Chapter 1. Intro & Group Properties

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Pharm.

PHR103 Medicinals
Inorganic

Dr. Brian B. Castrence,RPh,MSChem


Professor, Pharmacy Department
Orientation to
the Course
• Course Code and Title:

– PHR103 – Pharmaceutical Inorganic Chemistry with


Qualitative Chemistry

• Credit Units: 4 (3hrs Lecture and 1 unit Laboratory)

• Term: First Semester


Course Description

• The course covers the chemistry and pharmacy of inorganic


compounds and medicinals, with emphasis on those official in
the USP/NF, their preparations, properties, test and uses.

• It includes the concepts and chemical reactions related to


qualitative analysis of inorganic compounds.

• This also includes the study of structure and physico-chemical


properties in relation to biological activity, preparation and/or
synthesis, uses and doses of inorganic medicinals.
Learning Outcomes

• To produce a Paulinian Pharmacists that is knowledgeable on


the concepts and principles of Chemistry and Pharmacy of
Inorganic Medicinals with depth understanding on the
different inorganic compounds and their medicinal and
pharmaceutical use and intention of applying such knowledge
and skills for the development of the Pharmaceutical
profession and betterment of the community.
Course Objectives

At the end of the course, the students will be able to:

1. apply the knowledge, skills and principles of inorganic chemistry to


medicinal and pharmaceutical industry;

2. discuss the official inorganic substances used as therapeutic and diagnostic


agents;

3. manifest and appreciate of the pharmacist’s social and professional


responsibilities in maintaining or restoring the health of the community;

4. correlate the structure of the drugs with its absorption, biological activity
and metabolism;
Course Objectives

At the end of the course, the students will be able to:

5. correlate the various aspects of Chemistry and Pharmacy of Medicinals 1


with drug development and administration;

6. recognize the relevance of Chemistry and Pharmacy of Medicinals 1 to the


other major Pharmacy disciplines and its role in the practice of Pharmacy;

7. identify diseases that can be cured by inorganic compounds;


Course Objectives

At the end of the course, the students will be able to:

8. explain the importance of knowing the therapeutic value of inorganic


substance available in the community; and

9. understand the high moral and ethical standards of the pharmacy


profession.
Introduction

• Pharmaceutical Inorganic Chemistry:


– study of both non-essential and essential elements
concerning:
• preparation, standards of purity, test for identification
• limit tests to be performed for determining the quality
• extent of purity, storage, different formulations and their
storage conditions and therapeutic uses.
Pharm.
Importance Chemistry
Inorganic
1. Use medicinally for their therapeutic purpose.
2. Use as pharmaceutical aids.
e.g. Buffers, antioxidants, waters
3. Modify the reaction of body fluid. (acidify or alkalize).
4. Replacing or replenishing the normal content of body fluids.
e.g.: Sodium, potassium, calcium, chloride, phosphate etc.
5. Useful as reagents to carry out the reactions.
Example: Catalysts, oxidizing and reducing agents

6. Useful in Pharmaceutical analysis.


Topics

1. Group Properties of Elements


2. Pharmaceutical Aids and Necessities
3. Major Intracellular & Extracellular Electrolytes
4. Essential & Trace Ions
5. Gastrointestinal Agents
6. Topical Agents
7. Dental Products
8. Miscellaneous Inorganic Pharmaceutical Agents
9. Radiopharmaceutical and Contrast Media
Group
Chapter 1 Elements
Properties

Dr. Brian B. Castrence,RPh,MSChem


Professor, Pharmacy Department
Group 1A Alkali Metals
Group 1A Alkali Metals

• Consists of the following metals


Alkali
Group 1A Properties
Metal

• has largest atomic size with one valence electron

• lowest first ionization energy.

• relatively weak effective nuclear charge makes it easier to


remove the electron in the valence shell.

• light and soft – they can easily be cut with a knife


Alkali
Group 1A Properties
Metal

• Pure form of these metals must be stored in kerosene or


mineral oil and must be dissolved in ethyl alcohol prior to
disposal.
• most reactive of all metals, never found free in nature and exist
is salt form.
– Increasing reactivity as atomic size increases (down group)
– Cs most active metal
– Fr exist as radioactive metal
Hydroxides Alkali Metals

• Alkali metals react with water to form basic hydroxides and liberate
hydrogen.
• Reaction of the metal is exothermic
• Explosive leading to fire from lithium to cesium

2Na(s) + 2H2O(l)  2NaOH(aq) + H2(g) + heat


Halides Alkali Metals
• Alkali metals react vigorously with all the halogens to form solid ionic
halides.
• Reactivity decreases from fluorine to iodine.

– 2Na(s) + Cl2(g)  2NaCl(s);


– 2K(s) + Br2(l)  2KBr(s)
Other Important Reactions

• Reaction with oxygen gas to form different types of oxides:


– lithium forms a simple oxide
– sodium forms peroxide while potassium and the other form superoxide:

(a) 4Li(s) + O2(g)  2Li2O(s);


(b) 2Na(s) + O2(g)  Na2O2(s);
(c) M(s) + O2(g)  MO2(s); (M = K, Rb, or Cs)
• Alkali metals react with hydrogen gas to form ionic (salt like)
hydrides:
– 2Li(s) + H2(g)  2LiH(s);
– 2Na(s) + H2(g)  2NaH(s);
Identification
Using Flame Test
Test
Identification
Using Flame Test
Test
Chemical
Official Lithium
Tests

1. 2Na2HPO4 + 6Li+  2Li3PO4 + 4Na+ + H2


– Partial ppt on neutral sol’n
– More ppt on boiling and with the presence of NaOH or
NH3.
– ppt is more soluble in NH4Cl (distinction from Mg2+)
Chemical
Official Lithium
Tests

2. H2SO4 + 2Li+ Li2SO4 + H2


- No ppt

3. (NH4)2CO3 + 2Li+  Li2CO3 + 2NH3 + H2


– White ppt of lithium carbonate of conc.sol’n of NH3
– No ppt in the presence of high conc of NH4Cl
Chemical
Official Sodium
Tests

1. 2NaCl + 2KH2SbO4 + K2CO3  Na2H2Sb2O7 +


2KCl + H2O
- No ppt upon add’n of 15%pot.carbonate until boiling
- Add’n of 4mL of pot. pyroantimonate TS boil and cool
slowly to induce ppt gently rub the inner walls of the test
tube.
Chemical
Official Sodium
Tests

2.

- Yellow crystalline precipitate form’n


Chemical
Official Potassium
Tests

1.

- Yellow precipitate form’n


- Insol. Dil HAC, ppt immediate form’n upon add’n
conc.sol’n or warming.
- Brown or black ppt is form in alkaline sol’n Co(OH)3
Chemical
Official Potassium
Tests

2.

- White precipitate form’n, highly sol.H2O add’n of 50%


ROH
- The reagent must be buffered with sod.acetate since the
rxn  strong acid that dis.ppt
- Ppt’n acceleration done by agitation and scratching the
walls of test tube
Chemical
Official Potassium
Tests

3.

- White crystalline precipitate form’n, slightly sol.H2O


- Insol. ROH
- Alcoholic sol’n must not be heatedexplosion
Chemical
Official Potassium
Tests

4.

- Yellow precipitate, instant form’n on conc.sol’n,


- Dil sol’n  slow ppt but hastened pptn upon cooling
and rubbing the sides of the vessel; Slightly sol.H2O,
insol.in 75% ROH
Group 1B Coinage Metals
Group 1B Coinage Metals

• Members of the family:


– Copper, silver & gold
– “Coinage metals” – employed as ornamental &
coinage purposes
– Resembles alkali metals with respect to single
valence electron.
Group 1A Group 1B Comparison

Group 1A Group 1B
Do not occur free in nature Occur free in nature and are easily
recovered from their compounds
through reduction
Very active chemically, displace all Low in reactivity series and not
other metals from their compounds. chemically active; they are displaced
Chemical reactivity increases as the by metals and chemical reactivity
atomic weight increases decreases as the atomic weight
increases.
Oxides and hydroxides are strongly Oxides and hydroxides are feebly
basic. basic
Group 1A Group 1B Comparison

Group 1A Group 1B Group 1B


Alkali halides are Ag, Cu (I) & Au (I) halides are AgCl, CuCl, AuCl
soluble in water nearly insoluble in water AgX; X=halides (F, Cl, Br, I)
and not AgX are hydrolyzed in water
hydrolyzed. forming different basic salt.
Univalent, Cu(I) and Cu(II) each form a Cu+ , Cu2+
forming one series of compounds Au+ , Au2+
series of Ag+ one series while Au+ and Ag+
compounds Au++ forms one series each.
Form simple All form complex anions such
cation, never as Cu(CN)2 , Ag(CN)2- ,
occur in complex Au(CN)2-
anion and don’t
form complex
with NH3
Group 1A Group 1B Comparison

Group 1A Group 1B

Form simple cation, never occur in Form complex cation with NH3 such
complex anion and don’t form as Ag(NH3)2-, Cu(NH3)42+ , Au(NH3)63+
complex with NH3

Rapidly oxidized in air Cu, slowly oxidized in air, but rapidly


oxidized when finely divided and
heated
Identification Tests Copper

• Two series of copper compound


– Cu+ comes from red Cu2O and readily oxidized to Cu2+
and salts of Cu+ are insoluble in water.
– Cu2+ comes from black CuO
– Cu2+ salt is blue color due to its complex form with water
[Cu(H2 O)4]2+ [tetraaquocuprate (II)]
– Anhydrous form of Cu2+ salt gives white color.
Identification Tests Copper

1. Hydrogen sulfide

• Black ppt in an acidic sol’n to form crystalline and


filterable ppt
• Absence of acid colloidal brownish-black ppt or
colouration
• Ppt is insoluble in dil.H2SO4 (dist.from Cd)
Identification Tests Copper

2. Ammonia

• Blue ppt of basic salt. Basic copper sulfate

• X’ss reagent of NH3 give deep blue color due to


complexation

tetraaminocuprate(II) complex
Identification Tests Copper

3. Sodium hydroxide

• Blue ppt is formed.


• X’ss reagent ppt is insol.
• If heated ppt reverted to black due to dehydration.
Identification Tests Copper

4. KI

• White ppt but the sol’n is intensively brown due to


I3 _.
• X’ss sod.thiosulfate reduces I3_ to I_ creating a
visibly white precipitate and reduction of thiosulfate
to tetrathionate.
Identification Tests Copper

5. KSCN
copper (II) thiocyanate
thiocyanide

• black ppt that slowly decomposes and turns into


white ppt due to formation of Cu (I) thiocyanate and
thiocyanogen.
Identification Tests Silver

1. dil. HCl

• White ppt in dil. reagent; conc. Reagent ppt does


not occur due to dissolution and complex form

Dichloroargentate
Identification Tests Silver

1. dil. HCl

• ppt is sol.in dil. NH3 due to complex form’n,

• product of this rxn must be treated with 2M HNO3 prior to


disposal, if not ppt slowly turns to Ag3N (fulminating silver)
explodes readily even in wet!
• Sunlight or ultraviolet irradiation decomposes ppt to greyish
or black.
Identification Tests Silver

2. H2S (neutral or acidic media)

• Black ppt insol.in dil. NH3 , ammonium sulfide, ammonium


polysufide, KSCN [potassium thiocyanide] and Na2S2O3
[sod.thiosulfate]
• ppt is decomposes by conc.HNO3 with white ppt due to
sulfur

• Sulfur is oxidized if conc.HNO3 is heated forming sulfate


causing disappearance of the ppt.
Identification Tests Silver

3. Ammonia

• Brown ppt
• X’ss reagent dis.ppt due to complex form’n

• product of this rxn must be treated with 2M HNO3 prior to


disposal to avoid serious explosion!
Identification Tests Silver

4. NaOH

• Brown ppt and insol. In x’ss reagent


• Well-washed suspension of the ppt shows slight alkaline
due to hydrolysis reaction.
Identification Tests Silver

4. NaOH

• ppt is sol. In both NH3 and HNO3


Identification Tests Silver

5. KI

• Yellow ppt insol. to dil.or conc. NH3.


• Readily dis.in KCN & Na2S2O3
Identification Tests Silver

5. K2CrO4 (neutral)

• Red-rings of ppt form’n


• Rxn must be added with KCO3 to render any Pb +, Pb++ or
Hg+ unreactive by precipitation as insol.carbonates
• ppt is sol.in dil.HNO3 and NH3

• Orange is seen due to form’n of dichromate


Identification Tests GOLD

1. H2S

• Black ppt of Gold (I) sulfide in cold. (sometimes mixed with


free Au)
• Insol.dil acids
• Soluble in yellow (NH3)2S but reprecipitated with dil.HCl
• Forms red ppt of Au with Au2S if precipitated in hot sol’n
Identification Tests GOLD

2. NH3

• Fulminating gold of yellow ppt


• Dry form tends to explode upon heating or percussion.
Identification Tests GOLD

3. H2C2O4

• Precipitated as brown powder


• Under suitable condition Au, can reflect a colloidal state of
red, violet or blue sol’n.
Identification Tests GOLD

4. SnCl2 (neutral or weakly acidic)

• Purple ppt due to “Purple of Cassius”


– adsorption of Sn(OH)2 and colloidal gold ppt
• extremely dil.sol’n gives purple coloration
• Strongly acidic (HCl) dark-brown ppt of pure gold is formed.
Identification Tests GOLD

5. H2O2 (neutral or weakly acidic)

• Ppt of finely divided metals in the presence of NaOH


• appears brownish-black by reflected light
• Transmitted light gives bluish-green
Identification Tests GOLD

5. NaOH
• Au3+ + Na+ + OH-  Au(OH)3

• Reddish-brown ppt of Au(OH)3


• Amphoteric property and dis.in’x’ss reagent

Tetrahydroxoaurate (III)
Alkaline
Group 2A Metals
Earth
Alkaline
Group 2A Metals
Earth
• Members of the family are:
– Be, Mg, Ca, Sr, Ba and Ra
• All are metals while Ra-is a radioactive
• “alkaline”
– compounds of these metals are alkaline basic in nature.
• “Earth”
– most compounds are insoluble to water.
Alkaline
Group 2A Metals
Earth

• Members of the family are:


– Be, Mg, Ca, Sr, Ba and Ra
• All are metals while Ra-is a radioactive
• “alkaline earth”
– Oxides of these metals are alkaline when dis.in water and
remains solid at temperature available to ancient
alchemist.
• Like Group 1A elements, the alkaline earth metals are too
reactive to be found in nature in their elemental form.
Alkaline
Group 2A Metals
Earth
• 2 valence electrons in their highest-energy orbitals
• smaller than the alkali metals of the same period, and therefore have
higher ionization energies.
• They are ionized to form a 2+ charge.
• The alkaline earth metals have much higher melting points than the
alkali metals:
– Be melts at 1287ºC
– Mg melts at 649ºC
– Ca at 839ºC
– Sr at 768ºC
– Ba at 727ºC, and
– Ra at 700ºC
Alkaline
Group 2A Metals
Earth

• They are harder metals than the Group 1A, but are soft and
lightweight compared to many of the transition metals.
• Salts of Group 2A metals are less soluble in water than those of
Group 1A due to higher charge densities on the 2+ cations.
• Group 2A salts are at least moderately soluble.
• Some Group 2A salts bond strongly to water molecules, and
crystallize as hydrates
– e.g. Epsom salt, MgSO4·7H2O
– Gypsum, CaSO4·2H2O.
Official Tests Beryllium

1. NH3 or (NH3)2S

– White ppt of Be(OH)2


– Insol. x’ss reagent but readily sol.in dil. HCl forming colorless
sol’n.
– ppt’n is prevented by tartrates and citrates.
Official Tests Beryllium

2. NaOH TS

– White gelatinous ppt of Be(OH)2


– readily sol. x’ss reagent due complex form’n.

tetrahydroxoberyllate ion

– On boiling Be(OH)4 is reprecipitated and sol.in NaHCO3


Official Tests Beryllium

3. (NH4)2CO3 TS

– White ppt of Be3(CO3)2 .(OH)2 [Basic Beryllium carbonate ]


– Sol. in x’ss reagent and reprecipitated upon boiling.
– On boiling Be(OH)4 is reprecipitated and sol.in NaHCO3
Official Tests Magnesium

1. Flame Test
– No coloration is observe
– Burns readily in air or oxygen with white brilliant light forming
MgO and Mg3N2
– Slowly decompose in water at ordinary temperature
– Boiling water the reaction proceeds rapidly:
Official Tests Magnesium

2. NH3 TS

– Partial precipitation of white gelatinous form


– Very sparingly sol.in water
– Very sol.in NH4 salts.
Official Tests Magnesium

3. NaOH TS

– white ppt
– Insol. X’ss reagent
– Very sol.in NH4 salts.
Official Tests Magnesium

4. (NH4)2CO3 TS

basic magnesium carbonate

– white ppt in the absence of NH4 salts


– Presence of NH4 salts results to no ppt’n due to equilibrium state
Official Tests Magnesium

5. Na2HPO4 in ammonium chloride

Magnesium ammonium phosphate

– white crystalline ppt in the absence of NH4 salts


– Presence of NH4 salts is req’d to prevent the ppt’n of Mg(OH)2
and NH3 sol’n
Official Tests Calcium
• Silver-white color and soft metal
• Attacked by atmospheric oxygen and humidity forming CaO &
Ca(OH)2.
• Calcium decomposes water forming Ca(OH)2 & H2.
• Solid CaCl2 is hygroscopic, thus used as drying agent.
Hygroscopic-substances absorbs or adsorbs water or moisture in
air
Deliquescent- subs that absorbs water in air and dissolves in it.
Efflorescent- substance that has water in its molecule and releases
or losses water upon air exposure
Official Tests Calcium
1. NH3 TS

– No ppt is seen as Ca(OH)2 is fairly soluble


– With aged precipitantturbidity may occur due to CaCO3.
Official Tests Calcium
2. (NH4)2CO3 TS

– White amorphous ppt; upon boiling ppt becomes crystalline


– ppt is sol.H2O which may contain carbonic acid leading to the
form’n of soluble ..

– Thus, freshly prepared soda water should be used, boiling the


mixture will caused reprecipitation as CO2 will be remove.
.
Official Tests Calcium
3. Dil. H2SO4 TS

– White ppt; more sol.H2O than Ba2+ and Sr2+ sulfate


– Presence of ethanol decreases sol.ppt
– ppt dis.hot, conc. H2SO4 due to the form’n of _____.

.
Official Tests Calcium
4. Potassium hexacyanoferrate (II) Sol’n

– White ppt of mixed salt


– More sensitive in the presence of NH4Cl to which the K+ can be
replaced by NH3.
Official Tests Calcium
5. (NH4 )2 (COO)2 Sol’n (Ammonium oxalate sol’n)

– White ppt, rapid ppt’n with conc. sol’n but slowly in diluted one
– Ppt’n can be facilitated with the add’n of NH3 making it relatively
alkaline
– Insol. to H2O & Hac
– Sol. in mineral acids
Official Tests Strontium

1. NH3 TS
– No ppt’ form’n,
• due high sol of ppt but upon exposure to air CO2 deposit
turbidity

2. (NH4)2CO3 (ammonium carbonate)

– White ppt, less sol.in H2O as compared with BaCO3 ppt


– Slightly sol.in NH4 salts
– Decomposed in the presence of acids.
– Sol. in mineral acids
Official Tests Strontium

3. H2SO4 TS

– White ppt, low sol.in H2O


– Insol.in NH4 sulfate even in boiling (distinction from Ca2+)
– Slightly sol.in boiling HCl
– Can be converted to strontium carbonate upon boiling with it
conc. Sod.carbonate sol’n.
Official Tests Strontium

4. Sat.CaSO4 TS
– White precipitate
– Rapid ppt’n upon boiling and slowly in cold. (distinction from Ba2+)

5. (NH4 )2 (COO)2 Sol’n

– White ppt
– Sparingly sol.in H2O
– HAC does not attack
– Mineral acid dis.ppt
Official Tests Strontium

6. K2CrO4 TS

– Yellow precipitate
– Sol in H2 O and HAC (distinction from Ba2+)
– and sol. mineral acids
Official Tests Barium
1. NH3 TS
– No ppt, high sol of ppt but upon exposure to air CO2 deposit
turbidity Barium carbonate
2. (NH4)2CO3 TS

– White ppt, sol.in HAC and dil.mineral acids


– Slightly sol.in NH4 salts of mineral acids
3. (NH4)2(COO)2 Sol’n

– White ppt, slightly sol.in H2O and readily dis.by hot HAC
(distinction from Ca2+ ) and by mineral acids.
Official Tests Barium
4. Dil. H2SO4
– Heavy white finely divided ppt, insol.in H2O and in dil.acids and NH4
salts.
– Sol.in boiling conc.H2SO4
– Rapid ppt’n upon boiling or in a presence of ammonium acetate.

– Partial transformation into carbonate ppt upon boiling it with


conc.sod.carbonate
– BaSO4 ppt readily dis.in Na2 EDTA in a presence of NH3.
Official Tests Barium
5. Sat. CaSO4

– Immediate white ppt is seen,


– Least soluble among the three alkaline earth metal sulphate salts
– Sat.sol’n of both Ca2+ & Sr2+ sulfate, has higher SO42- ions to cause the
ppt’n of BaSO4.
Official Tests Barium
6. K2CrO4

– Yellow ppt, insol.dil HAC (distinction from Sr2+&Ca2+)


– Readily dis.in mineral acids
– Add’n of acid causes change of yellow color to reddish-orange color due
to form’n of Cr2O7

– Sol.product of both SrCrO4 & CaCrO4 are much large than BaCrO4
thus, they require larger CrO4 ion conc.to precipitate them.
– Add’n of HAC to K2CrO4 lowers CrO4 ion conc.thus both Ca2+ & Sr2+ will not
be precipitated.
Introduction Group 2B Metals
Introduction Group 2B Metals

• Members of this group:


– Zinc, Cadmium and Mercury
• Both Zn, Cd are soft metals
• Mercury exist in a liquid state at room temperature with
relatively low melting point.
• Quicksilver-due to its state and silver white appearance
Chemical Group 2B Metals

• They are classified as “terminal elements” instead of transition


metals due to a filled set of “d” orbitals.
• They usually used the 2+ oxidation state in chemical bonding
or reaction.
• They exist in divalent ions, except for Hg that is a monovalent.
• Hg2+ is the result of Hg+ sharing a pair of electrons together.
Chemical Group 2B Metals

• They can react with halogens, oxygen, nitric acid & other
oxidizing agents
• Forms complexes and coordinate compounds (cyano, amino,
halo groups)
• They form oxides & basic CO3 coatings upon exposure to air that
prevents further oxidation of metals.
– Zn-used in the manufacture of “galvanized iron”
– All these 3 metals are used in prod’n of alloys
– Hg-used in the prod’n of amalgams.
Chemical Group 2B Metals

• Oxides & OH_ are weak bases and strength of basic character
increases as move down the periodic table.
• Zn(OH)2 is amphoteric in nature.
• Mainly used the prod’n of alloys
– Brass- contains copper & zinc
– Bronze- contain copper & tin

• General Rxns
– M + X2  MX2
– 2M + O2  2MO
– M + 4HNO3  M(NO3)2 + 2NO2 + 2H2O
Official Tests Zinc

• 1. NaOH TS

– White gelatinous ppt


– ppt is sol.in acid and in x’ss reagent.
– ppt is amphoteric compound.
Official Tests Zinc

• 2. NH3 TS

– White ppt, readily sol.in x’ss reagent and NH4 salts due to form’n of
complex compound [Zn(NH3)4] 2+
– None pptn in the presence of NH4Cl due to low OH – to which Zn(OH)2 in
not attainable.
Official Tests Zinc

• 3. (NH4)2S TS

– White ppt from neutral or alkaline sol’n


– Insol.x’ss reagent, HAC and in caustic alkalis.
– Dis. in dil.mineral acids.
– ppt is partially colloidal that is difficult to wash and filtered on washing.
– readily filterable ppt must be carried upon boiling in the presence of x’ss
NH4Cl or washing it with x’ss NH4Cl
Official Tests Zinc

• 4. H2S

– Partial ppt’n in neutral sol’n.


– conc.acid of about 0.3M sulfide-ion conc.from H2S is depressed thus,
Hydrogen-ion conc.from acid is too low to exceeds the solubility product of ppt
and results to ppt’n cessation.
– when alkali acetate is added to the sol’n, H+ is reduced due to feebly
dissociated Acetate. Thus, sulfide ion conc. Is increase and ppt’n is nearly
complete.

– ZnS can be precipitated from alkaline sol’n of [Zn(OH)4]2-


Official Tests Zinc

• 5.Na2HPO4 Sol’n

– White ppt will be observed


– Presence of NH4 + zinc ammonium phosphate is formed

– Both ppts are sol.in acids and the reaction will reversed
– Sol.in NH3
Official Tests Zinc

• 6.K2[Fe(CN)6 ]2

– White ppt with variable composition


– X’ss reagent added the composition of the ppt is purely K2 Zn3 [Fe(CN)6 ]2

– ppt insol.in dil.acids but readily dis.in NaOH. This rxn is used to distinguish
Zn+2 from Al+3
Official Tests Cadmium

• Properties:
– Silver-white, malleable and ductile metal.
– Dis.slowly in diluted acids and produces hydrogen gas due to its
negative electrode potential.

– Forms bivalent ions and colorless


– Salts of cadmium as to chlorides, nitrates & sulfates are sol.in
water while its sulfide salt is insol.with yellow characteristics.
– All compounds of cadmium are all TOXIC!
Official Tests Cadmium

• 1. H 2S (gas or sat. aqueous sol’n)

– Yellow ppt & rxn is reversible.


– If conc.sol’n of strong acids of 0.5M will be added ppt’n is
incomplete and dissolved ppt in some reasons.
– Ppt is insol.with KCN (poisonous) (distinguishes Cd2+ from
Cu2+)
Official Tests Cadmium

• 2. NH3 (dropwise added)

– White ppt dis.in acid as it shifts the rxn going to the left.
– X’ss reagent dis.ppt as it forms colorless complex.

Tetraaminocadmiate (II)
Official Tests Cadmium

• 3. KI
– No ppt form’n differentiates it from Cu2+

• 4. NaOH TS

– White ppt insol. X’ss reagent


– Color & composition is unchanged upon boiling.
– Diluted acids dis.ppt by shifting the to the left.
Official Tests Cadmium

• 5. KCN (Poison)TS

– White ppt if it is added to the sol’n slowly


– X’ss reagent dis. ppt with colorless complex.

– Complex is unstable, when H2S is added, CdS will be precipitated.


– Complexes with cyano serves as a basis for distiguishing Cd2+ from
Cu2+
Mercury
Official Tests
(I)

• 1. dil.HCl

– White ppt of “calomel”


– Insol.dil acids
– NH3 converts the ppt to mixtures of salts of Hg2+ & Hg+ metal to
which both are insol.to NH3

Mercury (II) amidochloride


Mercury
Official Tests
(I)

• 1. dil.HCl
– NH3 converts the ppt to mixtures of salts of Hg2+ & Hg+ metal to
which both are insol.to NH3

– Hg(NH2)Cl
• White ppt but finely divided mercury makes it shiny black
– Hg2Cl2
• dis.in agua regina forming undissociated sol.HgCl2
Mercury
Official Tests
(I)

• 2. H2S (gas or sat.aqueous sol’n)

– Neutral or dil.acidic media


– Mixture of black ppts of elemental mercury an mercury (II sulfide)
– Aqua regina dis.ppt, yielding undissociated mercury (II) chloride and
sulfur

– If heated with aqua regina, sulfur will be oxidized to sulfuric acid and
the sol’n becomes clear.
Mercury
Official Tests
(I)

• 3. NH3 TS
– Mixture of black ppt of both _____.
– Used to differentiate between Hg+ from Hg2+

Basic mercury (II) amidonitrate (white ppt)


Mercury
Official Tests
(I)

• 4. NaOH TS (Hg+)

– Black ppt of _______.


– insol.,x’ss reagent but dis.readily in dilute HNO3
– ppt turns to grey upon heating due to disproportionation as HgO and
Hg+ ppts are formed.
Mercury
Official Tests
(I)

• 5. K2CrO4 (hot sol’n)

– Red crystalline ppt of ______.


– If carried out in a cold, brown amorphous ppt with undefined composition.
– When heated the ppt turns to red forming the desired red ppt.
– Add’n of NaOH sol’n turns ppt into black.
Mercury
Official Tests
(I)
• 6. KI

– Added slowly in cold sol’n


– Green ppt will be observed
– Disproportionation reaction takes place upon add’n of x’ss reagent
resulting to form’n of soluble ______ and black ppt of finely divided
_______.

– When boiling the mixture Hg2I2 ppt with H2O, disproportionation takes
place  red ppt of Hg I2 and black of finely divided Hg+.
Mercury
Official Tests
(I)

• 7. Na2CO3

– Yellow ppt, slowly turns to blackish-grey due to the form’n of elemental


mercury and Hg)
– Decomposition of the ppt can be hastened upon heating the mixture.
Mercury
Official Tests
(I)

• 8. Na2HPO4
– White ppt is seen.

• 9. KCN (POISON)
– Black ppt of elemental mercury and clear sol’n of ______
Mercury
Official Tests
(I)

• 10. SnCl2
– Reduces Hg+ to Hg0
– Form’n of greyish-black ppt
Mercury
Official Tests
(II)

• 1. H2S (gas or sat. sol’n) Mercury chlorosulfide

– In the presence of dil.HCl initially white ppt ____,


– further reacts with H2S to formed a black ppt of merury (II) sulfide.
– ppt is insol. To water, alkali hydroxides, hot dil.nitric acid and
(NH4)2S
Mercury
Official Tests
(II)

• 1. H2S (gas or sat. sol’n)


– Na2S dis.ppt forming complex product of _____

– Add’n of NH4Cl to the above sol’n causes reprecipitation of HgS.


– Add’n of aqua regina dis.ppt.

– HgCl2 remaines undissociated while sulfur forms white ppt that will
dis.readily if sol’n is heated  sulfate ion.
Mercury
Official Tests
(II)

• 2. NH3
– White ppt of mixed composition of ________.
– Mercury salts will sublime at atmospheric pressure.

Mercury (II) oxide & mercury (II)amidonitrate


• 3. NaOH
– Brownish-red ppt with varying composition
– Add’n in stoichiometric amts slowly turns to yellow as HgO is produced.
– ppt is insol. x’ss reagent while acids dis.ppt.
Mercury
Official Tests
(II)

• 4. KI

– Slowly added, red ppt will be produced.


– Dis. x’ss reagent forming colorless sol’n of ____.

– K2 [HgI4] (Nessler’s Reagent)


• Serves as a selective & sensitive reagent for NH4+
Mercury
Official Tests
(II)

• 5. KCN (POISON)
– Does not cause any change in dil.sol’ns.

• 6. SnCl2

– Added in moderate amts produces white-silky ppt of “calomel”


– Used to remove excess Sn2+ for redox rxn titrations
– X’ss reagent added calomel will be reduced and black ppt is seen.

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