Inorganic Medicinal Chemistry (Group IA, IB, IIA, IIB) - PDF

Why use metal-based drugs? Metal complexes exhibit unique properties Coordination and redox behavior Metal ions interact with biomolecules which allow scientists to safely administer even toxic metal ions to the human body Ability to be involved in reduction and oxi...

Why use metal-based drugs? Metal complexes exhibit unique properties Coordination and redox behavior Metal ions interact with biomolecules which allow scientists to safely administer even toxic metal ions to the human body Ability to be involved in reduction and oxidation reactions  photodynamic therapy (PDT) Transition metals bind to electron-rich biomolecules  deformation of DNA and ultimately to cell death Magnetic moments Metals w/ magnetic moment - used as imaging reagents Radioactivity Radioactive isotopes – used for therapy and imaging High aqueous solubility of their cations  Inorganic Medicinal Chemistry Area of research concerned with metal ions and metal complexes and their clinical applications Include the development of metal-based therapeutic agents, the interaction of metals and proteins, metal chelation and general functions of metals in living systems  Periodic Table A map that gives a picture of the relationships among the elements Groups or Families – elements w/ similar properties placed in a column Hindu-Arabic (1-18) - recommended by IUPAC Roman Numerals which distinguishes A and B groups (older notation)] Periods – rows of elements in the periodic table (#1- 7) Period 6 (Lanthanides) and Period 7 (Actinides): Inner Transition Metals  Inorganic Medicinal Chemistry DR. NIMFA B. GAMBALAN The Elements and their Compounds  Group IA Alkali Metals  Chemical Properties One valence electron, thus the elements in the group forms +1 ion when they react with non-metals Form white solid hydrides when heated with hydrogen: 2M + H2 ——> 2MH They have high affinity to oxygen (affinity increases with the atomic wt.) 4M + O2 ——> M2O 4Li + O2 → 2Li2O (oxide formation) 2Na + O2 → Na2O2 (peroxide formation) K + O2 → KO2 (superoxide formation) Reacts vigorously with water to form H 2 gas M + H2O ——> M2O + H2 (thus they should be protected from water )  Chemical Properties Only Lithium reacts with Nitrogen gas Li + N2 ——> Li3N + H2O ——> NH3 + LiOH Oxides of these metals react with water to form a base (alkalinity of the base produced increases with the atomic radius of the metal) M2O + H2O ——> 2MOH Alkali metal halides are soluble in water All the salts of the alkali are water-soluble ( thus they are usually tested using the flame test)  HYDROGEN Aka “inflammable air” Most abundant element in the universe (followed by He & O) Lightest element (followed by He) Colorless, odorless, tasteless Diffuses more rapidly than any other gas Absorbed by many metals forming metal hydrides Preparation of Hydrogen: Interaction of superheated steam with red hot iron (Lane process) Electrolysis of water Separation from water gas (a mixture of H2 & CO produced by passing steam over coke at about 1000oC) (Messerschmitt process) Interaction of ferrosilicon (an alloy or compound of iron and silicon) with NaOH solution Hydrolysis of metallic hydrides Use/s of Hydrogen: Used as a reactant in various states of purity and its peroxide (0.3% solution) are official and it is the element common to all official acids Present in various other compounds such as ammonia, ammonium salts, NaOH, hydrates, etc. Isotopes of Hydrogen H (Protium) - hydrogen from natural sources consists of 1 1 more than 99.8% in nature 12D (Deuterium) Occurs in nature My be isolated from liquid H2 by fractional distillation or by electrolysis of deuterium oxide (heavy water) Used as a bombarding agent in the form of deuterons and as a tracer in pharmacologic investigations 13T (Tritium) Does not occur in nature and its preparation is therefore exclusively synthetic Prepared by bombarding beryllium with deuterons Radioactive and has a half life of about 12 years Hydrogen Oxides of Pharmaceutical Importance: Water (H2O) Odorless, tasteless, clear liquid, clear in small quantity but greenish blue in deep layers About 3 quarters of the earth’s surface is covered with liquid water and it constitutes 70% of the human body Types of Naturally occurring waters Mineral waters Alkaline waters Carbonated water Chalybeate water Lithia water Saline water Sulfur water Siliceous water Potable water – water which is fit to drink Composition of Natural water Salts of Ca, Fe, K and Na Organic matter from falling leaves and twigs Traces of CO2, N2, NH3 and other gases from atmosphere Suspended matter such as fine particles of clay, sand, microscopic organisms including bacteria and fragments of vegetation Water Purification Methods Removal of insoluble matter through appropriate coagulation, settling and filtering processes Destruction of pathogenic microorganisms by aeration and chlorination Improvement of palatability through aeration and filtration through charcoal For hard water, softening can be done by partial chemical removal of dissolved/calcium, Mg and Fe by coagulation, precipitation or by reaction with ion exchange resins On small scale, water may be purified (free from microorganisms)) by boiling for 15- 20 min or by treatment with a chlorinating agent such as Halazone Types of Water: Non-potable H2O not used for drinking but are used for cleaning of outer surface of factory Potable (drinkable) water H2O used for washing and extraction of crude drugs, preparation of products for external use Purified water, USP H2O used for non-parenteral preparation, for all types of tests and assay, cleaning of non-parenteral product preparation, preparation of some bulk chemicals and preparation of media in microbiology laboratory Types of Water: Water for injection (WFI), USP Sterile and non-pyrogenic H2O used in parenteral solutions, cleaning parenteral product contact components Sterile water for injection (SWFI), USP H2O that is sterilized and packaged in single dose containers (Type 1 glass) Used as sterile diluent for parenteral products and in extemporaneous preparation compounding Sterile water for inhalation, USP H2O for injection that is used for the preparation of inhalators and inhalant solutions Types of Water: Bacteriostatic water for injection, USP H2O which contains anti-microbial agent/s Used in the preparation of parenteral products and compounding small volumes of extemporaneous parenterals for IM injection Sterile water for irrigation, USP H2O for injection used to moisten body tissues and in performing urologic procedure Hydrogen Oxides of Pharmaceutical Importance: Hydrogen peroxide Colorless, odorless liquid having an odor resembling that of ozone Usually deteriorates on standing or on protracted agitation A germicide active by virtue of the release of nascent oxygen Prepared by metathesis reaction between BaO2 and phosphoric acid and by electrolysis of ammonium persulfate Anhydrous H2O2 contains 47% by weight of available oxygen Offered commercially as aqueous solutions containing 3 - 90% H2O2 by weight Strength of H2O2 (based on the volume of active oxygen it yields): 1% by weight is equivalent to about 3.3% by volume 100% volume corresponds to 30% by weight 30% volume to 9% by weight  LITHIUM Aka “Earth” Lightest metal Resembles Mg (some extent Ca) more closely than Na Occurs widely in nature in the form of silicates and phosphates and usually associated with other metals Prepared by electrolysis of its fused chloride Compounds of Li: Lithium bromide – depressant Lithium carbonate/citrate – useful in the treatment of manic state of Bipolar Disorder  Identification Tests Flame test – carmine red flame Phosphate test – Reacts w/ Na2HPO4 + NH3 forming a white ppt of Li3PO4 (soluble in HCl and will not be reprecipitated with the addition of NH3)  SODIUM Aka “Natrium” Major extracellular cation  muscular contraction Naturally occurring Na compounds: Sodium chloride – most important Na mineral Sodium nitrate Sodium aluminum fluoride (Cryolite) Sodium tetraborate (Borax)  Compounds of Sodium Compounds of Sodium: NaCl (table salt, rock salt, soler salt) – electrolyte replenisher & antidote for Ag poisoning NaHCO3 (Baking soda) – buffer, antacid (causes rebound hyperacidity, systemic alkalosis and edema), DOC for metabolic acidosis Na2B4O7.10H2O (Borax) – water softener & antiseptic Na2CO3.10H2O (washing soda, sal soda) – antacid ; produced via Solvay process Ringer’s solution – aqueous solution containing NaCl, CaCl2 & KCl, used as electrolyte replenisher Lactated Ringer’s solution (Hartmann’s solution) – aqueous solution containing NaCl, Na lactate, CaCl2 & KCl, used as electrolyte replenisher Darrow’s solution – aqueous solution containing NaCl, Na lactate & KCl, used as electrolyte replenisher  Compounds of Sodium Na3C6H5O7 (Sodium citrate) – buffer, alkalinizers, sequestering agent, diuretic, shorten coagulation time NaF – dental prophylactic NaOH (Caustic soda,lye, sosa) – saponifying agent NaOCl (Chlorox, Dakin’s solution) – bleaching agent & antiseptic Na3PO4 – saline cathartic Na2SO4·10H2O (Glauber’s salt)- cathartic Na2S2O3.5H2O (Hypo)- antidote for HCN poisoning Na2C4H4O6 – primary standard for Karl Fischer reagent NaSCN – hypotensive agent NaH2PO4 – Fleet® enema, cathartic and source of P or phosphate Na3PO3 – reducing agent  Compounds of Sodium Na2SiO3 – water glass Na2CO3 (Soda ash, soda) – primary standard for HCl and other acids NaBr – sedative NaNO3 (Chile saltpeter) – meat preservative, produced via Solvay process NaC2H3O2 – diuretic, urinary alkalinizer, systemic antacid NaHSO3 – water soluble antioxidant NaNO2 –vasodilator, antidote for cyanide poisoning  Identification test: Na2SiO3 – water glass Na2CO3 (Soda ash, soda) – primary standard for HCl and other acids NaBr – sedative NaNO3 (Chile saltpeter) – meat preservative, produced via Solvay process NaC2H3O2 – diuretic, urinary alkalinizer, systemic antacid NaHSO3 – water soluble antioxidant NaNO2 –vasodilator, antidote for cyanide poisoning  Compounds of Sodium Na2SiO3 – water glass Na2CO3 (Soda ash, soda) – primary standard for HCl and other acids NaBr – sedative NaNO3 (Chile saltpeter) – meat preservative, produced via Solvay process NaC2H3O2 – diuretic, urinary alkalinizer, systemic antacid NaHSO3 – water soluble antioxidant NaNO2 –vasodilator, antidote for cyanide poisoning  Identification Tests Flame test – persistent golden yellow flame Antimonate Test – uses KH2SbO4 or K2H2SbO7 giving a white ppt. of NaH2SbO4 or Na2H2Sb2O7 (Sodium dihydrogen pyroantimonate) Acetate test – uses Zn(C2H3O2)2 giving a pale yellow ppt. of NaC2H3O2 potassium-thumb.webp POTASSIUM Predominant intracellular cation Most reactive of all metals Gives brown and light-resistant glass Important in muscular contraction and possesses diuretic effect Important K minerals include: Sylvite (KCl) Carnallite (KCl·MgCl2·6H2O) Kainite (K2SO4·MgSO4·MgCl2·6H2O) Polyhalite (K2SO4·MgSO4·2CaSO4·2H2O) potassium-thumb.webp POTASSIUM Predominant intracellular cation Most reactive of all metals Gives brown and light-resistant glass Important in muscular contraction and possesses diuretic effect Important K minerals include: Sylvite (KCl) Carnallite (KCl·MgCl2·6H2O) Kainite (K2SO4·MgSO4·MgCl2·6H2O) Polyhalite (K2SO4·MgSO4·2CaSO4·2H2O) potassium-thumb.webp Compounds of Potasium KHC4H4O6 (Potassium bitartrate, cream of tartar) – cathartic KBr – sedative KOH (Caustic potash) – saponifying agent KMnO4 (Mineral chameleon) – oxidizing agent & antiseptic KNaC4H4O6 (Rochelle salt) – saline laxative & sequestering agent K2Sx + K2S2O3 (Sulfurated potash, liver of sulfur, hepar sulfuric) – used for the preparation of white lotion K2CO3 (Potash) – for preparation of K compounds KNO3 (Saltpeter, salitre) – meat preservative potassium-thumb.webp Compounds of Potasium KI – expectorant and solubilizing agent of iodine KCl – electrolyte replenisher KClO3 – ingredient of toothpaste, mouthwashes and gargles K3C6H5O7 – diuretic, expectorant and diaphoretic Identification test: Flame Test – violet flame Cobaltinitrite test [Na3Co(NO2)6] – gives yellow ppt of K2Na[Co(NO2)6] (insoluble) Tartrate test (H2C4H4O6) – gives white ppt. of KHC4H4O6 which upon the addition of NaOH form KNaC4H4O6 (Rochelle salt) potassium-thumb.webp Identification Tests Flame Test – violet flame Cobaltinitrite test [Na3Co(NO2)6] – gives yellow ppt of K2Na[Co(NO2)6] (insoluble) Tartrate test (H2C4H4O6) – gives white ppt. of KHC4H4O6 which upon the addition of NaOH form KNaC4H4O6 (Rochelle salt) potassium-thumb.webp RUBIDIUM Rubidium is a silvery-white and very soft metal — and one of the most highly reactive elements on the periodic table pharmaceutical Rubidium has a density about one and a half times that of water and is solid at room temperature, although the metal will melt if it's just a bit warmer No known Like the other alkali metals (lithium, sodium, potassium, cesium and francium), rubidium reacts violently with water, oxidizes when use reacting with oxygen, and ignites due to humidity in the air, so great care must be taken when working with the element potassium-thumb.webp CESIUM pharmaceutical No known use RUBIDIUM (Rb) and CESIUM (Cs) Rb and Cs are similar in behavior and they do not have pharmaceutical significance Cs – catalyst in polymerization of resin forming material potassium-thumb.webp FRANCIUM Second rarest element in the earth’s crust next to Astatine ( occurs in < 30 grams ) It is a heavy, unstable , radioactice metal pharmaceutical with a maximum life of only 22 minutes When placed in water, it is the most reactive among the alkali metal No known use  Group IB Coinage Metals Physical & Chemical Properties All 3 members of the group are employed for ornamental and coinage purposes have smaller size than the alkali metals Occur free in nature not very active and are displaced by most metals Ag/Cu/Au gold halides are nearly insoluble in water Form complex anions and complex cations with ammonia Used in the preparation of alloys like Cu forms brass (Cu & Zn) and bronze (Cu & Sn) potassium-thumb.webp COPPER Aka “Cuprum” 2nd best conductor of electricity 3rd most malleable and ductile Only reddish-colored metal Present in Cytochrome P450 and hemocyanin Essential trace element which enhances the physiologic utilization of iron Toxicity – Wilson’s disease (Antidote: Penicillamine potassium-thumb.webp Compounds of Copper CuSO4·5H2O (Blue vitriol, bluestone) – preparation of Fehling’s and Benedict’s solution, fungicide, antidote for P poisoning Copper citrate – 8% ointment is used as astringent Copper acetoarsenite (Cu(AsO2)2·Cu(C2H3O2)2, Paris green, Parrot green) – pigment, rodenticide & insecticide Basic copper acetate (Cu(OH)2·Cu(C2H3O2)2, Verdigris) – paint pigment, pesticide & fungicide Copper hydrogen arsenite(CuHAsO3, Scheele's green, Schloss Green) – insecticide & fungicide CuSO4·5H2O·CaO (Bordeaux mixture) – algaecide and fungicide for swimming pool potassium-thumb.webp Identification tests Flame Test- green colored flame Ferrocyanide test (K4[Fe(CN)6]·3H2O) – reddish brown ppt. of Cu2[Fe(CN)6] which is soluble in excess NH3 forming Cu(NH3)4 2+ ion which is a blue solution Flame Ferrocyanid Test e Test potassium-thumb.webp SILVER Aka “Argentum” 2nd most malleable metal, 2nd most ductile metal & Best conductor of electricity Poisoning is called Argyria (Antidote: NSS) Has oligodynamic property (ability to kill or inhibit the growth of microorganisms) potassium-thumb.webp Compounds of Silver AgNO3- Lunar caustic,Indelible ink, Lapiz infernalis removal of warts Silver nitrate (1% opthalmic solution-eyewash for newly born babies for treatment of gonorrhea Ammoniacal AgNO₃ used for Tollen’s test (silver mirror test) 0.5% solution used s wet dressing treats third degree burns potassium-thumb.webp Compounds of Silver Silver Proteinates: `Mild Silver protein- Argyrol 19-25% Ag –used as antiseptic for eyes Strong Silver proteins-Protargin ( 7.5 and 8.5%), the protein is partially hydrolyzed providing higher concentration of Ag⁺ resulting to a more irritating and bactericidal action for irrigation of urethra and bladder for treatment of gonorrhea Colloidal Ag Protein- Collargol-germicidal Colloidal silver iodide- Neo-silvol (18-22%) Silver picrate- Picritol, Picragol- treatment of vaginitis potassium-thumb.webp Identification Test Chloride test (HCl) –white ppt. of AgCl sol in NH3 forming Ag(NH3)2+ ion which precipitates back to AgCl upon addition of HNO3. May also be tested using AgBr and AgI potassium-thumb.webp GOLD Aka “Shining dawn” King of all metals Most malleable metal, most ductile metal & 3rd best conductor of electricity Gold compounds are toxic. Dimercaprol is an effective antidote Dissolved by: Selenic acid Aqua regia (Royal water: 3 parts HCl and 1 part HNO3) potassium-thumb.webp Gold Compounds Used in the treatment of lupus erythematous and rheumatoid arthritis [Aurothioglucose (IV), Gold sodium thiomalate, Auranofin (PO)] Radioactive isotope of Au is used in the treatment of certain malignancies potassium-thumb.webp Gold Compounds Gold Compounds are used in the management of Rheumatoid Arthritis.They are DMARDDs potassium-thumb.webp Zsigmondy Number of Gold Solution of colloidal gold is used to determine the protective power of colloids (Gold or Zsigmondy number) potassium-thumb.webp GOLD Purity of Au is expressed in carats %Au= (K/24) x 100 Nuggets – refers to gold dust or free gold  Group IIA Alkaline Earth Metals Physical & Chemical Properties Has 2 valence electrons, thus forms +2 ions when they react with non-metals Beryllium is the only member of the group that forms covalent compounds with non-metals. Reacts with O2 except for Be M + O2 ——> MO Salts of these metals are not as soluble as the salts of the alkali metals since they are hydrated Physical & Chemical Properties Elements are strictly metallic They function uniformly with a +2 oxidation number Do not occur free in nature because of high order of chemical reactivity Hydroxides of Ca, Sr and Ba are relatively insoluble in H2O and are strongly basic Carbonates, sulfates, phosphates and fluorides are quite insoluble potassium-thumb.webp BERRYLIUM Amphoteric As a bridge element, it resembles Al Used to make x-ray tubes due to the fact that they are better at letting x-rays mthrough rather than glass Present in minerals like aquamarine and emerald potassium-thumb.webp Amphoteric As a bridge element, it resembles Al Used to make x-ray tubes due to the fact that they are better at letting x-rays mthrough rather than glass Present in minerals like aquamarine and emerald potassium-thumb.webp MAGNESIUM Lightest of all structurally useful metal 2nd most abundant intracellular cation & a natural Ca2+ channel blocker Burns in air with a blinding bluish light-active rays hence used in photography, in flash bulbs and signal lights Used in research involving photosynthesis for it is present in plats specifically in chlorophyll Metal present in Grignard Reagent (organometallic compound) potassium-thumb.webp Compounds of Magnesium Mg(OH)2 (Milk of magnesia) – antacid & laxative MgCO3 (Magnesia) – antacid & laxative MgO (Calcined magnesia) – antacid & component of universal antidote Magnesium trisilicate – antacid (has prolonged effect due to gelatinous consistency of preparation) MgSO4 – cathartic & anticonvulsant (IM) Hydrated Magnesium silicate (Talc, soapstone) – adsorbent, filtering aid, clarifying agent & dusting powder Magnesium citrate (purgative limon, limonada purgante) – cathartic potassium-thumb.webp Identification Tests Magnesium (2+) Biphosphate test (Na2HPO4, NH3 and NH4Cl) – white crystalline ppt. of MgNH4PO4 + Titan Hydroxide test (NaOH) – white ppt. of Mg(OH)2 yellow Mg(OH)2 which has the capacity of adsorbing color of dyes w/ Titan yellow(produce a red lake) while with p-nitrobenzene azo- resorcinol (blue lake) Red lake potassium-thumb.webp CALCIUM Cation of hydroxyapatite (major constituent of bones and teeth) 2nd most abundant extracellular cation Essential factor in blood coagulation/clotting Ca salts are more soluble in cold than in hot solutions Sources: CaCO3 (marble, limestone, chalk) CaSO4·2H2O (gypsum, selenite) 3Ca3(PO4)2.CaF2 (apatite) Ca3 (PO4)2 (phosphate rock) CaF2 (fluorspar) potassium-thumb.webp Compounds of Calcium CaCO3 (Precipitated chalk) – antacid & dentifrice CaCl2.H2O (Muriate of Lime) – electrolyte replenisher Ca(OH)2 (Milk of lime, liquor calcium) – antacid Calcium lactate – source of Ca ion CaO (lime, quicklime) – use in preparation of various insecticides CaSO4·1/2H2O (Plaster of Paris) – use for preparing bandages Ca(ClO)₂ (Chlorinate lime) – bleaching agent & disinfectant Ca3(PO4)2 (Bone ash) – most important constituent of teeth and bones CaCO3· MgCO3 (Dolomite) – antacid CaBr2 – sedative potassium-thumb.webp Identification Tests Flame test – brick red or dull red flame Oxalate test (K2C2O4) – white ppt. of CaC2O4 insoluble in CH3COOH( which is different from Ba and Sr) potassium-thumb.webp STRONTIUM SrCl2 – temperature desensitizing agent Sr-89 chloride injection – palliative for the relief of bone pain in patients w/ skeletal metastases) Used in industry of pyrotechnics (red signal flare). Sources: SrCO3 (Strontianite) SrSO4 (Celestite or Celestine) potassium-thumb.webp STRONTIUM SrCl2 – temperature desensitizing agent Sr-89 chloride injection – palliative for the relief of bone pain in patients w/ skeletal metastases) Strontium behaves like Ca in the body, thus it is dangerous because it can take up the Calcium spot in the bones Used in industry of pyrotechnics (red signal flare). Sources: SrCO3 (Strontianite) SrSO4 (Celestite or Celestine) potassium-thumb.webp Properties of Strontium malleable Has extreme reaction with water to produce hydrogen gas It has the same relative abundance as Carbon and sulfur but does not occur in free form potassium-thumb.webp Identification Tests Flame Test – crimson red Biphosphate test (Na2HPO4, NH3 and NH4Cl) – white ppt. of Sr3(PO4)2 soluble in HCl and precipitates back upon addition of NH3 (difference from Li+) Sulfate test (H2SO4) – white ppt. of SrSO4 potassium-thumb.webp BARIUM Most active Group IIA element Salts are used in green pyrotechnics All Ba compounds soluble in water or dilute acids are poisonous (Antidote: MgSO4) BaSO4 – used as a radiopaque agent for X- ray imaging and other diagnostic procedures Ba(OH)2 – employed as carbon dioxide absorber potassium-thumb.webp Identification Tests Flame test – yellowish green Chromate test (K2CrO4) – yellow ppt. insoluble in CH3COOH (difference from Ca and Sr) Sulfate test (H2SO4)- white ppt. of BaSO4 which is insoluble in all acids  Group IIB Volatile Metals Physical & Chemical Properties Oxides of these metals become less stable to heat as atomic number increases Chlorides are hydrolyzed with decreasing case in the order (Zn, Cd, Hg) Cd and Zn form complex ions (Cd having a greater tendency toward coordination) Cd salts are less soluble than the corresponding salts indicating a greater degree of covalency  General Chemical Reactions M + X2 ——> MX2 2M + O2 ——> 2MO M + 4HNO3 (conc.) ——> M(NO3)2 + 2NO2 + 2H2O Zn(OH) 2 + 2HCl ——> ZnCl2 + 2H2O Zn(OH)2 + 2NaOH ——> Na2ZnO2 + 2H2O potassium-thumb.webp ZINC Metal present in insulin and carbonic anhydrase Deficiency: Parakeratosis (thick, scaly inflamed skin) Uses: Protective coating for galvanized iron Container for dry cells and batteries For embalming ( ZnCl2) Antidote for Zinc poisoning: NaHCO3 (Baking soda) potassium-thumb.webp Compounds of Zinc ZnO ( component of Lassar’s pastes) – mild antiseptic, astringent & protectant ZnCO3 – astringent and desensitizer for dentin ZnSO4 – ophthalmic astringent ZnSO4·7H2O (White vitriol) – emetic, astringent & ingredient of white lotion ZnCl2 – antiseptic found in mouthwashes, topical protective, dentin desensitizer Zinc peroxide – antiseptic Hydrated Zinc silicate (Natural calamine) –topical protectant & anti-itch Zinc Eugenol cement – dental protective & dentifrice potassium-thumb.webp Identification Tests Sulfide test (H2S)- white ppt. of ZnS Ferrocyanide test (K4[Fe(CN)6]·3H2O) – white ppt. of K2Zn3[Fe(CN)6]2 Reaction w/ Aqueous ammonia – white ppt. of Zn(OH)2 soluble in excess of the reagent forming Zn(NH3)4 2+ ion potassium-thumb.webp CADMIUM Causes Itai-itai disease (MOT: replaces Ca in bones) Compounds: Cadmium chloride – emetic & treatment of tinea infections Cadmium sulfide – antiseborrheic agent Cadmium sulfate – ophthalmic antiseptic potassium-thumb.webp CADMIUM potassium-thumb.webp Identification Tests Sulfide test- yellow ppt. of CdS insoluble in Na2S reagent Ferrocyanide test – white ppt. of Cd2[Fe(CN)6] Reaction w/ Aqueous ammonia – white ppt. of Cd(OH)2 soluble in excess of the reagent forming Cd(NH3)4 +2 ion Cd+2 in with H2S forms yellow precipitate potassium-thumb.webp MERCURY The only liquid metal Forms amalgams with other metals Causes Minamata disease Industrial use: manufacture of thermometers & formation of amalgams Pharmacologic actions: diuretic, antiseptic, antisyphilis, cathartic, parasiticide & fungicide Present in Alkaloidal solutions like Mayer’s reagent potassium-thumb.webp Compounds of Mercury Hg₂Cl₂ (Calomel) – antiseptic & cathartic HgCl2 (Corrosive sublimate) – disinfectant Mercuric oxide - ophthalmic antiseptic Ammoniated Mercury (HgNH2Cl, White precipitate) – a topical and ophthalmic anti- infective Mercurous iodide – anti-syphilis Potassium mercuric iodide – antiseptic & ingredient of Mayer’s reagent potassium-thumb.webp Identification tests Mercurous ion Chloride test (HCl) – white ppt. of Hg2Cl2 which blackens upon addition of aqueous NH3 due to formation of metallic Hg Iodide test – green ppt. of Hg2I2 soluble in excess of the reagent forming K2HgI4 and metallic Hg Mercuric ion Chloride test(HCl) – HgCl2 soluble. in water Reduction test (SnCl2) – white ppt. of Hg2Cl2 turning white or gray due to metallic Hg Iodide test – red ppt. of HgI2 soluble in excess of the reagent forming K2HgI4  Group IIIA Boron Group or Icosagens Physical & Chemical Properties B and Al are the most important members of this group in Pharmacy Al – most abundant metal and the 3rd most common element in the earth’s crust [Oxygen (1st) and Silicon (2nd)] Boron is a non-metal Metals of this group are readily oxidized in air Readily react with halogens and sulfur Hydroxides of these elements are amphoteric except B and Tl potassium-thumb.webp BORON Bridge element that resembles Si Decreases the coefficient of heat expansion of glass Used in vulcanizing rubber Oxyacids of Boron: H3BO3 (Orthoboric acid) (HBO2)n (Polymetaboric acid) H2B4O7 (Tetraboric acid) HBO3 (Perboric or peroxyboric acid) potassium-thumb.webp Compounds of Boron H3BO3 – topical anti-infective & ophthalmic irritant Na3BO3 – bacteriostatic & ingredient in cold cream, eye washes and mouth washes Sodium perborate – oxidizing type of local anti- infective Sodium tetraborate – antiseptic, eyewash & wet dressing for wounds potassium-thumb.webp Identification tests Borate ion (BO3-3) Flame test CH3OH + H2SO4 ——> (CH3) 3BO3 green bordered flame of methyl borate Turmeric Paper test Acidic solution of borate will turn turmeric paper brownish red while basic or alkaline medium will turn The green the turmeric paper greenish black bordered flame produced by borate ion potassium-thumb.webp ALUMINUM Metal and its hydroxides are amphoteric Al compounds are used as antacid, antiperspirant & deodorant Thin Al foil is used to treat burns Al silicates: Kaolin (Native hydrated Al silicate) – adsorbent Bentonite (Native colloidal hydrated Al silicate) – suspending agent Pumice (complex silicate of Al, Na & K) – dental abrassive potassium-thumb.webp Compounds of Aluminum Al(OH)3 (Amphogel, cremalin gel) – used as antacid & protectant (may cause constipation and phosphate deficiency) AlPO4 (Phosphagel) – astringent, antacid & demulcent (does not interfere with phosphate absorption) Al2(CO3)3 – treatment of phosphate calculi Al2O3 (Alumina) – treatment of silicosis AlCl3 – astringent, antiseptic, antiperspirant & deodorant Aluminum acetate (Burrow’s solution) – astringent Potassium aluminum sulfate (Alum) – astringent, antiperspirant & deodorant potassium-thumb.webp Identification Tests Reaction w/ Aqueous ammonia – white gelatinous ppt. of Al(OH)3 Thernard’s blue test /Charcoal test Co(NO3)2 + NH3 ——>Co(AlO2)2 (blue ash of cobalt meta-aluminate)