General Chemistry Course v5 PDF
General Chemistry Course v5 PDF
AcademicDirect, 2013
Version 4: Online from January 29, 2013
http://ph.academicdirect.org
Version 5: Online from July 12, 2013
General Chemistry
Lorentz JNTSCHI
Periodic system
Periodical properties
Electronic structure
http://vl.academicdirect.org/general_chemistry/periodic_system
Periodic system
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
1 H He
2 Li Be B C N O F Ne
3 Na Mg Al Si P S Cl Ar
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
6 Cs Ba Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
7 Fr Ra Lr Rf Db Sg Bh Hs Mt Ds Rg Cn
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb
Ac Th Pa U Np Pu AmCm Bk Cf Es Fm Md No
At the basis of the classification of the elements stays
the atomic number, Z representing the total number
of electrons in the atom and in same time the number of
protons in the nucleus
Elements in the periodic system are placed on vertical
columns the groups, and in horizontal rows the
periods. The succession in the periods is with respect to
the main levels of energy and to the electrons layers.
The period number is equal to the main quantum
number (of the layer being filled). The number of the
group represents the number of the electrons of this
layer being filled, and plays the main role in the
expression of the chemical properties. Thus, it exists a
similarity of the properties inside groups.
Chemical properties are determined by the atom's
tendency to reach as much as possible at stable electron
configurations and to use as many as possible the orbital
valences.
96Cm
87Fr 97Bk
86Rn 95Am
71Lu 103Lw
7N
15P 22Ti 40Zr 72Hf 104Rf
6C 5B
33As 73Ta 105Ha
23V 41Nb
51Sb 14Si 74
13Al W
83Bi 30Zn 24Cr 42Mo
32Ge 29Cu
31Ga
48Cd
Mn Tc Re
50Sn 28Ni 25 43
49In 75
47Ag
26Fe
82Pb 80Hg 27Co
81Tl 46Pd
79Au 44Ru
45Rh
78Pt
Os
76
77Ir
The periodic "law" of chemistry recognizes that
properties of the chemical elements are periodic
functions of their atomic number (that is, the number of
protons within the element's atomic nucleus). The
periodic table is an arrangement of the chemical
elements ordered by atomic number in columns
(groups) and rows (periods) presented so as to
emphasize their periodic properties.
There are many different ways, sometimes ingenious, of
arranging the chemical elements according to which
properties are of particular interest but that shown here
is a standard form of the periodic table. The relative
merits of various other periodic table organizations is still
the subject of debate.
Atomic measures
Anion: atom or group of atoms containing more electrons
than protons consequence any negative charged
system is referred as anion; Cation: idem opposite
Atomic radius: measure of the relative dimension of the
atoms (see O2 and H2O)
Electron affinity: measure of the ability or tendency of a
atom to get electrons energetic concept formal
definition refers just one electron: X + 1e- X-1 + E.A.
Electronegativity: ability of a bound atom to attract
electrons; at the bond level, the electron may be shared or
transferred; there are many electronegativity scales.
Ionization potential: from energetic process leading to the
cation: X + I.P. X+ + 1e-; it exists also superior (or
supplementary) ionization potentials (ex. X+ +I.P.2 X2+ +
1e-)
Periodical tendencies
Refers the change of the atoms properties when moving
to another group or period
In period from left to right: I.P., E.A., electronegativity
increases; Dimension (radius) decreases;
In group from top to bottom: I.P., E.A., electronegativity
decreases; Dimension (radius) increases;
Stability factors refers the electrons taken or given
during the process of bond formation with the purpose of
stability increase:
Tendency to reach a configuration of a noble gas;
Tendency to loose all valence electrons (sometimes only p
sublevel electrons);
Tendency to keep: occupied, half occupied and unoccupied the
sets of the orbital
Temperature scale
~1859 ~1714 ~1732 ~1848
Rankine Fahrenheit Celsius Kelvin
Brine
freezes
Water freezes
(-17.8C
= 0F) 491.67R 32F 0C 273.15 K Mercury
freezes
(-38.8C
419.67R -40F -40C 233.15 K = -37.9F)
0R -459.67F -273.15C 0K
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
H He
1
14
Melting points of chemical elements [K] 1
Li Be B C N O F Ne
2
453 1551 2573 3820 63 55 54 24
Na Mg Al Si P S Cl Ar
3
371 922 933 1683 317 386 172 84
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
4
336 1112 1814 1933 2160 2130 1517 1808 1768 1726 1357 693 303 1211 1090 490 266 117
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
5
312 1042 1795 2125 2741 2890 2445 2583 2239 1825 1235 594 429 505 904 723 387 161
Cs Ba Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
6
302 1002 1963 2503 3269 3680 3453 3327 2683 2045 1338 234 577 600 545 527 575 202
Fr Ra Lr Rf
7
300 973 1900 2400
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb
1194 1072 1204 1294 1441 1350 1095 1586 1629 1685 1747 1802 1818 1097
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No
1338 2023 2113 1405 913 914 1267 1610 1259 1173 1133 1800 1100 1100
Solid state and density
Plasma
Recombination
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb
6146 6689 6640 6800 7264 7353 5244 7901 8219 8551 8795 9066 9321 6570
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No
10070 11724 15370 19050 20450 19816 13780 13510 14780 15100 13500 8840
Ionization potential
U
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
H He
1
13.6
First ionization potential [eV] 24.6
Li Be B C N O F Ne
2
5.4 9.3 8.3 11.3 14.5 13.6 17.4 21.6
Na Mg Al Si P S Cl Ar
3
5.1 7.6 6.0 8.2 10.5 10.4 13.0 15.8
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
4
4.3 6.1 6.6 6.8 6.7 6.8 7.4 7.9 7.9 7.6 7.7 9.4 6.0 7.9 9.8 9.8 11.8 14.0
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
5
4.2 5.7 6.2 6.6 6.8 7.1 7.3 7.4 7.5 8.3 7.6 9.0 5.8 7.3 8.6 9.0 10.5 12.1
Cs Ba Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
6
3.9 5.2 5.4 6.8 7.9 8.0 7.9 8.7 9.1 9.0 9.2 10.4 6.1 7.4 7.3 8.4 9.5 10.7
Fr Ra Lr Rf Db Sg Bh Hs Mt Ds Rg Cn
7
3.9 5.3 4.6 6.0 6.9 7.9 7.7 7.6 8.3 9.9 10.6 12.0
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb
5.6 5.5 5.5 5.5 5.6 5.6 5.7 6.2 5.9 5.9 6.0 6.1 6.2 6.3
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No
5.2 6.1 5.9 6.2 6.3 6.1 6.0 6.0 6.2 6.3 6.4 6.5 6.6 6.7
Electronegativity
% of ionic character of "AB"
100
y=-14.6x+38; r2=0.9887
80
60
40
20
-2.23 2
y=126/(1+(x/2) ); r =0.9996
0
0.2 0.8 1.4 2.0 2.6 3.2
Difference between electronegativity of A and B
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
H He
1
2.20
Electronegativity [revised Pauling]
Li Be B C N O F Ne
2
0.98 1.57 2.04 2.55 3.04 3.44 3.98
Na Mg Al Si P S Cl Ar
3
0.93 1.31 1.61 1.90 2.19 2.58 3.16
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
4
0.82 1.00 1.36 1.54 1.63 1.66 1.55 1.83 1.88 1.91 1.90 1.65 1.81 2.01 2.18 2.55 2.96 3.00
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
5
0.82 0.95 1.22 1.33 1.60 2.16 1.90 2.20 2.28 2.20 1.93 1.69 1.78 1.96 2.05 2.10 2.66 2.60
Cs Ba Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
6
0.79 0.89 1.27 1.30 1.50 2.36 1.90 2.20 2.20 2.28 2.54 2.00 2.04 2.33 2.02 2.00 2.20 2.20
Fr Ra Lr Rf Db Sg Bh Hs Mt Ds Rg Cn
7
0.70 0.90 1.31
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb
1.10 1.12 1.13 1.14 1.13 1.17 1.20 1.20 1.20 1.22 1.23 1.24 1.25 1.10
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No
1.10 1.30 1.50 1.38 1.36 1.28 1.30 1.30 1.30 1.30 1.30 1.30 1.30 1.30
Pauling Electronegativity Scale
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
1 H He
2.1
2 Li Be B C N O F Ne
1.0 1.5 2.0 2.5 3.0 3.5 4.0
3 Na Mg Al Si P S Cl Ar
0.9 1.2 1.5 1.8 2.1 2.5 3.0
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
0.8 1.0 1.3 1.5 1.6 1.6 1.5 1.8 1.8 1.8 1.9 1.6 1.6 1.8 2.0 2.4 2.8
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
0.8 1.0 1.2 1.4 1.6 1.8 1.9 2.2 2.2 2.2 1.9 1.7 1.7 1.8 1.9 2.1 2.5
6 Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
0.7 0.9 1.1 1.3 1.5 1.7 1.9 2.2 2.2 2.2 2.4 1.9 1.8 1.8 1.9 2.0 2.2
Linus PAULING. 1932. The Nature of the Chemical Bond. IV. The Energy of Single
Bonds and the Relative Electronegativity of Atoms. Journal of the American
Chemical Society 54(9):3570-3582. doi: 10.1021/ja01348a011
Allred Rochow Electronegativity Scale
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
1 H He
2.20
2 Li Be B C N O F Ne
0.97 1.47 2.01 2.50 3.07 3.5 4.1
3 Na Mg Al Si P S Cl Ar
1.01 1.23 1.47 1.74 2.06 2.44 2.83
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
0.91 1.04 1.20 1.66 1.82 2.02 2.20 2.48 2.74
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
0.89 0.99 1.11 1.46 1.49 1.72 1.82 2.01 2.21
6 Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
0.86 0.97 1.08 1.44 1.44 1.55 1.67
Electronic
6
10
6d
14
levels 5f
2
7s 6
6p
10
5d 14
2
4f
6
6s 10
5p
2
4d
6
5s 10
4p
2
3d
6
4s
3p 2
3s 6
2p 2
2s
1s 2
Electronic structure tree for Hg
Electronic shell Order of
1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2 4f14 5d10 filling (energy)
1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 4f14 5s2 5p6 5d10 5f14 5g18 6s2 appearance (quantum)
l (0..n-1) m (-l..l) s () n
=0 =0 = 1s2 =1
=0 =0 = 2s2 =2
=1 =-1,0,1 = 2p6
=0 =0 = 3s2 =3
=1 =-1,0,1 = 3p6
=2 =-2,-1,0,1,2 = 3d10
=0 =0 = 4s2 =4
=1 =-1,0,1 = 4p6
=2 =-2,-1,0,1,2 = 4d10
=3 =-3,-2,-1,0,1,2,3= 4f14
etc. ...
Atomic properties
Valence is an atomic property (other atomic property: atomic
number Z) and it reflects the tendency of elements to "stabilizes"
their electronic structure; the path to stabilization tends to reach one
of the following (meta)"stable" structures: s2, p3, p6, d5, d10, etc. For
example, at C - carbon (Z=6): 1s2, 2s2, 2p2 1s2, 2s2, 2p6 :C4-
(CH4). There are main ("preferred"), secondary ("rare") and
elemental ("homoatomic" molecules) valences: H: +1 (HCl), -1 (LiH,
BeH2), 0 (H2); O: -2 (H2O, CaO), -1 (NaO-ONa), 0 (O2); Cl: -1 (HCl),
+1 (HClO), +3 (HClO2), +5 (HClO3), +7 (HClO4). Following address
locates a periodic system developed using a database and can be
queried for valences:
http://vl.academicdirect.ro/general_chemistry/periodic_system/ [1].
Chemical combinations classifies in homoatomic and heteroatomic;
also in binary, ternary, quaternary, etc. Following series gives
representatives according with these classifications: O2, O3, H2O
(binary combination!), H2SO4.
[1] Lorentz JNTSCHI, Delia M. GLIGOR, 2003. Periodic Systems
of Elements Information (Software). Online: AcademicDirect. URL:
http://vl.academicdirect.ro/general_chemistry/periodic_system/
Interaction models
(covalent bond model) The covalent bond model is a
representation of the chemical bond which assumes that
every bond is created when two (by two) atoms are put
together (by two by two atoms). It has as limit cases the
metallic bond (Me - metal; Men molecule; n metal
network), ionic bond (A, B chemical species with - see
below - different electronegativity; AB molecule; A+B-
separating of the electric charges; A+, B- ions) and
coordinative (such as: CaCl2, Ca2+: 1s2 2s2 2p6 3s2 3p6
3d0 4s0; CaCl26H2O, Ca2+: 1s2 2s2 2p6 3s2 3p6 3d10 4s2 -
antarcticite).
(hybridization models) Hybridization models are able to
explain the differences of the energies (at electronic
orbital levels) when they join together in chemical bonds
(see Representation of hybridization process).
Hybridization conserves the total number of energy
levels (orbital levels).
s *ss ss *ss s
Hybridization A A B B
process
s *sp sp *sp p
A A B B
p *pp pp *pp p
A A B B
p *pp pp *pp p
A B
A A A B
AB*
A
B
AB
Molecular orbital levels
Based on hybridisation the occurrence of molecular
orbital levels is explained (see Representation of
hybridization process). Under absence of energetic
excitation (of a energy transfer to the molecule) filling
with electrons of molecular energy levels is in increasing
order of the energy of the levels (see Diatomic
homomolecules of 2nd period). On molecular orbital
forming basis and ordered filling of them with electrons
the molecular stability are explained. A derived from
model of the molecular orbital levels is the bond order.
We count as bond order the difference between
occupied "bond" orbital levels (lower energy split of the
pair of orbital levels) and occupied "anti-bond" orbital
levels (upper energy split of the pair of orbital levels).
Bond order may take rational values, as in CC from
C6H6: 9(bonds)/6(atoms) = 3/2.
Diatomic molecules of 2nd period
Molecular Orbital eV
Anti-bonding Li2 Be2 B2 C2 N2 O2 F2
Unoccupied 30
Occupied 20
10
0
-10
-20
-30
-40
-50
1 0 1 2 3 2 1 Bond order
2.7 3.5 1.9 1.4 1.1 1.2 1.3 Distance
1.1 0.7 3.0 4.8 9.8 5.1 2.5 Energy (eV)
Energy H2O (eV)
80 77.5
60
40
Molecular O2p
34.8
orbital & 20
1 1* 3 2 2* 3*
Course 2
Abundance of elements;
chemical formulas; stoechiometry
Relative abundance of elements in
the Galaxy*
Relative (to Carbon) number of atoms
10000
1928
1000
157
100
10
1.7
1
1
0.1 0.17 0.18
0.04 0.05 0.06 0.06
0.01 S Fe Si Mg Ne N C O He H
~5100 km boundary 250 500 750 1000 1250 1500 1750 2000 2250
~6378 km layer
Inner core 0m 573 nm
Core Underground Log scale
Atmosphere
-9 2 106m
7.5210 N/m
MM Log(VM)
T vT 3.5610-15 kg/m3
3.94 g/mol
105m
727 K 187 K
2318 m/s 370 m/s
5.07107 l/mol
104m
28.964 g/mol
3
10 m
4 2
7.9510 N/m 28.8 l/mol
1.01 kg/m3
275.15 K (2C)
102m
p 448.5 m/s
1.01105 N/m2
1.23 kg/m3 101m
288.15 K (15C)
458.9 m/s 23.6 l/mol
100m
Spread of the elements in the
atmosphere
Gas shell surrounding the Earth is the
atmosphere. Planetary boundary layer is
formed mostly from nitrogen (78%) and
oxygen (21%), along with others in small
quantities (H2O, Ar, CO2, Ne, He, CH4, Kr, H2).
Atmosphere composition
6
m
10
H
He
O
4105
N2
105
O2
0
0% 78% 99%
Soil composition
5 45 30 20
30 20 20 30
Organic Mineral Air Water
Organics for 1g of soil: Typical minerals of soil:
Bacteria: [3106, 5108] SiO2, CaCO3
Actinomycetes: [106, 2107] MAlSi3O8, M = Na, K, Ca
Fungi: [5103, 106] KAlSi3O10(OH)2
Yeast: [103, 106] K(Mg,Fe)3AlSi3O10(OH)2
Protozoa: [103, 5105] MSiO3, M = Mg, Mn
Algae: [103, 5105] (Mg,Fe)2SiO4
Nematodes: [101, 5103] Ca2Mg5Si8O22(OH)2
Elemental composition at Earths surface
mg/kg
6 O Si Al Ca Fe K Mg C Na S Mn P N Zn Ni Cu Mo
10
Human body
Topsoil
105
Sediments
104 Crust
103
102
101
100
O Si Al Ca Fe K Mg C Na S Mn P N Zn Ni Cu Mo
% of elements in crust + upper mantle
Element O Si Al H Na Ca Fe
% of atoms 59.4778 20.4663 6.2294 2.8963 2.5455 1.8774 1.8471
% 59.48 79.94 86.17 89.07 91.62 93.49 95.34
Element Mg K Ti C F P Mn
% of atoms 1.8016 1.3739 0.1896 0.1724 0.0871 0.0801 0.0376
% 97.14 98.52 98.70 98.88 98.96 99.04 99.08
Element S Cl V Ba N Sr Li
% of atoms 0.0323 0.0291 0.0077 0.0076 0.0074 0.0071 0.0059
% 99.11 99.14 99.15 99.16 99.17 99.17 99.18
Element Cr Zr Ni Zn Cu B Ce
% of atoms 0.0056 0.0045 0.0032 0.0025 0.0023 0.0019 0.0009
% 99.18 99.19 99.19 99.19 99.20 99.20 99.20
Structure Property
-Universe Whole observing space
-Radiant energy Speed comparable with light
+Radiations such as , Differentiated through properties
-Matter Whole not relativistic observables space
-Body Speed much less than the light
-Materials ensemble Variable and discontinue (chemical) composition
-Material Variable and continue (chemical) composition
-Substance mixture Well defined composition
+Heterogeneous substance Variable (chemical) composition
-Solution Solid or liquid aggregation state
+Alloy Mixture of metals in solid or liquid aggregation state
-Homogenous substance Constant (chemical) composition
+Chemical compound Unique and well defined chemical structure
Structure Property
-Universe Whole observing space
-Radiant energy Speed comparable with light
+Radiations such as , Differentiated through properties
-Matter Whole not relativistic observables space
-Body Speed much less than the light
-Materials ensemble Variable and discontinue (chemical) composition
-Material Variable and continue (chemical) composition
-Substance mixture Well defined composition
+Heterogeneous substance Variable (chemical) composition
-Solution Solid or liquid aggregation state
+Alloy Mixture of metals in solid or liquid aggregation state
-Homogenous substance Constant (chemical) composition
+Chemical compound Unique and well defined chemical structure
+
Anti
Gauche g+
Representation levels
Chlorophylls Porphine
Chlorophyll Ref. Molecular formula Present in e,HOMOH1,UMO & Spread [1]
NH N a [2] C55H72O5N4Mg Universal 1.84 ****
b [3] C55H70O6N4Mg Many plants 1.54 ***
d [4] C54H70O6N4Mg Cyanobacteria 1.38 **
N HN c1 C H O N Mg Different algae 1.33 **
[5] 35 30 5 4
c2 C35H28O5N4Mg Different algae 1.38 **
f [6] C55H70O6N4Mg Cyanobacteria 1.21 *
c1 c2 general structure
1
Lorentz JNTSCHI, Sorana D. BOLBOAC, Mugur C. BLAN, Radu E. SESTRA, 2011. Chlorophylls - natural
solar cells. BUASVM. Agriculture, 68(1):181-187.
2
James B. CONANT, Emma M. DIETZ, Carroll F. BAILEY, S. E. Kamerling, 1931. Studies in the chlorophyll series.
V. The structure of chlorophyll a. Journal of the American Chemical Society 53(6):2382-2393.
3
James B. CONANT, Emma M. DIETZ, Tyrrell H. WERNER, 1931. Studies in the chlorophyll series. VIII. The
structure of chlorophyll b. Journal of the American Chemical Society 53(12):4436-4448.
4
Hideaki MIYASHITA, Hisato IKEMOTO, Norihide KURANO, Kyoko ADACHI, Mitsuo CHIHARA, Shigeto
MIYACHI, 1996. Chlorophyll d as a major pigment. Nature 383(6599):402.
5
Harold H. STRAIN, Benjamin T. COPE, Geraldine N. McDONALD, Walter A. SVEC, Joseph J. KATZ, 1971.
Chlorophylls c1 and c2. Phytochemistry 10(5):1109-1114.
6
Min CHEN, Martin SCHLIEP, Robert D. WILLOWS, ZhengLi CAI, Brett A. NEILAN, Hugo SCHEER, 2010. A red-
shifted chlorophyll. Science 329(5997):1318-1319.
a b d f
Spread of
chlorophylls
Molecular topology - graph fragments
[Sz] 1 2 3 4 5 6
1 1 1 12 123 123
2 5 2 2 2 12 123 123
1 4 3 3456 3456 123 123 123
3 6 4 456 456 456 1234 1234
5 456 456 56 5 5
6 456 456 56 6 6
[cM] 1 2 3 4 5 6 [Mx] 1 2 3 4 5 6
1 2 3456 456 5 6 1 13456 12 123 12346 12345
2 1 3456 456 5 6 2 23456 12 123 12346 12345
3 1 2 456 5 6 3 23456 13456 123 12346 12345
4 1 2 123 5 6 4 23456 13456 456 12346 12345
5 1 2 123 1234 6 5 23456 13456 456 56 12345
6 1 2 123 1234 5 6 23456 13456 456 56 12346
[Cy] 1 2 3 4 5 6 [Cf] 1 2 3 4 5 6
1 123 123 1 1 1 12 12 12
2 123 123 2 2 2 12 12 12
3 123 123 3 3456 3456 123 123 123
4 456 456 4 456 456 456 1234 1234
5 456 456 5 56 56 56 5 5
6 456 456 6 56 56 56 6 6
Molecular topology - graph polynomials
Graph [G] Matrix ([M]) Polynomial Characteristic
Distance CP(Di;x)=8x3+8x2+14x1+6x0
3 2 Maximal CP(Mx;x)=20x5+6x3+4x2+6x0
[Ch] 1 2 3 4 5 6
1 x -1 -1 0 0 0
http://l.academicdirect.org/Fundamentals/Graphs/polynomials/
http://l.academicdirect.org/Fundamentals/Graphs/cycles_count/
http://l.academicdirect.org/Fundamentals/Graphs/indices/
http://l.academicdirect.org/Fundamentals/Graphs/terminal_paths/
http://l.academicdirect.org/Fundamentals/Graphs/vertex_cutting/
Molecular geometry theory levels
Molecular mechanics uses the Newtonian mechanics to model molecular
systems and its main application is energy optimization [1].
The empirical or semi-empirical methods, including Austin Model 1
(AM1 [2]), CFF [3], Del-Re [4], Parameterized Model (PM3 [5],[6], PM6 [7]),
RM1 [8], Gasteiger [9],[10], Hckel [11],[12],[13],[14], Pullman [15],
Optimized Potentials for Liquid Simulations (OPLS [16]), MM+, Assisted
Model Building with Energy Refinement (Amber [17]) and Merck Molecular
Force Field (MMFF [18],[19],[20],[21],[22]), are widely implemented in
software, including MOPAC [23], Gaussian [24], SPARTAN [25],
HyperChem [26], ChemBioOffice [27], and MolecularModellingPro [28],
due to their speed.
[1] K. I. Ramachandran, Gopakumar DEEPA, Krishnan NAMBOORI, 2008. Computational Chemistry and Molecular Modeling: Principles and Applications. Berlin: Springer.
[2] Michael J. S. DEWAR, Eve G. ZOEBISCH, Eamonn F. HEALY, James J. P. STEWART, 1985. Development and use of quantum mechanical molecular models. 76. AM1: a new general purpose quantum mechanical molecular model. Journal of the
American Chemical Society 107(13):3902-3909.
[3] Jon R. MAPLE, Jeong M. HWANG, Thomas P. STOCKFISCH, Uri DINUR, Marvin WALDMAN, Carl S. EWIG, Arnold T. HAGLER, 1994. Derivation of class II force fields. I. Methodology and quantum force field for the alkyl functional group and alkane
molecules. Journal of Computational Chemistry 15(2):162-182.
[4] G. del RE, B. Pullman, T. Yonezawa, 1963. Electronic structure of the -amino acids of proteins: I. Charge distributions and proton chemical shifts. Biochimica et Biophysica Acta 75:153-182.
[5] James J. P. STEWART, 1989. Optimization of parameters for semiempirical methods I. Method. Journal of Computational Chemistry 10(2):209-220.
[6] James J. P. STEWART, 1989. Optimization of parameters for semiempirical methods II. Applications. Journal of Computational Chemistry 10(2):221-264.
[7] James J. P. STEWART, 2007. Optimization of Parameters for Semiempirical Methods V: Modification of NDDO Approximations and Application to 70 Elements. Journal of Molecular Modeling 13(12):1173-1213.
[8] Gerd B. ROCHA, Ricardo O. FREIRE, Alfredo M. SIMAS, James J. P. STEWART, 2006. RM1: A reparameterization of AM1 for H, C, N, O, P, S, F, Cl, Br, and I. Journal of Computational Chemistry 27(10):1101-1111.
[9] Johann GASTEIGER, Mario MARSILI, 1980. Iterative partial equalization of orbital electronegativity - a rapid access to atomic charges. Tetrahedron 36(22):3219-3228.
[10] Johann GASTEIGER, Mario MARSILI, 1978. A new model for calculating atomic charges in molecules. Tetrahedron Letters 19(34):3181-3184.
[11] Erich HCKEL, 1931. Quantentheoretische Beitrge zum Benzolproblem - I. Die Elektronenkonfiguration des Benzols und verwandter Verbindungen. Zeitschrift fr Physik 70 (3-4):204-286.
[12] Erich HCKEL, 1931. Quantentheoretische Beitrage zum Benzolproblem - II. Quantentheorie der induzierten Polaritaten. Zeitschrift fr Physik 72(5-6):310-337.
[13] Erich HCKEL, 1932. Quantentheoretische Beitrage zum Problem der aromatischen und ungesattigten Verbindungen. III. Zeitschrift fr Physik 76(9-10):628-648.
[14] Erich HCKEL, 1933. Die freien Radikale der organischen Chemie - Quantentheoretische Beitrage zum Problem der aromatischen und ungesttigten Verbindungen. IV. Zeitschrift fr Physik 83(9-10):632-668.
[15] H. Berthod, C. Giessner-Prettre, A. Pullman, 1967. Sur les rles respectifs des lectrons et dans les proprits des drivs halogns des molcules conjugues. Application l'tude de l'uracile et du fluorouracile. Theor. Chim. Acta. 8(3):212-222.
[16] William L. JORGENSEN, Julian TIRADO-RIVES, 1988. The OPLS [optimized potentials for liquid simulations] potential functions for proteins, energy minimizations for crystals of cyclic peptides and crambin. Journal of the American Chemical Society
110(6):1657-1666.
[17] Scott J. WEINER, Peter A. KOLLMAN, David A. CASE, Chandra U. SINGH, Caterina GHIO, Guliano ALAGONA, Salvatore PROFETA, Paul WEINER, 1984. A new force field for molecular mechanical simulation of nucleic acids and proteins. Journal of the
American Chemical Society 106, 765-784.
[18] Thomas A. HALGREN, 1996. Merck molecular force field. II. MMFF94 van der Waals and electrostatic parameters for intermolecular interactions. Journal of Computational Chemistry 17(5-6):520-552.
[19] Thomas A. HALGREN, 1996. Merck molecular force field. III. Molecular geometries and vibrational frequencies for MMFF94. Journal of Computational Chemistry 17(5-6):553-586.
[20] Thomas A. HALGREN, 1996. Merck molecular force field. IV. Conformational energies and geometries for MMFF94. Journal of Computational Chemistry 17(5-6):587-615.
[21] Thomas A. HALGREN, Merck molecular force field. V. Extension of MMFF94 using experimental data, additional computational data, and empirical rules. Journal of Computational Chemistry 17 (1996) 616-641.
[22] Thomas A. HALGREN, 1996. Merck molecular force field. I. Basis, form, scope, parameterization, and performance of MMFF94. Journal of Computational Chemistry 17(5-6):490-519.
[23] David YOUNG, 2001. Appendix A (A.3.2 p.342, MOPAC) In: Computational Chemistry, New York: Wiley-Interscience.
[24] ***, 2004. Publishers Note: Sir John A. POPLE, 1925-2004. Journal of Computational Chemistry 25(9):v-viii.
[25] David YOUNG, 2001. Appendix A (A.1.6 p.330, SPARTAN) In: Computational Chemistry, New York: Wiley-Interscience.
[26] Hypercube, 2002. HyperChem7 (software). Website: http://www.hyper.com/
[27] CambridgeSoft, 2010. ChemBioOffice2010 (software). Website: http://www.cambridgesoft.com/software/chembiooffice/
[28] ChemSW, 2007. MolecularModellingPro (software). Web: http://www.chemistry-software.com/modelling/13052.htm
Molecular geometry theory levels
A series of ab initio methods were developed (for example STO-
3G, 3-21G, 6-31G*, 6-31G**, Gradient, MP2, Hamiltonian, Huckel,
CNDO, INDO, etc. [62]) although, the time-consuming calculations is
a major barrier in their utilization. A very good software (which I
recommend) for ab initio calculations is Massively Parallel
Quantum Chemistry Program (abbreviated as MPQC). The MPQC
program computes properties of atoms and molecules from first
principles using the time independent Schrdinger equation [1]. The
version 2.3.1 released on 2006-03-22 was used [2] under a
FreeBSD operating system platform.
Minerals
Physical and chemical properties
Chemical reactions
Minerals
Mineral class Examples
Native Diamond, coal, S, Au, Ag, Cu, Pt, Pd
Halogenated NaCl (also known as salt, common salt, table salt
or halite), KCl, CaF2, KClMgCl26H2O
Oxides and Al2O3, AlO(OH), Al(OH)3, Fe2O3, FeO, Fe3O4,
hydroxides MnO2, TiO2, SnO2, SiO2, UO2, U3O8
Sulfides, arsenides FeS2, PbS, ZnS, HgS, CuS, Sb2S3, Bi2S3, MoS2,
CuFeS2, NiAs, CoAsS
Carbonated CaCO3, MgCO3, CaCO3MgCO3, FeCO3, MnCO3,
Cu2(CO3)(OH)2, Cu3(CO3)2(OH)2
Nitrates NaNO3, KNO3
Heliodor
(some V replaces Al)
Emerald
(Be3Al2(SiO3)6)
Riesling
(some V & Fe replaces Al)
Aquamarine
(some Fe replaces Al)
Morganite
(some Mn replaces Al)
Corundum (Al2O3)
Sapphire
Sapphire
Sapphire Sapphire
Citrine (some
Fe3+)
Quartz
Milky (some CO2,
H2O) (SiO2)
Topaz (Al2SiO4(F,OH)2)
Native & S2-
O2- & CO32-
X - & SO4 2-
PO43-, AsO43-, VO43-
SiO44-
Physical and chemical properties
Activation Energies Environmental Fate Isoelectric Point
Activity Coefficients Equilibrium Constants Kinetic Data
Adsorption and Adsorption Coefficients Expansion Coefficient
Lattice Energies Antoine Coefficients and Constants
Explosive Properties Log P Atomic Mass Constant Exposure
Limits Luminescence Atomic Radius Extinction Coefficient
Melting Point Avogadro's Constant Flammability Molar
Absorptivity Bioconcentration Factor Flash Point Molecular
Weight Biodegradation Free Energy NFPA Chemical Hazard
Labelling Bohr Radius Freezing Point Octanol/Water Partition
Coefficient Boiling Point Friction Coefficient Optical Rotation
Boltzmann Constant Fundamental Physical Constants
Oxidation-Reduction Potentials Bond Energies G-Factors
Oxidation States Bond Lengths/Bond Angles Gas Law Ozone
Depletion Potential Compressibility Gibbs Free Energy Partition
Coefficients Conductivity Global Warming Potential Phase
Diagrams Conversion factors Half Life Physical Properties,
General Corrosion Hazard Ratings, Code and Reactions pK
Critical Properties Heat Capacity Proton Affinity Crystal
Structure and Space Groups Heat of Combustion Radii Debye-
Huckel Coefficients Heat of Dilution Rate Coefficients
Decomposition Rate Heat of Formation Rate Constants
Degradation Heat of Fusion Refractive Index Density Heat of
Hydration Solubility Dielectric Constant Heat of Ionization
Space Group Diffusion (Molecular) Heat of Mixing Specific
Gravity Dipole Moment Heat of Neutralization Specific Heat
Dissociation Constant
Heat of Polymerization Specific Rotation Distribution Coefficient
Heat of Reaction Stability Constants Electrical Conductivity
Heat of Solution Surface Tension Electrical Resistivity Heat of
Sublimation Tensile Strength Electrode Potentials Heat of
Transformation Thermal Conductivity Electron Affinity Heat of
Transition Thermal Diffusivity Electron Binding Energies Heat of
Vaporization Thermal Expansion Electron Configuration
Henry's Law Constants and Coefficients Thermodynamic
Properties Electronegativity Internuclear Distance Vapor
Pressure Enthalpy Ionization Constant Virial Coefficient
Enthalpy of... Ionization Energy Viscosity Entropy Ionization
Heat Young's Modulus Ionization Potential
NaOH H2O
Heat of solution
NaOH(s) NaOH(aq)
HCl(aq)
Heat of reaction
MgO(s) + 2HCl(aq) MgCl2(aq) + H2O
MgCl2(aq) Mg2+ + 2Cl-
Thermometer
Flash point
Open cup
Heater
Electrode potential V
U
R
A
Zn
Closing circuit method Cu
ZnSO4
Chemical reactions
The simplest reactions are of forming of
compounds from elements. For instance: C + S
CS2
Terms in the left of are the reactants and
terms in the right of are products
A problem is to establish the coefficients the
ratio between the participants; for the above
example: C + 2S CS2
Other case is when reactants are
homomolecues. For instance: H2 + O2 H2O
and with coefficients: H2 + O2 H2O
If are imposed that all coefficients be integers,
then: 2H2 + O2 2H2O
Establishing the coefficients of the reactions are
the subject of stoechiometry.
Conservation laws
Stoechiometry is based on conservation laws for
the electrons and for the atoms.
Electrons conservation: in a reaction the total
number of electrons given by the atoms (or atom
groups) equals with the total number of the
electrons taken by the atoms. Exception is when
electrical current is involved (subject of
electrochemistry) when partial reactions not obey
this principle, but the global reactions obey.
Atoms number conservation: in a reaction the
number of atoms from each species which enters
in the reaction is equal to the number of atoms
which result from the reaction. Exception is for
nuclear reactions and in this case only the total
rest mass is conserved.
Algebraic method
Are labeled as unknowns the coefficients of the reaction:
aKMnO4 + bHCl cKCl + dMnCl2 + eH2O + fCl2
It considers only the atoms number conservation. Please
see that we have 5 equations and 6 unknowns; let us
express all depending on one of them. Let be e the
independent one. Then (after calculation): (K ) a = c
(Mn ) a = d
a = e/4; b = 2e; c = e/4;
(O) 4a = e
d = e/4; e = e; f = 5e/8, (H) b = 2e
Let be placed it in the initial equation: (Cl) b = c + 2d + 2f
(e/4)KMnO4+(2e)HCl (e/4)KCl+(e/4)MnCl2+(e)H2O+(5e/8)Cl2
The coefficients are natural expressed when are integers
and do not have a common divisor greater than 1. A
simple arithmetic give thus e = 8 as unique solution.
Coefficients of reactions: algebraic
method
App for: Cu + HNO3 Cu(NO3)2 + NO + H2O
F2
Si Cl2
C O2
CH4 H2 H2 O
P4 s8
N2
PH H2 S
3
NH3
Chemical properties of hydrogen.
Reactions with metals
LiH
+Li
+Na
MgH2 +Mg H2 NaH
+Ca
CaH2
With other metals does not react, but may associate,
through specific interactions, to give interstitial metallic
hydrides, very similarly to alloys
H absorption on Pt
face-centered cubic
Pt
close-packing of equal
spheres: /32 0.7405 d(Pt,Pt) = 0.277nm
d(Pt,Pt) = 0.277nm
H2 d(Pt,Pt) = 0.277nm
0.74 (H:Pt)max
Reduction character of the hydrogen
With many combinations, organic included, hydrogen
have a reduction character, similarly with the one from
the reaction with nonmetals (oxidants). Due to this
character, hydrogen is industrially used in the reaction
for copper (or other metals) reduction: Cu2+(aq) + H2(g) =
Cu(s) + 2H+(aq)
Thus, after extracting as cooper sulfate of the cooper
from ore, though bubbling of hydrogen, metalic cooper
may be separated. About 1/3 from all industrial hydrogen
is used for such kind of reductions. The necessary
condition for this reduction is that the redox potential ()
of the metal to be positive.
Also, a large number of oxides can be reduced with
hydrogen to metals, by using a high temperature, and
thus serving to the obtaining of the metals. For instance,
wolfram trioxide reduces to metal via: WO3 + 3H2 W +
3H2O
LiAlH4
2M + yH2O Li + Al M + xHCl
MClx
M2Oy
O C
C O
H3C OH H2 HO CH
C C
C C
C C C C
On another hand, a large quantity of hydrogen is used in
the alimentary industry for hydrogenation of vegetable oils
(they have a isolated double bond in a saturated chain, R,
from a fatty acid (R-COOH):
H2 + -CH2-CH= CH-CH2- -CH2-CH2 CH2 -CH2-
The process is a reduction too. Due to this treatment the
oils (liquid fats), containing double bonds, become solid
fats (margarine) due to the fact that din cauza faptului c,
embedding better, the interactions between chains are
stronger
Hydrogen is used in the industry practice due to the
catalytic hydrogenation reactions; one important is
hydrogenation of nitrogen, carbon oxide and natural oils:
nitrogen (Haber procedure);
Carbon oxide: CO + 2H2 CH3OH (methanol);
Unsaturated oils to saturated ones for margarine.
All below mentioned reactions are with catalysts and using
energetic conditions.
Alternative sources of energy
Polymer Electrolyte Membrane Fuel Cell
(PEMFC)
Solid Electrolyte Cell Fuel or Ion Exchange
Membrane Fuel Cell (IEMFC)
The anodes are expensive because of
platinum. One thus seeks to decrease the
quantities of Pt used: large progress was
made making pass the content of 4 mg/cm2 to
0.1 mg/cm2 but it would seem that one cannot
decrease still much this content.
Hydrogen fuel cell
The negative ions
Proton exchange membrane (electrons) are retained
by the catalyst of H+
(usually Platinum) at
Catalyst Catalyst anode.
Only H+ are mobile and
Air free to transport the
positive load through
+ H+ the membrane
H O2 consisting of an organic
compound.
At the surface of
H2 H2O cathode (usually Nickel)
water are produced.
(+): H2
2H+ + - - (-): O2 +
4H+ + 4e-
+ 2e- e H2O
Oxygen
Oxygen is the first element of group 16 and have the
following electronic configuration 2s22p4; is the second
element by the electronegativity, after fluorine
Oxygen is the most spread in the nature (46.59%) in air
in free state (20.9% volume), n water (88.89%) and in
crust being part of the most rocks and ores (46.6%).
Existence of the oxygen makes happen the occurrence
of the superior life forms on Earth. Oceans cover of
the Earth surface. In crust, oxygen are found as oxy-
salts silicates and alumino-silicates, carbonates,
sulfates, nitrates, nad as oxides.
It has 3 isotopes: 16O (99.759%), 17O (0.0374%), 18O
(0.239%). Through fractioned distilling of water till 97%
we may concentrate 18O and 4% 17O. 18O uses as tracer
in the reactions involving oxygen. 17O has nuclear spine
and may serve in (magnetic) resonance studies, for
instance to make distinction between the complex fixed
water and the water from solution: Co(NH3)5H2O.
Allotropic states. Oxygen has two allotropic states: O2
di-oxygen, and O3 tri-oxygenor ozone.
Reaction of forming O3 from O2 is endothermic and its
reverse is exothermic:
3O2 2O3 H = +8.1 kJmol-1
2O3 3O2 H = -142 kJmol-1
O3 results also from thermal dissociation of O2 at over
1500C, when O2 dissociates in 2 atoms of O with which
O2 leads to O3.
The action of the ultraviolet radiation (UV) on O2
produces traces of O3 in the upper atmosphere
(stratosphere). Highest concentration of ozone are about
25Km altitude. The presence of the ozone is of vital
importance for protecting Earths surface on excessive
exposure to UV radiations.
Methods obtaining O2
Industrial
Fractioned distilling of liquid air. O2 have b.p. = -182.9 C
and N2 have b.p. = -195.7 C, and thus may be easily
separated one to each other. Oxygen are kept in steel tubes
at pressures of about 150 atm.
Acidic or alkaline water electrolysis. For instance NaOH
15-20% solutions, by using cathode of Fe and anode of
graphite. At cathode are separated H2 and at anode are
separated O2.
In lab
Small quantities of O2 can be obtained from thermal
decomposition of some combinations:
- oxides: 2HgO O2 + 2Hg, 3MnO2 O2 + Mn3O4
- peroxides: 2BaO2 O2 + 2BaO
- salts: KClO33/2O2 + KCl, 2KMnO4 O2 + MnO2 + K2MnO4
Other way is from some redox reactions, such as:
4MnO4- + 12H+ 5O2 + 4Mn2+ + 6H2O
Ionomolecular species of oxygen
O2 + O2 O2 - O22-
O O
O B O
B O O B
O O
O A O
O B B O
O O
O B O
O O
Phosphorus oxides
P4O10 (P4O9)3
Oxyacids
Hexagonal
Hexagonal d(OH)=172pm
not to scale d(OH)=285pm
to scale
Cubic
Were found no less than 15 phases of ice.
At pressures till up about 1000 atm. and for
temperatures till down about -200C ice
adopts two crystal structures, both close-
packed: hexagonal (at upper
temperatures) and cubic (at lower
temperatures).
Water properties: pH
As following diagram shows, pH ranges from 0 to 14, with
7 being neutral. pHs less than 7 are acidic while pHs
greater than 7 are alkaline (basic). You can see that acid
rain can be very acidic, and it can affect the environment
in a negative way. Other data: http://www.iapws.org/release.htm
16
In solid state: p H 2O (4C) = 19.7
15.5
15 1 atm.
Liquid Gas
14.5
14
13.5
p H 2O
13
12.5
p H 2O = 10.87 4.1 e t / 93 D2O
12
0.639
11.5 H2 O
t(C)
11
0 25 50 75 100 125 150 175 200 225 250
pH scale
-9.3 ~ HI 0 HCl Acid rain
Battery acid
1 (1M)
Lime
2 Lemon
"Cola"
3 Vinegar
Adult fish die
Increasing 4 Tomatoes
Fish reproduction affected
acidity 5 Bananas
Potatoes Normal range precipitation
6 Urine
Cow milk Stream water
Neutral 7
Sea water Blood
8
Baking soda
Increasing 9
alkalinity H3BO3 (1M) Juvenile fish die
10
Mg(OH)2 Adult fish die
11 50C
H2O2 NH4OHsat
12 0C
Ca(OH)2
13 NaOH
KOH (1M)
38 ~ KNH2 14
Indicator Color low Range Color high
Picric acid 0.6-1.3
pH indicators Thymol 'blue'
2,4-dinitrophenol
0.6-1.3
0.6-1.3
Methyl 'yellow' 2.9-4.0
Bromophenol 'blue' 3.0-4.6
pH Congo 'red' 3.0-5.0
Methyl 'orange' 3.1-4.4
Bromocresol 'green' 3.8-5.4
mV Methyl 'red' 4.3-6.2
Azolitmin 4.5-8.3
Bromocresol 'purple' 5.2-6.8
Bromothymol 'blue' 6.2-7.6
Phenol 'red' 6.4-8.0
Toluylene 'red' 6.8-8.0
Cresol 'red' 7.2-8.8
Naphtholphthalein 'blue' 7.3-8.7
Thymol 'blue' 8.0-9.6
Phenolphthalein 8.3-10.0
E (H + / H 2 ) + E ref E 0 ref Thymolphthalein 8.3-10.0
pH = Alizarine 'yellow' 10.1-12.0
ln(10) RT / F
Picrylnitromethylamine 10.8-13.0
Cyanidin <3.0 7.0-8.0 >11
Course 5
W - + Graphite Hg (l)
C Na
Cl2 H2 O
+ H2(g)
Na
Ti + NaCl M + Na 2 O
Uses
NaCN, KCN (electrolytic processes);
Na2O2 (oxidant) indoor air renewal (Na
pigboats; Li lighter - spacecrafts):
Na2O2(s) + CO2(g) Na2CO3(s) + 1/2O2(g)
Na: with Ti (TiCl4 + Na) is thermal agent in
nuclear reactors (high thermal conductivity, low
melting point); monochromatic lamps (with
vapors of Na); alloying element (in small
quantities)
Na-K: liquid thermometers for high temperatures
(replacing Hg);
Rb, Cs: has special use for cathodes in solar
cells
Lithium ion polymer batteries
Anode (Li2TiO3) -
Organic material, low
production cost durability (20 years, 9000
90 milliamp hours per cycles), safety, -50 to
gram after 50 70C operating
charge/discharge temperature
cycles
Cathode (1,2,4-Trihydroxyanthraquinone) +
Complex coordinative combinations
Inorganic Components of Detergents
Builders and Other Additives
Complex (or condensed) Phosphates
These have a lower alkalinity than trisodium
phosphate. The commonly used complex
phosphate are:
Tetrasodium pyrophosphate Na4P2O7
Sodium tripolyphosphate Na5P3O10
Sodium tetraphosphate Na6P4O13 (hygroscopic)
Sodium hexametaphosphate (NaPO3)6
(hygroscopic) Na Na Na Na
Carbonates O O O O
Soda ash (sodium carbonate) Na2CO3
Oxygen Releasing Compounds P P
Sodium Perborate Na2B2O4(OH)4 O O O
dibenzo-18-crown-6 representative of a
class of alkali complexes
O
CH2 CH2 O O
O CH2
CH2 N ONa
Ca
N ONa
O O
M O
O
O O O
Al: blue
O: red
3 electrolysis
MgCl2 /2H2O Mg
Two step Ca electrolysis
Graphite + - W - +
Cl2 C C
Al2O3
Al2O3
CaCl2
Ca
CaSn3
Sn CaSn3
tC electrolysis
Na
SrO Sr
C Na2CO3
BaSO4 BaS BaCO3
tC
Al
Ba BaO
Physical properties
Z 4 12 20 38 56 88
Symbol Be Mg Ca Sr Ba Ra
Mass (g/mol) 9.0 24.3 40.1 87.6 137.4 226.1
M.p. (C) 1280 657 850 757 710 700
B.p. (C) 2967 1102 1439 1364 1638 1140
(g/cm3) 1.85 1.74 1.54 2.61 5.5 6
Ip (eV) 18.1 15.1 11.9 10.9 10.0 10.2
0 (V) -1.69 -2.35 -2.87 -2.89 -2.90 -2.92
The general rule of monotony has almost always
exceptions (see for instance m.p. for Mg).
In non-oxidized state all solid states of the
elements from 2nd group are white-silver colored
(exception Be - white-gray).
Ionization energies degreases in group (from top
to bottom) being tree times higher than of the
corresponding alkali.
Redox potentials (0), all negative, are few less
negative than of the alkali and thus alkaline
earth elements are less chemical active than the
alkali.
Chemical properties & reactions
MX2
MC2 X2
MO
Only berilium and magnesium Be2C
may be kept in the air safely. C O2
Rising the temperature in air S2
produces a bright crust on all P4
N2 MS
due to a mixture of oxide and M3P2
nitride formed on the surface.
At Be and Mg the oxide at the M3N2
surface creates a protective
shell which protects the metal to
be oxidized in depth.
Uses
Magnesium is far the most industrial used element as
precursor for obtaining of other less active metals as well
as alloying component. Beryllium follows it as importance
and the third comes Calcium.
Most important alloys are magnalium (Al main
component, 2%Mg, smaller amounts of Co, Ni, Pb),
duralumin (Al main component, 4.4%Cu, 1.4%Mg,
0.6%Mn) both for the car wheel bag, elektron (94-
95%Mg, small amounts of Al, Zn, Mn) incendiary
bombs, magnesium-zirconium alloys (Mg main
component, 3%Zn, 0-7%Zr) for aircraft parts.
Beryllium is a hard, mechanical resisting element, light,
with high melting point and corrosion resistant. It passes
these properties to their alloys. Bronzes of Be (Cu main
component, 2%Be, smaller amounts of Ni) are steel-like
properties but with some better improvements for
instance no sparks at hits, important property in
flammable environments.
Mg based alloys for structural components
Data N.-Am. Die Cast. Ass. A-3-10-06 standard
Mechanical properties Manufacturability RE Rare earths (50% Ce, 25% La, 15% Nd)
IS Impact strength (J)
Density Vehicle Safety
HD Hardness, Brinell hardness number
structural
Homogeneity component Cost YS Yield strength (MPa)
El Elongation (%)
Chemical resistance Working regime TE Thermal expansion (m/mK)
TC Thermal conductivity (W/mK)
Alloy of Mg AZ81 AZ91 AM60 AM50 AM20 AS41 AE42 AE44
Al 8 9 6 5 2 4 4 4
Additives (%)
Zn 0.7 0.7 6
Mn 0.2 0.2 0.3 0.4 0.6 0.4 0.3 0.4
Si 1
RE 2.5 4
Oth <0.07 <0.15 <0.35 <0.35 <0.25 <0.20 <0.30 <0.03
IS N/A 2.2 6.1 9.5 N/A 4.1 5.8 5.5
HD 72 75 62 57 47 75 57 56
Properties
Engine
Lift gate
Seat frame
Instrument panel
Transfer case
Mg alloys use reduces the weight with:
65% (replacing Fe alloy) for instrument panel & car seat frame;
40% (replacing Al alloy) for lift gate & steering column;
30% (replacing different other alloys) for wheel core, door inner & transfer case;
20-70% (replacing different other alloys) for engine.
Magnesium Oil and Sports Medicine
With magnesium oil, the concentrate can simply be
applied to the skin or poured into bath water, and in
an instant we have a powerful medical treatment.
http://magnesiumforlife.com/transdermal-
magnesium/magnesium-oil/
Beryllium uses
p1 p2 p3 p4 p5 p6
2 B C N O F Ne
3 Al Si P S Cl Ar
4 Ga Ge As Se Br Kr
5 In Sn Sb Te I Xe
6 Tl Pb Bi Po At Rn
- 2 1 2 2 2 3 2 4 2 5 2 6
e ns np ns np ns np ns np ns np ns np
N, P, As, Sb, Bi
Air
-60C
Black Violet
White Red
N, P chemical properties
Li3N
NO PX5
Li Nitrides
O2 M H2S + H3PO4
X2 PH3
H2SO4 H2
B CH4
BN N2 HCN + H2
- O2
P4
PH3 + PH2O2 NaOH P4 P4O6, P4O10
Si
H2 HNO3 Al
Si3N4 PN M
I
95pm 96pm
143pm 141pm
118pm 120pm
121pm
HNO3
NO2
H2SO4
toluene O 2N TNT
Ammonia & nitric acid chemical properties
NH4Cl + N2
2+
[Cu(NH 3)4] Cl2 N2 + H2O
Cu2+ O2
+ - HA O2
NH4 A NH 3 o
NO + H 2O
Pt; 1000 C CO2 + NO2
CuO Nitro-
Na cellulose C HIO3 + NO
Cellulose
Cu + N 2 + H2O NaNH 2 + H2 I2
H+
N2 + 3H2 Nitro- Glycerin Mg
glycerin HNO3 Mg(NO 3)2 + H2
(H2SO4)
MII
C6 H 6 Sn
(H2SO4)
C6H5-NO2 M(NO3)2 + NO
Sn(OH)4+ NO
Phosphorus oxyacids
3+
H3AsO3, Sb4O6, Bi As4O6, Sb4O6, Bi2O3
H3AsO5, Sb2O5,
MX3 MX5
O2
HNO3 M
-
AsO3- + H2 OH H2
M (As, Sb, Bi) H3As, H3Sb
Na +
S
H
Na3M M2S3
3+ 3+
H3AsO3, Sb , Bi
As, Sb, Bi - Toxicity
As, Sb and all their combinations including oxides and salts
are toxic. Bi is not toxic, but their compounds, with some
exceptions, are. Volatility of As and its compounds coupled
with the toxicity makes that As to be a very dangerous
element. As and their compounds may occurs as pollutants of
water and air. As in the case of Hg, As may be transformed
by bacteria in methyl-derivatives, even more toxic and
mobile:
Methyl-cobalt-amine = B12 vitamin
H3AsO4 + 2H+ + 2e- H3AsO3 + H2O
H3AsO3 + B12 CH3AsO(OH)2 methyl-arsenic acid
CH3AsO(OH)2 + B12 (CH3)2AsO(OH) di-methyl-arsenic acid
(CH3)2AsO(OH) + 4H+ + 4e- 2H2O + (CH3)2AsH - dimethylarsine
Sulfur allotropes
Over 30 (more than any other element)
A mixture of allotropes mainly contains S8 with small amounts of S6 & S7.
S6 S8 S7
S18
S12
Sulfur: chemical properties
SO2
SF6 H2S
F2 O 2 H2
Cl2 Si, C
S2Cl2 S SiS2, CS2
II
M P
I
M
MS P 4S 3
M2S
Sulfur biochemistry
Sulfur is an essential constituent, even in minor quantities, to
proteins, and amino-acids such as cysteine and methionine.
In both proteins and enzymes sulfurs is found as SS
bridges. Vitamin B1, coenzyme A and many other organics
contains S (for instance mustard and garlic). Sulfur based
fermentations made by some anaerobic microorganisms
which in their oxidation processes reduces the sulfates to
sulfides (SO42- to S2-) play an important role in formation of
oil reserves.
It exists bacteria which process sulfur as other process
oxygen and it survives to temperatures till 150C.
Sulfur-based living organisms
Riftia pachyptila
worm (till 2m long)
lives from 1Km to
10Km in ocean
deep, near black
smokers and is in
symbiosis with
Hyphomicrobium
sulfonivorans
dimethylsulfone (CH3)2SO2 CH3SH methanethiol
Assimilation of formaldehyde
NADH + H+
NAD+ + H2O 1 1 H2O + O2
H2O2
dimethylsulfoxide (CH3)2SO HCHO+ H2S
NADH + H+
NAD+ + H2O 1 CH3SO3H methanesulfonate
NADH + H+ + O2
dimethylsulfide (CH3)2S
NADH + H+ + O2 1 NAD+ + H2O
NAD+ + H2O 1 HCHO+ H2SO3
methanethiol CH3SH +HCHO
S, Se, Te - Uses
Sulfur has uses mainly as combinations. On large scale are produced
sulfuric acid (90% of sulfur involved in). About 60% from sulfuric acid is
for production of fertilizers. Sulfites, bisulfites and SO2 are used in large
quantities as bleach. Elemental S are used to obtain CS2 (precursor of
CCl4) and viscose fibers. An important application is on rubber
vulcanization. Other applications includes obtaining of fungicides,
pesticides and gunpowder (a mixture of KNO3 75%, C 15%, S
10%).
Selenium is used for glass discoloration (and a mixture of Cu, S & Se for
coloring the glass in red colors range). Applications include photocopy
machines, image capturing (thin film of Se on Al support) and photovoltaic
cells. Selenides are used for toning in photographies development.
Adding of Se in steels and alloys generally increases the resistance to
corrosion. In small quantities is a part of some enzymes. Large quantities
are toxic.
Tellurium is used as alloying element for steels and non-ferrous alloys
(with Cu, Ag, Pb) to color in blue the glasses, in photography
development as well as for rubber vulcanization.
Trophic chain, biomass & energy conversion
Others+ Na+ K+ Mg2+ Ca2+ NH4+ Si(OH)4 H2PO4- SO22- NO3- Others-
Soil
Halogens physical properties
Property F Cl Br I At
M.p., C -220 -101 -7 114
B.p., C -188 -35 59 183
Solubility, in water, at 20C - 0.09 0.21 0.002
Electronegativity (Pauling) 4 3 2.8 2.5 2.2
0 reduction potential, V 2.87 1.36 1.07 0.54 0.3
Dissociation energy, kJmol-1 157 244 193 15.1 116
Atomic radius, nm 6.4 9.9 11.1 21.8 -
Ionic radius, nm 13.3 18.1 19.6 -
H2 Au Mirrors
F F
107
105
Electronic/chemical energy
Temperature, K
magnetism
Electronic
101 Liquid 4He
Universe Superconductivity
Superfluid 4He
10-1
Superfluid 3He
10-3 magnetism
Nuclear
3
3
He
2
1
Superfluid phase "B" Gas
0
10-4 10-3 10-2 10-1 100 101 T[K]
Noble gases physical properties
http://www.lps.ens.fr/~caupin/fichiersPDF/PhysicaB_2003_3
29-333_380-381.pdf, Very fast growth and melting of 4He
crystals He (at 2.5 MPa ~10 atm.): -272.2 C (0.95 K)
d1-d5 block
Elements groups
3 (d1) 4 (d2) 5 (d3) 6 (d4) 7 (d5) 8 (d6) 9 (d7) 10 (d8) 11 (d9) 12 (d10)
21 22 23 24 25 26 27 28 29 30
4
Sc Ti V Cr Mn Fe Co Ni Cu Zn
39 40 41 42 43 44 45 46 47 48
5
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
57-71 72 73 74 75 76 77 78 79 80
6
La-Lu Hf Ta W Re Os Ir Pt Au Hg
89-103 104 105 106 107 108 109 110 111 112
7
Ac-Lr Rf Db Sg Bh Hs Mt Ds Rg Cn
57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Transition elements, period 4, oxidation state - rule?
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Electronic d1s2 d2s2 d3s2 d5s1 d5s2 d6s2 d7s2 d8s2 d10s1 d10s2
Structure
Oxidation I I
Numbers II II II II II II II II II II
III III III III III III III III III
IV IV IV IV IV IV IV
V V V V V
VI VI VI
VII
Fe(C5H5)2 Mo(CO)6
absorption
transmission
385 416 447 478 509 540 571 602 633 664 695 726
Colors of transition
3-
(MnO4) (aq) DarkBlue #00008B
Cu2+(aq) MediumBlue #0000CD
ions
2+
(VO) (aq) Blue #0000FF
(MnO4)2-(aq) DarkGreen #006400
Cr3+(aq) Teal #008080
The most important source CuCl22H2O DarkTurquoise #00CED1
Oh Td D4h
d(z2)
d(yz) d(xz)
d(yz) d(xy) d(xz) d(x2-y2) d(z2)
Interstitial compounds
Crystalline networks of transition elements are generally
compact and contain tetrahedral or octahedral gaps, where
can enter small volume nonmetallic atoms (H, B, C, N)
forming interstitial compounds, which are usually non-
stoechiometric (with variable composition). These
combinations - carbides, nitrides, borides - melts at very high
temperatures (TiC - 3140C, ZrC - 3430C, HfC - 3890C),
have very good hardness (8 to 10 on the Mohs scale) and
some are extremely inert to chemical attack. Because of
these properties have special technical applications (see
discussed refractory ceramics).
Scandium, Yttrium, Lutetium, Lawrencium
Scandium is apparently a much more
Chemical properties abundant element in the sun and certain stars
M2O3 than on earth. Scandium iodide, along with
sodium iodide, when added to a modified
form of mercury-vapor lamp, produces a form
of metal halide lamp. This lamp is a white light
O2 source with high color rendering index that
sufficiently resembles sunlight to allow good
Cl2 acid color-reproduction with TV cameras.
MCl3 M M3+ About 31 ppm of the Earth's crust is yttrium
(28th) - 400 times more common than silver.
N2 H2 Lunar rock samples collected during the
American Apollo Project have a relatively high
content of yttrium. Even if Yttrium has no
LaN MHx (LaH2,9) known biological role, tends to concentrate in
the liver, kidney, spleen, lungs, and bones of
humans. With up to 700 ppm, the seeds of
woody plants have the highest known
concentrations.
Lawrencium synthesis
Lutetium aluminium garnet (Al5Lu3O12) has
been proposed for use as a lens material in
98Cf + 5B 103Lr high refractive index immersion lithography.
Lutetium tantalate (LuTaO4) is the densest
known stable white material (9.81 g/cm3). The
only denser white material is thorium dioxide,
(10 g/cm3), but the thorium radioactive.
Titanium, Zirconium, Hafnium, Rutherfordium
Metals are very resistant to chemical agents
Chemical properties at moderate temperatures due to the
formation of a protective oxide layer on the
MO2 surface. At room temperature are not
attacked by acids or bases. Have the
property of absorbing gases (H2, O2, N2) are
MxHy O2 t MX4
X2 therefore used to produce advanced vacuum.
H2 Titanium has many uses: has the advantage
600 that it is stronger than steel, more light and
M
HF N2 with greater corrosion resistance, keeping its
t
C MN mechanical properties at high temperatures.
H2[MF6] Zirconium is used in the manufacture of
chemical equipment, and nuclear technology
MC because it absorbs neutrons.
Hafnium is used in the construction of
Rutherfordium synthesis nuclear reactors and nuclear submarines.
80% TiC and 20% HFC mixture is highly
98Cf + 6C 104Rf refractory (m.p. 4215 C). ZrO2+15%Y2O3
gives an intense white light and is used in
specialty lamps (Nernst lamps).
Titanium alloy with 6% Al and 4% V has good mechanical properties and
is used for gas tanks (H2, O2, F2) and missiles. The fortunate combination
of the basic characteristics of titanium finds in the aerospace industry its
applicability. 90% of current production of titanium is used in the
construction of supersonic aircrafts and spaceships.
Girder
Exhaust Frames
nozzle Piloting channel
Mother Russia gigantic statue
Memorial Park, Kiev, Ukraine
Is a gigantic titanium female figure -108
meters (40 m - pedestal & 68 m - figure),
to compare - Statue of Liberty in New York
has the size of 100 meters (65m + 35 m).
Sword was shortened after independence
in 1991.
Historians say this statue was initially
proposed to be built atop Mount
Poklonnaya in Moscow.
The construction of the statue made of
titanium in Kyiv turned out to be a
complicated task. Employees of the Kyiv-
based ProektStalKonstruktsiya R&D
Institute were interested in the experience
regarding the reconstruction of the Statue
of Liberty in New York.
Was completed on May 9, 1981. Soviet
leader Leonid Brezhnev paid a special
visit to Kyiv for the unveiling of the great
monument.
Vanadium, Niobium, Tantalum, Dubnium
Vanadium is used especially for
Ferrovanadium (Fe-V alloy) - for improved
Chemical properties
mechanical properties, increased hardness,
M2O5 corrosion and shock resistance. Vanadium
MF5 pentaoxide, V2O5, is a good catalyst for
MxHy oxidation reactions (such as for obtaining of
F2 O2
H2 H2SO4 - catalyst for oxidation of SO2 to SO3).
VCl4 Nb and Ta have high capacity for electron
Cl2 N2
NbCl5 V, Nb, Ta MxNy emission, and are able to absorb gases at
TaCl5 NaOH C hot. Alloys with Nb, Ta, and NbC are
top Br2, I2 thermoresistant, thermostable, hardly
MxCy attacked by acids, and mechanically
NaMO3, Na3VO4 superhard.
VX3, NbX4 Ta replaces Pt, Au, Ag and their alloys in the
construction of chemical apparatus resistant
Dubnium synthesis to concentrated acids or bases such as heat
exchangers, pumps, valves. Ta catalyses
98Cf + 7N 105Db making synthetic diamonds from graphite
(pressure ~ 1 GPa and temperatures of about
2200 C. Ta wires are used in surgery.
[V18O30]12+ cage, part of [V18O42]12- cage
[V18O42]12- properties (Spartan '10)
Chromium, Molybdenum, Tungsten, Seaborgium
Chemical properties
W possess highest elemental
Cr2O3, MO3 m.p. (3380 C).
CrX3,
MoX6, Cr2S3, MoS2, WS2 Cr dissolve in diluted acids (HCl,
X2 t, O2 H2SO4), while W is dissolved
WX6 t, S
C only in HF+HNO3 mixture
WC, W2C Se, Te MSe2, MTe2
M (eliminating NO in place of H2).
M = Mo, W
In HNO3 Cr are covered with a
CO NaOH + NaNO 3 protective layer of oxide.
molybdates, At normal temperature, Cr, Mo
M(CO)6 wolframates
and W are resistant to air and
moisture.
Seaborgium synthesis Cr reacts only at high
temperatures with non-metals:
98Cf + 8O 106Sg O2, X2, N2, S, B, C. Mo and W
reacts bit harder.
W is highly resistant to acids.
Cr-W-Co-C super hard high-speed tool steel
C Cr W Mo V Co Si Mn Fe
1.7-4.1% 3-10% 1-20% 1-15% 1-15% 15% 2% 1% remaining
Carbon 0.1C-Ceq0.6; Ceq=0.06Cr+0.033W+0.063Mo+0.2V
Molybdenum 18%W+2Mo40%
Steel (88%-98%) above mixture and (2-12%) G1, G2, or G3
G1 nitrides of M, M= Ti, V, Zr, Nb, Hf, Ta
G2 carbides of M, M= Ti, V, Zr, Nb, Hf, Ta
G3 carbonitrides of M, M= Ti, V, Zr, Nb, Hf, Ta
Hardness HRC71 (ASTM E18 & EN ISO 6508)
USPTO US4880461 (Norimasa UCHIDA, November 14, 1989)
Chromium - uses
Chromium is alloying element for special steels, giving better
mechanical properties and high corrosion resistance.
Alloys of Cr with Ni and Cu have uses in the manufacture of
thermocouples.
Electrolytic chromating is one of the most effective methods
of protecting metals against corrosion.
Dichromates (especially of sodium, cheaper) and chrome
alum is used in tanning (process of treating skins of animals)
and as a mordant (to fix the dyes) in dyeing.
Dichromates are used as oxidants in organic chemistry.
Some combinations of Cr have important uses as pigments,
producing beautiful and very stable colors.
Chromium pigments
O O O 2-
O O Cl
O Cr O Cr O Cr O
O Cr O Cl Cr
O Cr O O O O
O O n O Cl
O O O Cl O Cr
O Cr O KO Cr O Cr OK Cl Cr6H2O
Pb O O O Cl
O S
Mo
S
C N C
N C
C C
C
C C C
C
N N N O
O
Keggin structures
[AM12O40]n,
A = P5+, Si4+, B3+
M = Mo, W
The first Keggin anion,
(NH4)3[PMo12O40] (ammonium
phosphomolybdate), was first
reported by Berzelius in 1826.
J.F. Keggin with the use of X-
ray diffraction experimentally
determined the structure of
Keggin anions in 1934.
Keggin anions uses as
catalysts in hydration,
polymerization and oxidation.
Manganese, Technetium, Rhenium, Bohrium
MnO2
MnX2 Mn(OH)2
O2
Mn chemical properties
X2 H2O (Tc, Re similar) Bohrium synthesis
HX Mn C
97Np + 20Ca 107Bh
MnX2 N2 Si Mn3C
Mn3N2 Mn3Si
O.N. -3 -2 -1 0
Compound MnH3 MnH2 H[Mn(CO)5] (CO)5Mn-Mn(CO)5
Color White/Colorless White/Colorless White /Colorless
O.N. 0 +1 +2 +3
Compound Mn(OH2)6 Br[Mn(CO)5] MnCl2 MnF3
Color
O.N. +4 +5 +6 +7
Compound MnO2 K3MnO4 K2MnO4 KMnO4
Color
Manganese - uses
A supplement to
the gasoline
additive
tetraethyllead to
increase the fuel
octane rating
d6-d10 block
Iron, Ruthenium, Osmium, Hassium
Cobalt, Rhodium, Iridium, Meitnerium
Nickel, Palladium, Platinum, Darmstadtium
MC, M3C
MS, FeS2 C O2 MO, M2O3
S X2
MSi, MSi2, M2Si M MX2, FeX3, CoX3
Si B
M2P, MP2 P CO M2B, CoB, NiB
Mm(CO)n
N N
Fe
N N
0.75
f(x)=1/(1+1/2.5x) f(x)=1/(1+1/x2.9)
Myoglobin Hemoglobin
-Higher affinity for ligands 0.5 -Lower affinity for ligands
-Good for storage -Bad for storage
-Bad for transport -Good for transport
0.25
[L]=x
0 1
Hemoglobin oxygen binding
H + L HL k1 v1=k1[H][L] [H]=x; [HL]=y; [HL2]=z
HL + L HL2 k2 v2=k2[HL][L] k1=a; k2=b; [L]=c
H: d[H]/dt=-v1 d[H]=-k1[H][L]dt x& = acx
HL: d[HL]/dt=v1-v2 d[HL]=(k1[H][L]- k2[HL][L])dt y& = acx bcy
HL2: d[HL2]/dt=v2 d[HL2]=k2[HL][L]dt z& = bcy
Cases Initial Iterative [HL] 1 + [HL 2 ] 2
m=
#1: a=1<4=b x0=1; y0=0; z0=0; xn+1=xn-act [H ] + [HL] + [HL 2 ]
#2: a=1=1=b c=16 yn+1=yn+(acxn-bcyn)t y 1 + z n 2
#3: a=4>1=b t=0.01 zn+1=zn+bcynt mn = n
m: H saturation with L (simplified case, only 2 ligand sites) x n + yn + zn
m#1/m#2 > 1
1.5 positive
Pick-up
cooperative
binding (a<b)
Transport
m#2/m#2 = 1
1.0
non-cooperative
Release binding (a=b)
m#3/m#2 < 1
time (arbitrary units) negative
0.5 cooperative
0.00 0.05 0.10 0.15 0.20 0.25 binding (a>b)
Coenzyme F430 & B12 vitamin
NiC42N6O13H50 CoC63N14O14PH89
(C5H5)M(C5H5) IR spectra (cm-1)
1500 1000 0500 1500 1000 0500 1500 1000 0500 1500 1000 0500 1500 1000 0500
(C5H5)M(C5H5) - molecular modeling & UV-VIS
(C5H5)M(C5H5) properties (Spartan '10, DFT, RBLYP, 6-31G* + LANL2DZ>Kr, Vacuum)
Formula C5H5CrC5H5 C5H5FeC5H5 C5H5NiC5H5 C5H5RuC5H5 C5H5OsC5H5
Energy (a.u.) -1427 -1650 -1891 -481 -478
EHOMO (eV) -8.62 -3.68 -2.50 3.69 8.43
ELUMO (eV) 3.05 -0.86 -0.60 3.86 10.46
(nm) 106 440 653 7293 611
Absorbed light
Visible color
Dipole Moment (debye) 0.00 0.01 0.00 0.05 0.07
Pt. Group D5d D5 D5d D5d D5d
2
Area ( ) 192 180 198 196 195
3
Volume ( ) 171 170 173 174 174
Ovality (dimensionless) 1.29 1.21 1.32 1.30 1.29
Accessible Area (2) 140 133 156 259 283
min(ElPot) (kJ/mol) -118 -92 -143 -329 -460
min(LocIonPot) (kJ/mol) 48.5 34 17.4 2.6 7.1
3
Polarizability ( ) 52.5 54.5 55.0 55.5 55.0
Zero Point Energy (kJ/mol) 473 434 462 427 427
0
S (J/mol, 298.15K) 350.1 348.5 378.9 363.5 368.3
0 0
H , G (a.u., 298.15K) -1427 -1650 -1890 -481 -478
Cv (J/mol, 298.15K) 143.5 156.5 161.9 165.9 166.2
Ru, Rh, Pd, Os, Ir, Pt, Ag, Au - extraction
Finding the orebody and creating access to it
Breaking the orebody and harvesting the ore by mining
Transport the ore to the processing and refining site
Processing
Refractory ore treatment:
M2Sn + nO2 2M + nSO2
Solubilization (leaching):
M(s) + KCN(aq) + O2(air) + H2O K[M(CN)n+1](aq) + KOH
Concentrating:
Adsorption with carbon
C(s)-K[M(CN)n+1](s) K[M(CN)n+1](aq)
Re-solubilization (re-leaching)
Refining (>95%)
Reduction: Mn+(aq) + nH2(g) M(s) + 2nH+(aq)
Solubilization (with aqua regia 3HCl+1HNO3, excepting Ru, Os, Ir):
Ag(s) + M(s) + nH+ + HNO3 AgCl + Mn+ + NO2 + H2O
2Rh3+ + 6NaHSO4 Rh2(SO4)3 + 3Na2SO4 + 6H+
Ru + Os + 8Na2O2 + 2H2O Na2[RuO4(OH)2] + Na2[OsO4(OH)2] + 6Na2O
Iridium is the most corrosion-resistant metal known; Ir + F2 IrF6
Electrolytic refining (>99%)
Platinum Metals Reviews (http://platinummetalsreview.com)
journal (open access)
Patents, January 2012 (Issue 1)
Producing Iridium-Containing Catalysts
Ruthenium-Based Carbene Catalyst
Platinum-Palladium in Exhaust System
Palladium-Bismuth Catalyst
Hydrogen Production Apparatus
Osmium in a Series of Penetrator Rods
Ru, Rh,
Osmium(II) Arene Azo Anticancer Complexes
Palladium-Based Dental Alloy
Pd, Os,
Bridged Ring Metal Complexes for photoconversion
Patents, October 2012 (Issue 4)
Ir, Pt -
Carbon Supported Palladium Catalyst
Ruthenium-Carbene Complexes
uses
Manufacture of Vinyl Chloride
Saccharifi cation of Biomass Materials
Hydrogenation of Vegetable Oil
Lean-Burn Engine Oxidation Catalyst
Oxygen Evolution Catalyst
Os and Ru Analyte Sensor
Novel Platinum Nanoparticles
Manufacturing Osmium Membrane
Copper obtaining and use
Copper can be found as native or combined (as CuS2 - chalcocite,
CuFeS2 - chalcopyrite). Separating Cu from Fe is conducted with silica
(see the image).
Cu2+ are water-soluble, and serves at low concentration as
bacteriostatics, fungicides, and wood preservatives as well as is an
essential trace nutrient to all higher plant and animal life. At high
concentrations are poisonous to higher organisms. The main places
where copper is found in animals are liver, muscle and bone.
Applications of copper includes electrical wires - 60%, roofing and
plumbing (pipes) - 20%, and industrial machinery - 15%. When a higher
hardness is required then are alloyed (5% of total use) in brass and
bronze. A small part is used in production of nutritional supplements and
fungicides in agriculture.
O O O O
O Si O Si O + CuFeS2 + 2O 2 2SO 2 + Cu + O Si O Fe O Si O
O O O O
Copper acetate
adopts the "paddle-
wheel" structure
seen also for Rh(II)
and Cr(II)
tetraacetates.
The uses are as
catalyst or oxidizing
agent in organic
syntheses.
Polymer composite textures design
Cu-S-PNIPAM
Ag2-S-PNIPAM
Cu-S-PNIPAM-MAA
Ag2-S-PNIPAM-MAA
N Mg N 3 S Fe S
S Fe S
S Fe S
N
Fe, Cu, Mg Light to chemical energy
biological role
N N
6 N Fe N S Cu S
N N
Plastocyanin
Cytochrome f
Silver - uses
AgCdO is withstand arcing and is used in high-voltage
contacts. Small devices, such as hearing aids and watches,
use AgO batteries (long life & high energy-to-weight ratio).
Another usage is high-capacity Ag-Zn and Ag-Cd batteries.
By sputtering along with other optically transparent layers,
silver is applied to glass (layer of 10-15 nm thick), creating
low emissivity coatings used in high-performance insulated
glazing. Solar reflectors may use Ag as the reflective coating.
Ag readily absorbs free neutrons and is used to make control
rods regulating the fission chain reaction in nuclear reactors,
as an alloy (80% Ag, 15% In, 5% Cd).
Silver ions and silver compounds show a toxic effect on
some bacteria, viruses, algae and fungi, but without the high
toxicity to humans which gives a wide range of medical
applications.
Gold - uses
As gold is a good reflector of electromagnetic radiation such as infrared
and visible light as well as radio waves and can be manufactured so thin
that it appears transparent.
Therefore it is used in some aircraft cockpit windows for de-icing or anti-
icing by passing electricity through it, for the protective coatings on many
artificial satellites, in infrared protective faceplates in thermal protection
suits and astronauts helmets. Gold is used as the reflective layer on
some high-end CDs and automobiles may use gold for heat shielding
(such as in the engine compartment).
Some gold salts do have anti-inflammatory properties and are used as
pharmaceuticals in the treatment of arthritis and other similar conditions.
Gold based injections have been explored as a means to help to reduce
the pain and swelling of rheumatoid arthritis and tuberculosis.
Gold alloys are used in restorative dentistry, especially in tooth
restorations, such as crowns and permanent bridges. The gold alloys
slight malleability facilitates the creation of a superior molar mating
surface with other teeth and produces results that are generally more
satisfactory than those produced by the creation of porcelain crowns.
Zinc, Cadmium, Mercury, Copernicium
(M=Zn, Cd):
M + 2HX MX2 + H2
2M + O2 (tC) 2MO
Zn + NaOH + H2O Na2[Zn(OH)4] + H2
Hg:
3Hg + 8HNO3(conc) = 3Hg(NO3)2 + 2NO + 4H2O
Hg + 2H2SO4 = HgSO4 + SO2 + 2H2O
2Hg + O2 (0-400C) 2HgO
2HgO (t>400C) 2Hg + O2
Copernicium synthesis
Eagle
2
310 ppm
Pike
5100 ppm
Minnow
100 ppm
Plankton
510-2 ppm
Water
10-4 ppm
Chemical elements in human body
Rank % Elemental composition by mass
1 O 65 9.5 Cl 0.15 19 Br 2.9E-4 28 As 2.6E-5 37 Sb 1.1E-5
2 C 18 11 Mg 0.05 20 Pb 1.7E-4 29 Sn 2.4E-5 38 Li 3E-6
3 H 10 12 Fe 6.0E-3 21 Nb 1.6E-4 30.5 Se 1.9E-5 40 Co 2E-6
4 N 3 13 F 3.7E-3 22 Cu 1.0E-4 30.5 Hg 1.9E-5 40 Cr 2E-6
5 Ca 1.4 14 Zn 3.2E-3 23 Al 8.7E-5 32 Mn 1.7E-5 40 Cs 2E-6
6 P 1.1 15 Si 2.0E-3 24 Cd 7.2E-5 33 I 1.6E-5 42 Ag 1E-6
7.5 S 0.25 16 Zr 6.0E-4 25 B 6.9E-5 34 Ni 1.4E-5
7.5 K 0.25 17.5 Sr 4.6E-4 26 Ce 5.7E-5 35.5 Ti 1.3E-5
9.5 Na 0.15 17.5 Rb 4.6E-4 27 Ba 3.1E-5 35.5 Mo 1.3E-5
Rank % Elemental composition by atoms number
1 H 63 10 Cl 0.024 19 Al 1.5E-5 28 Ba 1.2E-6 37.5 Cr 9E-8
2 O 24 11 Mg 0.007 20 Cu 1.0E-5 29 I 8E-7 37.5 As 9E-8
3 C 12 12 Si 5.8E-3 21.5 Pb 4.5E-6 30 Sn 6E-7 37.5 Sb 9E-8
4 N 0.58 13 F 1.2E-3 21.5 Cd 4.5E-6 31 Ce 4E-7 40.5 Se 5E-8
5 Ca 0.24 14 Fe 6.7E-4 23 B 3.0E-6 33 Zr 3E-7 40.5 Mo 5E-8
6 P 0.14 15 Zn 3.1E-4 24 Nb 1.7E-6 33 Ti 3E-7 42 Ag 9E-9
7 S 0.038 16.5 Sr 3.3E-5 26 Ni 1.5E-6 33 Co 3E-7
8 Na 0.037 16.5 Rb 3.3E-5 26 Mn 1.5E-6 35 Cs 1E-7
9 K 0.033 18 Br 3.0E-5 26 Li 1.5E-6 37.5 Hg 9E-8
Metal containing enzymes
Enzymes\Element Ca Na K Mg Fe Zn Sr Rb Al Cu Pb Cd Nb Ni Mn
Hydrolases 2752 1265 231 1437 184 2451 9 9 0 30 7 99 0 148 429
Transferases 593 553 213 1762 9 896 6 0 0 11 7 59 0 59 368
Oxidoreductases 545 413 217 394 412 758 6 0 0 473 5 41 0 105 203
Lyases 168 348 108 498 27 747 1 1 0 8 2 10 0 23 121
Ligases 36 35 25 263 0 327 0 0 0 0 0 3 0 18 51
Isomerases 47 90 14 203 7 87 0 0 3 1 1 8 0 19 117
The Research Collaboratory for Structural Bioinformatics (RSCB), www.rcsb.org
Query on December 27, 2012
Ca
Na
Zn
Cd
Mn
Mg
Ni
Fe
Cu
Hydrolases
Oxidoreductases
Transferases
Isomerases
Lyases
Ligases
f block
Lanthanoids and actinoids - separating
Because almost perfect likeness of the chemical and
electrochemical properties, lanthanides and actinides
separation, one by one, pure, is very difficult. Earliest
attempts were based on separation by fractional
crystallization of double salts of nitrates, hydroxides or
decomposition of fractional oxalate - these processes were
long and about 20,000 operations required to obtain pure
samples from a single element. Today, the separation is
made easier due to the emergence of ion exchangers. Thus,
a column of cathion, RH, apply a solution consisting of a
mixture of salts of all lanthanides. Heavier ions are less bulky
stronger will be complexed by citrate ion and will spend a
period of time in solution and obviously, a shorter phase
resin. In other words, less bulky ions will migrate faster along
the column, coming first in the column.
Sample: mixture of lanthanoids and actinoids
Problems: Pressure control
Similar mass
Similar charge
Resin column
Sample
+
Eluent Temperature control
-
Separating
lanthanoids
and actinoids On-line spectra
analyzer with
separating control
Solution:
Process Eluent: Alcohol + HCl/HNO3 mixture
optimization Resin: alternate copolymer of phenylene and
substituted pyridine rings
Mass spectrometry
R C
S
P
E B
N
+
U
Applying an electric potential U can create a flow of positive ions to the negatively
charged electrode and a flow of electrons to positively charged electrode, the flow of
positive ions is passed through a region of magnetic field B and suffer deviations from
the straight path, the screen photosensitive C positive electrical charge carriers are
separated according to the ratio m/q where m is the mass and q is the charge of the
wearer. The method used to determine the quantitative composition of samples.
Mobile phase (eluent) optimization
HNO3:H2O:CH3OH 1:0:9 4:0:6 3:5:2
Lu Yb Tm Y Er Ho Dy Tb Gd Eu Sm Nd Pr Ce La
0.9
0.7
0.5
0.3
0.1
60 120 180 240 300 360 420 480 540 600 660
Lanthanoids chemical properties
LnX 3
Ln2S3 LnH 2
S2 X2
H2
N2 O2 Ln2O3
LnN Ln
(CeO2 - exc.)
H2O acizi-H +
CO2 La3+ + H2
Ln(OH) 3 + H2
Ln2(CO3)3 + H2
Las & Acs thermodynamic properties
Symbol La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Z 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
6s 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2
4f 0 1 3 4 5 6 7 7 9 10 11 12 13 14 14
5d 1 1 0 0 0 0 0 1 0 0 0 0 0 0 1
Radius CN=6 (pm) 103 101 99 98 97 96 95 94 92 91 90 89 88 87 86
Radius CN=8 (pm) 122 120 118 116 114 113 112 111 110 108 107 106 105 104 103
Hsub (kJ/mol) 431 420 357 327 318 207 177 398 389 290 301 312 232 156 428
Gsub (kJ/mol) 323 318 257 227 157 108 81 288 277 188 198 215 134 61 313
MM3+ (kJ/mol) 34563530363337013709387140363749 3802389938233934404541943887
Symbol U Np Pu Am Cm
Z 92 93 94 95 96
6s 2 2 2 2 2
4f 3 4 6 7 7
5d 1 1 0 0 1
Radius CN=6 (pm) 103 101 100 98 96
Radius CN=8 (pm) 116 114 112 111 109
Hsub (kJ/mol) 531 465 343 284 387
Gsub (kJ/mol) 425 358 237 178 281
3+
MM (kJ/mol) 36273702376938473774
Ln3+ 4fn ground level colour g [J(J+1)]1/2 obs
Ce 1 2F
5/2 colourless 2.54 2.3-2.5
Pr 2 3H
4 green 3.58 3.4-3.6
Nd 3 4I
9/2 lilc 3.62 3.5-3.6
Pm 4 5I
4 pink 2.68 -
Sm 5 6H
5/2 yellow 0.85 1.4-1.7
Eu 6 7F
0 pale pink 0 3.3-3.5
Gd 7 8S
7/2 colourless 7.94 7.9-8.0
Tb 8 7F
6 pale pink 9.72 9.5-9.8
Dy 9 6H
15/2 yellow 10.65 10.4-10.6
Ho 10 5I
8 yellow 10.6 10.4-10.7
Er 11 4I
15/2 rose-pink 9.58 9.4-9.6
Tm 12 3H
6 pale green 7.56 7.1-7.5
Yb 13 2F
7/2 colourless 4.54 4.3-4.9
Lu 14 1S
0 colourless 0 0
Lanthanides apps
Superconductors: LaO1-xFxFeAs become superconductor at
T ranging from 26K to 43K(at 4GPa); SmO1-xFxFeAs at 55K;
most of the discovered superconductors are copper-based;
Strong permanent magnets: SmCo5, ~150 kJ/m3 (maximum
energy density); Sm2Co17, ~160 kJ/m3; Nd2Fe14B, ~270
kJ/m3; comparing: SrFe, ~35 kJ/m3; AlNiCo HDD (812%
Al, 1526% Ni, 524% Co, up to 6% Cu, up to 1% Ti, Fe is
the rest) ~ 35 kJ/m3;
Optoelectronics: the incorporation of Eu3+ & Dy3+ ions to
heavy metal glass materials increases red & yellow/blue
luminescence;
Tunable microwave resonators: (x)A1/2Ln1/2TiO3(1-
x)NaNbO3 (A = Na, Li; Ln = La, Nd, Sm) tunable as
microwave resonators through changing the values of x;
X-ray screens, neutron detectors, alpha particle scintillators;
for X, n0, & detectors: Gd2O2S:Ln, Ln = Tb - green (peak
at 545 nm), Ln = Eu - red (627 nm), Ln = Pr - green (513
nm)
Rare-earth magnets
NdFeB strong permanent magnets
Nd2Fe14B Remanence Coercivity Intrinsic H BH max t max Comparison
(std) (Br, T) HcB (kA/m) HcJ (kA/m) kJ/m3 C Magnet kA/m T
N35 1.17-1.21 868 955 263-287 80 BaFe12O19 360 0.4
N38 1.21-1.25 899 955 287-310 80 Co10Fe7Ni4Ti2CuAl 50-150 0.6
N40 1.25-1.28 923 955 302-326 80 Fe50Ni10Al2Nb 50 1.2
N42 1.28-1.32 923 955 318-342 80 MnBi 370 0.5
N45 1.32-1.38 876 955 332-366 80 Ce(CuCo)5 450 0.7
N48 1.38-1.42 835 876 366-396 80 SmCo5 1000 0.8
N50 1.38-1.45 835 876 374-406 80 Sm2Co17 600 1.1
N52 1.44-1.48 836 876 390-422 80 Nd2Fe14B 1100 1.2
N35M 1.17-1.21 868 1114 263-287 100
N38M 1.21-1.25 899 1114 287-310 100
N40M 1.25-1.28 923 1114 302-326 100
N42M 1.28-1.32 963 1114 318-342 100
N45M 1.32-1.38 995 1114 332-366 100
N48M 1.37-1.42 1018 1114 358-390 100
N50M 1.40-1.45 1042 1114 374-406 100
N28AH 1.04-1.10 772 2786 207-231 220
N30AH 1.08-1.17 812 2786 223-255 220
N33AH 1.14-1.22 851 2786 247-279 220
N35AH 1.17-1.25 876 2786 263-295 220
Magnetic levitation apps
S EM S EM N EM N
N N S N S N S S
S N S N S N
S N S N S N
UH 3 UO 2
500oC
HF C2Cl4F2
H2O
UF 4 UF 4.nH2O (n=1,2,5)
F2 +Q
100oC
Al 900oC
UF 5 H2 F2
F2 ClF 3 UF 3
+Q
UF 6 Na3UF 6
3NaF
U extraction
In the dry process, uranium oxide concentrates are first
calcined (heated strongly) to drive off some impurities,
then agglomerated and crushed. For the wet process,
the concentrate is dissolved in HNO3. The resulting
solution of UO2(NO3)26H2O is fed into a countercurrent
solvent extraction process, using tributyl phosphate
dissolved in kerosene or dodecane. The uranium is
collected by the organic extractant, from which it can be
washed out by diluted HNO3 and then concentrated by
evaporation. The solution is then calcined in a fluidised
bed reactor to produce UO3.
Purified U3O8 from the dry process and UO3 from the wet
process are then reduced in a kiln by hydrogen to UO2:
U3O8 + 2H2 3UO2 + 2H2O & UO3 + H2 UO2 + H2O
This reduced oxide is then reacted in another kiln with
HF to UF4: UO2 + 4HF UF4 + 2H2O
The UF4 is then fed into a fluidised bed reactor or flame
tower with F2(g) to produce UF6: UF4 + F2 UF6
235U enrichment
UF6
Tanks
Heating
Steel
F
239
Pu + v
S
B
Cyclotron
Ca2+
B
~
f (Hz) Ca20+
+
U (V)
-
Fission & fusion
1 4 22 n+
0n 2He 10Ne 41 0 n
21 18
10Ne 8O
249 267
97Bk 107Bh
4
2He
2 1
1H 0n
240 236 3 4
94Pu 92U 1H 2He
Fission Fusion
Crystallography
In the growth of a crystal particles are arranged in rows and
orderly and symmetrical networks. The shortest distance
between corresponding points of an infinite sequence is
called shifting the shortest or fundamental translation. In the
crystal structure, it is the distance between atoms.
Strings, flat networks and three-dimensional networks are
considered infinite. In most crystals, the distance between
atoms is 3-5 and in only 1 mm3 volume is then about 1021
particles, which provides practical infinity assumption.
Considering a linear displacement of a point (source) until
observable and measurable properties of that point are again
the same (destination) get a basic translation. One of the
features of a basic shift is that it is the lowest point translation
that makes repeating properties. Constant movement is
usually marked with a.
Crystalline nets
Structure of halite (NaCl)
model scheme
Elementary cells
A pair of elementary translations nonparallel iteration
scheme defines homologous points in a plane. A 3-
necoplanar basic translation of the first 2 generates a
three-dimensional network of homologous points.
Constants of the 3 basic movements usually is denoted
a1, a2 and a3. Parallelepiped of elementary translations
(a1, a2, a3) form the basic cell, (a1, a2, a3) = (a, b, c).
Z
c
b
a Y
X
Chemical formula vs. crystal structure
Reds: (nx-1)(ny-1)(nz-1)
z
x Blacks: nxnynz
y Ratio: (1-nx-1)(1-ny-1)(1-nz-1) 1
Polyhedra Polyhedra count for given
number of vertices (or faces)
4 1 9 2606 14 1496225352
5 2 10 32300 15 23833988129
6 7 11 440564 16 387591510244
7 34 12 6384634 17 6415851530241
8 257 13 96262938 18 107854282197058
Polyhedra count for given number of edges
6 1 12 12 18 4199 24 5623571 30 10204782956
7 0 13 22 19 13384 25 19358410 31 36249143676
8 1 14 58 20 43708 26 67078828 32 129267865144
9 2 15 158 21 144810 27 233800162 33 462669746182
10 2 16 448 22 485704 28 819267086 34 1661652306539
11 4 17 1342 23 1645576 29 2884908430 35 5986979643542
4 5 6 7 8 9 10 11
4 1
5 11
edges = 6 12 2 2
vertices +
7 2 8 11 8 5
faces - 2
8 2 11 42 74 76 38
9 8 74 296 633 768
10 5 76 633 2635 6134
11 38 768 6134 25626
Polihedra (1)
Polihedra (2)
Polihedra (3)
Course 10
Boron group
Carbon group
p block
p1 p2 p3 p4 p5 p6
2 B C N O F Ne
3 Al Si P S Cl Ar
4 Ga Ge As Se Br Kr
5 In Sn Sb Te I Xe
6 Tl Pb Bi Po At Rn
- 2 1 2 2 2 3 2 4 2 5 2 6
e ns np ns np ns np ns np ns np ns np
Boron
Crystalline structure: a structure repeating a icosahedra
(12 vertices and 20 faces); 7 allotropic forms, binding
different the icosahedra;
Natural state: Clark: 510-3%. Its presence is essential to
plant growing; minerals: borax Na2B4O710H2O, kernite
Na2B4O74H2O, borocalcite CaB4O74H2O and colemanite
Ca2B6O115H2O
Obtaining: Na2B4O7 HClNaCl H3BO3 QH2O B2O3 MgMgO B -
a brown amorphous solid solution of boron and boron oxide
are obtained. High purity boron are obtained from electrolysis
of kalium tetrafluoroborate KBF4 or thermal decomposition of
diborane: B2H6 Q 2B + 3H2
Purification: procedure Van Arkel de Boer:
B + I2 Q BI3 Q B + I2
Aluminum
Crystalline structure: metal, hexagonal-compact;
Natural state: Clark: 7.45%; many minerals; bauxite,
AlO(OH) industrial way to obtain aluminum; corindon,
Al2O3 and its colored varieties (due to ions impurities): rubine
(Cr), saphire (Ti), topaz (Ni); hydrargilite Al(OH)3; spinel
MgAl2O4; criolite Na3[AlF6];
Obtaining electrolytic:
CO2
Graphite
CO2
Al2O3
ZrC
+
Al
Graphite 5V
Steel -
Obtaining of alumina (Al2O3)
Bauxite
NaOH H2O (grinded and calcined) Mud (Fe2O3, SiO2, TiO2)
AlX3
AlO2- + H2 or
[Al(OH)4(H2 O)2 ]- + H2 BX3
X2 Al2 O3
HBO2- + H2 B2O3
alkali O2
X2
HCl N2 alkali O2
AlCl3 + H2 Al AlN
HNO3 N2
Oxides S H3BO3 + NO B BN
C
Metals Al2S3 P4O10 S
(Aluminothermy)
C
Al4 C3
P4+B2O3 B2 S3
B4C
Boron and aluminum physical properties
Property B Al
I.P.(1), eV 8.30 5.95
I.P.(2), eV 25.15 18.82
I.P.(3), eV 37.92 28.44
0M3+/M (V) -0.73 -1.67
(g/cm3) 2.4 2.7
M.p. (C) 2300 660
B.p. (C) 2550 2500
Atomic radius (pm) 90 143
Covalent radius (pm) 843 1214
Van der Waals radius (pm) 192 184
Boron and aluminum - uses
Boron: uses as alloying element in steels (giving a
increasing of impact resistance); in alloys provide hardness
and corrosion resistance; metal borides have good
mechanical and chemical properties; in nuclear plants is
used to control fission neutrons energy;
Aluminum: after iron most used element; cheep, light,
corrosion resistant, keeps in time its properties, may be can
be drawn into sheets and wires, good thermal conductivity; at
relative to the density is the best electrical conductor;
From aluminum light and mechanical resistant alloys are
designed and used in constructions and vehicles. Have good
alloying properties with iron, silicium, magnesium, copper
and zinc.
Boron and aluminum complex combinations
Al Ga R
O O C O
CH (-) CH
B HC Al
CH O O CH N
O C O
R
Al/3 3
Boron likely provide tetra-covalent combinations; have a
series of di-hydroxyl and poly-hydroxyl combinations such as
glycerol or mannitol (6 -OH); Aluminum provides complexes
with -di-ketones;
Borazole B3N3H6 named inorganic benzene:
3LiBH4 + 3NH4Cl B3N3H6 + 3LiCl + 12H2
Boron nitride BN some of its allotropes possess
properties diamond-like;
Ga, In, Tl chemical properties
X2 Alloy X2
E2S3 EN Tl2O3
S NH3 M O2
Ga,In Tl
S
O2
H2SO4 H2SO4 Tl2S3
H2O
Tl2SO4
E2(SO4)3 E2O3
Ga, In, Tl physical properties
Property Ga In Tl
I.P.(1), eV 6.0 5.8 6.1
I.P.(2), eV 20.4 18.8 20.3
I.P.(3), eV 30.6 27.9 29.7
0M3+/M (V) -0.52 -0.34 0.72
0M+/M (V) - -0.25 -0.34
(g/cm3) 5.93 7.29 11.85
M.p. (C) 29.8 156 449
B.p. (C) 2070 2100 1390
Atomic radius (pm) 135 167 170
Covalent radius (pm) 1223 1425 1457
Van der Waals radius (pm) 187 193 196
Ga, In, Tl - uses
Galium: obtaining low-melting alloys used as electrical fuses.
Being non-toxic and melting down, it also serves as heat
transfer medium in nuclear industry heat exchangers as
liquid thermometers for high temperatures and as a means of
vacuum sealing technique. Also used to obtain compound
semiconductors GaAs and GaP.
Indium: have the property to reflect most of the visible
spectra very useful for mirrors in this range. Production of
alloys for bearings (self-lubricating eg, In-Pb), some power of
reflection mirrors (similar to Ag, but more resistant to
corrosion).
Talium: obtaining special bottles, increasing the refractive
index of the glass or the manufacture of catalysts.
Group 13. Chemical bonds
Group 13 gives compounds
with covalent bonds MX3 (M X X
= B, Al, ) which are
deficient in electrons are M X M X
not quite stable and
stabilization occurs through X X
electrons transfer from inside
or outside of the molecule. If
the electrons comes from X X
atoms of same type, it results
dimers or polymers; if comes M X M X
from atoms of other type then
donor-acceptor compounds X X
are obtained and have Td or
Oh symmetry.
Coordinative compounds and dimers
H
H F
H B H
H N B F
H B H
H F
H
Br Cl
Br Ga Br Cl Al Cl
Br Ga Br Cl Al Cl
Br Cl
Group 14. Physical properties
O O O
O O
C C O C
O O
O O O C O
O
C O O
O O O O
C C C C
O O O O O O O
Boron Carbide is one of the hardest materials known,
ranking third behind diamond and boron nitride. It is the
hardest material produced in tonnage quantities. It has no
clear repetitive structure. It have a ratio Boron:Carbon
varying from 23:2 to 19:6. Below are given two possible
arrangements in which a part of boron atoms are replaced
by carbon atoms.
B:C B:C
12:0 18:0
11:1 16:2
10:2 14:4
Boron nitride
Hexagonal form is a good lubricant
Cubic close-packed form is thermal and Hexagonal
chemical stable; hardness inferior only
to diamond
Hexagonal close-packed has never
been synthesized but is likely to be
harder than the cubic close-packed form
Quartz
Glass
6
4, 6
4, 6, 10
Zeolites
5, 8 4, 8 4, 6, 12
Zeolites formation
Si4O8 NaAlSi3O8H2O
Zeolites have the ability to act as
Zeolites uses
catalysts for chemical reactions which
take place within the internal cavities. An
important class of reactions is that
catalysed by hydrogen-exchanged
zeolites, whose framework-bound protons
give rise to very high acidity. This is
exploited in many organic reactions,
including crude oil cracking, isomerisation
and fuel synthesis.
Polystyrene sulfonate
Zeolites can also serve as
oxidation or reduction O
catalysts, often after S O
-
K+
metals have been O
introduced into the O
framework. Examples are S O
-
the use of titanium ZSM-5
O Ca2+
in the production of O
caprolactam, and copper -
S O
zeolites in NOx
decomposition. O
Silica copolymerization
(C,H,N,O,S,P)
O Si O + 3H (C,H,N,O,S,P)
HO Si (C,H,N,O,S,P) + OH2
(C,H,N,O,S,P)
Silica powder Organics
Organic-silica compounds Water
(SiO2) (possibly polymer)
(C,H,N,O,S,P)
O Si O Si O + OH2
2O Si O + 2H (C,H,N,O,S,P)
(C,H,N,O,S,P)
Organic-silica compounds contains Si-C bonds. In well controlled conditions,
are obtained cyclosiloxanes (rings with 3-6 Si atoms, which oxidants used
in waterproofing of buildings, cars, and shoes).
Silicones are compounds with special properties, well valuable in technique
and include silicone oil, grease, rubber, resin, and caulk.
Comparing it with organic polymers the silicones have better thermal
stability it can be used in warm environments. It have chemical inertia
resisting to oxidation, to water and wide range of chemical agents.
CH3 CH3 CH3 Silicones O Si CH3 CH3
CH3 Si O Si O Si CH3 CH3 Si O Si O Si CH3
CH3 CH3 CH3 O Si CH3 CH3
n CH3 CH3 n
(H3C)3SiO Si O Si O Si(CH3)3
CH3 C20H61
a b
With 20n500 & C/Si>2 are silicone oils. Apps include lubricants,
dielectrics, hydraulic liquids. See for instance US Patent no. 8355209 /
Jan. 15, 2013.
With 900n2000 & C/Si>2 are silicone greases, used as lubricants too.
See for instance US Patent no. 8017684 / Sept. 13, 2011.
With 6000n60000 & C/Si~2 are silicone rubbers. See for instance US
Patent no. 8344067 B2 / Jan. 1, 2013.
With C/Si<2 are silicone resins (bakelite-like). See for instance US
Patent no. 8334022 / Dec. 18, 2012.
Copolymers with about 1% long organic chains are silicone caulks. See
for instance US Patent no. 5783719 / Jul. 21, 1998.
Ge, Sn, Pb chemical properties
Organic chemistry
Hardness & hard materials
Alkanes Gauche g-
General structure
R H
Functional group
+
None
Example
CH3CH2CH2CH3
Name
n-Butane +
n-Butane isomers Anti
Rotamers:
"Gauche g-"
"Gauche g+"
Conformer:
"Anti" +
Gauche g+
Alkanes structural formula isomers
n = 1; CH4 1 (CH4)
n=2; C2H6 1 (CH3-CH3)
n=3; C3H8 1 (CH3-CH2-CH3)
n=4; C4H10 2 (butane (3 geometry isomers) & 2-methyl-propane)
n=5; C5H12 3
n=6; C6H14 5
n=7; C7H16 9
n=8; C8H18 18
n=9; C9H20 35
OH O
OV(CH3COCH2COCH3)2
Carboxylic acids General structure: R-COOH Functional group: COOH
Example: HCOOH Remarks: Formic acid occurs naturally, most notably
Name: Formic acid in the venom of bee and ant stings.
Example: CH3COOH Remarks: Acetic acid is the main component of
Name: Acetic acid vinegar.
Example: HOOCCOOH Remarks: It is used as a mordant in dyeing processes,
Name: Oxalic acid and in bleaches, especially for pulpwood.
Example: C4H6O6 OH OH
Name: Tartaric acid
HOOC CH2 CH2 COOH
Found in grapes, bananas
Example: C6H8O7 COOH
Name: Citric acid
HOOC CH2 C CH2 COOH
Found in lemons, oranges,
limes OH
Example: C9H8O4
COOH
Name: Acetylsalicylic acid
Aspirin is used in the treatment O C CH3
of a number of conditions, O
including fever, pain, and
inflammatory diseases
Anhydrides General structure: R(CO)O(CO)R' Functional group: OC-O-CO
Example: (CH3CO)2O; Ac2O, Ac=(CH3CO) Name: Acetic anhydride
Remarks: Is a widely used reagent in organic synthesis.
HO O HO O
O OH
OH + O O +O
O
O
Salicylic acid Ac2O Acetylsalicylic acid HAc
Example: C4H2O3 and its dimmer Name: Maleic anhydride
O O O O Remarks: cyclobutane
tetracarboxylic dianhydride
(maleic anhydride dimer) is
O ;2 O O O used in the production of
polyimides and as an alignment
O O O O film for liquid crystal displays.
Poly- Remarks: Anhydride bonds in aromatic polyanhydrides are water-labile - the
anhydrides polymer chain breaks apart at different reaction rates at the anhydride bond.
Resulted carboxylic acid groups are easily metabolized and therefore
biocompatible. Applications include releasing of physically entrapped or
encapsulated drugs by well-defined kinetics.
Esters General structure: R(COO)R' Functional group: COO
Remarks: Naturally occurring fats and oils are the fatty acid esters.
Example: EtOAc; Et=CH2CH3; Ac=CH3CO Name: Ethyl acetate
Remarks: Ethyl acetate, with a characteristic sweet smell (like pear drops) and
is used in glues, and decaffeinating tea and coffee (is manufactured for use as a
solvent). Ethyl acetate is the most common ester in wine.
Inorganic General structure: compounds derived from the condensation of
esters RCOOH and R'OH. Examples:
Li
O O O O
B
O O O
O O
O P O Apps include Li ion cell batteries with
O high temperature stability (until 302C),
It is used as a plasticizer and a fire high power density, and long shelf life as
retardant. well as super-capacitors.
See http://www.arl.army.mil/www/pages/556/0933TFSPurifiedLiBOB.pdf
Amides General structure: R(CO)NR'R'' Functional group: OCN
Remarks: Amides are used in nature and technology as structural materials.
O CH3 Example: (CH3)2NCHO Name: Dimethylformamide; DMF
Remarks: DMF is a solvent with low evaporation rate; is used
HC N
in the production of acrylic fibers and plastics and as a solvent
CH3 in peptide coupling for pharmaceuticals, in the development
and production of pesticides, and in the manufacture of
O
adhesives, synthetic leathers, fibers, films, and surface coatings.
H2N C Example: Remarks: Acrylamide is used to
H2C CH (H2CCH)(CO)NH2 synthesize polyacrylamides
Name: Acrylamide; Remarks: One of the properties of
O Acrylic amide polyacrylamide is to flocculate solids
Example: in a liquid and find its uses in
H2N C wastewater treatment, papermaking,
polyacrylamide
H2C CH pesticides, cosmetics, sugar
n manufacturing, and soil conditioning.
Nitriles General structure: RCN Functional group: CN
Example: H3CCN Name: acetonitrile
Acetonitrile is used mainly as solvent for purification of butadiene in refineries.
Example: (CH3)2CHCN Name: Isobutyronitrile
It is used as organic solvent, for producing insecticides, and as gasoline additive.
H3C O Example: C5H5NO2 Example: C5H5NO2 H5C2 O
Name: Methyl cyanoacrylate Name: Ethyl cyanoacrylate
O C O C
(MCA) (ECA)
H2C C Remarks: MCA and ECA are colorless liquids with low H2C C
N C viscosity, being used as the main component of certain N C
glues. Both polymerizes rapidly in presence of moisture.
Example: NCCCCN Name: Dicyanoacetylene
Dicyanoacetylene is liquid which can explode to carbon
powder and nitrogen gas. It burns in oxygen with a bright
blue-white flame at a temperature of 5000 C - hottest
flame of any chemical.
Amines
General structure: R3N Functional group: N
Example: H2NCH3 Example: HN(CH3)2 Example: N(CH3)3
Name: Methylamine Name: Dimethylamine Name: Trimethylamine
Methylamines are gases with strong odor similar to fish; are used as
building blocks for the synthesis of many compounds.
Example: (C6H5)3N
Name: Triphenylamine
Remarks: Triphenylamine derivatives have
useful applications in electric conductivity and
N electroluminescence, and they are used in
organic light-emitting diodes.
Triphenylamine derivative for solar cells
N N
Cyclodextrins Sugar molecules bound together in a ring.
d
Sclerometer - a mineralogist's (usually) instrument used to
measure the hardness of materials. The instrument is designed
to determine the degree of hardness of a given mineral by
applying pressure on a moving diamond point until a "scratch"
has occurred.
Hardness with scleroscope (intender)
Knoop Vickers Brinell Rockwell
136 D
140
136
17230'
130
[F]=N; [D] = [] = mm
F
H K = 0.01423 2
F
H V = 0.001854 2 H B =
2F
D
(D D2 2 ) F {600, 1000, 1500}
1 H R = 100 182
Hardness scales
Brinell BS EN ISO 6506 Parts 1, 2, 3, and 4: 2005,
Metallic materials - Brinell hardness test
Knoop ISO 4545 Parts 1, 2, 3, and 4: 2005, Metallic
materials - Knoop hardness test
Rockwell BS EN ISO 6508 Parts 1, 2, and 3: 2005,
Metallic materials - Rockwell hardness test (scales A, B,
C, D, E, F, G, H, K, N, T)
Vickers BS EN ISO 6507 Parts 1, 2, and 3: 2005,
Metallic materials - Vickers hardness test
Mohs A scale to measure hardness was devised by
Austrian mineralogist Frederick (Friedrich) Mohs in 1822
Barcol ASTM D2583-95 e1:2001, Standard Test Method
for Indentation Hardness of Rigid Plastics by Means of a
Barcol Impressor
http://courses.washington.edu/me354a/chap5.pdf
Ultra-hard advanced materials -CN
In 1989, Marvin Cohen and his graduate student Amy
Liu (then at UC Berkeley) devised a theoretical model to
predict a crystal's stiffness. Cohen's model clearly
indicated that a carbon nitride crystal should be stiffer
(and possibly harder) than diamond. The race was on to
obtain the stuff in crystalline form and measure its
properties. Some early efforts by the team of Yip-Wah
Chung (Northwestern University) resulted in a layered
composite of titanium nitride and carbon nitride (a so-
called superlattice) which was, surprisingly, almost as
hard as diamond. Estimates from proposed molecular
structure indicate the hardness of beta carbon nitride
should also be greater than diamond. This material has
not yet been successfully synthesized.
Ultra-hard advanced materials - CC
In the December 4th,
2005 issue of The
Jerusalem Post,
Professors Eli Altus,
Harold Basch and
Shmaryahu Hoz, with
doctoral student Lior
Itzhaki report the
discovery of Polyyne,
a material 40 times
harder than diamond.
It is a superhard
molecular rod,
comprised of acetylene
units.
Ultra-hard advanced materials
centered faces cubes crystallized C60
C60-Fullerene at 153 K, C60
crystallizes in a face
centered cubic
arrangement -
H-B Burgi, E Blanc, D
Schwarzenbach,
Shengzhong Liu, Ying-jie
Lu, M M Kappes, J A
Ibers, Angew Chem Int Ed
Engl 1992;31:640
Ultrahard fullerite
Ultra-hard advanced materials - ADNRs
Synthetic diamond (Lonsdaelite allotrope) obtained by
submitting to 2400K and 5-7 GPa crystals synthesized by a
chemical vapor deposition (CVD) process was found to be at
least 50% harder than natural diamond.
Ultrahard fullerite (C60) were found to be harder than
diamond, and which can be used to create even harder
materials, such as aggregated diamond nanorods.
Aggregated diamond nanorods, or ADNRs, are an
allotrope of carbon believed to be the least compressible
material known to humankind, as measured by its isothermal
bulk modulus; aggregated diamond nanorods have a
modulus of 491 gigapascals (GPa), while a conventional
diamond has a modulus of 442 GPa (hardness 1.11 times
than diamond). ADNRs are also 0.3% denser than regular
diamond. The process to produce the substance consists in
compressing the C-60 molecules to 2-20 GPa, and heating
to 300-2500 K. ADNRs is a series of interconnected diamond
nanorods, with diameters of between 5 and 20 nanometres
and lengths of around 1 micrometre each.
Hardness relativity
C allotrope Hardness (GPa)
CCP Diamond 1003; 1675
HCP Diamond 1524
Ultrahard fullerite 29030
ADNRs 31040
wurtzite-BC2N 792
BC2N (with same arrangement of CCP as diamond) possess an anisotropy
due to the non-uniform charge distribution (B have 3 valence electrons and
N have 5). Consequently, this leads to electrostatic effects at surface much
higher than of diamond with other materials like iron, nickel and even silicon
in a tribological environment. This seems to be a plausible reason why
BC2N was found as an efficient cutting tip to machine ferrous alloys and
silicon in comparison to a diamond tip. Same explanation should be given
for the unexpected polyyne hardness compared with diamond.
Fullerene, nanotube & nanofoam
Number of fullerenes
n Fullerenes n Fullerenes
<20 0 34 6
20 1 36 15
22 0 38 17
24 1 40 40
26 1 42 45
28 2 44 89
30 3 46 116
32 6 48 199
2n A007894 (http://oeis.org/A007894)
Nanocages
Course 12
Ceramics
Semiconductors
Superconductors
Ceramics types
Structural (for constructions)
bricks, pipes, floor and roof tiles
Refractories
kiln linings, gas fire radiants, steel and
glass making crucibles
Whitewares
tableware, cookware, wall tiles, pottery
products and sanitary ware
Technical (engineering, advanced, special)
tiles used in the Space Shuttle program,
gas burner nozzles, ballistic protection,
nuclear fuel uranium oxide pellets,
biomedical implants, coatings of jet
engine turbine blades, ceramic disk
brake, missile nose cones
Technical ceramics
Oxides
alumina, beryllia, ceria,
zirconia
Nonoxides
carbide, boride, nitride,
silicide
Composite materials
particulate reinforced,
fiber reinforced,
combinations of oxides
and nonoxides
BeO: Formation of BeO from beryllium and oxygen releases the highest
energy per mass of reactants for any chemical reaction, close to 24Mj/kg.
Technical ceramics for apps
Lock
Al balls
Lock
HV conductor
Ceramics with special electric properties
Electrical breakdown voltage (in volts per millimeter of
thickness) is an important factor in high stress conditions,
where ceramics loss is irreversible; the values of these
voltages ranges from 100 V/mm to 200 V/mm;
Volume resistivity (, expressed in cm), at different
temperatures; most ceramics have about 1014 cm at room
temperature; this value decreases with increasing
temperature; at 900C falls in 103-107 cm range;
Dielectric constant ' (the ratio of the capacity of a
condenser which has insulating material the ceramics and
the capacity of the condenser having air); ' for ceramics are
from 4 to 10, but rutile (TiO2) have 100;
The temperature coefficient of ', d'/dT;
The frequency coefficient of ', d'/d;
Loss factor '' (the energy lost in ergs per cubic centimeter
per cycle of oscillation) is important for high frequency uses;
BaTiO3: Dielectric constant ' and loss factor ''
Excepting the peak at 190C (see figure) have relatively low loss factor.
Ferroelectrics
These materials joins good dielectric constants with low electrical loss
factors.
For example, if a ferroelectric material is placed between the plates of a
capacitor, and electric field strength increases resulting charge will not
be proportional as in simple dielectrics (behaves hysteresis cycles).
Most ferroelectric materials are with perovskite-like structure.
Elementary cell contains 3O2-, 1M2+ and 1Ti4+. R is usually Ba2+ (Ca2+,
Mg2+, Sr2+, Rb2+, Cd2+ can be added to provide a wide range of
ferroelectric properties).
E
0
P polarization
E electric field
Ferromagnets
All ferromagnetic materials possess an irreversible
relationship between the applied field H and magnetization
induced B. This causes hysteresis, revealed to all magnetic
materials: the crystals that are formed in these magnetic
materials contain entities (quantum elementary units of
volume). When is not magnetized, the magnetic fields is
random. When is partially magnetized, there are some
alignment, but by no means all. But when it is saturated
magnetic, all fields are aligned.
It is used for surface magnetic disk drives (diskettes, hard
disks). For example, floppy drives 3.5 "and 1.44 MB must be
applied magnetic field of 300 Oersted to achieve a correct
writing. It is therefore the saturation magnetic field.
Overcoming this field is also prohibited, as it affected
neighboring areas on which there is writing field.
Magnetic memories
-HC
B(T)
0
HC
-BR
-BS
Magnetic hysteresis - explanation
This diagram is represented with applied field (H) on the abscissa and
induced magnetization (B) on the ordinate. From the point of no magnetic
conditions (0) relationship between H and B evolves as S-shaped curve
(with an inflection point) to the point of maximum magnetic intensity
applied HS, the induced magnetization is +BS. If now applied field
decreases, the magnetization evolves curves 2, 3 and 4 intersect ordered
in BR (remanent magnetization) abscissa in -HC (field strength
cancellation of residual magnetization) and if continuous -HS
magnetization to magnetization will then -BS. Reapply now increasing
magnetic field will cause the magnetization to evolve curves 5, 6 and 7,
with the same meaning for point -BR, +HC and +BS. Even if it stops
applying the magnetic field for a long time curve from 0 to +BS will not
ever be followed ceramic material unless it is previously demagnetized.
This can be done for example by heating above the Curie temperature.
The second quadrant, or demagnetization curve is very important for
materials used in the manufacture of permanent magnets.
Curie temperature: the temperature at which a material loses its magnetic
properties
Ferrites
These lightweight magnetic materials have a spinel structure:
MFe2O4 where M can be Mg, Ni, Co, Cd, Zn or Mn. Antenna
wires are used, magnetostrictive materials, memory cores,
components of deflection cathode-ray tubes and
transformers.
Must have both good physical and electrical properties and
these properties should be uniform both mass component
and from one component to another. These ceramic
magnets are valuable in high-frequency transformer cores
due to a very low hysteresis losses. Special ferrites with
square-shaped hysteresis as shown, are used as memory
elements in high-speed computers.
Computer memories: hysteresis loop and
structural elementary cells
H (A/m)
Mn
Zn
Fe
B(T)
0 O
N S
Radioceramics
Were manufactured several types of ceramic able to deliver
streams of high frequency radio waves with minimal
distortion. The materials used are alumina, corrindonite and
sintered glass of silicon oxide. It is essential that the porosity,
if any, should be evenly distributed and therefore have very
low tolerances surface. A problem that arises here is the
large size required for these ceramic bodies.
50 22 16 8 4
SiO2 M2O M2O3 MO Other
%wt
Typical
%at
composition
for a
radioceramic
Li Na K Rb Cs B Al Y Mg Ca Sr
18 26 33 12 11 32 58 10 56 13 31
Piezoelectics, pyroelectrics and ferroelectrics
476% KNbO3 I (A) R()
0.060.04% LiNbO3
0.060.035% SrTiO3
0.0030.002% BiFeO3
F (N)
526% NaNbO3
Piezoelectric: 100-200 pC/N
Piezoelectric
I (A) R()
Pyroelectric
Ferroelectric t (C)
U(V)
Conductor ceramics
Some of the most guarded secrets of Corning Glass Co. was the tinning
materials for the oxide electrodes used in kinescope tubes. Production
patents were issued in the United States on this issue: 1952 (SnO2, 0.5-
5% As, Bi, Sn, firing at 1400 C, = 2cm-3) 1963 (+0.5-5% V2O5, firing
at 1300-1500 C, = 1cm-3), 1966 (+0.1-0.5% CuO, ZnO 0.5-1%, 0.3-
1.2% SnO2, = 1cm-3). Even so, problems contact terminals is
always a problem. Magnesium titanate (MgTiO4) is used for resistors
requiring high currents and stability.
U (V)
Air Exhaust
ZrO2 sensor
used to monitor
automobile O2 O2
exhaust gases.
ZrO2 membrane
Termistors
Large positive temperature A thermistor is a type of
coefficient thermistors finds resistor whose resistance
many applications in varies significantly with
thermostats and thermal temperature, more so than in
switches. Barium titanate standard resistors.
doped with a rare metal used Resistance
in the manufacture of fine
Negative temperature coefficient thermistor
granules which are then
sintered in ceramic. For this, Positive temperature coefficient thermistor
lanthanum is folost in
Resistance temperature detectors
quantities of 0.001 to 0.005
Thermocouples
molar percent. Barium titanate
can be precipitated, then Resistors
mixed with rare metal and
heated in a controlled Temperature
atmosphere at 1400 C.
Heating ceramics
Nonmetal electric heating elements consist of silicon carbide
and molybdenum oxides. Rod-shaped or spiral tube CSi
elements are widely used for electrical heating at high
temperatures. They can be used at temperatures of 1600 C
for short periods and 1500 C under continuous working.
MoSi2O6 heating elements can be used at temperatures of
100 C - 200 C above the limit of SiC elements and are
used for elements exposed to high temperatures in furnaces.
Heating elements as oxides of zirconium and thorium
become conductors when are heated to red. Furnaces built
with these elements are capable of temperatures of 2000 C
in air.
U(V)
Refractory ceramics
A refractory material is one that Compound Density (g/cm3) Melting (C)
retains its strength at high HfC 12.8 3900
temperatures. TaC 14.5 3800
Ultra high temperature ceramics ZrC 6.6 3400
are good choices for several HfN 13.9 3385
extreme applications: thermal HfB2 11.2 3380
protection materials on hypersonic
aerospace vehicles or re-usable ZrB2 6.1 3245
atmospheric re-entry vehicles, TiB2 4.5 3225
specific components for TiC 4.9 3100
propulsion, furnace elements, TaB2 12.5 3040
refractory crucibles, etc. This ZrN 7.3 2950
family of ceramic compounds is TiN 5.4 2950
made of borides, carbides, and TaN 14.3 2700
nitrides such as ZrB2, HfB2, ZrC,
HfC, TaC, HfN which are SiC 3.2 2545*
characterized by high melting * dissociates
points.
Solid state electronic bands
1
(1)
(a)
Conduction band
1 2
(2)
(b) Forbidden band
1 2 3 Valence band
(3)
(c)
1 2 3 4
(4)
(d)
Conduction band
Overlapping
Valence band
()
(e)
E Semiconductor
Anti-bond
band
Bond
band
Isolator Conductor
Conductors vs. semiconductors and isolators
Populating the allowed bands with electrons in solids
E E E E
T = 0K T = 0K T > 0K T > 0K
Conductor Isolator Conductor Isolator
Ge-Si alloy forbidden band
0 20 Si(%) 100
1.2
1.0
0.7
100 80 Ge(%) 0
Doped semiconductors
Ge Ge Ge Ge
As Ga
Ge Ge Ge Ge
E E E E
a 1 / T
, a >1 cT 3 , c < 1
arbitrary units
bT, b < 1
0
0 1 2
The Meissner effect
N S N S
S EM S EM N EM N
N N S N S N S S
S N S N S N
Void
N2 He
In T(K)I(kA)
50 0.4
Ag (Cu) 4.2 2.8
Hg Hg
Hg Ba Ba
Ba Cu Cu
Cu Ca Ca
O HgBa2CuO4+ O HgBa2CaCu2O6+ O HgBa2Ca2Cu3O8+
Course 13
Advanced materials
Polymers & plastics
Reactions & mechanisms
Biomolecules
Advanced materials
Materials: :Applications
ZnO Bionic Superhydrophobic Surfaces
WO3 Organic Light-Emitting Diodes
Fe3Al Thin-Film Transistors
Copper Sulfide Superconductors
Barium Titanate Liquid Crystals
Protein Particles Solar Cells
Peptide Nanorings
Carbon Nanotubes
Magnesium Diboride
Fullerene Nanoparticles Example from the content
of Adv Mater 2006;18(6)
Hybrid (organic-inorganic) solar
"p" cells "n"
Semiconductors
Antireflective layer
Electrical
wires grids
Si O H + HO Si Si O Si + H2O
Natural sources of polymers
Latex is a natural polymer of isoprene.
Typically, a small percentage (up to 5% of dry ONO 2
mass) of other materials, such as proteins,
n fatty acids, resins and inorganic materials
(salts) are found in natural rubber. Discovered O
in 1736. Rubber - latex vulcanization (thermal O
treatment with sulfur) discovered in 1839.
Guncotton. Obtained nitrating cellulose
through exposure to nitric acid. Discovered in O 2NO ONO 2
n
1832. Precursor of celluloid ("plasticized"
with camphor, in 1880).
Galalith (Plastic buttons from shirts) is a
synthetic plastic material manufactured by the
interaction of casein (about 80% of the
proteins in cow milk) and formaldehyde.
Discovered in 1897.
Bakelite. Formed from an elimination reaction
of phenol with formaldehyde. Discovered in
O 1907. OH
Polylactide. Derived from cornstarch, tapioca n
O
n roots, or sugarcane. Discovered in 1932.
Biopolymers
Cellulose is the most Different plants Drying time
common biopolymer. 1.0
About 33% of plant
dry matter is 0.8
OH
cellulose.
Cotton contains 90% 0.6
cellulose while wood O
about 50%. 0.4
O water/total ratio
0.2
HO OH cellulose/total ratio
n
Peptide (20AA): Ala- AA Formula AA Formula AA Formula
Arg-Asn-Asp-Cys- His C6H9N3O2 Cys C3H7NO2S Asn C4H8N2O3
Glu-Gln-Gly-His-Ile- Ile C6H13NO2 Gln C5H10N2O3 Asp C4H7NO4
Leu-Lys-Met-Phe- Leu C6H13NO2 Pyl C12H21N3O3 Glu C5H9NO4
Pro-Ser-Thr-Trp-Tyr- Lys C6H14N2O2 Orn C5H12N2O2 Gly C2H5NO2
Val
Met C5H11NO2S Pro C5H9NO2 Aib C4H9NO2
DNA strain:
Phe C9H11NO2 Sec C3H7NO2Se Cit C6H13N3O3
(A=Ala; C=Cys;
G=Gly; T=Thr) Thr C4H9NO3 Ser C3H7NO3 Dha C3H5NO2
CTTTTCATT Trp C11H12N2O2 Tau C2H7NO3S Gaba C4H9NO2
CTGACTGCA Val C5H11NO2 Tyr C9H11NO3 Hcy C4H9NO2S
ACGGGCAAT Arg C6H14N4O2 Ala C3H7NO2 Hyp C5H9NO3
Synthetic polymers (1/2)
Monomer, polymer & its uses
Polyacrylonitrile. NC C6H5 Polystyrene.
Ultra filtration Disposable cutlery,
membranes, hollow H 2C CH H2 C CH housings; flow if heated
fibers for reverse Polypropylene. Poly-1-butene. above 100C, behavior
osmosis, fibers for Packaging and labeling, Pressure piping, exploited for plastic
textiles, oxidized reusable containers, flexible packaging, models, molding, and
flame retardant fibers laboratory equipment, water heaters, hot melt extrusion
H3C textiles, banknotes adhesives C2H5
H C CH Cl HO
2 H C CH
2
Polyvinyl chloride. H2C CH H2C CH Polyvinyl alcohol. Hard
Pipes for residential Polyacrylic acid. Polyvinyl acetate. contact lens solution as
sewerage and water Disposable diapers and Component of widely lubricant
supply systems for to thicken, disperse, used glue type (wood
HOOC suspend and emulsify glue, white glue, H3COC O
pharmaceuticals and carpenter's glue, school
H2C CH cosmetics glue) H2C CH
Synthetic polymers (2/2)
Monomer, polymer & its uses
Polyoxymethylene. CH2 O CH2 CH2 Polyethylene.
Precision parts that Packaging (plastic
Polytetrafluoroethy Polydimethylsiloxane.
require high stiffness, bag, plastic films,
lene. Teflon; water Silicones; inert, non-toxic
low friction and membranes,
and water-containing and non-flammable;
excellent dimensional containers
substances do not contact lenses, medical
stability including bottles)
wet it; very low devices, elastomers;
F F CH3
friction coefficient present in shampoos
C C against any solid (makes hair shiny and Si O
slippery), lubricating oils,
F F CH3
and heat-resistant tiles
Poly(methyl H3COOC HC CH Polybutadiene.
methacrylate). Synthetic rubber
Lightweight and H2 C CH H 2 C CH for automobile tires
shatter-resistant H3C
alternative to glass
Nylon 6. Bristles for toothbrushes, surgical sutures, strings for
H2C C4H8 acoustic and classical musical instruments (guitars, sitars, violins,
violas, and cellos), threads, ropes, filaments, nets, tire cords, and
HN OC hosiery and knitted garments
Polymers apps
Rheological fluids - suspensions of non-conducting particles
in an electrically insulating fluid at which viscosity changes
reversibly by an order of up to 100,000 in response to an
electric field. Apps: flexible electronics (rollable screens and
keypads), shock absorbers (bulletproof vests).
Thermoplasts - pliable or moldable above a specific
temperature, and reversible return to solid state upon
cooling. Apps: gluings, plugging holes in asphalt and walls
Elastomers transverse elasticity modulus does not change
appreciably and has values in the range 1..10 daN/cm2.
Apps: rubbers, flexible control devices, seals, adhesives and
molded flexible parts
Duroplasts elasticity modulus does not change
appreciably and has values over 100 daN/cm2. Being light,
flexible, and strong are recommended for apps exploiting
these qualities.
Plastic materials
Polymers are mixed with auxiliary materials in order to obtain plastics:
plasticisers: minimize polymer intramolecular forces of attraction which
add irreversibly changes the physical properties of polymers;
stabilizers: mitigate or eliminate reactions that cause degradation;
packing materials (such as dust, threads, fibers, paper, textiles) - modify
certain physicochemical properties;
reinforcement materials - fillers that increase resistance;
dyes - organic and inorganic pigments;
lubricants - is applied on surfaces to facilitate separation of plastics and
metals;
antistatic substances - prevent accumulation of electrostatic charges;
flame retardants - increase the fire resistance;
fungistatic agents - increase resistance to the action of microorganisms
on auxiliary materials;
blowing agents - to obtain porous plastics;
odorization agents - to cover the inadequate smell due to chemical
constitution, auxiliaries or oxidation processes;
Reaction types and conservation laws
Type Reaction Example
Rearranging AB cyclopropane propene
Combustion CaHbNcOd + (a+ /4- /2)O2 (a)CO2 + (b/2)H2O + (c/2)N2
b d
5 0.3
9 .e 1
0.2
0.1
0 0
0 5 10 15 20 25
0 t 25
1. Writing of elementary reactions; writing of reaction rates equations
mechanism
n=5105 r=1
z0 = 0 pi+1 = pi+(k3yi-k4pi) k3=5
7. Excel sheet:
A B C D E F G
1 x0= 1 i xi yi pi
2 y0= 1 =0 =B1 =B2 =B3
3 p0= 0 =D2+1 =D2*(1+(B$5*B$4 =E2*(1+(B$6*D2- = F2+(B$7*E2
-B$6*E2)*B$9) B$7)*B$9) -B$8*F2)*B$9
4 r= 2
5 k1= 3
6 k2= 4
7 k3= 5
8 k4= 3
9 = 1e-4
8. Plots:
x y p
3.5 2.5
3 2
2.5
2
1.5 y=y(x)
1.5 1
1
0.5
0.5
0 0
0 5000 10000 15000 20000 25000 30000 35000 0 0.5 1 1.5 2 2.5
Remarks: the y=y(x) equation is almost impossible to be extracted analitically, but we may extract
it aproximately (numerically). Thus, for the simulated mechanism above, the y=y(x) equation is:
(x-1.32)2+0.824(y-1.57)2 = 0.350.05
1. Writing of elementary reactions and of reaction rates equations ([R]=r, [X]=x, [Y]=y, [P]=p):
R X, v(1) = k1r X + 2Y 3Y, v(2) = k2xy2 Y P, v(3) = k3y
2. Applying of atoms conservation principle (unknowns [X] = x; [Y] = y):
(X): x& = v(1) - v(2) = k1r - k2xy2 (Y): y& = (2) - (3) = k2xy2 - k3y (P): p& = k 3 y
3. Approach (simplifying r = 1, k1 = 1 and k3 = 1):
x& = 1-k2xy2 y& = k2xy2-y
4. Solving numerically (i=1..n): Case 1 Case 2
Brusselator
k2 = 0.88 xn+1 = xn+(1-k2xnyn2) =10-2 x0 = 1.5 x0 = 2
yn+1 = yn+(k2xnyn2-yn) n=10000 y0 = 2 y0 = 2.5
5. Excel sheet:
A B C D E F G H
0
0 0.5 1 1.5 2 2.5 3
2.5 2.5
2 2
1.5 1.5
1 1
0.5 0.5
0 0
0 1000 2000 3000 4000 5000 0 1000 2000 3000 4000 5000
8. Simulation analysis
Not for any values the attractor appears. For a given k2 (such is 0.88) exists minimum values of x0
and y0 (x0-min, y0-min) from which periodical oscillations occurs and the system tends to the attractor.
1. Writing of elementary reactions and of reaction rates equations ([X]=x, and idem for the rest of):
A+YX X+YP A + X 2X + Z 2X Q ZY
v(1) = k1ay v(2) = k2xy v(3) = k3ax v(4) = k4x2 v(5) = k5z
2. Applying of atoms conservation principle (unknowns [X] = x; [Y] = y, [Z] = z):
(X): x& = k1ay k 2 xy + k 3ax 2k 4 x 2 (Y): y& = k1ay k 2 xy + k 5 z (Z): z& = k 3ax k 5 z
3. Solving numerically (i=1..n, after a long series of substitutions and rescaling):
xn+1 = xn+(qyn-xnyn+xn(1-xn))/ x0=0.2
= 8e-3 q=2e-3 =1e-3
Oregonator yn+1 = yn+(-qyn-xnyn+fzn)/
4. Excel sheet:
zn+1 = zn+(xn-yn)
y0=1
z0=0.3
=1e-1 f=1 n=19800
mechanism A B C D
1 q= 8e-3 i
2 = 1e-1 =0
xi
=B6
E
yi
=B7
F
zi
=B8
F
100
10
1
0.6
0 5000 10000 15000 20000
0.1
0.8
1
log10y 1 0.01
0
1.2
log10z
log10x 0
0.001
1 1
1.4
2
Cells functions
Signaling
Mutation
Enzyme action
Translucent isolator
Air
Tank
Nutrients
Acquisition, storage, retrieval of
sensor's data
Sensor1: Global Sensor2: Diffuse Intranet switch Clients Internet switch Clients
Acquisition Server Storage Server Retrieval Server
IP: 172.27.211.4 IP1: 172.27.211.1 IP: 193.226.7.203
Acquisition software IP2: 193.226.7.211 MySQL client
MySQL client MySQL server Web server
ADC *Co Ethernet Ethernet1 Ethernet2 Ethernet
S1 S2 Intranet Internet
p=nRT/V
T
Chemical separation methods
pH=0.5;
HCl(dil) KOH NH3 + NH4Cl H2S
H2S (exs)
Pp: CoS,
MnS, ZnS,
Pp: Bi2S3, Sol: SbS2-, Sb(OH)4-, NiS, Fe2S3,
Sol: Mg2+, Pp: Hg2Cl2, HgS, PbS, HgS2-, AsO2-, AsS2-, Al(OH)3,
Na+, K+ AgCl, PbCl2 CuS, CdS Sn(OH)62-, SnS32- Cr(OH)3
H2O; NH4Cl; (NH4)2CO3 CH3COOH
Pp: BaCO3, SrCO3, CaCO3, MgCO3
H2S schema
NMR
R
S RF Out
EM A
RF D
RF In RF In
d(Na,O) = 27546 pm
d(K,O) = 2704 pm
NaCl aqueous solution
H2O
- + - +
HO Na Cl H
Electrolysis in water
Element F O Cl H Li Na
Electronegativity 3.98 3.44 3.16 2.20 0.98 0.93
Electrode Reaction -U+
Cathode (-): ox + ne- red H2 Cl2
Anode (+): red - ne- ox
Reactions & potentials V
2Li+ +2e- 2Li(s) -3.04
2F- F2(g) + 2e- -2.87
2Na+ +2e- 2Na(s) -2.71
2H2O H2O2 + 2H+ + 2e- -1.78
HO- 1/2O2(g) + H+ + 2e- -1.73
2Cl- Cl2(g) + 2e- -1.36
H2O 1/2O2(g) + 2H+ + 2e- -1.23
2H2O + 2e- H2(g) + 2HO- -0.83
H2O2 O2(g) + 2H+ + 2e- -0.70
2HO- 1/2O2(g) + H2O + 2e- -0.40 Na+, Li+ H+, Cl-, HO-, O2-, F- (aq)
2H+ + 2e- H2(g) -0.00
Linear regressions
Linear( x , y )
400
C12
C30
300 C11
C20
200 C8
C7 C10
100
C4 C9
0 C3 C6
0 50
C5 100 150 200 250
-100
C2 -H_F
-200
C1
Image from: Studia Universitatis Babe-Bolyai. Series Chemia LV(4):61-68.
URL: http://studia.ubbcluj.ro/download/pdf/581.pdf
Plants photosystem II
PA
C7 C6
PN C5 PF C5
C3 C1 C2
C8
PE PH
C3 PJ C3 C3
PK C8
C8
C3 C3
C3 C3 C3
PI C3 PZ
PV C3 C3 PL
C3 C3 PU C3 PB C3
C3 C3 C3 C3
C3 C3 C6
C3 PX C3 C3 PM PT
C3 PC C3 C4
C3
C8 C3 C3 C8 C4 PO C3
C3 C3 C3 C8 C3
C8
C1
PD
PAPX: different proteins C3: chlorophyll A C5: haem like C8: -carotene
http://www.ncbi.nlm.nih.gov/Structure/mmdb/mmdbsrv.cgi?Dopt=s&uid=26605
Chlorophylls - natural solar cells
Chlorophylls are small molecules containing a Magnesium
atom responsible for conversion of the solar energy into
chemical energy and represent the engine of any vegetal
living organism. A in-vitro approach of molecular design was
conducted on the series of six chlorophylls in order to relate
the chemical properties with their natural occurrence.
By combining many reports
on chlorophylls, we may Chlorophyll ChemSpider ID Occurrence
conclude that their a 16736115 universal
b 16739843 many plants
occurrence is not equal, and
d 16736116 cyanobacteria
this diversity may be arisen f 2763140 cyanobacteria
from a long evolution and c1 391649 different algae
adaptation process. Table c2 17229531 different algae
gives a guess about the
occurrence of chlorophylls.
Chlorophylls
molecular
models
A B D
C2 C1 F
Chlorophylls molecular analysis
Method: Extract from PM3 structure models the Molecular
Orbitals calculate energies of electronic transitions
(OMO-UMO)
Analysis: Relate occurrence with e-
density(HOMO)*Entropy(UMO)
Results: showed that the in-vitro molecular orbital states of
chlorophylls are in good agreement with the observed
natural occurrences of chlorophylls
Observed HOMO Estimated
Occurrence HUMO occurrence Observations
Probability to be different from the mean of
a universal 1.84 **** {1.54, 1.38, 1.21, 1.33, 1.38} is over 99.9%
Probability to be different from the mean of
b many plants 1.54 *** {1.38, 1.21, 1.33, 1.38} is over 99.4%
d cyanobacteria 1.38 ** Probability to be different one to each other
c1 different algae 1.33 ** is less than 22%
c2 different algae 1.38 **
Probability to be different from the mean of
f cyanobacteria 1.21 * {1.84, 1.54, 1.38, 1.33, 1.38} is over 96.1%
Polarity vs. polarizability
Polarity is separation of electric charge leading to an electric
dipole or multipole and its moment in the molecule.
Polarizability is measure the change in electron distribution
in response to an applied electric field.
Dipole
Permanent: independent of the environment
Induced: when one molecule with a permanent dipole
induces a dipole in other molecule
Dipole moment: the product of magnitude of charge on a
molecule and the distance between two charges of equal
magnitude with opposite sign.
The electronic polarizability is the ratio of the induced dipole
moment of an atom to the electric field that produces this
dipole moment (DM/E).
Polarity & polarizability: two series of molecules
H2 LiH BeH2
BH3 CH4
NH3 OH2 FH
HF LiF BeF2
BF3 CF4
NF3 OF2 F2
40
35
30
25
20
Polarity & 15
polarizability: 10
5
values 0
H2 LiH BeH2 BH3 CH4 NH3 OH2 HF
HF LiF BeF2 BF3 CF4 NF3 OF2 F2
0
5
10
15
20
25
30 Isotropic Anisotropic Polarity
Polarizability Polarizability Dipole moment
35
(10-30 m3) (10-30 m3) (10-30 Cm)
40
London dispersion forces
Molecules without dipole and
without exterior polarization
field still interact due to the
nonsymmetrical charge
distribution surrounding the
nucleus. The forces keeping
together the atoms are called
London dispersion forces.
Only for Helium (1s2 2s2)
these forces are so small, that
liquid helium surrounds all
surfaces of the vessel in
which are kept.
Bibliography