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    Halogen

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    Putri Dierla Dela
    The document summarizes information about the halogens. It discusses their [1] position in the periodic table, [2] general properties such as melting/boiling points and electronegativity, [3] bonding and oxidation states, [4] colors, [5] variation in chemical properties including oxidizing power and reactions with water, alkalis, acids, and silver nitrate. The halogens become less reactive down the group as atomic size increases due to weaker electron attraction.

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    Halogen

    Uploaded by

    Putri Dierla Dela
    50 views37 pages
    The document summarizes information about the halogens. It discusses their [1] position in the periodic table, [2] general properties such as melting/boiling points and electronegativity, [3] bonding and oxidation states, [4] colors, [5] variation in chemical properties including oxidizing power and reactions with water, alkalis, acids, and silver nitrate. The halogens become less reactive down the group as atomic size increases due to weaker electron attraction.

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    Halogen

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    The document summarizes information about the halogens. It discusses their [1] position in the periodic table, [2] general properties such as melting/boiling points and electronegativity, [3] bonding and oxidation states, [4] colors, [5] variation in chemical properties including oxidizing power and reactions with water, alkalis, acids, and silver nitrate. The halogens become less reactive down the group as atomic size increases due to weaker electron attraction.

    Copyright:

    © All Rights Reserved
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    50 views37 pages

    Halogen

    Uploaded by

    Putri Dierla Dela
    The document summarizes information about the halogens. It discusses their [1] position in the periodic table, [2] general properties such as melting/boiling points and electronegativity, [3] bonding and oxidation states, [4] colors, [5] variation in chemical properties including oxidizing power and reactions with water, alkalis, acids, and silver nitrate. The halogens become less reactive down the group as atomic size increases due to weaker electron attraction.

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    The Halogens

    Position in Periodic Table


    Gp VII

    Cl

    Br

    At
    General information
    Halogen Atomic Ionic Melting Boiling Density (g Abundance
    radius (nm) radius (nm) Point (oC) Point (oC) cm-3) on Earth
    (%)
    Fluorine 0.072 0.133 -220 -188 1.11 0.062

    Chlorine 0.099 0.181 -101 -34.7 1.56 0.013

    Bromine 0.114 0.195 -7.2 58.8 3.12 0.0003

    Iodine 0.133 0.216 114 184 4.93 0.00005

    Astatine - - 302 380 - Trace


    Characteristic properties
    • Very reactive non-metals
    – High electronegativity
    – High electron affinity
    • Bonding and Oxidation states
    • Colour
    Electronegativity

    A measure of the attracting Element EN value


    ability of bonding electrons.
    F 4.0
    Due to their large effective
    Cl 3.0
    nuclear charge,
    halogens are the most Br 2.8
    electronegative element
    in the periodic table. I 2.5
    Electron Affinity

    Element EA
    Generally high electron
    affinity. All are exothermic.
    kJ/mol
    F -348
    X(g) + e-  X-(aq)
    Cl -364
    Br -342
    I -285
    Bonding and Oxidation State
    • ns2np5
    • Ionic or covalent bond with oxidation
    state –1 or +1 (F shows –1 only)
    • Except F, all other halogens can expand
    their octet by using the low-lying, vacant d-
    orbitals to form bonding. Their oxidation
    states range from –1 to +7.
    Bonding and Oxidation State

     nd

    nd    np

       np  ns

     ns (+3 states)

    (0, +1, -1 states) HClO2, ClO2-


    Cl2, Cl-, OCl2
    Bonding and Oxidation State

       nd

      nd    np

       np  ns

     ns (+7 state)

    (+5 state) Cl2O7, HIO4


    HClO3, HBrO3, I2O5
    Colour
    Element Colour

    In Standard State In Water In 1,1,1-


    trichloroethane
    F Pale yellow Pale yellow Pale yellow

    Cl Greenish yellow Pale yellow Yellow

    Br Reddish brown Yellow Orange

    I Violet black Brown Violet


    Colour

    White light

    Iodine
    Check point 40-1

    E2

    E1

    Iodine Fluorine
    Variation in properties of
    Halogens

    b.p.
    400

    (Temp. oC) m.p.

    m.p./b.p. increase as Mr increase


    0because Van der Waals’ Force increase
    with Mr F Cl Br I At

    -300
    Electronegativity

    4 4.0
    F form ionic compound
    3.0 with –1 oxidation state.
    3 2.8
    2.5
    I shows highly positive
    2 oxidation states with
    more electronegative
    1 element.
    e.g. KIO4

    F Cl Br I
    Electron affinity
    EA decrease from
    Cl to I due to increasing
    atomic size which lowers
    340
    the nuclear attraction to
    the added electron.
    320
    F has exceptional lower
    EA because its 2nd shell
    is already crowded with
    280
    7 e-, the additional e-
    will experienced a greater
    F Cl Br I e-e repulsion than other
    halogens.
    Variation in Chemical Properties
    of elements
    All are good oxidizing agents. (F2>Cl2>Br2>I2)
    H
    ½ X2(std.state)  X-(aq)

    Hatom
    Hhyd
    X(g)

    HEA

    X-(g)
    H = Hatom + HEA+ Hhyd
    Oxidizing power
    Element
    Hatom HEA Hhyd H
    F 79.1 -348 -506 -774.9

    Cl 121 -364 -364 -607

    Br 112 -342 -335 -565

    I 107 -314 -293 -500 Oxidizing


    strength
    Oxidizing properties
    Standard electrode
    1. Oxidation of metals potential (V)
    a. F2 oxidizes all metals Cl2+e- 1.36
    including Au and Ag. Cl-
    b. Cl2 oxidizes common
    Br2+e- 1.07
    metals such as Na and Cu. Br-

    2. Reactions withFe2+(aq) I2+e- 0.54


    I-
    2Fe2+ + Cl22Fe3+ + 2Cl-
    2Fe2+ + Br22Fe3+ + 2Br- Fe3++e- 0.77
    2Fe3+ + 2I-2Fe2+ + I2 Fe2+
    Oxidizing properties
    3. Reaction with phosphorus
    2P + 3X2  2PX3
    2P + 5X2  2PX5

    F2 and Cl2 form PX5 as they have high oxidizing


    Strength. They combine with P to exhibit its maximum
    oxidation state.

    Br2 and I2 form PX3 only.


    Reaction with water
    Fluorine oxidizes water to form HF and O2

    2F2 + 2H2O  2HF + O2

    Chlorine undergoes disproportionation(self oxidation


    and reduction) to form HCl and HOCl.

    Cl2 + H2O  HCl + HOCl


    Reaction with water
    A mixture of Cl2(aq), HCl(aq) and HOCl(aq)
    is called chlorine water.

    OCl- , chloric(I) ion

    1. Strong oxidizing agent with bleaching property


    OCl- + dye (coloured)  Cl- + dye (colourless)
    2. Unstable to heat and light
    2OCl-  O2 + 2Cl-
    Reaction with water

    Br2 is only slightly soluble in water.


    Br2 (aq) + H2O (l)  HBr(aq) + HOBr(aq)

    OBr-(aq) is unstable and with bleaching property:


    1. 2OBr-  O2 + 2Br-
    2. OBr- + dye(coloured)  Br- + dye(colourless)
    Reaction with water

    I2 does not react with water and only very


    slightly soluble in water.

    I2 is more soluble in ethanol or in KI(aq).


    I2(aq) + I-(aq)  I3-(aq)
    Reaction with alkalis

    All halogens react with aqueous alkalis and


    disproportionate in it. The products depend on
    temperature
    and
    concentration of the alkalis.
    Reaction with alkalis
    Cold 2F2 + 2NaOH  2NaF + OF2 + H2O
    dil.NaOH
    Cl2 + 2NaOH  NaCl + NaOCl + H2O

    Br2 + 2NaOH  NaBr + NaOBr + H2O


    3NaOBr  2NaBr + NaBrO3
    (3Br2 + 6NaOH  5NaBr + NaBrO3 + 3H2O

    I2 + 2NaOH  NaI + NaOI + H2O


    3NaOI  2NaI+ NaIO3
    (3I2 + 6NaOH  5NaI + NaIO3 + 3H2O
    Reaction with alkalis
    More 2F2 + 4NaOH  4NaF + O2 + 2H2O
    concentrated
    NaOH
    Hot Cl2 + 2NaOH  NaCl + NaCl + H2O
    concentrated 3NaOCl  2NaCl + NaClO3
    NaOH (3Cl2 + 6NaOH  5NaCl + NaClO3 + 3H2O
    Reaction with alkalis
    The reverse reaction of I2 and KOH is used
    to prepare standard iodine solution for iodometric
    titration. Know amount of iodine is generated by
    dissolving known quantity of KIO3 in excess KI
    and H+.

    5KI + KIO3 + 3H+  3I2 + 6K+ + 3H2O


    Variation in properties of halides
    Halogen Displacement reactions

    Oxidizing strength : F2 >Cl2 >Br2 >I2

    Cl2 + 2Br-  2Cl- + Br2

    Cl2 + 2I-  2Cl- + I2

    Br2 + 2I-  2Br- + I2


    Halide + c. H2SO4
    NaCl + H2SO4  NaHSO4 + HCl
    2NaCl + H2SO4  Na2SO4 + HCl (500oC)

    2NaBr + 2H2SO4  2HBr + Na2SO4


    2HI + H2SO4  SO2 + Br2 + 2H2O

    2NaI + 2H2SO4  2HI + Na2SO4


    8HI + H2SO4  H2S + 4I2 + 4H2O

    Relative reducing power: HCl < HBr < HI


    Halide + c. H3PO4
    3NaCl + H3PO4  Na3PO4 + 3HCl
    3NaBr + H3PO4  Na3PO4 + 3HBr
    3NaI + H3PO4  Na3PO4 + 3HI

    H3PO4 is NOT a strong oxidizing agent.


    It reacts with halides to form HX.
    Halides + +
    Ag (aq)
    Ag+(aq) + Cl-(aq)  AgCl(s) , white precipitate

    Ag+(aq) + Br-(aq)  AgBr(s) , pale yellow precipitate

    Ag+(aq) + I-(aq)  AgI(s) , yellow precipitate


    Halides + +
    Ag (aq)
    Ion Action of Effect of Effect of
    AgNO3= Standing in adding excess
    sunlight aq. NH3
    Cl- White ppt. Turns grey White ppt.
    dissolves

    Br- Pale yellow ppt. Turns Pale yellow ppt.


    yellowish grey slightly
    dissolves
    I- Yellow ppt. Remains Yellow ppt.
    yellow does not
    dissolve
    Relative acidity of HX
    Hydrogen Halide Dissociation constant Degree of dissociation
    in 0.1M solution
    HF 7x10-4 0.085

    HCl 1x107 0.920

    HBr 1x109 0.930

    HI 1x1011 0.950
    Relative Acidity of HX
    H
    HX(aq) H+(aq) + X-(aq)

    H5 H6
    H1
    H+(g) + X-(g)

    H3 H4
    H2
    HX(g) H (g) + X (g)
    Relative Acidity of HX

    HX H1 H2 H3 H4 H5 H6 H TS G

    HF 48 566 1311 -333 -1091 -515 -14 -29 15

    HCl 18 431
    Explanation of weak acid strength
    1311 -348 -1091 -381 -60
    of HF:
    -13 -47
    • HF has the greatest bond dissociation
    HBr 21 366 energy-324
    1311 and exceptionally
    -1091 -347 small -64 -4 -60
    electron affinity. It has the least
    HI 23 299 1311 -295 H.
    exothermic -1091 -305 -58 4 -62
    2. Due to formation of strong hydrogen
    bond and greatest degree of hydration,
    HF has the smallest decrease of TS.
    Anomalous behaviour of HF

    According to La Chatelier’s Principle, the degree


    of dissociation of a weak acid increases with dilution.
    HA H+ + X-
    However, the acidity of conc. HF is greater than
    dilute HF. Why?

    In conc. HF, HF molecules form dimers H2F2 by


    hydrogen bond. The acid strength of H2F2 is
    stronger than HF.
    H2F2  H+ + HF2-
    Uses of Halogens and Halides
    • Teflon
    • Na2SiF6 or NaF is used to fluoridate drinking
    water.
    • Chlorine bleach, sterilization of water, PVC.
    • Anti-knocking agent (leaded petrol)
    • AgBr coating in film
    • Iodine tincture
    • AgI in coating film

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