Pharmaceutical Inorganic Chemistry Unit IV Miscellaneous compounds Expectorants Emetics, Haematinics, Poison and Antidote and Astringents. Expectorants: Potassium iodide, Ammonium chloride*. Emetics: Copper sulphate*, Sodium potassium tartarate Haematinics: Ferrous sulphate*, Ferrous gluconate Poison and Antidote: Sodium thiosulphate*, Activated charcoal, Sodium nitrite333 Astringents: Zinc Sulphate, Potash Alum

1. Pharmaceutical Inorganic chemistry
UNIT-IV (Part-I)
Miscellaneous compounds
Presented By
Ms. Pooja D. Bhandare
(Assistant Professor)
DADASAHEB BALPANDE COLLEGE OF PHARMACY BESA NAGPUR

2. Content:
• Expectorants: Potassium iodide, Ammonium chloride*.
• Emetics: Copper sulphate*, Sodium potassium tartarate
• Haematinics: Ferrous sulphate*, Ferrous gluconate
• Poison and Antidote: Sodium thiosulphate*, Activated charcoal, Sodium
nitrite333
• Astringents: Zinc Sulphate, Potash Alum

3. EXPECTORANTS
• The cough is a protective physiological reflux (both, voluntary and involuntary) to
clear the air way.
• Infections , chemical irritants, retained body secretions and the presence of foreign
bodies that block one's air ways and causes coughing by stimulating the nerve endings
in the respiratory tract.
• Dry and Productive Cough: Irritative or unproductive cough is dry cough, which
may be caused by colds or by inhalation of irritating dust and gases and produces no
sputum or other discharge,
• Where as productive cough is sputum or exudate producing cough and is often
associated with asthma and bronchitis.

4. • Expectorants are drugs used to help in the removal (of secretions or exudate
from the trachea, bronchi, or lungs, and hence they are used in the treatment of
cough
• They act upon the respiratory tract in two ways
• By decreasing the viscosity of the bronchial secretion and facilitating their
elimination local irritants are expelled and ineffectual coughing is alleviated and
• By increasing the amount of respiratory tract fluid, a demulcent action is
exerted on dry mucosal linings, thus relieving the unproductive cough It is
believed that many of them act by reflux by irritating the gastric mucosa which,
in turn, stimulates respiratory tract secretions

5. AMMONIUM CHLORIDE
NH4Cl
• Ammonium chloride is prepared by neutralizing hydrochloric acid with
ammonia.
• The resulting solution of ammonium chloride is evaporated to dryness The
crude product thus formed is purified either by recrystallization or by
sublimation
• Properties: Ammonium chloride occurs as colourless crystals or as white
crystalline powder It is somewhat hygroscopic It is odourless and possesses
cooling saline taste It is freely soluble in water but sparingly soluble in alcohol
• Its 5 solution is acidic (pH 4 5 to pH 6 0 On heating it sublimes without
melting

6. • ASSAY METHOD (VOLHARD’S METHOD)
(A) Earlier it was previously assayed by precipitation titration using Volhard’smethod.
1. This method is as follows1. An accurately weighed 0.2gm of ammonium chloride is
dissolved in 40ml of water,
2. Then, the solution is acidified with 3ml of nitric acid.
3. The solution is shaken vigorously after adding 50ml of 0.1N silver nitrate and 5ml of
nitrobenzene.
4. The excess of silver nitrate is titrated with 0.1N ammonium thiocyanate, using 2ml of
ferric ammonium sulphate as an indicator.
• Each ml of 0.1N AgNO3 = 0.005349 gm of NH4Cl

7. • Uses
(l) Expectorant Ammonium Chloride in doses of 300 mg to 1 gm is used as an
ingredient in expectorant cough mixtures
• Diuretic It is given for its diuretic action especially to help the excretion of
over dosage of basic drugs such as amphetamine and in the treatment of lead
poisoning, by increasing its excretion
• Systemic acidifier It is helpful in producing mild acidosis For this purpose, it
is given by mouth in a dose of 2 g It is rapidly absorbed through

8. • G I T and is converted into urea in the liver
• Thus, the anion liberated into the blood stream and extracellular fluids,
causes a metabolic acidosis and decreases the pH of the urine (this is
followed by transient diuresis
• It is also used to increase the diuretic effect of mercurial diuretics or to
correct hypochloraemia alkalosis caused by prolonged use of mercurial
and in the treatment of urinary infections when a low pH is required

9. POTASSIUM IODIDE (KI)
• Preparation It is prepared by treating slight excess of iodinewith a hot
aqueous solution of potassium hydroxide The pale yellow solution is
evaporated to dryness and residue is heated with charcoal to reduce the
iodate
• The product is extracted with water and filtered and the filtrate is
evaporated to crystallization.

10. • Properties:
1. It occurs as cubic or hexahedral crystals either transparent and colourless or
somewhat opaque and white or as a white granular powder
2. It is slightly hygroscopic
3. Its solution is neutral or slightly alkaline to litmus It is very soluble in water and
even more so in boiling water, freely soluble in glycerin and soluble in alcohol
4. On long exposure to air it becomes yellow due to liberation of iodine and small
quantity of iodate may be formed Light and moisture accelerate the decomposition
5. Iodine readily dissolves in an aqueous solution of potassium iodide, forming a dark
brown solution containing potassium triiodide

11. Uses
1. Expectorant It is used as an ingredient of expectorant mixture The usual
expectorant dose is 300 mg four times a day with dosage range of 300 mg to 2 g
daily
2. Source of iodine It may be used for the prophylaxis and treatment of simple goitre
3. Antifungal It is used as antifungal agent in veterinary practice
4. Iodine solutions It is one of the most important ingredient ofvarious official iodine
solutions (Antimicrobials).

12. Emetics
• An emetic is a drug which induces vomiting. Emetics act either directly by
stimulation of the chemoreceptor trigger zone, located in the area of medulla
oblongata located in the brainstem in cerebellum or by inducing irritant action on
gastrointestinal tract.
• Emetics takes a valuable part in poisoning cases.
• Emetics are added to cough preparations in low doses to stimulate flow of
respiratory tract secretions.
• Inorganic compounds such as copper sulphate, sodium chloride, zinc sulphate and
sodium potassium tartarate are used.

13. Copper sulphate
Molecular Formula (CuSO4 .5H2O)
Molecular Weight -249.7
Colour: Deep blue, crystals of pentahydrate or as blue crystalline granules or
powder
Solubility: Soluble in water and very soluble in in boiling water, slowly
soluble in glycerol and almost insoluble in alcohol.
Stability: The salt has been stable to heat up to 60oC.

14. Preparation
• It is obtained by roasting copper containing sulphide ore in presence of air or by
heating copper in a furnace with sulphur. The mixture of copper sulphate and
CuO formed in the above process is treated with dilute sulphuric acid. The
resulting solution is filtered, concentrated and allowed to crystallise when
crystals of copper sulphate separate out.
• It is also obtained by treating granulated copper in the presence of air with
sulphuric acid.
2Cu+2H2SO4+O2 2CuSO4+2H2O
• The solution is filtered and evaporated to crystallisation when crystals of copper
sulphate separate out.

15. Assay
• An accurately weighed quantity of copper sulphate is dissolved in water. To
this a slight excess of potassium iodide is added followed by acetic acid.
• The liberated iodine is titrated with standard sodium thiosulphate solution by
using starch as an indicator.
• The titration is continued until faint blue colour persists. 2g of potassium
thiocyanate is then added and the titration is continued until the blue colour
disappears.
Uses
• It finds use as an emetic in a dose of 300mg in 30ml of water. But its use as an
emetic can be dangerous because of large and corrosive doses.
• It is used as chemical antidote in phosphorous poisoning.
• It is used as fungicide.
• It is an ingredient of Benedict’s and Fehling’s solution.

16. Sodium potassium tartarate (Rochelle salt)
• Molecular formula- C4H4KNaO6 .4H2O
• Mol wt-283.23 Colour: White colourless crystalline powder
• Odour: Odourless
• Solubility: Freely soluble in water and insoluble in alcohol
• Taste: Saline

17. Preparation
• The starting material is tartar with a minimum tartaric acid content 68 %.
• This is first dissolved in water. It is then saponified with hot caustic soda to pH 8,
decolorized with activated charcoal, and chemically purified before being filtered.
• The filtrate is evaporated at 100 °C and salt is separated.
Uses:
• It is used as emetics
• It is used in effervescent powder.
• It is also used as laxative to relief from constipation

18.  Hematinics
• The recommended dietary allowances per day are 10 mg in male and 18 mg in female
• During growth, menstruation, pregnancy and pathological bleeding demand of iron
increases considerably
• It is absorbed according to the body requirements and the absorption increases in presence
of HCl and ascorbic acid (vitamin C)
• Apart from haemoglobin, it is also associated with myoglobin, catalase, ferredoxin,
cytochromes, electron transport and enzyme cofactor
• The deficiency of iron in the body is clinically manifested by anaemia hypochromic i e lack
of haemoglobin in the blood) and the excess of iron results in haemochromatosis

19. • Internal iron preparations are used to supplement the iron present in the body
which is so essential in the formation of haemoglobin and various
physiological necessities mentioned in the previous paragraph
• Currently, the IP 1996 includes Ferrous Fumarate Ferrous Gluconate Ferrous
Sulphate including Dried Ferrous Sulphate and Iron Ammonium Citrate as
oral official substances in the monograph and other includes sodium iron
edetate iron dextran injection and iron sorbitol injection

20. FERROUSSULPHATE FeSO4.7H2O
• Molecular formula FeSO4• xH2O
• Molar mass FeSO4•7H2O 278.02 g/mol
• Synonym Green vitriol, Iron vitriol, Copperas and Iron(II)sulphate
Properties
• Appearance : White crystals (anhydrous); White yellow crystals (monohydrate); Blue
green crystals (heptahydrate)
• Crystal structure : Orthorhombic (anhydrous); Monoclinic (heptahydrate);
• Odor : Odorless
• Taste : Astringents and metallic taste
• Density : 3.65 g/cm3 (anhydrous); 3 g/cm3 (monohydrate); 1.895 g/cm3 (heptahydrate)
• Melting point : 6800C (anhydrous); 3000C (monohydrate); 60–640C (heptahydrate)
• Solubility in water : Monohydrate: 44.69 g/100 mL (770C); Heptahydrate: 15.65 g/100
mL (00C); 20.5 g/100 mL (100C); 29.51 g/100 mL (250C); 39.89 g/100 mL (40.10C);
51.35 g/100 mL (540C)
• [ Refractive index : 1.591 (monohydrate); 1.471 (heptahydrate)

21. Preparation
• In the finishing of steel prior to plating or coating, the steel sheet or rod is
passed through pickling baths of sulfuric acid. This treatment produces large
quantities of iron(II) sulfate as a byproduct.
Fe + H2SO4 → FeSO4 + H2
• Ferrous sulfate is also prepared commercially by oxidation of pyrite
2 FeS2 + 7 O2 + 2 H2O → 2 FeSO4 + 2 H2SO4

22. Assay :based on oxidation-reduction titration methods. –
• Weight accurate about 0.5 gm of ferrous sulfate, dissolved in a mixture of 25 m of dilute sulfuric acid and 25 ml of freshly
boiled and cooled water, and titrate with 0.02M Potassium permanganate.
• Each ml 0.02M Potassium permanganate is equivalent to 27.802 mg of FeSO4•7H2O (ferrous sulfate heptahydrate)
• Each ml 0.02M Potassium permanganate is equivalent to 27.802 mg of FeSO4 (Anhydrous ferrous sulfate)
• Uses:
1. Ferrous sulfate is a haematinic agents, it is used to treat and prevent iron deficiency anaemia.
2. Ferrous sulfate was used in the manufacture of inks, most notably iron gall ink
3. Woodworkers use ferrous sulfate solutions to color maple wood a silvery hue.
4. In horticulture it is used for treating iron chlorosis. –
5. Ferrous sulfate is sometimes added to the cooling water flowing through the brass tubes of turbine condensers to form a
corrosion resistant protective coating.
6. It is used in gold refining. - Green vitriol is also a useful reagent in the identification of mushrooms

23. Dose: 60 mg to 600 mg
Ferrous sulfate side effects
• Constipation
• Upset stomach
• Black or dark‐colored stools or
• Temporary staining of the teeth
Drug-Drug interaction with ferrous sulfate
• Chloramphenicol –
• Cimetidine
• Levodopa
• Methyldopa
• Penicillamine
Storage: Store in amber color bottle or light resistant container.

24. Ferrous Gluconate
[CH2OH(CHOH)4COO]2Fe.2H2O
• Glucose is oxidised by bacterial fermentation to gluconic acid.
• The gluconic acid so obtained is treated with ferrous carbonate to give
ferrous gluconate. It is crystallized with 2 molecules of water of
hydration and dried.

25. Physical and Chemical Properties:
• Ferrous gluconate occurs as yellowish grey or pale greenish yellow fine powder or granules
• It has a slight odur like that of burnt sugar
• It is fairly soluble in cold water and more soluble in warm water
Medicinal Uses:
• Haematinics
• It is used in the prevention and treatment of iron deficiency anaemias

26. Poison and Antidote
POISONS
A poison may be defined as any substance administered in whatever way ( by
mouth, injection , inhalation , skin ) produces ill health, disases or death. Self
medication is a major cause of drug poisoning.
Poisoning can be classified as :-
(A) Intentional poisoning – taking substances without intention of causing harm
to self. E.g. :- Suicide

27. (B) Unintentional poisoning – Taking substances without knowing its toxic
effects. E.g. :- Accidental
• Signs and symptoms of poisoning:-
• Reduced breathing rate
• Nausea
• Vomiting and Diarrhoea
• Alteration in heart rate
• Muscle cramps
• Partial Consciousness.

28. (C) Heavy Metal poisoning –
• This poisoning occurs due to intake of salt of As, Pb , Hg or Fe resulting into
the toxic effect
• Treatment :- Activated charcoal given initially to absorb heavy metal ↓
followed by emetics to eliminate any poison left in the stomach.
(D) Cyanide poisoning :-
• This poisoning may occur by inhalation of fumes of hydrocyanic acid (HCN)
or inorganic cyanide salt.
• Consumption of 300 mg of KCN may cause death.
• Treatment :- Sodium nitrite and Sodium thiosulphate injections as an
antidotes.

29. ANTIDOTES
• Antidotes are the substances which react specifically without the ingested poison or
toxic substances or with potent drugs in case of overdose.
CLASSIFICATION :-
• According to their mechanism of actions, they are classified as:
1. Physiological Antidotes –
They are antagonists i.e. produce the effect opposite to that of the poison, or to
counteract the effect of poison physiologically. E.g.:-
Antagonists and Physostigmine are two antidotes for each other.
Sodium nitrite in CN- poisoning.

30. (A) Chemical Antidotes –
They react by combining with the poison and change its chemical nature by
converting poison into inactive compounds.
(B) Mechanical Antidotes E.g. – Sodium thiosulphate convert toxic cyanide into
non-toxic thiocyanate.
EDTA as chelating agent for heavy metal poisoning. They act by preventing the
absorption of poison into the body or expel out the poison by emesis
E.g. :- Activated charcoal absorbs the poison to absorption into intestinal wall.

31. SODIUM THIOSULPHATE [Na2S2O2]
• Synonyms :- Sodium hyposulfite, Anti-chloral
Preparation– Prepared by boiling Sodium Sulphite Na2S2O2 with Sulphur (S)
Na2SO3 + S —∆⟶ Na2S2O3 (Sodium thiosulfate)
• By reacting sodium hydroxide with Sulphur.
6NaOH + 4S ⟶ Na2S2O3 + 2 Na2S + 3H2O
• Physical properties –
• Large, prismatic crystalline powder
• Effervesces in dry air
• Practically soluble in H2O and insoluble in alcohol
• Melting point- 50°c

32. Chemical properties –
• Decomposition of aq. Solution as Sodium thiosulfate Sodium sulfate Sodium
4Na2S2O3 ⟶ 3Na2SO4+ Na2S5 ⟶ Na2S + 4S
• Barium chloride reacts without to give white ppt. of barium thiosulphate
• Na2S2O3 + BaCl2 ⟶ BaS2O3↓ + 2NaCl
• Mechanism of antidotes :- low infusion of sodium thiosulfate
react with CN- in the blood
Convert CN- to SCN- (thiocyanate)
SCN- excreted out from the body by kidney.
Na2S2O3 + CN- ⟶ SCN- + Na2S2O3
(Active cyanide) (inactive thiocyanate)

33. Assay :
• The assay of Na2S2O3 is based on iodometric titrations.
In this titration, solution of Na2S2O3 is titrated with Iodine directly using starch solution as an indicator.
Excess I2 reacts without starch to give blue colour (end point).
Iodometric Reactions involved :-
2S2O3
– → S4O6
2- + 2e– (oxidation)
I2+2e– → 2I– (Reduction)
2S2O3
2- ≡ I2
Over all reaction:-
2Na2S2O3 + I2 → Na2S4O6 + 2NaI
• Equivalent factor:-
• I2 ≡ 2Na2S2O3
• 100ml 1M I2 ≡ 2*248.2g Na2S2O3
1ml 0.05M I2 ≡ 0.02482g Na2S2O3

34. • Uses :-
*Used as antidote in cyanide poisoning as IV
*Effective antidote in Pb, Hg and iodine poisoning.
*Use as antioxidant for solution containing iodides
*Standard titrant in Iodometric analysis.
• Dose = 0.3 – 1g (10ml) administrated by intra muscular and Intra venous route.

35. ACTIVATED CHARCOL
• It is a dark grey residue consisting of carbon and any remaining ash obtained
by removing water and other volatile constituent.
Preparation:-
Burning of wood in absence of air
↓
Residue obtained consists of pure carbon
↓
(Activation of charcoal )
Absorptive powder of charcoal increased by treating it with various substance
such as steam, CO2, ZnCl2 at high temperature 500-1000∙c
↓
Charcoal activation results in increase in total surface area

36. Properties:-
• (Fine, black, odorless powder)
Insoluble in H2O and other organic solvent.
Uses:-
1.Emergency antidotes in many forms of poisoning high preventing absorption of poison in
intestinal tract.
2.Used as protective and adsorbent
3.Due to its high surface area, it is used as a fitter acid
4.Disinfectant in wounds
5.Constituent for gum powder
6.Used in overdose of aspirin

37. SODIUM NITRATE (NaNO2)
Synonyms:-Nitrous acid sodium salt or Etinitrit
Preparation:- By adding heating sodium nitrate
2NaNO3 → 2NaNO2 + O2
(Sodium nitrate)
By heating sodium nitrate with lead
NaNO3+ Pb → NaNO2+ PbO
Properties:-
• Yellow and white crystalline powder.
• Freely soluble in H2O and less soluble in alcohol.
• Odorless
• On exposure to air, it readily forms sodium nitrate.

38. Mechanism of antidotes action:-
• Injection of NaNO2 causes oxidation of ferrous ion of haemoglobin (Fe2+) into
ferric ion (Fe3+) of methemoglobin
↓
Methemoglobin combines with serum cyanide and produce cyano-meth
haemoglobin.
↓
Prevention of harmful of CN–
HB (Fe3+) NaNO2 → MeHB (Fe3+)
Methemoglobin
MeHB(Fe3+)+CN– → MeHB(Fe3+)CN– (Inactive cyanide ion)
Cyano-meth haemoglobin

39. Uses:-
• Used as antidote in cyanide poisoning.
• Vasodilator action due to nitrite ions relax the smooth muscle of blood
vessels.
• Anti – rust solution : to prevent the rusting of surgical instruments
Doses of injection :- 10-15 ml of 3% solution I.V.

40. Astringent
Defination:
• An astringent (occasional alternative: adstringent) substance is a chemical
compound that tends to shrink or constrict body tissues and precipitate the
protein and astringent form protective layer on the surface.
• Due to their protein action, astringents are able to reduce the cell
permeability.
• This reduces local edema, exudation and inflammation.
• The word "astringent" derives from Latin “adstringere”, meaning "to bind
fast".
• They are usually applied to damaged skin topically or to the mucous
membrane of GIT including the mouth

41. ZINC SULPHATE ZnSO4.7H2O
Properties:
• Zinc sulphate occurs as colourless, transparent crystals or as a crystalline
powder.
• It is odourless and has an astringent, metallic taste.
• It is efflorescent in dry air. It is easily soluble in water, insoluble in alcohol
and soluble in glycerin. Aqueous solution of zinc sulphate is slightly
acidic.
Preparation: It is prepared by boiling a slight excess of metallic zinc with
dilute sulphuric acid.
Zn + H2SO4 ZnSO4 + H2

42. Uses:
1. Emetic (induces vomiting): zinc sulphate is used as reflex emetics
especially in narcotic poisoning (opium poisoning), for this 1% solution
contains 0.6 to 2 g given orally.
2. Astringent: it is used externally for its antiseptic and astringent properties
in powder and in lotions
3. It also serve as aid in healing of wounds 4.A 0.25 % zinc sulphate aqueous
solution is used as an ophthalmic astringent.

43. POTASH ALUM (ALUMINIUM POTASSIUM SULPHATE)
(KAl(S04)2.12H20)
Physical and Chemical Properties
• Alum occurs as large, octahedral, colourless crystals or in small crystals or as a
white powder.
• It is without odour and has a sweetish, strongly astringent taste. Alum is
soluble in cold water but more soluble in hot water.
• Alum is transparent but it is sometimes opaque on the surface due to traces of
basic salt being formed. When basic salt is present, alum will not give a clear
solution.
• When alum is heated it melts at 920 C and loses all the water of hydration at
2000C leaving a white residue known as burnt alum containing anhydrous
aluminium and potassium sulphates.

44. • Alum of the Pharmacopeia (official in I.P. 1 966 and B.P. 1988) is potash
alum, i.e., double aluminium sulphate and potassium sulphate with 12
molecules of water of hydration.
• Preparation: Potash alum is prepared by adding a hot; concentrated
solution of potassium sulphate to a hot solution of an equivalent quantity of
aluminium sulphate. The solution is cooled and the alum crystallizes out.
By crystallizing slowly it is possible to get large regular, octahedral
crystals.

45. Thank You !