Chapter I | Pharmaceutical Chemistry of Inorganic Medicinals | Suzette Pamela G.

Santos | 1FPharmacy

Inorganic Chemistry the study of inorganic substances used as medicines or needed in the preparation
of pharmaceutical products.
Electron configuration periodic variation with increasing atomic number
decreasing metallic properties increasing metallic property

ATOMIC SIZE
ELECTRON AFFINITY

IONIZATION ENERGY
ELECTRONEGATIVITY
GROUP PROPERTIES OF ELEMENTS
GROUP 1-A: Alkali Metals (Soluble)
Lithium
Sodium
Potassium
Rubidium
Cesium
Francium
- radioactive element

Alkali metals - very good reducing agents
- has only one valence electron
- never free in nature
- very active metals

atomic weight = reactivity
*Cesium is the most active
- always occur in compounds with +1 oxidation states (usually salts)
- form strongly basic hydroxides except Li(OH)
*maliit kasi size

- combines with H
+
forming hydrides
& halogens forming halides
- with oxygen: Li ----> Li
2
O (normal oxide)
Na --> Na
2
O
2
(peroxide)
K
Rb (superoxides, O
2
-1/2 oxidation state)
Cs

- reacts with H
2
O H
2(gas)
+ OH
0

- oxides react with H
2
O hydroxides
- peroxides & superoxides oxygen
o salts of alkali metals are water soluble
o they are more soluble than salts of any periodic group
EXCEPTION:
Lithium + Fl
+ CO
3
INSOLUBLE
+ PO
4


Group 1-A:
LiNaKRbCsFr
PEROXIDES -> -1
NORMAL OXIDES -> -2
SUPEROXIDES -> -1/2
Chapter I | Pharmaceutical Chemistry of Inorganic Medicinals | Suzette Pamela G. Santos | 1FPharmacy

GROUP 1-B: The Coinage Metals
Copper (most active)
Silver
Gold
- resemble the alkali metals only
with respect to the single valence electron

- free in nature
- chemically inactive atomic size = activity

- halides are insoluble in water
- forms complex cations with NH
3
and complex anions
Ag
+

Monovalent
state
Polyvalent
Ion is
colorless
Colored
diamagnetic paramagnetic

Disproportionation reactions (auto-oxidation)

Cu
+
+ Cu
+
---> Cu
+2
+ Cu
0
(forward)
Ag
+
+ Ag
+
---> Ag
+2
+ Ag
0
(backward)

Au
+
+ Au
+
+ Au
+
---> Au
+3
+ Au
0
(forward)

GROUP 2-A: Alkaline Earth Metals
Beryllium (least metallic)
Magnesium
Calcium
Strontium TOO REACTIVE
Barium
Radium *radioactive

- conductors of heat and electricity
- all strong reducing agents except Be
- all combine directly with oxygen, halogens, nitrogens, sulfur & hydrogen (except Mg)
- *Beryllium oxide amphoteric
- all other oxides are basic
- salts of these metals are not as soluble
atomic radii = activity (greater ability for bond formation)

GROUP 2-B
Zinc
Cadmium soft metals
Mercury
- colorless solution, at room temperature, quicksilver because of its silver white appearance
- classified as terminal elements, not transition elements
- have filled set of orbitals
- oxidation state +2, they utilize both electrons in the outer shell for binding purposes
- divalent ions in compounds except Hg
2
+2
(monovalent)
- reacts with : halogens
oxygen
nitric acid

Group 1-B:
CuAuAg
Group 2-A:
BeBaCaRaMgSr
oxidizing agents
Group 2-B:
ZnCdHg
Chapter I | Pharmaceutical Chemistry of Inorganic Medicinals | Suzette Pamela G. Santos | 1FPharmacy

- readily forms complex ions
amines
cyano-
halo-
- forms basic carbonate coating which prevents further oxidation of metals when exposed to air
Zinc is used in galvanized iron
all is used in alloys
- oxides and hydroxides are weak bases
group = base strength

Uses: Preparation of Drugs




GROUP 3-A
Boron
Aluminum
Gallium
Indium
Thallium

- only Aluminum is abundant
- most common metals
- 3
rd
most common element in the Earths crust next to oxygen and silicon
- amphoteric
- Boron covalent bonding; Aluminum both covalent and ionic
- metals readily oxidizes when heated in air
- stable at ordinary temperature
- oxides readily reduced to free metals
- metals readily react with sulfur and halogens
- hydroxides have ampotheric properties except boron and thalia


GROUP 3-B: Scandium Subgroup
Scandium
Yttrium
Lanthanum
Actinium
Lanthanides
(58-71)

Actinides
(96-103)


- forms compounds with +3 & +2 oxidation states
Lanthanides occur in mixtures which are hard to be separated due to similar chemical properties
Actinides are prepared synthetically, exist as radioactive isotopes
- all are quite chemically reactive and oxides are basic
o considered as metals









BRASS
(Copper
& Zinc)
BRONZE
(Copper
& Tin)
Group 3-A:
BAlGaInTl
Inner Transition
Group 3-B:
ScanYLALA
Chapter I | Pharmaceutical Chemistry of Inorganic Medicinals | Suzette Pamela G. Santos | 1FPharmacy

GROUP 4-A: Carbon Family
Carbon
Silicon
Germanium - metalloid
Tin
Lead

- oxidation states: +2, +4 (s
2
p
2
)
Carbon basic building unit of inorganic compounds
- also occurs in inorganic compounds like carbonates, oxalates, tartrates & acetates
- reducing agent in preparing many metals
- combines directly with oxygen and halogens, with most non-metals
Silicon never exists in free state
*Silica (SiO
2
), found everywhere on Earths crust
Germanium occurs in minute quantities, rare
Tin occurs mainly as the oxide, SnO2
Lead occurs mainly as the sulfide, PbS(galena)
Forming common oxides +OH
-
(amphoteric)
Tin SnO
2

Stable tin oxide
SnO
2
-2

Stannite
+4 Stannate SnO
3
-2
Lead PbO
Stable lead oxide
PbO
2
-2

Plumbite
+4 Plumbate PbO
3
-2


GROUP 4-B: Titanium Subgroup
Titanium
Zirconium
Hafnium

- forms compounds with oxidations states:
+2 (good reducing agents)
+4(most common)
+3
- titanium dioxide used as pigment
o Titanium red color produced by hydrogen peroxide in acid solution

GROUP 5-A: Nitrogen Family
Nitrogen
Phosphorous
Arsenic
Antimony
Bismuth metal

- s
2
p
3

- +3 & +5 oxidation states

nitrogen ---> nitrides
antimony ---> antimonides
arsenic ---> arsenides
phosphorous ---> phosphides

- combines with hydrogen to form hydrides
ammonia (NH
3
) Stibine (SbH
3
)
phosphine (PH
3
) Bismuthine (BiH
3
)
arsine (AsH
3
)
metals
non metals
Group 4-A:
CSiGeSnPb
Group 4-B:
TiZrHf
non metals
metalloids
Group 5-A:
NPAsSbBi
Chapter I | Pharmaceutical Chemistry of Inorganic Medicinals | Suzette Pamela G. Santos | 1FPharmacy

- react with chlorine to form tri- & penta- halides
P
4
O
6
- dimer of P
2
O
3
(combination of 2 molecules of P
2
O
3

- oxides of
o Nitrogen
o Phosphorous
o Arsenic
o Antimony
o Bismuth basic

Nitrogen forms triple bonds (N=N)
- a stable, non-polar tetrahedral
Phosphorous exist in two allotropic forms:





*same molecular structure, different structural formula and properties

GROUP 5-B: Vanadium Subgroup
Vanadium
Niobium
Tantalum
o similar to GRP5 only in
electronic structure
- forms compounds with oxidation states of +2 -------> +5
reducing oxidizing
- Vanadium is ampotheric in its highest oxidation state
oxidation state = basicity of hydroxide
- compounds of these elements in lower oxidation states are colored (transition metals)
volatility of compounds = more covalent bonding
- good reducing agents based on oxidation potentials
Tantalum used for corrosion resistant applications in medicines, as pins, wires, plates, that is
left in the human body to strengthen a broken bone (orthopedic)

GROUP 6-A: Oxygen Family
Oxygen (O=O, double bond) O
2,
gas, diatomic molecule
Sulfur S
8
, solid
Selenium
Tellurium
Polonium
*radioisotope

- Sulfur is solid because of its high intermolecular forces of attraction (chain structures)
- brimstone burning stone (yellow)

strongly acidic
amphoteric
YELLOW PHOSPHOROUS
- volatile, flammable,
toxic
o heat without
air, converted
to red
phosphorous
RED PHOSPHOROUS
- non volatile,
inflammable,
non-toxic

Group 5-B:
VNbTa
Group 6-A:
OSSeTePo
Sulfur family
Chapter I | Pharmaceutical Chemistry of Inorganic Medicinals | Suzette Pamela G. Santos | 1FPharmacy

- s
2
p
4

- among the most electronegative elements
- Sulfur 2-, 0, 2+, 4+, 6+
- Oxygen -> 2-, 1-, 0, second most electronegative of all elements
- can form monoatomic anions(oxides, sulfides..)
- increases acidity as molecular weight increases
- hydrides are highly odoriferous and poisonous
- higher oxidation state = very good oxidizing agents
allotropy property of a substance of existing in more than one physical form
allotropes different forms
Sulfur:
96
o
113
o
immersed in cold water
rhombic monoclinic straw-colored viscous sulfur amorphous sulfur
free-flowing darkened, rubbery, plastic mass
liquid thick and sticky

shape of needle-like
crystal crystalline
most stable

GROUP 6-B: Chromium Subgroup
Chromium
Molybdenum
Tungsten
Uranium

- metals with high melting points, great hardness and excellent resistance to corrosion
- form oxides that are acidic, those with higher molecular weight
- Chromium (III) hydroxide is ampotheric soluble in excess forming chromite
- Chromium (medicinal) forms compounds with O.S 2+
3+ most stable
6+

GROUP 7-A: Halogen Family
Fluorine best oxidizing agent
Chlorine
Bromine
Iodine
Astatine

- halogen sea salt (FClBrI) because the sodium salts of the respective hydroacids are very
similar to ordinary salt (Berzelius)
- there is gradual change in their physical states:
o Fluorine pale yellow gas
o Chlorine greenish yellow gas
o Bromine reddish brown liquid
o Iodine black solid
- most active family of non metals
- s
2
p
5

- Fluorine as Fluorite(CaF
2
) & Cryolite (Na
3
AlF
6
) trisodium aluminum hexafluoride
- Chlorine as sodium chloride in sea water
- Bromine found with sodium chloride as sodium, potassium & magnesium bromide
- Iodines most important commercial source is sodium iodate (NaIO
3
)
- -1 oxidation state
- Fluorine is the most electronegative of all elements
- their salts are hypohalites, halites, halates, perhalates

Group 6-B:
CrMoWu
Group 7-A:
FClBrIAt
size of radius = IMFA

good reducing agents
Chapter I | Pharmaceutical Chemistry of Inorganic Medicinals | Suzette Pamela G. Santos | 1FPharmacy

GROUP 7-B: Manganese Subgroup
Manganese
Technetium
Rhenium

- manganese is the only metal of pharmaceutical importance
+2, good reducing agent
- technetium is a product of radioactive decay
- rhenium is extremely rare

- manganese : +2 ---> +7
- colored ions

GROUP 8 Elements
- grayish-white metals
Iron Triad
Iron
Cobalt
Nickel

- do not occur free in nature
- chief source of iron is hematite, Fe
2
O
3

- FeS
2
, iron pyrite: fools gold
- ores of cobalt and nickel are obtained from sulfide ores
- +2 &

+3
- iron(iii) hyrdroxide, very weak base
- has magnetic properties
- tendency to form simple cations

Platinum Metals
Ruthenium
Rhodium
Palladium
Osmium
Iridium
Platinum

- very non- reactive elements, occur chiefly in free state
- corrosion-resistant metals, good catalysts
- called noble metals because of low reactivity and oxidation potentials
- Osmium is the heaviest known substance

GROUP 8-A: Inert Gases
Helium
Neon luminescence
Argon most abundant
Krypton
Xenon
Radon
*radioactive element
Group 7-B:
ReMnTc
Iron Triad
FeCoNi
less reactive
light platinum metals
heavy platinum metals
Platinum Metals
RuRhPdOsIrPt
Group 8-A:
HeNeArKrXeRn
general anesthetics