Carbon

Page 1

CARBON Occurrence:
Lime StoneDolomiteCalamineSpastic Fe oreIn air as C Mineral oils, natural gas, hydrocarbons, carbohydrates, starch, protein Type of coal: Peat- 60% carbon(low grade coal) Lignite-67% carbon(low grade coal) Bituminous-88.4% carbon(High grade coal) Anthracite-94.1% carbon(Very high grade coal)

Characteristics of carbon atom:

Carbon-1st member of Gr-14

Most electronegative element in Grp-14 (2.5). Combines with electropositive as well as electronegative elements (occupies mid-position). Catenation: The unique property of carbon atoms to combine with other carbon atoms through chains or rings. The high M.P of carbon(3930 during melting. Allotropy Of Carbon: The property of an element to exist two or more different forms which different physical properties but the same chemical properties is known as allotropy Different Types: EDUDIGM 1B Panditya Road, Kolkata 29
www.edudigm.in 40034819

results from, the very stable arrangement of diamond

Type of lattice- High heat energy is required to break the numerous covalent bonds

Carbon Due to different arrangement of atoms in structure crystals. In difference in no. of atoms in molecules In difference in the available energy as in Rhombic and Molecular sulphur.

Page 2

Diamond
X- ray analysis have proved that many of the non-crystalline structure of the amorphous varieties of carbon consists of micro crystals of graphite, which are distributed throughout their mass in haphazard manner. Most Ds contain a trace of Diamond: Two types of natural diamonds are found in nature. A colorless and glistering variety A back opaque variety known as Carbonado Properties of Artificial Diamond: Moissan, 1893 tried first. Pure Fe + Sugar Charcoal taken in a graphite oxcible and heated to 8000 . The molten Fe dissolved a good amount of sugar charcoal. The crucible with its contents was then immersed in molten lead. On rapid cooling, molten Fe solidified out as small crystals of diamond. D separated from Fe by boiling in HCl. , blue Ds

Properties:
Physical Properties: Hardest Substance Colorless, transparent, lustrous, crystalline solid Diamond heaviest- specific gravity=3.5 High refractive index (2.42) shines brightly. (Light rays are slowed down by tightly held electrons. Transparent to X-ray. Non-conductor of heat and electricity. Much of the light falling on a diamond is internally reflected of interior surfaces. The refraction of different colour of light is not equal so, white light passing through it gives rise to brilliant display of colour Chemical Properties: Diamond is chemically inert not attacked by acid, alkalies valuable gemstone.

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 3

Oxidized by chromic acid (conc. Diamond dissolves in molten iron.

to produce

Structure of Diamond:
Diamond is the hardest substance known Diamond does not conduct electricity. The melting point of diamond is very high m.p=3930 The structure of diamond consists of carbon atoms each of which is situated at the centre of regular tetrahedron, surrounded by four other carbon atoms. These four C-atoms are situated at the four corners of tetrahedron. As a result the C-C-C bond angle becomes 19228. Thus each C-atom is strongly bonded to its 4 neighbors by strong covalent bonds resulting from hybridization, joined by strong sigma bonds throughout the entire crystal in 3 dimensions and each crystal is regarded as macro molecule. Due to the extremely tight strength of the covalent bonds holding numerous c-atoms, together diamond is very hard and high density. Bond . As all the available electrons of c-atoms are completely paired up in forming the sigma bonds, no free electrons are left in the system for conducting electricity. So D is a non-conductor of electricity. The force acting between the covalently linked carbon atom in diamond are very strong and consequently a large amount of heat energy is required to break so many covalent bonds in the crystal. So a large amount of heat energy is required to melt it which explains the high melting point of diamond. D has a series of cleavage planes || to its octahedral faces which help in shaping rough ds & forming cut ds.

Graphite: Artificial preparation of graphite:

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon ACHESONs METHOD: Mixture of mixture heated strongly at 3500

Page 4 and anthracite coke in a electro-thermal for 30 hours.

furnace two carbon electrodes, connected by a central core of c rod i passed

REACTIONS:

(Si being more volatile escapes out ). Process is carried out in absence of air to prevent the oxidation carbon

Properties
Physical Properties: Dark grey crystalline substance. Metallic luster Soft and slippery. good conductor of heat and electricity. s.g=2.2 and marks paper. Chemical Properties:

Graphite reacts with graphitic acid.

in presence of conc.

and

to produce .

Not attacked by dilute acids or fused alkalies. Oxidised by chromic acid to and 60,000 atm. The vapor of K, Ru, Cs are absorbed by graphite forming bronze+ blue sheet increase their distance from 3.35 to 10 . Graphite is diamagnetic, paramagnetic.

Graphite is thermally stable. Diamond can be formed from graphite at 1600 or is

colored compounds(Intercalation). In these compounds the graphite

Structure of Graphite:

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 5

Graphite is soft slippery and good conductor of heat and electricity because the structure of graphite consists of a number of 2-D sheets like parallel layers of Catoms. The C atoms arranged in a network of flat regular hexagons. Such layers are identical. Each of the C-skeleton atom of given layer is joined to its adjacent 3-C atoms in the same layer, by using used to form hybrid orbitals. Thus, in forming the hexagons electron of each C-atom is each C atom uses 3 electrons top form 3 bonds, the

bond. The C-C bond distance in any layer is 1.42 and between two

adjacent layers is 3.35 . This layer distance rules out the possibility of a covalent bond between C-atoms in different layers. These layers are loosely linked together by weak Vander walls forces. the low density and softness of graphite is due to the wide separation of the sheet like carbon layers, Since the different layers are loosely linked together, they can easily slide each other and as a result graphite is slippery and possesses lubricating property in contrast to the abrasive property of diamond. As the electrons of carbon atom are mobile and are free to move through the graphite crystal graphite is a good conductor of electricity and heat. Any specially treated charcoal having high power of adsorption and decolorizing power is called activated or active charcoal. Active charcoal has a power to adsorb coloring matters from the colored solutions. Active charcoal is good adsorbent for gases than ordinary charcoal. It has the power to adsorb taste of a substance. Active charcoal acts as a catalyst. It can accelerate many chemical reactions.

, , , ,

High temperature

Carbides are formed

www.edudigm.in 40034819

EDUDIGM 1B Panditya Road, Kolkata 29

Carbon ,

Page 6

Lamp black is the purest form of amorphous carbon. The heat of combustion of graphite (-94.052) Kcal/g atom and diamond (-94.505) Kcal/G atom at N.T.P Graphite is the thermodynamically more stable form of C Graphite can be converted into diamond at 1600 Charcoal dissolves slowly in hot dilute tenin. With conc. by a pressure of 50000-60000 atm. forming a brown substance called artificial

Oxides of Carbon:
Carbon dioxide ( 2. Carbon Monoxide (CO) 3. Carbon Sub-Oxides

Carbon Monoxide: Preparation:

] The CO thus produced is dried by as it is oxidized From Sodium formate: (reverse reaction) From potassium ferrocynaide: Dil. extremely poisonous substance. From is passed over red hot coke when is reduced by carbon to carbon which is removed should not be used it gives HCN, an and collected over Hg. It is not dried over

monoxide. The issuing gas may contain some traces of unreduced

by passing the gas through NaOH solution. CO is collected by the displacement of water.

(Oxides of heavy metals Fe, Zn etc.)

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 7

Properties
Physical Properties: CO is colorless, tasteless gas Slightly soluble in water but more soluble in alcohol Liquefied to a colorless liquid at -191C at ordinary pressure. It is highly poisonous CO is poisonous, combines with haemoglobin producing carboxy haemoglobin, which do not supply the necessary required to the different parts of the body. This explains why a person sleeping inside a closed room with charcoal fire dies. A victim of CO when unconscious is given artificial respiration with carbogen( a mixture of and 5-10% ) should be given. Th no. of There is a similarity between the molecular structure of valance electrons in them are the same. Chemical Properties: Co is combustible but not a support of combustion. It burns in air or oxygen producing a blue flame with the formation of Reducing property:

. C atom has a tendency to increase from +2 to +4 at the expense of reducing others. Action on Alkali: CO is neutral oxide. It can not change the color of litmus. So it does not react with bases alkalies at ordinary condition. But it reacts with NaOH when CO is passed through a strong solution of NaOH at 150C under high pressure yielding sodium formate.

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon Formation of Addition Compounds(Carbonyls):-

Page 8

(Highly Poisonous) (Carbonyl Chloride or phosgene)

With transition metals like Fe, Co, Ni carbonyls formed

Absorbent of CO:- Co is completely absorbed by a solution of or in (white compound) crystalline

in Conc. HCl additional

Tests of CO:CO burns with a pale blue flame when ignited. (Both blue when ignited. burns and (Lime water milky) CO turns ammoniacal solution brown. solution CO is completely absorbed by ammoniacal CO to to and Co burns with a pale from form steam which which

A filter paper soaked with a solution of platinum or palladium chloride, when comes in contact with CO turns pink or green or black due to reduction of salt.

Structure of CO: Though there is a large difference in the electronegativities of C and O, it is found that CO molecules exhibit only a small dipole moment. This is due to the shift of electron pair

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 9 in

from oxygen atom to carbon atom which compensates the difference base and can form a c0-ordinate bond some metal known as carbonyls. , M = Fe, Ni, Cr

electronegativity values. Due to the presence of electron pair in CO, it acts as a Lewis etc.

Q) How will you prove that CO Contains C:-

Comparison between CO & NO:

CO A colorless gas soluble in water Neutral Oxide Combustible gas-burns with a pale blue flame At high temp.(burning) NO A colorless gas insoluble in water Neutral Oxide. Non-combustible gas Ordinary Temperature

At 200C, under high pressure CO reacts with Does not react with NaOH. NaOH under high pressure to form HCOONa Forms additional compounds It also forms, NOCl

CO is observed by ammoniacal forming a white additive product. CO is highly poisonous gas CO has reducing property

solution NO

is

absorbed

in

solution

forming additive compound NO is a poisonous gas. NO has both oxidizing and reducing property.

Carbon Di-Oxide (CO2):

Discovered by Van Helmont, 1630

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 10

Preparation:
Lab preparation. Room temperature. passing the gas through a solution of . Thus, pure and dry Carbonates(metallic) on dilute acids:is collected by the upward displacement of and moisture by passing it through conc.

air.Purification: Contains some HCl vapors and moisture. HCl vapor is removed by is collected over Hg.

Thermal decomposition of carbonates and bicarbonates (Important):- (Except carbonates of alkali metals), metallic carbonates at elevated temperature deco mpose to evolve and the corresponding oxides.

on heating evolve . Fermentation:

From water gas :(Water Gas).

Properties:
Physical Properties: Colorless, odorless gas having a faint taste. 1.5 times heavier than air

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 11

Fairly soluble in water, solubility decreases with increase of pressure and rise of temperature. Not poisonous but does not support life.

Chemical Properties: Combustibility: Neither combustible nor a supporter of combustion, but burning Mg, Na, and K continue to burn in it with the separation of carbon, tremendous heat breaks into C and . of the

Acidic Property: Acidic oxides, aq. solution carbonic acid weak, dibasic acid.

Lime Water

Oxidizing Property:

posses no reducing property.

C in +4 oxidation state has no scope to increase its own state by reducing other as this is the max which C can attain. Red hot Fe, Zn powder, burning Mg are oxidized to the corresponding oxides.

When a mixture of water, insoluble sulphate.

and

is passed through a suspension of gypsum in through this process.

is precipitated with the formation of Ammonium can be prepared without

At 200-210C, 180 Kg pressure,

(photosynthesis)

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 12

Absorbent of bicarbonate.

:- Strong NaOH or KOH solution forming carbonates or

Tests of Carbon dioxide:

Lime water turning milky. but show the same type of reaction with lime water turning it milky, but while cannot change the orange color of to green, can.

Uses of Carbon dioxide:

Manufacture of Dry Acid: Refrigeration. Aerated Drinks Fire Extinguishers. Dry Ice: When is subjected to a process of 60 atm at ordinary temp. it is at 20 C and under a pressure of 70 liquefied to a colorless liquid . The liquid by Solvays process, urea,

atm, is introduced into a chamber through a jet where rapid evaporation of liquid takes place and the required atm of latent heat for its evaporation is supplied by the liquid liquid itself, taking its temperature down to 0 . Now the at 0 C is admitted to press chamber where further evaporation takes directly passes into gas

place and the colorless liquid freezes like snow (white). This is called dry ice because with the rise of temperature this solid without going through sold state. Very good refrigerant , Creation of exceedingly low temperature required for research work in lab, Local anesthetic in surgical operation (commercial name drinkeold). USES OF AS FIRE EXTINGUISHERE:-

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 13

Foam type extinguishers:- At present foam type extinguishers are used to extinguish oils and petrol fires. The bubbles of produce stable foams with and these is formed which foams are ejected forcibely and applied on the fire where a layer of

covers oil. Thus, the oil or petrol can not come in contact with air or oxygen. Q) is harmful in extinguishers fires where the temperature is very high or burning At high temperature is decomposed to give CO instead aggravates it. producing : . The CO thus produced is combustible which

Mg can not be extinguished by and oxygen or C & Thus

burns with a blue flame which is supporter of combustion. So

is harmful in extinguishing fires when the temperature is very high.

Burning Mg produces a tremendous heat and it continues to burn in oxides of Mg MgO , atom giving rise to .

is a gas but

is a hard solid with high melting point :- In silica, each Si atom is tetrahedron, each atom are

surrounded tetrahedrally by 4

being shared with another tetrahedron leading to a 3-D giant molecular structure. on the other hand is a discrete molecule. The intermolecular forces in weak. The size of c-atom being very small, the neucleous of C-atom attracts its outermost electrons very firmly and does not allow o-atom to combine with outer carbon atoms. The radius of Si-atom on the other hand is pretty large and hence the attraction between the nucleolus of Si atom and its outermost electron is weak. Hence one atom may be shared between two Si-atoms, giving rise to Si-O-Si until leading to bond both the atom 3-D structure. Again, C-O bond can be easily formed since in the formation of the formed. On the other hand in case of formation of are quite different. Hence, the effective difficult. Hence no orbitals are used by Si atom to form bond in use 2p orbitals of same size and energy. As a result monomeric O=C=O molecule is , it requires the use of is very hybrid is 3p orbitals of Si and two p orbitals of oxygen. But the size and energy of two P orbitals bond formation between Silicon and Crystal structure of bond is formedin Silicon molecules. Instead, four

therefore very stable because of infinite 3-D structure. To break this structure considerable amount of energy is required. This explains why m.p and discrete structure of is hard with high specially its gaseous character at room temperature.

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon STRUCTURE OF :

Page 14 is linear, non-polar, posses 0 dipole moment (dipole on one O=C=O Net = 0

side is canceled by the other side

The C-C bond distance is 1.15 , rhezonence hybrid COMPARISON BETWEEN CO Colorless & odorless V.D= 22.1.5 times heavier than air Colorless gas heaving a faint smell V.D= 14, slightly lighter than air.

Neither combustible nor supporter of Burns with a pale blue flames does not combustion, but Mg(burning) continues to support combustion burn in it. Acidic First forms carbonates and oxide, Neutral oxide. then Does not react with alkali at ordinary temp. but at 200C and under pressure it . combines with NaOH to give HCOONa.

bicarbonates with alkalies.

As it is saturated compound, does not form CO is an unsaturated compound forms any additive product solution. due to lack of additive compounds. by ammoniacal cuprous with the chloride solution forming poisonous-combines haemoglobin of blood and destroy its ability to carry Has no reducing property. itself is reduced It is a strong reducing agent, reduces by C, Fe, Zn, Mg at high temp. metallic oxides at high temp. to metals. Completely absorbed by NaOH or KOH Absorbed Not poisonous-causes death by suffocating Highly

CARBON SUBOXIDE:
Linear structure O=C=C=C=O

[Foul smelling gas with b.p = 6C] EDUDIGM 1B Panditya Road, Kolkata 29
www.edudigm.in 40034819

Carbon

Page 15

CARBONIC ACID:
When acidic oxide is passed through water a part of it dissolve in water, a part of it get dissolves in water forming [Whole of . is not used up in forming , a greater part of it exists as

PROPERTIES:
is very unstable. Very weak acid.

Turn blue litmus wine red. Dibasic- Forms two types of salt. Normal Salts, Acidic salts-bicarbonates

with the exception of the carbonates of alkali metals and Ammonium Carbonate, all other carbonates are insoluble in Metallic Carbonates: . Alkali carbon doesnt decompose on heating.

Action of Heat: Alkali carbonates oxides &

only melt on strong heating

but do not decompose. The carbonates of other metals decompose on heating to

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 16

Metallic Bicarbonates:- By passing excess hydroxides.

through the solution of the

Bicarbonates are generally soluble in water. On heating they decompose to evolve

Due to weak nature of react in alkaline aqua solution

the carbonates of alkali metals

As the aqua solution of the alkali carbonates produces strong alkali (NaOH or KOH) and weak acid concentration of HCl, The titration takes place in 2 stages. In the first stage one eq. of acid is used to produce the bicarbonate slat and the end pt. of the reaction is indicated by phenopthaline indicator. Thus phenoptheline changes the colour when half of the neutralization takes place. , the final solution is alkaline due to higher ions in the solution. Thus, the aqua solution of a

carbonates of alkali metal can be treated against the solution of strong acids like

CARBIDES:
Compounds of C with elements of nearly the same or lower electro negativity that itself. These are of mainly 3 types.

Salt Like carbides:

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon Methanides

Page 17

Acetylides

ion.

] Allylides Covalent ion. Carbides: (Carborundum) Extremely hard cov, polymeric thermally stable

Metallic Interstial Carbides: [Formed with transition metals ][The C atom occupy gaps in the lattice structure of metal atom WC,VC .Varies with the radius of the metal atoms.]

SILICON
Silicon the 2nd most abundant element on the earth crust is an important constituents of igneous rocks, clay.(2 nd to Allotrope 1. Amorphous 2. Crystalline

Amorphous Silicon: Preparation:

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 18

(Diagonal relationship Analogy)

Properties:Amorphous Si (sg 2.25) is a brownish powder. Burns brilliantly in but superficially in air.

It is soluble in KOH and a mixture of Decompose steam at red heat. It ignites spontaneously in From giving

and HF.

. In

: In electric furnace

To avoid SiC fermentation excess On fusion with it gives sodium silicate and carbon and

Si dissolves in fused NaOH to displace

Crystalline Silicon:-

Preparation:-

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 19

Crystalline silicon (sp.gr 2.49) posses light orange color and a metallic lusture

Properties:
Very hard and scratches glass. It does not burn in even on strong heating (different from amorphous Si). When fussed with alkali it gives a silicate. It reacts with boiling water or steam. It combines spontaneously with F_2 in cold but on heating with The difference in chemical behavior of Si and C are because: Si has larger size (117 ppm). c(77 ppm) Si shows great reluctance to form multiple bonds with itself and with difference concept and size). C can easily form Si can utilize 3d orbitals for bonding and can form penta & hexa co -ordinated compounds while C can not (d orbital not present). (energy

SILICONES
These are organosilicon polymer containing Si-O-Si linkage. These are prepared from allyl or aryl organic compounds. Chlorosilanes which in turn are obtained from Grignard reagent and silicon tetrachloride.

[Rochow Direct Process] Silicon may be linear, cyclic or cross linked.

PREPERATION:
EDUDIGM 1B Panditya Road, Kolkata 29
www.edudigm.in 40034819

Carbon

Page 20

Linear Silicones:- Hydrolysis of the chlorides yield the corresponding silane polymerize by condensation.

Now since an active OH group is left at each end of the chain, polymerization continues at both ends and thus the chain, polymerization continues at both ends and thus the chain increase in length and ultimately forms a linear thermoplastic polymer

Hydrolysis under carefully controlled condition produce rings with 3,4 or 5 Si atoms. Prep Of Cyclic Silicones: Cyclic(ring) silicones are formed when water is eliminated from the terminal Oh group of linear silicones. Preparation of Cross-linked silicones: Hydrolysis of alkyl trichlorosilane, cross linked polymer. gives the monomethyleslane ion which then undergoes polymerization to a very complex

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 21

[Methyl Silatrol]

Hydrolysis of

yields

which condenses to a compound which is

has no OH group & cannot polymerize further - So, to stop chain, some mixed with others & hydrolyze to block the end of straight chain. Thus mixture. is a chain stopping unit, ratio of

in the starting

The length of the chain, the extent of the cross linked and ratio of the alkyl or aryl substituent determine the nature of the polymer which may be oily liquid, rubber or solid. A silicone of shirt chain molecule is an oily liquid , a silicone with medium chain behave as viscous oil, jelly & grease, while a silicone of very long chain has rubber like character.

Properties & Uses:

Silicones may be regarded as intermediate between organic compounds and silica as their properties are blend of those of the hydrocarbons. Eg

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon lubricating properties which are properties of hydrocarbons oil, and is uncreative even at high temp. Silicones are stable to heat at least upto a temperature of 200

Page 22 which

(pure organic

polymers do not withstand high temp.) and non-volatile on heating. The most heat stable side group is phenyl, followed by methyl, ethyl and propyl groups in descending order. On heating in air to 350-400 , silicones are rapidly oxidized and cross links are formed. They are durable and chemically inert. These properties are due to stable silica like arrangement of Si-O-Si-O-Si , and very high bond energy (502 KJ/mol) of the Si-O bond. They are non-toxic. Walden inversion in case of hydrolysis of optically active as well as with . Intermediate

In case of fluid, their viscosity not change more with temperature. They posses good electrical insulating properties, because they are more stable to heat than organic polymers. Even if they break they dont produce conducting material like carbon. Silicones posses outstanding water repellenary power. This property is due to the high content of alkyl or aryl halides (Acidic Oxide) .

Silica:
Pure is colorless but sand is brownish or yellowish due to the presence of . impurities of

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 23

SILICATES:
Silicates are the chemical compounds having fundamental unit earth crust (about 87%). & others. Because of the strength of the Si-O bond which is only cleaved by reagents like HF most of the silicates are insoluble, sod silicate or water glass is the only commonly soluble silicate. Silicates acquire different structure ranging from simple structure to complex structure. In silicates, each Si atom is bonded tetrahedrally to 4 structural unit tetrahedron. atoms i.e they have a basic . A large part of the

The

hybridised Si atom form 4 covalent bonds with

atoms, the later are arranged

around the Si atom to form form Si and six from each

having a regular tetrahedron. The four valancy electron atom are insufficient to complete the octets of all the atoms

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon in . The octal is completed in case of Si, but each of the four .

Page 24 atoms is short of 1

electron with the result the The electro negativity of ionic, 50% covalent). The Si-O bond distance

atoms tend to get electrons from some other atoms and is 3.5 and that of Si is 1.8. The electronegativity difference is

thus acquired a ve charge and ultimately forms

1.7 suggests that Si-O bond though covalent, has an app. degree of ionic character. (50%

1.62 , O-O

The two most striking properties of the zeolites (used a lot in water purification) are their capacity for the base and the ability of the hydrated materials to loose or reabsorb water without any change in optical or crystallographic properties. Like of their molecules may be absorbed by the zeolites. , a variety

IMPORTANT: Zeolites act as molecular sieves by trapping small molecules in their interstices reversibly. Act as a natural ion exchangers e.g permutit water softeners are sodium zeolites. They take up water ions form hard water and release ions in water, thereby softening the

Sodium Silicate:
The only soluble silicates are alkali the following ways:By dissolving in alkali metal hydroxide solutions at about 100 silicates. Soluble silicates are prepared in

By fusing sand with By fusing sand with

in open hearth type in presence of a reducing agent pure carbon.

Used in fire proofing and fire proofing. (in N-Si the N has no donor properties as it has no lone pair, C has no d orbitals so it forms polymerization)

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 25

SILICATE GARDEN:
Crystals of heavy hydrates, such as are dropped into a 20% solution of sodium silicate. A blue gelatinous member around the coba lt salt crystals is formed, while a brownish envelope formed around the iron salt crystals. Osmosis through the members causes them to swell and burst, the escaping salt solutions forms new membrane, and the process competes with ultimate formation of attractive plant like green. have similar formulae but different structures. Electronic structure of 3 unpaired electrons is form bond with . In trysilylamine, groups tetrahederal arrangements of 3 bp and 1lp for 6 bonding giving rise to a plane results p -d bonding, bond length. orbitals are used

sturcutre. The lp of electrons occupy a p orbital

at 90 to the plane . This overlaps the empty d orbitals on each of 3 Si atoms, and it is from a full p-orbital to empty d-orbital. This shorts the

SILICON CARBIDE (SiC)-(Carborundum)An extremely hard, infusible, thermally stable and chemically ineart solid. The structure of SiC is similar is similar to exact of diamond, if alternate carbon is replaced by Si. SiC has infinite 3-D structure of Si and C atoms, each is tetrahedral surrounded by four atoms of the other, C-Si The diamond type structure of carborundum explains its hardness , high dissociation temperature above 200 ) and chemical inertness. Unaffected by acids (except with at 100 . It is oxidized by fused NaOh in contact with air. ,

It is obtained when a mixture of sand, carbon, common salt and saw dust is strongly heated in an electric furnace.

SiC is widely used as an abrasive and refractive bricks. It has a better thermal conductivity at higher temperature than any other ceramic and is very resistant to abrasion and corrosion when bonded with silicon nitride.

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 26

SiC is often dark purple, black or dark green due to the presence of impurities (Fe). Pure samples pale yellow to colorless.

Glass:
Man made silicate. Transparent or translucent super cooled complex mixture of non crystalline silicates. Preparation: Glass is prepared by cooling the molten silicates abruptly. The rapid cooling leads to the formation of transparent & non-crystalline material. glass is not a true solid, it has no definite melting point. It softens when heated to a certain temp.

Types:
Ordinary Glass: Mixture of at 1700 Na & Ca silicates, produced by heating a mixture of in a furnace.

Soda glass or soft glass Colored Glass:

Composition

Heat resistant boro-silicate glass: Addition of High refractive index glass: Addition of Crookes glass: lusture. Flint Glass: instruments.

or

Pyrex glass.

(Cerium Oxide). Cuts of ultra violet rays lens making shining . High refractive index & shining lusture. Used in optical

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 27

Tin (Sn)
Electronegativity = 1.8

Occurrence:
contains about 1-5% of tin oxide which is contaminated with sand., earthly matters, pyrites of Cu & Fe & Wolframite The metallurgy of Sn consists of 6 operations:Concentration: the tin ore is crushed to powder and the finally crushed ore is conc. by washing with a stream of water. The light siliceous earthly matters are washed and carried away by the current of water leaving behind the heavy minerals which are dried. Roasting:- The Impure ore is further crushed and roasted in presence of air. During roasting The sulphure and arsenic present in the ore are volatilized away in the form of their oxides. Fe & Cu present are converted to their oxides & sulphates. Washing: The roasted ore is washed with hot water dissolving sulphates of Cu & Fe. the ore now contains oxides of Sn, Fe and Electromagnetic separation: The washed and finely divided ore is carried by a travelling belt over a magnetic roller. When the belt take a turn near the magnet, the magnetic particles, Fe & are pulled towards the magnetic roller. and is called black tin. The final conc. ore contains about 75% of .

CARBON-REDUCTION: The black Sn is further crushed and mixed with anthracite coke and some lime stone and the mixture is heated on a reverberatory furnace at 12001300 , when is reduced by the coke to give metallic Sn. The molten Sn is run out of the furnace & costs into ingots. Sn(99% pure). The upper layer of the slag contains about 10-20% Sn. This is smelted with coke and limestone n a blast furnace to remove metal Refining: The crude Sn is refined by liquation or sweating process. The ingots of oxides Sn are heated on the sloping hearth of a reverberatory furnace. Tin melts (m.p = 231.8 and flows down leaving Fe, Cu oxides & W. Sn is melted again and stirred with . poles of green wood. The impurities of Fe & C are reduced by C. Sn

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon Electronically electrolyte acid bath of . Cathode

Page 28 Pure Sn,

Anode impure Sn. Pure Sn is deposited at the cathode which is 99.98% pure. Recovery of Sn from scrap Sn plates:- The scrap Sn plates free from moisture of grease are in an fe cylinder & dry gas is passed into the cylinder when Sn reacts with form to form Sn . water to form to being a liquid, is volatized away & is condensed. This is boiled with which is filtered off & reduced by coke by usual process

At 100 , it is very malleable & ductile can be beaten into sheets- tin foil.

PHYSICAL PROPERTIES OF Sn:

Sn is a soft, crystalline, easily fusible, silvery white metal which is stable between . A rod of Sn emits a cracking sound when bent. This is known as cry tin. Mechanical twisting of Sn crystals is the cause. Sn exists in 3 allotropic form: White Sn crystallizes tetragonal crystals. is the ordinary Sn & most stable form. It

5.74 g/c.c

7.29g/c.c

6.56 g/c.c passes into gray Sn which crustallises in cubic why the orange pipes

White tin on being cooled at 13.2

system(diamond like). The conservation is accompanied by an increase in volume and the gray Sn becomes brittle and easily crumbles to powder disease, Sn pest or plague, White Sn(crystalline) . Stable between . and other tin article crumble down to fine powder in extreme cold. Phenomenon Sn

CHEMICAL PROPERTIES of Sn:

Action of air or :-

Water:- Sn is attacked by decomposes .

at ordinary temperature but at high temperature

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 29

Action on Alkali: Sn dissolve in hot & conc. alkali to liberate Action on acid: It is slowly attacked by dil. HCl but liberates formation of stannous chloride. Sn liberates Cold & dilute with hot and conc. when heated with conc. reacts with Sn to for

and stannate salt.

with hot & conc. HCl with the

forming stannic sulphate. .

, a vigorous reaction takes place with the formation of a

white ppt. of meta stannic acid and evolution of brown fumes of

It has no action on organic acids and so Sn plated Fe containers are used for the preservation of citrous fruits & pickles. Sn is ppted from its salt solution by stronger reducing agent like Zn, Fe, Al because their standard reduction potential is more negative.

When a piece of Zn rod is placed in a solution of of Sn is formed on the surface of Zn rod. ,

a bright crystalline Tree .

USES of Sn:
Tinning: Cu & Fe utensils are first cleaned with sand & then heated with over the hot surfaced & polished until a uniform layer of Sn is formed. Preventing rusting by tin plating Sn foils are used in wrapping cigarettes, confetionary etc. . It being acidic in nature, removes the oxide films from the utensils. Metallic Sn is then rubbed

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon Alloys:Pewter Solder Type Metal Bell Metal Babbit Metal Sn amalgam is used for mirror making. COMPOUND OF Sn:- Sn exhibits 2 valancies -- 2(ous) & 4 (ic)

Page 30

Stannous compound are easily oxidized to stannic state and therfor behave as a strong reducing agent. In accordance to Fajans Rule, stannic compounds are covalent while stannous are ionic. Simple ion does not exist. Both the bivalent & tetravalent Sn compounds form etc. complex anions of the type

STANNOUS OXIDE Preparation:

:-

Stannous oxide is obtained by heating crystals of stannous oxalate out of contact with air.

Also obtained by heating

in absence of water ,

is formed as a white

ppt when calculated quantity of alkalis added to stannous chloride solution.

Properties:
SnO is a dark gray powder, insoluble in water but soluble in acids. Dry is readily oxidized and when exposed to air, it changes to white stannous oxide

It is amphoteric in nature and thus dissolve both in acids and alkalies to form stannous salt and stannites. Stanites are a powerful reducing agent.

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 31

Stannites are stable only in aq. solution. In air absorb

stannates

A finally divided black metallic Bi result when a bismuth salt is added to solution. When boiled with very conc. solution of alkali, it is converted into a stannate & spongy tin.

STANNIC OXIDE (Cassiterite) Tin stone PREPERATION:-

:-

It is also formed by treating Sn with conc. the produced metastannic acid.

of specific gravity 1.25 and then igniting

PROPERTIES:
It is white powder insoluble in water in all acid. Ignited It dissolves in hot & conc. is insoluble in aqua regia. with the formation of unstable

Being amphoteric but more of acid characteristic (higher oxidation number), it reacts with fused NaOH or KOH to form soluble stanntes. In quantitative inorganic analysis, the insoluble with S powder & fusion mixture. USES: As putty powder for polishing purpose. Opaque white enables & titles (white Glazes) is brought into solution. by fusion

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 32

STANNOUS CHLORIDE: PREPERATION:

Sn foil or granulated Sn dissolves readily in conc. HCl to liberate of stannous chloride. On evaporation, the salt crystallizes out and forms hydrated stannous chloride . This is known as tin salt. Since the hydrogen stannous chloride on heating gives off HCl, steam and SnO, anhydrous cannot be obtained by heating the salt directly. with the formation

Anhydrous

is obtained by heating Sn or hydrated

in a current of dry HCl.

PROPERTIES:
is a colorless, crystalline solid soluble in water, ether 7 alcohol. It absorbed from air. With access water, it undergoes hydrolysis giving a white ppt. of stannous oxychloride. When a clear aqueous solution of to oxidation. This explains the way why a piece of metallic tin is always added to preserve a solution of . is exposed to air the same turbidity appears due

In strong HCl medium it forms chloro stannous acids

is a powerful reducing agent.

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 33

It readily combines with

to form

- odometric estimation of Sn.

[Angular covalent molecule,

STANNIC CHLORIDE, PREPERATION:

When dry

:-

gas is passed over matter Sn in a distilling flask, Sn reacts with

to form

a colorless, strongly fuming liquid

which distils over and collects in the receiver. is distilled.

is formed when a mixture of powdered Sn and excess 2HgCl_2 +Sn=SnCl_4 +2Hg(gray ppt) is also formed by dissolving Sn in aqua regia.

PROPERTIES:
is a heavy colorless liquid of specific gravity 2.28 which boils at 114 . It dissolves both in water and in organic solvents. It has zero dipole moment, electrical conductivity is negligible. Typical covalent molecule. It fumes in air due to hydrolysis fumes of HCl It produces hissing sound when it is dropped into water to form hydrated saltsA dil. solution of in water undergoes hydrolysis giving first white ppt. of basic

stannic chloride & finally hydrated stannic hydroxide in the colloidal form.

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 34

With HCl it forme chloro stannic acid which on crystallization form m.p = 19.2 With it forms ammonium chloro stannate is known as pink salt and used in calico printing. is known as butter of tin or oxymuriate of Sn and is used as a mordant.

- a colorless octahedral

crystalline compound.

is used in preparation of cassius (colloidal particles of Au absorbed by colloidal ppt. of stannic acid)

:Chocolate brown solid.

It dissolves in yellow ammonium sulphide to form ammonium thio stannate which dil HCl pptes yellow

-stannic acid is more basic than -stannic acid is insoluble in all acid even in aqua regia, but soluble in caustic alkali to form thio stannate & stannate.

Soluble in yellow ammonium sulphide solution to form ammonium thiostannate. On adding dil. HCl, is ppted.

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 35

MOSAIC GOLD: Pure crystalline, golden yellow shining colored stannic sulphide is known as mosaic gold.

DETECTION OF Sn:
Dry test: A mixture of a Sn compound, reaction with hot & conc. are heated to yield white beads which on produce a white mas of

Borax Bead Test: A pale blue colored bead obtained by a trace of Cu salts turns ruby red in the reducing flame when the colored bead is touched with Sn salt. Wet Test: Fluorescent test: Sn salt +1 ml of conc. HCl + Zn +water test tube non. luminous zone of the bb .Beautiful blue fluorescence confirms the presence of Sn salt. Stannous salt gives anythyst(violet) coloration with cacotheline(nitro derivatives of brucine(7X3=21)

DISTINCTION BETWEEN
Reagent solution

salt.
Solution ppt of is

Chocolate brown ppt. of Yellow soluble Solution White ppt. in of yellow

SuS in obtained which is obtained , soluble in yellow solution

, No ppt. is obtained

becomes grey on excess stannous salt solution. Freshly Solution of prep. Blue ppt. of turn bulls blue No reaction. is obtained.

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 36

Lead
At No: 82, Wt -207.1, Oxidation no: +2, +4 OCUURANCE: Galena: PbS AnglesiteCasseterite Crocoisite-

EXTRACTION:
SELF REDUCTION: Galena rich in Pb content is extracted by self reduction processes: ROASTING: At moderate temp. and in a controlled supply of air, finely divided conc. ore is roasted when PbS is oxidized partially to PbO & partially to unchanged. SELF-REDUCTION: When the oxidation of PbS has proceeded to half the air supply into the furnace is cut off and the temperature is raised to bright red heat. The unchanged PbS now reduces the produced PbO & to metallic Pb. . Some PbS remains

PURIFICATION: Lead thus obtained contains Cu, Sb, Sn, As, Bi, Ag, Au. The presence of these impurities renders impure lead hard. To soften lead all impurities except Ag & Au to be removed . In a reverberatory furnace, in presence of air, impurities are oxidized and form scum which is skimmed off. Ag & Au are removed by Parkes or Pattinsons process: Lead freed from Ag & Au further purified by Betts electrolytic process. Discoverised Pb is used as anode & thin sheet of Pb are used as cathode. Electrolyte some hydrofluosilicic acid in eposinting a smooth layer of Pb. lead silicoflouride, & gelatin. Pure lead is deposited at the cathode.

& HCl cant be used as electrolyte , so they form insoluble salts of Pb. Geletin helps

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 37

PROPERTIES OF Pb:
PHYSICAL PROPERTIES: Lead is a bluish gray soft meatl s.g=11.34. M.P= 327 , B.P= 1200 . Marks paper black and can be scratehed easily. Malleable and can be rolled into sheet. Poor conductor of electricity. CHEMICAL PROPERTIES: Action On Air: Perfectly dry coated with action on Pb but in moist air it is rapidly coated with white film of basic carbonate, causing Pb to cause to loose its bright metallic lusture in moist air. When Pb is strongly heated in air on oxygen it is oxidized first into litharge(yellow) & finally to red lead ( or minimum).

Finely divided Pb is pyrophoric. Pyrophoric lead is obtained by thermally decomposing lead tartarate. It catches fire spontaneously. PLUMBOSOLVENCY (Action on water): Lead is not attached by air free water but water containing dissolved hydroxide, rapidly attracts Pb with the formation of a loose deposit of lead , which is highly soluble in water & poisonous. (The dissolution of

Pb by water is known as plumbosolvancy). Lead Poisoning: Soluble salts of Pb are highly poisonous & act as cumulative poison, drinking water which is often conveyed through Pb pipes, must be hard water containing carbonates & insoluble do not corrode lead pipes. They form a coating of on the inner surface of the Pb pipes which protects the metal

from further action. Soft water containing nitrates, ammonium salts, organic acids should not be conveyed through Pb pipes as pb readily forms soluble Pb compounds. Lead poisoning is a slow but dangerous process. In Pb poisoning a b lue produced on the edge of gum. Action on Acid: Pb is insoluble in dil. HCl or . The hot conc. HCl & attack Pb but the action is or on the slowed down due to the formation of a coating of insoluble chloroplumbous acid, it goes into conc. HCl solution.

surface of the metal. (Pb is ppted. by cold dil HCl, but due to the formation of

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon At above 200 . Pb is attacked by Cold and dilute Cold and 1:1 Hot and conc.:[Below 200 in all concentrations. (imp) conc. is slowly reduced to

Page 38 by Pb, with the formation of

is inert towards Pb, it is largely used for making Pb pans for the .

concentration of sulphuric acid] Pb is also attacked by organic acids like acetic acid in presence on

Action on alkalies: Caustic alkalies have feeble action on Pb. On being heated with NaOH or KOH, Pb forms plumbite salts slowly. . In Pb II state is more stable. Action on & S : When dry gas or S vapours is passed over hot metal,

USES: Making shots, bullets, plates for storage cells, lead pipes chrome yellow, read, white lead, litharge, for protection against -radiation. Alloy Pewter Solder Type Metal ULCO Frary Metal Linotype Metal Compound Pb(20), Sn(80) Pb(50), Sn(50) Pb(60), Sb(30), Sn(10) Pb, Ca Pb, Ba(2), Ca(1) Pb(83), Sn(3), Sb(19).

COMPUNDS OF LEAD: Plumbous(2), plumbic(4). Plumbous compounds are more stable than plumbic compounds (Inert pair effect). Plumbic compounds are strong oxidants. . OXIDES: 5 oxides formed when any of the 4 oxides is heated. . PbO is the most stable, PbO is

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 39

Lead Suboxide: PREPERATION:

It is obtained by heating PbO in Co at 300 .

PROPERTIES:
Black powder, insoluble in water & on heating gives PbO.

Lead Monooxide: (PbO):

It exists in the two forms (i) yellow powder massicot, (ii) reddish yellow colored crystalline variety called litharge.

PREPERATION:
When Pb is heated slowly in air PbO is formed as a yellow powder, known as massicot. When massicot is heated it melts at 170 . The molten mass on cooling solidifies to give the crystalline variety called litharge (reddish yellow).

Also formed during cupellation process of Ag refining.

PROPERTIES:
Massicot & Litharge differ in crystalline form with a transition temp. of 585 . PbO is either yellow powder or reddish yellow coloured crystalline solid insoluble in water but dissolves in acids and alkalies. . It is readily reduced to metallic state by C, CO, in hot condition.

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 40

Lead sesquioxide:PREPERATION:
Phembous meta phumbite or PbO, . obtained as a reddish yellow powder when, sodium hypochlorite solution or any oxidizing agent like is added to a cold solution of PbO in NaOh solution.

PROPERTIES:
Reddish yellow solid, decomposed by dil. into .

gives back the +4 & +2

Red Lead
Minium

:-

PREPERATION:
By heating litharge in a current of air in a reverberatory furnace for 48 hrs, around 360 . Higher temperature should be avoided as above 470 it decomposes into .

PROPERTIES:
reddish yellow crystalline powder. Insoluble in water.

Dil. acids decompose behind Conc. HCl & conc.

into dissolve both PbO &

. PbO being soluble in dil. acid leaves .

With conc.

it gives brown ppt of PbO_2

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 41

Chemical behavior of red lead suggest that it is a mixed oxide, ortho plumbate of lattice type, each layer of

or plumbous

. X-ray crystallography study shows that the solid has a layer been sandwiched between 2 layers of PbO.

Lead Dioxide PREPERATION:

Lead dioxide sometimes erroneously called lead peroxide is obtained as a chocolate residue when conc. reacts with red lead. (Choco. brown ppt.) is obtained by the action of strong oxidizing agents on alkaline lead salt solution lead acetate solution. Na hypochlorite or bleaching powder is used as oxidizing agent.

The ppt. of

is digested with hot. dil.

to remove bleaching powder.

PROPERTIES:
It is a chocolate brown amorphous powder. Mixture of S and spontaneously and when a mixture of red P and explodes violently. It is decomposed into PbO, and when strongly heated. but when warned with conc. HCl and conc. inflames is a morter with a pestle, it

It does not react with cold dil. HCl or , it liberates .

It dissolves in conc. alkali to form plumbates.

is a strong oxidizing agent.

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon When is warmed with and

Page 42 , a purple color is formed due to the

oxidation of Mn(II) salt into HMnO_4 (VII)- a test for the conformation of the presence on Mn(II) salt. (Purple) It oxidizes oxalic acid to In alkali medium (+3) in presence of is oxidized to yellow chromate solution. (+4) (+6) (+2)

is an amphoteric oxide as it have as an acidic oxide towards strong base giving rise to plumbates & formation of plumbic salts. Lead acetate sugar of lead.(sweet but poisonous)

LEAD CHLORIDE:( PREPERATION:

When a soluble chloride KCl, NaCl or dil. HCl is added to an aq. solution of Pb salt, a white ppt. of of . is obtained. The resulting ppt. is dissolved on cooling yields crystals

PROPERTIES:A colorless crystalline salt, insoluble in cold water but soluble in boiling water. It dissolves in conc. HCl to form complex used in dyeing industries. LEAD STORAGE BATTERY: Cathode Anode Electrolyte

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon Reaction: Anode:

Page 43

is consumed during the discharge of lead storage battery. A fully charged cell has of = 1.25-1.3 g/c.c. When it falls below 1.20 g/c.c charged. POISONING ACTION OF LEAD COMPOUNDS: All compounds of Pb are highly poisonous and the action is cumulative. Workers Lead poisoning A blue line at the edge of the gum symptoms of chronic . poisoning. L.P damages cells in the spinal cord. Paralysis, Anaemia, head attacks bone marrow & destroy the manufacturing centers of rbc which carry

DETECTION OF LEAD: DRY TEST:

Pb compounds are mixed with finely powdered and the mixture is melted on a charcoal groove by reducing blow pipe flame. A lemon yellow colored incrusation along with malleable metallic bead is produced that makes paer. All Pb compounds when subjected to flame test, impalambent blue color to the non luminous flame.

WET TEST:
When dil. HCl is added to any soluble pb salt, a white ppt. of soluble in boiling water but reappears on cooling. When formed. On adding KI solution to an aq. solution of Pb salt a yellow ppt. of is formed which solution is added to a soluble Pb salt, a deep yellow ppt. of is is formed which is

dissolves in boiling water but reappears as golden yellow spangles on cooling To an acidified solution of Pb salt when which is soluble in hot dil . gas is passed, a black ppt. or pbS is formed

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 44

Basic lead carbonate Lithopone

Prep by Carter process

LEAD TETRACHLORIDE, PLUMBIC CHLORIDE, PREPERATION:

By dissolving in well cooled HCl (conc.) at 273 k

:(0

PROPERTIES:
It is only slightly stable . It is decomposed by access of water. It forms a double chloride with ammonium chloroplumbate when treated with is a covalent liquid. it decomposes to known as animonium plumbichloride or . Although the latter compound is fairly stable, .

GENERAL PROPERTIES OF GROUP-14 - (C, Si, Ge, Sn, Pb)

Ge is a rare element. Others are well known. C, Si non-metal, Ge configuration semi-metal (metalloid), Sn, Pb metals. All have 4 electrons is their valance shells. Electronic shows that they whould show similar properties. On the other C has hand, the penultimate (last but one) shell of these element have different config Electro ve C Si Ge Tin Pb 6 14 32 50 82 2.5 1.74 2.01 1.72 1.55 3.51 2.34 5.32 7.26 11.34

2 electrons , Si has 8, Ge has 18 electrons, Sn and Pb have 18 electrons(unsaturated). M.P(K) 4373 1693 1218 505 600

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 45

PHYSICAL PROPERTIES:
Density:- The density of the members belonging to this group is found to increase down the group. Increase in mass per unit volume. Melting & B.P: The M.P & B.P decrease from carbon to Lead. The melting point and B.P of carbon & Si are very high. This is due to the tendency of these elements to form giant molecules. The M.P and B.P are much higher as compared to those of group-13 atoms of Gr-14 can form cov. bonds with each other, so strong binding force exist both in solid and liquid states. Atomic Radii: Smaller than of group 13 elements, electrons are added in the same shell so size decreases. (Atomic radii increases down the group due to increase in the no. of shells) C 0.77 Si 1.18 Ge 1.22 Sn 1.4 Pb 1.46 the nuclear charge increases but

Ionisation Energy: The values of I.E decreases on moving down the group, through not in a regular order. The irregularity is due to filling of intervening d and f orbitals in Ge, Sn & Pb which does not screen the valance electrons effectively. As the sizes of elements belonging to group-14 are smaller than the corresponding elements of group 13, the first I.E are higher than gr-13 elements. C>Si>ge>Sn<Pb [I.E of Pb is higher because of extremely poor shielding of inner f orbitals as a result of which effective charge exp. by the outermost electrons increases. Metallic Character : The element of gr-14 are less metallic due to large values of I.E as compared to gr-13. The metallic character increases down the group. Electronegativity: The elements belonging to this group are more electronegative than elements of gr-13, because they have a small size. Electronegativeity value decreases from top to bottom in the group but not in a regular manner. Oxidation State: tendency to form config. indicates formation of both ions by gaining 4 electrons, although ions to attain ion is present in & inert gas configuration. But, due to high I.E, these elements do not exihibit much . These elements, particularly C & Si, from mainly covalent bonds in which these elements exihibt oxidation state +4. Tetravalancy of C & Si can explained by promotion of an electron from ns to vacant np orbital four hybrid degenerate orbitals regular tetrahedron.

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon The last 3 elements (Ge, Sn & Pb) have a tendency to form in the heavier elements. Elements of gr-14 exhibits both +2 & +4 oxidation states, +4 covalent, +2 as well as

Page 46 ions, the

+2 oxidation state arises due to the inert pair effect which becomes more pronounced ionic. +4

shown by all, predominant in C & Si in which +2 Oxidation state (or ionic compound formation) becomes increasingly important. This is alos in accordance with Fajans Rule which state that smaller the cation, greater is the % of covalent character. in its compounds. Thus nature while down the group. Tendency to form chains(Catenation): Carbon exhibits remarkable property of catenation, tendency of an element to form long chains of identical atoms. The property of catenation in carbon is due to the fact that in C atom, the number of valance orbitals (1s +3p). Hence, C in tetravalent state is fully saturated Bond C-C Si-Si Ge-Ge Sn-Sn Pb-Pb C>>>Si>Ge = Sn>>Pb The reason for greater tendency of C for catenation than other elements may be because the C-C bond energy is approximately of the same magnitude as energies of bond between c & other elements. But Si-Si bond weaker than with other elements. Allotropy: All elements, except lead, show allotropy & exist in various allotropic forms. Acids: All elements give acid of the type (metastaninc acid) & metaplumbic acid. (Sillicic acid), B.E (kj/mol) 348 180 167 155 it has neither any vacant Catenation Tendency Very Strong Little Very little Very Little Nil orbital nor any lone pair due to which the C-C bond is extremely stable. ion is smaller than ion, compounds are covalent in are ionic. Thus , the tendency to form ionic compounds increases

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 47

CHEMICAL PROPERTIES: Reactivity:Diamond is inert to all reagents at ordinary conditions. It burns at about 700 forming or air. However Pb forms a monoxide.(Inert Pair Effect) in . Si, Ge & Sn form the corresponding dioxide when heated in

Si, Ge, Sn react with halogens to form corresponding tetra halides. Pb only forms a dichloride Cols aq. HCl does not react with Si & Ge to form chlorohydrides, solution of & dissolve Ge, Sn, Pb. gas. Other Aq. NaOH dissolves only Si forming sodium silicate with the liberation of elements do not react with aq. base. Hydrides: Elements of this group form covalent hydrides, formation decreases on moving down the group as well as number. C Silicon Ge Sn Pb Thermal Stability: Decreases from C to Pb. Decmp. Temp because of different in electronegativity(C=2.5, Si=1.8, H=2.1). Since C(2.5) & H(2.1) are nearly similar, the electrons are very nearly equally shared in C-H bond & so the C-C bond is not weakened. But in silanes H withdraws the electrons towards itself and so weakens the S-S bonds. But the decreasing stability of germanes, stannanes & plumbanes is not due to weakening of M-M bond but due to th eweakening of H-H bond due to the poor overlapping. 800 480 285 150 0 The ease of hydride Conc. aq.

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 48

So the thermal stabilities of the hydrides decreases down the group, the ability to act as reducing agent increases. Thus, unlike alkanes, Silanes are strong reducing agents and readily hydrolysed by alkaline solution to liberate .

Silanes are the least stable to hydrolysis, they are hydrolysed even by neutral water.

Stability of the hydrides towards water: Unattached by alkali by 33% by 15%.

Eeasily attacked even by water . More reactivity of silane than alkanes can be explained on the basis of polarity of the Si-H bond & availability of d-orbitals with Si atom. OXIDES: All form two types Monoxide & dioxide. The tendency from monoxide

increases on moving down the group.

co is neutral, GeO is basic, SnO & PbO are amphoteric. is a gas at ordinary temp. while all other dioxide are crystalline solids of high m.p. weak acid v.w acid amphoteric amphoteric basic.

Basic character increases.

In

easy overlap of p-orbitals takes place. The C-O bond length is 1.16 indicating

triple bond character. EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in 40034819

Carbon

Page 49

Net dipole moment is zero. So, ordinary temp.

are held only by weak vanderwals forces, gas at why Hf should not be kept in glass bottles.

HAILIDES:
Gr-14 form fact that agents. The Non existence of ion to The except . The non existence of is due to the ions are highly reducing ion & is reduced to to oxidize ion. ion is a strong oxidizing agent while cannot survive in presence of

can be explained by inability of

. Also size wala concept. For big ions cannot occupy proper space & tetrahalides are covalent, except which is ionic,

effective overlap of p orbitals is not possible. hybridisation(tetrahedral). Thermal stability with a common halogen: with a common atom fluorocarbons are most stable and inert. The tetrahalides, except C halides are readlily hydrolised by water. The trend towards hydrolysis decreases down the group. [ fumes in moist air liberating HCl. (Reason Yourself)

mech. comes(d-orbitla) comes in Intermediate co-ordination no cannot be extended beyond 4. Si & other elements

C has no d-orbital

have vacant d-orbitals to which water molecules can co-ordinate & hence their halides are hydrolyzed by water. NOTE: Empty orbitals with higher energy are always available with any atom and they can be utilized if sufficient energy is provided for the reaction to occur. This explains the hydrolysis of with super heated steam especially in presence of Fe or Cu.

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819

Carbon

Page 50

The tetrahalides of Si, Ge, Sn & Pb from hexahalo compound(complex) like with the halide ions by increasing their co-ordination number of accepting electron pair from donor th etetrahalides (except carbon halides) act as strong Lewis acids. Hydrolysis of ordinate bond. In the 1st step, molecule attacks the central atom & forms a co-

In the 2nd step, a molecule of HCl is eliminated resulting in the replacement of 1 atom with OH group. This process continues till all the atoms are replaced by Oh groups to form (Hydrated Silicic Acid). Si co-ordination 6 Dihalides have greater ionic character & hence higher M.p and B.p. whereas is a liquid at room temp. is a solid

EDUDIGM 1B Panditya Road, Kolkata 29

www.edudigm.in

40034819