Inorganic

Chemistry

Duward Shriver
and
Peter Atkins
Dr. S. M. Condren
CHEM422 Lab
• Wednesday
• Friday
• Other

Dr. S. M. Condren
Dr. S. M. Condren
Periodic Table Exam
• Write chemical symbol for first 36 elements in
proper location on blank periodic table
• Worth 40 points total
• Up to 36 for elements 1-36
• No more than 4 points for other elements
• First attempt during week of Feb. 10.
• Part of 400 total points for “Homework”

Dr. S. M. Condren
 Chapter 1

Atomic Structure

Dr. S. M. Condren
Structure of the Atom
Composed of: protons
found in nucleus
• protons relative charge of +1
• neutrons relative mass of 1.0073 amu

• electrons neutrons
found in nucleus
neutral charge
relative mass of 1.0087 amu

electrons
found in electron cloud
relative charge of -1
relative mass of 0.00055 amu

Dr. S. M. Condren
Atomic Number, Mass Number, & Isotopes
• Atomic number, Z
• the number of protons in the nucleus Nuclear Notation
• the number of electrons in a neutral atom
A
• the integer on the periodic table for each element E Z
• Mass Number, A
• integer representing the approximate mass of an atom
• equal to the sum of the number of protons and neutrons in the
nucleus
• Isotopes
• atoms of the same element which differ in the number of neutrons in the
nucleus
• designated by mass number

Dr. S. M. Condren
Isotopes vs. Allotropes
Isotopes - atoms of the same element with different
numbers of neutrons
- different compounds with the same formula
Allotropes - different forms of an element
Carbon exhibits both
• Isotopes: C-12 C-13 C-14
• Allotropes: graphite, diamond, and fullerenes

Dr. S. M. Condren
Big-Bang
• starts with universe as a singularity with infinite
density and temperature, only radiation exists
• sudden expansion leads to rapid drop in
temperature and density
• nuclear particle transformations convert most of
universe’s energy to protons and deuterons

Dr. S. M. Condren
The Origin of the Elements
• Nucleosynthesis of light elements
• Nucleosynthesis of heavy elements

Dr. S. M. Condren
Hydrogen Burning
Hydrogen Burning (fusion)

4 1H ---> 4He + 2 positrons + 2 neutrinos

+ 2.5 x 106 MJ/mol

after about 1/10 of hydrogen consumed, changes to

helium burning

Dr. S. M. Condren
Helium Burning
and Helium Reactions
Helium Burning (fusion)
3 4He ----> 12C
Helium Reactions
12
C + 4He ---> 16O
16
O + 4He ---> 20Ne
20
Ne + 4He ---> 24Mg
when temperature reaches 5 x 108 K, carbon fusion

Dr. S. M. Condren
Carbon Burning
2 12C ---> 23Na + 1H
2 12C ---> 20Ne + 4He
etc.

Dr. S. M. Condren
Neutron Capture
Zn + 1n ---> 69Zn* --->
68 69
Ga + 
80
Br + 1n ---> 81Br* ---> 81
Kr + 
etc.

Dr. S. M. Condren
Average Binding Energy per Nucleon

Dr. S. M. Condren
Relative Penetrating Powers of Radiation

Dr. S. M. Condren
Decay Scheme for Uranium Series

Dr. S. M. Condren
Classification of the Elements
Metals
• Lustrous, malleable, ductile, electrically conducting
solids at room temperature
Nonmetals
• Often gases, liquids, or solids that do not conduct
electricity appreciably
Metalloids
• Elements, alloys or compounds that possess some
of the characteristics of metals and some of
nonmetals

Dr. S. M. Condren
Classification of the Elements
• Metallic elements combine with nonmetallic
elements to give compounds that are typically
hard, non-volatile solids
• When combined with each other, the nonmetals
often form volatile molecular compounds
• When metals combine (or simply mix together)
they produce alloys that have most of the physical
characteristics of metals

Dr. S. M. Condren
Development of Periodic Table
Dmitri Mendeleev - Russian
1869 - Periodic Law - allowed him to
predict properties of
unknown elements

Dr. S. M. Condren
Missing elements: 44, 68, 72, & 100 amu

Dr. S. M. Condren
Dr. S. M. Condren
 C&EN COVER STORY:
Dec. 20, 2004
Organometallic and Inorganic Chemistry
A stable compound containing a silicon-silicon triple bond. Zinc-Zinc Bond
Sekiguchi A, Kinjo R, Ichinohe M.

Department of Chemistry, Graduate School of Pure and

Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-
8571, Japan. [email protected] Decamethyldizincocene,
synthesized by Carmona and
The reaction of 2,2,3,3-tetrabromo-1,1,4,4- coworkers, is the first stable
tetrakis[bis(trimethylsilyl)methyl]-1,4-diisopropyltetrasilane molecule with a bond between
with four equivalents of potassium graphite (KC8) in two zinc atoms (green).
tetrahydrofuran produces 1,1,4,4- Hydrogens are not shown.
tetrakis[bis(trimethylsilyl)methyl]-1,4-diisopropyl-2-
tetrasilyne, a stable compound with a silicon-silicon triple
bond, which can be isolated as emerald green crystals stable
up to 100 degrees C in the absence of air. The SiSi triple-bond
length (and its estimated standard deviation) is 2.0622(9)
angstroms, which shows half the magnitude of the bond
shortening of alkynes compared with that of alkenes. Unlike
alkynes, the substituents at the SiSi group are not arranged in
a linear fashion, but are trans-bent with a bond angle of
137.44(4) degrees.

Dr. S. M. Condren
 Periodic Table
Periodic of the
Table ofElements
the
Elements
IA II A III B IVB VB VI B VII B VIII B IB II B III A IVA VA VI A VII A VIII A
1 1 2
1 H H He
1.008 1.008 4.0026
3 4 5 6 7 8 9 10
2 Li Be B C N O F Ne
6.939 9.0122 10.811 12.011 14.007 15.999 18.998 20.183
11 12 13 14 15 16 17 18
3 Na Mg Al Si P S Cl Ar
22.99 24.312 26.982 28.086 30.974 32.064 35.453 39.948
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.102 40.08 44.956 47.89 50.942 51.996 54.938 55.847 58.932 58.71 63.54 65.37 69.72 72.59 74.922 78.96 79.909 83.8
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.468 87.62 88.906 91.224 92.906 95.94 * 98 101.07 102.91 106.42 107.9 112.41 114.82 118.71 121.75 127.61 126.9 131.29
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
6 Cs Ba **La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.91 137.33 138.91 178.49 180.95 183.85 186.21 190.2 192.22 195.08 196.97 200.29 204.38 207.2 208.98 * 209 * 210 * 222
87 88 89 104 105 106 107 108 109 110 111 112 113 114 115 116 118
7 Fr Ra ***Ac Rf Ha Sg Ns Hs Mt Uun Uuu Uub Uut Uuq Uup Uuh Uuo
* 223 226.03 227.03 * 261 * 262 * 263 * 262 * 265 * 268 * 269 * 272 * 277 *284 *285 *288 *292 *294
Based on symbols used by ACS S.M.Condren 2007
58 59 60 61 62 63 64 65 66 67 68 69 70 71
* Designates that **Lanthanum Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
all isotopes are Series 140.12 140.91 144.24 * 145 150.36 151.96 157.25 158.93 162.51 164.93 167.26 168.93 173.04 174.97
radioactive 90 91 92 93 94 95 96 97 98 99 100 101 102 103
*** Actinium Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Series 232.04 231.04 238.03 237.05 * 244 * 243 * 247 * 247 * 251 * 252 * 257 * 258 * 259 * 260

Dr. S. M. Condren
Dr. S. M. Condren
Quantum Mechanics:
Wave Nature of Electrons
Atomic Force Microscope

Crommie, Lutz & Eigler

http://www.almaden.ibm.com/vis/stm/corral.html

Dr. S. M. Condren
Dr. S. M. Condren
 http://mrsec.wisc.edu/
http://mrsec.wisc.edu/

Developed in collaboration with the

Institute for Chemical Education and the
Magnetic Microscopy Center
University of Minnesota
http://www.physics.umn.edu/groups/mmc/

Dr. S. M. Condren
 http://www.nsf.gov/mps/dmr/mrsec.htm
Sample

http://www.nsf.gov/mps/dmr/mrsec.htm

Probe Pull Probe Strip

Pull Probe Strip

Dr. S. M. Condren
Which best represents the poles?
(a) (b) (c)

North South

Dr. S. M. Condren
Quantum Numbers
n => principal quantum number, quantized energy
levels, which energy level
n = 1, 2, 3, 4, 5, 6, 7, etc.

Dr. S. M. Condren
Quantum Numbers
l => secondary quantum number, quantized orbital
angular momentum, which sublevel or type of
orbital
s type orbital l = 0
p type orbital l = 1
d type orbital l = 2
f type orbital l = 3
g type orbital l = 4

Dr. S. M. Condren
 Quantum Numbers
m => magnetic quantum number, quantized orientation of
angular momentum, which orbital within sublevel
s type orbital m=0
p type orbital m = +1, 0 or -1
one value for each of the three p orbitals
d type orbital m = +2, +1, 0, -1 or -2
one value for each of the five d orbitals
f type orbital m = +3, +2, +1, 0, -1, -2 or -3
one value for each of the seven f orbitals

Dr. S. M. Condren
Hydrogenic Energy Levels

hcZ2R
E = - -----------
n2
where n = 1, 2, 3, 
R = Rydberg constant

mce4
R = ----------- = 13.6 eV
8h3co2
Dr. S. M. Condren
s- and p-orbitals

Dr. S. M. Condren
d-orbitals

Dr. S. M. Condren
 f-orbitals

Dr. S. M. Condren
Many Electron Atoms
• Electronic Configuration
• Pauli exclusion principle
• No more than 2 electrons can occupy a single orbital
• No two electrons can have the exact same four
quantum numbers

Dr. S. M. Condren
Electron Filling Order Diagram
Start here
1s
2s 2p
3s 3p 3d
4s 4p 4d 4f
5s 5p 5d 5f
6s 6p 6d
7s 7p

Dr. S. M. Condren
Ground state electronic configurations

Dr. S. M. Condren
Electronic Configuration
As atom
33 electons
1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d10, 4p3
or
[Ar] 4s2, 3d10, 4p3

Dr. S. M. Condren
 Mn: [Ar]4s2 3d?
How many d electrons does Mn have?

4, 5, 6

Dr. S. M. Condren
Electronic Configuration
negative ions
add electron(s), 1 electron for each negative charge
S-2 ion
(16 + 2) electrons
1s2, 2s2, 2p6, 3s2, 3p6

Dr. S. M. Condren
 Electronic Configuration
positive ions
remove electron(s), 1 electron for each positive
charge
Electrons are first removed from orbital with highest
n&l
Mg+2 ion
(12-2) electrons
1s2, 2s2, 2p6
Fe atom Fe+2 ion
(26) electrons (26-2) electrons
[Ar]4s23d6 [Ar]4s03d6

Dr. S. M. Condren
How many valence electrons are in Cl, [Ne]3s2 3p5?

2, 5, 7

Dr. S. M. Condren
Shielding
Z* => effective nuclear charge

Z* = Z - S

S => shielding as defined by Slater’s Rules

http://en.wikipedia.org/wiki/Slater's_rules

Dr. S. M. Condren
Slater's Rules for Calculating Shielding
1. for [ns, np] electrons (e-s), e-s to the right in the
modified electronic configuration contribute
nothing
2. for [ns, np] e-s, other electrons of same group
contribute 0.35 each (except 1s, 0.3)
3. each electron in n - 1 group, contribute 0.85
4. each electron in n - 2 group, contribute 1.0
5. nd & nf group, rules 1 & 2 remain the same, all
electrons to the left contribute 1.0
modified electronic configuration
[1s][2s2p][3s3p][3d][4s] etc

Dr. S. M. Condren
Examples: for the 4 s electron in Cu atom
[1s2][2s22p6][3s23p6][3d10][4s1]
n - 2 group => 10 * 1.0
n - 1 group => 18 * 0.85
n group => 0 * 0.35

Z* = 29 - ((10 * 1.0) + (18 * 0.85) + (0 * 0.35))

= 29 - 10 - 15.3
= 3.7

Dr. S. M. Condren
Example: for a 3 d electron in Cu atom
[1s2][2s22p6][3s23p6][3d10][4s1]
rule 5. group
18 * 1.0
9 other d electrons * 0.35

Z* = 29 - ((18 * 1.0) + (9 * 0.35))

= 29 - 18 - 3.2
= 7.8

Dr. S. M. Condren
Effective Nuclear Charge
Effective Nuclear Charge
Name Z n-2 n-1 n Z*
hydrogen 1 1
helium 2 1 1.7
lithium 3 2 1.3
beryllium 4 2 1 1.95
boron 5 2 2 2.6
carbon 6 2 3 3.25
nitrogen 7 2 4 3.9
oxygen 8 2 5 4.55
fluorine 9 2 6 5.2
neon 10 2 7 5.85
sodium 11 2 8 2.2
magnesium 12 2 8 1 2.85
aluminum 13 2 8 2 3.5
silicon 14 2 8 3 4.15
phosphorus 15 2 8 4 4.8
sulfur 16 2 8 5 5.45
chlorine 17 2 8 6 6.1
argon 18 2 8 7 6.75
potassium 19 10 8 2.2
calcium 20 10 8 1 2.85
scandium 21 10 9 1 3
titanium 22 10 10 1 3.15
vanadium 23 10 11 1 3.3
chromium 24 10 13 2.95
manganese 25 10 13 1 3.6
iron 26 10 14 1 3.75
cobalt 27 10 15 1 3.9
nickel 28 10 16 1 4.05
copper 29 10 18 3.7
zinc 30 10 18 1 4.35
gallium 31 10 18 2 5
germanium 32 10 18 3 5.65

Dr. S. M. Condren
 Effective Nuclear Charge vs. Atomic Number
9

7
Effective Nuclear Charge

0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36

Atomic Number

Dr. S. M. Condren
Atomic Radius
• decrease left to right across a period
• as nuclear charge increases, number of electrons
increase; however, the nucleus acts as a unit charge
while the electrons act independently, pulling electrons
towards the nucleus, decreasing size
• increase top to bottom down a group
• each additional electron “shell” shields the outer
electrons from the nuclear charge
• increases from upper right corner to the lower left
corner

Dr. S. M. Condren
 Elemental Properties vs. Atomic Number
9

5
Z*
4

3 a.
radius
2

0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36

Atomic Number

Dr. S. M. Condren
Ionic Radius
• same trends as for atomic radius
• positive ions smaller than atom
• negative ions larger than atom
Isoelectronic Series
• series of negative ions, noble gas atom, and
positive ions with the same electronic confiuration
• size decreases as “positive charge” of the nucleus
increases

Dr. S. M. Condren
Ionization Energy
• energy necessary to remove an electron to form a
positive ion, I
• low value for metals, electrons easily removed
• high value for non-metals, electrons difficult to
remove
• increases from lower left corner of periodic table to
the upper right corner

Dr. S. M. Condren
Ionization Energies
first ionization energy
• energy to remove first electron from an atom
second ionization energy
• energy to remove second electron from a +1 ion
etc.

Dr. S. M. Condren
 Elemental Properties vs. Atomic Number
30

25

20

Z*
15
1st I. E.

10

0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36

Atomic Number

Dr. S. M. Condren
Electron Affinity
• energy released when an electron is added to an
atom
• same trends as ionization energy, increases from
lower left corner to the upper right corner
• metals have low “Ea”
• nonmetals have high “Ea”

Dr. S. M. Condren
 Elemental Properties vs. Atomic Number
30

25

20

15
Z*
1st I. E.
E.A.
10

0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36

-5

Atomic Number

Dr. S. M. Condren
Electronegativity
Pauling Scale
• relative attraction of an atom for electrons, its
own and those of other atoms
• same trends as ionization energy, increases from
lower left corner to the upper right corner
• fluorine: E.N. = XP = 4.0
• based on the energetics of bond formation

Dr. S. M. Condren
Electronegativity
Milliken Scale
• Based on the average of the ionization energy and
electron affinity
• XM = ½(I + Ea)

Dr. S. M. Condren
 Elemental Properties vs. Atomic Number
30

25

20

15 Z*
1st I. E.
E.A.
10 EN.

0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36

-5

Atomic Number

Dr. S. M. Condren