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    HSAB Priciple

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    negow57669

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    HSAB Priciple

    Uploaded by

    negow57669
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    9 views5 pages

    HSAB Priciple

    Uploaded by

    negow57669

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    © All Rights Reserved
    Download as DOCX, PDF, TXT or read online from Scribd
    Download as docx, pdf, or txt
    of 5

    Hard and Soft Acids and Bases (HSAB)Theory

    Hard and Soft Acids and Bases (HSAB) Theory is a qualitative concept introduced
    by Ralph Pearson to explain the stability of metal complexes and the mechanisms of
    their reactions.

    However it is possible to quantify this concept based on Klopman's FMO


    analysis using interactions between HOMO and LUMO.

    According to this theory, the Lewis acid and bases can be further divided into
    hard or soft or border line types.

    Hard Acids Soft Acids

    Small ionic radii, High


    positive charge, Strongly Large ionic radii,
    solvated, Lowpositivecharge,
    Empty orbitals in the valence shell High Completelyfilledatomicorbitals Low
    energy LUMOs. energy LUMOs.

    H+, Li+, Na+, K+, Be2+,Mg2+, Ca2+, Sr2+,


    Cu+, Ag+, Au+, Hg+, Cs+, Tl+, Hg2+Pd2+,
    Sn2+
    Cd2+, Pt2+
    Al3+, Ga3+, In3+, Cr3+, Co3+, Fe3+, La3+, Si4+,
    Ti4+, Zr4+, Th4+,

    Page1
    Hard Bases Soft Bases

    Small ionic radii, Large ionic radii,


    Highly electronegative, Intermediate electronegativity,
    Weakly polarizable, highly polarizable
    Strongly solvated,High Low energy LUMOs.
    energy LUMOs.

    H2O,OH-,F-,Cl-,CH3CO2-,PO43-, RSH, RS-, R2S, I -, CN-,


    SO42-, CO32-, NO3-, ClO4-, ROH, SCN-,S2O3-,R3P,R3As(RO)3P,R
    RO-, R2O, NH3, NC, CO, C2H4, C6H6, R-, H-

    The Borderline Lewis acids and bases have intermediate properties.

    HSAB Principle:
    According to HSAB concept,

    1. Hard acids prefer binding to the hard bases to give ionic complexes,
    whereas
    2. Soft acids prefer binding to soft bases to give covalent complexes.

    * The large electronegativity differences between hard acids and hard bases give
    rise to strong ionic interactions.

    * The electronegativities of soft acids and soft bases are almost same and hence
    have less ionic interactions.i.e.,the interactions between them are more covalent.

    * The interactions between hard acid-soft base or soft acid-hard base are mostly
    polar covalent and tend to be more reactive or less stable. The polar covalent
    compounds readily form either more ionic or more covalent compounds if they are
    allowed to react.

    Page2
    APPLICATIONS OF HSAB PRINCIPLE

    1. Recovery of Au

    The softest metal ion Au+(aq) is recovered in mining operations by


    suspending it in a dilute solution of CN-,which dissolves the Au.

    4Au(s)+8CN-(aq)+O2(g)+2H2O=>4[Au(CN)2]-(aq)+4OH-

    2. WhyisAgI(s)water-insoluble,butLiIwater-soluble?

    AgI is a soft acid-soft base combination, while LiI is hard-soft. The

    interaction between Li+ and I- ions is not strong.

    AgI(s)+H2O(l)essentiallynoreaction LiI(s) +

    H2O(l) Li+ (aq) + I- (aq)

    3. InHydrogenBonding:

    The strong hydrogen bond is possible in cases ofH2O, NH3and HF, since
    the donor atoms(F, O& N)areHARD BASESand their interactions with partially
    positively charged H, which is a HARD ACID, are stronger.

    4. Precipitationreactions:

    ThesofteracidslikeAg+,Hg+,Hg2+etc.,andborderlineacidslikeFe2+, Ni2+, Cu2+,


    Zn2+, Pb2+etc., can be precipitated as sulfides from their aqueoussolutions since S 2-
    ion is a softer base.

    CuS,HgS,NiS,FeS,ZnS,PbSetc.

    Page3
    ButCa2+andMg2+hardacids appearas carbonates CaCO3,MgCO3

    Page4
    5. OtherReactionsformationofstablecompounds:

    1 LiI + CsF ----------->LiF + CsI

    Hard-hard soft-soft

    2. AgI2-isstablebutAgF2-isuinstable.

    3. [CoF6]2-is stable but [CoI6]2-is not so stable because Co+3and F- both


    are hard and hard.

    4. Precipitates formedin the QualitativeAnalysis

    Page5

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