CHEM501

Tutorial 3: Atomic Structure Answers

1) Which of these electronic transitions correspond to absorption of energy and which
to emission?
a) n = 2 to n = 4 b) n = 3 to n = 1
c) n = 5 to n = 2 d) n = 3 to n = 4
The quantum number n is related to the energy level of the electron. An electron
absorbs energy to change from a lower energy (lower n) to a 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.
a) absorption
b) emission
c) emission
d) absorption

2) The atomic energy levels of hydrogen (and other elements) are quantised. What
does this mean?
The electrons in these atoms can only have certain specific energy values. A property
that cannot change continuously, and is restricted to certain specific values, is said to
be quantised.

3) For one electron systems (like hydrogen), the 2s and 2p, and the 3s, 3p and 3d
orbitals are degenerate. a.) What does this mean?
This means that the orbitals have the same energy.
b.) For atoms with more than one electron, are these orbitals degenerate?
No - they are no longer degenerate.

4) An X-ray has a wavelength of 1.30 × 10-10 m. Calculate the energy (in J) of one
photon of this radiation. (h = 6.626 × 10-34 J s and c = 3.00 × 108 m s-1)

hc (6.626 10−34 J s)(3.00 108 m s −1 )

E= = = 1.53  10−15 J
 1.30 10−10 m

5) Barium salts in fireworks generate a yellow-green colour. Excited-state Ba2+ ions

emit photons having wavelengths of 487, 514, 543, 553 and 578 nm. Convert these
wavelengths into frequencies. (c = 3.00 × 108 m s-1)
c
Calculate the frequencies using  =

The calculation for 487 nm is shown below:

c 3.00 108 m s −1
= = = 6.16  1014 s −1
 −7
4.87 10 m
 / nm 487 514 543 553 578

 / s-1 6.16  1014 5.83  1014 5.52  1014 5.42  1014 5.19  1014

6) A ground state hydrogen atom absorbs a photon of light and the atom is excited to
the n = 4 energy level. (h = 6.626 10-34 J s and c = 3.00 10 m s-1).

a) What is the value of n for the H atom in the ground state?

The H atom absorbs energy, so Efinal > Einitial. We are given nfinal = 4, so ninitial = 1.

b) Calculate the change in energy of the atom.

2.18 10−18 J
E1 = − = −2.18  10−18 J
12

2.18 10−18 J
E4 = − = −1.36  10−19 J
42

E = E4 – E1 = -1.36  10-19 J – (-2.18  10-18 J) = 2.04  10-18 J.

c) Calculate the wavelength (in nm) of the photon.

hc
E = h =


hc (6.626 10−34 J s)(3.00 108 m s −1 )

Therefore  = = −18
= 9.74  10−8 m = 97.4 nm
E 2.04 10 J

The energy change is positive, which is consistent with absorption. The

wavelength is within the UV region (about 10 – 380 nm).

7) What feature of an orbital is related to each of the following?

a) Principal quantum number, n
b) Azimuthal quantum number, l
c) Magnetic quantum number, 𝑚𝑙

a) n is related 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) l is related to the shape of the orbital.
c) 𝑚𝑙 is related to the orientation of the orbital in three-dimensional space.
8) Are the following combinations of quantum numbers allowed? If not, show one
way to correct them:
a) n = 2; l = 0; 𝑚𝑙 = -1
b) n = 4; l = 3; 𝑚𝑙= -1
c) n = 3; l = 1; 𝑚𝑙= 0
d) n = 5; l = 2; 𝑚𝑙 = +3

The allowed values of quantum numbers are as follows:

n = positive integers;
l = integers from 0 to 𝑛 − 1;
𝑚𝑙 = integers from -l through 0 to +l
a) This combination is not allowed.
Correct: n = 2; l = 1; 𝑚𝑙= -1 or n = 2; l = 0; 𝑚𝑙 = 0
b) Combination is allowed.
c) Combination is allowed.
d) Not allowed.
Correct: n = 5; l = 3; 𝑚𝑙 = +3 or n = 5; l = 2; 𝑚𝑙= 0

9) The following combinations of quantum numbers are not allowed. If n and 𝑚𝑙 are
correct, change the l value to create an allowed combination:
a) n = 3; l = 0; 𝑚𝑙 = -1
b) n = 3; l = 3; 𝑚𝑙= +1
c) n = 7; l = 2; 𝑚𝑙 = +3
d) n = 4; l = 1; 𝑚𝑙 = -2

a) Increase the l value to 1 or 2 to create an allowed combination.

b) Decrease the l value to 1 or 2 to create an allowed combination.
c) Increase the l value to 3, 4, 5, or 6 to create an allowed combination.
d) Increase the l value to 2 or 3 to create an allowed combination.

10) List the selection rules for any electronic transition.

∆ 𝑛 = anything
∆𝑙 = ± 1
∆𝑚𝑙 = 0, ±1

11) For the hydrogen atom, suggest four possible allowed transitions for an electron
starting at n = 3 or n = 4 and ending at n = 2.

Only certain transitions from one energy level to another are allowed, as given in the
answer to Question 9. In one electron species, the change in l of an allowed transition
is ±1. For example, a 3p electron can move to a 2s orbital but not a 2p.
The first four transitions are therefore as follows:
3s → 2p
3d → 2p
4s → 2p
3p → 2s

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 𝑙 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 d orbital
to 2p (l = 2 to l = 1). The problem specifies a change in energy level. (Although a
change from 2p to 2s would result in a +1 change in l, this is not a change in energy
level).

12) State Hund’s rule in your own words, and show its application in the orbital
diagram of the nitrogen atom.

Hund’s rule states that electrons will fill empty orbitals in the same set of degenerate
orbitals before filling half-filled orbitals. This lowest-energy arrangement has the
maximum number of unpaired electrons with parallel spins. In the correct electron
configuration for nitrogen shown in (a), the 2p orbitals each have one unpaired
electron; in the incorrect configuration shown in (b), electrons were paired in one of
the 2p orbitals while leaving one 2p orbital empty. The arrows in the 2p orbitals of
configuration (a) could alternatively all point down.

a) correct

b) incorrect
13) Write a full set of quantum numbers for the following:
a) The outermost electron in the Li atom.
𝑛 = 2; 𝑙 = 0; 𝑚𝑙 = 0; 𝑚𝑠 = +1/2

b) The highest energy electron in the ground-state B atom.

𝑛 = 2; 𝑙 = 1; 𝑚𝑙 = −1; 𝑚𝑠 = +1/2

14) Write the full ground-state electron configuration for each of the following atoms:
a) Mg b) Ar c) S
The atomic number gives the number of electrons and the periodic table shows
the order for filling orbitals. Recall the s orbitals hold a maximum of 2 electrons,
and a p orbital set holds 6 electrons.
a) Mg: 1s²2s²2p⁶3s²
b) Ar: 1s²2s²2p⁶3s²3p⁶
c) S: 1s²2s²2p⁶3s²3p⁴

15) None of the following energy level diagrams describes the ground state of a
sulfur atom. For each, state the reason why it is not correct.
a) b)

c) d)
 The ground state has electrons in the lowest energy orbitals, consistent with the
Aufbau principle and maximises parallel electron spin in sets of degenerate orbitals
(Hund's rule). Of the configurations shown, (a) and (d) are incorrect because these
contain the wrong number of electrons; (b) and (c) are incorrect because these do not
maximise parallel electron spins.

16) An excited state hydrogen atom emits a photon as it undergoes an electronic

transition from the n = 5 state to the n = 1 state.

a.) What is the wavelength of the photon?

2.18 10−18 J
E1 = − = −2.18  10−18 J
12

2.18 10−18 J
E5 = − = −8.72  10−20 J
52

E = Efinal – Einitial = E1 – E5 = -2.18  10-18 J – (-8.72  10-20 J) = -2.09  10-18 J.

Note that ∆𝐸 is negative (the atom loses energy), we use its absolute value, |∆𝐸|,
because λ must have a positive value.
hc
E = h =


hc (6.626 10−34 J s)(3.00 108 m s −1 )

Therefore  = = −18
= 9.51 10−8 m = 95.1 nm
E 2.09  10 J

b.) In what region of the electromagnetic spectrum is this photon found? This photon
is in the ultraviolet region.

17) An excited state hydrogen atom emits photons whose associated wavelengths lie in
the visible region at 656 nm, 486 nm, 434 nm and 410 nm.

a) Calculate the frequency of a photon of wavelength 656 nm.

c
Use the equation  = to calculate the frequency

c 3.00 10 m s −1
8
= = = 4.57  1014 s −1
 6.56 10 m−7

b) Calculate the energy of a photon of wavelength 656 nm.

E = h = 6.626 × 10−34 J s−1 × 4.57 × 1014 s−1 = 3.03 × 10−19 J

c) The line at 656 nm arises from the electronic transition n = 3 → n = 2. Calculate

the energies of the n = 3 and n = 2 levels and comment on the energy difference
between these levels with respect to your answer in b.)
 2.18 10−18 J
E3 = − 2
= −2.42  10−19 J
3

2.18 10−18 J
E2 = − 2
= −5.45  10−19 J
2

E = Efinal – Einitial = E2 – E3 = -5.45  10-19 J – (-2.42  10-19 J) = -3.03  10-19 J.

The energy difference between the two levels is the same as the energy of the photon
emitted calculated in part (b).

d.) All emission lines in the Lyman series of the hydrogen atom result from electronic
transitions terminating at the n = 1 level. One line in the Lyman series occurs at
94.9 nm. Determine the electronic transition to which this line is due.

c
Begin by using the equation  = to calculate the frequency of the photon.

c 3.00  108 m s −1
= = = 3.16  1015 s −1
 9.49  10−8 m

Now calculate the energy of the photon using this frequency.

E = h = 6.626 × 10−34 J s−1 × 3.16 × 1015 s−1 = 2.09 × 10−18 J

Realising that this value is now equal to the energy difference between the final n
= 1 level and the starting n = ? level, we can now write
E = E1 – E? = -2.09  10-18 J

2.18 10−18 J
We know that E1 = − 2
= −2.18  10−18 J , and therefore
1

-2.18  10-18 J – E? = -2.09  10-18 J,

hence E? = -2.18  10-18 J – (-2.09  10-18 J) = -9  10-20 J
We now know that the starting level has an energy of -9  10-20 J. We now use the
2.18 10−18 J
equation En = − = −9  10−20 J and solve this for n.
n2
2.18  10−18 J
Rearranging gives n = − = 24.2
2

−9  10−20 J
Thus n2  25, and n = 5. The electronic transition is therefore n = 5 → n = 1
Note that n2 doesn't come out exactly equal to 25 in this case, because of rounding
during the calculation.
18) Sketch an s orbital and describe its shape.
An s orbital is spherical

19) Sketch a p orbital and describe its shape.

A p orbital is shaped like a dumbbell.

20) Write the condensed ground-state electron configuration and draw the orbital
diagram for each:
a.) O b.) Cl
Add up all of the electrons in the electron configuration to obtain the atomic number
of the element which is then used to identify the element and its position on the
periodic table. Remember to put one electron in each orbital in a degenerate set
before pairing electrons.
a) [He] 2s22p4

b) [Ne] 3s23p5