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    Stabilty

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    PKA19005Dini Anggraini
    The document discusses the stability of coordination compounds and factors that influence their stability. It defines stability constants and explains how thermodynamic parameters like change in free energy, enthalpy and entropy determine if a complex formation reaction is spontaneous. It also discusses various factors that can influence the stability of complexes, including the metal's oxidation state, size, and electronic configuration, as well as the properties of the ligands. Chelation is also described as increasing stability through the formation of fused chelate rings.

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    Stabilty

    Uploaded by

    PKA19005Dini Anggraini
    415 views24 pages
    The document discusses the stability of coordination compounds and factors that influence their stability. It defines stability constants and explains how thermodynamic parameters like change in free energy, enthalpy and entropy determine if a complex formation reaction is spontaneous. It also discusses various factors that can influence the stability of complexes, including the metal's oxidation state, size, and electronic configuration, as well as the properties of the ligands. Chelation is also described as increasing stability through the formation of fused chelate rings.

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    PPT Stabilty

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    The document discusses the stability of coordination compounds and factors that influence their stability. It defines stability constants and explains how thermodynamic parameters like change in free energy, enthalpy and entropy determine if a complex formation reaction is spontaneous. It also discusses various factors that can influence the stability of complexes, including the metal's oxidation state, size, and electronic configuration, as well as the properties of the ligands. Chelation is also described as increasing stability through the formation of fused chelate rings.

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    © All Rights Reserved
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    Download as ppt, pdf, or txt
    415 views24 pages

    Stabilty

    Uploaded by

    PKA19005Dini Anggraini
    The document discusses the stability of coordination compounds and factors that influence their stability. It defines stability constants and explains how thermodynamic parameters like change in free energy, enthalpy and entropy determine if a complex formation reaction is spontaneous. It also discusses various factors that can influence the stability of complexes, including the metal's oxidation state, size, and electronic configuration, as well as the properties of the ligands. Chelation is also described as increasing stability through the formation of fused chelate rings.

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    STABILITY of COORDINATION

    COMPOUND

    AMARIA
    Jurusan Kimia FMIPA
    Sub-CLO (Course Learning Outcome)

     Students are able to explain the stability of coordination


    compounds and the factors that influence

    Indicator
    1. Students are able to explain the stability constants
    2. Students are able to explain the thermodynamic parameters of
    complex compounds
    3. Students are able to explain the factors that affect the stability of
    complex compounds
    4. Students are able to predict the stability of complex compounds based
    on their reaction data
    CoCl3.6NH3 CoCl3.5NH3
    Write complexes in square brackets, with charge on
    outside
    Ex: Cu2+(aq) + 4NH3 (aq) → [Cu(NH3)4]2+ (aq)

    2+

    :NH3
    H
    | H 3
    Cu (aq) + 4 :N ─ H (aq) →
    2+
    Cu :N
    :
    | H 3N

    :N
    H

    H3
    Oxidation Numbers

    +2 +4(0) = +2

    [Cu(NH3)4]2+

    Knowing the charge on a complex ion and


    the charge on each ligand, one can
    determine the oxidation number for the
    metal.
    Thermodynamic Stability
     Stability of a complex in solution (in Lab)
     refers to the degree of association between the two
    species involved in the state of equilibrium
     the greater the association, the greater the stability
    of the compound
     The factor which actually determines whether a
    chemical process can take place spontaneously is the
    change in free energy (G) of system
     A reaction can proceed spontaneously in the direction
    corresponding to a decrease in the free energy of the
    system (negative value of G)
     The more greater negative G is the greater the
    tendency of the reaction to occur and the greater the
    capacity of the system to do useful work when
    undergoing the reaction
     G = 0, The system is in a state of equilibrium
     At the constant temperature and pressure the
    change in free energy, accompanying a
    reaction at absolut T is equal to the change in
    enthalpy H-T.S
     The entropy S is a measure of disorder of
    system.
     The change in entropy S is the increase
    (S positif) or decrease (S negatif) in the
    disorder of the system accompanying of
    reaction.
    Example : an increase a number particles of
    system
     The magnitude of the (stability or formation)
    equilibrium constant for the association,
    quantitatively expresses the stability.
     Thus, if we have a reaction of the type:
    M   +   4L    →   ML4
     Then the larger the stability constant, the higher
    the proportion of ML4 that exists in the solution.
     Free metal ions rarely exist in solution so that M,
    will usually be surrounded by solvent molecules
    which will compete with the ligand molecules, L,
    and be successively replaced by them
    For simplicity, we generally ignore these solvent
    molecules and write four stability constants as
    follows:
    1. M + L → ML            K1 = [ML] / [M] [L]
    2. ML + L → ML2        K2 = [ML2] / [ML] [L]
    3. ML2 + L → ML3      K3 = [ML3] / [ML2] [L]
    4. ML3 + L → ML4      K4 = [ML4] / [ML3] [L]

    where K1, K2 etc are referred to as stepwise stability


    constants. Alternatively, we can write the "Overall
    Stability Constant" thus:
    M   +   4L    →   ML4      β4 = [ML4]/ [M] [L]4
    The stepwise and overall stability constants are therefore
    related as follows:
    β4 =K1.K2.K3.K4 or more generally,
    βn =K1.K2.K3.K4 ..................Kn
     Formation of complex in water does not take place by the
    simultaneous formation of all metal-to ligand bonds, but
    the ligand replace the H2O molecules in successive step
     For formation of complex [MLn] we can write a series of
    stepwise equilibrium reaction:

    [M(H2O)6]z+ (aq) + L(aq) [M(H2O)5L]z+ (aq) + H2O (l) (1)

    [M(H2O)5L]z+ (aq) + L (aq) [M(H2O)4L2]z+ (aq) + H2O (l) (2)

    [M(H2O)4L2]z+(aq) + L (aq) [M(H2O)3L3]z+(aq) + H2O (l) (3)

    [M(H2O)3L3]z+(aq) + L (aq) [M(H2O)2L4]z+(aq) + H2O (l) (4)

    [M(H2O)2L4]z+(aq) + L(aq) [M(H2O)L5]z+(aq) + H2O (l) (5)

    [M(H2O)L5]z+(aq) + L(aq) [ML6]z+ (aq) + H2O (l) (6)


    TASK 1
    1. Please write of stepwise stability of constant of
    K1 until K6
    2. Please write of formula for β6
     The addition of the four ammine groups to
    copper shows a pattern found for most
    formation constants, in that the successive
    stability constants decrease.
    The four constants are:
    logK1 = 4.0,
    logK2 = 3.2,
    logK3 = 2.7,
    logK4 = 2.0 or
    logβ4 = 11.9
    A number of texts refer to the instability
    constant or the dissociation constant of
    coordination complexes. This value corresponds
    to the reciprocal of the formation constant,
    since the reactions referred to are those where
    fully formed complexes break down to the aqua
    ion and free ligands.

    ΔG° = -RTLnβ
    ΔG° = -2.303 RTLog10β
    ΔG° = ΔH° - TΔS°
    Worked Example
    Formation of [Ni(H2O)6 – x (NH)x]2+
    Results of pH study using a glass electrode (in 2M
    NH4NO3 aqueous solution) give values of the stepwise
    stability constant (at 303 K) of [Ni(H2O)6-x(NH3)x]2+
    (x = 1- 6) as: log K1 = 2.79; log K2 = 2.26; log K3 = 1.69;
    log K4 = 1.25; log K5 = 0.74; log K6 = 0.03.
    Calculate (a) β­6 for [Ni(NH3)6]2+, and (b) ΔG°1 (303 K). (c) if
    the value of ΔH°1 (303 K) = -16.8 kJ mol-1, calculate ΔS°1
    (a) β6 =(R
    (303 K). 𝐾1=𝑥 8.314
    𝐾2 𝑥 𝐾3 J𝑥 𝐾
    K4-1𝑥mol
    𝐾5 𝑥-1𝐾)6
    log β6 = 𝑙𝑜𝑔 𝐾1 + 𝑙𝑜𝑔 𝐾2 + 𝑙𝑜𝑔 𝐾3 + 𝑙𝑜𝑔 𝐾4 + 𝑙𝑜𝑔 𝐾5 + 𝑙𝑜𝑔 𝐾6
    log β6 = 2.79 + 2.26 + 1.69 + 1.25 + 0.74 + 0.03
    log β6 = 8.76
    β6 = 5.75 𝑥 108
    (b) ΔG°1 (303 K) refers to the stepwise formation
    of [Ni(H2O)5(NH3)]2+
    ΔG°1 (303 K) = −𝑅𝑇 ln 𝐾1
    = −ሺ8.314 𝑥 10−3 𝑥 303ሻln 102.79
    = −16.2 𝑘𝐽 𝑚𝑜𝑙 −1 A negative free energy
    indicates spontaneity

    (c) ΔS°1 (303 K)


    ΔG°1 = ΔH°1 - T ΔS°1
    ΔH°1− ΔG°1
    ΔS°1 =
    𝑇
    −16.8 −(−16.2)
    ΔS°1 (303 K) =
    303
    = −1.98 𝑥 10−3 𝑘𝐽 𝐾 −1 𝑚𝑜𝑙 −1 A negative entropy indicates
    the surrounding water is
    ΔS°1 = −1.98 𝐽 𝐾 −1 𝑚𝑜𝑙 −1 becoming more ordered
    Metal complex formation is governed by thermodynamic
    processes in aqueous solution. Free energy change (Go)
    is negative if the process is spontaneous and favored---
    which is based on enthalpy and entropy.
    Go = Ho - TSo

    When complex formation occurs between charged


    cations and anions, with a resulting partial or total
    cancellation of charge, the changes in enthalpy for these
    processes are significantly negative and usually the
    predominant factor in complex formation.

    However, the accompanying changes in entropy are


    significantly more positive because less order is imposed
    on the H2O molecules around the uncomplexed metal
    cations and anionic ligands.
    The corresponding values for Go are substantially
    negative indicating that very stable complexes are
    formed.
    FACTORS INFLUENCING THE STABILITY
    CONSTANTS OF COORDINATION
    COMPOUND
     The infuence of Oxidation state of metal
    Stability Constants of Some Fe(II) and Fe(III) Complexes

    Oxidation State +2 Oxidation State +3

    Complex Ion β n (25°C) Complex Ion β n (25°C)


    [Fe II(CN)6]4- ~1035 [Fe III(CN)6]3- ~1042

    [Fe II(phen)3]2+ ~1021 [Fe III(phen)3]3+ ~1014

    [Fe II(oxalato)3]4- ~105 [Fe III(oxalato)3]3- ~1018

    [Fe II(bipy)3]2+ ~1017 [Fe III(bipy)3]3+ ~1012


    The influence of the Size of metal ion
    Stepwise Formation Constants of Some Alkaline-Earth Complexes* (arrows
    indicate increasing stability

    Metal Ion Mg2+ Ca2+ Sr2+ Ba2+

    Ionic Radius, Å 0.65 0.99 1.13 1.35

    Complex K1 [Mg(C2O4)] [Ca(C2O4)] [Sr(C2O4)] [Ba(C2O4)]

    3.7 x 103 1.0 x 103 7.3 x 102 4.9 x 102

    Complex K1 [Mg(S2O3)] [Ca(S2O3)] [Sr(S2O3)] [Ba(S2O3)]

    0.9 x 102 1.0 x 102 2.1 x 103 4.7 x 103

    Complex K1 [Mg(EDTA)]2- [Ca(EDTA)]2- [Sr(EDTA)]2- [Ba(EDTA)]2-

    2.0 x 109 2.6 x 1011 2.3 x 109 1.7 x 108

    * The coordinated H2O molecules are not shown in the formulas of the complexes
    The influence of the electronic configuration
    of metal
    Mn(II) < Fe(II) < Co(II) < Ni(II) < Cu (II) > Zn(II) disebut deret Irving Wiliam

    Stability Constants of Som e Metal-Halide Com plexes

    Compd. βn Compd. βn Compd. βn

    [SnF3]- ~1010 (25°) [SnCl3]- 9.3 x 103 (25°) [SnBr3]- 3.6 x 102 (25°)

    [PtF4]2- not known [PtCl4]2- ~1016 (25°) [PtBr4]2- ~1020 (25°)

    [CuF4]2- not known [CuCl4]2- 2.4 x 106 (18°) [CuBr4]2- 5.2 x 108 (18°)
    Effect of Chelation on Stability Constants of Zn(II) Com plexes
    (arrows indicate increasing stability)
    Complex β n (20°C) Chelate Rings
    [Zn(NH3)4]2+ 3.1 x 1010 none
    [Zn(NH2CH2CH2NH2)2]2+ 7.9 x 1012 two, isolated
    [Zn{N(CH2CH2NH2)3}]2+ 2.5 x 1015 three, fused
    [Zn(NH3)2(H2O)2}]2+ 1.6 x 105 none
    [Zn(NH2CH2CH2NH2) (H2O)2]2+ 1.2 x 106 one
    [Zn(NH3)3(H2O)]2+ 5.0 x 108 none
    [Zn{NH(CH2CH2NH2)2}(H2O)]2+ 1.6 x 1010 two, fused
    Task 2

    1. (a) Write all the stepwise (K’s) and overall (β’s) stability
    constants for the following reactions
    (b) Estimate which of all the stepwise constants will be the
    greatest
    (c) Predict which of all the stepwise constants will be the
    smallest

    2. The value for formation constants for each step in the


    formation of [Ni(en)3]2+ are log K1 = 7.52, log K2 = 6.28, and
    log K3 = 4.26 at 30oC in 1.0 M KCl. (a) What is log β3 for
    overall formation from Ni2+ and 3 en?, (b) Why do value of K
    decrease with K1 > K2 > K3 ?
    Kinetic stability

     Inert: not easily replaced by other ligands


     labile: easily replaced by other ligands

    Influenced by external factors, such as ligands

    Read text books of Fred Basolo p. 97-106, or


    Quagliano, J. V. and Vallarino, L.M. P. 80-90

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