Chem 5

Chapter 10

The Periodic Table and Some

Atomic Properties

Part 4

November 8, 2002
 Noble Prize in Chemistry, 2002

Kurt Wüthrich John B. Fenn Koichi Tanaka

“The Nobel Prize in Chemistry for 2002 is being shared between scientists in
two important fields: mass spectrometry (MS) and nuclear magnetic
resonance (NMR). The Laureates, John B. Fenn and Koichi Tanaka (for MS)
and Kurt Wüthrich (for NMR), have contributed in different ways to the further
development of these methods to embrace biological macromolecules. This
has meant a revolutionary breakthrough, making chemical biology into the "big
science" of our time. Chemists can now rapidly and reliably identify what
proteins a sample contains. They can also produce three-dimensional images
of protein molecules in solution. Hence scientists can both "see" the proteins
and understand how they function in the cells.”

http://www.nobel.se/chemistry/laureates/2002/public.html
Mass Spectroscopy for
Macromolecules

Electrospray technique

Time-of-flight mass spectrometer

http://www.nobel.se/chemistry/laureates/2002/chemadv02.pdf
 Approach for high throughput microbial proteomics
Identification of more than two thousand proteins in a bacterium
Dimension one

Capillary LC-FTICR 2-D display of peptides from a yeast soluble protein digest
2-D display
>160,000 of detected
isotopic distributions peptide
corresponding “spots”
to >100,000 polypeptides detected
2,500

2,243

1,987

1,731

MW
1,475
0 42 84 126 168
Liquid columntography elution time (min)
1,218

Dimension two 962

706

450
24 33 44 52 62 71

1500
Time (min)
750 1000 1250
m/z Smith et al., Proteomics, 2, 513-523 (2002)
 Electrons have spin.

So do protons.

∆E = hν is sensitively dependent on
the surrounding electrons, i.e
chemical bonds around the proton.

Low resolution
NMR spectrum of
ethanol

Transition at
Radio frequency

In the presence of a uniform

external magnetic field

Nuclear Magnetic Resonance (NMR) Spectroscopy Radio frequency

Nuclear Magnetic Resonance Spectroscopy of Macromolecules

Determine the structures of proteins

Nature 418, 207 - 211 (2002)

Magnetic Resonance Imaging
Non-uniform magnetic field

hν = Energy splitting
is position
dependent.

Position
x x

http://www.washingtonopenmri.com/a2.htm

Professor William Klemperer
Freshman Seminar 22j
For Spring 2003
Seeing by Spectroscopy
William Klemperer
The seminar will explore diverse topics and areas of science
in which spectroscopy — the observation of energy emitted
from a radiant source — plays a leading role. Although there
are many practical applications of spectroscopy, the seminar
will concentrate on selected topics from chemistry, physics,
astronomy, and atmospheric science. Among these are the
structure of molecules from the simple measurement of the
bond length of a diatomic species to finding out the structure
of proteins. The seminar will emphasize spectroscopy as the
basis for remote sensing, choosing the grand topic of looking
out — astronomical observations and seeing what is in the
universe. Participants also will study (Nuclear) Magnetic
Resonance Imaging as a model for looking in. This seminar
will exploit the great increase in understanding nature that
occurred throughout the twentieth century as a result of the
invention of quantum mechanics. Participants will cooperate
in developing and maintaining a seminar web page.
Although the seminar is directed towards students with an
interest in physical science, the required background is not
extensive since the seminar will not derive relations but
rather state and use them. Participation will involve some
use of computational packages.
Freshman Seminar Program Web Pages
Magnetic property
A paramagnetic atom or ion has unpaired
electrons and the individual magnetic effects
do not cancel out.

A diamagnetic atom or ion has all electrons

paired and the individual magnetic effects
are canceled.

Gd3+ [Xe]4f7
4f
Summary

Closed shell
most stable
Reducing Abilities of Group 1 and Group 2
Demos
Comparison of the reducing ability of K and Ca
for water

→ 2 Li + (aq ) + 2OH − (aq ) + H 2 ( g )

2 Li ( s ) + 2 H 2 0 

→ 2 Na + (aq ) + 2OH − (aq ) + H 2 ( g )

2 Na ( s ) + 2 H 2 0 

→ 2 K + (aq ) + 2OH − (aq ) + H 2 ( g )

2 K ( s) + 2 H 2 0 

→ Ca 2+ (aq ) + 2OH − (aq) + H 2 ( g )

Ca ( s ) + 2 H 2 0 

K being the most active metal among the four because of its lowest I.E.
Oxidizing Abilities of Halogen Elements

Demo

− −
Cl2 ( g ) + 2 I (aq ) 
→ I 2 (aq ) + 2Cl (aq )

Cl2 has higher oxidizing ability than I2.

− −
Cl2 ( g ) + Br (aq) 
→ Br2 (aq) + 2Cl (aq)

This reaction (not shown) occurs, but very slowly.

 Nonmetals tend to gain
electrons to attain noble gas
Metals tend to lose
electron configurations.
electrons to attain noble gas
electron configurations
Na(g) → Na+(g) + e-
2
[Ne]1s2 [Ne] I1=496kJ/mol Z eff
I = RH 2
Na+(g) → Na2+(g) + e- I2=4562kJ/mol n
[Ne] [He]2s22p5 I2 >> I1 because n = 3 Æ n = 2
That is why we do not see Na2+ around.
General Trends 2s22p1
and Exceptions E2p>E2s

2s22p3

Half full stable

4s23d10

It is important to
write down the
electron
4s23d104p1 configurations!
 Summary of Chapters 9 &10
• Energy quantization explains three spectroscopic experiments:

– Blackbody radiation E= hν

– Photoelectric effect hν = hν0+ 1/2mu2

– Hydrogen atom lines RH RH

hv = ∆E = E f − Ei = 2
− 2
ni nf

•Two key concepts of quantum mechanics

– Particle-wave duality λ = h / p de Broglie wavelength

– Uncertainty principle ∆x ∆p ≥ h/4p

• Schrödinger equation
– Probability interpretation of wave functions (orbitals)
Ψ2 − probability density
– In an atom, four quantum numbers, n, l,ml, ms for an electron

– Shapes of the orbitals s,p,d,f

Number of nodes, radial and angular nodes

• Periodic table
– Screening and penetration, Zeff Zeff=Z – S
– Electron configurations - Aufbau process
–Minimizing energy, Pauli Exclusion, Hund Rule
– Qualitative explanation of the periodic trends in connection with the
electron configurations
 E=0
Ionization Ι.Ε. = − Εn

e- Z eff2
En = − RH
Electron affinity n2

e-

Emission
Spectroscopy n=1
Transition between hν n=2
n=3
two orbitals
r n=4
Z eff 2 2
Z eff hν
hv = ∆E = RH 2
− 2
absorption
n
i n f

c = v/λ
n 2 a0
Atomic or ionic radius rn ∝ average size of an orbital
Z eff not orbit