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    Pseudohalogen and Imterhalogen Compounds

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    Savita Chemistry
    1. Pseudohalogens are formed when two or more P-block elements combine with a unit negative charge. Examples include CN- and SCN-. 2. Pseudohalogens form dimers called pseudo halogens, such as (CN)2 and (SCN)2, which show similar chemical properties to halogens. 3. Pseudohalogens and halogens share several similarities including being dimeric, isomorphous crystal structures, undergoing addition reactions, and reacting with alkalis to form salts. They also form monobasic hydracids when reacted with hydrogen.

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    Pseudohalogen and Imterhalogen Compounds

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    Savita Chemistry
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    1. Pseudohalogens are formed when two or more P-block elements combine with a unit negative charge. Examples include CN- and SCN-. 2. Pseudohalogens form dimers called pseudo halogens, such as (CN)2 and (SCN)2, which show similar chemical properties to halogens. 3. Pseudohalogens and halogens share several similarities including being dimeric, isomorphous crystal structures, undergoing addition reactions, and reacting with alkalis to form salts. They also form monobasic hydracids when reacted with hydrogen.

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    1. Pseudohalogens are formed when two or more P-block elements combine with a unit negative charge. Examples include CN- and SCN-. 2. Pseudohalogens form dimers called pseudo halogens, such as (CN)2 and (SCN)2, which show similar chemical properties to halogens. 3. Pseudohalogens and halogens share several similarities including being dimeric, isomorphous crystal structures, undergoing addition reactions, and reacting with alkalis to form salts. They also form monobasic hydracids when reacted with hydrogen.

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    © All Rights Reserved
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    Download as pdf or txt
    78 views9 pages

    Pseudohalogen and Imterhalogen Compounds

    Uploaded by

    Savita Chemistry
    1. Pseudohalogens are formed when two or more P-block elements combine with a unit negative charge. Examples include CN- and SCN-. 2. Pseudohalogens form dimers called pseudo halogens, such as (CN)2 and (SCN)2, which show similar chemical properties to halogens. 3. Pseudohalogens and halogens share several similarities including being dimeric, isomorphous crystal structures, undergoing addition reactions, and reacting with alkalis to form salts. They also form monobasic hydracids when reacted with hydrogen.

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    PART I

    INORGANIC CHEMISTRY

    HALOGEN GROUP

    PSEUDOHALOGENS

    When two or more P-block elements combine together with a unit negative charge, they form
    pseudohalogens. E. g. CN-.

    PSEUDOHALIDE AND PSEUDOHALOGEN

    PSEUDOHALIDE-

    Univalent negative inorganic radicals composed of two or more electronegative atoms, which shows
    similar reaction to those of the halide ions.(X) –

    E.G. – CN-, SCN-, N3-

    PSEUDOHALOGEN

    Dimer of pseudohalogens is called pseudo halogens. They show similar chemical properties with
    halogens. Example – (CN)2, (SCN)2,

    SIMILARTIES WITH HALOGENS AND PSEUDOHALOGENS

    1. Like halogens pseudohalogens are also dimeric in nature and fairly volatile in the free state.

    2. pseudohalogens are isomorphous with halogens. Example (CN)2 is isomorphous to Cl2.

    3.Pseudohalogens are added to ethylene double bond like ethylene double bond.

    H2C=CH2 + Cl2 ---------------------------- H2C—CH2

    Ι Ι

    Cl Cl

    4. They show same reaction with alkali for example-

    (i) (SCN)2 + 2 KOH (COLD AND DILUTE) ----------- KSCN + KOSCN + H2O

    Cl2 + 2 KOH ----------------- KCl + KOCl +H2O

    (ii) 3(SCN) 2 + 6 KOH ( HOT AND CONC.) ----------------- 5KSCN + KSCNO2 + 3H2O

    3Cl 2 + 6KOH ( HOT AND CONC.) --------------- 5 KCl + KClO3 + 3H2O


    5. MONOBASIC HYDRACIDS

    Pseudohalogens are also combine with H2 to form monobasic hydracids like halogens.

    Cl2 + H2 ----------------- 2 HCl(CN)2 + H2 ------------ 2HCN

    6. Pseudohalogens and halogens show similar reaction with metals, for example with lead and mercury
    to form insoluble salts AgCN, Pb (SCN)2

    Ag+ + Cl- ------------- AgCl,

    Ag+ + CN- --------------- AgCN

    7. FORMATION OF MONOBASIC ACIDS

    With hydrogen theh form monobasic hydracids.

    Cl2 + H2 ------------ 2HCl

    (CN)2 H2 ----------- 2HCN

    Examples of symmetrical pseudohalogens (Ps–Ps)


    include cyanogen (CN)2, thiocyanogen (SCN)2, selenorhodane (SeCN)2, azidodithiocarbonate
    (N3CS2)2. Another complex symmetrical pseudohalogen is dicobalt octacarbonyl, Co2(CO)8. This
    substance can be considered as a dimer of the hypothetical cobalt tetracarbonyl, Co(CO)4.
    Examples of non-symmetrical pseudohalogens (Ps–X), analogous to the binary interhalogen
    compounds, are cyanogen halides (ICN, ClCN, BrCN), and other compounds. Sometimes nitrosyl
    chloride NOCl also is considered as pseudohalogen.
    INTERNALHALOGEN COMPOUND ( STRUCTURE AND REACTION)

    Interhalogen compounds are formed when two or more halogens connected with each-other through
    bond.

    Less electronegative atom is central atom and having positive oxidation state. General principle of
    oxidation state is that – odd numbered group exhibit odd oxidation state, while even numbered group
    exhibit even number oxidation state.

    CLASSIFICATION

    Interhalogens have general formula AXn , where n is equal to – 1,3,5,7

    AX- ClF, BrF, BrCl, ICl, IBr

    AX3- ClF3, BrF3, ICl3

    AX5- BrF5 , ClF5

    AX7- IF7

    THE LESS ELECTRONEGATIVE ATOM IS WRITTEN FIRST IN REPRESENTATION.

    STRUCTURE-
    Figure pentagonal bipyramidal structure of AX7
    COMMON PROPERTIES OF HALOGEN GROUP-

    IONISATION ENERGY

    ELECTRON AFFINITY

    ELECTRONEGATIVITY

    OXIDISING STATE

    OXIDISING POWER

    IONISATION ENERGY OR IONISATION POTENTIAL ( IE OR IP)

    IP is knowmn as the amount of energy required for the removal of valence electron from valence cell of
    isolated gaseous atom to form cation.

    So the ionization energy is depend on the attraction between outermost electron and nucleus. As
    moving down in a group the distance between the valence electron and nu cleus increase , the
    attraction between them are also decreases and less amount of energy is required to remove the
    electron from the shell. More over the shielding effects also works here, so the less amount of energy is
    required to remove the electron is required as we go down to the group. Iodine lose an e- easily and
    form cation and display metallic character.

    So in halogen IP decreases in a group. F shows highest IP in the group.


    ELECTRONEGATIVITY (DECREASES DOWN IN THE GROUP)

    It is a measure of tendency to attract the bondinng pair of electron of sigma bond towards itself.

    As moving down in a group the distance of e- from nucleus increases and also due to shielding effect
    electron egativity decreases down the group. F is most electronegative element in pereiodic table.
    Electronegativity decreases down in the group.

    OXIDISING STATE

    All halogens show -1 oxidation state. Accept F ,other halogens shows positive oxidation state.

    HALOGEN OXIDATION STATE


    F -1
    Cl -1,+1,+3
    Br -1,+1,+3,+5
    I -1,+1,+3,+5,+7

    OXIDISING POWER

    Halogens are strong oxidizing agent.

    Fluorin is strongest oxidizing agen, oxidizing power decrease in a group.fluorine oxidize other halogens
    also.

    F2 + 2X- ----------- 2F- + X2 (X=Cl,Br,I)

    The reactivity of the halogens decreases down in the group.

    Electron affinity decreases down in the group. But due to small size of fluorine the electron affinity of Cl
    is greater than F.

    ABNORMAL BEHAVIOR OF “F”

    F differs from other family members. The following point are responsible for the abnormal behavior of F

    - Small Size
    - High Electronegativity
    - Non availability of d orbitals.

    Hydrogen fluoride has high melting point and boiling point than other hydrogen halide, this is due to
    hydrogen bonding. Due the difference in electronegativity hydrogen fluoride make interhydrogen bond
    which is responsible for high M.P & B. P. , and this is the reason why hydrogen fluoride is liquid.
    H-F ------------ H-F------------H-F

    BY – REENU MISHRA

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