Fluorine

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Group 17
Chlorine
Atomic Number: 17 Atomic Weight: 34 Metals which exhibit valencies, (Cu, Fe, Sn, Mg etc.) on combination with Cl2 produce chlorides in which then metals are in their highest oxidizing state. (a) P burns in Cl2, 2P+3Cl2= 2PCl3, 2P+5Cl2=2PCl5. (b) 2S (boiling) +Cl2= S2Cl2(orange), 2B+3Cl2= 2BCl3.

Properties of Chlorine
Action on water- (i) On passing Cl2 through ice cold water, crystals of diff. hydrates of Cl2 are formed. Cl2+6H2O=Cl2.6H2O, Cl2+8H2O=Cl2+8H2O (ii) Cl2 dissolves in water to form a light yellow solution. having a strong smell of Cl2.This is known as Cl2 water. It consists of HCl and HOCl. H2O+Cl2=HCl+HOCl On long standing HOCl decomposes to give nascent O and HCl. (iii) In bright sunlight, Cl2 reacts with water to form HCl and O2. 2 2 4

Action on alkali: - (i) Cl2 react with cold and dilute solution. of NaOH or KOH to produce chlorides and hypo chloride.

(i)With hot and conc. Solution of alkalis, Cl2 forms chlorides and chlorates. 6NaOH+3Cl2=5NaCl+NaClO3+3H2O. (iii) Cl2 reacts with cold lime water i.e. dil. Ca(OH)2 to produce CaCl2 and cal. Hypochlorite.

(iv)Excess of Cl2 reacts with hot milk of lime to produce CaCl2 and cal. Chlorate. EDUDIGM 1B Panditya Road, Kolkata 29
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Fluorine 6Ca(OH)2+6Cl2=5CaCl2+Ca(ClO3)2+6H2O (v) When dry Cl2 is passed over slaked lime at 40 [Calcium Chloro hypochlorite]

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bleaching powder is produced.

Ca(OH)2+Cl2=Ca(OCl)Cl+H2O. (vi)Cl2 on being passed over red hot CaO, O2 is liberated over with CaCl2 formation. 2CaO+2Cl2=2CaCl2+O2 Oxidation property:- Cl2 is a strong oxidizing agent. Its oxidation action is due to the fact that it gives off nasc nascent O in produce of moisture. H2O+Cl2=HCl+HOCl HOCl=HCl+O (i)2FeSO4+H2SO4+Cl2=Fe(SO4)3+2HCl. (ii)2FeCl2+Cl2=2FeCl3 (iii)SnCl2+Cl2=SnCl4. (iv) With excess of NH3:8NH3+3Cl2=6NH4Cl+N2 (v) With excess of Cl2:-

(vi)H2S+Cl2=S

(vii)SO2+Cl2+H2O=2HCl+H2SO4 (viii)Na2SO3+Cl2+H2O=Na2SO4+2HCl (ix)Na2S2O3+5H2O+4Cl2=Na2SO4+H2SO4+8HCl (x)2KBr+Cl2=2KCl+Br2, 2KI+Cl2=2KCl+I2 (xi)

(xiii) 2K4[Fe(CN)6]+Cl2=2K3[Fe(CN)6]+2KCl. Reducing action:-

and other halogen compounds.

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Formation of additional compounds:(i) CO+Cl2=COCl2 (phosgene) poisonous gas.COCl2+2NH3=2HCl (ii) 2NO+Cl2=2NOCl (Nitrosyl chloride) (iii) SO2+Cl2= SO2Cl2 (iv) C2H4+Cl2=C2H4Cl2 C2H4+2Cl2=C2H2Cl4 Bleaching property:- Dry Cl2 has no. b.p but in presence of moisture, Cl2 can bleach veg, coloring matters. H2O+Cl2= 2HCl+O Vegetative matter+O colourless product. Cl2 cannot bleach the printing ink or marks of Pb pencil because printing ink is made of C and the Pb pencil is made of graphite which is an allotrope. Cl2 has no action on C at ordinary temperature. Moist litmus paper at first turns red and then colorless when introduced into a jar of Cl2The moist blue litmus paper turns red due to the action of HCl and HOCl, which are produced by the action of Cl2 on water. Cl2+H2O=HCl+HOCl Then HOCl decomposes to give nascent O which oxides the veg. coloring of litmus to a colourless product. HOCl=HCl+O Veg.colouring of litmus

Colourles product

Prove that KClO3 contains Cl2:2 2 3

2KCl+MnO2+H2SO4=2KHSO4+Cl2+2H2O.

Tests
(i) Cl2 is a greenish yellow gas having the smell of bleaching powder. (ii)

(iii) 2KI+Cl2= 2KCl+I2 Starch +I2= deep blue colour.

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Uses
(i) As a bleaching agent. (ii) Manufacture of PVC, CHCl3, D.D.T etc. (iii) Poisonous gases like COCl2, mustard gas( chloropicrin. (iv) Used for sterlising water. (v) In swimming pools as germicide and disinfectant. )) tear gas (CCl3.NO2),

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Bromine
Atomic Number: 35 Atomic Weight: 79.9 [Ar] 3d104s24p5 Bromides of Na, K, Mg are found in sea water. Carnalite KCl.MgCl2, 6H2O contains .01 to 1% of MgBr2.

Preparation
1. By heating a mixture of MnO2, conc. H2SO4 and a bromide:2KBr+MnO2+3H2SO4=2KHSO4+MnSO4+Br2+2H2O. Purification:-Br2 contaminated with H2O, Cl2 and I2 is distilled over a mixture of KBr and ZnO. 2KBr+Cl2=2KCl+Br2, 2ZnO+2I22ZnI2+O2

H2O is removed by distilling over H2SO4 (conc) 2. By passing Cl2 through a sat.solution of KBr:2KBr+Cl2=2KCl+Br2 3. From carnalite:- Mineral carnalite is dissolved in , 2

Properties
Bleaching action:- Moist Br2 has a mild bleaching action. It bleaches veg. colors by oxidizing.. Br2+H2O=HOBr+HBr Veg.colured matter colourless product.

Reducing property:- Br2 exhibits mild redn prop.It reacts with F and Cl to form Interhalogen compounds.

Br2 is absorbed by alkali solution and moist R.P.

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Fluorine Tests:(i) By its deep colour (red) and pungent, irritating smell. (ii) It turns starch to orange yellow. (iii) Br2 shaken with OS2 dissolves giving a reddish brown solution. Uses:(i) Prep of KBr (used in meds), AgBr (photography).

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(ii) Manufacture of org. dyes, CH3Br (fire extinguish), tear gas, TEL; an antiknock compound. C2H6+Br2=C2H5Br+HBr 4C2H5Br+4Na-Pb=(C2H5)4Pb+4NaBr+3Pb Br2 and NO2 are both reddish gases:-Although they are nearly of the same colour, they can be distinguished as:(i) Br2 dissolves in CS2 giving a reddish brown solution.while NO2 does not dissolve in CS2. (ii)Br2 dissolves in water giving a reddish brown colour to it while NO2 dissolves in H2O giving a colorless solution. of HNO2 and HNO3.

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Iodine
Atomic Number: 53 Atomic Weight: 127.9 [kr] 4d105s25p5 I2 is the rarest of all halogens. Imp. sources-KClp (burnt sea weeds), caliche (oxide NaNO3) which contains I2 as NaIO3.

Preparation
1. 2KI+MnO2+3H2SO4=2KHSO4+I2+MnSO4+2H2O. Purification:ICl+KI=KCl+I2 IBr+KI=KBr+I2 2. By passing Cl2 through sat. solution of KI:2KI+Cl2=2KCl+I2 3. Commercial method: - (a)-From Kelp:- Kepl is extracted with hot water and the crystals of K2SO4, Na2SO4, KCl and NaCl sep. out on cooling. The mother liquor contains iodide which is then mixed with MnO2 and conc. H2SO4. NaI+3H2SO4+MnO2=2NaHSO4+MnSO4+I2+2H2O. (b) From Caliche:- Chile saltpeter (NaNO3) contains about 2% NaIO3. 2NaIO3+5NaHSO3=2Na2SO4+3NaHSO4+H2O+I2 If NaHSO3 is present in excess, it will react with I2 to produce HI. NaHSO3+I2+H2O=NaHSO4+2HI

Properties
Physical Properties:(i)I2 is a deep brown crystalline solid having shining metallic lusture. (ii)Its =4.9 (iii) It is sparingly soluble in water but readily soluble in NaI or KI due to the formation of triiodide. KI+I2=KI3. This solution. behaves as a simple mixture of KI and 1 free I2Tincture of I2-1/2 ounce I , ounce KI and 1 pint of rectified spirit. (iv)It is soluble in many organic solvents. Its solution in CS2 and CHCl3 is violet, while in alcohol, ether and CCl4 is brown.

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Water and KCl and MgCl2 are crystallized out. The mother liquor contains about 25% of Br as MgBr2 and is known as bittern. MgBr2+Cl2=MgCl2+Br2 4. By conc. HNO3:- 6KBr+8HNO3=6KNO3+2NO+3Br2+4H2O 5. With Na2CO3 and Br2:3 3 6 Chemical Properties:I2 resembles Cl2 and Br2 in many respects but it is less reactive than Cl2 and Br2. 1. Action on non-metals:(i) 2P+3I2 2 5 6 3 3 3

(ii) 2AS + 3I2= 2AsI3 (iii) 2Sb+3I2=2SbI3 (catches fire) (iv) I2 has much less affinity for H2than that of Cl2 or Br2. Even in sunlight it does not combine H2 readily. In presence of a cat. Like Pt, I2 combines with H2 on heating. 2 (v) Interhalogen compounds:- Reducing prop. Of I2. I2+3Cl2=2ICl3 (yellow). I2+Cl2=2ICl (red), I2=2IF7. I2+Br2=2IBr (black).

2. Action on metals:(i) Hg+I2=HgI2 (red)

(ii) 2Na+I2=2NaI,

2K+I2= 2KI.

(iii) 3Fe+4I2= FeI8, Pb+I2=PbI2 (Ferrosoferric iodide) 3. Action with alkakis:-

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Fluorine [NaOI is crystable, it is hydrolysed to hypo-iodous acid. NaOI+H2O=NaOH+HOI.]

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4. Action on sodiumium thiosulphate:- When a colorless solution. of Na2S2O3 is added to I2 Suspended in H2O, or to a brown solution. of I2 in KI, the thiosulphate is oxididsed to a Colorless solution of sodium. Tetrathionate. The blue colour of the starch I2 solution is discharged by this reaction. and so it is employed in iodometry. [If the titration is allowed to stand for 2-3 min, the indicator turns blue again, because Some atm. Oxidation has taken place] 2Na2S2O3+I2=Na2S4O6+2NaI 5. Reaction with KI: - I2 is sparingly soluble in water, but the crystals of I2 readily in a Colourless solution of KI turning it brown. This is because I2 reacts with KI to form a Complex salt pot. Tri-oxide which is highly soluble in water. [Ion induced dipole attraction] [The mixture may be separated by sublimation when I2 Is obtained as sublimate and KI is left as residue]. KI+I2=KI3 6. Oxidizing property:(i) H2S+I2=2HI+S (ii) SO2+I2+H2O=H2SO4 +2HI (iii)Na2SO3+I2+H2O=Na2SO4+2HI. 7. Displacement of Cl and Br:- I2 cannot displace Cl2 and Br2 from chlorides and Bromides because it is less electronegative than them. But it can displace them from Chlorates and bromates as the two halogens are present as the electro+ve part in them. So, I2 can displace them.

I2 and graphite look alike- How would you distinguish them:-

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(i) On heating the two solids separately, I2 sublimes yielding violet vapours. On the other hand Graphite at relatively low pressure remains unaffected. (ii) When a small amount of I2 is shaken with CS2 , the solution. turns violet but when small Amount of graphite is shaken with CS2 it does not dissolve in it. (iii) I2 when comes in contact with R.P catches fire PI3, while graphite remains unaffected. (iv) I2 forms blue complex with starch solution. while graphite does not. Forming I2 which reacts with starch to give the blue colour again. 2 1 2 2 , .

The brown colour of an acidified dil. Solution. of I2 in aq. KI solution is intensified by the addn of a nitrate, but is discharged by the addn of a sulphite: - When nitrite salt is added to an acidifies solution. of I2 in aq. Solution in aq. KI solution. nitrous acid is produced by the action of nitrite which oxidizes KI to I2 and the brown colour of the solution. is intensified. NaNO2+HCl=HNO2+NaCl. 2KI+2HNO2=I2+2KOH+2NO. With sulphite, sulphurous acid is produced which then reduces the produced I2 to colorless HI. Na2SO3+2HCl=2NaCl+H2SO3. I2+H2SO3+H2O=H2SO4+2HI

Tests:(i) Crystals of I2 sublimate when heated to produce violet vapours. (ii) I2 dissolves in CS2, CHCl3 giving a violet solution, while in alcohol, ether and CCl4. (iii) It turns starch solution. deep blue.

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Fluorine
Property F2 Cl2 Br2 Deep I2 red 5.

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1. Physical state, 2.Pale colour, odour. yellow

greenish 3. Greenish yellow 4. gas gas with

Dark

red solid

an liquid with an crystalline extremely irritating smell. with lusture. 127, 53 , 4.94 . ,

having a pungent irritating smell. irritating smell. 2. At. Wt. and No 3. H.P and B.P 4. 5. Solubility 19, 9 -233 , 1.2 2.5 35.5, 17 . ,

metallic

79.9, 35 . 3.19

Decomposes H2O Fairly soluble in Less to O2 and D3. water. 3 . . than Cl2. 2.8 1.14

soluble Almost insoluble.

6. Electro-veity 7. Atomic radius 8.

2.5 .

Ionisation Very high (1681 High KJ/mol) -1 KJ/mol)

(1256 Less than Cl2 (1143 KJ)

Lowest. Can form I+ ion (1009 KJ)

potential 9. state 10. affinity

Oxidation Only

(most -1, +1, +3, +5, +7

-1, +1, +3, +4, -1, +1, +3, +5, +6 +7 than F2 Lowest. (296)

electro-ve) Electron Less than Cl2 Maximum. (349)

Less (325)

(333 KJ/mol) with Combines

11. Affinity for Combines H2

in Combines

on Combines

on in

explosion even in presence of light heating to form heating dark to form HF. to form HCl. HBr.

presence of Pt. cat. To form HI.

12. Bond energy 13. H2O

126 KJ/ mol

210 KJ/mol

158 KJ/ mol

118 KJ/ mol

Action on Decomposes H2O Forms

chlorine Slightly soluble Insoluble in H2O. water and in

to form HF and hydrate with cold in ozonised O2. (ice) Otherwise HCl and O2.

water. decomposes

forms sunlight to form HBr and O2. Less reactive. Less than Br2.

14. reactivity 15.

Chem.- Highly reactive.

Quite reactive.

Displaces I2, Br2, Displaces Br2 and Displaces I2 from Cannot form their I2 from tromides iodides. and iodides. and dil- Cold and dil-Cl- Cold and OCland dil- Cold

displace

Displacement of Cl2 halides. 16. salts.

any halogen.

Action on Cold

and

dil-I-

alkalis

flouride and OF2

OBr- and Br-

and OI-

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Fluorine
17. power 18. action Oxidation Very strong Strong power. oxidation Mild power. veg- Has bleaching power. oxidation Very

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feeble

oxidation power. Bleaching Highly Destroys vegetable coloring matter.

oxidation power. mild Has no bleaching power.

active. Bleaches

colours with ease.

19.

Action on No

change

of No change.

Turns yellow.

Turns deep blue.

starch solution. 20. Action on O2

colour. Cannot oxidsed be Indirectly oxidized Indirectly Oxidized by conc.

. to Cl2O, ClO2, Cl2O7 oxidized to BrO2, HNO3, O2 etc. Br2O.

Oxidizes O2 to etc. OF2, O2F2 21. Action on With

the Except O2, N2, C Combines with many

with Combines

only

non-metals

exception of N2, combines

non- with P and As

O2 combines with many non-metals. all non-metals. 22.

metals except C, directly. N2, O2 and Si. with Reacts with few

Action on Reacts with all Reacts with many Reacts metals to form metals fluorides. to

metals

form many to form metals. bromides.

chlorides.

Hydrohalic acids:- All the members of the halogen family combine with H2 by covalent bond to form hydrogen halides (HX). These hydrides are known as halogen acids, hydracids or hydrohalic acids (aq. Solution) Hydrogen Fluoride:- (a) Preparation:- F2 combines with H2 directly to form HF, but the reaction is so vigorous that explosion takes place even in the dark, which prevents prep. Of HI by the direct combination method. 1. From fluorspar- By distilling a mixture of powdered fluorspar and 90% H2SO4 below 300 on a sand bath. 2 HF cannot be stored in a glass or porcelain vessel:- HF attacks glass or porcelain . It reacts with silica, one of the constituents of glass forming SiF4 and H2SiF6. SiO2+4HF=SiF4+2H2O SiF4+2HF=H2SiF6 HF may be stored in gutta purcha or polythene or wax coated bottle.

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2. Prep. Of anhydrous HF:- By heating Pot. Hydrogen fluoride or freneys salt, when KHF2 is thermally decomposed to yield anhydrous HF. KHF2=KF+HF Frenys salt:- 2HF+K2CO3=2KF+CO2+H2O KF+HF=KHF2 (white crystals)

Properties:(a)Physical Properties:(i) Anhydrous HF is a colorless fuming liquid below 19.5 . Above 19-5 colourless gas. (ii) It is highly soluble in water. (iii) Anhydrous HF is a non-conductor of electricity but the aq. Solution conducts. (iv) It is highly poisonous and causes painful wounds on skin. it is a

(b) Chemical Properties:1. Acid property:- HF though a mono basic acid it can form acid. In aq. Solution, HF ionizes giving H+ and F- ions and consequently should behave as a monobasic acid. The F- ion thus produced, forms H-bond with an undissociated HF molecule to form HF2ion. So it can form salts like:- KHF2, NaHF2 H2F2+KOH=KHF2+H2O H2F2+NaOH=NaHF2+H2O HF has higher b.p than HCl and behaves as a weak acid:- In liquid state HF molecules are associated by H-bonding. HF consists of polymers of zigzag chains joined by H- bonds, the H-F-----H bond L being 140. So, HF is a liquid while HCl is a gas inspite of higher mol.wt. Hence b.p of HF > HCl. In aq. Solution, HF ionizes as . The ion thus produced combines with .

undissociated HF molecule by H-bond to from H

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7.2 10 , is a strong acid. 5.5

HF is a very weak acid but

2. Action on metals: - Except the noble metals, aq. HF attacks all yielding H2 and fluorides. Anhydrous acid does not attack metals except K. 2Na+2HF=2NaF+H2, 2Ag+2HF=2AgF+H2 NaF+HF=NaHF2, Fe+2HF=FeF2+H2. 3. Action on carbonates:- An aq. Solution of HF reacts with carbonates forming fluorides With the evolution of CO2. Na2CO3+2HF=2NaF+CO2+H2O. 4. Action on glass: - Glass contains silica, which is attacked by HF; it cannot be kept in glass vessel. HF is kept in containers made of gutta-percha, polythene or glass bottles having a layer of wax inside the bottle. Glass consists of SiO2, Na2SiO3, CaSiO3 etc to form SiF4, H2SiF6 and its salts. SiO2+4HF=SiF4+2H2O SiF4+2HF=H2SiF6 (Hydroflousilicic acid) Na2SiO3+2HF=2NaI+H2O+SiO2 SiO2+4HF=SiF4+2H2O CaSiO3+6HF=CaSiF6+3H2O. The etching of glass is based on these reactions- The glass article is first coated with a thin layer of wax. The design is then drawn on the layer of wax with a needle to remove wax. The surface is then trested with an aq. Solution of HF or exposed to vapours of HF in a Pb vessel. The article is then washed with turpentine to remove the wax. 4. Stability:- HF is extremely stable as the H-F bond is very strong. It cannot be oxidized even by the strongest oxidation agents. It is not decomposed by heat. 5. Action on AgNo3= HF gives no ppt. AgF is soluble in water (other silver halides are insoluble in water). AgNO3+HF=AgF+HNO3

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6. With BaCl2- It produces BaF2 which is obtained as a white ppt. and it is insoluble in HNO3 but soluble in conc. HCl (diff. from other Barium halogens) BaCl2+2HF= 2 .

7. Formation of complex acids:- HF reacts with H3BO3 or BF3 to form complex flouboric acid (HBF4) and with SiF4 to form hydroflou silicic acid. BF3+HF=HBF4 H3BO3+4HF=HBF4+3H2O SiF4+2HF=H2SiF6. Tests:(i)HF by its etching of glass. (ii) Finely powdered fluoride is treated with conc. H2SO4 and the mixture is heated with evolution of SiF4 fumes. A water drop on exposure to the fumes turns opalescent (opaque) due to the formation of a thin waxy layer of H4SiO4 around it. CaF2+H2SO4= CaSO4+2HF

(iii) BaCl2 is added to a fluoride or HF, a white ppt of BaF2 is formed; which is insoluble in HNO3 , but soluble in conc. HCl. Uses:1. HF is used for etching gas. 2. Manufacture of Teflon, cryolite, UF6, SnF2. 3. LIq. HF is used petroleum industry.

Hydrochloric acid: - HCl Preparation

1. By heating NaCl with conc. H2SO4 :- Two step reaction:(i) At 150 , NaCl reacts with conc. H2SO4 to form NaHSO4 and HCl. NaCl+H2SO4=NaHSO4+HCl (ii) At above 500 , NaHSO4 reacts with NaCl to form Na2SO4 and more HCl. NaCl+NaHSO4=Na2SO4+HCl. HCl cannot be dried by quicklime (CaO) or P5O5.

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as,

2. From non-metals chlorides:PCl3+3H2O=3HCl+H3PO3 SiCl4+4H2O=Si(OH)4+4HCl PCl5+H2O=2HCl+POCl3 3. From metallic chlorides:CaCl2+H2SO4=CaSO4+2HCl CuCl2+H2SO4=CuSO4+2HCl. 4. From H2S or SO2:-By passing H2S or SO2 through an aq. Solution of Cl2. 2 2 2

5. Synthetic method: - By the direct combination of H2 and Cl2. 2 6. Le-Blanc process: - HCl is obtained as a by-product in the manufacture if Na2CO3 by Le-Blanc process.

Properties:Physical Properties:(i) HCl is a colorless gas with a pungent smell. (ii) It is heavier than air and fumes strongly in air (moist). (iii) It is highly soluble in water. About 450 vol. of HCl dissolves in 1 vol. of H2O. (iv) The gas can be easily liquefied into a colorless liquid which boils at 83 . (v) The gas forms a constant boiling mixture b.p=110 with H2O when it contain

22.2% of the acid. It is not possible to conc. An aq. Solution of HCl by boiling beyond 22.2%. The azeotropic mixtures are formed because of a ve deviation from Raoults Law. (b) Chemical Properties:1. Combustibility: - Neither combustible nor a supporter of combustion. 2. Acidic nature: - HCl is gaseous is not acidic, but the aq. Solution of the gas is highly acidic and one of the strongest acids. HCl is a monobasic acid and turns blue litmus red.

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It ionizes comp. in aq, solution. It is hydroxonium H3O+ ion responsible for its acidic property. , (a) Action on bases:- CaO+2HCl=CaCl2+H2O. NaOH+HCl=NaCl+H2O, MgO+2HCl=MgCl2+H2O Action on carbonates and bi-carbonates:Na2CO3+2HCl=2NaCl+CO2+H2O. NaHCO3+HCl=NaCl+CO2+H2O. Action on metals:The metals which are above H2 in the ecs with the exception of Pb, react with HCl at ordinary temperature with the evolution of H2 and chlorides. Zn+2HCl=ZnCl2+H2 Fe+2HCl=FeCl2+H2 (Nascent H reduces the produced FeU3 FeCl2) 2Al+6HCl=2AlCl3+3H2. (ii) Cu, Pb, Ag dissolve slowly on boiling with conc. HCl in presence of air or O2. 2Cu+4HCl+O2=2CuCl2+2H2O 2Pb+4HCl+O2=2PbCl2+2H2O 4Ag+4HCl+O2=4AgCl+2H2O. (iii) Au or Pt do not react with HCl. 3. Action on salts:Na2S+2HCl=2NaCl+H2S Na2SO3+2HCl=2NaCl+SO2+H2O Na2SO3+2HCl=2NaCl+SO2+S+H2O 2NaNO2+2HCl=2NaCl+NO+NO2+H2O 4. Reducing property:- HCl can strong oxidation agents itself being oxidized to Cl2. MnO2+4HCl=MnCl2+Cl2+2H2O On boiling PbO2+4HCl=PbCl2+Cl2+2H2O Pb3O4+8HCl=3PbCl2+Cl2+4H2O K2Cr2O7+14HCl=2KCl+2CrCl3+3Cl2+7H2O At ord. temp:- 2KMnO4+16HCl=2KCl+2MnCl2+5Cl2+8H2O Fe (OH)3+3HCl=FeCl3+3H2O

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5. Stability: - HCl is quite stable but thermally dissociated to give H2 and Cl2 at About 1500 . 6. Action on NH3:- (g) HCl+NH3 (g) = NH4Cl (s) Dense white fumes. 7. Precipitation reaction: - HCl on being added to the solution of a soluble salt of Ag, Pb (2), Hg(2), yields the corresponding chloride as curdy white ppt. 2 2 2 2 . .

AgCl is insoluble in HNO3 but soluble in NH4OH forming [Ag (NH3)2]Cl complex White ppt of PbCl2 is soluble in hot water while the white ppt of Mg2Cl2 in aqua Region. 8. Action on conc HNO3:- 3 vol. of conc. HCl and 1 vol of conc. HNO3 react to Produce NOCl with the evolution of nascent Cl. This mixture of HCl and HNO3 is Known as aqua regia. It dissolves noble metals like Au, Pt. The evolved nascent Cl Attacks those metals. 3HCl+HNO3=NOCl+2Cl+2H2O

Tests:
(i) When a glass rod moistened with strong NH4OH is held in HCl, dense white fumes of NH4Cl are produced. NH4OH+HCl=NH4Cl+H2O (ii) HCl (conc) on being treated with MnO2 gives Cl2 which turns starch (iii) An aq. Solution of HCl or a chloride gives a white ppt. of AgCl which is insoluble in HNO3 But readily soluble in excess of NH4OH forming a soluble complex salt. 2 ammonium c chloride) (iv) Chromyl chloride test: - On heating a chloride salt with solid K2Cr2O7 and conc. H2SO4, red vapours of chromyl chloride are produced. EDUDIGM 1B Panditya Road, Kolkata 29
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(complex argen to

Fluorine K2Cr2O7+4KCl+6H2SO4=6KHSO4+2CrO2Cl2+3H2O

Page 19

When the vapour of CrO2Cl2 are passed through NaOH solution, a yellow solution. of sodiumium Chromate is formed which on treatment with lead acetate, a yellow ppt. of lead chromate is obtained.

CrO2Cl2+2NaOH=Na2CrO4+2HCl (CH3COO)2Pb+Na2CrO4=2CH3COONa+PbCrO4 (yellow ppt)

Uses:(i) In manufacture of aqua regia, chlorides, pickling pf iron, medicines, dyeing and textile industry.

Hydrobronic Acid:- (HBr) :Preparation : HBr is prepared by heating a chloride salt with conc. H2SO4 but HBr cannot be prep. By Heating a bromide with conc.H2SO4:- Conc. H2So4 is an oxidation agent. On heating it is Thermally decomposed to give nascent O and SO2. H2SO4=H2O+SO2+O When NaCl is heated with conc. H2SO4 , HCl is produced but as the difference in electro Electronegative of Cl and O is not high it is not possible for O evolved from H2SO4 To oxidize HCl to Cl2. But as the electroveity of O is much higher than Br the HBr Produced is easily oxidized by the nascent O to Br2. NaBr+H2SO4=NaHSO4+HBr H2SO4=H2O+SO2+O 2

1. Lab prep: - By the action of Br2 on R.P in presence of water. PBr3 & PBr5 formed suffer Hydrolysis to form HBr. (i) P4+6Br2=4PBr3, (ii) P4+10Br2=4PBr5. (iii) PBr3+3H2O=3HBr+H3PO3, 2. 3KBr+H3PO4=K3PO4+3HBr 3. Direct combination: - H2 and Br2 do not combine even in bright sunlight. When a EDUDIGM 1B Panditya Road, Kolkata 29
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PBr5+4H2O=5HBr+H3PO4.

Fluorine

Page 20

Mixture of H2 and Br2 is passed over a pt spiral heated to redness by electric current. HBr isproduced.

4. From Br2:- H2S+Br2=2HBr+S SO2+H2O+Br2=H2SO4+HBr H2SO4+BaBr2=BaSO42HBr

Properties:(a) Physical Propeties:(i) HBr is a colorless gas having pungent smell. (ii) It is heavier than air. (iii) It is highly soluble in water and fumes in moist air. (iv) An aq. Solution containing 48% forms a constant boiling mixture at 126 . Chemical Properties:1. Stability:- 2 800

2. Neither combustible nor a supporter of combustion. 3. Acidic property:- Gaseous HBr is not acidic but aq. Solution . is acidic; It is a strong Monobasci acid which turns blue litmus red. (a) Metals: - Zn+2HBr=ZnBr2+H2, Mg+2HBr=MgBr2+H2 (b) Carbonates and bicarbonates:Na2CO3+2HBr=2NaBr+CO2+H2O NaHCO3+HBr=NaBr+CO2+H2O. (c) Base Salt (bromides) and H2O:NaOH+HBr=NaBr+H2O CaO+2HBr=CaBr2+H2O 4. On. NH3 :- NH3 (g) +HBr(g) =NH4Br (s) 5. Redn action:- HBr is easily decomposed to give nascent H, so it acts as a Redn agent. MnO2+4HBr=MnBr2+Br2+2H2O 2KMnO4+16HBr=2KBr+2MnBr2+5Br2+8H2O EDUDIGM 1B Panditya Road, Kolkata 29
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Fluorine 2HBr+Cl2=2HCl+Br2 2HBr+H2SO4=Br2+SO2+2H2O K2Cr2O7+14HBr=2KBr+2CrBr3+3Br2+7H2O

Page 21

An aq. Solution of HBr turns brownish red when exposed to air and sunlight as It is oxidized by aerial O2 to Br2. 4HBr+O2=2Br2+2H2O. 6. Pptation reaction: - Aq. HBr reacts with AgNO3solution give a pale yellow ppt Of AgBr which is insoluble HNO3 but sparingly soluble in excess of NH4OH. AgNO3+HBr=AgBr

Pb (NO3)2+2HBr=PbBr2+2HNO (soluble in hot water) Tests: (i) 2HBr+H2SO4=Br2+SO2+2H2O (brown vapours) (ii) 2HBr+Cl2=2HCl+Br2 (turns CS2 layer reddish brown) (iii) AgNO3+HBr=AgBr NH4OH) Hydrogen Iodide:-HI :- Preparation (1) By the action of water on a mixture of R.P and I2 at ord.temp:(i) 2P+3I2=2PI3 (ii) PI3+3H2O=3HI+H3PO3. Net: - 2P+3I2+6H2O=6HI+2H3PO3. Not dried by CaO or conc. H2SO4 as they react with HI. CaO+2HI=CaI2+H2O H2SO4+2HI=I2+SO2+2H2O-this is why HI cannot be prep. By action of iodided On conc. H2SO4. HI is highly soluble in water and attacks Mg. So not used for collecting it. 2. H2S+I2=2HI+S 3. 4. By and conc. H3pO4 has no Oxidation action, it can be used for for the prep of HI. 3NaI+H3PO4=3HI+Na3PO4. the action of H3PO4 on metallic iodides:- As hot (pale yellow ppt. sparingly soluble in

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Fluorine 5. SO2+2H2O+I2=H2SO4+2HI BaI2+H2SO=BaSO4 2 .

Page 22

Property:- (a) Physical 1. Colorless gas having a pungent smell. 2. Fumes in moist air. 3. Highly soluble in water and is heavier than air. 4. It can be liquefied to a colorless liquid, b.p of which is -35.4 . 5. It forms a cons. Boiling mixture at 127 (b) Chemical:1. Stability: - It is the least stable of all halogen acids. It is easily Decomposed to give H2 and violet vapours of I2 on heating. when the solution contains 57% HI.

2. monobasic acid

Acidic and

property:

It

is

strong

turns blue litmus red.

It ionizes comp. in solution:-

(a) NaOH+HI=NaI+H2O.

Action on bases: - CaO+2HI=CaI2+H2O

(b) Carbonates and bicarbonates:Na2CO3+2HI=2NaI+CO2+H2O. NaHCO3+HI=NaI+CO2+H2O. (c) Metals:- Zn+2HI=ZnI2+H2, Mg+2HI=MgI2+H2

3. Action on Oxygen:- HI is oxidized by the aerial oxygen in presence of Sunlight to form H2O and I2. for this reaction is +ve, so it takes place. 4HI+O2=2H2O+2I2, I.e. why a freshly prep. Colourless solution of HI when kept exposed to air turn brown because of dissolution of free I2 in HI. 4. Reducing property: - Strong redn agent. It is itself oxidized to I2. 1. 2KMnO4+3H2SO4+10HI=K2SO4+2MnSo4+5I2+8H2O. 2. K2Cr2O7+6HI+4H2SO4=K2SO4+Cr2(SO4)3+3I2+7H2O. 3. 2HNO3+2HI=I2+2NO2+2H2O 4. H2O2+2HI=I2+2H2O 5. 2FeCl3+2HI=2FeCl2+I2+2HCl.

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Fluorine 6. Fe2(SO4)3+2HI=2FeSO4+H2SO4+I2 7. 2CuSO4+4HI=Cu2I2+I2+2H2SO4 [This reaction as well as ferric salt redn reactions Are not given by HCl and HBr proving that HI is a stronger agent than HCl and HBr) 8. 2HNO2+2HI=2NO+I2+2H2O 9. SnCl4+2HI=SnCl2+2HCl+I2 10. Conc. H2sO4 is redn to SO2, S or to H2S depending upon the amount of HI Consumed.

Page 23

HCl cannot reduce H2SO4, 11. 2HI+F2=2HF+I2, 2HI+Cl2=2HCl+I2,

while HBr can reduce it to only SO2. 2HI+Br2=2HBr+I2

5. Action on AgNO3solution:- HI gives a yellow ppt of AgI which is insoluble in HNO3 and NH4OH.

6. Action on lead acetate solution. :- Pb(CH3COO)2 gives a yellow ppt of PbI Which is soluble in boiling water. Tests:1. HI and iodides give violet vapours of I2 on being heated with conc H2SO4. A paper soaked in starch solution turns blue when comes in contact with this Vapour. 2HI+H2SO4=I2+SO2+2H2O I2+Starch solution= Blue 2. NaI+AgNO3=AgI (yellow ppt insoluble in HNO3 and NH4OH) 2 .

3. An aq. Solution of HI is treated with Cl2 water and the mixture is shaken with CS2 which turns violet on standing. 4. HgCl2+HI=HgI2
Property 1. Physical state at N.T.P 2.Colour 3.B.P and

2
HF Liquid Colourless HCl Gas Colourless HBr Gas Colourless -66.T , .82 HI Gas Colourless -35.4 (vanderwaals)

Dipole 19.4

(due -85 , 1.08

movement

to H.B) 1.82

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Fluorine
D 4.Solubility at 0 5.Thermal stability Miscible Stable 42% 68%

Page 24
.44D 90% Dissociates 180 Strongest acid. at

Dissociates at Dissociates at 800 1500

6.Acid prop.

Weak

acid Aq.solution is Stronger than HCl.

because of H- a strong acid. B. 7.Reducing prop. No Prop. redn. Least redn More than HCl. Strongest Prop. red.

power. Redn strong oxidizing agents.

8.The solid is heated HF is given Colourless with conc. H2SO4 in a off test tube.

Reddish

brown Violet vapours of

which HCl is given vapours of Br are I2 are given off. which given off oxidised by

attacks glass off

forming SiF4. forms dense H2SO4. The evolving white fumes gas turns a of NH4Cl with drop of H2O NH3. opalscent. 9.Action of a mixture of F2 MnO2 and H2SO4 is not A Greenish yellow having pungent smell turns which starch Reddish brown Violet vapours of

liberated.

vapours of Br2 which I2 are given off gas turns starch paper which turns starch a yellow. blue.

iodine paper blue. 10.M.P (K) 11.Action AgNO3solution 190 2nd with No ppt 158 4th 186 3rd 222 1st

is A curdy white A pale yellow ppt. of A yellow ppt. of AgBr which is AgI is obtained

formed. AgF ppt.AgCl is soluble which insoluble HNO3

is insoluble in HNO3 but which is insoluble in spraringly soluble in in but excess NH4OH. HNO3 and

NH4OH.

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Fluorine
soluble excess NH4OH. 12.With BaCl2solution A white ppt is No ppt. obtained. BaF2 soluble is in No ppt. in of

Page 25

No ppt.

conc. HCl but insoluble in

HNO3 BaSO4 is insoluble in conc HCl. 13.Solution is shaken No with Cl2, H2O and CS2 colouration of layer. 14.Action CuSO4solution on No action. Not that Same as HCl. Reduces it to Cu+ ion with lib. Of I2. No colouration. CS2 layer turns CS2 layer turns

reddish brown.

violet.

strong a redn agent reduce. to

15.Action of X2

Cl2

is Br2

is by

lib. I2 is liberated by F2, Not (F2) liberated F2 Cl2. Br2 by any halogen.

liberated only Only by F2 16.Action on glass. HF

and Cl2 reacts No reaction. No reaction. No reaction.

with SiO2 of glass to form SiF4 H2SiF6. 17.Confirmatory Test F2 is heated Cl- is heated To the aq. Solution of To the aq. Solution with and glass with conc. K2Cr2O7 solid a bromide, Cl2 water of I- Cl2 water and and and starch are added, starch are addedH2SO4 the starch turns the starch turns blue. and

H2SO4. A drop conc

of water on red fumes of yellow. being exposed CrO2Cl2 to evolved. are

the evolving

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Fluorine
gas.

Page 26

Bleaching powder:-Ca(OCl)Cl-Cal.Chloro hypochlorite

Bleaching powder is the calcium salt of the hypochlorous acid rep. by Ca(OCl)Cl CaOCl2. Actually it is a mixture of CaOCl2.4H2O and basic calcium chloride, CaCl2, Ca(OH)2. H2O. Manufacture :- Bleaching powder is prep. By slowly moving forward dry slaked Lime through a series of shelves (provided with rotating rakes) against a current Of Cl2 below 40 (Hesenclevers or Beckmanns plant) or

Properties :Physical Properties:1.Bleaching powder is a very light yellow (whitish) amorphous powder Having strong smell of Cl2. 2.It is soluble in water, but as some unconverted slaked lime [Ca(OH)2] is a always present, a clear solution is never obtained. Its aq. Solution confirms the Presence of calcium, chloride and hypochlorite ions. 3. Decomposition:- On standing long +also on heating sloe decomposition with the formation of calcium chloride and chlorate. 6Ca(OCl)Cl=Ca(ClO3)2+5CaCl2 In presence of cobalt chloride (CoCl2), it liberates O2, 2Ca(OCl)Cl=2CaCl2+O2 With excess of dilute acids it evolves Cl2:Ca(OCl)Cl+2HCl=CaCl2+Cl2+H2O

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Fluorine Ca(OCl)Cl+H2SO4=CaSO4+Cl2+H2O. Even CO2 in moist air evolves Cl2 from bleaching powder. This is why it has Smell of Cl2. Available Cl2:- Although bleaching powder has 56% of Cl2 whole of it is not

Page 27

available for reaction. This is because of the fact that bleaching powder on Standing undergoes slow auto-oxidation to form a moisture of CaClO3 and CaCl2. The amount of Cl2 which is liberated by the action of excess of dil-acids or CO2 on b.p is known as available Cl2.It is expressed as the number of parts By wt. of Cl2 which is liberated from 100 parts by wt. of b.p on treatment With dil.acids .A good sample contains 35-37% of available Cl2. Chemical Properties:- Reaction with insufficient dilute acids, HOCl is produced which is decomposed to give nascent O. This nascent O is responsible for the Oxidizing and bleaching action of b.p. 2 Oxidizing action:1. Ca(OCl)Cl+H2S=CaCl2+H2O+S 2. Ca(OCl)Cl+2KI+2HCl=CaCl2+2KCl+H2O+I2 3. Na3AsO3+Ca(OCl)Cl=Na3AsO4+CaCl2 4. Ca(OCl)Cl+2FeSO4+H2SO4=Fe2(SO4)3+CaCl2+H2O. 5. Ca(OCl)Cl+KNO2=KNO3+CaCl2 6. Ca(OCl)Cl+2NH3=CaCl2+N2+3H2O. 7. CaOCl2+MnSO4+2NaOH=CaCl2+MnO2+Na2SO4+H2O 8. CaOCl2+Pb(NO3)2+2NaOH=CaCl2+PbO2+2NaNO3+H2O Bleaching action:- Coloured matter 0

Uses
(i) Bleaching cotton, linean and wood pulp. (ii) As disinfectant and germicide for drains and for sterlising drinking Water. (iii) Manufacture of CHCl3 and oxidizing agent. When KI and CH3COOH are added to a suspension of B.P in water a brown colour is obtained. EDUDIGM 1B Panditya Road, Kolkata 29
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Fluorine CaOCl2+2CH3COOH=(CH3COO)2Ca+Cl2+H2O 2KI+Cl2+2KCl+I2 (brown colour).

Page 28

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