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    Thermochemistry 4 (Born-Haber Cycle and Bond Energy) - 2022

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    The document discusses the Born-Haber cycle, which is a technique for determining the lattice energy of ionic compounds using standard enthalpy changes. It involves breaking down the formation of an ionic solid, such as NaCl, into steps including ionization, electron affinity, and lattice formation. The lattice energy can then be calculated using Hess's law and experimentally determined standard enthalpy values for the other processes. Bond energies, bond dissociation energies, and how to calculate them from standard enthalpies of formation and atomization are also explained through examples.

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    Thermochemistry 4 (Born-Haber Cycle and Bond Energy) - 2022

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    Glory
    70 views13 pages
    The document discusses the Born-Haber cycle, which is a technique for determining the lattice energy of ionic compounds using standard enthalpy changes. It involves breaking down the formation of an ionic solid, such as NaCl, into steps including ionization, electron affinity, and lattice formation. The lattice energy can then be calculated using Hess's law and experimentally determined standard enthalpy values for the other processes. Bond energies, bond dissociation energies, and how to calculate them from standard enthalpies of formation and atomization are also explained through examples.

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    Thermochemistry 4 (Born-Haber Cycle and Bond Energy) -2022

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    The document discusses the Born-Haber cycle, which is a technique for determining the lattice energy of ionic compounds using standard enthalpy changes. It involves breaking down the formation of an ionic solid, such as NaCl, into steps including ionization, electron affinity, and lattice formation. The lattice energy can then be calculated using Hess's law and experimentally determined standard enthalpy values for the other processes. Bond energies, bond dissociation energies, and how to calculate them from standard enthalpies of formation and atomization are also explained through examples.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    70 views13 pages

    Thermochemistry 4 (Born-Haber Cycle and Bond Energy) - 2022

    Uploaded by

    Glory
    The document discusses the Born-Haber cycle, which is a technique for determining the lattice energy of ionic compounds using standard enthalpy changes. It involves breaking down the formation of an ionic solid, such as NaCl, into steps including ionization, electron affinity, and lattice formation. The lattice energy can then be calculated using Hess's law and experimentally determined standard enthalpy values for the other processes. Bond energies, bond dissociation energies, and how to calculate them from standard enthalpies of formation and atomization are also explained through examples.

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    © All Rights Reserved
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    of 13

    CHM 101

    (INTRODUCTORY CHEMISTRY I)

    THERMOCHEMISTRY (4)
    Born-Haber Cycle:
    • This is a technique for applying Hess’s law to the standard enthalpy
    changes which occur when an ionic compound is formed.

    • The Born-Haber cycle allows us to understand and determine the


    lattice energies of ionic solids which are difficult to determine
    experimentally (but are calculated by means of Born-Haber Cycle).

    • Lattice energy is the enthalpy change when one mole of an ionic


    compound is formed from its constituent ions in gaseous state.
    • E.g. Na+ + Cl- NaCl ∆H = Lattice energy.
    (g) (g) → (s) L
    Born-Haber Cycle for Sodium chloride
    ……The heat of formation of sodium chloride (ΔHf0) from the sodium metal and chlorine
    gas can be experimentally measured.
    Na(s) +½Cl2(g) → NaCl(s) ΔHf0 = -411 kJ mol-1

    The formation of ionic solid sodium


    chloride form solid sodium metal and
    gaseous chlorine is not a single step
    process but goes through several
    processes. Heat changes of all the
    processes except the lattice energy
    can be experimentally measured.
    ΔHL

    Source: https://byjus.com/jee/born-haber-cycle/
    The steps involved are: (4) Chlorine atom accepts an electron to form
    (1) Solid sodium atom sublimes to gaseous chloride ion and releases energy equivalent to
    atom by absorbing heat energy (∆Hosub) electron affinity.
    Na[s] → Na[g] : ∆Hosub = Standard enthalpy of Cl(g) + e- → Cl-(g) : E.A = Electron Affinity
    sublimation or vaporization.

    (2) Gaseous sodium atom absorbs the (5) Gaseous sodium ion and gaseous chloride ion
    ionization energy to release one electron and combine to form solid sodium chloride molecule
    forms gaseous sodium ion. and releases energy equivalent to lattice energy.
    Na[g] → Na+[g] + e- : I.E = Ionization energy. Na+(g) + Cl-(g) → NaCl(s) : ∆HL = Lattice energy,
    i.e. energy involved when ions are completely
    (3) Diatomic gaseous chlorine breaks into separated in the gas state and are allowed to
    two individual atoms by absorbing bond combine to form ionic solid
    energy, such that each chlorine atom absorbs Recall:
    half of the bond energy of chlorine molecule
    1 1 1
    Cl2(g) → Cl(g) : ∆Hodiss = Heat of dissociation Na(s) + Cl2(g) → NaCl(s); ∆Hf⁰ = Change in enthalpy
    2 2 2
    of formation
    Using Hess’s Law for NaCl:
    1
    ∆Hf⁰ = ∆H sub + I.E + ∆Hodiss + E.A + ∆HL
    o
    2
    1
    ∆HL = ∆Hf⁰ - ∆Hsub - I.E - ∆Hdiss - E.A
    2

    Na(s) → Na(g) : ∆Hosub = 109 kJ mol-1


    1 1
    Cl → Cl(g) : ∆Hodiss= 121 kJ mol-1
    2 2(g) 2
    Na(s) → Na+ + e- : I.E = 494 kJ mol-1
    Cl(g) + e- → Cl-(g) : E.A = -364 kJ mol-1
    1
    Na(s) + Cl2(g) → NaCl(s); Hf⁰ = -411 kJ mol-1
    2
    1
    ∴ ∆HL= ∆Hf⁰ - ∆Hosub -
    I.E - ∆Hdiss -
    E.A
    2
    = - 411 -109 - 494 - 121 - (-364)
    = -771 kJ mol-1
    BOND ENERGY AND BOND DISSOCIATION ENERGY
    • When bonds are formed, energy is released but when bonds are broken, energy is
    absorbed.
    • The bond dissociation energy (B.D.E) for a given bond in a molecule is ∆H for the
    process in which that bond is broken in the molecule in the gas phase and the
    resulting fragments are separated by an infinite distance.
    e.g. H2(g) → 2H(g) ∆H = +422 kJ mol-1
    ∆H here ≡ ∆Hatomisation.
    For the dissociation of N2O4,
    N204(g)→2NO2(g) ∆H = +58 kJ mol-1
    ∆H ≡ Bond energy of the N – N bond in N2O4

    • Bond energy is the average value of gas-phase bond dissociation energies existing
    between the same type of bond.
    Note that Bond energy is not the negative of ∆Hf⁰
    Calculating Standard Bond Energy
    Example: CH4(g) → C(g) + 4H(g) ∆Hatom = 1662 kJ mol-1
    • 4 C-H bonds are broken.
    ∆Hatom 1662
    ჻ Average C-H bond energy = = = 415.5 kJ mol-1
    4 4

    ∆H = sum of the energies required to break old bonds(+ve) plus the sum of
    the energies released in the formation of new bonds (-ve)

    Since ∆H⁰ is +ve when bonds are broken and ∆H⁰ is -ve when bonds are
    formed,
    ∆H⁰reaction = ∑nB.Ereactants – ∑mB.Eproducts

    • B.E = Bond energy terms of the products and reactants involved in a


    chemical reaction
    • n & m are number of bonds broken and formed in the reactant(s) and
    product(s) respectively.
    • The sum of the bond energy terms in a particular compound approximately equals
    the enthalpy of atomization of that compound.

    Bond ∆H⁰ kJ mol-1 Bond ∆H⁰ kJ mol-1

    C–H 412 C–I 218

    C–C 348 N–H 391

    H–H 436 O–H 463

    C – Cl 327 S–H 344

    C – Br 284 C=C 612

    • Bond energies represent difference in enthalpy between a molecule and the atoms.
    • Heat of formation, on the other hand refers to the enthalpy difference between the
    compound and the elements in their standard states. Hence, a bond energy is not
    the negative of ∆H⁰f.
    In HCl, for example, the two processes are
    Bond breaking: HCl(g) → H(g) + Cl(g)
    1 1
    ∆H⁰f : H2(g) + Cl2(g) → HCl(g).
    2 2
    Example (1):
    Calculate the bond energy in the HCl molecule from the following information.
    ∆H⁰f for HCl = - 92.4 kJ mol-1
    Bond energies: H2, 432 kJ mol-1
    Cl2, 238 kJ mol-1
    Solution
    Hint: B.E can help us to work out ∆H⁰f values for H atoms and Cl atoms.
    432
    ∆H⁰f for H = = 216 kJ mol−1
    2
    238
    ∆H⁰f for Cl = = 119 kJ mol−1
    2
    • The bond energy of HCl is ∆H for the reaction HCl(g) → H(g) + Cl(g) (atomization)

    ∆H = 216 + 119 − − 92.4 = 427 kJ mol−1


    EXAMPLES
    Example 2:
    Calculate the B.E of C – C in C3H8 given that ∆Hatom of H= 218 kJmol-1, ∆Hatom of C = 715 kJ mol-1; ∆Hf = -98.7 kJ mol-1 and Bond energy of C –
    H = 412 kJ mol-1
    Solution:
    C3H8 → 3C(g) + 8H(g)
    ∆Hatom(C3H8) = [3∆Hatom(c) + 8∆Hatom(H)] – [ ∆Hf(C3H8)]
    = [(3 × 715) + (8 × 218)] – [-98.7]
    ∆Hatom(C3H8) = 3987.7 kJmol-1

    ∆Hatom(C3H8) = ∆Hreaction = 3987.7 kJmol-1


    In C3H8 we have,
    8 C – H bonds and 2 C – C bonds, which account for the B.D.E of C3H8.
    ჻ 3987.7 = 2B.E(C – C) + 8 B.E (C – H).
    2 B.E(C – C) = 3987.7 - 8 B.E (C – H)
    = 3987.7 – 8(412)
    = 3987.7 – 3296
    2 B.E(C – C) = 691.7
    691.7
    ჻ B.E(C – C) = = 345.8 kJ mol-1.
    2
    Example 3:
    Calculate the ∆H⁰ for the reaction below, given the following bond enthalpies
    at 298 K Bonds ∆H⁰ kJ mol
    -1

    C-H +411
    Cl-Cl +243
    C-Cl +327
    H-Cl +431

    CH4(g) +Cl2(g)→ CH3Cl +HCl


    Solution
    ∆H⁰reaction = ∑nB.Ereactants – ∑mB.Eproducts
    = [4(C-H) +1(Cl-Cl)]- [3(C-H) +1(C-Cl) +1(H-Cl)]
    = [4(411) +1(243)] –[3(411) +1(237) +1(431)
    = -104 kJ mol-1
    Example 4
    Determine the bond energy of CO2 and hence the average bond energy of C=O in CO2 given the following
    information:
    𝐶 𝑔𝑟𝑎𝑝ℎ𝑖𝑡𝑒 → 𝐶 𝑔 : ∆Ho = 715 kJ (sublimation)
    ½𝑂2 𝑔 → 𝑂 𝑔 : ∆Ho = 249 kJ (atomization)
    𝐶 𝑔𝑟𝑎𝑝ℎ𝑖𝑡𝑒 + 𝑂2 𝑔 → 𝐶𝑂2 𝑔 : ∆Ho = -393 kJ

    Solution
    𝐶𝑂2 𝑔 → 𝐶 + 2𝑂 𝑔 (atomization)
    B.E (or ∆HOatom ) = [∆Ho(sub)𝐶(𝑔𝑟𝑎𝑝ℎ𝑖𝑡𝑒) + 2 ∆Hoatom(O2] ] – [∆Hof𝐶𝑂 ]
    2
    𝑔
    = [715 +2(249)] – [-393]
    = 1606 kJ mol-1
    The structure of CO2 is O=C=O
    ∴ there are 2 C=O in CO2
    𝐵.𝐸(𝐶𝑂 )
    Average bond energy of C=O in CO2 = 2
    2

    1606
    = = 803 kJ mol-1
    2
    • Alternative method: from the information provided…..
    𝐶 𝑔𝑟𝑎𝑝ℎ𝑖𝑡𝑒 → 𝐶 𝑔 : ∆Ho = 715 kJ (sublimation)
    ½𝑂2 𝑔 → 𝑂 𝑔 : ∆Ho = 249 kJ (atomization)
    𝐶 𝑔𝑟𝑎𝑝ℎ𝑖𝑡𝑒 + 𝑂2 𝑔 → 𝐶𝑂2 𝑔 : ∆Ho = -393 kJ

    To determine bond energy of CO2 (i.e ∆Hatom of CO2); we rearrange the equations to
    ensure CO2 appears on the LHS of the equation and apply Hess’s law……..

    𝐶 𝑔𝑟𝑎𝑝ℎ𝑖𝑡𝑒 → 𝐶 𝑔 : ∆Ho = 715 kJ


    𝑂2 𝑔 → 2𝑂 𝑔 : ∆Ho = 2 × 249 kJ = 498 kJ
    𝐶𝑂2 𝑔 → 𝐶 𝑔𝑟𝑎𝑝ℎ𝑖𝑡𝑒 + 𝑂2 𝑔 : ∆Ho = +393 kJ
    𝐶𝑂2 𝑔 → 𝐶 𝑔 + 2𝑂 𝑔 : ∆Ho = 1606 kJ mol-1

    𝐵.𝐸(𝐶𝑂 )
    Average bond energy of C=O in CO2 = 2
    2

    1606 803 kJ mol-1


    = =
    2

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