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Lecture 16. The Halogens. PhD Halina Falfushynska. Group 17 elements properties. The Group 17 elements are known as the halogens. All are non-metals. • The elements exist as diatomic molecules, X2.

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Lecture 16.

The Halogens

PhD Halina Falfushynska


Group 17 elements properties
Group 17 elements properties

  • The Group 17 elements are known as the halogens. All are non-metals.

  • • The elements exist as diatomic molecules, X2.

  • • Fluorine is the most electronegative element, and forms compounds only in the –1 oxidation state. For the other halogens the oxidation states up to +7 are also observed.

  • Their melting and boiling points steadily increase with atomic number.

  • • Going down the group, the elements become less oxidizing.


  • • Astatine is radioactive, with the longest lived isotope having a half life of only several hours.

  • Fluorine and chlorine react with water. Bromine and iodine are only sparingly soluble in water but are soluble in various organic solvents such as chloroform, carbon tetrachloride, carbon disulphide and hydrocarbons to give coloured solutions.

  • • The X2 bond dissociation enthalpies generally decrease going down the group, but the value for F2 is anomalously low due to a high degree of electron–electron repulsion.


Preparation of chlorine and other halogens
Preparation of Chlorine and other halogens having a half life of only several hours.

  • By heating manganese dioxide with concentrated hydrochloric acid.

  • MnO2 + 4HCl → MnCl2 + Cl2 + 2H2O

    4NaCl + MnO2 + 4H2SO4 → MnCl2 + 4NaHSO4 + 2H2O + Cl2

  • By the action of HCl on potassium permanganate.2KMnO4 + 16HCl → 2KCl + 2MnCl2 + 8H2O + 5Cl2

  • Deacon’s process: By oxidation of hydrogen chloride gas by atmospheric oxygen in the presence of CuCl2 (catalyst) at 723 K.


Preparation of chlorine
Preparation of Chlorine having a half life of only several hours.



Preparation of chlorine and other halogens1
Preparation of Chlorine electrolysis of brine (concentrated NaCl solution). and other halogens

  • K2Cr2O7 + 6KJ +7H2SO4  4K2SO4+ Cr2(SO4)3 +3J2+ 7H2O

  • 2NaCl + 4H2SO4 + PbO2 Cl2 + Pb(HSO4)2 + 2NaHSO4 + 2H2O

  • 4HCl + CaOCl2  CaCl2 + 2Cl2  + 2H2O

  • 4HCl + O2 2H2O + 2Cl2 

  • HJO + H+ + e  1/2J2 + H2O


Preparation of bromine
Preparation of Bromine electrolysis of brine (concentrated NaCl solution).

2NaBr + H2SO4 + H2O2 = Br2 + Na2SO4 + 2H2O


Reactivity towards metals
Reactivity towards metals electrolysis of brine (concentrated NaCl solution).

They react with metals to form halides. The reactivity of the halogens decreases down the group.

Mg (s) + Br2 (l) → MgBr2 (s)

2Al + 3Cl2 → 2AlCl3

The ionic character of the halides decreases in the order MF > MCl > MBr > MI where M is a monovalent metal.

2Na + Cl2 2NaCl


Reactivity towards oxygen electrolysis of brine (concentrated NaCl solution).

Halogensformmanyoxideswithoxygenbutmostofthemareunstable. Fluorineformstwooxides OF2and O2F2. Botharestrongfluorinatingagents. O2F2oxidisesplutoniumto PuF6andthereactionisusedinremovingplutoniumas PuF6fromspentnuclearfuel.

Chlorine, bromineandiodineformoxidesinwhichtheoxidationstatesofthesehalogensrangefrom +1 to +7. Orderofstabilityofoxidesformedbyhalogens, I > Cl > Br. Thehigheroxidesofhalogenstendtobemorestablethanthelowerones.


The halogens some reactions

H electrolysis of brine (concentrated NaCl solution).

H

Cl

Cl

Halogen + metal ionic salt

Na

+

-

Cl

Na

Cl

Halogen + non-metal covalent molecule

The halogens – some reactions

1) Halogen + metal:

+

2) Halogen + non-metal:

+


Reactivity of halogens towards other non metals

Reactivity of halogens towards other halogens electrolysis of brine (concentrated NaCl solution).

Reactivity of halogens towards other non-metals

Halogens combine amongst themselves to form a number of compounds known as interhalogens of the types XX ′ , XX3′, XX5′ and XX7′ where X is a larger size halogen and X’ is smaller size halogen

Halogensreactwith a numberof non-metalstoformhalides

P4 + 6Cl2 → 4PCl3

S8 + 4Cl2 → 4S2Cl2

H2 + Cl2 → 2HCl


Reaction of Aluminium with Bromine. electrolysis of brine (concentrated NaCl solution). Aluminium is oxidized by liquid bromine.

Reaction of read Phosphorus with Bromine. The oxidation of red phosphorus with bromine proceeds under combustion.


Reactivity of halogens towards alkalies

Reactivity towards water electrolysis of brine (concentrated NaCl solution).

Reactivity of halogens towards alkalies

2NaOH + Cl2 → NaCl + NaOCl + H2O(cold and dilute)6 NaOH + 3Cl2 → 5NaCl + NaClO3 + 3H2O(hot and conc.)With dry slaked lime it gives bleaching powder.2Ca(OH)2 + 2Cl2 → Ca(OCl)2 + CaCl2 + 2H2O

Ca(OH)2 + Cl2 → CaOCl2 + H2O

When chlorine is inhaled at concentrations above 30 ppm, it begins to react with water and cells, which change it into hydrochloric acid (HCl) and hypochlorous acid (HClO) - Chlorine water.

Cl2 + H2O → HCl + HClO


Disproportionation and Comproportionation of Bromine and Iodine. Aqueous solutions of bromine and iodine are disproportionated under the influence of NaOH.

Oxidation of Iodide with Halogenates. The formation of iodine by oxidation of iodide with halogenates is dependent on the pH value.


  • A Iodine. halogen oxidises halide ions of higher atomic number.F2 + 2X– → 2F– + X2 (X = Cl, Br or I)Cl2 + 2X– → 2Cl– + X2 (X = Br or I)Br2 + 2I– → 2Br– + I2

  • The relative oxidising power of halogens can be illustrated by their reactions with water

    2F2 (g) + 2H2O (l) → 4H+ (aq) + 4F− (aq) + O2 (g)X2 (g) + H2O (l) → HX (aq) + HOX (aq)( where X = Cl or Br )4I− (aq) + 4H+ (aq) + O2 (g) → 2I2 (s) + 2H2O (l)


Chlorine water has strong oxidising and bleaching properties
Chlorine Iodine. waterhas strong oxidisingandbleachingproperties

  • Itoxidisesferroustoferric, sulphitetosulphate, sulphurdioxidetosulphuricacidandiodinetoiodicacid.2FeSO4 + H2SO4 + Cl2 → Fe2(SO4)3 + 2HClNa2SO3 + Cl2 + H2O → Na2SO4 + 2HClSO2 + 2H2O + Cl2 → H2SO4 + 2HClI2 + 6H2O + 5Cl2 → 2HIO3 + 10HCl

  • Itis a powerfulbleachingagent; bleachingactionisduetooxidation.Cl2 + H2O → 2HCl + OColouredsubstance + O → Colourlesssubstance


Hydrogen halides
Hydrogen Halides Iodine.

  • In laboratory, HCl is prepared by heating sodium chloride with concentrated sulphuric acid

    NaCl + H2SO4 → NaHSO4 + HCl (420K)

  • Hydrogen Halides can also be prepared by the hydrolysis of certain reactive halide compounds.

    PCl5 + H2O → POCl3 + 2 HCl

    2PBr3 + 6H2O → 2H3PO3 + 6HBr

  • 2P + 3Br2 + 6H2O → 2H3PO3 + 6HBr

  • S + 3Br2 + 4H2O → 6HBr + H2SO4


Hydrogen chloride
Hydrogen Chloride Iodine.

  • When three parts of concentrated HCl and one part of concentrated HNO3 are mixed, aqua regia is formed which is used for dissolving noble metals.Au + 4H+ + NO3− + 4Cl− → AuCl−4 + NO + 2H2O3Pt + 16H+ + 4NO3 + 18Cl− → 3PtCl6− + 4NO + 8H2O

  • Hydrogen chloride is a monoprotic acid. In aqueous hydrochloric acid, the H+ joins a water molecule to form a hydronium ion, H3O+:HCl + H2O → H3O+ + Cl−


  • Hydrochloric acid decomposes salts of weaker acids, e.g., carbonates, hydrogencarbonates, sulphites, etc.Na2CO3 + 2HCl → 2NaCl + H2O + CO2NaHCO3 + HCl → NaCl + H2O + CO2Na2SO3 + 2HCl → 2NaCl + H2O + SO2

  • Hydrochloric acid is the preferred acid in titration for determining the amount of bases. Azeotropic or "constant-boiling" hydrochloric acid (roughly 20.2%) can be used as a primary standard in quantitative analysis.

  • It is use in the pickling of steel, to remove rust or iron oxide scale from iron or steel before subsequent processing: Fe2O3 + Fe + 6 HCl → 3 FeCl2 + 3 H2O


Hydrochloric acid application
Hydrochloric acid application carbonates, hydrogencarbonates, sulphites, etc.

  • Regeneration of ion exchangers. Cation exchange is widely used to remove ions such as Na+ and Ca2+ from aqueous solutions, producing demineralized water. The acid is used to rinse the cations from the resins.

  • Hydrogen chloride is used to produce the hydrochloride salt of methamphetamine.

  • Hydrochloric acid is used in veterinary medicine as a gastric acidifier.


Oxoacids of halogens
Oxoacids of Halogens carbonates, hydrogencarbonates, sulphites, etc.


The structures of oxoacids of chlorine
The structures of carbonates, hydrogencarbonates, sulphites, etc.oxoacids of chlorine


Testing for halides
TESTING FOR HALIDES carbonates, hydrogencarbonates, sulphites, etc.


Uses of fluorine
Uses of Fluorine carbonates, hydrogencarbonates, sulphites, etc.

Uses of Bromine

The main use of fluorine is toothpaste even though it isn’t as fluorine itself but instead as fluoride, a compound of fluorine.

Bromine is one of the main ingredients in camera films (as silver bromide).


Uses of chlorine
Uses of Chlorine carbonates, hydrogencarbonates, sulphites, etc.

---for bleaching woodpulp (required for the manufacture of paper and rayon), cotton and textiles

--in the extraction of gold and platinum

--in the manufacture of dyes, drugs and organic compounds such as CCl4, CHCl3, DDT, refrigerants, etc.

--in sterilising drinking water

---preparation of poisonous gases such as phosgene (COCl2), tear gas (CCl3NO2), mustard gas (ClCH2CH2SCH2CH2Cl).

Chlorine gas has also been used by insurgents against the local population and coalition forces in the Iraq War in the form of chlorine bombs. On March 17, 2007, for example, three chlorine filled trucks were detonated in the Anbar province killing two and sickening over 350.


Uses of iodine
Uses of Iodine carbonates, hydrogencarbonates, sulphites, etc.

When dissolved in water, iodine can be used as a strong antiseptic or as a test for starch.


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