Group VA (15) Elements – Nitrogen Family PDF

Summary

This document provides information about the Group VA (15) elements, including Nitrogen, Phosphorus, Arsenic, Antimony, and Bismuth. It details their properties, uses, and relevant chemical reactions. The document includes information regarding their historical uses and their important roles in various applications like medicine and industry.

Full Transcript

GROUP VA (15) ELEMENTS – NITROGEN FAMILY MEMBERS: Nitrogen – N Phosphorus – P Arsenic – As Antimony – Sb Bismuth – Bi Old Name: Phictogen (nitrogen’s property to cause choking/coughing in the absence of air)...

GROUP VA (15) ELEMENTS – NITROGEN FAMILY MEMBERS: Nitrogen – N Phosphorus – P Arsenic – As Antimony – Sb Bismuth – Bi Old Name: Phictogen (nitrogen’s property to cause choking/coughing in the absence of air) oxides of N & P are acidic oxides of As & Sb are amphoteric oxide of Bi is basic Cyanide (CN) - MOA: inhibits cytochrome oxidase (ETC) Source: cassava, Na nitroprusside Treatment: 1. NaNO2/Amylnitrite MOA: methemoglobinemia 2. Sodium thiosulfate MOA: CN to thiocyanate 3. Methylene blue MOA: methemoglobinemia A. NITROGEN (N) (Mephitic air, azote, without life) o Most abundant gas in air: 71% N2, 29% O2 o 78.09% of Earth’s atmosphere o most abundant gas in the air (atmosphere; followed by O) o prepared by fractional distillation of liquid air o essential nutrient of plant and animal tissues, in proteins & amino acids o most stable diatomic molecule (N2) o nitrates & other nitrogen compounds used as fertilizers (NPK) & explosives o Nitrogen gas: inert atmosphere for oxidizable pharmaceuticals (substitute: Argon) o Liquid Nitrogen: refrigerant (cryogenic preservation- process of cooling and storing cells, tissues, or organs at very low or freezing temperatures to save them for future use) o MOT of Nitrites & Nitrates: nitrites are potent oxidizing agents & cause methemoglobinemia (ferrihemoglobin) o ANTIDOTE: 1% methylene blue (accelerates enzymatic reduction of metHB) Nitrogen, NF Azote very stable because of 3 covalent bonds N2 “mephitic air” ; colorless and Cont: BLACK odorless gas USE: diluent for oxygen for deep sea diving purposes but can cause bends; decompression sickness, injuries caused by a rapid decrease in the pressure that surrounds a diver, causing formation of bubbles in tissues & blood. (replaced by He) INERT ATMOSPHERE Liquid nitrogen – refrigerant Nitrous Oxide N2O Laughing Gas, weakest but probably the safest general Cont: BLUE Nitrogen monoxide, anesthetic and as dental Anesthetic; least potent Dinitrogen monoxide inhalational anesthetic SE: diffusion hypoxia (Following discontinuation of nitrous oxide, the concentration gradient between the gases in the lung and alveolar circulation rapidly reverses.) Inhalational anesthetic (general) Nitric Oxide causes vasodilation NO an important endogenous NT produced by neurons and other cells associated with the mechanism of drugs like Sildenafil & Nitroglycerin (nitric oxide-mediated vasodilation Vasodilator, For CN poisoning Nitrite (NO2 - ) vasodilator; (also nitrate) used as antidote for CN poisoning (have high affinity to CN) forms red color with Giess-Ilosvay Test (sulfanilic acid- 1-naphthylamine reagent) Nitrate (NO3 - ) preservative ion when warmed with concentrated sulfuric acid & metallic Cu, evolved brown gas: (+) results with Brown Ring Test; & no visible reaction w/ diluted sulfuric acid gives white crystalline precipitate w/ the presence of Nitron Reagent (diphenyl-endo-anilo- dihydrotriazole) *Lunge Test – most sensitive test for nitrate *Pentaerythritol Tetranitrate – longest acting nitrate Nitric Acid, NF HNO3 Spirit of Nitre, an aqueous solution containing not less than 69% & not more than 71% by weight of HNO3 Aqua Fortis/Fuerte/Eau Forte B. PHOSPHORUS (P) (light carrier, St. Elmo’s Fire) Allotropes of P:  Scarlet - tribromide ∆240°C with Hg  Violet - white ∆200°C with Na  Metallic/Black - 530° with Pb  Red - white + chromic acid o 11th most abundant element in Earth’s Crust o essential for life, both as structural material in higher animals & essential in metabolism of both plants & animals o Occurs as phosphate in the body [PhIClO] o TOXICITY: may cause severe burns and chronic poisoning may cause bony necrosis, especially of mandible; “Phossy Jaw” o USES: antacids; cathartics o White/yellow (poisonous), Red (non-poisonous) o TWO FORMS:  a. Red Phosphorus  - non-poisonous & non-flammable in air, except at high temperature; less active form of phosphorus.  - formed when White P is heated to 250°C or at a lower temp in the presence of sunlight.  b. White Phosphorus or Yellow Phosphorus  - phosphorescence: when exposed to air in the dark, it emits greenish light & gives off White Fumes (exothermic) with garlic odor  - has distinctive, disagreeable, ozone-like odor  - toxic / poisonous form of phosphorus ALLOTROPIC MODIFICATIONS:  a) Black/Metallic P (white P w/ Pb @ 500-530°C under high pressure); most stable allotrope of P  b) Scarlet P (PbBr with Hg @ 240°C); used in match industry  c) Violet P (white P w/ Na @ 200°C under very high pressure) o CuSO4 Phosphate PO4 USE: antacids; cathartics insoluble phosphates: Mg ; Sr ; Ba ; Ca Phosphoric Acid, NF H3PO4 used to form soluble salts of insoluble medicinal base (Orthophosphoric Acid) Hypophosphorous Acid PH2O2 used as an antioxidant in Hydroiodic Acid Syrup & Ferrous Iodide Syrup powerful reducing agent C. ARSENIC (As) (Lewisite Metal) o component of Salvarsan (Antisyphilis)/ Arsphenamine o binds to –SH (keratin of nails & hair) o Identification Test: Gutzeit’s Test (modified version of Marsh Test) o Protoplasmic poison o Insecticide: Copper Aceto Arsenate (Paris green) o Mee’s Line | BAL (British Anti Lewisite) o First anti-syphilis (Paul Ehrlich) – Arsphenamine/Salvarsan/Magic bullet/Compound 606 o Chemistry  – Trivalent Arsenic (Arsenous ion)  more toxic; most common form of As  in combination with halides, it is present as cation  Inorganic arsenic toxicity; trivalent is more acutely toxic than pentavalent As  Pentavalent Arsenic (Arsenic ion)  Common; veterinary anthelmintics and treatment of amoebiasis and trypanosomiasis (potent trypanoside)  Organic arsenic toxicity; pentavalent are less toxic than trivalent organoarsenic and inorganic As  Acute Poisoning: Aldrich-mees lines (transverse) whiter straying in the nails  Chronic Poisoning: “Rain-drop” hyperpigmentation of the torso and extremities  ANTIDOTES:  1st line: Unithiol (DMPS- Dimercaprol Propane Sulfonic Acid) – a water-soluble analog of BAL that is best for acute arsenic poisoning.  2nd line: Dimercaprol/BAL; chelating agent of 2nd choice is Unithiol is not available.  3rd line: Oral Unithiol or Oral Succimer: once patient is stable.  Arsenic is usually alloyed with Pb to make it harder; doping semiconductors and light emitting diodes 1. A r s e n i c - Insecticide, Anti-leukemic T r i o x i d e As2O3 Trisenox® (old brand) - was reintroduced to USP for treatment of leukemia (given IV together with tretinoin) primary standard for Ce(SO4)2 used as rat & ant poison; wood preservative to prevent wood rot used in preparation of Paris Green; Fowler’s Solution; Donovan’s Solution 2. Potassium Ars AKA: Fowler’s Solution antileukemic enite Solution 3. CopperAceto Paris Green - used as insecticide Arsenite 4. Donovan’s red solution containing AsI3 + 1%HgI Solution 5. Arsine (AsH3) most toxic form of Arsenic D. ANTIMONY (Sb) AKA: Stibium in the presence of Rhodamine B w/ HCl forms Violet Precipitate Principal Source: Antimony Glance (Stibnite) Pharmacologic Action -expectorant -emetic -anthelmintic Chemistry:  – Trivalent Inorganic Antimony Compound  (Stannous/Antimonous)  more toxic  – Pentavalent Organoantimony Compound  Both are used as antiprotozoal agents  Used as emetics  Treatment of certain helminth infections (schistosomiasis & filariasis)  Pentavalent is more active against protozoa while trivalent is more useful in against helminth ALLOTROPES OF ANTIMONY  Metallic Antimony – crystallizes in rhombohedrons; most stable  Amorphous Antimony – unstable; explosive allotrope  Black Antimony – less stable than metallic  Yellow Antimony – easily converted back to black allotrope Antimony Potassium Tartrate, “Tartar Emetic” or USES: emetic & expectorant in Brown USP “ Brown Mixture” Mixture; DOC for treatment of Schistosomiasis (Liver Fluke) *no longer use as emetic because it is toxic Antimony Black a black metallic antimony, obtained by the action of Zn upon solutions of antimony trichloride Alloys: Babbit Metal - 80% Sn + 20% Sb Antifriction Metal - 75%Sn +12.5% Sb + 12.5% Cu Stibine (SbH3) toxic form of antimony Na stibogluconate - Leishmaniasis E. BISMUTH (Beautiful Meadow) o will not react with acids to produce Hydrogen o Basic salts are employed for their astringent, mildly germicidal and antacid properties o Bismuth salt: ulcer treatment o Pharmacologic Actions:  Antidiarrheals  Astringent  Antiseptic  Used in silvering of mirror  Internal Protective for Ulcer (PUD: (+) H. pylori) o *Insoluble Bismuth à 30%concentration as ointment o Side-Effects:  Dark-black Stool (intestinal H2S acts upon Bi salts to form bismuth sulfide (Bi2S3) causing black stool from oral administration of bismuth preparation)  Blue-black gums  Antidote: BAL/Dimercaprol Bismuth Citrate, USP Pylorid®, contains Ranitidine & Bismuth Citrate Colloidal Bismuth Subcitrate is used for tx of PUD - (+) Helicobacter pylor Milk of Bismuth, USP “Bismuth Cream”; Components: Bi subcarbonate ((BiO)2CO3) and Bismuth Magma Bi hydroxide in suspension of water Primary USE: antacid/internal protective (especially for gastric patient) because it can inhibit growth of H. pylori Bismuth Subcarbonate, Basic Bismuth Carbonate Generated in situ in Milk of Bismuth USP USES: antacid, astringent, antiseptic Bismuth Subnitrate, USP Basic Bismuth Nitrate, has a well-recognized incompatibility w/ Bismuth Oxynitrate, tragacanth in w/c it precipitates as hard mass in Spanish White, the presence of the salt Bismuth Paint, Bismuthyl Nitrate USE: x-ray shielding; necessity in Milk of Bismuth, USP Bismuth Subsalicylate Basic Bismuth Subsalicylate USES: for indigestion; nausea & vomiting; tx for Traveller’s Diarrhea Antidiarrheal agent which shows good activity against Salmonella (causes Traveller’s diarrhea) but less activity with E.coli 1. Bi Subcarbonate, Subgallate, Subnitrate - Antacid, Astringent, Antiseptic 2. Milk of Bi (Bismuth Cream) Bi subnitrate + Bi OH - Antacid, Internal protective, Inhibits H. pylori GROUP VB (5) ELEMENTS – Vanadium Subgroup A. VANADIUM - amphoteric property B. TANTALUM - more important - used for implant purposes since it is unaffected by body fluids - used in recent years in the surgical repair of large abdominal hernias - used as sheet form for surgical repair of bones, nerves & tissues o Not affected by any body fluid, Sheet form used in repair of bones, nerve and tissue GROUP VIA: (16) ELEMENTS – OXYGEN FAMILY CHALCOGENS MEMBERS: Oxygen – O Sulfur – S Selenium – Se Tellerium – Te Polonium - Po A. OXYGEN (Empyreal air, Dephlogisticated air, Yne, Aire Vital, Fire Air, Aire Puro) o Most abundant element on earth, discovered by Scheele o AKA: “Acid Former”; “Yne”  Also named as “Empyreal Air” by Carl Scheele (Swedish apothecary);  “Dephlogisticated Air” by Joseph Priestly (English scientist); “  Oxygen” by Antoine Lavoisier (French chemist) o 2nd most electronegative atom o Has 3 stable isotopes (16O, 17O, 18O) o Odorless, colorless & tasteless gas o It condenses into a pale blue, mobile paramagnetic liquid  3 ALLOTROPES:  nascent oxygen - O Oxygen Requirement:  atmospheric/molecular oxygen – O2 1. Anoxic - inadequate O2 tension in air 2. Anemic - lack of O2 carrier in heme  ozone – O3 (poisonous gas) 3. Stagnant - blood circulation is retarded o Uses: 4. Histotoxic - cell defect interference of 1. Treatment of hypoxia/asphyxia cell metabolism 2. Oxidative metabolism for the production of energy 3. Final e- acceptor in ETC o Container: GREEN o Manufacture of Oxygen: Fractionation of Liquid Air – Lindle-Frankl à Oxygen nlt 99% Used of Molecular Sieves – Oxygen 93% and subjected to CO and CO2 test Carbon Dioxide (Carbonic Acid Gas, Carbonic Anhydride)  Container: GRAY  Solid Carbon Dioxide or “Dry Ice” - refrigerant  Official Oxygen  Oxygen: contains nlt 99.0% v/v of O2; 99% produced by air fractionation process (Lindle-Frankl process) exempted from CO2 and CO test  Oxygen 93%: oxygen gas produced from air by molecular sieve process requires CO2 and CO test  Hyperbaric Therapy (100% oxygen) -treatment for decompression sickness, a hazard of scuba diving  Conditions based on Oxygen Requirement:  Anoxia – oxygen supply to the tissues is inadequate because the blood arrives with its oxygen at a lowered tension  Anemia – oxygen tension is normal but amount of Hemoglobin is inadequate  Stagnant - general circulation is interfered  Histotoxicity – cellular respiration is interfered; eg. poisoning to the tissues caused by CN  Uses: – Iron-smelting, steel cutting – Glass manufacture, rocket fuel – oxy-gas welding – Production of TiO2 – Oxidation of ethane – Sewage treatment A. a OZONE  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 solution but it is more stable in alkaline solutions  Production:  Welsbach Method: subjecting cold dry oxygen or air to an electrical discharge  may be produces in small quantities by various chemical reactions  UV irradiation of Oxygen Identification:  Odor: garlicky odor similar to SO2  Starch-KI Paper: formation of violet/blue-violet  KI-litmus paper: red litmus paper turns blue  USES:  disinfectant,  bleaching agent  synthesis of organic compounds  good oxidizing agent B. SULFUR (S) (Brimstone, Shubari, Enemy of Copper) o AKA: “Shulbari”; “Enemy of Copper”; “Brimstone” o Commercial Manufacture: Frasch Process (Sulfur Mining)  PHARMACOLOGIC USES:  preparation of scabicidal & keratolytic ointment  stimulant cathartic  depilatory  fumigant  anti-dandruff  ALLOTROPES OF SULFUR:  Rhombic/α-Sulfur – most common & most stable allotrope of sulfur  has good electrical and thermal insulator  eg. roll sulfur, flower of sulfur, milk of sulfur  Monoclinic/β-sulfur – less dense than α-Sulfur  γ-sulfur – nacreous/mother-of-pearl sulfur  Liquid Sulfur– prepared by heating rhombic sulfur at a temp of 160°C until about 180°C and rapidly cooling it; the product becomes dark brown with maximum viscosity  eg. Amorphous sulfur – 70% rhombic sulfur Other Forms of Sulfur:  Precipitated Sulfur Lac – Lac Sulfur or Milk sulfur; has fine particles used as scabicide  Sublimed Sulfur – Flower of Sulfur; parasiticide & scabicide; cathartic; has coarse particles used in the preparation of Vleminck’s Solution (+ Lime)  Plastic Sulfur – resembles rubber and is insoluble in carbon disulfide Ores of Sulfur:  Brimstone (burning stone); Gypsum; Galena (PbS) o Antifungal, Parasiticide, Scabicide, Depilatory agent Sulfur Dioxide Sulfurous Anhydride Antioxidant;good reducing agent colorless, non-flammable gas possessing a characteristic pungent and irritating odor (suffocating) turns filter paper green when moistened with acidified Potassium Dichromate Used in the manufacture of H2SO4 Oil of Vitriol Dehydrating agent in Pyroxylin Sulfuric Acid H2SO4 Vitrilic Acid Nordhausen acid – Fuming H2SO4 Aceitede de Vitriolo most common dehydrating agent used in chemical reactions Hydrogen Sulfide (H2S) a highly toxic, colorless gas with an unpleasant odor (rottened egg) Flower of Sulfur Cathartic Sublimed Sulfur (condensed sulfur vapors) Asufre, Rhombic S + Lime  Vleminckx’s solution Precipitated Sulfur (sulfur + metal Milk of Sulfur Prepared by mixing hydroxides) Psoriasis, Parasiticide Sulfurated Potash (K polysulfides + K Liver of Sulfur thiosulfate) White lotion (ZnS) C. SELENIUM (Se) (Selena, Moon)  AKA: “Selena” or “Moon”  essential trace element ; rare element (found in nature associated with S or sulfides)  promotes absorption of Vit E (Synergistic of Vit E)  cofactor of glutathione peroxidase enzyme  used in the making “red glass” & in rubber industry  Pharmacologic Actions:  Antioxidant Allotropes of Selenium  Red Selenium  α, β, γ  Selenium rings which differ only in intermolecular packing  Gray Selenium  most thermodynamically stable  consists of unbranched helical chains.Selenium Sulfide (SeS2) Selsun Blue® 2.5% suspension in topical treatment of seborrheic dermatitis USE: antidandruff/anti-seborrheic agent Selenic Acid only single acid that can dissolve Au Other Selenium – Selenious Acid, USP Compounds – Selenious Acid Injection, USP – Selenium Sulfide, USP – Selenium Sulfide Lotion, USP (Selsun Blue®) – Selenium Sulfide Topical Solution USES: antidandruff, photoelectric cells, xerography, important trace element D. POLONIUM (Po) radioactive metal occuring in nature only as a product of the radioctive decay of Uranium GROUP VIB (6) ELEMENTS – Chromium Subgroup MEMBERS: Chromium – Cr Molybdemun – Mo Tungsten – W Uranium – U Chromium – Cr A. CHROMIUM (Glucose tolerance factor) - hyperglycemia (K2Cr2O7- powerful oxidizing agent) essential trace element glucose tolerance factor Deficiency: Hyperglycemia Natural Sources: – Chromite (FeCr2O4) – Ochre (Cr2O3) Potassium Dichromate (K2Cr2O7) powerful oxidizing agent Chromate à yellow in solution *Chromate ion – yellow *Dichromate ion – orange B. MOLYBDENUM - Co-factor enzyme (Molybdenum Oxide + FeSO4 – hematinic) essential trace element cofactor of flavin dependent enzymes important constituent of Xanthine Oxidase & Aldehyde Oxidase involved in bacterial fixing of atmospheric nitrogen *Molybdenum Blue Test – sensitive test for reducing substances Natural Sources: – Wulfenite (PbMoO4) – Powellite (Ca(Mo,W)O4) – Molybnite (MoO3) C. URANIUM - Becquerel, Atomic bombs discovered by Becquerel radioactive element used for manufacture of atomic bombs no pharmaceutical use D. TUNGSTEN (W) AKA: “Wolfram” because it is found in nature as Wolframite or as Wolfram Ocher is most desirable in making filaments in electric bulbs imparts great hardness to steel GROUP VIIA: HALOGENS (Salt-forming group) salt-forming elements Electronegativity: F > O > N = Cl Decreasing Acidity: HI > HBr > HCl > HF MEMBERS: Flourine – F Chlorine – Cl Bromine – Br Iodine – I Astatine - At A. FLUORINE (F) o AKA: “superhalogen” o strongest oxidizing agent o most EN element (4.0) [followed by oxygen (3.5)] o pale yellow gas having a characteristic odor resembling mixture of ozone and chlorine o Moissah (1886): French chemist; isolated F by Electrolysis o Fluorine compounds are anticariogenic agents (i.e. sodium monofluorophosphate) o Identification Test: Glass etching Test (CaF2) o Poisoning (F- ): Fluorosis – Principal Manifestations: Mottled Enamel; Abnormal Bone Growth 1. Sodium Fluoride NaF - anticariogenic at 2% solution 2. Stannous Fluoride SnF2 - anticariogenic at 8% solution 3. Na2FPO3 - anticariogenic 4. Dichlorodifluoromethane CCl2F2 - refrigerant, aerosol propellant (Freon®) B. CHLORINE (Cl) (Dephlogisticated muriatic acid) o greenish-yellow gas having a characteristic unpleasant, suffocating odor and astringent taste o most abundant extracellular anion (Cl- ) green gas o was named as the following: > “dephlogisticated muriatic acid” by Scheele (1774) > ”oxygenized muriatic acid” by Berthollet (1785) > coined the term “Chlorine” (also “Bromine” and “Iodine”) by Davy (1810-1811) o Chlorine compounds (as chlorides) o Used as water disinfectant Hydrochloric Acid, NF (HCl) MURIATIC ACID; 36.5-38.0% w/v Colorless, clear, highly corrosive, highly pungent toilet bowl cleaner neutralizing, stabilizing, solubilizing agent Diluted Hydrochloric Acid, NF treatment of Achlorhydria; expressed in 9.5-10.5% w/v Concentrated HCl expressed in %w/w; used to differentiate Group I Cations Chloride of Salts of Na, K, Ca Electrolyte replenisher Components of Ringer’s solution and Lactated Ringer’s solution 1. Hypochlorite (Na, K) - bleaching agent 2. HCl (Muriatic acid, Spirit of Sea Salt, Marine Acid, Espiritu de Sal Marine) - treatment of achlorhydria C. BROMINE (Br) o Dark reddish brown fuming liquid with suffocating odor o Has a high vapor pressure o Balard (1826); isolated Br from the salts of Montpellier o Bromyrite (AgBr) o Br- possess sedative & depressant activity o powerful caustic & germicide o if in contact w/ skin, wash immediately w/ a solution of NaHCO3 & treated w/ glycerin o added to Quinalizarin Reagent, a reagent to differentiate Mg & Be o Three Bromide Elixirs: Na, K, & Ammonium o Pharmacologic Actions: Sedative Depressant o Poisoning: Brominism 1. Manifestations: Skin eruption; headache; weakness; psychosis – ANTIDOTE: NaCl & NH4Cl Koppeschaar’s Solution Bromine, Tenth Normal Solution (0.10N Solution) solution of K Bromate & K Bromide Used in the Assay Of Phenol Potassium Bromide, USP for bipolar disorder and mania Sodium Bromide, USP D. IODINE (I) o grayish-black solid with a metallic luster and a characteristic penetrating odor o Courtois (1811); isolated iodine by Sublimation (H2SO4 + seaweed ash) o most metallic of all halogen (if except, Astatine) o present in thyroid gland o *1:5000 (0.02%) – iodine concentration effective to combat many common bacteria in distilled water o Poisoning: Iodism o Antidote: Starch & Sodium Thiosulfate o Oldest known germicide o Expectorant, Antifungal o Preparation of T3 and T4 o Deficiency: Goiter o Elemental Iodine preparation: 1. Strong Iodine Solution (Lugol’s Solution) - 5% 2. Iodine Solution - 2% 3. Iodine Tincture - 2% with 50% alcohol (Disinfectant) 4. Povidone-Iodine (Betadine®) - PVP (nonionic surfactant) Betadine® (10% Iodine) 5. Iodophor - complex of Iodine 6. Boulton’s Solution - Phenolated Iodine Solution 7. HI - most acidic among the acids of halogen E. ASTATINE (At) o synthetic, radioactive & metallic halogen o resembles Iodine, but more metallic o has no pharmaceutical applications o Rarest element Properties of Group VIIA: Fluorine: capable of only 1 oxidation state (-1) Chlorine, Bromine, Iodine: Interhalogens:  Type XX’: ClF, BrF, BrCl, ICl, Ibr  Type XX’3: ClF3, BrF3, ICl3  Type XX’5: BrF5, IF5 – Type XX’7: IF7 *Ibr, ICl, ICl3: exist as solids while others are either volatile liquids or gases Pseudohalogens – (halogenoids)molecules resembling halogens  CN-  (CN)2 – cyanogen  N2 - - azide GROUP VIIB (7) ELEMENTS – Manganese Subgroup are colored are metallic in character MEMBERS: Manganese – Mn Technetium – Tc Rhenium – Re A. MANGANESE o third most abundant transition element o Occurrence: Pyrolusite (MnO2) o forms a pink ppt with sulfur-containing reagent o major cofactor of Pyruvate Carboxylase o Co-factor of Enzymes Involved in: 1. Protein synthesis 2. Phosphorylation 3. Fatty acid and cholesterol synthesis o Poisoning: Parkinson-like symptoms (resting tremors) COMPOUNDS OF Manganese: Permanganates (Potassium – potent oxidizing agent; deep purple color Permanganate (KMnO4) – intense color due to “charge transfer” -- antiseptic Manganates – aqueous solutions are colored green Mn (V – Exists as the blue MnO4 3- ion Manganite – Occurs naturally as Pyrolusite – Prepared by oxidation of Mn2+ salts Manganic – Disproportionates in aqueous solution – Mn3+ (aq.) can be stabilized by using acid solutions or complex formation Manganous – most common and most stable – aqueous solutions are colored pink Official Compounds:  Manganese Chloride, USP;  Manganese Gluconate, USP;  Manganese Sulfate, USP B. TECHNETIUM (Technetos) o AKA: “Technetos” “eka-Manganese” o 1st element produced artificially; made by the bombardment of Mo by deuterons; Perrier and Segre o Used in preparation of radiopharmaceuticals o 99mTc Compounds are most commonly used radiopharmaceuticals; derived from the decay of Mo o mainly for bone imaging (i.e. 99mTc – Etidronate) o available as reagent kits; composed of buffers, preservatives, Sn2+ salts then freeze dried RADIOPHARMACEUTICALS 1. Tc99m-Phytate Liver imaging & potency studies 2. Tc99m-heptagluconate Kidney imaging, determine renal function 3. Tc99m-IDA Hepatobiliary studies 4. Tc99m-Etidronate Bone imaging 5. I-131-Human Serum Albumin Blood plasma volume/cardiac output determination 6. NaI-125 Thyroid function 7. Sodium Phosphate Serum Localization of ocular tumors, polycythemia vera 8. Sodium Chromate Cr 51 RBC mass, volume, survival time, scanning of spleen 9. Gold Au 198 Scintillation scanning of the liver 10. Chlormerodin Hg 197/203 Scintillation scanning of the kidneys or the brain 1 Alpha particles (a 42He2+)  heaviest and slowest of all radioactive emissions (0.1 the speed of light)  penetrating power is very low and can be stopped by a sheet of paper or a very thin sheet of Al  usually emitted only from elements having atomic numbers greater than 82 2 Beta particles (B or B+)  negatively charged species having a mass of an electron  move at a faster velocity (0.9 the speed of light)  their emissions from elements do not alter the mass number but do alter the atomic number  more penetrating power and able to travel 10 to 15 cm in water or penetrate almost 1 inch thickness of Al  sometimes called negatrons  emitted by unstable nuclei having neutrons in excess of protons 3 Gamma Radiation (t)  photon of electromagnetic radiation  demonstrates both wave and particle properties as do electrons and beta particles  short wavelength similar to x-rays and travel at the speed of light  no mass and no charge  excellent penetrating power (very thick lead is required to protect against it) GROUP VIIIA: 0 (18) ELEMENTS: INERT/NOBLE GASES All Group 0 elements except radon occur in the atmosphere Complete electrons (8); highest ionization energy; no compound except Xe are all monoatomic & unreactive MEMBERS: Helium – He Neon – Ne Argon – Ar Krypton – Kr Xenon – Xe Radon - Ra A. HELIUM (He) o 2nd lightest gas/AIR o Container: Brown o Inhalation of pure He produces a “Donald Duck-like Sound” or “Chipmunk-like Sound” o Use: 1. Carrier/diluents of medically important gases 2. Component of artificial gas/synthetic airs (80%He + 20% O2) B. NEON (Ne) o “new” o For advertising C. ARGON (Ar) o “lazy” o Most Abundant noble gas o Substitute for N2 in providing inert atmosphere; Container: RED (Argon methane) o By-product of fractionalization of liquid air for possible use as anesthetics D. KRYPTON o “hidden” o Least abundant of all noble gases o investigational anesthetic o *Ramsay & Travers (isolated Kr from Ar) E. XENON (Xe) o “stranger” o virtually ideal anesthetic inert gas sufficiently potent to provide rapid induction of & emergence from surgical anesthesia o Xenon Hexafluoride (XeF6) F. RADON (Ra) (Niton) o AKA: “Niton” by Ramsay o only synthetic and radioactive noble gas o treatment for cancer (Cervical Cancer) o *Ramsay & Soddy (succeeded in liquefying Ra) o *Ramsay & Collie (demonstrated the characteristic spectrum of Ra) Metals present in cytochrome oxidase:  FIRST TRIAD 1. Fe Iron toxicity: Hemochromatosis/Hemosiderosis 2. Cu (Prussian blue stain of the heart)  IRON  fourth most abundant of all elements  Silvery white; attracted by a magnet and can be temporarily magnetized  Chemistry: – Fe2+à aqueous solutions are colored green; mild reducing agent esp. in acidic solution hematinic agent for microcytic hypochromic anemia MOHR’S SALT: Fe2SO4(NH4)2SO4. 6H2O – – Fe3+ à aqueous solutions are orange to yellowish-brown FORMS OF IRON Wrought Iron purest form of Iron contains from 99.8% to 99.9% of pure iron Cast Iron impure form of Iron – White Cast Iron (Cementine) is a solid solution of hard brittle iron carbide formed when molten iron is rapidly cooled. – Gray Cast Iron (Graphite Scales formed when liquid iron is run into sand molds & allowed to cool Reduced Iron odorless, grayish-black powder; must pass through a No. 100 sieve is made from ferric oxide with the addition of hydrogen Galvanized Iron (Chrome alloyed with Zn; iron is protected when it is in contact with a metal that is more reactive Steel): Pig Iron Iron solidified into blocks IRON essential trace element present in tyrosine hydroxylase enzyme Present in: -Hemoglobin -Transferrin -Ferritin -Cytochrome Oxidase Enzyme Compounds of Iron: – Use: hematinic (increases Hb concentration) – Other uses: astringent and styptic Enhance Absorption with: -Vitamin C -Copper Alloy: Steel (Iron + 35% Carbon) *Misch Metal – is 70% Ce & 30% Iron Toxicity: GIT Distress; Cardiac Collapse Antidote: Deferoxamine Ferrous Sulfate (FeSO4) AKA: “Green Vitriol” USE: Hematinic Agent most economical & most satisfactory form of iron preparation in the market SE: Constipation Ferrous Gluconate most preferred; hematinic Fergon® less gastric irritating Ferrous Ammonium “Mohr’s Salt” most important double salt of ferrous sulfate w/ alkali Sulfate sulfate Ferric Ammonium Sulfate ‘Ferric Alum’ indicator used in precipitation method of analysis [FeNH4(SO4)2] Ferrous Fumarate Toleron® (hematinic agent) more stable than ferrous sulfate most tolerable form of iron less irritating to the GI tract than any other iron preparations Ferrous Carbonate “Chalybeate Pills”; Hematinic Agent (FeCO3) “Ferruginous Pills”; “Blaud’s Pills” Ferric Chloride (FeCl3) USES: astringent & styptic; detection test of tannins and phenols will react with: - Morphine (blue) - Benzoic Acid (flesh) - Resorcinol (violet) Iron + Ammonium “Basham’s Mixture” USES: astringent & styptic Acetate Iron Dextran Injection administered IM only Iron Oxide use as pigment Iron Pyrite “Fool’s Gold” Ferri Ferrocyanide, “Prussian blue” blue print dye Fe4[Fe(CN)6]3 Ferro Ferricyanide, “Turnbull’s Blue” blue print dye Fe3[Fe(CN)6]2  COBALT pinkish-white or bluish-white in appearance similar to Fe in terms of chemical reactivity essential in the development of erythrocyte & hemoglobin used in the manufacture of beer to enhance foaming quality. Chemistry: – Cobaltous (Co2+) - aqueous solutions are pink; a weaker reducing agent than Fe2+; the water is easily replaced by other ligands; anhydrous salts have a different color. – Cobaltic (Co3+) - powerful oxidizing agent; unstable in aqueous solution component of Vitamin B12 (cyanocobalamin) *Deficiency: Pernicious Anemia *Vogel’s Reaction – test for Co2+ with ammonium thiocyanate producing beautiful blue color Cobaltous Chloride (CoCl2) aka “Lover’s Ink”; Cobaltous Chloride “Sympathetic Ink” Anhydrous form: blue; hydrous form: pink indicator in silica gel beads & other dehydrating agents (desiccator) Cyanocobalamin (Vitamin B12) important in erythropoiesis Deficiency causes pernicious anemia Cobalt Zincate aka “Rinmann’s Green” Cobalt meta-aluminate aka “Thenard’s Blue”  NICKEL AKA: “Old Nick’s Copper” moderately lustrous silvery metal attacked by dilute aqueous acids but not alkalis used extensively in alloys metal in fancy jewelries found in fossil fuel combustion specified by dimethylglyoxime reagent which formed red ppt As a poison: Nickel itch = contact dermatitis Ni2+ - green in solution Nickel Pectinate à Tomectin *utilized for the treatment of diarrhea Raney Nickel à alloy of Ni & Al Nickel Hydroxide à Green solution German Silver à Ni + Zn + Cu Constantan à alloy of Cu + Ni  SECOND TRIAD  RUTHENIUM Klaus (1844); discovered in the Ural Mountains, named after the :Latin name of Russia, “Ruthenia” has +8 O.S Use: catalyst for the production of NH3 / NH4 (Haber process)  PALLADIUM Wollaston (1803); isolated from the remaining mother liquor after isolating platinum; named after Pallas, a newly discovered asteroid has the lowest density and melting point of the platinum metals Uses: manufacture of electronic components; dentistry; hydrogenation; dehydrogenation catalysts  RHODIUM Wollaston (1803); named after the Greek word for rose due to the rose-color of its aqueous solutions Uses: catalyst; control of car exhaust emissions; hydrogenation and hydroformylation reactions  THIRD TRIAD  OSMIUM Tennant (1803); named after the Greek word for odor due to the characteristic odor of OsO4 heaviest and densest metal Not affected by oxidizing acids and aqua regia; stable to atmospheric attack USE: dentistry as hardening agent in gold alloys IMPORTANT COMPOUNDS 1. Osmic Acid 2. Osmium Tetroxide *both used in staining microorganism for microscopic study  IRIDIUM Tennant (1803); named after ‘Iris’, the Greek Goddess of rainbows due to the varied color of its compounds USE: catalyst in the production of acetic acid  PLATINUM named after Platina, Spanish for little silver permanent in air and unaffected by hot or cold oxygen catalyst in finely divided steel called “Noble Metals” because it shows low oxidation potential & low reactivity USES: catalytic control of car exhaust emissions, in jewelry; petroleum and glass industries, making crucibles present in Cisplatin & Carboplatin CISPLATIN – Treatment for prostate cancer – aka Platinol – platinum complex – antineoplastic agent prepared treating potassium chloroplatinate with ammonia

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