Q1 De ne metallurgy and note hydro metallurgy?

De ne metallurgy:-The scienti c and technological process of isolation of metals from

their ores by economical means is called metallurgy..HYDRO-metallurgy:-Hydro
metallurgy: This is the most selective method for separating metals from their ores and it is
based on the formation of metal complexes. It involves bringing the metal in solution by the
action of suitable chemical reagents, like sodium cyanide solution or chlorine in presence
of water thus separating it from the insoluble gangue. The process is carried out in two
steps: Leaching and Displacement reaction. Noble metals like Au and Ag are extracted by
this method. For example, gold is often found as tiny akes of the metal, usually in
association with quartz or pyrite deposits.
Leaching: Concentrated ore is leached with dilute solution of NaCN and kept agitated by
current of air. Gold forms a stable gold-cyanide soluble complex leaving behind the
impurities.
4Au(s) + 8NaCN(aq) + 02(g) + 2H20(1) →
Na[Au(CN)2](aq) + 4NaOH(aq)
Displacement reaction: The gold complex thus obtained is ltered and treated with Zn
dust. Since Zn is more electropositive than gold, it displaces gold from the complex. The
gold precipitate obtained is impure. So, it is further puri ed by electrolysis.
Zn(s) + 2(Au (CN)2] (aq) →> [Zn(CN),|'-(aq) + 2Au(s)

Q2.following terms (a)minerals (b)gangue?

Answer:-ii) MINERALS:From monazite or clevite helium can be obtained by heating the
mineral in a red hot tube (at about 1273 K). The occluded gas escapes and is then
collected over potash solution which absorbs CO,, The gas is also obtained by treating the
mineral with dilute mineral acid. When monazite is heated to 1273 K, it evolves one cm' of
helium at N.T.P. from one gram mineral.
ii)GANGUE :-The minerals from which metals can be economically and conveniently
extracted are called ores. So, all minerals are not ores but all ores are minerals. Earthy
and undesired materials or impurities associated with the ore is known as gangue or
matrix.

Q3 ROASTING AND SMELTING?

Anser:-(a)Roasting:-Roasting is a process in which ore is heated below its melting point
in presence of air or oxygen to bring about oxidation. Generally, it is carried out for
sulphide ores or arsenide ores. During roasting, metallic sulphides get oxidised to metallic
oxides and impurities like sulphur, arsenic and antimony are removed in the form of their
volatile oxides SO2, As203 and Sb20 respectively. The roasting operation is carried out in
the furnace like reverberatory or blast furnace or multiple hearth roaster.
4As + 302CuS + 202→ 2As203→ CuSO4
Roasting is of three types.
(i) Oxidizing roasting: It is also called dead roasting. In oxidizing roasting, ore is heated at
very high temperature of 1150-1250 K, in a free supply of air to convert sulphides into
oxides either partially as in copper metallurgy or completely as in Zn, Pb and Ni
metallurgies.
Most of the sulphide roast reactions are exothermic.
22nS + 30г22n0 + 2502 :2CuS + 30г→ 2C20 + 2502
(ii) Sulphatizing roasting: In this type of roasting, a metallic sulphate is formed rather than
oxide. In some of the metallurgies like electrometallurgy, sulphide ores are required to be
oxidized to sulphates.
For example, in electrometallurgy of Zn, ZnS is oxidized to ZnSO4-To get ZnSO4, ZnS ore
is heated at low temperature between 773 K
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 to 873 K in a limited supply of air.
ZnS + 202 —)znso4 pbs+zo2—-)pbso4 cús+zo2~>cuso4
(iii) Chloridizing roasting: Sulphide ores are mixed with a chloride salt and roasted. The
sulphide ore changes to chloride ore.
AgS2 + 2NaCl + 202 → 2AgCl + Naz S04
(ii) Smelting: Smelting is a process in which the oxide ore in molten state is reduced to
free metal. It can be carried out in two ways: (i) by using reducing agent (ii) by self-
reduction process where no external reducing agent is used. Smelting operation is carried
out either in reverberatory furnace or blast furnace.
(i) By using reducing agent: A large number of metal oxides obtained during roasting can
be reduced to metals by heating with carbon at elevated temperatures (1273 K). The
roasted ore is mixed

Q4xenon hexa uoride and discuss their structure?

Anser :-Xenon hexa uoride — XeE
Preparation: (a) It is prepared by heating a mixture of xenon and uorine in the ratio of 1:
20 in a scaled nickel vessel at 500-575 K temperature under a pressure of 50
atmospheres.
500-575. Xef6
50-60atm
100% yield can be obtained at 973 K and under pressure of 200 atmospheres.
(b) It can also be prepared by the reaction between xenon tetra uoride and dioxygen
di uoride at the temperature between 40 K and 193 K.
XeF + 02F2~>XeF+Or
(c) XeF, is also prepared by passing electric discharge through a mixture of xenon and
uorine in the ratio of 1:3 at low temperature.
Xe + 3F2~>XeFo
Diasma of
Chemistry of Group 18
Structure
Electronic con guration
Xe(54) = 2, 8, 18, 18, 8
F(9) = 2,7
205
Outer con guration
Xe = 55 5p° =8
F = 252p = 7

: Lewis electron dot structure of XeF6

Number of bonding pairs around Xe = 6
Number of lone pairs around Xe
•. Steric number
=1
= 6 + 1=7
Hence, XeF, is AB,E type molecule.

Q5 Discuss the role sodium and potassium ion biological system?

Answer:-(1) Sodium and potassium: The two alkali metals, sodium and potassium are
very important and play a vital role in biological systems.
These are highly mobile, unipositive cations forming soluble salts.
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 They are strongly solvated in water. Our bodies obtain them from plants, i.e., from fruits
and vegetables, common salt is the most important source of sodium in the diet.
Potassium is present in coffee, tea, cocoa, dried beans, molasses, green leafy vegetables,
milk, sh bananas, oranges, pinapples, potatoes etc.
distribution:-Sodium is a major cation in blood plasma of vertebrates, i.e., outside the
cells (extracellular) while potassium is a major cation in cytoplasm, i.e., inside the cells
(intracellular).
Functions: The metabolism of sodium, potassium have been intimately related to certain
fundamental physiological mechanisms.
(i) Maintenance of normal hydration and osmotic pressure: The main function of Nat, K+
ions in the body has been to maintain the normal osmotic pressure of the different body
uids throughout the body and thereby to protect the body against excessive loss of uids,
which otherwise will disturb the normal hydration.(ii) Maintenance of normal acid-base
equilibrium
iii) Transport of CO2: Both Nat, K+ are known to play role in the transport of gaseous co2

Q3A1.)Discuss two method (a)metal-metal exchange reaction,(b)reaction-addition

reaction?
Anser~>(a) Metal-metal exchange - Transmetallation reactions
In transmetallation reactions, one metal M' replaces the other metal M and it is the most
convenient method for the synthesis of organometallic compounds.
RM + M' → RM' + M
This reaction is favourable only when M' is higher than M in the electrochemical series,
i.e., displacing metal is higher in the series than the displaced metal. The transmetallation
reaction is analogous to the simple inorganic reaction where a more reactive metal
displaces a less reactive metal from its compounds. The most versatile reagents (RM) in
this reaction are the derivatives of heavy metals such as mercury,thallium, lead, bismuth,
etc. The most widely used compounds are organomercury compounds R,Hg as Hg-C
bonds are extremely weak.
Metals that are alkylated by transmetallation reaction method are sodium, magnesium,
zinc, aluminium, calcium, gallium, etc.
(CH3)2 Hg + 2Na → 2(CH3)2 Na + Hg
(CHs)2 Hg + Zn →→ (CH3)2 Zn + Hg
3(CH3)2 Hg + 2A1 → 2(CH3)3A1 + 3Hg
3(CH3)2 Hg + 2Ga → 2(CH3)3 Ga + 3Hg
2(CH3)2 Hg + Sn → (CH3)4 Sn + 2Hg
Mercury is collected at the bottom and is reused.
(B)Reaction-addition reaction:-Many metals react with alkyl halides (RX) under suitable
conditions and form organometallic compounds. These reactions may be termed oxidative-
addition as they involve oxidation of metal by the addition of RX. These reactions are
favoured by electropositive metals as they show strong af nity towards halogen.
2M + RX → > MR + MX (RX = Alkyl or aryl halide)
In this reaction, oxidation state of M increases by one unit (M*) and hence, it is one
electron oxidative-addition reaction. Organolithium compounds arè commercially prepared
by this method.
8Li + 4CHCI → Li4(CH3)4 + 4LiCl
This reaction can be carried out in petroleum ether or benzene in an atmosphere of dry
nitrogen.
Other active metals like magnesium, aluminium, zinc also undergo oxidative-addition
reactions. Well-known example is of Grignard's reagent, an alkyl magnesium halide.
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 M + RX -
→ MRX
e. 8.,
Mg + CH,Br.
diethyl ether , CHMgBr
This is two electron oxidative-addition reaction (Mg to Mg2+).
Other similar reactions are -

The alkyls of less electropositive metals are prepared by using the metal in the form of an

Q3B(a)reaction with protic reagent (b)reactions with oxygen and halogen.?

Answer:-The elements of rst three main groups being more electropositive form
alkyls or aryls which easily undergoes hydrolysis reaction.
CH,Li + HOH → C,H,0 + LiOH
CH MgBr + HOH→ CH4 + Mg(OH)Br
Less electropositive boron reacts with water at higher temperatures.
B(C4H9)3 + H20 _
450 K→ B(CHg)2 OH + C4H10
In the tetra-alkyls of Group 14 and trialkyls of Group 15, the metals have lled low energy
orbitals and hence nucleophilic attack is not favoured.
The reactivity of metal alkyls with other protic reagents like alcohols, amines,
cyclopentadiene and other reagents with acidic hydrogen atom is mostly mild.
BeMe + MeH - → Be(OMe) Me + MeH
AlMe + MeOH→ Al(OMe) Mez + MeH
LiPh + C3H6> LiC,Hs + PhH
Alkyls of rst three main group elements react with stronger protic reagents like hydrogen
halides and form the corresponding metal halides.
LiR + HX →→ LiX + RH
Alkyls of Group 14 react slowly with hydrogen halides resulting in the cleavage of only one
M-R bond.
РЬМе4 + НХ → РьМез Х + МеН
The organoderivatives of Group 15, show an interesting variation in their reactivity when
treated with hydrogen halides.
Reaction of AsPh in liquid hydrogen chloride is an addition reaction.
AsPh + 3НС! =>[ph3AsH]+[HCl2]_
Trialkyls of Sb3+ react with hydrogen halides and get oxidised to Sb5+ derivatives.
SbMez + 2HCl -_>SbMez Cl + H2
But tri phenyl bismuth reacts in a different way. It forms trị chloride with HCl as Bi is more
stable in its trivalent state.
BiPh + 3HCI -→ BiCl + 3PhH
B)Reaction with oxygen and halogen:—Since organometallics spontaneously in ame in
air, their reactions with oxygen are highly exothermic particularly, the lower alkyls of rst
three main groups.
2M R3 + 02→ 2M R3(0)•(M = As, Sb)
limited
2E R2 + 02→ 2E R2(0)(E = Se, Te)
Halogens decompose organometallics and form hydrocarbon halides.
CHsL1 + Bi2→ CH,Br + Li Br
H3C - Si - + Ch→→ CIH2 C - Si - + H CI
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Halogens generally cleave the M - C bond and the ease of completion of the cleavage
reaction mainly depends upon the electropositive character of the metal/element.
Li R + X2 -Li X + RX
Al R3 + 3X2A1 X3 + 3RX
B R3 + 12~> BI R2 + RI
Ga R3 + A2~>Ga X R2 + RX
Similarly, Cle and Biz react with tetraalkyls of Group 14.
Si Me + Ch2____hv~>SiCIMe3 + MeC!
Ge Me + Brz→ Ge Br Me + MeBr
controlled
Sn Me + Cl2-> Sn Cl Mez + MeCI
conditions
Trialkyls of P, As, Sb and dialkyls of Se, Te undergo oxidative addition with halogen
M R3 + X2→ M R3X2
E R2 + X2→ E R2X2
Trialkyl of Bi prefers to undergo cleavage reaction.
Bi R3 + X2 → Bi R2X + RX
Pentaphenyls of As, Sb and Bi on reaction with halogen, undergo cleavage and form
tetraphenyl arsonium, stibonium and bismuthonium trihalides respectively.
AsPhs + 2X2 → [As Ph4]+ X5 + PhX

Q3c(b) short note bonded covalent organometallic compound?

Answer:-bonded covalent organometallic compounds
Most of the OMCs of non-transition elements are covalent compounds involving M - C o
bonds (with some ionic character). In these o bonded OMCs, carbon atom of organic
group is linked to the metal through normal electron pair or 2 centred 2 electron bond, e.g.,
alkyls like BeRz, Mg(CHs)2, etc. The polarity of M - C covalent bond depends upon the
difference in electronegativity between M and C atoms. In some OMCs, it also depends
upon the availability of metal orbitals and polarizability of its electron cloud.e.g., B(CH3)3,
Al(CH3)3-Elements of Group 12, i.e., Zn, Cd and Hg, though are the members of transition
series, they behave as Group 2 elements in the formation of o bonded OMCs as their d
orbitals are completely lled, e.g., R2Hg, Zn(CHs)2, etc. The reactivity of R2M, particularly
towards hydrolysis, increases with the decrease in electronegativity of M. Thus, (CH3)2 Zn
hydrolyses faster than (CH3)2 Hg. The M-C bond In Zn(CH3)2 is only o with no i bonding.

D) Describe the method of preparation of ferrocene?

Answer:-1. By the oxidation of cyclopentadienyl Grignard reagent Kealy and Pauson
in 1981, tried to synthesize fulvalene by oxidation of cyclopentadienyl Grignard
reagent with ferric chloride.
But surprisingly instead of fulvalene an unexpected product which
- was orange coloured was obtained. This was stable, and could be sublimed in air without
decomposition. This new compound was later identi ed and named as ferrocene.
One of the methods to synthesize ferrocene is the oxidation of cyclopentadienyl Grignard
reagent with FeCl.
The ferric ion Fet used for oxidation is rst reduced to ferrous ion Fe?+ by
cyclopentadienyl Grignard reagent and then Fe? reacts with Grignard reagent to form
ferrocene:
Fe3+C5H5MgXMgX→ Fe2+C5H5MgX~>Fe(CsHs)2 + 2Mg + 2x
2C5H5MgBr + 2FeCl3 → 2FeCl2+ C5H5 - C5H5 + MgBr2 + MgCl2
2C5H5MgBr + FeCl2 → (C5H5)2 Fe + MgCl2, + MgBr2 Therefore,
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[Fe3+ → Fe2→ Fe(C5H5)2l
2. Direct reaction between iron and cyclopentadiene
Fe + 2C5H6 → (CsHs)2 Fe + H2
Ferrocene was independently discovered during the direct reaction between reduced iron
and cyclopentadiene at 575 K temperature. In this method, bases like amines have been
used as they facilitate the removal of the acidic hydrogen of cyclopentadiene so that
ferrocene is obtained at relatively lower temperatures.
The mechanism of the reaction is:
Fe + 2R,NH + CI ->FeCh + 2R,N + H2
FeCh + 2C,H6 + 2RN → Fe(CHs)2 + 2RNH*Cl
:. Net reaction:
Fe + 2C,H6 → Fe(CsHs)2 + H2
(3) Better synthesis uses cyclopentadiene with metallic sodium and dihalide of transition
metal, FeCh.
2C5H5 + 2Na → H2 + 2NaC5H5_ FeCl2, Fe(CsHs)2 + 2NaCl

E)sulphonation and alkylation reaction of ferrocene?

Answer:-(ii) Sulphonation: Ferrocene undergoes sulphonation with concentrated H,SO4
and forms mono substituted derivative.
C5H5•Fe-C5H5 + H2SO4 glacial —->acetic acidCsH,SOH•Fe•CsHs + H,0
(iii) Alkylation: Ferrocene when treated with ethylene at 30-40 atm pressure and about
400 K temperature in presence of aluminium chloride catalyst, forms its ethyl derivative.
(C5H5)2 Fe + H2C = CH2catalyst~>H5C5Fe - C5H4CH2CH3