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"One of the most significant achievements in science”

The Chemical Elements

Trieste May, 16, 2019

Periodic Table of the Elements affixed on the building of the University of Murcia (Spain) The composition

78.04 % Nitrogen Ocean 70 % Continents 30 % 20.94 % (weight) Crust 2.5 % 0-100 0.93 % 46.6 % Oxygen Air km 4.0 10-2 % dioxide 27.7 % 8.1 % Aluminum Lithosphere (0 to -100 km) 181.4 10-5 % Helium Mantle 20-200°C (15 tectonic plates) -5 5.0 % Iron 2900 km 52.4 10 % Neon Asthenosphere (-100 to -400 km) -5 3.6 % 11.4 10 % Krypton (84 % (Molten rocks) 2.8 % , volume) 2.6 % Potassium Alumino (-700 to -2900 km) 2.1 % silicates Viscous liquid High convection area 200 to 4000°C Earth radius 35% Iron 6378 km 30% Oxygen Outer core 15% Silicon Core 2200 km 13% Magnesium 3450 km 5000°C 02% Liquid 02% Iron Nickel Inner core 01% Calcium 1250 km 01% Aluminum 5000°C 01% Others Solid Tectonic plates: North American, Caribbean, South American, Scotia, Antarctic, Eurasian, Arabian, African, Indian, Philippine, Australian, Pacific, Juan de Fuca, Cocos, Nazca Chemical elements Chemical elements in human life Chemical elements in human life

Pactol river (, Cresus) Art (Jewelry) Construction

Gold coin Lydia Industry 550 BC Silicon 27.7 % Aluminum 8.1 % Energy Iron 5.0 % Gold 3.1×10-7%

Tutankhamun’s iron dagger 1340 BC Anteros Piccadilly Circus (1892) Head (1816) of 'antiquarian’ collections of the future National Museum of Denmark (Copenhagen).

3.400.000 BC 8700-2000 BC 3000 BC 1200 BC 1200 BC 50 BC 9 Elements

(1) Identification & extraction of , (2) Separation of the or its from the , (3) Invention of chemical reactions 2 Fe2O3 + 3 C -> 4 Fe + 3 CO2 (4) Invention of the concept of “” to 300 AC 1300 AC 1600 AC 1820 AC 1960 AC produce bronze (Cu + Sn), 9 Elements (5) Mastering fire, (6) Mastering ceramic art, (7) Mastering molding, (8) Mastering the metal ( to hammer, bend, and cut), (a) Mastering economic exchanges, 1945 AC (b) Invention of the “recycling” concept. 118 Elements The of elements: Comments , Atomic Symbol, Name; 22, Ti, ; 61, Pm, Promethium; 100, Fm, ; 23, V, ; 62, Sm, Samarium; 101, Md, Mendelevium; 24, Cr, ; 63, Eu, Europium; 102, No, Nobelium; 25, Mn, ; 64, Gd Gadolinium; 103, Lr, Lawrencium; 26, Fe, Iron; 65, Tb, Terbium; 104, Rf, Rutherfordium; 27, Co, ; 66, Dy, Dysprosium; 105, Db, Dubnium; 28, Ni, Nickel; 67, Ho, Holmium; 106, Sg, Seaborgium; 29, Cu, ; 68, Er, Erbium; 107, Bh, Bohrium; 30, Zn, ; 69, Tm, Thulium; 108, Hs, ; 31, Ga, Gallium; 70, Yb, Ytterbium; 109, Mt, ; 32, Ge, Germanium; 71, Lu, Lutetium; 110 ,Ds, Darmstadtium; 33, As, ; 72, Hf ; 111, Rg, Roentgenium; 34, Se, Selenium; 73, Ta, ; 112, Cn, Copernicium; 35, Br, Bromine; 74, W, ; 113, Nh, Nihonium; 36, Kr, Krypton; 75, Re, Rhenium; 114, Fl, Flerovium; 37, Rb, ; 76, Os, ; 115, Mc, Moscovium; 38 Sr, Strontium; 77, Ir, Iridium; 116, Lv, Livermorium; 39, Y, ; 78, Pt, ; 117, Ts, Tennessine; 118, Og, Oganesson, 1, H, ; 40, Zr, Zirconium; 79, Au, Gold; 2, He, Helium; 41, Nb, ; 80, Hg, ; 3, Li, ; 42, Mo, ; 81, Tl, Thallium; 4, Be, ; 43, Tc, ; 82, Pb, ; 5, B, Boron; 44, Ru, ; 83, Bi, Bismuth; 6, C, Carbon; 45, Rh, Rhodium; 84, Po, Polonium; 7, N, Nitrogen; 46, Pd, Palladium; 85, At, Astatine; 8 O Oxygen; 47, Ag, Silver; 86, Rn, Radon; 9, F, ; 48, Cd, Cadmium; 87, Fr, Francium; 10, Ne, Neon; 49, In, Indium; 88, Ra, Radium; 11, Na, Sodium; 50, Sn, ; 89, Ac, Actinium; 12, Mg, Magnesium; 51, Sb, Antimony; 90, Th,239 Thorium4 ; 13, Al,242 Aluminum1 ; 52, Te, Explosion of a 94 Pu + 2He 96 Cm + 0 n (162 days) ; 91, Pa, Protactinium; 14, Si, Silicon; 53, I, ; 92, U, ; 15, P, ; 54, Xe, Xenon; 93, Np, ; 16, S, Sulfur; 55 Cs Cesium; 94, Pu, Plutonium; 17, Cl ; 56 Ba Barium; 95 Am Americium; 18 Ar Argon; 57, La, Lanthanum; 96, Cm, Curium; 19, K, Potassium; 58, Ce, ; 97, Bk, Berkelium; 20, Ca, Calcium; 59, Pr, ; 98, Cf, Californium; 21, Sc, .118 elements Organization of chemical elements in 2019

Name Symbol Atomic number Atomic weight/ Periodic system Periodic table

LowerP e r i o d Groups

Higher

Original vertical version of the periodic system in original handwriting and in print from D. Mendeleev (1869) Chemical elements and elemental substances

Carbon Carbon allotropes : Refers to: • A collection of chemical substances composed of one or several that possesses the same number 11-Carbon Lesedi la Rona 222.2 g of protons in their atomic nucleus. (Elementary Substance)

12-Carbon • Collection of atoms present in chemical substances (elementary substances, chemical compounds and allotropes) that possess each 13-Carbon the same number of protons C-60 Fullurene in their atomic nucleus.

14-Carbon AlCl Li 4 H H C SbF6 C CholesterolC C H H H Nanotube

Hydrocarbons Elements

Theophrastus Philippus Aureolus Bombastus von Honenheim

9 Elements known Chemical elements 1661-1869

Elements are the indecomposable constituents of materials and are 1661, R. Boyle 13 Elements including S, Hg composed of particles of different sorts and sizes, Sceptical Chymist Earth, air, fire, water + salts Boyle made the distinction between compounds and mixtures, and was the first disclose the term “Analysis” to detect ingredients.

1789, A. Lavoisier 28 Elements All substances which we have not yet been able by any means Traité élementaire de Chimie Light + caloric to decompose

Atomic weight as a useful characterization of a chemical 1808, J. Dalton 45 Elements element

Properties of elements periodically related to their atomic 1869, D. Mendeleev 65 Elements weights, organized in a periodic system. Predict the existence of some unknown elements. Known chemical elements prehistory-2019

+28 98/118

+17 +15 +12 +16 33/118 114/118 58/118

70/118

+4 118 +1 +1 +2 16/118 Pure wrought iron13/118 pillar 14/118 Tour Eiffel (400 AC, New Dehli (1889, Paris) 1400 1500 1600 1700 1800 1900 2000 (7x0.42 m, 6000 Kg) (125x324 m, 7300x103 Kg) Known chemical elements prehistory

Prehistory

Stibine ”Khol” (Louvre) Sb2S3 Known chemical elements in 1661 (Alchemists)

Prehistory Alchemy Known chemical elements in 1789

Prehistory Alchemy Lavoisier Known chemical elements in 1808

Prehistory Alchemy Lavoisier Dalton Prehistory Alchemy Lavoisier Dalton Mendeleev

Mw 44 Mw 68 Mw 72

Mw 98

Periodic table of Elements 1869 Chemical elements in the 1800’s

Organize some elements by three in a 1817, J. W. Dobereiner (Triads) and predicts the atomic weight of the middle one from the others

Organize some elements by three in groups in a 1817, L. Gmelin “Y” arrangement related to their atomic weight

He was the first to propose a periodicity of elements 1862, A.-E. Béguyer de Chancourtois arranged in order of their atomic weights.

Organize the 56 elements known (no more) according to their increasing atomic weight using its octave rule 1863, J. Newlands in which every eight element possess similar properties to that of the first

Organized according to the valence then to the 1864-1869 J. Lothar Meyer atomic weight of elements Dobreiner triads

Organize some elements by three in a group (Triads) and predicts the atomic weight of the middle one from the others. Gmelin system Atomic number Z and the chemical elements

A. van den Broek proposed that atomic charge is Proposed the concept of atomic number leading the determining character of an element. He was the modern form of the periodic table. Paved the instigator of the work of G. J. Moseley. the way for the discovery of seven new elements unknown in 1914.

1911, van den Broek Moseley discovered that X-rays characteristic of each element present in a solid are emitted when this solid is hit by high-energy . Moseley law states that the square of the frequency of the emitted X-ray is proportional to He found that atomic charge is the determining the atomic number of the element character of an element and therefore that 1913, G. J. Moseley elements can be organized according to their atomic numbers.

Isotopes are variants of a particular chemical element Discovered isotopes which differ in neutron number, and consequently in nucleon number. 1913, F. Soddy 89 Elements Prehistory Alchemy Lavoisier Dalton Mendeleev Moseley

Periodic table of Elements 1913 Natural-/synthetic-/radiaoactive-isotopes

Natural 1896, 339 natural Natural H. Becquerel 253 primordial stable nuclides radioactive Radioactivity 33 radioactive natural nuclides Very unstable Synthesis of chemical elements

Synthesized the first unnatural element (curium) Proposed that actinides fill an f-sub-level as and 9 other including plutonium and more than lanthanides instead in the d-block row unnatural isotopes using Berkley cyclotron built by Was the last one to involve a change at the E. McMillan. periodic table 1945, G. Seaborg 95 Elements

New Zealand stamp honoring the first transmutation 1896, H. Becquerel German stamp honoring Otto Hahn for described by the New-Zealander Rutherford Discovery of radioactivity discovering nuclear fission Prehistory Alchemy Lavoisier Dalton Mendeleev Moseley 2019

Periodic table of Elements 2017 Mono-isotopic natural chemical elements Polyisotopic natural chemical elements

339 natural nuclides + 29 synthetic radionuclides 253 primordial stable nuclides 33 radioactive natural nuclides

3000 synthetic nuclides F. Soddy 1913 Carbon isotopes (15)

Synthetic Natural Natural Natural/ cosmogenic

Carbon-11 Carbon-12 Carbon-13 Carbon-14 5 neutrons 6 neutrons 7 neutrons 8 neutrons 6 protons 6 protons 6 protons 6 protons 6 electrons 6 electrons 6 electrons 6 electrons 14 14 1 11 11 4 12 13 14 1 14 1 N + p C + He + n C + p 7 1 6 C 6 2 6 C 6 C 7 N 0 6 6 C 1

t1/2: 20 min. Stable (98.9 %) Stable (1.1 %) t1/2: 5730 years Positron emission NMR Radio-tracer tomography Spectroscopy Radio-dating Messages from the periodic table of elements Periodic table and valence electrons

P e r i o d Elements in the same group have their valence electrons in the same shell Group

Elements in the same have the same number of electrons on their outermost shells (valence electrons) that belong to different shells

Valence electrons are related to: • Number of bonds One valence • Reactivity Seven valence electrons Periodic table as s,p,d,f-blocks

s p d f Periodic table as /non-metals

metals non-metals

Metals are: 95/118 elements 25% of earth crust Periodic table as families

metals metaloids non-metals

Metals are: 95/118 elements 25% of earth crust

Alkali Alkali-earth Transition-metals Post transition-metals Inner transition-metals Lanthanides Actinides Periodic table: Rare-earth-metals

metals metalloids non-metals Rare earth metals (17)

Gadolinite (Ce)2FeBe2Si2O10 (Ce,La,Nd,Y)

Ytterby quarry

S. A. Arrehnius Periodic table: Palladium-group metals

metals metalloids non-metals

Platinum G-metals (6) PPGM (Pd) l-PGM (Ir)

Bushveld Igneous complex (SA)

More than 27 % from recovery

Khabarovsk Krai 35×23×14mm; 112g Critical elements Companionnality elements

CuO Cu Se EUCHEM 2019 Periodic table with surface of each related to the use of the related element Synthesis of chemical elements Methods used to discover Chemical Elements

Sources Detection Separation methods Reducing agents Living organism Emission spectroscopy Crystallization Carbon Quarries X-ray spectroscopy Cation exchange Hydrogen Oceans chromatography Metals Earth atmosphere Radioactivity counters

Bombardment tools Bombardment type Natural decomposition Alpha-ray Linear accelerator Neutrons Cyclotron Protons nucleus Discovery of “elementary substances”/ “elements”

R. Bunsen observed (1859) that each element emits a light of characteristic wavelength (Atomic emission spectroscopy) allows him to discover cesium and rubidium alkali metals

• Detection G. J. Moseley discovered (1913) that • Isolation the X-ray is characteristic of an element • From elemental substances and the emitted X-ray is proportional to • From mixtures the atomic number of the element. • From compounds High frequency spectra of some elements -> • Identification • Homologation F. W. Aston built (1919) the first mass spectrometer Mass spectrum of boron as a mixture of C-10 & C-11 isotopes X-Ray & chemical elements

Portable hand X-ray fluorescence instruments

Moseley original X-ray

X-ray emission beamline at synchrotron, Berkeley

X-ray spectrometers embarked on Curiosity Probe Tools to split the atomic nucleus

Cockcroft and Walton built a particle linear accelerator able to produce 500 kV

The 28 cm cyclotron (1,2 MeV) at Berkley (1932) invented by Prof. E. McMillan

Cockcroft and Walton performed (1932) the first: (1) Artificial disintegration of an atomic nucleus (splitting the atomic nucleus). (2) Experimental demonstration that E = mc2

J. CocKcroft, E. Rutherford & E. Walton G. Seaborg & E. McMillan Discovery of “elementary substances”/ “elements”

Lesedi la Rona • Detection 222.2 g Native • Isolation • From elemental substances • From mixtures (separation) Kaware mine • From compounds (reactions) Bostwana • Identification (Method of detection) • Homologation (Name/Symbol)

Super Pit gold mine () Gold nugget weighting 36,2 kg, mined in the Urals in 1842 with a 91 % purity, (Kremlin in Moscow () . 2 Na [Au(CN)2] + Zn 2 Na [Zn(CN)2] + Au Discovery of “elementary substances”/ “elements” Lavoisier operates his solar to prevent contamination from combustion products

• Detection He: Emanating from U ore Cleveite Native Present in Naturel gas fields US. • Isolation • From elemental substances Ne: Evaporation of liquid argon • From mixtures (separation) • From compounds (reactions) Ar: Separation from nitrogen (from air) by reacting with magnesium ->MgO +Mg N • Identification (Method of detection) 2 3 • Homologation (Name/Symbol) Kr: liquefaction/evaporation of Ar.

Xe: liquefaction/evaporation of liquid air. Map of Europe showing closed and operating mines

• Base metals • • Precious metals • Iron • Energy metals • Special metals

Green circles represent the calculated amount the largest more than 500 Mt of waste stone Discovery of “elementary substances”/“elements”

• Detection Synthetic • Isolation • From elemental substances Through • From mixtures (separation) • From compounds reactions) • Identification (Method of detection) • Homologation (Name/Symbol) Na Ar Reduction • H2 • C • M D • e- Hymphry Davis LaX3 + M La + y M(X)n (1807)

D Discovery of “elementary substances”/“elements”

• Detection • Isolation Synthetic • From elemental substances Through • From mixtures (separation) amalgam • From compounds reactions) Other methods • Identification (Method of detection) did not work MnO + HCl ->Cl • Homologation (Name/Symbol) Na Ar 2 2

Cu2Se-> H2SeO3 + SO2->Se NaBr + Cl2 ->BrReduction2 • H2 KNO3 + water •-> I 2C • M At:: Rarest naturally •occurringe- D element in the Earth’s crust Hymphry Davis LaX3 + M La + y M(X)n (1807)

D Phosphorus the first elementary substance ever discovered

• Collected 5.500l of urine Bone ashes (CaO + P O ) • Evaporate and heat the red residue. 2 5 • Wash and heat at >280°C with carbon O O O • Recover after distillation 120 g white P OH Heat C NaO NaO P P + C=O + NaO C OH phosphorus that solidifies in water O NH4 O “cold fire'’

The alchymist, in search of Kunckel, J. the Philosopher’s Stone, Sweeden discovers phosphorus, and Krafft, D. (1678) Brand, H. prays for the successful Dresden Liebnitz, G. Friedrich Wilhelm conclusion of his operation. (1672) Prussia Duke of Prussia J. Wright of Derby (1771) (1675) 1676, 04, 24 200 Thalers Boyle, R. Brand, H. 25g silver England Hambourg (1669) (1680-92) Weeks, M. E. J. Chem. Educ. 1932, 9, 16-21 Hennig Brand." Famous Scientists. famousscientists.org. 24 May. 2018. Web. 3/30/2019 Extraction of eka-aluminum (gallium) from Blende

Ga/Zn 1/60000

Rost Lecoq de Boisbaudran Zinc mines of Gallium (mp: 29,7 °C) (1875) Argelès Valley, Pierrefite Pyrénés, France, Dissolve in aqua regia Original blende Precipitate Cd, In,Tl, Hg, Se, Ag, used (ZnS) Reduce with Zn plates at 100°C • Solar cells (GaAs as semi- Bi, Sn, Sb, Au conductor) • Smartphone (amplifiers) Al O , SiO , Cr, Co & other metals • Computers, phones televisions Discard the precipitate 2 3 2 (LEDs Backlighting) Add HCl To produce GaCl3

Bubble H2S/NH4Ac/AcOH To produce ZnS Filter To remove ZnS

Electrolyse GaCl2 To produce Ga

Use of Gallium per year James, C. J. Amer. Chem. Soc. 1911, 33, 1332

Separation of , bromates, Altogether 15.000 operations

Colombite Norway

Elution of trivalent lanthanide on a Dowex 50 cation exchange resin (Frank Spedding) with ammonium alpha-hydroxybutyrate (eluant) Katz, J.J. Mors, L.R. Seaborg G.T. The chemistry of Actinide elements 1986 Vol 2, 1131-33 Chapman U-238 (99,27) U-235 (0,72) Klaproth (1789) FirstKlaproth isolation (1789), of a chemical element Becquerel (1896) He-4 He-4 Becquerel (1896)

Th-235 Trace Curie, M. & P. (1898) He-4 Ra-226, Trace Curie, M. & P. (1898) He-4 Na2U2O7 Rn-222, Trace Curie, M. & P. (1898)

He-4 Po-218, Trace Curie, M. & P. (1898) He-4 1 t natural U-238 (HL: 4.47 B-y) equilibrium with: 360 mg Ra-226 (HL:1590 y) 7,2 kg U-235 (HL: 704 M-y) UO , UO UCl 550 ng Ra-223 (HL: 11,4 d). 2 3 4 U3O8 /K 0.1 mg Po-210 (HL-138 d) /Electrolysis First isolation of a chemical element

First transmutation 14 4 17 E. Rutherford 1919 N + He + 1 (to natural element) 7 2 8 O 1 H

F. & I. Joliot-Curie First synthesis unnatural 27 4 30 1 30 30 1 1934 of a natural Al + He + 15 P Si + p (HL: 150 s) 13 2 15P 0 n 14 1 element)

G. Seaborg & I. Gandhi

First synthesis unnatural 239 4 242 1 Bombarded by 40 106 volts 1944 + He + n element 94 Pu 2 96 Cm 0 (162 days) helium ions using a 1.5 m cyclotron

E. Segrè

First predominantly artificial A 1 A 1 1937 Mo + 1 p Tc + n Cyclotron plates in molybdenum element to be produced 42 43 0 Bombarded by protons Missing on the earth Impact of the organization of chemical elements on chemical sciences