Scribd
Upload
44 views33 pages

Self Help

The document discusses several key concepts related to atomic structure: 1. Penetration of orbitals and shielding effects determine the energy levels of orbitals for a given principal quantum number. The 3s orbital penetrates more than 3p or 3d orbitals, so 3s electrons are less shielded. 2. Effective nuclear charge (Z*) considers shielding effects and influences orbital energies and properties like ionization energy and electronegativity. Z* increases left to right and decreases down a group. 3. Atomic properties like size, ionization energy, electron affinity, and electronegativity follow trends across periods and down groups based on changes in Z*, shielding, and orbital

Uploaded by

Himanshu Kumar
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
44 views33 pages

Self Help

The document discusses several key concepts related to atomic structure: 1. Penetration of orbitals and shielding effects determine the energy levels of orbitals for a given principal quantum number. The 3s orbital penetrates more than 3p or 3d orbitals, so 3s electrons are less shielded. 2. Effective nuclear charge (Z*) considers shielding effects and influences orbital energies and properties like ionization energy and electronegativity. Z* increases left to right and decreases down a group. 3. Atomic properties like size, ionization energy, electron affinity, and electronegativity follow trends across periods and down groups based on changes in Z*, shielding, and orbital

Uploaded by

Himanshu Kumar
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 33

Self Reading!

Based on the number of nodes the


following concepts can be
explained
Penetration of orbitals

Shielding

Effective nuclear charge

Nuclear influence on electrons


Penetration of orbitals
Penetration of Orbitals

The penetration potential


of an orbital varies as:

ns > np > nd > nf

The penetration of 3s electron through the inner core


is greater than that of a 3p (or 3d) electron because
the latter vanishes at the nucleus. Therefore, the 3s
electrons are less shielded than the 3p electrons.
Shielding

Penetration and Shielding


effect leads to the energy of
the orbitals for a given n as
follows:

ns < np < nd < nf


Electronic configuration of an atom

This is an approximate energy order applicable only


upto atomic number 21
Electronic configuration based
on
1. Aufbau (Building up
principle)
2. Hund’s rule
3. Pauli’s exclusion principles
Effective nuclear charge
The reduction of the true nuclear
charge to the effective nuclear
charge by the other electrons is
called shielding.
The effective nuclear charge
is sometimes expressed in terms
of the true nuclear charge and
an empirical shielding constant
() , by writing Zeff = Z-  .
.
Shielding
The energy order of orbitals for a
given quantum number depends
on shielding effects (σ), effective
nuclear charge (Z*) & penetration
of orbitals

Z* = Z - σ
How to estimate the Z*?
{If the electron resides in s or p orbital}
1. Electrons in principal shell higher
than the e- in question: contribute 0 to σ
2. Each e- in the same principal shell:
contribute 0.35 to σ
3. Electrons in (n-1) shell: each
contribute 0.85 to σ
4. Eelectrons in deeper shell: each
contribute 1.00 to σ
P.S.: There may be other ways of calculating these as given in the
literature. Please stick to this procedure as far as this course is concerned.
How to estimate the Z*?
Example: Calculate the Z* for the 2p electron
Fluorine (Z = 9) 1s2 2s2 2p5
Screening constant for one of the outer electron
(2p):
6 (six) (two 2s e- and four 2p e-) = 6 X 0.35 = 2.10
2 (two)1s e- = 2 X 0.85 = 1.70
σ = 1.70+2.10 = 3.80 & Z* = 9 - 3.80 = 5.20

P.S.: There may be other ways of calculating these as given in the


literature. Please stick to this procedure as far as this course is concerned.
How to estimate the Z*?
{If the e- resides in a ‘d’ or ‘f’ orbital}
1. All e-’s in higher principal shell contribute
0
2. Each e- in the same shell contributes 0.35
3. All inner shells in (n-1) and lower
contributes 1.00

P.S.: There may be other ways of calculating these as given in the


literature. Please stick to this procedure as far as this course is concerned.
Trends in Z* (Zeff): Down a group

n Z Z* Effective nuclear
H 1 1 1.0 charge Z* increases
Li 2 3 1.3 very slowly down a
Na 3 11 2.5 group for the
K 4 19 2.2 “valence electron”.
Rb 5 37 2.2 Example of Valence
Cs 6 55 2.2 configuration as ‘ns1’
Consequence of this?
Trends in Z* (Zeff): Across a period
Effective nuclear charge Z* increases
rapidly along a period. For example, take
period two
Li Be B C N O F Ne
3 4 5 6 7 8 9 10
1.3 1.95 2.4 3.1 3.8 4.5 5.1 5.8
2s1 2s2 2p1 2p2 2p3 2p4 2p5 2p6
Consequence of this?
Influence of nucleus on electrons
Two electrons present in the same d-orbital repel each other
more strongly than do two electron in the same s-orbital.
The electrons present in f are much less influenced by the
nucleus as compared to d, those present in d much less
influenced as compared to p, than s, etc.

It is essential to consider all contributions to the energy of a


configuration, and just not one-electron orbital energies.
The following properties are important in
order to address the compounds formed
•Atomic size (radius)
•Ionic size (radius)
•Ionization energy
•Electron affinity
•Electronegativity
Size (Radius)
The METALLIC RADIUS is half of the
experimentally determined distance between
the nuclei of nearest neighbors in the solid
The COVALENT RADIUS of a non-metallic
element is half of the experimentally
determined distance between the nuclei of
nearest neighbors in the solid
The IONIC RADIUS of an element is
related to the distance between the nuclei
of neighboring cations and anions
Ionic radius of O2- is 1.40 Å;
What is the ionic radius for Mg2+?
Measure the Mg-O distance in MgO and
subtract 1.40 Å
Trend in Size (Radius)
In a period, left to right: atomic radius decreases
1. n (number of shells) remain constant.
2. Z increases (by one unit)
3. Z* increases (by 0.65 unit)
4. Electrons are pulled close to the nucleus by
the increased Z*
In a group, top to bottom: atomic radius
increases
1. n increases
2. Z increases
3. No dramatic increase in Z* - almost remains
constant
Trends in atomic radii
Table of atomic radii

Decreases with increase in Z in a period


Increases moving down a group
Metallic Radius in 5d- elements
Metallic radii of 5d- block elements are
expected to be larger than that of the 4d-
elements, but found that these are not larger.
Of course these are larger than 3d- block
elements.
Lanthanide Contraction
f-orbitals have poor shielding properties;
low penetrating power.
Hence, Z* increases from left to right across the
period in lanthanides and actinides lead to
Lanathanide (actinide) contraction.
All anions
are larger
than their
parent atoms

The cations
are smaller
than their
parent atoms
Ionisation Energy (IE)
The minimum energy needed to remove an
electron from a gas phase atom
Depends on: (a) Size of the atom - IE decreases as
the size of the atom increases; (b) Nuclear Charge - IE
increases with increase in nuclear charge; (c) The
type of electron - Shielding effect
1st IE: H =1312 KJ mol-1 Li =520 KJ mol -1
Reasons: (1) Average distance of 2s electron is
greater than that of 1s; (2) Penetration effect; 3.
Electronic configuration
Ionisation Energy (IE)
On moving down the group: IE decreases
1. nuclear charge increases
2. Z* due to screening is almost constant
3. number of shells increases, hence atomic
size increases.
4. there is an increase in the number of inner
electrons which shield the valence electrons
from the nucleus.
On moving across the period: IE increases
1. the atomic size decreases
2. nuclear charge increases
Trends in Ionisation Energy (IE)
Table of
ionization
energies
Electron affinity (EA)
- the amount of energy associated with the
gain of electrons
The greater the energy released in the
process of taking up the extra electron,
greater is the EA
The EA of an atom measures the tightness
with which it binds an additional electron to
itself.
Trends in Electron affinity (EA)
On moving across a period,
-As the size decreases, the force of attraction by the nucleus
increases. Consequently, the atom has a greater tendency
to attract added electron, i.e., EA electron affinity increases
-Generally the EA’s of metals are low while those of non-
metals are high
-Halogens have high EA. This is due to their strong tendency
to change their configuration to ns2np6
On moving down a group,
- the atomic size increases and therefore, the effective
nuclear attraction decreases and thus electron affinity
decreases
Electronegativity
measure of the tendency of an element to attract
electrons to itself (from its neighbour)
On moving down the group: EN decreases
-Z increases but Z* almost remains constant
-number of shells (n) increases
-atomic radius increases
-force of attraction between added electron and
nucleus decreases
On moving across a period: EN increases
-Z and Z* increases
-number of shells remains constant
-atomic radius decreases
-force of attraction between added electron and
nucleus increases
Trends in electronegativity (Pauling scale)
Table of
electro-
negativities

You might also like

pFad - Phonifier reborn

Pfad - The Proxy pFad of © 2024 Garber Painting. All rights reserved.

Note: This service is not intended for secure transactions such as banking, social media, email, or purchasing. Use at your own risk. We assume no liability whatsoever for broken pages.


Alternative Proxies:

Alternative Proxy

pFad Proxy

pFad v3 Proxy

pFad v4 Proxy