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SOLUTION MANUAL FOR CHEMISTRY CANADIAN

2ND EDITION BY SILBERBERG AMATEIS LAVIERI
VENKATESWARAN ISBN 1259087115 9781259087110
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CHAPTER 6 QUANTUM THEORY AND

ATOMIC STRUCTURE
The value for the speed of light will be 3.00x108 m/s except when more significant figures are necessary, in which cases,
2.9979x108 m/s will be used.

TOOLS OF THE LABORATORY BOXED READING PROBLEMS

B6.1 Plan: Plot absorbance on the y-axis and concentration on the x-axis. Since this is a linear plot, the graph is of the
type y = mx + b, with m = slope and b = intercept. Any two points may be used to find the slope, and the slope is
used to find the intercept. Once the equation for the line is known, the absorbance of the solution in part b) is
used to find the concentration of the diluted solution, after which the dilution equation is used to find the
concentration (mol/L) of the original solution.
Solution:
a) Absorbance vs. Concentration:

0.45
0.4
Absorbance

0.35
0.3
0.25
0.2
0.15
0.1
0.05
0
0 0.00001 0.00002 0.00003 0.00004

Concentration (mol/L)

This is a linear plot, thus, using the first and last points given:
y2  y1  0.396  0.131
m= = = 13,250 /mol/L= 1.3x104/mol/L
x2  x1  
3.0x105  1.0x105 mol / L
Using the slope just calculated and any of the data points, the value of the intercept may be found.
b = y – mx = 0.396 – (13,250/mol/L)(3.0x10–5 mol/L) = –0.0015 = 0.00 (absorbance has no units)

6-1
 b) Use the equation just determined: y = (1.3x104/mol/L) x + 0.00.
x = (y – 0.00)/(1.3x104/mol/L) = (0.236/1.3x104) mol/L = 1.81538x10–5 mol/L = 1.8x10–5 mol/L
This value is cf in a dilution problem (ciVi)= (cfVf) with Vi = 20.0 mL and Vf = 150. mL.

Mi =
 cf Vf  =
1.81538x105

mol / L 150. mL
= 1.361538x10–4 mol/L = 1.4x10–4 mol/L
Vi   20.0 mL 
END–OF–CHAPTER PROBLEMS

6.2 Plan: Recall that the shorter the wavelength, the higher the frequency and the greater the energy. Figure 6.3
describes the electromagnetic spectrum by wavelength and frequency.
Solution:
a) Wavelength increases from left (10–2 nm) to right (1012 nm) in Figure 6.3. The trend in increasing wavelength
is: x-ray < ultraviolet < visible < infrared < microwave < radio wave.
b) Frequency is inversely proportional to wavelength according to the equation c = λν, so frequency has the
opposite trend: radio wave < microwave < infrared < visible < ultraviolet < x-ray.
c) Energy is directly proportional to frequency according to the equation E = hν. Therefore, the trend in increasing
energy matches the trend in increasing frequency: radio wave < microwave < infrared < visible < ultraviolet <
x-ray.

6.7 Plan: Wavelength is related to frequency through the equation c =  ν. Recall that a Hz is a reciprocal second, or
1/s = s–1. Assume that the number “950” has three significant figures.
Solution:
c = ν
c 3.00x108 m/s
(m) = = = 315.789 m= 316 m
  103 Hz   s 1 
 950. kHz     
 1 kHz   Hz 
c  1 nm 
 (nm) = =  315.789 m   9 11 11
 = 3.15789x10 m= 3.16x10 nm
  10 m 

6.9 Plan: Frequency is related to energy through the equation E = h. Note that 1 Hz = 1 s–1.
Solution:
E = h
E = (6.626x10–34 J•s)(3.8x1010 s–1) = 2.51788x10–23 J= 2.5x10–23 J

hc
6.11 Plan: Energy is inversely proportional to wavelength ( E = ). As wavelength decreases, energy increases.

Solution:
In terms of increasing energy the order is red < yellow < blue.

6.13 Plan: Wavelength is related to frequency through the equation c =  ν. Recall that a Hz is a reciprocal second,
or 1/s = s–1.
Solution:
 109 Hz  s 1 
 = (s–1) =  22.235 GHz   
  = 2.2235x1010 s–1
 1 GHz  Hz 
c 2.9979x108 m/s  1 nm 
 (nm) = =   = 1.3482797x107 nm= 1.3483x10 nm
7
 2.2235x1010 s1  109 m 

6.16 Plan: The least energetic photon in part a) has the longest wavelength (242 nm). The most energetic photon in
part b) has the shortest wavelength (220 nm). Use the relationship c = to find the frequency of the photons and

6-2
 hc
relationship E = to find the energy.

Solution:
a) c = 
c 3.00x108 m/s  1 nm 
= = 
15 –1
 = 1.239669x1015 s-1= 1.24x10 s
 242 nm  109 m 

hc 6.626x10 34
 
J•s 3.00x108 m/s  1 nm 
–19
E= =  9  = 8.2140x10–19 J= 8.21x10 J
 242 nm  10 m 
c 3.00x108 m/s  1 nm 
b) = =   = 1.3636x1015 s-1 = 1.4x1015 s–1
 220 nm  109 m 

E=
hc
=
 6.626x10 34
 
J•s 3.00x108 m/s  1 nm 
 9  = 9.03545x10–19 J= 9.0x10–19 J
 220 nm  10 m 

6.18 Bohr’s key assumption was that the electron in an atom does not radiate energy while in a stationary state, and the
electron can move to a different orbit by absorbing or emitting a photon whose energy is equal to the difference in
energy between two states. These differences in energy correspond to the wavelengths in the known spectra for
the hydrogen atoms. A Solar System model does not allow for the movement of electrons between levels.

6.20 Plan: The quantum number n is related to the energy level of the electron. An electron absorbs energy to
change from lower energy (lower n) to higher energy (higher n), giving an absorption spectrum. An electron emits
energy as it drops from a higher energy level (higher n) to a lower one (lower n), giving an emission spectrum.
Solution:
a) The electron is moving from a lower value of n (2) to a higher value of n (4): absorption
b) The electron is moving from a higher value of n (3) to a lower value of n (1): emission
c) The electron is moving from a higher value of n (5) to a lower value of n (2):emission
d) The electron is moving from a lower value of n (3) to a higher value of n (4): absorption

6.22 The Bohr model has successfully predicted the line spectra for the H atom and Be3+ ion since both are one-

electron species. The energies could be predicted from En =

 
 Z 2 2.18x1018 J 
where Z is the atomic number
n2
for the atom or ion. The line spectra for H would not match the line spectra for Be3+ since the H nucleus contains
one proton while the Be3+ nucleus contains 4 protons (the Z values in the equation do not match); the force of
attraction of the nucleus for the electron would be greater in the beryllium ion than in the hydrogen atom. This
means that the pattern of lines would be similar, but at different wavelengths.

6.23 Plan: Calculate wavelength by substituting the given values into Equation 7.3, where n1 = 2 and n2 = 5 because
n2 > n1. Although more significant figures could be used, five significant figures are adequate for this calculation.
Solution:
1  1 1 
 R 2  2  R = 1.096776x107 m–1
 n 
 1 n2 
n 1 = 2 n2 = 5
 1 1 
1

  1
 1
 R  2  2  = 1.096776x107 m 1  2  2  = 2,303,229.6 m–1
n n2  2 5 
 1
 1   1 nm 
 (nm) =  1   9  = 434.1729544 nm= 434.17 nm
 2,303, 229.6 m   10 m 

6-3
6.25 Plan: The Rydberg equation is needed. For the infrared series of the H atom, n1 equals 3. The least energetic
spectral line in this series would represent an electron moving from the next highest energy level, n2 = 4. Although
more significant figures could be used, five significant figures are adequate for this calculation.
Solution:
 1 1 
1

   1 1 
 R  2  2  = 1.096776x107 m1  2  2  = 533,155 m–1
n n2  3 4 
 1
 1   1 nm 
 (nm) =  1   9  = 1875.627 nm= 1875.6 nm
 533,155 m   10 m 

6.27 Plan: To find the transition energy, use the equation for the energy of an electron transition and multiply by
Avogadro’s number to convert to energy per mole.
Solution:
 1 1 

E = 2.18x1018 J  2 
n
 2 
ninitial 
 final

 
 1
2
1
E = 2.18x1018 J  2  2  = –4.578x10–19 J/photon
5 
 4.578x1019 J   6.022x1023 photons 
E =     = –2.75687x105 J/mol= –2.76x105 J/mol
 photon  1 mol 
The energy has a negative value since this electron transition to a lower n value is an emission of energy.

6.29 Plan: Determine the relative energy of the electron transitions. Remember that energy is directly proportional
to frequency (E = h).
Solution:
Looking at an energy chart will help answer this question.
n=5 n=4

(d) n=3

(a) (c)
n=2

(b)

n=1

Frequency is proportional to energy so the smallest frequency will be d) n = 4 to n = 3; levels 3 and 4 have a
smaller E than the levels in the other transitions. The largest frequency is b) n = 2 to n = 1 since levels 1 and
2 have a larger E than the levels in the other transitions. Transition a) n = 2 to n = 4 will be smaller than
transition c) n = 2 to n = 5 since level 5 is a higher energy than level 4. In order of increasing frequency the
transitions are d < a < c < b.

6.31 Plan: Use the Rydberg equation. Since the electron is in the ground state (lowest energy level), n1 = 1. Convert
the wavelength from nm to units of meters.
Solution:
 109 m 
 =  97.20 nm    = 9.720x10–8 m ground state: n1 = 1; n2 = ?
 1 nm 
 1 1 
1

 
= 1.096776x107 m1  2  2 
 n1 n2 

6-4
  1 
1
9.72x108 m

= 1.096776x107 m 1   11 2
 
n22 

1 1 
0.93803 =  2  2 
1 n2 

1
= 1 – 0.93803 = 0.06197
n22
n22 = 16.14
n2 = 4
6.37 Macroscopic objects have significant mass. A large m in the denominator of  = h/mu will result in a very small
wavelength. Macroscopic objects do exhibit a wavelike motion, but the wavelength is too small for humans to see
it.

6.39 Plan: Use the de Broglie equation. Velocity in km/h must be converted to m/s because a joule is equivalent to
kg•m2/s2.
Solution:
a)
 19.8 km   10 m   1 h 
3
Velocity (m/s) =    1 km   3600 s  = 5.50 m/s
 h   

=
h
=
 6.626x10 34

J•s  kg•m2 /s 2


 = 1.147359x10–36 m= 1.15x10–36 m
m 
mu 
105 kg   5.50   J 
 s 
 0.1 km   10 m   1 h 
3
b) Uncertainty in velocity (m/s) =      = 0.02778 m/s
 h   1 km   3600 s 
h
x•mv 
4

x 
h

 6.626x10 34
J•s 
 kg•m2 /s 2


  1.807674x10–33 35 m 2x10–33 35 m
4  mv  0.02778 m  
4 105 kg  
J 

 s 

6.41 Plan: Use the de Broglie equation. Mass in g must be converted to kg and wavelength in nm must be converted to
m because a joule is equivalent to kg•m2/s2.
Solution:
 1 kg 
Mass (kg) =  56.5 g   3  = 0.0565 kg
 10 g 
 109 m 
Wavelength (m) =  5400 nm  
 1 nm  = 5.4x10 m
–7

 
h
=
mu

h 
6.626x1034 J•s   kg•m2 /s2 
  = 2.1717x10–26 m/s= 2.2x10–26 m/s
 
u= =
m  0.0565 kg  5.4x107 m  J 

6.43 Plan: The de Broglie wavelength equation will give the mass equivalent of a photon with known wavelength and
velocity. The term “mass equivalent” is used instead of “mass of photon” because photons are quanta of

6-5
 electromagnetic energy that have no mass. A light photon’s velocity is the speed of light, 3.00x10 8 m/s.
Wavelength in nm must be converted to m.
Solution:
 9 
Wavelength (m) =  589 nm   10 m  = 5.89x10–7 m
 
 1 nm 
h
=
mu

h 
6.626x1034 J•s 
 kg•m 2 /s2 
  = 3.7499x10–36 kg/photon= 3.75x10–36 kg/photon
  
m= =
u 5.89x10 m 3.00 x10 m/s 
7 8 J 
6.47 A peak in the radial probability distribution at a certain distance means that the total probability of finding the
electron is greatest within a thin spherical volume having a radius very close to that distance. Since principal
quantum number (n) correlates with distance from the nucleus, the peak for n = 2 would occur at a greater
distance from the nucleus than 52.9 pm. Thus, the probability of finding an electron at 52.9 pm is much greater
for the 1s orbital than for the 2s.

6.48 a) Principal quantum number, n, relates to the size of the orbital. More specifically, it relates to the distance from
the nucleus at which the probability of finding an electron is greatest. This distance is determined by the energy of
the electron.
b) Angular momentum quantum number, l, relates to the shape of the orbital. It is also called the azimuthal
quantum number.
c) Magnetic quantum number, ml, relates to the orientation of the orbital in space in three-dimensional space.

6.49 Plan: The following letter designations correlate with the following l quantum numbers:
l = 0 = s orbital; l = 1 = p orbital; l = 2 = d orbital; l = 3 = f orbital. Remember that allowed ml values are – l to + l.
The number of orbitals of a particular type is given by the number of possible ml values.
Solution:
a) There is only a single s orbital in any shell. l = 1 and ml = 0: one value of ml = one s orbital.
b) There are five d orbitals in any shell. l = 2 and ml = –2, –1, 0, +1, +2. Five values of ml = five d orbitals.
c) There are three p orbitals in any shell. l = 1 and ml = –1, 0, +1. Three values of ml = three p orbitals.
d) If n = 3, l = 0(s), 1(p), and 2(d). There is a 3s (1 orbital), a 3p set (3 orbitals), and a 3d set (5 orbitals) for a
total of nine orbitals (1 + 3 + 5 = 9).

6.51 Plan: Magnetic quantum numbers (ml) can have integer values from –l to + l. The l quantum number can
have integer values from 0 to n – 1.
Solution:
a) l = 2 so ml = –2, –1, 0, +1, +2
b) n = 1 so l = 1 – 1 = 0 and ml = 0
c) l = 3 so ml = –3, –2, –1, 0, +1, +2, +3

6.53 Plan: The s orbital is spherical; p orbitals have two lobes; the subscript x indicates that this orbital lies along
the x-axis.
Solution:
a) s: spherical b) px: 2 lobes along the x-axis

6-6
 The variations in colouring of the p orbital are a consequence of the quantum mechanical derivation of atomic
orbitals that are beyond the scope of this course.

6.55 Plan: The following letter designations for the various subshell (orbitals) correlate with the following l quantum
numbers: l = 0 = s orbital; l = 1 = p orbital; l = 2 = d orbital; l = 3 = f orbital. Remember that allowed ml values are
– l to + l. The number of orbitals of a particular type is given by the number of possible ml values.
Solution:
subshell allowable ml # of possible orbitals
a) d (l = 2) –2, –1, 0, +1, +2 5
b) p (l = 1) –1, 0, +1 3
c) f (l = 3) –3, –2, –1, 0, +1, +2, +3 7

6.57 Plan: The integer in front of the letter represents the n value. The letter designates the l value:
l = 0 = s orbital; l = 1 = p orbital; l = 2 = d orbital; l = 3 = f orbital. Remember that allowed ml values are – l to + l.
Solution:
a) For the 5s subshell, n = 5 and l = 0. Since ml = 0, there is one orbital.
b) For the 3p subshell, n = 3 and l = 1. Since ml = –1, 0, +1, there are three orbitals.
c) For the 4f subshell, n = 4 and l = 3. Since ml = –3, –2, –1, 0, +1, +2, +3, there are seven orbitals.

6.59 Plan: Allowed values of quantum numbers: n = positive integers; l = integers from 0 to n – 1;
ml = integers from – l through 0 to + l.
Solution:
a) n = 2; l = 0; ml = –1: With n = 2, l can be 0 or 1; with l = 0, the only allowable ml value is 0. This
combination is not allowed. To correct, either change the l or ml value.
Correct: n = 2; l = 1; ml = –1 or n = 2; l = 0; ml = 0.
b) n = 4; l = 3; ml = –1: With n = 4, l can be 0, 1, 2, or 3; with l = 3, the allowable ml values are –3, –2, –1, 0, +1,
+2, +3. Combination is allowed.
c) n = 3; l = 1; ml = 0: With n = 3, l can be 0, 1, or 2; with l = 1, the allowable ml values are –1, 0, +1.
Combination is allowed.
d) n = 5; l = 2; ml = +3: With n = 5, l can be 0, 1, 2, 3, or 4; with l = 2, the allowable ml values are –2, –1, 0, +1,
+2. +3 is not an allowable ml value. To correct, either change l or ml value.
Correct: n = 5; l = 3; ml = +3 or n = 5; l = 2; ml = 0.

6.62 Plan: For Part a, use the values of the constants h, π, me, and a0 to find the overall constant in the equation. Use the
hc
resulting equation to calculate E in part b). Use the relationship E = to calculate the wavelength in part c).

Remember that a joule is equivalent to kg•m2/s2.
Solution:
a) h = 6.626x10–34 J•s; me = 9.1094x10–31 kg; a0 = 52.92x10–12 m
h2  1 
2
h
E=  =   
8 2 me a02 n2 8 2 me a02  n2 

6.626x10 
34 2
J•s  kg•m2 /s2   1 
E=     2 
9.1094x10    n 
31 12 2
8 2
kg 52.92x10 m  J

 1   1 
= –(2.17963x10–18 J)  2  = –(2.180x10–18 J)  2 
n  n 
This is identical with the result from Bohr’s theory. For the H atom, Z = 1 and Bohr’s constant = –2.18x10–18 J.
For the hydrogen atom, derivation using classical principles or quantum-mechanical principles yields the same
constant.
b) The n = 3 energy level is higher in energy than the n = 2 level. Because the zero point of the atom’s energy is
defined as an electron’s infinite distance from the nucleus, a larger negative number describes a lower energy
level. Although this may be confusing, it makes sense that an energy change would be a positive number.

6-7
  1 1 
E = –(2.180x10–18 J)  2  2  = 3.027778x10–19 J = 3.028x10–19 J
3 2 
hc
c) E =


 (m) =
hc  
6.626x1034 J•s 2.9979x108 m/s 
= 6.56061x10–7 m= 6.561x10–7 m
 
=
E 3.027778x1019 J

 1 nm 
 
 (nm) = 6.56061x107 m  9  = 656.061 nm= 656.1 nm
 10 m 
This is the wavelength for the observed red line in the hydrogen spectrum.
6.63 Plan: When light of sufficient frequency (energy) shines on metal, electrons in the metal break free and a current
flows.
Solution:
a) The lines do not begin at the origin because an electron must absorb a minimum amount of energy before it has
enough energy to overcome the attraction of the nucleus and leave the atom. This minimum energy is the energy
of photons of light at the threshold frequency.
b) The lines for K and Ag do not begin at the same point. The amount of energy that an electron must absorb to
leave the K atom is less than the amount of energy that an electron must absorb to leave the Ag atom, where the
attraction between the nucleus and outer electron is stronger than in a K atom.
c) Wavelength is inversely proportional to energy. Thus, the metal that requires a larger amount of energy to be
absorbed before electrons are emitted will require a shorter wavelength of light. Electrons in Ag atoms require
more energy to leave, so Ag requires a shorter wavelength of light than K to eject an electron.
d) The slopes of the line show an increase in kinetic energy as the frequency (or energy) of light is increased.
Since the slopes are the same, this means that for an increase of one unit of frequency (or energy) of light, the
increase in kinetic energy of an electron ejected from K is the same as the increase in the kinetic energy of an
electron ejected from Ag. After an electron is ejected, the energy that it absorbs above the threshold energy
becomes the kinetic energy of the electron. For the same increase in energy above the threshold energy, for either
K or Ag, the kinetic energy of the ejected electron will be the same.

6.66 Plan: The Bohr model has been successfully applied to predict the spectral lines for one-electron species other
than H. Common one-electron species are small cations with all but one electron removed. Since the problem
specifies a metal ion, assume that the possible choices are Li2+ or Be3+. Use the relationship E = h to convert the
 Z2 
 
frequency to energy and then solve Bohr’s equation E = 2.18x1018 J  2  to verify if a whole number for Z
n 
can be calculated. Recall that the negative sign is a convention based on the zero point of the atom’s energy; it is
deleted in this calculation to avoid taking the square root of a negative number.
Solution:
The highest energy line corresponds to the transition from n = 1 to n = .
E = h = (6.626x10–34 J•s) (2.961x1016 Hz) (s–1/Hz) = 1.9619586x10–17 J
 Z2 
 
E = 2.18x1018 J  2  Z = charge of the nucleus
n 
En 2 1.9619586x1017 (12 )
Z2 = = = 8.99998
2.18x10 18 J 2.18x1018 J
2
Then Z = 9 and Z = 3.
Therefore, the ion is Li2+ with an atomic number of 3.

6.68 Plan: The electromagnetic spectrum shows that the visible region goes from 400 to 750 nm. Thus, wavelengths b,
c, and d are for the three transitions in the visible series with nfinal = 2. Wavelength a is in the ultraviolet region of
the spectrum and the ultraviolet series has nfinal = 1. Wavelength e is in the infrared region of the spectrum and the

6-8
 infrared series has nfinal = 3. Use the Rydberg equation to find the ninitial for each line. Convert the wavelengths
from nm to units of m.
Solution:
n = ?  n = 1;  = 121 nm (shortest  corresponds to the largest E)
 109 m 
 (m) = 121 nm    = 1.21x10–7 m
 1 nm 
 1 1 
1

 
= 1.096776x107 m1  2  2 
n 
 1 n2 

 1 


1 
 7 1
 = 1.096776x10 m
 1.21x107 m 
  11 2
 
n22 

1 1 
0.7535233 =  2  2 
1 
 n2 

 1 
 2  = 1 – 0.7535233
 n2 
 1 
 2  = 0.2464767
 n2 
n2 = 2 for line (a) (n = 2  n = 1)
n = ?  n = 3;  = 1094 nm (longest  corresponds to the smallest E)
 109 m 
 (m) = 1094 nm    = 1.094x10–6 m
 1 nm 
 1 
1

  1
= 1.096776x107 m1  2  2 
 n1 n2 
 1 


1 
 7 1
 = 1.096776x10 m
 1.094x106 m 
  312
 
n22 

 1 1 
0.083342158 =  2  2 
3
 n2 
1
0.083342158 = 0.111111111 
n22
 1 
 2  = 0.11111111 – 0.083342158
 n2 
 1 
 2  = 0.0277689535
 n2 
n22 =36.01143
n2 = 6 for line (e) (n = 6  n = 3)
For the other three lines, n1 = 2.
For line (d), n2 = 3 (largest   smallest E).
For line (b), n2 = 5 (smallest   largest E).
For line (c), n2 = 4.

6.72 Plan: Allowed values of quantum numbers: n = positive integers; l = integers from 0 to n – 1;
ml = integers from – l through 0 to + l.
Solution:

6-9
a) The l value must be at least 1 for ml to be – 1, but cannot be greater than n – 1 = 3 –1 = 2. Increase the l value to
1 or 2 to create an allowable combination.
b) The l value must be at least 1 for ml to be +1, but cannot be greater than n – 1 = 3 – 1 = 2. Decrease the l value
to 1 or 2 to create an allowable combination.
c) The l value must be at least 3 for ml to be +3, but cannot be greater than n – 1 = 7 – 1 = 6. Increase the l value to
3, 4, 5, or 6 to create an allowable combination.
d) The l value must be at least 2 for ml to be –2, but cannot be greater than n – 1 = 4 – 1 = 3. Increase the l value to
2 or 3 to create an allowable combination.

6-10
6.74 Plan: Ionization occurs when the electron is completely removed from the atom, or when nfinal = . We can use
the equation for the energy of an electron transition to find the quantity of energy needed to remove completely
the electron, called the ionization energy (IE). To obtain the ionization energy per mole of species, multiply by
Avogadro’s number. The charge on the nucleus must affect the IE because a larger nucleus would exert a greater
pull on the escaping electron. The Bohr equation applies to H and other one-electron species. Use the expression
hc
to determine the ionization energy of B4+ and to find the energies of the transitions listed. Use E = to convert

energy to wavelength.
Solution:
 Z2 

a) E = 2.18x1018 J  2
n   Z = atomic number
 
 1  2

E = 2.18x1018 J  2
n 
 2
1
 Z
 final ninitial 
 1 1  2  6.022x1023 

E = 2.18x1018 J  2  2   Z  
 n initial   1 mol 
= (1.312796x106) Z2 for n = 1
b) In the ground state n = 1, the initial energy level for the single electron in B4+. Once ionized, n =  is the final
energy level.
Z = 5 for B4+.
E = IE = (1.312796x106) Z2 = (1.312796x106 J/mol)(52) = 3.28199x107 J/mol= 3.28x107 J/mol
c) nfinal = , ninitial = 3, and Z = 2 for He+.
 1 1  2 18  1 1  2

E = 2.18x1018 J  2  2 
n  
 Z = 2.18x10 J  2  2  2 = 9.68889x10–19 J
 final ninitial   3 

hc
E=


 (m) =
hc
=
 
6.626x1034 J•s 3.00x108 m/s 
= 2.051628x10–7 m
E 9.68889x1019 J
 1 nm 
 
 (nm) = 2.051628x107 m  9  = 205.1628 nm= 205 nm
 10 m 
d) nfinal = , ninitial = 2, and Z = 4 for Be3+.
 1 1  2 18  1 1  2

E = 2.18x1018 J  2  2 
 n  
 Z = 2.18x10 J  2  2  4 = 8.72x10–18 J

 initial   2 

 (m) =
hc
=
6.626x10 34

J•s 3.00x108 m/s  = 2.279587x10–8 m
E 8.72x1018 J
 1 nm 
 
 (nm) = 2.279587x108 m  9  = 22.79587 nm= 22.8 nm
 10 m 

6-11
6.76 Plan: Use the values and the equation given in the problem to calculate the appropriate values.
Solution:
n2 h2  0
a) rn =
 me e2
2 C2 
 
12 6.626x1034 J•s  8.854x10 12 
J•m   kg•m /s  = 5.2929377x10–11 m= 5.293x10–11 m
2 2

r1 =  
  
31 19 2
 9.109x10 kg 1.602x10 C  J 

 C2 
 
2
102 6.626x1034 J•s  8.854x10 12 
J•m   kg•m /s  = 5.2929377x10–9 m= 5.293x10–9 m
2 2

b) r10 =  
  
31 19 2
 9.109x10 kg 1.602x10 C  J 

6.78 Plan: Refer to Chapter 5 for the calculation of the amount of heat energy absorbed by a substance from its
specific heat capacity and temperature change (q = c x mass x T). Using this equation, calculate the energy
absorbed by the water. This energy equals the energy from the microwave photons. The energy of each photon
can be calculated from its wavelength: E = hc/ . Dividing the total energy by the energy of each photon gives the
number of photons absorbed by the water.
Solution:
q = c x mass x T
q = (4.184 J/g°C)(252 g)(98 – 20.)°C = 8.22407x104 J

E=
hc
=
6.626x10
34

J•s 3.00x108 m/s  = 1.28245x10 –23 J/photon
 1.55x102 m

 
Number of photons = 8.22407x104 J 
1 photon


23 
 1.28245x10 J 
= 6.41278x1027 photons= 6.4x1027 photons

6.80 Plan: In general, to test for overlap of the two series, compare the longest wavelength in the “n” series with the
shortest wavelength in the “n+1” series. The longest wavelength in any series corresponds to the transition
between the n1 level and the next level above it; the shortest wavelength corresponds to the transition between the n1
1  1 1 
level and the n =  level. Use the relationship = R  2  2  to calculate the wavelengths.
 n 
 1 n2 
Solution:
 1 1   1 1 
1


= R  2  2  = 1.096776x107 m 1  2  2 
n n2 

 1  n1 n2 
a) The overlap between the n1 = 1 series and the n1 = 2 series would occur between the longest wavelengths for
n1 = 1 and the shortest wavelengths for n1 = 2.
Longest wavelength in n1 = 1 series has n2 equal to 2.
1

 1
1 
= 1.096776x107 m1  2  2  = 8,225,820 m–1
1 2 
1
= = 1.215684272x10–7 m= 1.215684x10–7 m
8,225,820 m 1
Shortest wavelength in the n1 = 2 series:
1


= 1.096776x107 m 1  2 
 1
2
 1 
2 
 = 2,741,940 m
–1

1
= = 3.647052817x10–7 m= 3.647053x10–7 m
2,741,940 m 1

6-12
Since the longest wavelength for n1 = 1 series is shorter than shortest wavelength for n1 = 2 series, there is no
overlap between the two series.
b) The overlap between the n1 = 3 series and the n1 = 4 series would occur between the longest wavelengths for
n1 = 3 and the shortest wavelengths for n1 = 4.
Longest wavelength in n1 = 3 series has n2 equal to 4.
1

   1 1 
= 1.096776x107 m1  2  2  = 533,155 m–1
3 4 
1
= = 1.875627163x10–6 m= 1.875627x10–6 m
533,155 m 1
Shortest wavelength in n1 = 4 series has n2 = .
1

 
= 1.096776x107 m 1  2 
 1
4
1 
2 
 = 685,485 m
–1

1
= = 1.458821127x10–6 m= 1.458821x10–6 m
685,485 m 1
Since the n1 = 4 series shortest wavelength is shorter than the n1 = 3 series longest wavelength, the series do
overlap.
c) Shortest wavelength in n1 = 5 series has n2 = .
1

 
= 1.096776x107 m 1  2 
 1
5
1 
2 
 = 438,710.4 m
–1

1
= = 2.27940801x10–6 m= 2.279408x10–6 m
438,710.4 m 1
Calculate the first few longest lines in the n1 = 4 series to determine if any overlap with the shortest wavelength
in the n1 = 5 series:
For n1 = 4, n2 = 5:
1

   1 1
= 1.096776x107 m1  2  2  = 246,774.6 m–1
4 5 
1
= = 4.052281x10–6 m
246,774.6 m 1
For n1 = 4, n2 = 6:
1

   1 1 
= 1.096776x107 m1  2  2  = 380,825 m–1
4 6 
1
= = = 2.625878x10–6 m
380,825 m 1
For n1 = 4, n2 = 7:
1

   1 1 
= 1.096776x107 m1  2  2  = 461,653.2 m–1
4 7 
1
= = 2.166128x10–6 m
461,653.2 m 1
The wavelengths of the first two lines of the n1 = 4 series are longer than the shortest wavelength in the n1 = 5
series. Therefore, only the first two lines of the n1 = 4 series overlap the n1 = 5 series.
d) At longer wavelengths (i.e., lower energies), there is increasing overlap between the lines from different series
(i.e., with different n1 values). The hydrogen spectrum becomes more complex, since the lines begin to merge into a
more-or-less continuous band, and much more care is needed to interpret the information.

6-13
6.82 Plan: The energy differences sought may be determined by looking at the energy changes in steps. The
hc
wavelength is calculated from the relationship  = .
E
Solution:
a) The difference between levels 3 and 2 (E32) may be found by taking the difference in the energies for the 3  1
transition (E31) and the 2  1 transition (E21).
E32 = E31 – E21 = (4.854x10–17 J) – (4.098x10–17 J) = 7.56x10–18 J

=
hc  
6.626x1034 J•s 3.00x108 m/s 
= 2.629365x10–8 m= 2.63x10–8 m
 
=
E 7.56x1018 J
b) The difference between levels 4 and 1 (E41) may be found by adding the energies for the 4  2 transition (E42)
and the 2  1 transition (E21).
E41 = E42 + E21 = (1.024x10–17 J) + (4.098x10–17 J) = 5.122x10–17 J

=
hc  
6.626x1034 J•s 3.00x108 m/s 
= 3.88091x10–9 m= 3.881x10–9 m
 
=
E 5.122x1017 J

c) The difference between levels 5 and 4 (E54) may be found by taking the difference in the energies for the 5  1
transition (E51) and the 4  1 transition (see part b)).
E54 = E51 – E41 = (5.242x10–17 J) – (5.122x10–17 J) = 1.2x10–18 J

=
hc  
6.626x1034 J•s 3.00x108 m/s 
= 1.6565x10–7 m= 1.66x10–7 m
 
=
E 1.2x1018 J

6.84 Plan: For part a), use the equation for kinetic energy, Ek = ½mu2. For part b), use the relationship E = hc/to find
the energy of the photon absorbed. From that energy subtract the kinetic energy of the dislodged electron to
obtain the work function.
Solution:
a) The energy of the electron is a function of its speed leaving the surface of the metal. The mass of the electron is
9.109x10–31 kg.
2 
Ek = 1 mu2 =
2
1
2 
9.109x1031 kg 6.40x105 m/s 
J
2 2 
 kg•m /s 
= 1.86552x10–19 J= 1.87x10–19 J

b) The minimum energy required to dislodge the electron () is a function of the incident light. In this example,
the incident light is higher than the threshold frequency, so the kinetic energy of the electron, Ek, must be
subtracted from the total energy of the incident light, h, to yield the work function, . (The number of significant
figures given in the wavelength requires more significant figures in the speed of light.)
 109 m 
 (m) =  358.1 nm    = 3.581x10–7 m
 1nm 

E = hc/ =
6.626x10 J•s 2.9979x10
34 8
m/s  = 5.447078x10 –19

3.581x10 m 7
J

 = h – Ek = (5.447078x10–19 J) – (1.86552x10–19 J) = 3.581558x10–19 J= 3.58x10–19 J

6.86 Plan: Examine Figure 7.3 and match the given wavelengths to their colours. For each salt, convert the mass of
salt to moles and multiply by Avogadro’s number to find the number of photons emitted by that amount of salt
hc
(assuming that each atom undergoes one-electron transition). Use the relationship E = to find the energy of

one photon and multiply by the total number of photons for the total energy of emission.

6-14
 Solution:
a) Figure 7.3 indicates that the 641 nm wavelength of Sr falls in the red region and the 493 nm wavelength of Ba
falls in the green region.
b) SrCl2
 1 mol SrCl2   6.022x1023 photons 
Number of photons =  5.00 g SrCl 2      = 1.8994449x1022 photons
 158.52 g SrCl2   1 mol SrCl2 
 109 m 
 (m) =  641 nm    = 6.41x10–7 m
 1nm 

hc
=
 6.626x10 34
 
J•s 3.00x108 m/s  1 kJ 
Ephoton =  3  = 3.10109x10–22 kJ/photon
 6.41x107 m  10 J 
 3.10109x1022 kJ 

Etotal = 1.8994449x1022 photons 
 
1 photon
 = 5.89035 kJ= 5.89 kJ
 
BaCl2
 1 mol BaCl2   6.022x1023 photons 
Number of photons =  5.00 g BaCl 2      = 1.44620557x1022 photons
 208.2 g BaCl2   1 mol BaCl2 
 109 m 
 (m) =  493 nm    = 4.93x10–7 m
 1nm 

hc
=
 6.626x10 34
 
J•s 3.00x108 m/s  1 kJ 
Ephoton =  3  = 4.0320487x10–22 kJ/photon
 4.93x107 m  10 J 
 4.0320487x1022 kJ 

Etotal = 1.44620557x1022 photons  
1 photon
 = 5.83117 kJ= 5.83 kJ
 

6.88 Plan: Examine Figure 7.3 to find the region of the electromagnetic spectrum in which the wavelength lies.
Compare the absorbance of the given concentration of Vitamin A to the absorbance of the given amount of fish-
liver oil to find the concentration of Vitamin A in the oil.
Solution:
a) At this wavelength the sensitivity to absorbance of light by Vitamin A is maximized while minimizing
interference due to the absorbance of light by other substances in the fish-liver oil.
b) The wavelength 329 nm lies in the ultraviolet region of the electromagnetic spectrum.
c) A known quantity of vitamin A (1.67x10–3 g) is dissolved in a known volume of solvent (250. mL) to give a
standard concentration with a known response (1.018 units). This can be used to find the unknown quantity of
Vitamin A that gives a response of 0.724 units. An equality can be made between the two concentration-to-
absorbance ratios.
 1.67x103 g 
Concentration (C1, g/mL) of Vitamin A =   = 6.68x10–6 g/mL Vitamin A
 250. mL 
Absorbance (A1) of Vitamin A = 1.018 units.
Absorbance (A2) of fish-liver oil = 0.724 units
Concentration (g/mL) of Vitamin A in fish-liver oil sample = C2
A1 A
= 2
C1 C2

C2 =
A2 C1
=

 0.724  6.68x106 g/mL 
= 4.7508x10–6 g/mL Vitamin A
A1 1.018

6-15
  4.7508x106 g Vitamin A 
Mass (g) of Vitamin A in oil sample =  500. mL oil    = 2.3754x10–3 g Vitamin A
 1 mL oil
 

Concentration of Vitamin A in oil sample =

 2.3754x10 g  = 1.92808x10
3
–2 g= 1.93x10–2 g Vitamin A/g oil
 0.1232 g Oil 
6.92 Plan: First find the energy in joules from the light that shines on the text. Each watt is one joule/s for a total
hc
of 75 J; take 5% of that amount of joules and then 10% of that amount. Use E = to find the energy of one

photon of light with a wavelength of 550 nm. Divide the energy that shines on the text by the energy of one
photon to obtain the number of photons.
Solution:
The amount of energy is calculated from the wavelength of light:
 109 m 
m) =  550 nm    = 5.50x10–7 m
 1 nm 

E=
hc
=
6.626x10 34

J•s 3.00x108 m/s  = 3.614182x10–19 J/photon
 5.50x107 m
 1 J/s 
Amount of power from the bulb =  75 W    = 75 J/s
1W 
 5% 
Amount of power converted to light =  75 J/s    = 3.75 Js
 100% 
 10% 
Amount of light shining on book =  3.75 J/s    = 0.375 J/s
 100% 
 0.375 J   1 photon 
Number of photons:   19 
= 1.0376x1018 photons/s= 1.0x1018 photons/s
 s   3.614182x10 J 

6.95 Plan: In the visible series with nfinal = 2, the transitions will end in either the 2s or 2p orbitals since those are the
only two types of orbitals in the second main energy level. With the restriction that the angular momentum
quantum number can change by only ±1, the allowable transitions are from a p orbital to 2s (l = 1 to l = 0), from
an s orbital to 2p (l = 0 to l = 1), and from a d orbital to 2p (l = 2 to l = 1). The problem specifies a change in
energy level, so ninit must be 3, 4, 5, etc. (Although a change from 2p to 2s would result in a +1 change in l, this is
not a change in energy level.)
Solution:
The first four transitions are as follows:
3s → 2p
3d → 2p
4s → 2p
3p → 2s

6-16