Many Electron Atoms and Periodic Properties.

I. Electron Structure
A. The Aufbau Principle.
1. We can solve Schrödinger equation only for the hydrogen atom. Therefore, we will
build up the structure of many electron atoms in the following way:
a. Start with hydrogen solutions. Increase the nuclear charge by one and
place another electron in atom. Starting with the hydrogen solutions, use
the rules of quantum mechanics to determine the energy and wave
function of the two electron system; this is the structure of He.
b. To obtain structure of Li, start with the He results, increase nuclear charge
by one and add another electron. This process is repeated and the
structures of the heavier atoms are obtained by " building out " from
lighter atoms. (Aufbau = building out)
2. The results.
a. n,l,ml and ms are still good quantum numbers for describing the behavior of the
electrons, that is, the electrons exist in hydrogen-like orbitals.
b. In the absence of strong magnetic fields, the energy depends on both n and l
. The order of the subshells encountered in following the aufbau principle is:
1s<2s<2p<3s<3p<4s<3d<4p<5s<4d<5p<6s....
c. This sequence can be remembered by the following scheme:
1s
2s 2p
3s 3p 3d Follow the diagonals.
4s 4p 4d 4f
5s 5p 5d 5f 5g
6s 6p 6d 6f 6g 6h
7s 7p 7d 7f 7g 7h 7I
8s 8p 8d……..
3. The electron structure of an atom is given by writing the electron configuration
of the atom.
a. Examples
element: 1H 2He 3Li 5B 6C 7N
electron configuration: 1s1 1s2 1s22s1 1s 2s22p1
2 1s 2s22p2
2 1s 2s22p3
2

32 Ge: 1s22s22p63s23p64s23d104p2 or : 1s22s22p63s23p63d104s24p2

Could also group according to n, but fill according to the aufbau principle
Write the subshells occupied and the number of electrons in the particular subshell
as a right-hand superscript.

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 b. The most important electrons in determining the physical and chemical
properties of an element are the outermost or valence electrons.
1) For the main group elements the valence electrons are all those electrons
with the highest value of the principle quantum number n, they will be s and p
electrons.
2) The inner electrons are called the core electrons . They are chemically
inert. Their main function is to shield the nuclear charge as seen by the
valence electrons.
3) Example: electron division in Ge:
2 2 6 2 6 10 4s24p2
32Ge: 1s 2s 2p 3s 3p 3d

core valence
4) Some valence configuration are:
1 2 1 2 2 2s22p3
3Li 2s 5B 2s 2p 6C 2s 2p 7N
B. Periodic Table and Valence Electron Configuration.
1. Main group elements (Representative elements, s and p-block elements)
a. Valence electrons are s and p electrons
b. All elements in the same group have the same valence electron configuration.
1) Group 1 (alkali metals)
H Li Na K Rb Cs Fr
1
1s 2s 1 3s1 4s1 5s1 6s1 7s1
All group 1 elements have an s1 valence configuration
2) Group 17 (halogens)
F Cl Br I At
2
2s 2p 5 3s23p5 4s24p5 5s25p5 6s26p5
All group 17 elements have an s2p5 valence electron configuration
c. For the main group elements
Group: 1 2 13 14 15 16 17 18
valence configuration: s1 s2 s2p1 s2p2 s2p3 s2p4 s2p5 s2p6
2. Transition elements ( d group elements, d-block elements)
a. Transition elements are those in groups 3 through 12.
b. The valence electrons are s and d electrons (nd and (n+1)s)
Group 3 4 5 6 7 8 9 10 11 12
valence configuration: d s d s d s d s1
1 2 2 2 3 2 5 d5s2 d s d s d s d s d10s2
6 2 7 2 8 2 10 1

Note that the groups 6 and 11 elements have electron configurations that are
out of sequence. This is due to the unusual stabilities of half filled ( d5 ) and
completely filled ( d10 ) subshells.

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 3. Rare Earths (inner transition elements, f-block elements)
a. Rare earths do not carry group designations.
b. The valence electrons are s and f electrons.
Lanthanides ( Z = 58-71) generally have a 4fn6s2 valence configuration
Actinides ( Z = 90-103 ) generally have a 5fn7s2 valence configuration.
c. Since the higher energy subshells are fairly close together the order of subshell
filling gets out of sequence near half filled and completely filled subshells.
C. Filling of Subshells (Hund’s Rules).
1. Electron configurations give the electronic structure in terms of subshells occupied.
Will consider how the orbitals in a subshell are filled.
a. Consider a p subshell. It is composed of three orbitals and can accommodate six
electrons. What is the sequence of occupation of the orbitals?
p1 ↑ __ __ p4 ↑↓ ↑ ↑
p2 ↑ ↑ __ p5 ↑↓ ↑↓ ↑
p3 ↑ ↑ ↑ p6 ↑↓ ↑↓ ↑↓

b. Note that in filling a subshell, the electrons will half-fill with their spins
parallel before pairing two electrons in the same orbital.
2. This gives rise to a lower energy for the following reasons.
a. Since electrons have the same charge, they will repel one another and will
tend to occupy different orbitals to get as far away from one another. Therefore
half-filling before pairing is to be expected.
b. One of the conclusions of quantum mechanics is that as an electron occupies
larger regions in space (is less confined) its kinetic energy decreases. Electrons
with the same spin can exchange places and thus occupy larger regions in space.
This phenomenon is called spin exchange. The greater the number of spin
exchange possibilities, the lower the energy. Therefore, the electrons will tend to
have their spins oriented parallel to one another. This is the reason for the
stability of half-filled subshells.
3. The number of unpaired electrons can be determined experimentally by studying
the magnetic properties of a substance.
a. When a substance is suspended above an inhomogeneous magnetic field, it
will either be attracted into the field or weakly repelled by it.
b. Paramagnetic substances are attracted into the field.
1) All paramagnetic substances have unpaired electrons.
2) The more unpaired electrons a substance has, the greater its paramagnetism.
3) Recall that the spin quantum number, ms , gives the relative orientation of

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 the electron's intrinsic magnetic moment. An unpaired electron's magnetic
moment will align itself with the magnetic field and be attracted into the field.
c. Diamagnetic substances will be weakly repelled by the field.
1) Diamagnetic substances have no unpaired electrons.
2) The diamagnetic repulsion forces are much weaker than the paramagnetic forces.
d. There are some substances that are Ferromagnetic.
1) When a paramagnetic substance is in a magnetic field the electron magnetic
moments of the atoms in the sample will be aligned with the field and the
sample itself will act as a bar magnetic with definite north and south magnetic
poles. When the sample is removed from the field, the moments will be
randomized by thermal motion and the sample will lose its bulk magnetic
properties.
2) Ferromagnetic substances have a large number of unpaired electrons ( are
strongly paramagnetic ) and have the ability to maintain their bulk magnetic
properties when removed from the field. These substances constitute the
permanent magnets.
3) Ferromagnetism depends not only on the number of unpaired electrons but
also on the distance between the atoms in the sample.
4. Examples
a. Fe [Ar]183d64s2 has 4 unpaired electrons ↑↓ _↑_ _↑_ _↑_ _↑_ ↑↓
3d 4s
and is paramagnetic. [Ar]18 = 1s22s22p63s23p6
b. Zn [Ar]183d104s2 has no unpaired electrons and is diamagnetic.

VIII. Periodic Properties.

A. Atomic Radius ( Size ).
1. One cannot define the radius of an isolated atom. The radius (or "size") of an atom is
determined by the extension in space of the valence electron density. The electron
density, obtained by evaluating Ψ2 , decreases exponentially with distance from
the nucleus.
2. Can develop from experimental data a set of parameters , called atomic radii, that
reflect the extension of electron density in space and that are useful in
understanding many physical and chemical properties of elements.
a. Experimentally one can accurately measure the internuclear distances in
substances. From the experimental internuclear distances in elements, a set of
atomic radii can be developed.
b. Examples:

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 1) The internuclear distance in Cl2 is 198 pm, therefore, the atomic radius of
Cl = 1/2(198 pm) = 99 pm.
2) The distance of closest approach in solid Al is 286 pm, therefore the atomic
radius of Al = 1/2(286 pm ) = 143 pm.

3. Trends in atomic radii.

ATOMIC RADIUS IN PICOMETERS
( 1 pm = 1x10-12 m )
Group
1 2 13 14 15 16 17
Li Be B C N O F
152 111 88 77 70 66 64
Na Mg Al Si P S Cl
186 160 143 117 110 104 99
K Ca Ga Ge As Se Br
231 197 122 122 121 117 114
Rb Sr In Sn Sb Te I
244 215 162 140 141 137 133
Cs Ba Tl Pb Bi Po At
262 217 171 175 146 150 140

a. For the main group elements atomic size increases as you go down a group
and decreases as you go across a period.
b. The electrons are held in the atom by their attraction for the positive nuclear
charge. However the valence electrons do not experience the whole nuclear
charge (Z), but only an effective nuclear charge (Zeff) due to shielding by the
other electrons in the atom.

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 c. The group variation then is due to the fact that the main quantum number, n, of
the valence electrons increases as you go down a group and that Zeff does not
change much. We have seen from plots of the radial distribution function, Pr,
vs. r that as n increases electron density is extended farther out in space. We
have seen above that Zeff does not change much in a group, therefore, size
should increase as you go down a group.
e. In a period the valence electrons are in the same main shell (have same n ). As
you go across a period, Zeff increases due to the inefficient shielding of one
valence electron by another ( they are only 35% effective in shielding the nuclear
charge) Therefore size decreases in a period.

B. Ionic Radii.
1. The lattice energy, and many other properties of ionic compounds depend on the
radii of the ions involved.
a. As with the atomic radius, the radius of an isolated ion cannot be defined. We are
interested in developing a set of parameters that reflect the extension of the electron
density of an ion in space and that add to give interionic distances.
b. Experimentally it is found that the apparent "size" of an ion depends on the structure
of the salt and the nature of the counter-ion. Therefore it is not possible to
generate a set of ionic radii that will reproduce the correct interionic distances of
all ionic compounds. However, one can generate a set of ionic radii that reproduce
experimental internuclear distances to within a few percent.
c. A number of methods have been developed to generate ionic radii, based on
measured interionic distances. These have been tabulated.
2. General
a. When atoms take on electrons to form anions, size (radius) increases.
When atoms lose electrons to form cations, size decreases.
b. Examples.
Li ---------> Li+ Na ------> Na+ Mg -----> Mg2+
152 pm 60 pm 186 pm 95 pm 160 pm 65 pm
F -----------> F - Cl ---------> Cl - O -------> O2 -
64 pm 136 pm 99 pm 181 pm 66 pm 140 pm

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 3. Periodic trends.
a. Some ionic radii in pm.
group
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
Li+ Be2+ N3- O2- F-
60 31 171 140 136
Na+ Mg2+ Al3+ Si4+ P3– S2- Cl-
95 65 50 40 212 184 181
K+ Ca2+ Sc3+ Ti2+ V2+ Cr2+ Mn2+ Fe2+ Co2+ Ni2+ Cu2+ Zn2+ Ga3+ Ge2+ As3+ Se2- Br-
133 99 81 80 88 83 80 74 72 69 72 74 62 87 72 191 196
2–
Rb+ Sr 2+ Pd2+ Ag+ Cd2+ In3+ Sn2+ Sb3+ Te I-
148 113 80 126 97 81 93 76 218 220
Cs+ Ba2+ Pt2+ Au3+ Hg2+ Tl+ Pb2+ Bi3+ Po4+
167 134 80 85 110 147 120 96 108
b. Ionic radius increases as you go down a group.
c. The variation in a period is not simple because of the change from cation formation
to anion formation. However, for a series of isoelectronic ions (= ions
having the same number of electrons) the ionic radius decreases as the atomic number
increases.
Example. N3- > O2- > F- > Na+ > Mg2+ > Al3+ All have 10 electrons.
d. For cations, the ionic radius decreases as the ion charge increases. For example the ionic
radius of Fe2+= 74 pm while that of Fe3+ = 60 pm. Cr2+ = 83 pm; Cr3+ = 64 pm.

B. Ionization potential (Ionization Energy).

1. Energy required to remove an electron from a gaseous atom.

∆H for the following gaseous ionization reactions.

M(g) ------> M(g)+ + e- Energy needed = I1 = first ionization potential
M(g)+ -----> M(g)2+ + e- Energy needed = I2 = second ionization potential
M(g)2+ -----> M(g)3+ + e- Energy needed = I3 = third ionization potential

a. For any atom I1< I2< I3 < I4 etc.

b. Lose highest energy electrons first; valence before core and p before s .
c. I should depend Zeff / rav ( rav = average distance from nucleus )

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2. Trends in I1.

a. Trends in a group.
1) I1 decreases as you go down a group. Size increases and Zeff does not
change much.

2) Element: Li Na K Rb Cs
I1(kJ/mol): 520 496 419 403 376
b. Trends in a period.
1) Group: 1 2 13 14 15 16 17 18
Element: Li Be B C N O F Ne
I1(kJ/mol): 520 900 801 1086 1402 1314 1681 2081

2) There is a general increase as you go across a period consistent with

an increase in Zeff and a decrease in size. However, two reversals occur.
Group 2 > Group 13.... in Groups 1 and 2 you are removing electrons
from low energy s orbitals while in Groups 13-18 you are removing
electrons from higher energy p orbitals, which requires less energy.

Group 15 > Group 16 ....example of the stability of half filled orbitals.

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 3. The trends in the higher ionization potentials can be rationalized using the same type
of arguments used for I1.
4. Transition metals.
a. In general, I1 increases as you go across a period. However, the changes are
not large and reversals occur.
b. The group variation is not simple, in going from the first to the second period
I1 generally decreases. However between the second and the third periods, this
trend is reversed. This reversal occurs after La and is due to the interjection of
the Lanthanide rare earths.

C. Electron Affinity (EA)

1. Energy released when a gaseous atom picks up an electron.

EA’s are – ∆H’s for the following reactions.

a. X(g) + e- -----> X(g)- Energy released = EA1 = first electron affinity
X(g)- + e- ---> X(g)2- Energy released = EA2 = second electron affinity
b. All electron affinities greater than the first are negative ( energy is required ).
c. Not as well known as ionization potentials. Not as large as I's. The smallest I1
is that for Cs ( 376 kJ/mol ), the largest EA1 is that for Cl ( 349 kJ/mol )
2. Trends in EA1.
a. There is a general increase in EA1 as you go across a period to the halogens..
b. The third period elements ( Na to Cl ) have higher EA1's than the corresponding
second period elements ( Cl has highest EA in Periodic Table).
D. Electronegativity ( χ )
1. Ability of an atom to attract electrons to itself in a covalent bond.
a. χ should be large for those elements that tend to hold on to their electrons
( have high ionization potentials ) and attract another electron ( have large
electron affinities).
b. Fluorine has to highest χ and Cs has the lowest χ. The electronegativity
increases as you go towards F and away from Cs ( increases as you go up a
group and increases as you go to the right in a period towards Group 17 ).
2. Electronegativity Scale.
a. Several quantitative scales have been developed. The Pauling scale is the most
used, it is based on F having a value = 4.0 and C = 2.5.

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 b. Some values:
Element: H
χ 2.1
Element: Li Be B C N O F
χ 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Element: Na S Cl
χ 0.9 2.5 3.0
Element: K Br
χ 0.8 2.0
c. The three most electronegative, in order of decreasing χ , are F,O,N.
E. Ionic Charge (Simple main group ions)
1. Cations -- Lose valence electrons.
a. Group 1 Valence configuration : s1 will form +1 ions. No exceptions.
Li [He]22s1 ----> Li+ [He]2
Na[Ne]10 3s1 ---> Na+[Ne]10
K[Ar]184s1 ---> K+[Ar]18
b. Group 2 Valence configuration : s2 will form +2 ions. No exceptions
Mg[Ne]103s2 ---> Mg2+ [Ne]10
Ca[Ar]184s2 ---> Ca2+[Ar]18
c. Group 13 Valence configuration: s2p1. Can lose all and form +3 ions or lose
just the p electron forming +1 ions. Heavier Group 13's tend to form +1 ions.
This effect is called the "inert pair" effect.
Al[Ne]103s23p1 ---> Al3+[Ne]10 only +3
Ga[Ar]184s24p1 ---> Ga3+[Ar]18 essentially all +3

In3+[Kr]36 Most stable

In[Kr]365s25p1
In+[Kr]365s2 Some compounds known

Tl3+[Xe]54 Very strong oxidizing agent

Tl[Xe]546s26p1
Tl +[Xe]546s2 Most stable
d. Group 14 ( Sn and Pb). Valence configuration: s2p2. Form both a +2 (retain s2)
or +4 (lose all). Both are known but the +2 are the most stable. The +4 is an
oxidation state rather than a simple charge.

e. Group 15 (Sb and Bi). Valence configuration: s2p3. Form both a +3 (retain s2) or
+5 oxidation state ("lose" all). The +3 are the more stable. BiO3- is a extremely
powerful oxidizing agent.
f. Group 16 ( Po only) most stable oxidization state is +4.

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 2. Anions. Gain enough electrons to attain an s2p6 valence configuration (completes its
octet).
a. Group 17 s2p5 + e- -----> s2p6 forming -1 anions
F- fluoride Br- bromide
Cl- chloride I- iodide
b. Group 16 s2p4 + 2e- -----> s2p6 forming -2 ions
All form simple -2 ions except Po
c. Group 15 s2p3 + 3e- ---> s2p6 forming -3 ions
N and P form simple -3 ions, others are oxidation states.
d. Group 14 do not tend to form simple anions.
F. Charges on transition metals.
1. In contrast to the main group metals that have one stable oxidation state, the
transition metals are characterized by variable valences.
a. The valence configurations are of the form (n - 1)dxns2 ( except for Groups 6
and 11 that have only one s electron).
b. In forming cations, the ns electrons are lost before the (n - 1)d
electrons. As more d electrons become involved in bonding, variable oxidation
states can are formed.
2. Oxidation states
a. Except for Sc and Zn all show variable oxidation states.
1) Sc (3d14s2) and the other Group 3 metals form only +3 ions.
2) Zn and Cd ( d10s2) form only +2 ions. Hg(I) exists as the dimer Hg22+.
b. All the others exhibit stable +2 states.
1) Fe, Co and Cr also have stable +3 states.
2) Group 11 metals also have +1 states. While Cu(I) is not stable, Ag(I) and
Au(I) are the most stable forms of these elements.
c. For Groups 3 through 7 the maximum oxidation states are the same as the group
numbers. The higher oxidation state compounds are excellent oxidizing agents.
Examples are MnO4- and Cr2O72-.

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 Problems

1. Write the electron configurations for the following.

S, Co, Cl, Rb, Si, Kr, Mg2+, O2-, Mn2+, Fe3+
2. Write the valence electron configurations of the neutral atoms in question 12.

3. Arrange the following in decreasing order of their first ionization energie and justify
your ordering. --Na, Mg, and Al-- Do the same for their second ionization energiess.

4. Account for the fact that the first ionization energies of the series Si, P, and S decrease in
the order P>S>Si while their second ionization energies decrease in the order S>P>Si.
5. Give the symbol for the element best described by each of the following.
a. The Group IIIA element with the largest atomic radius.
b. The Group IIA element with the highest first ionization energy.
c. The element in the period beginning with K that has the highest electron affinity.
d. The first row transition element having the largest number of unpaired electrons.
e. The first row transition element whose +3 ion has one unpaired electron.
f. The element with the valence electron configuration s2p4 having the lowest electron
affinity.
6. Arrange the following in order of decreasing ionic radius and justify your arrangement.
P3≠, As3–, Ca2+ and Cl–
7. The normalized ionization potential ( I ) is defined as the measured Ionization Potential ( I )
divided by the charge on the ion formed after ionization. The four I ‘s for Be, in kJ/mol, are
I1 = 899, I2 = 879, I3= 4950, I4=5251. Why are the first two and the last two of similar
magnitude while there is a big gap between I2 and I3?
8. Why do the first electron affinities of N, O and F vary as F>O>N while those of C, N and O
vary as O>C>N?
9. Show the filling of the electrons in the 3d subshell of Fe. Use arrows to indicate the direction
of the magnetic moments of the electrons. What type of magnetism will Fe exhibit ?
10. Rationalize the fact that in going from Fe2+ to Fe3+ paramagnetism increases while in going
from Cr2+ to Cr3+ paramagnetism decreases.
11. Assign quantum numbers the valence electrons of O.

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 Problems
Many Electron atoms and Periodic Propeerties
(Answers)

1. 16S 1s22s22p63s23p4 27 Co 1s22s22p63s23p64s23d7 37 Rb 1s22s22p63s23p63d104s24p65s1

14 Si 1s22s22p63s23p2 36 Kr 1s22s22p63s23p63d104s24p6 12 Mg2+ 1s22s22p6
8 O2– 1s22s22p6 25 Mn2+ 1s22s22p63s23p63d5 26 Fe3+ 1s22s22p63s23p63d5
2. In bold above.
3. I1: Mg>Al>Na I2: Na>>Al>Mg
4. P has stable half filled subshell therefore high I1. S+ has half-filled subshell therefore high I2
5. a. Tl; b. Be; c. Br; d. Cr; e. Ti and Zn; f. Po (or Uuh).
6. As3–>P3–>Cl–>Ca2+
7. In Be for I1 and I2 are removing electrons from the 2s subshell (vakence), for I3 and I4 are removing
from the 1s subshell (core).
8. N 1s22s22p3 N– 1s22s22p4; O 1s22s22p4 O– 1s22s22p7; F 1s22s22p5 F– 1s22s22p6
This is the expected order, in all cases you are adding an electron to a singly occupied p orbital.
∴ F>O>N
C 1s22s22p2 C– 1s22s22p3;; O 1s22s22p4 O– 1s22s22p7; N 1s22s22p3 N– 1s22s22p4
Expected order would be O>N>C, however C and N change places since C– would have stable half-
filled subshell.
9. Fe (d6) ↑ ↓ ↑ ↑ ↑ ↑ Paramagnetic
3d
10. Fe2+ ↑ ↓ ↑ ↑ ↑ ↑ Paramagnetic, 4 unpaired electrons
4s 3d
Fe3+ ↑ ↑ ↑ ↑ ↑ Paramagnetic, 5 unpaired electrons
4s 3d
Cr2+ ↑ ↑ ↑ ↑ Paramagnetic, 4 unpaired electrons
4s 3d
Cr3+ ↑ ↑ ↑ Paramagnetic, 3 unpaired electrons
4s 3d
11. Assign quantum numbers to all the valence electrons of oxygen. 2s22p4
electron 1 2 3 4 5 6
n 2 2 2 2 2 2
l 0 0 1 1 1 1
ml 0 0 1 0 -1 1
ms +1/2 -1/2 +1/2 +1/2 +1/2 -1/2

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