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GROUP VI Chalcogens

This document provides information about oxygen and other chalcogens. It discusses the history and discovery of oxygen by Scheele, Priestley, and Lavoisier. It also covers the physical and chemical properties of oxygen, including its atomic number, molar mass, density, and electronegativity. Additionally, it discusses the occurrence and distribution of oxygen in the atmosphere, lithosphere, and hydrosphere. The document then covers the chemical properties and commercial manufacture of oxygen, as well as its uses in medicine, industry, and other applications. Finally, it briefly discusses the history, properties, production, and uses of ozone, hydrogen peroxide, sulfur, and other chalcogen compounds.

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74 views57 pages

GROUP VI Chalcogens

This document provides information about oxygen and other chalcogens. It discusses the history and discovery of oxygen by Scheele, Priestley, and Lavoisier. It also covers the physical and chemical properties of oxygen, including its atomic number, molar mass, density, and electronegativity. Additionally, it discusses the occurrence and distribution of oxygen in the atmosphere, lithosphere, and hydrosphere. The document then covers the chemical properties and commercial manufacture of oxygen, as well as its uses in medicine, industry, and other applications. Finally, it briefly discusses the history, properties, production, and uses of ozone, hydrogen peroxide, sulfur, and other chalcogen compounds.

Uploaded by

Ark Olfato Parojinog
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© © All Rights Reserved
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GROUP VI: CHALCOGENS

James P. Jimenez, RPh


OXYGEN
HISTORY
 Greek; Oxys + Genes = Acid Forming
 Carl W. Scheele: Swedish apothecary.
 Between 1771-1773, he performed numerous experiments that lead
to the discovery of Oxygen and named his discovery ____________
 Joseph Priestley: English scientist
 In 1774, he published a paper describing the properties of Oxygen
and named this gas ___________________
 Antoine L. Lavoisier: French chemist
 In 1778, he repeated the experiments of Priestley and coined the
term Oxygen
 Phlogiston Theory: states that flammable materials
contain phlogiston.
ATOMIC & PHYSICAL PROPERTIES
 Has 3 stable isotopes 16O, 17O, 18O
 A colorless, odorless and tasteless gas
 It condenses into a pale blue, mobile paramagnetic liquid
 Solubility in water in 3cm3 in 100cm3 but solubility drops at
higher temperature

 Atomic Number?
 Molar Mass?
 Density?
 Electronegativity?
OCCURRENCE & DISTRIBUTION
 Atmosphere
 21% by volume
 23% by weight
 Lithosphere
 47% by weight
 Hydrosphere
 89% by weight
CHEMICAL PROPERTIES
 Functions primarily as an Oxidizing Agent
 Implications in paints, fats, rubber, fabric?
 Supports combustion more readily
 Unites directly with most Metals and Non-metals
 Forming what?
 Union between Nitrogen & Oxygen takes place only at
exceedingly high temperatures (3000˚C)
 Birkeland – Eyde Process?
COMMERCIAL MANUFACTURE
 Fractionation of Liquid Air
 Fractional distillation of liquidfied air
 Electrolysis of Water
 Direct current is passed between iron or steel electrodes
 The Boussingault – Brin Brother’s Process
 Based on thermal reversibility of the reaction between BaO &
Oxygen gas
 The Thessie du Motay-Marechal Process
 Uses hot alkali permanganate
PHARMACOLOGIC ACTION OF OXYGEN
 Oxygenation of the Blood
 Cooperative binding of oxygen to Fe
 Transfer of oxygen to myoglobin
 Electron Transport Chain
Assignment
 Four classification of Oxygen requirement in the body
OFFICIAL OXYGEN PREPARATIONS
 Oxygen 99%
 Oxygen 93%
USES
 Iron – smelting
 Glass manufacture
 Steel cutting
 Oxy – gas welding
 Rocket fuel
 Production of TiO2
 Oxidation of ethene to ethylene oxide
 Sewage treatment
OZONE
HISTORY
 Van Marum
 noted that oxygen or air through which electrical sparks have
been passed possessed a peculiar irritating odor and tarnishes
mercury
 Schönbein
 he demonstrated that the effects were caused by a new gaseous
substance w/c he named Ozone from the greek “To Smell”
PHYSICAL & CHEMICAL PROPERTIES
 Physical properties:
 Unstable pale blue diamagnetic gas w/ a pungent odor
 Strong absorption in the UV region between 220 – 290 nm

 Chemical Properties:
 More active oxidizing agent than molecular Oxygen
 Stable at low temperatures and decomposes into O2 at higher
temperatures
 Decomposition is rapid in acidic solutions but it is more stable
in alkaline solutions
PRODUCTION
 Welsbach Method: Subjecting cold dry oxygen or
air to an electrical discharge
 Produced in small quantities by various chemical
reactions
 Ultraviolet irradiation of O2.
IDENTIFICATION
 Odor: garlicky odor similar to SO2
 Starch – KI Paper: formation of the violet/blue –
violet starch – iodo complex
 Litmus paper: red litmus turns blue
 Tarnishing of Silver
 Oxidation of PbS to PbSO4
USES
 Disinfectant
 Bleaching agent
 Synthesis of organic compounds
HYDROGEN PEROXIDE
PHYSICAL & CHEMICAL PROPERTIES
 Physical Properties
 Colorless; less volatile liquid but more viscous and
dense than water.
 Miscible w/ water, alcohol & ether in all proportions
 Chemical Properties
 oxygen has oxidation state of -1 & spontaneously
disproportionate
 Can act as OA or RA in acidic or basic solutions
 Undergo proton acid/base reactions
COMMERCIAL PRODUCTION
 Reduction
 Electrolysis
STABILIZERS
 Acidic: inorganic/organic; alkaline solutions are
more unstable
 Complex forming: acetanilide, phenacitin, quinine
sulfate, 8 – hydroxyquinoline
 Adsorptive: alumina, silica, hydrous antimony oxide
or hydrous stannic oxide
USES
 Bleaching agent
 Antiseptic
 Production of epoxides
 PVC stabilizers and polyurethanes
 hydroquinone, cephalosphorins and tartaric acid
SULFUR
ORES
 Brimstone - “burning stone”
 Gypsum – CaSO4.2H2O
 Galena – PbS
 Zinc blende – ZnS
 Pyrites (Copper pyrites/Iron pyrites) – CuFeS2/FeS2
 Barytes – BaSO4
 Kieserite – MgSO4.2H2O,
 Celestite – SrSO4
OCCURRENCE & DISTRIBUTION
 The three major commercial sources of sulfur are:
 Elemental sulfur in the cap rock of salt domes/
evaporate deposits
 H2S in natural gas and crude oil, organosulfur
compounds in tar sands/bitumen, oil shales, coal
 Pyrites and sulfide-containing metals
COMMERCIAL MANUFACTURE
 FRASCH PROCESS
 Devised and perfected by Hermann Frasch
 Pumping of superheated water and forcing compressed
air to collect melted sulfur
ALLOTROPES OF SULFUR
 RHOMBIC/α-SULFUR
 Most common and most stable
 Exists as a ring of S8 atoms
 Nearly insol in H2O and Alc.
 Good electrical and thermal insulator
 Ex. Roll sulfur, flowers of sulfur, milk of sulfur
ALLOTROPES OF SULFUR
 MONOCLINIC/β-SULFUR
 stable from 96°C – 119.25°C
 less dense than α-SULFUR
 Can be prepared by rapidly cooling melted sulfur
ALLOTROPES OF SULFUR
 Ƴ-SULFUR
 nacreous/mother-of-pearl sulfur
 the more efficient packing leads to a greater density

 Liquid Sulfur/Plastic Sulfur


 Prepared by heating rhombic sulfur to above its
melting point then rapidly cooling it.
 Viscous fluid
 Ex. Amorphous sulfur – 70% rhombic sulfur
CHEMICAL PROPERTIES
 Reacts directly with all elements especially at elevated
temperatures ( exceptions: Noble gases, N, Te, I, Pt,
Au)
 Unaffected by non-oxidizing acids; reacts with
oxidizing acids and other oxidizing agents
 Alkalis: slowly dissolves to form sulphites and
sulphides
 Alkali cyanides: thiocyanates
BIO-INORGANIC CHEMISTRY
 Sulfur containing amino acid
 Oxidized dimer of cysteine
 Intrapolypeptide disulfide bonds
 Interpolypeptide disulfide bonds
SULFUR COMPOUNDS
SUBLIMED SULFUR
 Fine, yellow, crystalline powder having a faint odor and
taste
 Flowers of Sulfur
 Parasiticide; Scabicide
PRECIPITATED SULFUR
 Very fine amorphous or microcrystalline powder; pale
yellow and no odor or taste
 Boiling sublimed sulfur and Ca(OH)2 and acidification
with dil. HCl
 Lac sulfur or milk sulfur
 Scabicide
SULFURATED POTASH
 Potassium polysulfide, sulfate and thiosulfate
 Potassium carbonate and Sublimed Sulfur
 psoriasis; parasiticide
WHITE LOTION, USP
 Sulfurated Potash solution plus Zinc Sulfate solution
 Astringent and protective
SULFUR DIOXIDE
 Colorless, non-flammable gas possessing a characteristic
pungent and irritating odor
 Reducing agent
 Used in the manufacture of Sulfuric Acid
SULFUR TRIOXIDE
 SO3; A planar molecule with all the S-O bonds of equal
length
 Prepared from the thermal decomposition of Fe2(SO4)3
or FeSO4 and dehydration of H2SO4 with P4O10;
Reaction between SO2 and O2
 Reacts exothermically with
 Water forming?
 Alkali oxides forming?
HYDROGEN SULFIDE
 A highly toxic, colorless gas with an unpleasant odor
 Can be prepared by
 reduction of S with H2
 Action of acids with metal sulfides (FeS;Sb2S3)
 Hydrolysis of Al2S3 (Al2S3 + H2O  Al(OH)3 + H2S)
 Forms insoluble metallic sulfides, some in acidic solutions
others in alkaline environment.
 A reducing agent in both alkaline and acidic solutions
 Aqueous solutions oxidize in air, depositing sulfur
 Reduces halogens in aqueous solutions?
 Reduces sulfites forming Sulfur?
 Reduces dichromates to Cr+3; manganates to Mn+2; Fe+3 to Fe+2
SULFIDES
 ALKALI METAL SULFIDES
 Ionic solids that can exist as anhydrous compounds or
as hydrates
 Prepared by action of S on Alkali Metals; Reaction of
H2S on Alkali hydroxides

 ALKALI EARTH SULFIDES


 Less soluble than alkali metals. Not prepared by the
addition of H2S to a salt solution
SULFIDES
 Sulfides of Al and Cr
 Prepared by direct combination of the elements
 They are rapidly hydrolyzed forming the hydroxide
and H2S

 Sulfides of other elements


 Pb+2, Cu+2, Ag+1 – low Ksp; H2S in acid solution
 Zn+2, Fe+2, Ni+2,Co+2 – precipitated only in high S-2
concentrations/ H2S in basic solution
SULFITES & BISULFITES
 Reducing Agents
 Sulfites react with O2 or air to give sulfates: SO3-2 +
O2  SO4-2
 Sulfites react with Oxidizing agents such as: 2MNO4
+ 5SO3 -2 + 6H+  2Mn+2 + 5SO4 -2 + 3H2O
 Sulfites are oxidized by chlorine water, hypochlorous
acid and the hypochlorite ion
 Ferric ion is reduced to the ferrous ion
SULFITES & BISULFITES
 When treated with 3N HCl, solutions of sulfites evolved
_____ which blackens a filter paper moistened with
______
 BaCl2 forms a white precipitate with sulfite/bisulfite
solutions.This precipitate is soluble in acids.
 Reacts with aldehydes to form crystalline addition
products
 Name?
THIOSULFATES
 Reaction of H2S with soluble sulfites:
 2HS- + HSO3  3S + OH- then 3S + 3HSO3 
3S2O3-2 + H+
 Boiling of metal sulfites/bisulfites with S: Na2SO3 + S
 Na2S2O3
 Air-oxidation of polysulfides: Na2S5 + O2  Na2S2O3 +
S
 Used as a reducing agent?
SELENIUM, TELLURIUM &
POLONIUM
HISTORY
 Te: Reichtenstein (1782); Klaproth (1798)
 Se: J.J. Berzelius and J.G. Gahn in 1817
 Found in nature associated with Sulfur or sulfides; a
rare element
 Po: Marie Curie (1898)
 radioactive metal occurring in nature only as a product
of the radioactive decay of Uranium
ALLOTROPES OF SELENIUM
 “Red” Selenium
 “Gray” Selenium
CHEMICAL PROPERTIES
 Se and Te: burn in air to form oxides (SeO2/TeO2)
 Se and Te: unaffected by non-oxidizing acids
 Po: reacts with non-oxidizing acids
 Se and Te: in alkalis form Selenides and Selenates;
Tellurides and Tellurates
IDENTIFICATION OF SELENIUM
 Selenites
 Reaction? Visible result?
 Selenates
 Reaction? Visible result?
OFFICIAL PREPARATIONS
 Selenious Acid, USP
 Selenious Acid Injection, USP
 Selenium Sulfide, USP
 Selenium Sulfide Lotion, USP/ Selenium
 Sulfide Topical Solution
CHROMIUM, MOLYBDENUM &
TUNGSTEN
NATURAL SOURCES
 CHROMIUM
 NATURAL SOURCE: Chromite: FeCr2O4; Ochre: Cr2O3
 Ruby, Emeralds: color is caused by traces of Cr

 MOLYBDENUM
 NATURAL SOURCE Wulfenite: PbMoO4; Powellite:
Ca(Mo,W)O4; Molybdite: MoO3

 TUNGSTEN
 NATURAL SOURCE: Wolfram ocher: WO3; Metallic
tungstates: BaWO4, PbWO4, CuWO4
CHEMICAL PROPERTIES
 Resists atmospheric attack at ambient
temperatures
 Down the group: Increasing reactivity to acids
OXIDES
 HEXAVALENT
 Acidic and dissolve in aqueous alkali to form XO4-2 (CrO4-2,
MoO4-2, WO4-2)
 CrO4-2 is an OA but MoO4-2 and WO4-2 has no appreciable
oxidizing property
 a sensitive test for reducing substances?
 TETRAVALENT
 CrO2 – ferromagnetic
 MoO2, WO2 – diamagnetic
 TRIVALENT
 Cr2O3 – amphoteric; dissolves in acid forming [Cr(H2O)6]+3
and in alkali forming [Cr(OH)4]-1 or CrO2-1 (chromites)
IDENTIFICATION TESTS
 ID test for Chromium?
 ID test for Molybdenum?
Reading Assignment
 Read Selenium, Tellurium, Molybdenum, Tungsten and
Uranium in Rogers’ Inorganic Pharmaceutical Chemistry
during Lenten Season
Thank You for listening!
Enjoy your Vacation =)

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