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Chemistry 5 done

Chapter-9
Electrons in Atoms
Part-3

1/2 30 October 2002

done
 p-orbitals (l = 1)
ƒ Key features:
• 1- angular node at r = 0.

• probability density is not spherically

symmetric; 2-lobed orbitals

• Three degenerate p-orbitals: ml = 0, ±1

• n-2 radial nodes in wave function

signs (+, -) correspond to phases of

wavefunction, ψ, and do not signify charge.

n = 2; l = 1 n = 3; l = 1
 d-orbitals (l = 2)

signs (+, -) correspond to

ƒ Key features: phases of wavefunction, ψ
• Two angular nodes at r = 0.

• probability density is not spherically

symmetric; four-lobed orbitals designated
with respect to x,y,z axes

• Five degenerate d-orbitals; ml = 0, ±1, ±2

• n-3 radial nodes in wave function

 Orbitals– Summary

ƒ Variation of n for fixed l

For a given value of l, and increase in n leads to an
increase in the average distance of electron from nucleus
and thus average size of orbital.

ƒ Nodal properties
An orbital with quantum numbers n and l has l angular
nodes and n – l – 1 radial nodes with total of n – 1
nodes.
For 1-electron atom energy depends only on the total
number of nodes (i.e., n, but not l or m).

ƒ Probability at nucleus
As r approaches zero, ψ vanishes for all orbitals except
s. Hence, electrons in s orbitals are said to penetrate to
the nucleus.
 Electron Spin

ƒ Experimental observation?
A beam of atoms, which have an odd
number of electrons, is split into two
component when passed through an
inhomogeneous magnetic field: Stern
Gerlach experiment.

ƒ Electron Spin Quantum Number, ms

This observation can be explained by
introducing a fourth quantum number, the
spin quantum number, ms = ±½ , where
“+” signifies spin up (↑), and “-” spin
down (↓).
Qualitatively, this can be thought of in
classical picture where spinning electron
creates magnetic field (but don’t take too
literally!).
 Multielectron Atoms
ƒ Moving beyond hydrogen atom?

ƒ Subshells within a shell lose their degeneracy due to the

interactions between electrons.
 Electron Configurations
Given a set of orbitals, how are these filled with electrons?

ƒ Minimize energy:
Electrons occupy (are added to) orbitals in way that minimizes the energy of an atom;
this generally means starting with subshells of sequentially higher principle quantum
number.
The general order is: 1s; 2s, 2p; 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s,…

ƒ Pauli exclusion principle:

No two electrons in an atom may have the same 4 quantum numbers Î if two electrons
occupy the same orbital then these electrons must have opposite spins, ms = ±½ .
Hence, the electron capacity of a given subshell is 2x orbital degeneracy: s subshell can
hold 2 electrons; p subshell can hold 6 electrons.

ƒ Hund’s rule:
When orbitals of the same energy are available– degnerate orbitals– electrons
occupy orbitals singly with spin parallel; alternatively, maximize the number of
unpaired electrons in degenerate orbitals.

Lets apply these ideas – look at real atoms!

 Building Up Atoms: Start Simple
1s 2s 2p
ƒ Hydrogen: 1 electron ↑ 1s1

1s 2s 2p
ƒ Helium: 2 electrons 1s2
↑↓

1s 2s 2p
↑ ↑ 1s12s1
excited state

• orbital diagram– breaks each subshell into individual orbital boxes, which are
filled with electrons of spin up/down configuration.
• spdf notation– shows number of electrons in each subshell starting with lowest
principle quantum number
Building Up Atoms: More Interesting Examples?
1s 2s 2p
ƒ Li ↑↓ ↑ 1s22s1 or [He]2s1
1s 2s 2p
ƒ Be ↑↓ ↑↓ 1s22s2 or [He]2s2
1s 2s 2p
ƒ B ↑↓ ↑↓ ↑ 1s22s22p1 or [He]2s22p1
1s 2s 2p
ƒ C ↑↓ ↑↓ ↑ ↑ 1s22s22p2 or [He]2s22p2
1s 2s 2p
ƒ N ↑↓ ↑↓ ↑ ↑ ↑ 1s22s22p3 or [He]2s22p3
1s 2s 2p
ƒ O ↑↓ ↑↓ ↑↓ ↑ ↑ 1s22s22p4 or [He]2s22p4
1s 2s 2p
ƒ F ↑↓ ↑↓ ↑↓ ↑ ↓ ↑ 1s22s22p5 or [He]2s22p5
1s 2s 2p
ƒ Ne ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ 1s22s22p6 or [He]2s22p6
 Periodic Trends: Beginning

H He
1s1 1s2

Li Be B C N O F Ne
2s1 2s2 2p1 2p2 2p3 2p4 2p5 2p6

Na Mg Al Si P S Cl Ar
3s1 3s2 3p1 3p2 3p3 3p4 3p5 3p6

K Ca Sc Examples:
1. Phosphorous, P: [Ne]3s23p3

2. Calcium, Ca: [Ar]4s2

3. Scandium, Sc: [Ar]3d14s2
Periodic Trends: Overview & Predictions

Examples:
1. Thallium, Tl:
[Xe]4f145d106s26p1

2. Neodymium, Nd:
[Xe]4f35d16s2