Oxygen

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Group 16
Oxygen
Atomic Number=8 Atomic Weight=16 Configuration=1s2 2s2 2p4 Electronegativity=3.5 Oxygen Lavoisier. Oxygen means an acid producer. The products obtained by the chemical combinations of O2 with non-metals like S, P, C etc on being treated with water produces acid. It exists to about 21% by volume, 23% by wt and 46.5% of earths crust.

Difference between O2 and other members of group 16:Oxygen is the first member of Group VIB in the periodic table. The properties of oxygen differ with the other members because of the following:(i) (ii) (iii) Small size of O atom. Higher electro negativity of oxygen Absence of d orbital in the electronic configuration of O atom. Members Oxygen Sulphur 2 3 Periods At-no 8 16 34 52 Config of valence shell 2s22p4 3s23p4 4s24p4 5s25p4

Selenium 4 Tellurium 5 The main differences are:(i) (ii) (iii)

Physical state:- O2 is a gas while all others are solids Abundance in nature:- Max for oxygen. Abt-46.6% of earth. Atomicity:- O2 is diatomic. Other elements have a somewhat complex molecular structure. S and Se occur as Se8 and S8 at room temperature.

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Oxygen (iv)

Page 2 Oxidation state:- The various oxygen states of O2 are: (a) +2 in OF2, (b) -2 in general, (c) -1 in peroxides. The oxidation no of all other members is both +ve and ve, but majority of them in +ve state.

(v)

Maximum covalency:- As d orbital is not available in oxygen atom the max covalency exhibited by it is 2. But due to the presence of d orbital the other members of the group exhibit a max. covalency of 6 upto Se and 8 upto rest. This explains why SF6 is formed but O cannot.

(vi)

Existence of H-bond:- Due to high electronegativity and structure size of its atom, H-bond plays an important role in the properties of the compounds of O. Due to H-bonding, the b.p and m.p of H2O are much higher than other members whereas instead of H-bonding vanderwalls forces are present which increases down the group with increase in molecular weight.

(vii)

Nature of hydrides:- The hydride of O2i.e water is a colorless, odorless, neutral liquid but other hydrides are gases, combustible, poisonous, having bad odor and acidic nature.

(viii) O2 is more electronegative and hence more ionic in its compounds. (ix) O2 can use p orbitals to form strong double bonds. This tendency weakens as atomic no increases. Preparation:- O2 is prepared by heating a mixture of potassium chlorate and manganese dioxide, when KClO3 is decomposed to give KCl and O2. MnO2 acts as a positive catalyst in this decomposition and remains unchanged after the completion of the reaction.

Precautions:(i) Pure MnO2 free from C and Sb2S3 must be used, otherwise there may be explosion. (ii) (iii) (iv) (v) Half of the test tube should be filled for easy escape of O2. Slow and uniform heat should be supplied. The test tube must be kept with a slightly downward incline. The end of the delivery tube should be kept above water to prevent entry of water in the hot test tube.

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Oxygen

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Function of MnO2:- MnO2 acts as a +ve catalyst in this reaction. It brings down the decomposition temperature from 630 C to about 200-250 C and O2 evolfves more rapidly without the formation of KClO4. Properties:[A] PHYSICAL PROPERTIES:(i) Colourless, odourless, tasteless neutral gas. (ii) Little heavier than air. (iii) Slightly soluble in water (4%) (iv) (v) (vi) (vii) MP=-218 C, BP = -183C Supporter of respiration Paramagnetic It can be liquidified by cooling under pressure to a pale blue liquid.

[B] CHEMICAL PROPERTIES:(1) Allotropy:- O2 exhibits allotropy O3. Gaseous O2 is diatomic but ozone is triatomic. They are 2 different forms of the same element. (2) Chemical activity:- Very active element combines directly with most of the elements except the halogens and the inert gases. Its chemical activity is enhanced at high temperature and in presence of a catalyst. (3)Combustion: Oxygen is not combustible but a supporter of combustion. The combustible substance is oxidized by oxygen producing heat and light during combustion. (4) Formation of Oxides: a. Reaction with non-metals in formation of acidic oxides:-Non metals like, C, S, P on being ignited in oxygen burn with bright flames and combine with O2 producing acidic oxides. This class of oxides react with bases to form salts and water and produce acids when dissolved in H20. b.Formation of neutral oxides:- H2 burns in O2 with a blue-flame to form water which is a neutral oxide. 2H2 + O2 = 2H2O N2 combines with O2 at 3000C in presence of electric spark to form nitric oxide which is also a neutral oxide. 2N2 + O2 2NO.

Oxygen does not combine directly with Cl2, Br2 or I2. EDUDIGM 1B Panditya Road, Kolkata 29
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Oxygen (a) Reaction with metals :- (i) Formation of basic oxide :-

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The alkali metals like No, k etc. and the alkaline earth metals such as Ca, Sr etc. combine with O2 directly producing basic oxides [These oxide are generally ionic compounds with high m.p & b.p] Heated Na burns in O2 with golden yellow flame of form Na2O, with excess of O2 Na2O2 is formed Na2O dissolves in water to produce NaOH. 4Na + O2 = 2Na2O, 2Na2O + H2O = 4NOOH. 2Na + O2 = Na2 O2. BaO. BAO + H2O = Ba(OH)2 K burns with a violet (lilac) flame to produce K2O, with excess of O2, K2O2 is formed 4K + O2= 2K2O, 2K + O2 = K2O2 2Ca + O2 2Mg + O2

K2O + H2O = 2KOH

2CaO,

CaO + H2O = Ca(OH)2

2MgO (feebly basic)

Red hot fe on being introduced into a jar of O2 turns bright and combines with O2 to form ferrosoferric oxides 3Fe + 2O2 = Fe3O4 Wake electro positive metals like Cu, Ag etc on being heated are gradually converted to their oxides 2Cu + O2 = 2CuO, 4Ag + O2 = 2Ag2O (4) Formation of amphotoric oxide :- Metals like Al, Zn, Sn, Pb produce. Ampuoteric oxide. These oxide react both with the acids as well as with the alkalis to form salts d water 4AL + 3O2 = 2Al2O3 2Zn + O2 = 2ZnO 2 6 2 2 2 3

. (i) S, C, P neutral

O2 cannot combine directly with pt, Au to form their oxides. acidic oxide produces acid but with Na, Ca, K

(*) O2 means an acid producer, but sometimes the name is misnomer basic oxide of H2O, NO

(5) Oxidising Property:- O2 is a strong oxidizing agent it oxidises a substance by combining directly with it or by increasing the proportion of electronegative element in the substance

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Oxygen (i) (ii) 2NO + O2 = 2NO (broun fumes) 2H2SO3 + O3 = 2H2SO4 (Colourless) (Yellow)

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(iii)4FeSO4 + 2H2SO4 + O2 = 2Fe2 (SO4)3 + 2H2O (iv) 4FeCl2 + 4HCl + O2 = 4FeCl3 + 2H2O (v) 2SnCl2 + 4HCl + O2 = 2SnCl4 + 2H2O. (vi) 2Cu2Cl2 + 4HCl + O2 = 4CuCl2 + 2H2O (vii) 2SO2 + O2 450 C, Pt Cat
0

2SO3 (contact process) 4NO + 6H2O 2H2O

(viii) 4NH3 + 5O2 4HCl + O2

V2O5
Pt Cat

(ix) Deacons process:-

7500C

Cu2Cl2

400 5000 0C

(6) Reducing action: - 2F2O2 = 2OF2 (oxygen di flouride) F2 <e.n> O2. So. Oxygen looses electrons to F. Thus Oxygen is oxidized by fluorine 2F + 2e O+2 + 2FD2F- (reduction) , O 2e OF2 O+2 (Oxidation)

(7) ABSORBANTS OF O2 : - (i) AlK. SOLn of potassium pyrogalla absorbs oxygen and the colour of the solution turns broom. (ii) Ammoniacal Cu2Cl2 soln. Absorbs O2& the colour of the sloln. turns blue

* TESTS FOR OXYGEN

(i) A glowing piece of wood bursts into test when it is introduced into a jar of O2. By this test O2 may be identified from all other gases other than N2O. (ii) Colourless NO when comes in contact with O2 brown fumes of NO2 are produced. 2NO + O2 = 2NO2 (brown fumes). (iii) Alkaline. Pot. Pyrogallate brown * USES: - (i) Welding cutting

Only hydrogen & only acetylene flames

(ii) Artificial respiration (iii) Rocket jet fuel (iv)Uses in the L.D process for the manufacture of steed O2 oxidises the impurities of cast iron * Oxygen has 3 naturally occurring isotopes:-

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Oxygen Isotopes Abundance

. % . % . %

Page 6 is radioactive in nature

* Reaction of oxygen with hydrocarbons & CS2 :CH4 + 2O2 2C2H2 + 5O2 CS2 + 3O2 C6H12 + 6O2 CO2 + 2H2O 4CO2 + 2H2O CO2 + 2SO2 6CO2 + 6H2O + energy

Periodic Trend:- From left to right on moving in a period the nature of the oxide changes from very strongly basic to amphoteric to very strongly acidic . Na2O Strongly basic B2O3 Acidic N2O Neutral NaO Al2O3 eric Al2O3 Amphoteric NO N2O3 Weakly acidic SiO2 weakly acidic Ca2O3 In2O3 Tl2O3 Basic N2O4 Acidic N2O5 Strongly Acidic P4O10 acidic strongly acidic SO3 Cl2O7 Basic amphot

In contrast in moving down the group the basic character of oxides increases

Metallic oxides are generally basic while non- metal oxides are acidic.

Acidic character increases with increase of oxidation no

OXIDES
An oxide is defined as the binory compound formed by the union of O2an other element (except) (i) acids to produce salt water en Na2O, CaO, CuO, Fe2O3 CuO + 2HCl = CuCl2 + H2O NgO + H2SO4 = MgSO4 + H2O Basic oxides if solution in water, produces soluble base or alkali.This solm. Turns red litmus blue& gives OH- as anion 4Na + O2 = 2Na2O ; Na2O + H2O = 2NaOH NaOH Na+ + OHBasic oxides:- Basic oxides are generally the oxides of metals which react with

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Oxygen

Page 7 The basic oxide contains oxygen atoms with electron pairs avaitable for bonding. When the oxygen is linked to a strong electro + ve element, the bond beth.Them become, polar and O atom acquires O large negative charge. As the density of this ve charge inareases, the ability of oxygen for donating the lp of electrons also increase and thus the basic character of the oxides increases and thus the basic character of the oxides increases As cs is more electro + ve than Li CSO2 is more basic than LiO2. For the same reason Bi2O3 is more than P2O3. Soluble basic oxides give OH- ions in aq solm as O H bond is left polar than the bond betn oxygen and the metal in an oxide. The strong polar bond betn. The metal & oxygen becomes weaker in a polar solvent like water. This because the electron gativityidd. Betn the central element & oxygen is grater than betn (oxygen & H2) H O Mg O H + nH2O {Mg (H2O)x]+2 2OH-

(ii)

Acidic oxide:- The oxides of non metal which metal with bases to produce salt & water are known as acidic oxides. Such oxides if water to form acids e.g so2, co2, p2o5, SiO2, B2O3etc CO2 + 2NaOH = Na2CO3 + H2O. SO3 + Na2O = Na2SO4 CO2 + H2O = H2CO3 , SO2 + H2O = H2SO3, Cl2O + H2O = 2HOCl

The acidic oxide from which the acid is produced on treatment with water is called the anhydride of the acid. Metallic oxides containing larger amount of O2beha- ve like acidic oxide. In fact as the own no. of the metal increases, the acidic property of the metallic oxides also increases, I.e why MnO is basic Mn2O3 is amphoteric, Mn2O7 is strongly acidic

(Permanganic acid)

CrO3 + 2KOH = K2CrO4 + H2O Acidic oxides are acceptors of tone pair of electrons. The highly electromegative central atom bounded to O atom is acceptor. The acceptance ability of the central atom is further enhanced becor of the with drawl of electrons by the more electro-ve O atom.

Sometimes atom of low electronegativity such as Mn or Cr becomes highly electro-ve& thus O acquires the e acceptance ability when a no. of O atoms are attached to it. The

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Oxygen

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electron acceptance ability increases as O pulls the b-p more towards itself. Thus, SO3> acidic> SO2 is atoms in SO3 is a better acceptor of electrons) Acidic character increases with the increase of, the number of O atoms attached to the central atom. (iii) Amphoteric oxide:- The oxide which octs as both basic & acidic oxide. React with strong acids as well as strong alkalis to yield salt & water. e.g 2no.Smo, pbo, Al2O3 etc. 2nO + H2SO4 = 2nSO4 + H2O

2nO + 2NaOH = Na22nO2 + H2O. If the partial negative charge on the O atom of an oxide is in betn that of a typical acidic & basic oxide it will exhibit amphoteric behavior. acidic oxide which acts as acceptor. (1) Basic character when its bonded O atom acts as donor to the central atom of an 2n O: SO3 2nSO4

(2) Acidic behaviour when its central atom acts as acceptor when comes in contact with the bonded oxygen atom having high ve charge of a basic oxide In aq-med. Amphoteric oxide may give rise to both (H3O)+& OH- depending upon the nature of reactants if the diff. in electronegativity between O-H & M-O is comparable then there is equal chance of release of H3O+& OH(iv) Neutral oxide:- The oxide which reacts neither with the acid nor with the base to produce salt is called neutral oxide. The do not react with water to produce acidic or basic solution. E.g H2O, N2O, NO, CO. All neutral oxides are the oxides of non-metals. Although water is classified as neutral oxide it can act both as acid & base according to Bronsted Lowry idea of acids & bases. H2O Acid + H2O base2 H3O + OH base, Cao: 2no ca2no2.

acid2

(v) Peroxide:- An oxide which gives H2O2 on treatment with cold and dit mineral acids and which contains peroxo bond [- 0 0 -] is known as peroxide. The peroxide of an element contains more oxygen oxide. e-g Na2O2, BaO2. H2SO5 + H2O H2SO4 + H2O2 (caros acid)

BaO2 + H2SO4 = BaSO4 + H2O2

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Oxygen Na2O2 + 2HCl = 2NaCl + H2O2 O Ba , Na O Na [O O]2- ion

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O * Pbo2& Mno2 are known as dioxides & not peroxide because (i) they do not yield H2O2 on being treated with cold & dil mineral acids (ii) They do not contain any perow link (-O O-) in the molecule but the O atoms are attached to the metal covalent by = bonds.

O Mm , Pb

O they produce Cl2& O2 on being treated with cono& hot HCl &

O O H2SO4 Mno2 + 4HCl = MnCl2 + Cl2 + 2H2O 2Mno2 + 2H2SO4 = 2MnSO4 + O2 + 2H2O (vi) Mixed oxides:- The oxide which is formed by the union of 2 oxide of same metal in diff. valency state, is called a mined oxide. On being reacted with acids they yield minture of salts corresponding to metal in diff. valency state. e.g Fe3O4 (FeO. Fe2O3), pb3O4 (2pbo + pbo2) Mn3o4 (2Mno + Mno2) Fe3O4 + SHCl = 2FeCl3 + FeCl2 + 4H2O Pb3O4 + 4HNO3= pbo2 + 2pb(NO3)2 + 2H2O (vii) Poly oxide:- An oxide which contains more O2 than either the acidic or basic oxide but does not produce M2O2 on being treated with dil. Mineral acids is called poly oxide. (viii) Sub oxide:- There are some oxide in which the element combined with oxygen is in unusually low oxidation state. C3O2 (carbon suboride). O = C = C = C = O (ix) Super oxide:-Alkali metal like Na, K, Cs, Rb form a type of oxide which contains a lattice of CaC2 type in which the anionic species is [:O oxides are paramagnetic & coloured) [O2]-has 17 electrons:1

e.g Mn2O7, MnO2, Pbo2

ion. The anion has the structure

O] involving a single bond & a 3- electron bond betn 2 oxygen atoms. All super

1 2

, 2 ,

e.g lio2& NaO2 yellow, KO2arangered, RbO2 brown EDUDIGM 1B Panditya Road, Kolkata 29
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Increasing energy

2 2

Oxygen Cso2 arrange. Ca(o2)2

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Superoxides are even stranger oxide sing agents than perwxides. They differ from peroxides in stricture & reactivity. While peroxides liberate H2O2 with cold dil. Acids. Super oxide liberate O2, for which they are strong oxidizing agents 4KO2 + 2H2SO4 = 2x2SO4 + 2H2O + O2 With ice cold water they form O2 as well as breathing masks co2 it produces O2&romeves CO2. Both functions are imp. In life support systems 4KO2 + 2CO2 = 2K2CO3 + 3O2 *generally large atoms or ions form weaker bond than small ones. The peroxide & superoxide ions are large and it is noteworthy that the stability of the perosides&superxides increases as the metal ions becomes larger. This shows that large cations can be stabilized by large anions, since if both ions are similar in size the C.N will be high, and this gives a high lattice energy * There are 3 adv. Of using O2 in the kaldo d l.D process of converting pig iron to steel than using air in the Bessemer process:(i) The conversion to steel is quicker (ii) Large ingots of pic iron can be used (iii) The metal does not form nitrides, which can ocour when air is used * Oxygen (O2) is paramagnetic & therefore contains unpaired electrons. The structure on the basis of MOT is 1

1 2

2 2

2 2

* Liquid O2 is pale blue in colour, the solid is also blue. The colour arises from electronic transitions which excity the ground state (a triplet state) to a singlet state. This transition is forbidden in gaseous oxygen. In liquid or solid O2 a single photon may collide with 2 molecules simullancously& promote both to excited states. Absorbing red lies in the arrangement of electrons in the antibonding 2 Molecular orbitals:Second excited state First ercited state singlet singlet
/

yellow- green light, so O2 appears blue. The origin of the encitedsirglent states in O2 and 2

(electrons have opp. Spins)

92 (electrons paired)

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Oxygen Ground state triplet O (electrons have spins)

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Singlet O2is ercited& is much more reactive than normal ground state triplet O2. Singlet O2 can be generated photo chemically by irradiating normal O2 in presence of a sensitizer ( flour escain, methylene blue or some polycliccompounds) charieally it can be made as:H2O2 + OClO2 (singlet) + H2O + Cl-

Singlet O2 can add to a diene in the 1,4 positions rather like a Diels Alder reaction. CH2 singlet O2 CH CH CH2 +

* Oxygen, being smaller in size, is capable of forming

multttiple bonds with its

elf f & other which lead to its following abnormal charocteristies:(i) Its diotamic d gaseous nature; other elements exist as 8 membered ring or zi zag chain structures & are solid in nature. (ii) Its low b.p, m.p & density. (iii) Multiple bonds are shorter, the o o bond dist in o2 is less (1, 21 )which leads to high b.E & hence more energy must be supplied to break the o o bond thus, O2 is inert although it is the second most electro-ve element (F F b. E is much less &hance every (iv) oxide ion is not easily polasised (small ion with high charge density) (fajansruls), so it called a lard ion while the remainder ions are called soft ions so must oxygen compounds are ionic * Prep of O2:2MnO2 + 2H2SO4 = 2MnSO4 + 2H2O + O2 4KMnO4 + 2H2SO4 = 4MnSO4 + 2K2SO4 + 6H2O + 5O2 2K2 Cr2O9 + 8H2SO4 = 2K2SO4 + 2(r2(SO4)3 + SH2 O 1 3O2 reactive lp.lp repulsion on the two fatonrs)

Ozone (O3)
(I smell) Schon bein. Ozone is an allotrope of oxygen with molecular formula O3.

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Oxygen Formula O3 Due to irradiation of O2 with u.v light. O 2 O2 O2 O3

2

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(a ctivated) ( = 220 290 nm) O

PREPARATION
(i) Silent electric discharge through O2, O3 is prep. by passing silent electric discharge through pure &driy O2. 3O2 2O3 241 Kcal. This conversion of O2 to O3 is a reversible reach and the forward reaction is endothermiaSo according to le chateliers principle, the increase of temperature should the forward reaction& thus the yeid of O3 should increase But as O3 is very unstable tends to decompose into O2 even at room temperatureThis decomposition is accelerated by the increase of temperature during ordinary electric discharge much heat is produced along with the electric spark. If O2 is subjected to this ordinary electic discharge, the produced ozone will decompose to give oxygen by the gen- of heat. If the two electron des are covered by an insulating material such as glass & connected to the terminals of an induction material such as glass & connected to the terminals of an induction coil, silent electric producing e-spark & heat. Thus the decomposition of the produced O3 is considerably retarded & hence O2 is subjected to silent electric discharge. (2) Ozoniser:-Ozoniser is the apparatus used for preparing ozone from O2 by passing silent electric discharge time it. (i) Siemens ozoniser 7-10% ozonc (tinfoil) (ii) Brodies ozoniser 20% ozone (pt wire & dil H2SO4) (iii) Siemen Halskeozoniser large scale production:* Preparation of pure ozone from ozonized oxygen:(i) The ozonized O2 is condensed to give a deep blue liquid which contains liquid O2& O3. (ii) The blue liquid is subjective to fractional distillation O2 is more volatile than O3. Evaporates first& liq. O3 is left behind.

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Oxygen

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(iii) This liquid O3 is then very carefully vaporized when pure O3 is obtained as a deep blue gas. This purification should be carried out with extreme care as liquid O3 is highly explosive (*) Conditions for better yield of O3:(a) Temperature should be low. Around 273 k is maintained (b) Sparkless discharge is passed (iii) O2 should be pure & dry (dark)

Properties
[A] Physical Properties:(i) O3 is a pole blue gas (diamagnetic) having a fishy smell. (ii)It turns to a dark blue liquid on condensation liq. O3 is highly explosive (iii) O3 is more soluble in water than O2. It is also soluble in CCl4, CS2, CH3COOH etc. Due to its high solubility in turpentine, turpentine is used as an absorber of O3. (iv)Condenses to violet black solid (m.p = 80.6 k) (v) Poisonous in nature produces headaches in small does. (exposure to 1ppm must be avoided) [B] CHEMICAL PROPERTIES:(i) Stability:- when O2 is converted to O3 energy is absorbed 3O2 2O3 241 Kcal O3 contains more energy than O2 A consequently it is less stable & much active. Even at ordinary temp O3 decomposes slowly. Its decomposition becomes repid at higher temp (2000C). The decomposition of O3 is accelerated by finely divided Pt, Ag2O, MnO2, dust particles etc. At 3000C O3 is comp. decomposed to give O2. 2O3
3000

3O2 + heat

(2) Oxidising property:- As O3 contains more energy than O2, it is more active & vigorous oxidizing agent than O2, it is because of the evolution of nascent oxygen by its spontaneous decomposition Even at ordinary temperature O3 = O2 10. This nascent O is responsible for the superior oxidising properties of O3. There are 2 classes of oxidationreaction by O3:- [A] In which one molecule of O2 is given off for every molecule of O3 used in the reaction:(i) One of metals:- most metal are oxidesed to their corresponding oxides by O3 (a) 2Hg + O3 = Hg2O + O2 (dissolution)

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Oxygen

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Due to formation of Hg2o, Hg loses its mobility &molalliccusture& sticks to the glass when comes in contact with O3. This is called bailing of Hg. The meniscus can be (b) 2Ag + O2warmed Ag2O + O2 regained by shaking (brown layer) it water which dissoues Hg2O Ag2O + O3 aAg + 2O2 (Reducing action). (iii) Oxidation of compoundsi:- (a) Black pbs white pbso4. Pbs + 4O3 = PBSO4 + 4O2 Similarly, cus&zns are converted to cuso4& znso4. (b) colourlesssolm. Of acidified Pe+2 salts are osidised by O3 to yellow Fe+3 salts. 2FeSO4 + H2SO4 + O3 = Fe2(SO4)3 + O2 + H2O 2FeCl2 + 2HCl + O3 = 2FeCl3 + H2O + O2 (C) Colourless meutral or acidified som of KI or NaI is oxidized to free I2& the solm turns broom. Necutral:- 2Ki + O3 + H2O = 2KoH + I2 + O2 Acidified:- 2KI + O3 + 2HCl = 2KCl + I2 + O2 + H2O * Ki is not oxidized to I2 by O3 in presence of FeSo4, while H2O2 can oxidize Ki even in presence of FeSO4 (d) Mi\oist S, P & I2 are oxidized to their corresponding higher axy acids I + 3O3 + H2O = H2SO4 + 3O2 2P + 503 + 3H2O = 2H3PO4 + 5O2 I2 + 5O3 + H2O = 2HIO3 + 5O2 (e) O3 oxidises NaNO2& NH4NO2 to the mitrates

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Oxygen NaNO2 + O3 = NaNO3 + O2 NH4NO2 + O3 = NH4NO3 + O2 * Oxidation of metalloids:(i) 2Sb + 5O3 + 3H2O = 2H3 SbO4 + 5O2 (ii) 2AS + 5O3 + 3H2O = 2H3SAO4 + 5O2 (f) Halogen acids Hologens:2HCl + O3 = Cl2 + O2 + H2O 2HBr + O3 = Br2 + O2 + H2O (g) (i) H2S + 4O3 = H2SO4 + 4O2 (ii) 2K4
2 6

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O3 + H2O = 2K3

+ O3

Pole ferocyanide

pot fericyanide

(iii) 2 K2MnO4 + O3 + H2O = 2KMnO4 + 2KOM + O2 (green) (pink)

(b) Ozone molecule as a whole is used up for oxidation. (i) 3SnCl2 + 6HCl + O3 = 3SnCL4 + 3H2O * O3 is netural towards litmes B.P of O3 = - 1120C Excepting few reactions O2 is evohed in all other oxidation reactions carried out by ozone. As the oxidation. No brought about in these reans but one oxygen atom of O3 is resuced by deoreasing its oxidation no form O to 2, while the other O2 atom suffers no change
2 2
4

3
2

4 3

2 2

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Oxygen

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(3) Reaction with peroxides:-Reaction of O3 with BaO2& H2O2 results in their mutual redn with the evolution of O2. BaO2 is reduced to BaO& H2O2 is reduced to H2O. BaO2 + O3 + BaO + 2O2 H2O2 + O3 = H2O + 2O2 The oxygen of the peroxo group is oxidized of free O2i.c form -1 to 0 & one atom of O3 is reduced to BaO from 0 to 2 while O2 fO3 remains unattered. Oxidation
1
2

2 2

Red This prove that O3 is a powerfull oxidizing agent than H2O2. n (4) Bleaching Property:- O3 liberates nascent O which a oxidizes indigo & other colouring matters into colourless compounds. Litmus paper becomes colourless when exposed to an atomosphere of O3 (5) Formation of addition compounds:- With unsaturated organic compounds consisting of = or = bonds O3 farms addition products called ozonides CH2 = CH2 + O3 H [inert solvent like CH2Cl2, CCl4 at low temp = 195 K] H C C H + O3 Rubber contains unsaturation & so it io readily attacked by O3& as a result elasticity of rubber is lost (*) O3 is used as a disinfectant & to purify drinking H2O. Its adv. Over Cl2 is that is avaids unpleasant smell & taste of Cl2 (*) TESTS FOR OZONE:- (i) O3 is identified by its strong fishy smell. (ii) A filter soaked in KI & starch som.Turns blue when brought in contact with O3. O3 first oxisises KI to give free I2 and this free I2 reacts with starch producing blue colour. 2KI + O3 + H2O = 2KOH + I2 +O2 Starch + I2 Blue colour EDUDIGM 1B Panditya Road, Kolkata 29
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Oxygen H2O2, Cl2, NO2etc also respond to this test (iii) O3 turns benzidine paper brown &trimethyl base paper violet.

Page 17

(iv) A drop of Hg when brought in contact with O3, its mobility & metallic lustue are lost & it sticks to the glass (v) It does not decolourise KMnO4 or K2Cr2O7 (*) Uses of O3:(i) As germicide & disinfectant in sterilising water (ii) For bleaching oils ivaryetc (iii) as an oxidation agent & In prep. of KMnO4 (iv) In destroying bad odours from cold storage, slaughter louses etc. (*) Structure:- O3 is angular & the angle beth the 3O atoms is 1160491 b.d in O3 is 1.278 301. The O O

O O bond is O3 must have considerable double bond character & it is a rhesonance hybrid of the following:-

OO3 . Single O O b.d is 1.49 & O = O is 1.21, it is apparent that

(*) COMPARISON BETWEEN OXYGEN AND OZONE:Oxygen 1. Colourless & odourless gas 2. Absorbed in alk pot pyro gallate sol brown. 3. Does not attack Hg. Ozone 1. Pale blue gas having fishy smell. 2. Abosonbed in terp entire 3. Hg in contact with O3 loses its mobicity&

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Oxygen
metallic custure Hg2O formation.

Page 18

4. Stable but at high temp decomposes to give 4. At 3000C, decomposes to give O3 = O2 + O. nascent O. 5. Does not effect rubber Decomp is accelerated by HnO2, Ag or pt 5. attack rubber at ord temp & as a result it loser its elasticity 6. Cannot oxidize pbs to PbSO4 or KI Solm 6. Can oxidize both PbS + 4O3 = PbSO4 + 4O2 2KI + H2O + O3 = 2KOH + I2 + O2 7. At 4500C in presence of pt cat. Oxidizes So2 to 7. At ord temp it oxidizes SO2 to SO3 SO3. 2SO2 + O2

3SO2 + O3 = 3SO3 2SO3

* Destruction of O3 layer in atmosphere:- CFC & NO From car exhausts CF2Cl2 + h CF2Cl + Cl

ClO + O3 Cl + 2O2 * STRUCTURE OF O3:- The central O atom uses sp2 hybrid orbitals to bond to the terminal O atoms. The central atom has one lp, and the terminal O atoms have 2 lps. This leaves 4 electrons for bonding. The P2 atomic orbitals from the 3 atoms form 3 bond to the molecule in addition to 2 delucalised m. os covering all 3 atoms. One MO is bonding one non-bonding & one antibonding. The 4 electrons one delocalized bonds. Thus the bond order is 1.5 & the bond. * The dark blue colour of O3 is due to intense absorbtion of red light ( 557 nm & 602 nm). It also absorbs strongly in the uv region ( 255nm). * 2KOH + 5O3 2KO3 + 5O2 + H2O Pot. Ozoxide KO3 is an orange red coloured solid contains the paramagnetic O3 ion system is decribed as a four-electron 3 centre

Cl + O3 ClO + O2

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Oxygen

Page 19

SULPHUR (S) Natural sources

Well distributed in nature both in the free state& well as in combination, such as sulphides & sulphates of many metals:(i) FeS2 (Iron pyrites or fools gold) (2) copper pyrites (cu2S, Fe2S3) (3) Galena (pbs) or lead glance (4) zinc blend (zns) (5) ciypsune (caSO4. 2H2O) (6) Barytes (BaSO4) (7) Kiesserite (MgSO4, H2O) (8) MoS2 (Molybdenite) (9) Cinnabar (gas)

EXTRACTION OF SULPHUR:Deposites of free S occur particularly in the volcanic regions Sicilian process:- Mainly used for working up the Italian deposits. Purification:- Impure S molten S S melts
120
0

Vapours generated

as yellow powder

pure S is molulded (flowers of sulphur)

(roll of sulphur) From the underground deposits (American process):- The underground deposits of s are melted by pumping superheated water (1700C) under a pressure of 8 10 atm & a balst of hot compressed air at pressure of abt. 35 atm through the s beds. The molten S is then bloom out through with the compressed air From natural gas:- Recovering of S from the natural gas includes separating-out H2S by absorption into mono ethanol annulene& then converting H2S into S by the following sequence of reactions:2 1 2

1 8 8

A certain amount of SO2 is formed which can be removed as:2H2S + 3O2 2SO2 + 2H2O

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Oxygen 2H2S + SO2

2 3

Page 20
3 8 8

303

From spent iron oxide:- Obtained as a by-product in the manufacture of coal gas. It consists of mainly Fe2S3. This spent iron oxide is left is exposed to sir when free S is sep from it with the formation of Fe(OH)3 2Fe2S3 + 3O2 + 6H2O = 6S + 4Fe(OH)3 From sulphide ores:- A large amount of SO2 is obtaind as a by. Product during the roasting of sulphide ores of metals like pb, Cu, znetc Na2SO3 + SO2 + H2O = 2NaHSO3 2NOHSO3 = Na2SO3 + SO3 + H2O SO2 + C = COS + S From alkali wastes:-Cas + H2O + CO2 = CaCO3 + H2S 2H2S + O2 (limited) = 2H2O + S * ALLOTROPIC FORNS OF SULPHUR:- Like many other non-metals, s also exlibts the phenomenon of allotropy. It exists in a number of allotropic forms which possess different physical characteristics:[A] CRYSTALLINE ALLOTROPES:- (i) Rhombic or Octahedral or & sulphur:- (i) When roll sulphur is dissolved in CS2 and the solm is slowly evaporated transparent yellow octahedral crystal of rhombic sulphur are abt. 2. At ordinary temp, this is the most stable & common form of S. All other allotropic forms of S are gradually converted to this form. 3. Rhombic S is lemon yellow crystalline & the crystal are octahedral 4. Its m.p is 1140- 50C & b.p = 4450C. its density is 2.07 gcc 5. It is readly soluble in CS2, hot chloroform & C6H6 6. Non-conductor of heat & electricity 7. It exists as SS molecule. The 8 S atom in S8 molecule form a puckered ring, connected to one another by single covalent bond. * Conversion of & - S into substantces] S:- [The two sulphurs are called enantiont ropic

95. 5 95. 5
(Transition temp) = 95.50C

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Oxygen [B] Amorphous sulphur:(i) plastic sulphur:1. It is also called - sulphur & does not have sharp melting point.

Page 21

2. Plastic sulphur is a brown coloured clastic solid & is regarded as a super cooled liquid. 3. Its density is 1-95 g/c.c 4. Plastic sulphur in insoluble in water as well as in CS2 5. It is anstable& at ordinary temp, or even standing it gets converted to rhombic sulphur 6. itunterains long intervened zig zag chains of S atoms. These chains are formed by opening SS chains [ Supercolled liquid:- A liquid which due to rapid colling below its m.p had no time to sette in orystallim form] ii. Mick of sulphur:- By boling flowers of S with water & milk of lime, when a red coloured som. Of CaS5 is obatainedvarityprecipitetes out which is called milk of sulphur Its density is 1.82 g/cc. Insoluble in H2O but soluble in CS2. This variety tends to revert to the rhombic variety if kept over a long period iii. Colloidal sulphur:- (a) obtained as a milky suspension by passing H2S through a saturated solm of SO2 (b) By adding conc. H2SO4 to a saturated solm of sodium thiosulphate. On long standing C.S changes soidiumthiosulphate. On long standing C.S changes to normal (b) Na2S2O3 + H2SO4 = Na2SO4 + SO2 + H2O + S Form * 3Ca(OH)2 + 128 2CaS5 + CaS2O3 + 3H2O (a) SO 2H S 2H O S * CaS5 + 2HCl = CaCl2 + H2S + S

2CaS5 + CaS2O3 + 6HCl 3CaCl2 + 3H2O + 125

Cal pentasulphide cal thiosulphate

(Mainly used in medicines)

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Oxygen

Page 22

PROPERITES OF SULPHUR:[A] PHYSICAL PROPERTIES:i. Pale yellow crystalline solid ii. Britlle& cannot conduct heat & electricity iii. Enhibits allotropy iv. Insoluble in H2O but soluble in CS2, C6H6etc plastic S in insoluble even in CS2 * Action of heat on sulphur:- S echibits remarkable changes when it is heated gradually 120 1600C Instead of becoming more mobial it becomes thicker & darker to a deep orange liquid 160 1800C Becomes almost immobile & ciscous 110 1190C S melts to a clear mobile yellow liquid

2300-C Colour becomes block & its viscosity increases 444-60C begins to bail giving off yellow vapours when boiling S is allowed to cool down slowly reverse change occurs Explanation: Molecules of S are composed of 8 atoms arranged in a closed puckered ring. Just above its m.p. such type of molecules can easily slip over the other and so the liquid possesses mobility. At above 1600C rapture of the ring structure begins and is completed at 2300C when the ring structures are converted to large chains of S-atoms. This change is exhibited in deepening of its color. On more chains being formed & getting tangled up, the viscosity of the liquid increases and it loses its mobility. When temperature is further increased, the larger chains break up into smaller fragments and as a result the mobility of the liquid increases again. The liquid becomes darker in color, till at 444.60C it takes the form of a black liquid & begins to boil giving off a yellow vapour. At still higher temperatures, the vapour of S8 molecules dissociate forming S6, S4& S2 molecules. At 10000C, the V.d of S correspond to S2& above 22000 monoatomic molecules of S are produced. S2 molecule is paramagnetic & blue coloured like O2& has similar bonding [B] CHEMICAL PROPERTIES:Sulphur is inert at ordinary temperature but when it is heated, it becomes very active & reacts with a large number of elements 230 onwards becomes mobile again

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Oxygen

Page 23

1. Action on Nonmetals:- When S is strongly heated in air or O2, it combines with O2 to form SO2, with a trace of SO3 S + O2 = SO2, 2S + 3O2 = 2SO3 (b) Action on hydrogen:- When mixture of H2& S is passed even red hot pumice stone or when H2 is passed through molten S, H2S is produced H2 + S = H2S (c) Action on Cl2:- When Cl2 bubbled through boiling S, Sulpharmonocholoride an orange liquid is produced sulphide P4 + 10S = 2P2S5 also P4S3 (tetraphosph 10000C onus trisulphide) (f) Action with steam:- 3S + 2H2O 2H2S + SO2 (reverse of reaction both H2S & SO2) (e) Action on carbon:- C + 2S(Vapour) = CS2 (red out) 2S + Cl2 = S2Cl (orange liquid) (d) Action on phosphorus:- S reacts with P at ordinary temp yeicding phosphorus penta

2. Action on metals:- Heated metals like Cu2Zn, Fe, Na etc react with S yielding the corresponding sulphides. CutS =CuS (black) FetS = Fes (black) Na or K catches fire as soon as it it comes in contact with sulphuric vapour 2Na + S = Na2S At ordinary temp, Hg combines when S is powdered & titrated with Hg yielding HgS (cinnabar) Hg + S = HgS 3. Action on mineral acids:- S does not react with dil. HNO3, dil- H2SO4 or cons HCl 6 2H2 SO4 Chat & 5 6 3 & O S 4 3SO4
2

H2 O [Comproprtionation]
4

4. Action on alkali:- Sulphur dissolves in hot & conc. solution of strong alkalis [NaOH, KOH, Ca(OH)2] with formation of metallic sulphides &thiosulphates. The further combine with excess of S yeilding poly sulphides. 4S + 6NaOH = 2Na2S + Na2S2O3 + 3H2O Na2S + 4S = Na2S5. EDUDIGM 1B Panditya Road, Kolkata 29
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Oxygen (2S + 3Ca(OH)2 = 2CaS5 + CaS2O3 + 3H2O

Page 24

5. Metallic sulphites:- When a solm of Na or K sulphite is boiled with pawdered S, thiosalpliate is produced Na2SO3 + S 1000C Na2S2O3 (sodiumthiosulaphate) 6. Action on oxidizing agent:- S ighites with emplosir when it is heated with oxidizing agent like KClO3, KNO3 2KNO3 = 2KNO2 + 2O S + 20 = SO2 7. With pol carbonate:- K2CO3 on being treated with excess of S, a mixture of polysulphide&thiosulphate is obetaned. This brown aoloured substance is aalled liver of sulphur. 6S + 2K2CO3 = 2K2S2 +K2S2O3 + 3CO3 Liver of sulphur * Tests:- (i) sulphur is insoluble in water but soluble inCS2 (ii) S burns with a blue plame in air producing SO2 which is colourless & a pungent smelling gas when this gas is passed through smelling gas. When this gas is passed through acidified K2Or2O7solm, it turns green K2Cr2O7 + 3SO2 + H2SO4 = K2SO4 + Cr2(SO4)3 + H2O (orange) (ii) fungicides& disinfectant (iv) Valcanisation of rubber * At ord temp O2 is a colourless gas white S ia a pale yellow solid- Why ? O2 can form multiple bonds & is diatomic, covalenty linked. The altractionbetnits individual molecules is very weak & that is O2 is a gas. At ord temp, S aholecule consists of S atoms which are cavalenty linked to form a puckered octahedral ring. As a result, its mol, wt increases of so does the vanderurcle force
Properties Similarities 1. Pos in the p.t Same group 16, Valence Group 16. Valence group electrons 2 2 electrons 3 3 O2 S8

(green) ultramarime

* Uses:- (i) Manufacture of SO2, H2SO4, CS2, S2Cl2, Na2S2O3 (iii) Colloidal sulphur & mil of S are used as medicines

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Oxygen
2. Occurrence Occurs in free state

Page 25
Occurs in free state (less than O 2)

3. Allotropy

O3 is the allotrope form &

S exists both in amorp hour & crystalline form . & metallic sulphides when prodike acid sulphide, 3 . when dissolved in

4. catenation 5. Hydrides 6. Action on metals

In

In

Produces basic oxides which Porms prodices dissolved in alkalis

7. On non-metals

Produces acidic oxides which Produce

yeiled acids on treatrnent reacts with alkalis to produce with water thiocarbonate 6 Dissimilarities 1. Physical state is a colourless gas at S is a pale yellow solid ordinary temp 2. Oxidation.No 3. Conbustibitity 2 , 2, 1 supports combustion 4. Action on NO Reaction forms 2, 4, 6 & with . 2 3

It is not combustible but S is it selfcombusrible in air &

Reacts with conc the formation of

5. Mol structure 6. Multiple bonds

Diatomic & linear

8 atoms puckered ring

Due to small size O com form S due to its large size has very multiple bonds feeble tendency I.e why molecule is not

7. d-orbitals

No vacant d-orbitals

Enhibits

tetra

&

well

as

henavalency

of d orbitals

Hydrogen Sulphide(
[A] PREPARATION:(i)
2

is prepared by the action of cold and dilute sulphuric acid on Fes.

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Oxygen
2

Page 26

is collected by the upward displacement of air coz it is heavier than air, or aver hot wntains
2,

water as it is much less soluble in hot water * Purification:Fes) The gas is passed through a sat. solm of sodium hydrogen sulphite to remove the HCl vapours The gas is then passed there when
2 2 5 2

Moisture & HCl gas (if

is prep by the action on HCl on

which absorbs moisture. The gas is cooled by dry ice

2

becomes liquid. The uncondensed

is pumped out. This liquid

is

converted to gas at room temp *

2

or conc

of

produced by the action of

4,

is

in the prep of

an pes is oxidized to S due to the oxidizing action . So instead of 2 2

2

: Because of the fact that the we get yellow ppt. of S

, and get it self its rednced to & 4

2

With conc

cannot be dried by :

or CaO or conc

2
2 4

but can be drive by

or

Through fueed

is a good drying agent, but it cannot be used to dry weak dibasic 2

acid, as it reacts with it to form cas& HCl ii. Conc being a strong oxidizing agent, oxidizes to S due to the nascent O

produced by its decomp

2 2 4 2 2 2 2 2

iii.

&
5 is

is a basic oxide &

is a weak dibasic acid

reacts with

to form

a good brying agent as well as an acidic oxide.

being a weak acid does not

react with it

being an amphoteric oxide also can be used

2. By heating an aquewussolm of thioaccetamide:-

3. By heating antimony sulphide with conc HCl:-

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Oxygen 6 2 3 (pure
2

Page 27 )
2

4. Porm metallic suplhides:- Metallic sulphides on bingtrcated with dil. HCl or evolues
2

. 2

2 12
2

2 2
2

5. By the action of mascent

6. Synthetic process by passing a mixture of

2 4500 2

on non metallic sulphides:.

2&

s vapours over mi cat at 4500C.

PROPERTIES:[A] PHYSICAL PROPERTIES:(i) ii. iii. iv. v.

2

is a colourtes gas having an unpleasant amell resembling that of rotlen eggs.

2

Pairlysouble in cold

but not in hot water

It can heavier that air (v.d=17) It can easity be converted to a colourless liquid by cooling it to 60-70C or by It is a poisonous gas &produces headache when inhated in small quantities
2

applying high pressure. H2S is a gas but is liquid at room temp:- H- bond in molecule linked to 4 molecules form a chain of

water molecules due to due the high eteronegatintiy & small size of O-atom. (cage like structure with each
2 2

molecules)
2

But due to the large size & small electrongativety of a stom, form H- bond & the molecules are altracted only by weak vander waals force . [B] CHEMICAL PROPERTIES:i. Combustibility:2
2

cannot

is a non-supporter of combustion but it burns in air or 2 ,2 3 2 2 ,

with a

blue flame forming S d steam. In presence of excess of air it forms An aq. Solm of 2

partially oxidised by air to form insoluble S & as a result the solm. becomes turbid. (air) = 2 begind\s to decompose into

kept exposed in air becomes turbid cz the dissolved

is

Thermal decomposition:- when heated abobe 4000C & . The decomp is comptated at 17000C

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Oxygen 2 2

Page 28

3. Acid property:- The aq.som of water. It ionizes as follows:2

acts as a weak dibasic acid & is called hydro

sulphuric acid. It turns blue litmus red. Its aq. Som conducts electricity better than 2
2

It reacts with bases or alkalis to form salts with alkalis it gives 2 series of salts-acid salts (chloro sulphides) & normal salts (sulphides) 2 2 2 2 (sodium hydrogen sulphide) 2 (sodium sulphide)

Metals which are above

in the e-series disp-lace ,2 2

from

at elevated

temperature with the formation of the corresponding sulphides (black) Hg, Ag which are below
2

in the e-series, yet the metals liberate This is because &

from

with the

formation on of the sulphides. are highly stable compounds. & & Ag are . So the When is made to react with these metals, the oxidation potentials of takes place.

increased considerably making them very easly oxidisable to displacemert of

2

4. Reducing Property:-

acts as a strong reducing agent as S in the -2 oxidation state

,2

(lowest) for S compounder has an inherent tendency to inarease its oxidation no dt the expense of reducing others.
2

2
2

5. Formation of thionic acid:- At O0C, formation of thionic acid 5 10 3 2

reacts with an aq.som of

with the

(penta thionic acid) 2

2

6. Sulphur is ppted when

is passed through an aq.som oif sodium disulphite 3 3

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Oxygen 7. Precipitation of sulphides:radicals in q.A.

2

Page 29 is used as mp reagent for the detection of basic

Based on the solubilities of diff. metallic sulphides in diff. media, they are classified as:i. Metallic sulphides which are insoluble in dil HCl:Black CuS, PbS, HgS , , , , . 4 2

Orange Brown sulphide ii. medium

Yellow

[of these, AS, Sb, Sn are only] soluble in yellow

&..

ammonimum

Metallic sulphides which are soluble in acid med but insoluble in alkaline white ppt ,

MnSbuff (pink) ppt ,

iii. Soluble in water:- The sulphides of alkali & alkaline earth metals are soluble in water & are not ppted by water. , , , etc + also of , , ,

Black ppt

* Separation of the metallic radicals from a mixture of salts:- Suppose a mixture contains aq. Som of CuSO4, ZnSO4& Na2SO4. The mixture is dissolved indil HCl and H2S is passed through the acidified som of the mixture, when CuS(black) being insoluble in del. HCl gets ppted& is fittered off The filtrate is the boiled to remove H2S and is made alkalime by adding NH4OH. H2S is passed then this alk. Som when a white ppt. of ZnS is obtained. It is separated by fitration& the filtrate contains No salt only. Thus they are separated

TESTS OF H2S:(i) H2S ahs a characteristic unpleasant smell that of rotten eggs. (ii) It turns lead acetate paper black due to formantion of lead sulphide
3 2 2

2 (black) )

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Oxygen (iii)
2

Page 30 does not change the colour of sodium nitroprueside, but when
2

is passed

through freshly prepared alkaline sodium nitroprusside solution, a violet colouration is formed due to the formation of a complex salt. (sodiumnitroprusside) 2 (violet colour) 2

USES
(i)
2

is used in the prepn of polysulphides.

(ii) As a reagent for the detection of basic radicals in QA * How would you obtain
2

from a metallic sulphate sulphate

heated

strongly by a blow pipe in the rednflame (The sulpliate is first reduced by C particles) 2 2 4 2 4
2

* STRUCTURE:- In
2

the S atoms is surrowended by 2 lps and two H atoms. Like

has a bent structure with H-S b-l = 1.35 & H-S-H b.L = 92-50 which is much less
2

than in

(104-50). This is attributed to the small electronegativity of S atom. Due to

2

the more electronegtivity of O, the b.p in HOH b.L is > HSH b.c

are nearer & repulsive interaction are

more while in H2 O, the b.p are awdy and hency repulsive interaction are less i.e why

* H2S can be purified (inreqd) by passing it through HgO suspension in water * Allotropy of S:- 8 monoclinic sulphur (a third modification, apart from Is nacreous (looks like mother of peral). It can be made by chilling not conc. soms of S in solvents such as CS2 rings with a oroun conformation & differ only in the averallengels sulphur (e sulphur) is anstable and contains S6 rings arranged Na2S2O3 sol into conc HCl &cetracting the S with totuene it can be made a sa follows:2 4 2 2

(May hydrosulphide)

&

Several other ring S, Sq, S10, S11, S12, S18, S20 have also prepared by schxidt

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Oxygen

Page 31 In all these ring coxpounds the S S dist is 2.04-2.06 & the bond

S S- S range from 1020 - 1080

SULPHUR DIOXIDE Preparation

By heating Cu turning with conc
2 4

is collected by the upward displacement of air. * Lime cannot be used to dry producing calcium sulphite By burning sulphur in air:By the reduction of conc. 2
2 4:2

4 is

reduced by metallic

, an acidic oxide

2 cao(a

basic oxide) reacts with

may be abtained by the action of metals like Hg,

4.

Ag & non metals like C, S on conc

From sulphites and bisulphites:- At ord. temp , may be obtained by the action of dil. -1 on sulphite and bisulhite+ salts. [non redon reaction] HCl or Dil -1
2 4

2 Preparation of , , , ,etc, 2 4

4 2 2

from sulphide ores:- During the extraction of metals like is ottained as a hy-product when the sulphide ores of these , , from pyrites( 4
4

metals are roasted. Thus copper lysites

2

is obtained by voasting zinc blend (zns) galena (pbs), 2 ,2 or fools gold) 3 3 2 2

2 3

By heating anhydrite

110

, abt. From gypsam anhydrone MgClO

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Oxygen With C above 10000C:2 2 2

Page 32

PROPERTIES:[A] PHYSICAL PROPERTIES:1. 2. 3. 4. is a colourless gas having an irritating & suffocating smell of burning. It is fairly soluble in waters. It is nearly turce heavier then air. It can be liquefied even at atm. Pressure at -100C. liquid SO2 is colourless liquid

(b.p = 100C) & used as non aqueoussowent It freezes at 72.70C to snow like mass [B] CHEMICAL PROPERITES:1. Acidic properties:i.e., why is an acidic oxide. It dissolves in water to form
2 3on 2 3

which is & .

dibasic & which blue litmess red.

being heated decomposes to give

is called anhydride of sulphurous acid.

[so is a more powerful reducing agent in alkaline medium than in acid medium] When is passed through a som of ; , [Sulphites] at first their sulplites are formed. On 2 .

passing encess With lime water,

, the sulphites are converted to bisulphites

first forms insoluble CaSO3 due to which the clear solution turns , xisulpate is formed & so the milkiness disappears. On

milky. On passing excess

boiling the calcium disulphite som the milkiness reappears due to the decomp of calcium disulphite into insoluble calcium sulphite & SO2 2 (milky) (milkiness disappears) ,

2 also

gives similar test, but cannot reduce

(reappears)

2. Combustibility:sulphite&thiosulphate. 4 4 3 3

is not combustible neither a supporter of combustion, but the

burning Na, K, Mg, Fe, C etc continue to burn in the gas. Na or K burns in the gas to yield

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Oxygen Fe, Mg burn in SO2 with the formation of the their oxides & sulphides 3 2 ,3 2

Page 33

In these reactions, SO2 is partly decomposed to give. If mascent oxygen due to high temp by the burning metals. 3. Decomposition:- A sat. aqueoussom. Of SO2 on being heated in a sealed tube at 1500C, s separates out from the som. As a yellow ppt. which dissolves in CS2.
2 2 2 3

1000

2 2 3

all (Dispropor tionation)

4. Reducing property:atom. i. ii. iii. iv. v. 2. S. (2) Through Through Through 2

2 2 (yello

is a strong reducing agent in presence of moisture it can

liberate moscent H or in presence of an oxidising agent it can easily take an oxygen water: 2
2

in water:2

water
2

2 2 2
2 2

2
4

w)
2

In case of
2 7

clear green(colourles som.

2

(1) 4 dirty colourless som. Due to pption of s) dirty green som. Is obtained. 3 4 3 7

The free S makes the som, turbid & gives a dirty appearance
7

viii. ix. x.

2 2 7
2 2

5. OXIDISING PROPERTY:- i. 3 2

4 3

89

Burning Mg, Fe, K, Na etc continue to brown in ,2

hite formation of sulphide & oxide (sulphites &thisulphates) in case of K, Na,

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Oxygen 4 3 ,4 3

Page 34

ii. iii. iv. SO2) 6.

when 4

is passed over red hot ke at 11000C, C is oxidised to CO2 4 4 3 2

(This shos that H2S is stronger reducing agent than forms additive compounds with

FORMATION OF ADDITIVE COMPOUNDS:-

same elements or compounds. With Cl2 in presence to sunlight it forms sulphuryl chloride.

Or camphor (sulphuryl chloride)

can form additive compounds but In the molecule of

monovalent atom like Cl to complete its octet. Thus to atoms of Cl accepts one electron from the Lp of e of to form sulphuryl chloride.

, has a Lp of electrons. These electrons can be donated to

cannet:-

But in like 7.

, C atoms has no such Lp of electrons with whiath can form bonds with others BLEACHING PROPERTY:Perfectly dry has no bleaching property but in ith the evolution

presence of moisture it can bleach the vegetable colourless matters. It is due the fact that in presence of moisture compound by reduction. 2 at, first with water producing
2 4

of nascent hydrogen. This nascent H belaches the colouring matter to a colourless 2 Reduced colourless reduction product.

Colouring matter bleaching by

The colourless (reduced) compound is reoxidised by air to coloured compound, is temporary.

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Oxygen In certain cases, bleaching by sulphites &bisulphites. The coloura can be restored by dipping the bleaching matter in dilute acids. _ (colourless compound)

Page 35 takes place via the formation of colourless

* Comparison of the bleaching props of SO2& Cl2:i. ii. Both bleaches by redn through nascut H produced by reactionith 2 2 . & require moisture for bleaching, cannot bleacu in the dry state
2

Colouring matter

Colourless matter

in presence of moisture evolves nasceut O which bleaches the colouring matter to colourless by oxidation. 2 Oxidised colourless product. is not permanet. The original of the fabrics may be ,

Colouring matter iii.

The bleaching action of

restored by sinply to aitr due to oxidising action of O2 of air. The bleaching action of the substances cannot restore its original colour. iv. is milder bleaching agent that

& So delicate fabrics like silk, wool etc are

bleachied by Sometimg action of

as these delicate farbics may be affeated by the action of may also harm the fibres.

TESTS
i. ii. Colourless gas having smell of burning S. Changes colour of acidified soh of
2 2 7

from orange to green (clear),

2

from pink to colourless (clear) be redn. The same occurs ith found due to turbidity of S. iii.

but a dirty som. Is

A picec of blotting paper, soaked in KIO3& starch som, is introduced in a jar of . The paper turns blue as 2 5 4 is reduced by 3 2 to free
2.

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Oxygen

Page 36

Uses
1. bleaching. 3. 4. 5. 6. 7. compounds. Two 6 bonds These two form two & 1 Lp SP2hybridisationith oxygen In ( S & O are formed by SP2 P averlap& the other from It is imp to note that molecule has 2 diff. types of In the paper of
2

As a bleaching agent 2. As an antichlor for removing sxcess

4,

from a fabric after

sulphites & bisulphites .

In refining petroleum & sugar As a refrigerating agent

2

preservative& disinfectant for Killing geams, funge. Liq.

(non

aqueous (SO2 ordinary) is used as a solvent for many organic & inorganic & bonds bond. The 6 bonds betn. overlap. The bond bonds &

molecule, each O atom is joined to sulphur by a 6 & a

is slighty reduced from 1200 to 119-50 CO2 of the presence of Lp on S.

, but even then both the S O bonds are indentical (1 430A). this indicates that is a ohezonace hybrid of the folloing 2 structures. V shape of been linear like is in accordance ith its dipole moment (1 60D); had the molecule its M would have been zero. , it can act as leuris base.

Due to presence of Lp of electrons in shains of SeO2withbridging O-atoms

Gascous SeO2 has the sanie structure but the solid form consists of infinite non-planar

state consisits of chains of

is a gas & forms discrete molecules en in the solid state hile units.

in the solid

ACID RAIN

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Oxygen A large amount of

Page 37 is released into the atmosphere from al & poer plants. It is also

accompanied by some oxides of N2, causing environmental pollution. These gases also dissolve in rain water & make it acidic; acid rain hich is bad SO quantitative methods for measuring 1. 2. in the atmosphere are highley devaueped like:Oxidation. To
2 2 4 4

hich is determined by titration

Reaction with

to give a Hg complex hich reacts with dye 2 4

pararosaniline & is estimated calorinetrically.

2 4

3. *

Burning in a H flame in a inflame photometer& measuring the spectrum of S2 is used to make other products:2 2 2 2

3 2

1. Colourless & odourless gas 2. heavier than air

1.Colourless gas having a smell of burning s. 2. Havier than air

3.fairly soluble in water, can be liquefied by 3. fairly soluble in ater liquefied by applying cooling. pressure at tem. , strongly heate d metals like 2 .

4. Neither combustible mor a supporter of 4. Same as 2

combustion but burning Na, K, Mg, Fe burn init Na, K, Mg etc continue to burn in it 3Fe+SO2=2FeO+FeS. 5. Acidic oxide, forms 6. Alkalis forms sulphite&bisulphate

5. Acidic oxide 6. with alkalis forms carbonate & bicarbonate salts. 2 2

7. + Ve lime ater test 8. , 9.

7. + Ve lime water test has no reducing property. does not

has reducing prop it can reduce acidified 8. soms

react with them 9. only acts as oxidation agent . at high oxidiese metadllic zn to zno som

can act as an oxidies ng agent. (yellow) Burning

temperature

but it cannot oxidize

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Oxygen
10. coloured matters by redn 11. Forms additive compounds like etc has bleaching property. Bleaches 10. No bleaching property. &

Page 38

11. Forms no additive compounds as the C atom in CO2 has no lone pair electrons

12.

has V shaped molecule B.L = 119 50. 12. moment

is a linear molecule it has no dipole

It has dipole moment = 1.60 D

SULPHUR TRI-OXIDE (SO3)

anhydride of
2 4.

80

PREPARATION
1. By the direct combination of 2. By the dehydration of conc. metaphoshoric acid
2 2 4 2 5 3
3

&
2

:is dehydrated by to produce and

3. From metallic sulphates & bi-sulphates:2 3

PROPERITES:[A] PHYSICAL PROPERTIES: i. ii. SO3 is colourless transparent &erystalline solid itexixts in 3 forms:-

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Oxygen (a)

Page 39 (m.p = 6220C):- It is obatanied as colourless needle sliaped transparent ice vapour are cooled by liquid air when kept below on being exposed to moisture or kept belo 250C, .
3

(b)

250C, it is converted to form. (m.p = 32.50C):-

like crystals, when anhydrous

change to silky white, soft absestos like needles. This is known as (c) . It sublimaters at 500C at 50 1000C it change to

. its m w is 160

(m.p = 160.80C at 2 atm pressure):- It is abtalned by completely drying the is the most stable form & is made of chains cross linked into sheets. decompess into 2 2 & when passed through a red hot tube.

(SO3)3

varitely. It resembles icee-like structure (in appearance)& is a cyclik trimer

[B]CHEMICAL PROPERTIES:1. Decompostion:-

2.

Action with ater:-

has a strong offinites for water it reacts violenty with ,

water with a hissing sound producing sulphuric acid & pyro-sulphuric acid or olum. This racntaksplac with thvolution of much hat. Whn with th moistur to form whit fums of
2 4

is kpt xposd to air, it combins

4.

is calld th anhydrid of

3. Action with basic oxids:to produc mtallic sulphats. 2

is an acidic oxid it racts with many basic oxids & alkalis , ,

4. Action with acids:- (a) acid (b)

2

combins with anhydrous HCl to form chloro sulponic . .

4:

It is absorbd conc.

to produc olum or pyrosulphuric acid or fuming

2 32

5. Oxidising proprty:(a)

is a strong oxidising agnt sp. When hot. 2 to form red vapaurs of

oxidises colourless

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Oxygen (b) With urea:& 2 @

Page 40

reacts with urea acidified with . . 2

to make sulpharic acid .

Sulphuric acid is the only strong acid that exists as a solid at room temperature it is used for cleaning the plants at sugar refineries&traceries.

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