Z2 ⎜ − ⎟ 2 22 ⎠ ⎝5 −7. ⎛ 1 1 ⎞ ⎟ ΔE = RH Z2 ⎜ − 2 ⎜n nf2 ⎟ ⎝ i ⎠ ⎛ 1 1 ⎞ −7.58 × 10 −19 )Z 2 Z must be an integer because it represents the atomic number of the parent atom. The energy change associated with this transition can be calculated from the wavelength (27.34 × 10 J). and RH (RH = 2. We can then calculate the wavelength from the energy.11 × 10−8 m = 41.84 × 10−18 J) . Therefore.0 Z = 4 2 −18 J = (−4. we can substitute in ni and nf for the 3 → 2 (Line A) and the 4 → 2 (Line B) transitions to solve for ΔE.63 × 10−34 J ⋅ s)(3.CHAPTER 7: QUANTUM THEORY AND THE ELECTRONIC STRUCTURE OF ATOMS 215 7. E = hc (6. Now.34 × 10−18 J −9 λ (27. ni. and line C corresponds to the 5 → 2 transition. (ΔE = −7.84 × 10 λ = −18 J hc (6. which is the 3 → 2 transition.63 × 10−34 J ⋅ s)(3. energy is released and ΔE is negative.18 × 10 J).18 × 10−18 J)(4) 2 ⎜ − ⎟ 2⎟ 2 ⎜ n2 nf ⎠ 22 ⎠ ⎝3 ⎝ i ΔE = −4. ⎛ 1 Ef = − RH Z2 ⎜ ⎜ n2 ⎝ f ⎞ ⎟ ⎟ ⎠ and ⎛ 1 Ei = − RH Z2 ⎜ ⎜ n2 ⎝ i ⎞ ⎛ ⎛ 1 ⎟ − ⎜ − RH Z2 ⎜ ⎟ ⎜ ⎜ n2 ⎠ ⎝ ⎝ i (b) ⎞ ⎟ ⎟ ⎠ ⎞⎞ ⎟⎟ ⎟⎟ ⎠⎠ ⎛ 1 ΔE = Ef − Ei = − RH Z2 ⎜ ⎜ n2 ⎝ f ⎛ 1 1 ⎞ ΔE = RH Z2 ⎜ − ⎟ ⎜ n2 nf2 ⎟ i ⎝ ⎠ Line C corresponds to the 5 → 2 transition.00 × 108 m/s) = = 4.

The average kinetic energy of 1 mole of an ideal gas is 3/2RT.18 × 10−18 J)(4) 2 ⎜ ΔE = RH Z2 ⎜ − − ⎟ 2⎟ 2 ⎜ n2 nf ⎠ 22 ⎠ ⎝4 ⎝ i ΔE = −6.635 × 10 −18 ⎞ 1 ⎞ ⎛1 ⎟ = (2.216 CHAPTER 7: QUANTUM THEORY AND THE ELECTRONIC STRUCTURE OF ATOMS For Line B (4 → 2) ⎛ 1 1 ⎞ 1 ⎞ ⎛ 1 ⎟ = (2. Other means of exciting H atoms must be used to be practical. ⎛ 1 ⎛ 1 1 ⎞ 1 ⎞ ΔE = RH Z2 ⎜ − ⎟ = (2.022 × 1023 atoms 7.022 × 1023 /mol) = 7.54 × 10 λ = −18 J hc (6. we use Equation (7.635 × 10−18 J NA T = 2 (1.11 of the text.6) of the text.314 J/mol ⋅ K) This is an extremely high temperature. forming a continuum.135 (a) (b) To calculate the energy difference between the n = 1 and n = 2 levels in the hydrogen atom. The lines are so close together that they overlap. and we no longer have quantized energy levels associated with the electron. ⎛ 1 1 ΔE = RH ⎜ − 2 ⎜ n2 nf ⎝ i ΔE = 1. Converting to the average kinetic energy per atom. . which represents the energy levels for the hydrogen atom. The continuum shows that the electron has been removed from the ion.00 × 108 m/s) = = 3.54 × 10−18 J) (c) The value of the final energy state is nf = ∞.18 × 10 (d) −18 J As we move to higher energy levels in an atom or ion.171 × 10−21 J/atom 2 6. we have: 3 1 mol (8.63 × 10−34 J ⋅ s)(3.314 J/mol ⋅ K)(298 K) × = 6. In other words. Transitions from higher energy levels to the n = 2 level will be very close in energy and hence will have similar wavelengths. KE = ΔE 3 RT 2 = 1.04 × 10−8 m = 30.635 × 10−18 J)(6.180 × 10−18 J) ⎜ − ⎟ 2 ⎟ 22 ⎠ ⎝1 ⎠ J (c) For a collision to excite an electron in a hydrogen atom from the n = 1 to n = 2 level.18 × 10−18 J)(4)2 ⎜ − ⎟ 2⎟ 2 ⎜ n2 nf ⎠ ∞2 ⎠ ⎝4 ⎝ i ΔE = 2.90 × 104 K 3 (8. the energy levels get closer together.4 nm E (6. See Figure 7. Use the equation derived in part (b) to solve for ΔE. the energy of the electron can now vary continuously.

88 × 10−17 J −8 λ = 1. we first calculate ΔE and then calculate the wavelength.18 × 10−18 J)(3)2 ⎜ − = 1. and Z = 3. λ = hc (6.93 × 10−27 kg λ = h 6.137 (a) m = 10.93 × 10−27 kg)[(0.29 × 10 (b) mmoving = mrest m = 2.00 × 108 m/s)] −15 λ = 2.134 (b).85 × 10 2 ∞2 ⎠ ⎝5 To calculate the wavelength of the emitted photon in the electronic transition from n = 5 to n = 1.18 × 10−18 J)(3)2 ⎜ ΔE = RH Z2 ⎜ − − ⎟ = − 1. we have: ⎛1 1 ⎞ ΔE = (2. we use For ni = 1. we need to calculate the moving mass of the proton.00 × 108 m/s ⎝ ⎠ 2 = 1.136 To calculate the energy to remove at electron from the n = 1 state and the n = 5 state in the Li the equation derived in Problem 7. we have: ⎛ 1 1 ⎞ −19 ΔE = (2. nf = ∞.88 × 10−17 J 2⎟ 2 ⎜ n2 nf ⎠ 12 ⎠ ⎝5 ⎝ i We ignore the minus sign for ΔE in calculating λ.29 × 10 = −6 nm ≈ 6.6 nm First.00 × 108 m/s ⎟ ⎟ ⎝ ⎠ 2 ⎛u⎞ 1−⎜ ⎟ ⎝c⎠ 2 The equation is only important for speeds close to that of light.18 × 10−18 J)(3)2 ⎜ − J ⎟ = 7. and then we can calculate its wavelength using the de Broglie equation.0 × 10−2 kg ⎛ ⎞ 63 m/s 1−⎜ ⎜ 3. mmoving = mrest ⎛u⎞ 1−⎜ ⎟ ⎝c⎠ 2 = 1.06 × 10 7. otherwise. their moving mass would be infinite! . nf = ∞.50)(3.00 × 108 m/s) = ΔE 1.63 × 10−34 J ⋅ s)(3.CHAPTER 7: QUANTUM THEORY AND THE ELECTRONIC STRUCTURE OF ATOMS 217 7.50)(3.0 × 10−2 kg 6.673 × 10−27 kg ⎛ (0. ⎛ 1 1 ⎞ ΔE = RH Z2 ⎜ − ⎟ ⎜ n2 nf2 ⎟ ⎝ i ⎠ 2+ ion. and Z = 3. ⎛ 1 ⎛ 1 1 ⎞ 1⎞ ⎟ = (2.63 × 10−34 J ⋅ s = mu (1.00 × 108 m/s) ⎞ 1−⎜ ⎟ ⎜ ⎟ 3. Note that photons have a rest mass of zero.96 × 10−17 J 2 2⎟ ∞ ⎠ ⎝1 For ni = 5.

8 × 1010 m/s This value for the uncertainty is impossible.63 × 10−34 J ⋅ s)(9.67 × 10 −19 J Next.1094 × 10−31 kg)u 2 2 hν = W + (6.109 × 10 Δu = 4π(9. ν = c 3.0 × 10 m) = 5.58 × 1014 s−1 ) = (5. ν = c 3. and then calculate the velocity of the ejected electron. Consequently.138 We calculate W (the energy needed to remove an electron from the metal) at a wavelength of 351 nm.00 × 108 m/s = = 9.109 × 10 kg and taking Δx as the radius of the nucleus.218 CHAPTER 7: QUANTUM THEORY AND THE ELECTRONIC STRUCTURE OF ATOMS 7.55 × 1014 s −1 ) = W + W = 5. Solving for Δu: 4π h 4π h 4πmΔx −31 For the electron with a mass of 9.673 × 10 Δu = 6.63 × 10−34 J ⋅ s 4π(1.1094 × 10−31 kg)(0 m/s) 2 2 hν = W + (6.55 × 1014 s −1 −9 λ 351 × 10 m 1 me u 2 2 1 (9. it is impossible to confine an electron within a nucleus. we can then calculate the velocity of an ejected electron using light with a wavelength of 313 nm.2 × 107 m/s .87 × 10 m/s 7.0 × 10 −15 m) = 3.5547 × 10 5 −31 2 )u u = 3.673 × 10 −27 −27 kg gives: kg)(1.58 × 1014 s −1 −9 λ 313 × 10 m 1 me u 2 2 1 (9.67 × 10−19 J) + 6.63 × 10−34 J ⋅ s)(8. Once W is known.139 The minimum value of the uncertainty is found using ΔxΔp = Δx(mΔu ) = Δu = h and Δp = mΔu.82 × 10 −20 = (4. Repeating the calculation for the proton with a mass of 1. we convert wavelength to frequency.00 × 108 m/s = = 8. we find: −15 6. we convert a wavelength of 313 nm to frequency. as it far exceeds the speed of light. First.63 × 10−34 J ⋅ s −31 kg)(1.

Because the shape of the curve and the wavelength corresponding to the maximum depend on the temperature of an object.CHAPTER 7: QUANTUM THEORY AND THE ELECTRONIC STRUCTURE OF ATOMS 219 While still a large value. over billions of years. The large value does indicate the necessity of using quantum mechanics to describe nucleons in the nucleus. 7. organisms have adjusted their development to capture energy at or near this wavelength. (b) . and the confinement of a proton to the nucleus does not represent a physical impossibility. just as quantum mechanics must be used for electrons in atoms and molecules. Astronomers record blackbody radiation curves from stars and compare them with those obtained from objects at different temperatures in the laboratory. astronomers can reliably determine the temperature at the surface of a star from the closest matching curve and wavelength.140 (a) We note that the maximum solar radiation centers around 500 nm. Thus. the uncertainty is less than the speed of light. The two most notable cases are photosynthesis and vision.

Solutions Chang chapter 7

Solutions Chang chapter 7

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