General Chemistry I
Chemistry: The central science
Phong D. Tran
Department of Fundamental and Applied Sciences
University of Science and Technology of Hanoi
Email:
[email protected]Lectures 7, 8: Periodic properties of elements
1
Content
1. Development of the periodic table
2. Effective nuclear charge
3. Sizes of Atoms and Ions
4. Ionization energy
5. Electron affinity
2
Discovery of the elements
Ancient time
S
Cu
Ag
3
Discovery of the elements
By 1800: 33 elements
Ni Co
Bi Fe
W Zr
Sn S
N Pb Pt
Cu
Sb U
P Ag
Sc C
Au Hg
H Te
O Mg
Mo Mn
V
Sr Cl
Y
Cr
Be Nb
4
Discovery of the elements
By 1865: 63 elements
Ti
Th Al
Ni As Co
Tl K Se Bi Fe
Ru Rh
W Pd Os Zr
Ta Na Ba
Sn S
Cs Ir
N Er Pb Tb Pt
Cu
Nb Sb U
P Ag B I
Ce C
Sc
Au Hg Si
H Li Os Te
In Ir
Mo O La Mg
Mn
V
Sr Cl
F Y
Cr
Cd
Be Nb
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Development of the periodic table
• 1869 - Dmitri Mendeleev (Russia) & Lothar
Meyer (Germany) - independently proposed idea
of periodicity (recurrence of properties)
• Similar chemical and physical properties recur
periodically when the elements are arranged in
order of increasing atomic weight
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Periodic Table
Name
chemical
element Symbol Atomic mass
Hydrogen H 1
Lithium Li 6.941
Beryllium Be 9.012
Boron B 10.811
Carbon C 12.01
Nitrogen N 14
Oxygen O 15.9994
Sodium Na 22.989
Magnesium Mg 24.305
Aluminum Al 26.581
Silicon Si 28.0855
Phosphorus P 30.973
Sulfur S 32.066
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Mendeleev’s Table
H
Li Be B C N O F
Na Mg Al Si P S Cl
K Sc Ti V Cr Mn Fe Ni Co Cu As Se Br
Rb Sr Y Zr Nb Mo
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Development of the periodic table
• The tables of elements advanced by Mendeleev
and Meyer were the forerunners of the modern
periodic table
• Mendeleev
– Grouped elements according to properties
– Predicted properties for elements not yet
discovered (e.g. Ga and Ge)
>>> credited for finding the periodic table
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Ge properties: Mendeleev prediction vs.
actual measurement
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Periodic Table by Dates of Discovery
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The most recent version: dated Nov 28th, 2016
4 new elements 113, 115, 117 and 118
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Issues with Mendeleev table
• Based on atomic weight
• Properties of some elements do not follow the
proposed table
• MAr =19 > MK = 18
• Ar has similar properties as Ne and Kr
Li Be B C N O F Ne
Na Mg Al Si P S Cl Ar
K Ca Ga Ge As Se Br Kr
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Discovery of atomic numbers
• In 1913, Henry Moseley (1887-1915) developed
the concept of atomic numbers.
• Each element produces X-rays of a unique
frequency
• Identified the atomic number as the number of
protons in the nucleus of the atom.
• When elements are arranged in order of
increasing atomic number, rather than increasing
atomic weight, Ar and K appear in their correct
places in the table
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Atomic X ray: Characteristic for each atom
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2. EFFECTIVE NUCLEAR CHARGE
• Many of the properties of atoms depend on their
electron configurations and on how strongly their
outer electrons are attracted to the nucleus.
• the force of attraction between an electron and the
nucleus depends on
– the magnitude of the net nuclear charge acting on
the electron and
– the average distance between the nucleus and
the electron
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Effective nuclear charge
• Shielding effect: In a many-electron atom, each
electron is simultaneously attracted to the
nucleus and repelled by the other electrons.
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Effective nuclear charge
• The net attraction of each electron to the
nucleus is combination of the interaction with
– the average environment created by the
nucleus and
– the other electrons in the atom
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Effective nuclear charge
Effective nuclear charge (Zeff): net positive charge of
the nucleus experienced by the outer electrons
Z eff Z S
Zeff : effective nuclear charge
Z: nuclear charge = the number of proton in the nucleus
S: shielding or screening constant (greater than 0 but
less than Z)
S is usually close to the number of core electrons in an
atom
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Effective nuclear charge
The effective nuclear
charge in Na
The 3s electron has some
probability of being inside
the Ne core.
The core is not completely
effective in screening the
3s electron from the
nucleus. Thus, the
effective nuclear charge
experienced by the 3s
electron is somewhat
greater than 1+
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Effective nuclear charge and electron energy
• A carbon atom with electron
configuration: 1s22s22p2
• The energy of the 2p orbital (l = 1) >
2s orbital (l = 0) even though both of
these orbitals are in the n = 2 shell
• An electron in the 2s orbital is less
effectively screened/shielded by the
core orbitals than is an electron in the
2p orbital
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Effective nuclear charge
• In the periodic table. The effective nuclear
charge increases as we move across any row
(period) of the table
• Going down a column, the effective nuclear
charge experienced by valence electrons
changes far less than it does across a row
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3. SIZES OF ATOMS AND IONS
• Atoms and ions do not have sharply defined
boundaries at which the electron distribution
becomes zero.
Size of atom: The closest
distances separating the
nuclei during such collisions
determine the apparent radii
of the argon atoms
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Periodic Trends in Atomic Radii
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Periodic Trends in Ionic Radii
• Cations are smaller than their parent atoms
• Anions are larger than their parent atoms
Periodic Trends in Ionic Radii
For ions
carrying the
same charge,
size increases
as we move
down a
column in the
periodic table.
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Isoelectronic series
• Group of ions all containing the same number of
electrons
• O2-, F-, Na+, Mg2+, Al3+
• Each has 10 electrons
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Isoelectronic series
Is ion size important in devices engineering?
The case of Li ion battery:
30
Chemical exfoliation of MoS2
Zheng et al., Nature Communication, 2014, doi:10.1038/ncomms3995
4. IONIZATION ENERGY
• Ionization energy of an atom or ion is the minimum
energy required to remove an electron from the
ground state of the isolated gaseous atom or ion
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IONIZATION ENERGY
• First ionization energy, I1, needed to remove the
first electron from a neutral atom
Na(g) -> Na+(g) + e-
• Second ionization energy, l2, is the energy needed to
remove the second electron
Na+(g) -> Na2+(g) + e-
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Variations in Successive Ionization Energies
This trend exists because with each successive removal,
an electron is being pulled away from an increasingly
more positive ion, requiring increasingly more energy
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Energy required to boil water: 2257 kJ/kg
= 2257 J/g >>> 2257 x 18 J/ mol = 40626 J/mol
= 40.626 kJ/mol
I1(Na) = 495 kJ/mol >>> 12.18 mol H2O = 220 g = 220 mL H2O boil
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Periodic Trends in First Ionization Energies
Increasing atomic radii
Small
atomic radii
Increasing atomic radii
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Electron affinities
• Electron affinity is the energy change that occurs
when an electron is added to a gaseous atom
Ionization energy vs. electron affinity
• Ionization energy: how easy an atom loses an
electron
• Electron affinity: how easy an atom gains an
electron.
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Electron affinity (kJ/mol)
No obvious trend
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Key points
• The periodic table development
• Effective nuclear charge
• Atom size, ion size
• Ionization energy
• Electron affinity
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Bonus…
WO3 is a key component of electro-chromic glass (a smart glass that
changes color, thus change its light absorption/ transparency, in function of
applied voltage). WVIO3 is colorless but its reduced state WVO3-x shows
blue color. With your understanding about the electronic structure of W,
give an explanation for this phenomenon.
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https://en.wikipedia.org/wiki/Electrochromism#/media/File:Bare_bones_of_an_electrochromic_devices.png
In CECS Lab @ USTH, students develop a color-rule by their own
experiences as following:
a) A Mo complex showing green color should contain a MoV center but
not a MoVI center.
b) A colorless Cu complex should contain a CuI center but not a CuII
center.
Do you agree with these rules? Give your explanation.
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Si Technology
a) Please write down the electron configuration of 14Si, 5B and 15P
b) What will happen if a Si atom within the Si crystal is replaced by a B
(creating B-doped Si) or a P atom (creating P-doped Si)?
c) What will happen if combining (interfacing) a B-doped Si and a P-doped Si?
https://en.wikipedia.org/wiki/Silicon_Valley_(TV_series)
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Si Technology
Solubility
Adding Ag+ into an aqueous solution containing F-, Cl-, Br- and I-
anions generates precipitates. Assume the anions have identical
molar concentration.
What could be the chemical composition of the precipitates?
Solubility of AgX in 100 mL water at 20C
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Hypervalency
Hypervalent compounds are of great interests in chemistry.
The PF5 has been successfully synthesized while preparation of
NF5 is still challenging.
Give a prediction about the stability of PF5 and NF5 compounds?
PF5
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Hydrogen
The ionization energy of H is 13.6 eV.
What is difference in energy between then n=1 and n=6 level?
1 eV = 1.602 10-22 kJ
= 96.49 kJ/mole
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General Chemistry I
Chemistry: The central science
Phong D. Tran
Department of Fundamental and Applied Sciences
University of Science and Technology of Hanoi
Email:
[email protected]Lectures 7, 8: Periodic properties of elements
47
