PERIODIC TABLE HISTORY

"I have no idea who discovered the periodic system of chemical elements… When you open a chemistry
textbook today*, you can often find, next to its periodic table, a sidebar with a grizzled bearded man
who is depicted as “the discoverer” of the periodic law, the formulator of the table whose checkered
countenance greets you from the wall of every chemistry laboratory in the world. Almost always, that
bearded man is Dmitrii Ivanovich Mendeleev (1834–1907)… Sometimes he shares the space with the grizzled beard
of Julius Lothar Meyer (1830–1895)… The textbooks are endowed with a certainty I do not have; they know what
the periodic table is, and therefore they know who discovered it first."
*Zumdahl/DeCoste is no exception.
Michael D. Gordin, "The Textbook Case of a Priority Dispute: D. I. Mendeleev, Lothar Meyer, and the Periodic System"
In: M. Biagioli et al. (eds.), Nature Engaged (2012).
Curious for more? Check out Prof. Hepler-Smith’s courses on the history of chemistry.
LAST CLASS

¡ Wave-particle duality
¡ Schrödinger’s wave mechanics and its H solution
¡ Quantum numbers:
¡ Principal n
¡ Angular momentum l
¡ Magnetic ml
¡ Electron spin ms
¡ Nodes; Probability density
¡ Aufbau, Hund’s Rule, Pauli exclusion
¡ Core vs valence electrons
REVIEW PROBLEM

Identify the orbital (i.e. 3s, 4f).

REVIEW PROBLEM

Each of the following sets of quantum numbers is supposed to specify an orbital. Which of the
following sets of quantum numbers contains an error?
A) n = 2, l = 1, ml = -1
B) n = 4, l = 2, ml =-1
C) n = 3, l =3, ml = +2
D) n = 1, l = 0, ml =0
E) n = 3, l = 2, ml =0
3d AND 4s ORBITALS
MANGANESE
ELECTRON CONFIGURATIONS
EFFECTIVE NUCLEAR CHARGE

Shielding: electron-electron repulsion results in inner

electrons screening the nuclear charge from outer
electrons
𝑍eff = 𝑍 − 𝑆

Slater’s approximation for shielding ("rule") for

elements with only s and p electrons in valence level
Li: 1𝑠 ! 2𝑠 " n>1
• Electrons in level n shield by 35%
𝑍eff = 3 − 2×0.85 • Electrons in level n-1 shield by 85%
𝑍eff = 1.3 • Electrons in level n-2 or below shield by 100%

What about C : 1𝑠 ! 2𝑠 ! 2𝑝 ! ?

S=2x0.85+3x0.35=2.75
IONIZATION ENERGY (IE)

Minimum energy needed to remove an electron from an atom or ion

¡ Gas state (only nuclear attraction; no interaction; different from photoelectric effect)
¡ Endothermic process
¡ Valence electron is easiest to remove, lowest I E
¡ 𝑀 𝑔 + IE! → 𝑀!" 𝑔 + 1𝑒 #
¡ 𝑀!" 𝑔 + IE$ → 𝑀 $" 𝑔 + 1𝑒 #

¡ First ionization energy = energy to remove electron from neutral atom

¡ Second IE = energy to remove electron from 1+ cation
¡ etc.
IONIZATION ENERGY
EXCEPTIONS

By pairing e-, electron-electron

repulsion is enhanced; reduced
relative stability. (Effect beyond
Slater’s rule)
IONIZATION ENERGIES
Trends in Electron Affinity
Adding an electron X(g)+e. (g) → X. (g) + 𝐸 (exothermic)
¡ Alkali metals decrease electron affinity down the column.
¡ But not all groups do
¡ Generally irregular increase in EA from second period to third period
¡ “Generally” increases across period (more negative from left to right)
¡ But not absolute
¡ Group 5A generally lower EA than expected because extra electron
must pair
¡ Groups 2A and 8A generally very low EA because added electron
goes into higher energy level or sublevel
¡ Highest EA in any period = halogen
Electron Affinities of Selected Main-Group Elements

General trend:
for a same n, same energy
level, same nuclear distance

EA decreases (more
negative) as Z increases
ELECTRONEGATIVITY TRENDS

Electronegativity: How strongly

an atom wants an electron

Scale designed by Pauling.

Correlated with ionization
energies and electron affinities,
but more effective in the context
of chemical bonding/reactions.

From 0.7 (Cs) to 4.0 (F)

ATOMIC RADII

𝑛!
𝑟∝
𝑍eff
If 𝑍eff increases, then the radius decreases.
If n increases, then the atomic radius increases.
(pm)
Decrease of atomic radius is not as
pronounced in transition metals
because d orbital electrons
experience shielding (beyond
Slater’s rule).
f Orbitals (l = 3)

For n=4 and l=3

3 angular nodes
0 radial node

Cs: [Xe] 6s1

Ba: [Xe] 6s2
La: [Xe] 6s24f1
…
Hf: [Xe] 6s24f145d1
LANTHANIDE CONTRACTION

4d/5d transition metals are similar in

size. (In other words, lanthanides and
actinides have similar radii.)

4f orbitals are not effective at shielding,

thus increasing Zeff for 5d electrons,
which compensates for their larger n.
MODELS – GENERAL THOUGHTS

1. Models are human inventions, always based on an incomplete understanding/description of

nature. A model does not equal reality, and is always an oversimplification.
2. Models are often wrong. This property derives from the first.
3. Models tend to become more complicated as they age. As flaws are discovered, they get
patched with more details.
4. Understanding the underlying assumptions behind a particular model is key to interpreting
observations and making predictions. For a model to be used effectively, we must understand
its strengths and weaknesses and ask only appropriate questions. Simple models usually
involve very restrictive assumptions and can be expected to yield only qualitative
information.
5. When a model is wrong, we often learn much more than when it is right. If a model makes a
wrong prediction, it usually means we do not understand some fundamental characteristics
of nature.
CHEM 110 Unit II: Bonding
HONORS CHEMISTRY
PROF PATRICK CHARBONNEAU
LAST CLASS

¡ Thoughts on periodic table

¡ Slater’s "rule" (TO BE REVISED)
¡ Periodicity:
¡ Ionization energy
¡ Electron affinity
¡ Electronegativity
¡ Atomic radius (lanthanide contraction)
¡ Thoughts on models
EFFECTIVE NUCLEAR CHARGE

Shielding: electron-electron repulsion results in inner

electrons screening the nuclear charge from outer
electrons
𝑍eff = 𝑍 − 𝑆

Slater’s approximation for shielding ("rule") for

elements with only s and p electrons in valence level
Li: 1𝑠 ! 2𝑠 " n>1
• Electrons in level n shield by 35%
𝑍eff = 3 − 2×0.85 • Electrons in level n-1 shield by 85%
𝑍eff = 1.3 • Electrons in level n-2 or below shield by 100%

What about C : 1𝑠 ! 2𝑠 ! 2𝑝 ! ?

S=2x0.85+3x0.35=2.75
MOLECULAR REPRESENTATIONS (MODELS)

Empirical Molecular Line Sticks Space

formula formula structure and balls filling

Lewis structure

Line structure

33
LEWIS MODEL

G. N. Lewis, “The Atom and the Molecule,”

J. Am. Chem. Soc. 1916, 38, 762
Contemporary to the Bohr model – pre-
quantum mechanics. It remains a useful starting
point/back-of-the-envelope estimate.

Definitions/Representations:

a. A dot represents an electron.

a. A pair of electrons between neighboring

atoms is a bond (either ionic or covalent)

c. A pair of electrons that is not shared

with another atom is a lone pair.
34

d. The octet/duet rule???? (strict for C, N, O, F/H, He)

BONDING IS A
CONTINUUM:
IONIC,
COVALENT AND
METALLIC
Ionic bond model: charges redistributed eg Na+ Cl-

Covalent-non metal model (octed): bond with 2e-

H C N O F
e- config 1s1 [He]2s22p2 [He]2s22p3 [He]2s22p4 [He]2s22p5
valence 1 4 5 6 7
e- needed 1 4 3 2 1
Bond 1 4 3 2 1
needed
EXAMPLE

Carbon tetrachloride, CCl4

37
 EXAMPLE

Formate ion, HCO2-

39
 KEY IDEAS BEHIND RESONANCE STRUCTURES
1. Resonance structures are not real. An individual resonance structure does not completely represent the
structure of a molecule or an ion.
2. Resonance structures are not equilibrium structures. Delocalization does not imply that the electrons are
moving.
3. Resonance structures are not isomers.

Guidelines:
1. Never add more than 8 electrons to carbon (or N, O, F)
2. Never break a single bond.
3. Double/triple bonds can be broken to yield single/double bonds.
4. Formal charges can be moved onto different atoms.
41
PEPTIDE BONDS IN PROTEINS

H R
O
124 pm

125 121
C
123 C
pm
132
N 114 C
114
123

42
 MICROSOFT FORM: RESONANCE

CON-
**Carbon is the central atom.

Draw all resonance forms (that satisfy the octet) and rank their contribution.

A B C

Option D: all three forms are equally representative.

44
LINEAR AND TRIGONAL PLANAR
ELECTRON GEOMETRY
TETRAHEDRAL ELECTRON GEOMETRY
TRIGONAL BIPYRAMIDAL
ELECTRON GEOMETRY
OCTAHEDRAL ELECTRON GEOMETRY
LONE PAIRS ARE MORE PUSHY THAN BONDED PAIRS
WHICH IS THE BETTER STRUCTURE?
LAST CLASS
BOND STRENGTH AND STABILITY

Good approximation: Lennard-Jones potential

H! → 2H

Δ𝐸 = 7.24×10#"$ J/molecule
repulsion
no attraction nor repulsion

attraction

54
INTERNAL ENERGY, ∆𝐸

Or provide heat

∆𝐸 = 𝐸! − 𝐸"
∆𝐸 = ∆𝐾𝐸 + ∆𝑃𝐸

𝐾𝐸 ∝ 𝑇
SYSTEMS AND SURROUNDINGS

Energy
THE “FIRST LAW” OF THERMODYNAMICS

D Euniverse = D Esystem + D Esurroundings = 0

OBSERVED/MEASURED CHANGES

D Esystem = q + w
 HEAT AND TEMPERATURE

What is the difference between heat (q) and temperature (T)?

ACS Chemistry Textbook, 2005

WHAT IS ENTHALPY?

Definition of Enthalpy?

Conventions:

60
MEASURING CHANGES IN ENTHALPY

61
SINCE 1979, LAND TEMPERATURES HAVE INCREASED ABOUT
TWICE AS FAST AS OCEAN TEMPERATURES (0.25 °C PER DECADE
AGAINST 0.13 °C PER DECADE).

Why is the temperature on

land increasing faster than the
ocean temperature?

https://data.giss.nasa.gov/gistemp/graphs/#
SINCE 1979, LAND TEMPERATURES HAVE INCREASED ABOUT TWICE AS FAST AS
OCEAN TEMPERATURES (0.25 °C PER DECADE AGAINST 0.13 °C PER DECADE).

Water has higher heat capacity than air/land, therefore it can absorb more heat with
a smaller delta in temperature.
 EXAMPLE

Two solutions, initially at 24.60°C, are mixed in a coffee cup calorimeter. When a 100.0 mL
volume of 0.100 M AgNO3 solution is mixed with a 100.0 mL sample of 0.200 M NaCl
solution, the temperature in the calorimeter rises to 25.30°C. Determine the △ H°rxn for the
reaction as written below. Assume that the density and heat capacity of the solutions is the
same as that of water. The specific heat capacity of water = 4.18 J/g°C.

NaCl(aq) + AgNO3(aq) → AgCl(s) + NaNO3(aq) △ H°rxn = ?

 If 20 J of energy is applied to 1 g of a metal,
Al Aluminum 0.903 J/gC Cr Chromium 0.461 J/gC which will have the greatest final temperature?
Co Cobalt 0.440 J/gC Cu Copper 0.385 J/gC
Au Gold 0.132 J/gC Fe Iron 0.449 J/gC The initial temperature is 298K:
Pb Lead 0.129 J/gC Mg Magnesium 1.025 J/gC
Mn Manganese 0.448 J/gC Ni Nickel 0.465 J/gC
Pt Platinum 0.134 J/gC Ag Silver 0.213 J/gC A. Ni
Ti Titanium 0.528 J/gC W Tungsten 0.138 J/gC B. Ag
U Uranium 0.112 J/gC Zn Zinc 0.444 J/gC C. W
D. Al
 Predicting Reaction Enthalpy
We seek enthalpy changes in chemical reactions!

Problem: Enthalpies depend upon pressure, temperature, and state!

Solution: Define thermodynamic Standard States

Standard Enthalpy (change) of reaction:

Enthalpy is a state function. Therefore, we can use the differences in the final
and initial states.
 Understanding Standard Enthalpies of Formation
We need a reference level (sea level)!

Pick: “Sea Level” as enthalpy of elements in their standard state: DHf°≡ 0

E.G. C(s, graphite) DHf°=0

C(s, diamond) DHf°=1.895 kJ/mol diamond

H2O(l) DHf°=-285.85 kJ/mol H2O comes from

formation reaction
H2(g) + 1/2O2(g) →H2O(l)
H2, O2
0
The formation of water is exothermic.
The difference in enthalpy is -285.85 kJ/mol H2O.
Which has the more stable (lower potential energy)
bonds?
H2O
Using Enthalpies of Formation to Compute Std. Reaction Enthalpies
Basic Idea (an application of Hess’s Law):
1. Decomposition (“unformation”) of reactants in std. states to their constituent elements
in std. states
2. Formation of products in their standard states from their constituent elements in std.
states
E. G. CH4 (g) + 2O2 (g) ® CO2 (g) + 2H2O(l)

C(s) + 2H2(g) 2O2 C(s) +O2(g) 2H2(g) + O2(g)

0 0
DHfO = -75 kJ/mol
CH4(g)
DHfO = -394 kJ/mol DHfO = -286 kJ/mol
CO2(g)
2H2O(l)
UNSATURATED FATS

Br H
H H
+. Br2 H C C H
C C

H H H Br

C-Br. 276
REVIEW PROBLEM

Use the bond energies provided to estimate ΔH°rxn for the reaction below.

PCl3(g) + Cl2(g) → PCl5(l) ΔH°rxn = ?

Bond Bond Energy (kJ/mol)

Cl-Cl 243
P-Cl 331

A) -243 kJ
B) -419 kJ
C) -662 kJ
D) -67 kJ
E) -905 kJ
MOLECULAR ORBITAL THEORY
LCAO METHOD AND TENETS OF MO THEORY
THE FORMATION OF MOLECULAR HYDROGEN
THE FORMATION OF MOLECULAR OXYGEN
N2, C2, B2, CO, CN-,
O2, F2, Ne2, OF-
NO, etc.
CO
 POLL EVERYWHERE

Draw the molecular orbital diagram to determine which of the following is most stable.
A) C22⁺
B) N22⁺
C) B2
D) C22⁻
E) B22⁺
 POLL EVERYWHERE

Draw the molecular orbital diagram to determine which of the following is most stable.
A) C22⁺
B) N22⁺
C) B2
D) C22⁻
E) B22⁺
MOLECULAR ORBITALS FOR H3+
MOLECULAR ORBITALS FOR BERYLLIUM HYDRIDE
BERYLLIUM HYRIDE
WATER MOLECULAR ORBITALS
 THE BASIS FOR BONDING

Atomic Orbital Overlap

Methane
ACETYLENE, C2H2
BOND STRENGTH, BOND ENERGIES, AND BOND LENGTH
MAKING PREDICTIONS

Br H
H H
+. Br2 H C C H
C C

H H H Br
OZONE & DELOCALIZED BONDING
ROTATION
ABOUT THE
CARBON-
CARBON BOND
 CH3
N
F H 3C C N
F B
F H 3C CH3

IDENTIFY THE HYBRIDIZATION OF THE CENTRAL ATOM?

HOW MANY SIGMA AND PI BONDS ARE PRESENT?

O O
C
H
C NH2
H C
H
O
H
HOW MANY SIGMA AND PI BONDS ARE PRESENT?

H C O

C C

H C C C H

H
H