Students solutions manual for Burrows et.al.

Chemistry3

2
Atomic structure and properties
Answers to worked examples
WE 2.1 Interconverting wavelength and frequency What is the frequency of red light with a wavelength of 680 nm? Strategy Use Equation 2.1, c = , and rearrange to find the frequency, . The wavelength, , must be in metres. Solution Rearranging Equation 2.1 by dividing both sides by gives c =

c = 2.998 108 m s1
= 680 nm = 680 109 m

2.998 108 m s 1 680 109 m

= 4.41 1014 s1 = 4.41 1014 Hz

WE 2.3

The photoelectric effect

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Students solutions manual for Burrows et.al. Chemistry3

Calculate the kinetic energy of the ejected electrons (in kJ mol1) if ultraviolet radiation of wavelength 450 nm is used in this experiment. Strategy By rearranging Equation 2.1, c = , the frequency, . can be calculated. This value of , can then be combined with Equation 2.2, E = h, to calculate the energy (in J) of a single photon. The value of the work function, , for sodium has already been calculated in Worked example 2.3 as 3.68 1019 J. Using Equation 2.3, where hv = + EKE , allows EKE for a single electron to be calculated. Finally, the value for a mole of electrons can be calculated by multiplying EKE by the Avogadro constant. Solution Rearranging Equation 2.1 by dividing both sides by gives c =

c = 2.998 108 m s1
= 450 nm = 450 109 m

2.998 108 m s 1 450 109 m = 6.66 1014 s1 Using Equation 2.2, E = h, calculate the energy of one photon where h = Plancks constant = 6.626 1034 J s

E = (6.626 1034 J s) (6.66 1014 s1) E = 4.41 1019J

Since from Equation 2.3, h = + EKE, and the value of , for sodium has already been calculated in the worked example (pp.82-83) as 3.68 1019 J, rearranging for EKE gives
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Students solutions manual for Burrows et.al. Chemistry3

EKE = h E = (4.41 1019J) (3.68 1019 J) E = 7.3 1020 J

To convert this value for a single photon to a mole of electrons, requires multiplication by the Avogadro constant, NA.

EKE = (7.3 1020 J) (6.022 1023 mol1) EKE = 4.4 104 J or 44 kJ mol1

WE 2.5

The ionization energy of hydrogen What is the ionization energy for hydrogen when the electron has already been promoted to the n = 2 level? Strategy Use the Rydberg equation, Equation 2.6, to work out the frequency of the line corresponding to the transition n1 = 2 to n2 = (infinity). Then use Equation 2.2, E = h, to convert the frequency to the energy of the transition. Finally, this energy for a single atom needs to be converted to a molar quantity by multiplying by the Avogadro constant. Solution Using Equation 2.6,

= RH

1 1 2 and RH = 3.29 1015 Hz 2 n1 n2

n1 = 2 to n2 = (infinity)

= RH

1 1 1 2 = 0 = 8.23 1014 Hz (s1) 2 2 4

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Students solutions manual for Burrows et.al. Chemistry3

Using Equation 2.2, E = h, to find the energy of the transition. E = (8.23 1014 s1) (6.626 1034 J s) E = 5.45 1019 J or 5.45 1022 kJ Finally multiply by the Avogadro constant to determine the value for a mole in kJ mol1. E = (5.45 1022 kJ) (6.022 1023 mol1) E = 328 kJ mol1

WE 2.7

The Heisenberg uncertainty principle Calculate the uncertainty in the position of an electron whose velocity is known to within 1 106 m s1.

Strategy Since the momentum (p) = mass velocity, the uncertainty in the momentum is calculated using p = mv. Rearrange Equation 2.10 and use it to calculate the uncertainty q, in the position of the electron. Solution The uncertainty in the momentum p = mv, where the mass of an electron = 9.1094 1031 kg (Table 2.1, p.76) p = (9.1094 1031 kg) (1 10 6 ms1) p = 9.1094 1037 kg m s1

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Using Equation 2.10 h pq 4

Rearrange by dividing both sides by p to give

q = h 6.626 1034 kg m s 1 = 4p 4 3.1416 9.1094 1037 kg m s 1

q = 57.9 m

WE 2.9

Radial wavefunctions How many radial nodes does a 7s orbital have?

Strategy The number of radial nodes is directly related to the type of orbital. For an s orbital, there are (n 1) nodes where n is the principal quantum number. Solution As n = 7, the number of nodes for this s orbital is simply (n 1), therefore the 7s orbital has 6 nodes.

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WE 2.11 Effective nuclear charge What is the effective nuclear charges for (a) chlorine (Z = 17) and (b) bromine (Z = 35)?

Strategy First establish the electronic configuration of the elements using the Aufbau principle and Figure 2.25. Consider one electron in the outer set of orbitals and the effect the other electrons has on it and apply Slaters rules to calculate the shielding constant, S. The other electrons in the same set of orbitals shield at 0.35, in the (n 1) set of orbitals shield at 0.85 and the (n 2) set of orbitals (or below) shield at 1.0. Finally, use Equation 2.19 to calculate Zeff. Solution (a) The electronic configuration of chlorine (Z = 17) is 1s22s22p63s23p5. Considering one of the electrons in the 3p orbitals and the effect the other electrons have on it gives the following. There are four other electrons in the 3p orbitals and two electrons in the 3s orbital. As these electrons are in orbitals of the same principal quantum number they shield at 0.35. i.e. 6 0.35. Each of the eight electrons in the 2s and 2p orbitals contribute 0.85 to the shielding as they are in the (n 1) set of orbitals. This gives 8 0.85 for this shielding contribution. Finally the two 1s electrons are in the (n 2) set of orbitals and hence each contribute 1.0 to the shielding. This gives 2 1.0. Overall the shielding is therefore (6 0.35) + (8 0.85) + (2 1.0) = 10.9. Using Equation 2.19, where Zeff = Z S gives 17 10.9 = 6.1.

(b)

The electronic configuration of bromine (Z = 35) is 1s22s22p63s23p64s23d104p5.

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Considering one of the electrons in the 4p orbitals and the effect the other electrons have on it gives the following. There are four other electrons in the 4p orbitals and two electrons in the 4s orbital. As these electrons are in orbitals of the same principal quantum number they shield at 0.35. i.e. 6 0.35. Each of the eighteen electrons in the 3s, 3p and 3d orbitals contribute 0.85 to the shielding as they are in the (n 1) set of orbitals. This gives 18 0.85 for this shielding contribution. Finally the there are ten electrons in a combination of the 1s, 2s and 2p orbitals which are in the (n 2) (or below) set of orbitals and hence each contribute 1.0 to the shielding. This gives 10 1.0. Overall the shielding is therefore (6 0.35) + (18 0.85) + (10 1.0) = 27.4. Using Equation 2.19, where Zeff = Z S gives 3527.4 = 7.6.

Answers to boxes
Box 2.1 Radiation from the Sun Why does the Sun appear yellow?

Strategy Examine the solar spectrum and examine the maximum intensity in comparison to the visible region. Solution All colours are present in sunlight, but the maximum intensity of the solar spectrum occurs at around 500 nm which is in the yellow region of the visible region.

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Box 2.3

The composition of stars How would the emission spectrum from the elements surrounding the Sun differ from the absorption spectrum obtained by Fraunhofer?

Strategy Read the details of the Fraunhofer experiment given in Box 2.3 (p.91-92). The absorption spectrum gave missing lines in the visible spectrum according to the gases absorbing certain wavelengths of light. The emission spectrum should show the opposite behaviour where the missing lines corresponding to certain wavelengths are now emitted. Solution The emission spectrum at the Sun would be series of coloured lines on a dark background. The positions of the coloured lines (previously missing wavelengths) would exactly correspond to the position of the dark lines in the absorption spectrum

Box 2.7

Atomic numbers and the Periodic Table Moseley showed that copper emits X-rays with = 1.549 1010 m. Calculate the energy of a photon with this wavelength.

Strategy Use Equation 2.1, c = , to calculate the frequency of this X-ray and then Equation 2.2, E = h, to calculate the energy of the photon. Solution Rearranging Equation 2.1 by dividing each side by gives and inputting the wavelength (c = 2.998 108 ms1)
c 2.998 108 ms v= = 1.549 1010 m
1

= 1.935 1018 s 1 (Hz)

Using Equation 2.2 to determine the energy of the photon where E = h and h = 6.626 1034 J s

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Students solutions manual for Burrows et.al. Chemistry3

E = (6.626 1034 J s) (1.935 1018 s1) E = 1.282 1015 J

Box 2.9

Smoke detectors What is the nuclear equation of the decay of an atom of 241Am?

Strategy An alpha decay (see Table 2.7, p.121) is associated with a change of 4 in the atomic number and 2 in the atomic mass (i.e. the same as a He atom). Therefore the product must reflect these changes. Solution 241 95 Am

237 93 Np

+ 4 He 2

Answers to end of chapter questions

1.

What is the energy (in kJ mol1) of X-ray photons with a wavelength of 100 pm? Strategy Use Equation 2.1, c = , and rearrange to find the frequency, . The wavelength, , must be in metres. The frequency can then be converted to energy for a single photon using Equation 2.2, E = h and then multiplied by the Avogadro constant to find the energy of a mole of photons. (Where the Avogadro constant, NA, is the number of entities in a mole, see Section 1.3, p.16.) Solution Rearranging Equation 2.1 by dividing both sides by gives

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Students solutions manual for Burrows et.al. Chemistry3

c = 2.998 108 m s1

= 100 pm = 100 1012 m

2.998 108 m s 1 100 1012 m

= 2.998 1018 s1 = 2.998 1018 Hz

Using Equation 2.2, E = h to then calculate the energy of one photon where h = Plancks constant = 6.626 1034 J s
E = (6.626 1034 J s) (2.998 1018 s1) E = 1.986 1015J

The value for a single photon can then be converted into the energy for one mole of photons by multiplying by the Avogadro constant, 6.022 1023 mol1.
E = 1.986 1015 J 6.022 1023 mol1 E = 1.196 109 J mol1 or 1.196 106 kJ mol1

3.

What is the wavelength of light for a line in the atomic spectrum of hydrogen for which n1 = 2 and n2 =4 ? What part of the electromagnetic spectrum does this correspond to? Strategy Comparing these data to Table 2.4 (p.87) shows that this line is from the Balmer series of the atomic spectrum of hydrogen. Numerically this can be proven using Equation 2.6 to calculate the frequency of the line and then using Equation 2.1, c = , to convert the frequency to wavelength.
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Students solutions manual for Burrows et.al. Chemistry3

Solution Using Equation 2.6,

= RH

1 1 2 and RH = 3.29 1015 Hz 2 n1 n2

= RH

1 1 1 1 2 = RH = 6.169 1014 Hz (s 1 ) 2 2 4 4 16

From Equation 2.1 dividing each side by gives

= c =

2.998 108 ms 1 = 4.86 107 m = 486 nm 14 1 6.169 10 s

This is at the violet end of the visible region.

5.

Which of the following sets of quantum numbers are allowed? What atomic orbitals do the allowed combinations correspond to? (a) n = 2, l = 2, ml = 2 (b) n = 5, l = 3, ml = 2 (c) n = 3, l = 1, ml = 1 (d) n = 2, l = 1, ml = 1 (e) n = 4, l = 0, ml = 1 Strategy Use the definitions given for n, l and ml on page 96 to identify permitted values n takes integral values starting from 1 upwards and l can then take value from 0 up to (n 1). ml can take integral values between +l and l.
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Solution (a) These values are not allowed, the maximum value of l is (n 1). (b) These values are allowed and with n = 5 and l = 3, combine to give a 5f orbital. (c) These values are not allowed as l cannot be negative. (d) These values are allowed and with n = 2 and l = 1, combine to give a 2p orbital. (e) The values are not allowed as ml can only take values from +l to l. In this case as l is zero, ml = 1 is not allowed.

7.

The value of ml for a particular orbital is 2. What are the smallest possible values for n and l ? Strategy Use the definitions given for n, l and ml on page 96 to identify permitted values n takes integral values starting from 1 upwards and l can then take value from 0 up to (n 1). ml can take integral values between +l and l. Solution For ml to have a value of 2, where ml takes values from +l to l, the smallest l can be is 2. As l takes values up to (n 1), the smallest value of n where l = 2, must be l + 1 = 3.

9.

Of the following arrangement of p electrons, which represents the ground state, which are excited states and which are impossible? Strategy Apply the Pauli exclusion principle (no two electrons may have the same four quantum numbers) and Hunds Rule (the lowest energy configuration is the one with
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maximum number of parallel electrons) to the different configurations to determine which are allowed. Note in the answers that the difference between an allowed excited state (in violation of Hunds Rule) as opposed to a disallowed state (in violation of the Pauli exclusion principle). Solution (a) As one of the electrons could be placed in another orbital in a spin parallel configuration (according to Hunds rule) this is not the lowest energy configuration. This is therefore an excited state. (b) This is the ground state configuration with a maximum number of parallel electrons in agreement with Hunds rule. Although electrons are in separate orbitals, the spins are not parallel and hence this configuration does not obey Hunds rule. It is therefore an excited state. This configuration has two electrons with the same four quantum numbers and disobeys the Pauli exclusion principle. This configuration is disallowed.

(c)

(d)

11.

Which elements would you expect to have the following electronic configurations: (a) [Ar] 4s2, (b) [Ne]3s23p5, (c) [Kr]5s24d7. The actual configuration for the element in (c) is [Kr] 5s1 4d8. Suggest a reason for this. Strategy Use Figure 2.25 (p.105) to determine the order in which the orbitals are filled. Use the Periodic Table (on the inside front cover) to pinpoint the period of the element in question. E.g. from the noble gas configuration shorthand the element must be in the period after the last full noble gas configuration. Solution (a) This element has two more electrons than argon, it is therefore calcium. (b) This element has seven more electrons than neon, it is therefore chlorine.
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(c)

This element has nine more electrons than krypton, it is therefore rhodium.

The unexpected configuration for rhodium is due to Hunds rule. This configuration has a greater number of parallel electrons.

13.

Pb decays into 206 Pb in a pathway involving two emissions followed by an emission. What are the two intermediate isotopes? Strategy A emission causes a rise by 1 unit in the atomic mass. Use the Periodic Table (on the inside front cover) to determine which two elements are created after each emission. Solution 210 82 Pb
210 83

210

210 83

Bi +

0 1

Bi Po

210 84

Po +

0 1

210 84

206 82

Pb + 4 He 2

The two intermediate isotopes are bismuth-210 and polonium-210.

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Students solutions manual for Burrows et.al. Chemistry3

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