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Chemical structure
+
+ ++
+
nucleus (+)
10
GENERAL CHEMISTRY
12
C, 13C, 14C, 131I, 238U (isotopes of carbon (C), iodine (I) and uranium
(U))
The proton (gr. proton = first) is a subatomic particle with an electric
charge of one positive fundamental unit (+1 a.u. (atomic unit) = 1.6x10-19 C).
The electron is a subatomic particle with a negative electric charge of
1a.u.
The atom is characterized by the atomic number Z and the mass number A.
The difference A-Z represents the number of neutrons.
11
Chemical structure
electronic theory which establish that there are two types of chemical
bonds namely:
12
GENERAL CHEMISTRY
According to the quantum theory the ionic bond and covalent bond are
only apparently different. Each of them are two limit states of the unique way of
interaction of atoms, the covalent way.
It is possible to establish a chemical bond between atoms due to the
concentration of the positive charges in the atoms into a very small volume on one
side and the dispersion of the electronic clouds into a big volume on the other side.
In these conditions some mutual influences could exist between the nuclear field of
one atom and the electronic cloud of the other atom. When the interatomic
distances diminish the changes in the distribution of valence electronic clouds take
place, resulting in the formation of chemical bond. When sharing these electrons
there is a maximum density of the electronic cloud between the two nuclei and the
chemical bond is called covalent or homeopolar. When the electronic cloud is
concentrated around one of the atoms, this atom becomes a negative ion (anion)
and the atom with a deficit in electrons becomes a positive ion (cation). These ions
attract each other by electrostatic forces, and the chemical bond is called ionic or
heteropolar.
The quantum theory proved that a chemical bond between two atoms
cannot have a pure covalent character or a pure ionic character. It is possible to
affirm that the chemical bond is dominant ionic or covalent. A representative
example is considered the ionic compound CsF which is 93% ionic and 7%
covalent. In this way in the covalent compounds the chemical bond could be
partially ionic (covalent polar) with the increasing of electronegativity difference
between atoms. Covalent bond could be delocalized on many atoms. When the
electronic cloud is delocalized on a very large number of atoms belonging to a
Chemical structure
13
metallic lattice, the chemical bond is called metallic bond. In this case the electrons
move easily from one atom to another.
Special polarization interactions through van der Waals forces, hydrogen
bond, dipole-dipole bond could be established in case of atoms with stable
electronic configuration, that are without chemical affinity (e.g. noble gases) as
well as of molecules as stable structure units. Such interactions are not purely
chemical bonds because the deformation of the electronic cloud does not involve
any changes in the electronic configuration of the atoms. These bonds assure the
stability and some physical properties of molecular compounds: boiling
temperature, melting temperature.
Every type of chemical bonds determines some characteristics of chemical
substances:
covalent bonds from substances with atomic lattice lead to rigid
structures with high hardness and high physical thermal constants;
ionic bond leads to ionic lattice, a structure with salt character and ionic
conductibility in melt state or in solutions;
metallic bond leads to lattice with electric conductivity and metallic
character (aspect, color, etc.);
van der Waals bonds put together the particles into a weak lattice which
can be destroyed with a minimum energy.
In majority of the solid structures the types of chemical bonds coexist and
the dominant component determines the specific features of the substance.
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GENERAL CHEMISTRY
Na- Ist principal group (1 electron in the last level 1s22s22p63s1) can lose
one electron:
Na e Na +
-
Cl + 1e Cl
The ions formed in this way are not isolated. They attract each other by
electrostatic forces until a minim distance at which a repulsion force between
electronic clouds occurs:
Na + Cl : Na + : Cl :
The elements forming Ist and IInd principal groups have a few electrons on
the valence level. They can be easily lost giving positive ions (cations) while the
elements from VIIth and VIth principal groups accept easily these electrons resulting
in negative ions (anions). In this way ionic bonds are formed. Examples: NaCl, KI,
CsF, MgCl2, MgS, MgO, Na2O, K2O, CaO.
Factors which determine the ionic bond formation:
-
affinity for the electrons the energy resulting when one atom accepts
one electron in its valence level, becoming in this way a negative ion.
Halogens have the highest affinity, while the alkali metals have no electron
15
Chemical structure
affinity. The bivalent anion formation O2-, S2- requires some energy. This
phenomenon could be explained by the repulsion of the second electron by
the first already present in the molecule.
-
periods and from bottom to up in the groups. The ionic bond is characterized by
high melting and boiling points. Also the ionic compounds exhibit larger electrical
conductivities.
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GENERAL CHEMISTRY
H + H H :H
H H
: Cl + Cl : : Cl : Cl :
H2
Cl Cl
Cl 2
- sp2
- sp
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Chemical structure
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GENERAL CHEMISTRY
Energy
2px
2py
2pz
2pz
2py 2pz
sp sp
2s
fundamental state
sp3 hibridization
(ex. CH4)
sp2 hibridization
sp hibridization
(ex. H2C=CH2)
(ex. HC CH)
Chemical structure
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20
GENERAL CHEMISTRY
Dipole moment is the measured polarity of a polar covalent bond. It is defined as the
product magnitude of charge on the atoms and the distance between the two bonded atoms
Chemical structure
21
The energy of van der Waals bonds determine all the properties which
depend on cohesion energy: volatility, solubility, viscosity, plasticity.
22
GENERAL CHEMISTRY
Dispersed
medium
substance
Air
Fog
Examples
Inclusions in ores
Chemical structure
23
medium, corresponding to the solvent from a usual solution and the dispersed
phase corresponding to the solute. The amorphous phase isolated from a sol is
called gel.
The colloidal systems are classified as follows:
a) After the aggregation state of dispersed phase and the dispersion medium
(table 2):
b) After the mutual character of dispersion medium and dispersed phase
-
24
GENERAL CHEMISTRY
Optical properties:
o
Surface properties
o
Chemical structure
25
26
GENERAL CHEMISTRY
1.7. Semiconductors
1.7.1 History and importance of semiconductors
Semiconductors are materials having a conductivity ranging between
conductors (generally metals) and nonconductors or insulators (such as most of
ceramics). Semiconductors can be pure elements, such as silicon or germanium, or
compounds such as gallium arsenide or cadmium selenide. In a process called
doping, small amounts of impurities are added to pure semiconductors causing
large changes in the conductivity of the materials.
Due to their wide pallet of industrial applications in the fabrication of
electronic devices, semiconductors play an important role in our life. It is difficult
to imagine life without electronic devices. There would be no radios, no TVs, no
computers, no video games, no cell phones and rather poor medical diagnostic
Chemical structure
27
semiconductor.
1873 William Smith discovers the photoconductivity of selenium. Modern
copier machine take advantage of this property.
1927 Arnold Sommerfeld and Felix Bloch apply quantum mechanics to solids.
This allows scientists to explain the conduction of electricity in semiconductors.
1943 Karl Lark Horowitz uses high quality germanium to make diode detectors
used by Allied army to bomb Germany;
1947 Schockley, Brattain and Bardeen invent the transistor. The semiconductor
electronics industry is born !
1958 Robert Noyce, founder of Intel Corporation develops a planar process for
making semiconductors called monolithic IC technology;
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GENERAL CHEMISTRY
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Chemical structure
3A
4A
5A
6A
2B
Al
Si
Zn
Ga
Ge
As
Se
Cd
In
Sn
Sb
Te
Hg
Figure 6. Elements which can be found in semiconductor materials
30
GENERAL CHEMISTRY
completely occupied. The highest occupied energy band is called valence band.
However, there is a region that separates the valence band from the conduction
band with no orbitals. Electrons are not allowed to have these energies. In
insulators, this energy gap is relatively large and in semiconductors, the energy gap
is intermediate (figure 7).
Conduction band
E
N
E
R
G
Y
Energy Gap
Valence band
Metals
Semiconductors
Insulators
Atoms that form metallic conductors have many partially and fully
unoccupied levels with similar energies: a large number of mobile charge carriers
are able to move across the material when an electrical potential (voltage) is
applied. In a semiconductor or insulator, the valence band is completely filled with
electrons in bonding states so the conduction cannot occur. There are no vacant
levels of similar energy on neighbouring atoms. At absolute zero, its anti bonding
states (the conduction band) are completely empty. There are no electrons there to
conduct electricity. This is why insulators cannot conduct. In case of
semiconductors, as temperature increases, electrons in valence band acquire
enough energy to be promoted across the energy gap into the conduction band.
When this occurs, these promoted electrons can move and conduct electricity. The
smaller the energy gap is, the easier for electrons is to move to the conduction
band.
Chemical structure
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The process in which some impurities are added into a solid is called
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GENERAL CHEMISTRY
Solar cells are p-n junction devices which use sunlight to create
electrical energy. It is the energy of the suns photons that causes
the electrons to be promoted into the conduction bands and carry
the current. However, the current derived from the solar cell is
small. It takes many energy solar cells to produce enough current.
This is why nowadays the solar cells are use more for individual,
isolated applications than for industrial applications.
33
Chemical structure
Solid
LC
Liquid
Gas
Temperature
Figure 8. States of the matter with increasing temperature
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GENERAL CHEMISTRY
phase.
Molecule
made
by
binding
chemically
heptane
to
cyanobiphenyle, known under the commercial name 7CB (cf. Fig. 9c), exhibit a
nematic LC phase between 28.5C and 42C.
-91C
98.4C
Isotropic liquid
Crystal
Gas
Temp
i t
H3C
H2
C
C
H2
H2
C
C
H2
H2
C
CH3
(a)
88C
Crystal
Isotropic liquid
Temp
(b)
28.5C
Crystal
NLC
42C
Isotropic liquid
Temp
H3C
H2
C
C
H2
H2
C
C
H2
H2
C
C
H2
(c)
Figure 9. Phase transitions of heptane (a), cyanobiphenyle (b) and liquid crystal (c) 7CB
Chemical structure
35
36
GENERAL CHEMISTRY
z n
Nematic
N
Smectic C
Smectic A
SC
SA
a
b
c
Figure 10. Schematic presentation of the arrangements of mesogenes in nematic (a),
smectic A (b) and smectic C (c) liquid crystals; n represents the director vector of liquid
crystal
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Chemical structure
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GENERAL CHEMISTRY