Atomic Radius and Effective Nuclear Charge

Atomic radius is generally stated as being the total distance from an atom’s nucleus to
the outermost orbital of electron. In simpler terms, it can be defined as something
similar to the radius of a circle, where the center of the circle is the nucleus and the
outer edge of the circle is the outermost orbital of electron. As you begin to move
across or down the periodic table, trends emerge that help explain how atomic radii
change.

The effective nuclear charge (Zeff) of an atom is the net positive charge felt by the
valence electron. Some positive charge is shielded by the core electrons therefore the
total positive charge is not felt by the valence electron. Zeff greatly affects the atomic
size of an atom. So as the Zeff decreases, the atomic radius will grow as a result because
there is more screening of the electrons from the nucleus, which decreases the
attraction between the nucleus and the electron. Since Zeff decreases going down a
group and right to left across the periodic table, the atomic radius will increase going

down a group and right to left across the periodic table.

The effective nuclear charge (often symbolized as Zeff or Z*) is the net positive charge
experienced by an electron in a multi-electron atom. The term “effective” is used
because the shielding effect of negatively charged electrons prevents higher orbital
electrons from experiencing the full nuclear charge.

The effective nuclear charge on an electron is given by the following equation:

Zeff = Z – S

where Z is the number of protons in the nucleus (atomic number), and S is the number
of electrons between the nucleus and the electron in question (the number of
nonvalence electrons).

The calculation of orbital energies in atoms or ions with more than one electron
(multielectron atoms or ions) is complicated by repulsive interactions between the
electrons. The concept of electron shielding, in which intervening electrons act to
reduce the positive nuclear charge experienced by an electron, allows the use of
hydrogen-like orbitals and aneffective nuclear charge (Zeff) to describe electron
distributions in more complex atoms or ions. The degree to which orbitals with different
values of l and the same value of noverlap or penetrate filled inner shells results in
slightly different energies for different subshells in the same principal shell in most
atoms.
The shielding effect describes the attraction between an electron and the nucleus in any
atom with more than one electron. The shielding effect can be defined as a reduction in
the effective nuclear charge on the electron cloud, due to a difference in the attraction
forces of the electrons in the nucleus. It is also referred to as the screening
effect (or) atomic shielding.
Shielding effect

Effective nuclear charge, Zeff, experienced by an electron is less than the actual nuclear
charge, Z „ Electrons in the outermost shell are repelled (shielded) by electrons in the
inner shells. This repulsion counteracts the attraction caused by the positive nuclear
charge

As we move from left to right along the period, the effective nuclear charge “felt”
by the outermost electron increases while the distance from the nucleus doesn’t change
that much (electrons are filling the same shell) „ Outermost electrons are attracted
stronger by the nucleus, and the atomic radius decreases.
EXAMPLES:

 CADMIUM SULFIDE

If we were able to determine the atomic radius of an atom from experimentation, say
Se, which had an atomic radius of 178 pm, then we could determine the atomic radius
of any other atom bonded to Se by subtracting the size of the atomic radius of Se from
the total distance between the two nuclei. So, if we had the compound CaSe, which had
a total distance of 278 pm between the nucleus of the Ca atom and Se atom, then the
atomic radius of the Ca atom will be 278 pm (total distance) - 178 pm (distance of Se), or
100 pm. This process can be applied to other examples of ionic radius.

Cations have smaller ionic radii than their neutral atoms. In contrast, anions
have bigger ionic radii than their corresponding neutral atoms.

A detailed explanation is given below:

 The cation, which is an ion with a positive charge, by definition has fewer
electrons than protons. The loss in an electron will consequently result in a
change in atomic radii in comparison to the neutral atom of interest (no charge).
 The loss of an electron means that there are now more protons than electrons in
the atom, which is stated above. This will cause a decrease in atomic size because
there are now fewer electrons for the protons to pull towards the nucleus and
will result in a stronger pull of the electrons towards the nucleus. It will also
decrease because there are now less electrons in the outer shell, which will
decrease the radius size.
 An analogy to this can be of a magnet and a metallic object. If ten magnets and
ten metallic objects represent a neutral atom where the magnets are protons
and the metallic objects are electrons, then removing one metallic object, which
is like removing an electron, will cause the magnet to pull the metallic objects
closer because of a decrease in number of the metallic objects. This can similarly
be said about the protons pulling the electrons closer to the nucleus, which as a
result decreases atomic size.

 Consider a neutral neon atom (Ne), a sodium cation (Na+), and a fluorine anion
(F–). What is the effective nuclear charge for each?
Solution:

Start by figuring out the number of nonvalence electrons, which can be determined
from the electron configuration.

Ne has 10 electrons. The electron configuration is 1s22s2 2p6. The valence shell is shell 2
and contains 8 valence electrons. Thus the number of nonvalence electrons is 2 (10 total
electrons – 8 valence). The atomic number for neon is 10, therefore:

Zeff(Ne) = 10 – 2 = 8+

Flourine has 9 electrons but F– has gained an electron and thus has 10. The electron
configuration is the same as for neon and the number of nonvalence electrons is 2. The
atomic number for F– is 9, therefore:

Zeff(F–) = 9 – 2 = 7+

Sodium has 11 electrons but the Na+ ion has lost an electron and thus has 10. Once
again, the electron configuration is the same as in the previous examples and the
number of nonvalence electrons is 2 (by losing one electron, the valence shell becomes
the n=2 shell). The atomic number for Na+ is 11, therefore:

Zeff(Na+) = 11 – 2 = 9+

In each of the above examples (Ne, F–, Na+) an atom has 10 electrons but the effective
nuclear charge varies because each has a different atomic number. The sodium cation
has the largest effective nuclear charge, which results in electrons being held the
tightest, and therefore Na+ has the smallest atomic radius.

3. For each of the following pairs, select the one with the larger radius.
a. K or Cs
b. P or Cl
c. C or Br
d. Cl– or Cl
e. Ni+ or Ni2+
f. Br– or Rb+
Using shielding and effective nuclear charge, explain the following. a. The
atomic radius of Cl is smaller than that of P. b. Fe and Ni have similar atomic
radii?
Answers:

1. a. Cs: For comparison of atoms, the trend in atomic radius is increasing radii from top
to bottom and right to left on the periodic table. ↓←

b. P: See explanation in part a.

c. Br: See explanation in part a.

d. Cl has 17 protons and 17 electrons. Cl– has 17 protons and 18 electrons. Anions are
larger than their parent atom. The anion has more electrons with the same number of
protons in the nucleus than the atom. Therefore, Cl–- is larger.

e. Ni+ has 28 protons and 27 electrons. Ni2+ has 28 protons and only 26 electrons.
Cations are smaller than their parent atom. The greater the positive charge, the smaller
the ion is. Therefore, Ni+ is the larger ion.

f. Br– has 35 protons and 36 electrons. Rb+ has has 37 protons and 36 electrons. These
are isoelectronic ions. The ion with the fewest number of protons attracting the same
number of electrons will have the largest radii. Br– is the larger ion.

Note: a common error with the isoelectronic series is to just use the trend in size that is
used for part a, b, and c. Increasing ↓and ←. But that trend is for atoms and cannot be
use when comparing ions.

EXERCISES:

a. Which of these statements does not explain the decrease in the atomic
radii of elements as we move across a period from left to right?
i. The effective nuclear charge increases with the increase in atomic
number.
ii. An increase in the positive charge in the nucleus attracts the
valence electrons with greater force.
iii. The number of energy levels decreases with a decrease in the
atomic number.
iv. Electrons are added to the same energy level with an increase in
atomic
b. Atomic Radius ________________ down a group.
i. Stays the same
ii. varies
 iii. Decrease
iv. Increase
c. Which group contains the elements with the smallest radius on the
periodic table?
i. Alkaline Earth metals
ii. Noble Gases
iii. Halogens
iv. Alkali metals
d. What happens to the energy of a given orbital as the nuclear charge Z of a
species increases? In a multielectron atom and for a given nuclear charge,
the Zeff experienced by an electron depends on its value of l. Why?
e. The electron density of a particular atom is divided into two general
regions. Name these two regions and describe what each represents.
f. As the principal quantum number increases, the energy difference
between successive energy levels decreases. Why? What would happen to
the electron configurations of the transition metals if this decrease did not
occur?
g. Describe the relationship between electron shielding and Zeff on the
outermost electrons of an atom. Predict how chemical reactivity is
affected by a decreased effective nuclear charge.