Fundamentals of Chemistry EF1002

Problem Set 5
Total score: 100 pts
Total pages: 4
Name:
TEAM:
Question1. Particle-in-a-box Model
In Class, we learnt the particle-in-a-box model to describe the probabilistic nature of an
electron trapped in an atom. Now, we check if the wavefunctions we discussed in Class are
actually a solution of the Schrodinger Equation.

In the particle-in-a-box model, the particle is “free” in the confined region, but it does not
exist outside of the box with zero probability to find. In a one-dimensional model, the
potential energy V(x)=0 if x is between 0 and L, and V(x)=infinity otherwise. Here, L is the
one-dimensional box size. Then, the Schrodinger Equation for the particle inside the [0, L]
region is:
2
−ℏ2 d Ψ n (x) h
=E n Ψ (x ), ℏ=
2m dx
2
2π

(a) Get the expression of E1 by plugging Ψ 1 into the above Schrodinger Equation.
Compare your expression of E1 with the energy expression in Lecture slides if they
are consistent. Use the following mathematical facts:
d
(i) sin(ax)=a cos (ax)
dx
d
(ii) cos (ax )=−a sin (ax )
dx
2
d d d
(iii) 2
f ( x)= { f (x)}
dx dx dx

(b) Count the number of nodes in Ψ 1 and Ψ 5, and discuss how you can compare the
energy levels of the wave functions by looking at their shape.
Question 2. Electronic orbitals.
a) Describe the 3 quantum numbers (principal quantum number, orbital angular momentum
quantum number and magnetic quantum number and number of nodal planes) for 4p, 4f
and 5d orbitals
4p=(n=4, l=1, ml=3, nodal planes no=1)
4f= (n=4, l=3, ml=7, nodal planes no= 3)
5d= (n=5, l=2, ml=5, nodal planes no= 2)
b) If a shell contains a maximum of 18 electrons and 32 electrons then what is the principal
quantum number, n for each?
n=3 (for 18 electrons) and n=4 (for 32 electrons)
c) Provide a rough sketch of 1s orbital, and 2p orbitals .

1s or textbook figure 1D.6

2p or textbook figure 1D.8

d) Sketch the radial probability distribution for a 4d orbital in a carbon atom. You should
label the axes, but do not need to include numbers. Use arrows to indicate the radial nodes.
On your 3d radial probability distribution, label the most probable radius, R mp, with a mark,
*.
 *

node

Question 3. Provide the ground state electron configuration expected for

(a) Na (b) Cu2+ (c) Co3+
Note that you may always use the shorthand (noble gas) configuration unless
specifically asked otherwise.
Also correct if all of the core electrons are explicitly written out.
(a) [Ne]3s1 (b) [Ar]4s13d8 (c) [Ar]3d6

(a)
Question 4. The first and second ionization energies (I 1 and I2) of magnesium and aluminum
atoms are listed in the following table.

I1(kJ·mol-1)

N 1402

O 1314

Mg 738

Al 578

a) Explain why the first ionization energy of magnesium is greater than that of
aluminum.
The 1st ionization of Mg requires removal of an electron from the 3s subshell.
Ionization of Al, however, requires removal of an electron from a 3p subshell.
The 3p subshell is higher in energy than the 3s subshell. So Al loses an electron
 more easily from a higher-energy subshell than Mg does.

Al:

Mg:
b) Explain why the first ionization energy of nitrogen is greater than that of oxygen
whereas the second ionization energy of oxygen is greater than that of nitrogen.
The ionization energy of oxygen is slightly lower than that of nitrogen because in
a nitrogen atom each p-orbital has one electron, but in oxygen the eighth
electron is paired with an electron already occupying an orbital. The repulsion
between the two electrons in the same orbital raises their energy and makes
one of them easier to remove from the atom than if the two electrons had been
in different orbitals.

Question 5. Electron affinity is dependent on nuclear charge, shielding and atomic radius.
a) Explain the large decrease in electron affinity between chlorine and Ar.
In chlorine atom, the incoming electron occupies a p-orbital close to a nucleus
with a high effective charge and can experience its attraction quite strongly.
Argon is a noble gas. The noble gases have negative electron affinities because
any electron added to them must occupy an orbital outside a closed shell and
far from the nucleus: this process requires energy, and so the electron affinity is
negative.
b) Explain why less energy will be needed to make S -2 from S- than to make Cl2-
from Cl-
S is a group 16 atom which has two vacancies in its valence-shell and can
accommodate two additional electrons. The first electron affinity is positive
because energy is released when an electron attaches to S. However,
attachment of the second electron requires energy because of the repulsion by
the negative charge already present in S -. However, the valence shell of the S -
anion has only seven electrons and thus can accommodate an additional
electron.
Cl is a group 17 atom which has one vacancy in its valence-shell. Therefore, less
 energy will be needed to make S-2 from S- than to make Cl2- from Cl-, where no
such vacancy exists.

Question 6. The following question explores the trends in the atomic radius around the
periodic table.
a) Explain the trend in the atomic radius of the elements from Li to F,
From Li to F there is an increase in the number of protons and therefore of the
nuclear charge. Shielding of the outer-shell electrons remains approximately
constant because each element has the same number of inner shells of
electrons as each additional electron is held in the same outer energy level. The
force of attraction between the nucleus and the outer electrons therefore
increases sequentially and so the radius decreases.

b) Explain the trend in the atomic radius down group 1,

Down a group 1, there is an increase in both the nuclear charge and in the
number of shells of electrons that shield the outer electrons from the force of
attraction of the nucleus. The repulsion between the electrons, however, is
more significant than the increase in the nuclear charge and so the outer-shell
electrons experience a lower force of attraction for the nucleus down group 1
resulting in an increase in the atomic radius