Coinage Metals

Coinage Metals / Periodic Table / Handouts

1. Group 1B (Group 11) Coinage Metals
Copper Gold Silver

Coinage Metals
- Three nonradioactive members of group 11 of the periodic table.
- Used to make coins have to fulfill special requirements: Malleability
- Coinage metals are therefore mixed with other metals to form a so-
called alloy
- Relatively inert and corrosion-resistant metals and therefore are
useful for the production.

Coinage Metals: Chemistry
- Are excellent conductors of electricity and heat.
- The most conductive metal for electricity is: Ag > Cu > Au
Ag - most thermally conductive element and the most light-reflecting
element.
- Ag & Au: inert and not attacked by oxygen or non-oxidizing acids.
Cu: [Ar]3d
10
4s
1

Ag: [Kr]4d
10
5
1

Au: [Xe]41
14
5d
10
6s
1

Copper
Cuprum, Roman

Occurrence – Nature
- Chalcopyrite [CuFeS2]
- Chalcocite [Cu2S]
- Malachite [CuCO3.Cu(OH)2]
- Cuprite [Cu2O]
- Food source
 shellfish, dry legumes, whole grain cereals
Physiologic Occurrence
- Essential trace element
 small quantities enhance physiologic utilization of iron.
- Major ion: Cu
2+

 the oxidation state shifts between the cuprous (Cu+) and
cupric (Cu2+) forms.
 Incorporated into a number ofmetalloeznynes – so called
cuproenzymes.
-Lysyl oxidase: cross-linking of collagen and elastin.
- Ceruloplasmin (ferroxidase I) and ferroxidase II: Fe
2+
to Fe
3+
(with
transferrin to form RBC).
- cytochrome c and superoxide dismutase: antioxidants
- involved in the synthesis (dopamine-b-monooxygenase) and
metabolism (monoamine oxidase) of neurotransmitters.
- Respiratory pigment (hemocyanin)
- Component of enzymes
- Brain, liver, heart, and kidney.

Physical Properties – Copper
- Malleable and ductile
- Red
- Third best conductor of heat
 affected by impurities, arsenic
- Second best conductor of electricity

Chemical Properties – Copper
- Permanent in dry air, slowly oxidized in moist air
 2Cu + O2 2CuO (black)
 Cu + S CuS
 2Cu+ X2 2CuX
- Unreactive with water
- Dominant oxidation states of copper are Cu(II) and Cu(I)
- Acids with oxidizing properties
 Concentrated acid: Cu+ 4HNO3Cu(NO3)2 + 2H2O + 2NO2
- Diluted acid: 3Cu + 8NHO4 3Cu(NO3)2 +2NO + 4H2O
- Hot Concentrated: Cu + 2h2SO4 CuSO4 + SO2 + 2H2O
- Dissolved by acidified solutions of copper (II)
 Cu + Cu
2
 2Cu
+

 4Cu
+
+ 4H3O
3
+ O2 4Cu
4+
+ 6H2O
- Color
 Cu2S
 Cu2O

Chemical Properties – Cuprous
- Water-insoluble
- Soluble in conc hydrohalide acids
 2CuX + 4HX  H4(Cu2X6)
 Gas analysis: CO
- Soluble in amoonia water
 CuCl + 2NH4OH Cu(NH3)2Cl + 2H2O
 Assay of oxygen

Physical Properties – Cupric
- Blue, greenish-blue
- Anh: white, yellowish

Chemical Properties – Cupric
- Water-soluble salts: NO3
-3
, Cl
-
, Br
-
, F
-
, SO4
2-
, CH3COO
-
, C6H5O7
3-
(sl sol)
- Water-insoluble salts: tannate, proteinate, AsO4
3-
, AsO3
3-
, OH
-
, CO3
2-,

and PO4
3-

 mostly solubilized in acidified solutions
 precipitation can be prevented by sequestants
- citrate (Benedict’s)
- tartrates (Fehling’s)
- glycerin (Haine’s)
- sugar
- Actually exist in a hydrated form: [Cu(H2O)4]
2+

- Upon hydrolysis produces a sl. Acidic soln
 [Cu(H2O+4+]
2+
+ H2O  [Cu(H2)3OH]
+
+ H3O
3+

- Readily reduced to Cu
+

- with I
-
- with CN
-
- Completely reduced to Cu with aldehydes and ketones in alkaline
solution
 Red cuprous oxide
- Complex formation
Rxn with K4Fe(CN)6
 Antidote for acute cupric salt poisoning
- Rnx with KSCN
 Black cupric thiocyanate
 White cuprous thiocyanate
- Rxn with H2S
 Group 2 in cation analysis
Official ID Tests
REAGENTS Expected Result/s
HCl, Fe solution Red film of Cu
6N NH4OH excess
reagent
Bluish ppt Cu(OH)2 Deep blue colored
solution
K4Fe(CN)6 TS dilute acid Reddish brown insoluble
Physiologic Function
- Comp. of metalloproteins
- Abs and utilization of Fe
- Electron transport
- Connective tissue metabolism
- Phospholipid formation

2. - Purine metabolism
- Dev’t of nervous system
Pharmacologic Action
- External
 Protein precipitant (astringent)
 oligodynamic
 Fungicide (1:1000000)
 Algaecide (tx of waterm skin infxns)
 Mild antiseptic
- Internal
 Aid in assimilation of Fe
 Tx of anemia
 Optimum ration of Cu to Fe = 1:25
- Emesis
 Due to irritant action of small doses
 Large doses corrosive to Gl mucosa, kidneys. Spleen. Etc.
 Cupric nucleinate (liver, blood, bile)

Toxicity: Wilson’s Disease
- Excessive amounts of copper build up in the human body.
- The copper is mainly stored in the liver and brain, and therefore
causes liver cirrhosis and damage to the brain tissue.
- The damage to the brain tissue occurs mainly at the lenticular nucleus
and a typical brown ring is visible around the iris;
- Wilson disease is also called hepatolenticular degeneration.\
- Genetic disorder of copper metabolism manifestation: ATP7B
(abnormal gene)
- neuropsychiatric (behavioral changes, psychosis, extrapyramidal
signs)
- Liver (cirrhosis, hepatitis)
- Inability to excrete biliary Cu
- Absence/low ceruloplasmin
- Increase in aminotransferase
- Increase in urinary excretion of Cu

Treatment
- Chelating Therapy (2-3 weeks)
 EDTA
 Dimercaprol or BAL or British Anti-Lewisite
 D-Pencillamine or Cuprimine (1956)
 promote urinary excretion of copper in complexed form
- Oral zinc

Deficiency
- Anemia
- Growth depression
- Skeletal defects
- Demyelination and degeneration of nervous sys
- Ataxia (lack of oxygen)
- Defects in pigmentation and structure of hair
- Reproductive failure
- Cardiovascular lesion

Menke’s Disease
- An inborn disease characterized by all the symptoms of Cu deficiency
except anemia and neutropenia
- Defect in copper absorption by the intestine and the liver

Uses of Metallic Copper
- Motors, dynamos, wire. Ornamental vessels. roofing. ship plates.
electrotype plates
- Alloys:
 Brass(Cu + Zn)
 Bronze (Cu + Zn + Sn)
 Sterling (Cu + Ag)


Official Compounds of Copper
 Copper Gluconate, USP
 Cupric Chloride
 Cupric Sulfate, NF XII
Copper Gluconate, USP
USE: Oral deodorant

Cupric Chloride - CuCl2
- Definition: Cupric Chloride contains NLT 99,0% and NMT 100.5% of
CuCl2, calculated on the dried basis
- Dihydrate, anhydrous
- Catalyst for org and in org rxns
- Pyrotechniques, pigments for glass and ceramics, mordant,
disinfectant
- Has been used for cyanide poisoning

Cupric Chloride INJ., USP
- Cupric Chloride Injection is a sterile solution of Cupric Chloride in
WFI.
- It contains NLT 90% and NMT 110.0% of the labelled amount of
Copper.

Cupric Sulfate, NF XII – CuSO4•5H2O
- Cupric Sulfate, dried at 250
0
to constant weight, contains NLT 98.5%
and NMT 100.5 % o fCuSO4.
- Syn: Blue Vitriol or Blue stone
- Component of Fehling’s, Benedict’s solution
- Uses: algicide and fungicide in combo with Lime (Bordeaux Mixture)

Physical Properties
- Deep blue, triclinic crystals of the pentahydrate
- Blue crystalline granules or powder.
- Efflorescent
- Anhydrous salt = white

Unofficial Compounds
- Cupric Acetate
 External prep
- Basic Cupric Acetate
 green verdigris

Non-official Compounds
 Cuprous Oxide
 Cupric Hydroxide
 Cupric Hydrogen Arsenite
 Cupric Acetoarsenite
 Cuprous Acetate

Cuprous Oxide - CuO
- Cuprite, red mineral
- Opted by alkaline solns of Cu(II) when boilied with RA
- Manuf of red glass, red glazes for porcelain, paint
- Tx of seeds of fungus-infected veg

3. Cupric Hydroxide – Cu(OH)2
- Dissolves in ammonium hydroxide producing Schweitzer’s soln
- Prep by mixing milk of lime and cupric sulfate(Bordeaux misture)
 spray, fungicide

Cupric Hydrogen Arsenite - CuHAsO3
- Cupric arsenite
- Scheele’s mineral, Swedish green, Scheele’s green
- Intestinal antiseptic
- Insecticide, rodenticide
- Wall paper color

Cupric Acetoarsenite - Cu(C2H3O2)2•3Cu(AsO2)2
- Paris, Schweinfurt, Imperial, Vienna, Parrot Green
- Insecticide

Cuprous Acetate - Cu(CH3COO)2
- Hatchett’s brown
- 8% solns, antiseptic

Silver
Seolfor, Anglo-Saxon
Argentum, Latin
Argyros, Greek

Occurrence
- Tellurium
 Hessite [Ag2Te]
 Petzite [(AgAU)2Te]
 Sylvanite [AuAgTe4)
- Sulfide [Ag2S]
- Argentite, Acanthite
- Antimony or Arsenic
 Pyragyrite [3Ag2S•Sb2S3]
 Prousite [3Ag2S•As2S3]
 Polybasite[9Ag2S•Sb2S3]
 Pearcite[9Ag2S•As2S3]
- Halogens
 Cerargyrite or horn-silver
 Bromyrite
 Iodyrite

Physical Properties
- Most dominant oxidation state: Ag(I)
- White metal having metallic luster
- Second most malleable and cutile metal
- Second best conductor of heat
- Best conductor of electricity
- Spitting or sprouting
 Molten silver occludes about 22 vol of oxygen which is not
permanently retained. On cooling it is given off with great
violence causes the silver to form in irregular masses.

Chemical Properties – Ag
- Not oxidized by oxygen
- On heating, combines with free halogens and with sulfur
- Black Ag2S forms when it comes in contact with substances
containing sulfur (in the presence of O2)
- Unreactive with acids, except for oxidizing acids
 3Ag + 4HNO3 (cold, dilute)  3AgNO3 + NO + 2H2O
 2Ag + 2H2SO4 Ag2SO4 + SO2 + 2H2O

Ag
+
- Water-insol except NO3
-
, SO4
2-
, ClO3
-
, NO2
-
, C3H5O3
-
, CH3COO
-
, and F
-
- AgCl, Ag2O: reacts with and dissolves in ammonia water

- AgBr, Agl, Ag2S: insoluble in ammonia water
-

- Photosensitive

- One of the “heavy metals”: precipitates proteins, sulfides, tannins,
alkaloids

- Complex formation

 CN
-
, S2O3
2-
, NH3
- With reducing agents= “Silver mirror”
- With Na2CO3
 White Ag2CO3 black Ag2O

Expected result
HCl
HNO3
6N NH4OH
White curdy ppt (AgCl)
Insoluble
Soluble
6N NH4OH, HCHO Silver mirror

Commercial Manufacture
- Amalgation
 2AgCl + 2Hg --> 2Ag + H22Cl+2
- Lixivation or Leaching
 Roast Ag2S ores --> water-sol Ag2SO4
 Ag2SO4 + Cu --> 2Ag + CuSO
- Cyanide Process
 Ag(CN)2
-
+ Zn/S
2-

- Parke Process
 Recovery of silver from leads ores by +Zn

Pharmacologic Action
- Oligodynamic
- Water purification
- Astrigent, antiseptic, irritant, corrosive
 Unable to distinguish bet bacteria and human protein
 High germicidal efficiency
- No systemic effect
- Highly ionized silver salts
 silver nitrate, silver picrate
 irritant and corrosive
 destroy tissue or stimulat slow healing wounds
 effect is localized bec of option by proteins and chlorides in
tissues (coagulation membrane)
 late action
- Slightly ionized silver salts
 silver halides (choloride, iodide); silver proteinates (mild and
strong or collodial sivler preperations)
 Antiseptic, Astrigent
 Late action
 Avoid formation of coagulation membrain
 Eliminate pain

Toxicity
- Argyria
 Bluish to black discoloration of skin due to prolonged use of
silver preparations
 Bioreduction of silver ion to elemental silver may reside
permanently at the site of application

Treatment
- 6% Na2S2O3 and 1% K3Fe(CN)6 SC
 2Ag
+
+ 3S2O3
2-
 [Ag2(S2O3)3]
4-


Official Compunds
 Silver Nitrate, USP 36
 Silver Nitrate Ophthalmic Solutionm USP 36
 Toughened Silver Nitrate, USP 36
 Silver Sulfadianzine

4. Silver Nitrate – AgNO3

- agrenti nitras, indelible ink
- Low conc, silver-denatured protein is confined in interstitial spaces
and denuded areas --> antimicrobial, astrigent axn
- High conc, corroded site covered with scab of silver protein ppt -->
caustic
- Official Test: Lunge Test

+gtts of diphenylamine = blue color interface (NO3
-)
- Topical anti-infective
- Antiseptic: Silver Nitrate Ophthalmic Solution, USP
 1%soln: prophylaxis for ophthalmia neonatorum
- Astringent
 Tx impetigo vulgaris, pruritus, indolent ulcers, wounds,
fissures
 No longer used for burn therapy
- Caustic: podiatry
 Remove corns, warts, calluses
 Cauterize small nerve endings, blood vessels
- S/E: methemoglobinemia
- Not more than 0.5%: raw wounds, fresh cuts, broken skin
- Stain removal by l2 tincture ff by Na2S2O3

Toughened Silver Nitrate, USP 36
- Toughened Silver Nitrate contains NLT 94.5% of AgNO 3, the
remainder consisting of silver chloride (AgCl).
Toughened Silver Nitrate, USP
- Argenti Nitras Induratus, moulded of fused silver nitrate, lunar caustic,
caustic pencil, silver nitrate pencil, lapiz infernalis
- NLT 94.5% silver nitrate, the remainder of which consists of silver
chloride
- Prep by adding `4%(w/w) HCl to AgNO3 to lessen brittleness of the
pencil
- Cast into sticks and used as styptic or caustic.

Silver Sulfadiazine - C10H9AgN4O2S
- indicated for the prophylaxis and treatment of infection in burn
wounds
- highly insoluble in water, and as a result, it does not cause
hypochloraemia in burns in contrast to silver nitrate.
- The cream is kept applied to the burned skin at all times for the
duration of the healing period or until a graft is applied.
- It prevents the growth of a wide array of bacteria, as well as yeast, on
the damaged skin.
- Caution has to be given to large-area application as sulfadiazine
levels in the plasma may well reach therapeutic levels that can cause
side effects
- indicated for the prophylaxis and treatment of infections in burn
wounds.
- SSD, Silvadene, Flamazine, Flammazine
- Combines antibacterial property of silver ion and sulfadiazine
- Effective against Pseudomonas aeruginosa
 Prevent and tx wound sepsis in 2
nd
to 3
rd
degree burns

Unofficial Compunds
 Ammoniacal Silver Nitrate Solution
 Mild Silver Protein
 Strong Silver Protein
 Colloidal Silver Chloride
 Colloidal Silver Iodide

Ammoniacal Silver Nitrate Solution
- Howe's solution
- Aq soln of silver diammino nitrate, ctg in each 100g the equiv of NLT
28.5g and NMT 30.5g of Ag, and NLT 9g and NMT 9.7 of NH3
- Dental prep mixed with a RA (10%5 HCHO or eugenol) to deposit Ag
in infected area

Mild Silver protein (19-23% Ag)
- Mild protargin, argentum vitellinum, Silvol, Solargentum, Argyn,
Argyrol
- Silver rendered colloidal by presence of, or comb with protein. It
contains NLT 19% and NMT 23% Ag.
- Freshly prep in amber bottles
- Non-irritant
- 5-25%: mild antiseptic in eye, ear, nose. throat
- Ionization inc with dilution

Strong Silver Protein (7.5-8.5% Ag)
- Strong protargin, albumose silver, Protargol
- NLT 7.5% and NMT 8.5% Ag
- Freshly prep in amber bottles
- 0.25-0.5%: stronger germicidal axn
 irrigant
- No longer used as urethral injection in tx of gonorrheea

Colloidal Silver Chloride
- AgCl rendered colloidal by presence of sucrose or other suitable
colloid stabilizing agent. It contains NLT 9% and NMT 11% AgCl.
- Prototype: Lunosol
- Prophylaxis and tx of infections of GUT, EENT
- 3-100%
Colloidal Silver Iodide
- Neosilvol®
- Agl rendered colloidally stable by presence of gelatin. It contains NLT
18% and NMT 22% Agl.
- Freshly prep in amber bottles
- 2%: irrigating sinuses
- 50%: female genital tract

Non-official Silver Oxide
- Active basic hydroxide
- Comp of hopcalite
 Colloidal manganese and copper oxides activated by silver
and cobalt oxide
 oxidize CO to CO2 at ordinary temp
- Picragol, Picrotol
- Highly ionized
- 1-2%: antiseptic
 Vaginal suppositories: gonorrhea, urethritis

Gold
Aurum, Latin
King of All metals

Occurrence
- Sylvanite [AuAgTe4]
- Petzite [(AugAg)2Te]
- Calaverite [AuTe2]

Physical Properties
- Yellow, lowered by Ag, heightened by Cu
- Best conductor of heat
- Most malleable and most ductile metal

5. Chemical Properties - Au
- Most dominant oxidation state: Au (III)
 AuF3, AuCl¬3, and AuBr3
- Inactive metal
- Unaffected by air, oxygen, water or H2S
- Selenic acid (H2SeO¬4)
 Only single acid that dissolves Au
- 2Au + 3H2SeO4 Au 2(SeO4)3 + 3H2
- Free halogens
 2Au + 3X2 2AuX 2
- Aqua regia (3HCl:1HNO3)
 2Au + 2HNO3 + 8HCl 2HAuCl 4 + 2NO + 4H2O

Au
+

- Unstable to heat, light, mild RA
- Autoxidation
___________________

Au
3+

- Unstable to heat, light
- Complex formation
- NaOH  brown ppt sol in excess
- NH4OH  brown ppt sol in excess
- Amphoteric like Al, Sn, Zn, and Pb
- Strong OA
 Fe
2+
, I-, Sn
2+


Unofficial ID Tests
Expected Result/s
NaOH TS
Excess NaOH TS
Brown ppt. Au(OH)3
Soluble
SnCl2 TS Purple ppt
(purple of cassius)

Pharmacologic Action
- Lupus erythematosus
 Multisyystem disease of unknown etiology
 Women > men
 Autoimmune disease
 Skin (butterfly rash), musculoskeletal (arthralgia, arthritis),
neurological (seizures, strokes, psychosis, neuropathies),
renal (nephritis), hermatological (anemia, leukopenia,
thrombocytopenia, lymphopenia)
- Radioactive
198
Au use for certain cancers

Pharmacologic Action: Rheumatoid Arthritis
- Chronic, inflammatory. Progressive autoimmune disease that primarily
affects the joints
- Is characterized by swelling of the joints and increasing pain leading
to stiffness
- Inflammation occurs initially in the synovial membrane surrounding
the joints and then spreads to the synovium
- An irreversible erosion of the anticular cartilage on the bone joints
means that bones will directly rub against each other and cause severe
pain.
- Three diagnostic factors: painful joints, inflammation and the presence
of the so-called rheumatoid factor.

Toxicity
- Cutaneous (Gold Dermatitides)
 Dermatitis, alopecia, loss of nails
- Mucous Membrane
 Stomatitis, buccal ulcers, glossitis or gingivitis
- Pulmonary
 Insterstitialpneuomonitis, fibrosis, cough, shortness of breath
- Nephrotic syndrome
 Glomerulitis with hermaturia, renal failure
- Hematologic
 Granulocytopenia, thrombocytopenia, Ieucopenia,
eosinophilia, aplastic anemia
- Miscellaneous
 Flushing dizziness, sweating ,nausea, vomiting, malaise, fever

Treatment
- d/c therapy immediately if toxicity develops
- Topical or systemic corticosteroid to reduce inflammation
- BAL or dimercaprol to increase excretion

Uses
- Jewelry
 alloyed with Cu or Ag to inc hardness
 24-carat or pure gold
 14-carat = 58.33% gold
- Dentistry
- Decorative purposes

Official Compounds
 Aurothioglucose, USP 36
 Aurothioglucose Injectable Suspension, USP 36
 Gold Sodium Thiornalate, USP 36

Aurothioglucose, USP 36 - C6H11AuO5S


- DMARD (disease modifying antirheumatic drug)
- Aurothioglucose Injectable Suspenion, USP
 Sterile susp of aurothioglucose in a suit veg oil
 90%-110.0% of the label claim
 Sol in water with decomposition


Gold Sodium Thiomalate, USP 36 - C4H5AuNa2O5S

- mixture of mono and disodium salts of gold thiomalic acid
- C4H3AuNa2O4S + C4H4AuNaO4S
- 44.8% - 49.6% of Au
- 49% - 52.5% of Au on dry, ROH- and glycerine free basis

Gold Sodium Thiomalate Inj, USP
- sterile solution of Gold Sodium Thiomalate injection in WFI
- 95% - 105%
 Myochrysine
 IM or IV (sol in water)
- anti-rheumatic

6. Unofficial Compounds
- Auranofin
- Gold Sodium Thiosulfate

Auranofin - C20H35AuO9PS
- DMARD
- only orally active gold compound

Gold Sodium Thiosulfate - AuH4Na3O8S4
- For SLE and RA
- Sterile Gold Sodium Thiosulfate
 sterile salt in dry form
 sol’ns must be freshly prepared with WFI
 IV