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    TD 2 Enthuse

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    ipsita lahiri

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    TD 2 Enthuse

    Uploaded by

    ipsita lahiri
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    24 views43 pages

    TD 2 Enthuse

    Uploaded by

    ipsita lahiri

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    © All Rights Reserved
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    of 43

    Gibbs Energy

    To check spontaneity of a process we require knowledge of system


    as well as of surrounding.

    It is desirable and also more useful to define a parameter with the


    help of which we can check spontaneity by considering system only.

    A new mathematical term Gibbs energy was introduced to explain


    criteria of spontaneity in terms of system only.

    The Gibbs energy of a system is defined as the maximum amount of


    energy available to a system during a process that can be converted
    into useful work.
    Relationship between ∆G(P,T) and ∆Suniverse

    ΔS univ = ΔS sys + ΔSsurr

    −q sys −q sys
    ΔS univ = ΔS sys + As, ΔS surr =
    T T

    For a process at constant pressure, qp = H


    ΔHsys
    ΔS univ = ΔS sys −
    T

    TΔS univ = TΔSsys − ΔH sys

    −TΔS univ = (ΔH sys − TΔSsys൯

    ΔGsys (P,T) = −TΔSuniv ΔG sys = ΔH sys − TΔSsys


    Gibbs function 'G' is defined as,

    G = H – TS.

    Since 'G' is a combination of state variables, it is a state function.

    Gibb's energy is defined at constant pressure and temperature to


    predict spontaneity of a process considering system only.
    Criteria of Spontaneity

    GsysP = –TStotal

    (i) If, Stotal = +ve  ΔGsys (P.T) = –ve


     spontaneous process

    (ii) If, Stotal = –ve  ΔGsys (P.T) = +ve


     non-spontaneous process

    (iii) If, Stotal = 0  ΔGsys (P.T) =0

     process is at equilibrium
    Spontaneity of Reaction

    Prediction of spontaneity on basis of sign of ∆H, ∆S

    (G = H – TS)system

    H S G Description
    Reaction is spontaneous at all
    – + –
    temperature

    + – + Reaction is non-spontaneous at
    all temperature
    – Reaction is spontaneous at low
    – –
    temperature
    Reaction is spontaneous at high
    + + –
    temperature
    Note

    The temperature at which equilibrium is attained,

    G = H – TS

    At equilibrium  G = 0 ,

    ΔH
    Teq =
    ΔS
    Standard State

    Standard state of a substance is its most stable state at a pressure


    of 1 bar and at a specified temperature. (If temperature is not
    specified then it is conventionally taken to be 298 K).

    For a substance/ions in solution, standard state is 1M concentration.

    ∆Go is change in Gibbs energy at standard state while ΔG is change


    in Gibbs energy.
    Standard Gibbs free energy of formation (∆fG°)

    It is the change in Gibbs energy when 1 mole of a substance is


    formed from its elements in standard state.

    Conventionally, the Gibbs energy of formation of elements in their


    standard state is taken to be zero.

    EXAMPLE

    fGo (C, graphite) = 0

    fGo [H2(g)] = 0
    fGo [Br2(l)] = 0

    fGo [I2(s)] = 0
    Gibbs Free Energy
    change calculation

    Chemical Phase Expansion /


    Reaction Change Compression
    1. For chemical reaction at constant P and T

    (a) If H and S are given

    rG = rH – TrS

    rH = ∑ f H (products) – ∑ f H(reactants)

    rS = ∑ Sm (products) – ∑ Sm (reactants)


    (b) If standard Gibbs energy of formation(∆G∘f ) is provided

    ∆fG° = ∑ ∆fG° (products) – ∑ ∆fG° (reactants)

    Note

    The Gibbs energy of formation of elements in their standard state is


    taken to be zero.
    EXAMPLE
    Calculate the G° at 300 K for the reaction;
    Br2 (l) + Cl2(g)   2BrCl(g).
    For the reaction H° = 29.3 kJ mole-1 and the standard entropies of
    Br2 (l), Cl2(g) & BrCl(g) at the 300 K are 150, 220, 240 J mol–1K–1
    respectively.

    SOLUTION

    Ans : - 3.7 kJ
    EXAMPLE
    Show that the reaction CO(g) + 1 O 2(g)   CO2(g) at 300 K is
    2
    spontaneous and exothermic, when the standard entropy is – 0.094 kJ
    mole–1 K–1. The standard Gibbs free energies of formation for CO2 and
    CO are –394.4 and –137.2 kJmole–1, respectively.

    SOLUTION

    Ans : – 285.4 kJmole–1


    EXAMPLE
    Which of the following conditions regarding a chemical process ensures
    its spontaneity at all temperature?
    (A) H > 0, S < 0 (B) H < 0, S > 0
    (C) H < 0, S < 0 (D) H > 0, S < 0

    SOLUTION

    Ans : (B)
    EXAMPLE
    For the reaction at 25°C, X 2 O4 (l)   2XO2(g), H =2.1 kcal and
    S = 20 calK–1. The reaction wouldbe
    (A) Spontaneous (B) Non-spontaneous
    (C) At equilibrium (D) Unpredictable

    SOLUTION

    Ans : (A)
    EXAMPLE
    For the reaction at 298K, 2A+B   C
    H = 100 kcal and S = 0.050 kcal K–1. If H and S are assumed to be
    constant over the temperature range, above what temperature will the
    reaction become spontaneous?
    (A) 1000 K (B) 1500 K
    (C) 2000 K (D) 2500 K

    SOLUTION

    Ans : (C)
    EXAMPLE
    Standard entropy of X2, Y2 and XY3 are 60, 40 and 50 JK—1 mol—1,
    respectively. For reaction 1X2 + 3Y2 → XY3 ; H = — 30kJ to be at
    2 2
    equilibrium the temperature will be
    (A) 500 K (B) 750 K
    (C) 1000 K (D) 1250 K

    SOLUTION

    Ans : (B)
    2. For substance under going expansion or compression

    Consider a pure substance having a Gibbs function as follows :


    G = H – TS

    = (U + PV) – TS

    Let, the pressure and temperature are varied by infinitesimally small


    value :
    dG = dU + PdV + VdP – TdS – SdT
    dG = (dq + w) + PdV + VdP – TdS – SdT
    As, w = – PdV and dq = TdS [Assume reversible process.]

    dG = VdP – SdT
    As dG = VdP – SdT
    (a) If pressure is varied keeping temperature constant -

    dG = VdP

    Ideal Gas liquid/solid


    nRT (volume remains almost constant)
    dG = dP
    P P2
    P2
    ΔG = න VdP
    nRT
    ΔG = න dP P1
    P
    P1
    P2 Any change in pressure results in
    ΔG = nRT ln very small change in volume.
    P1
    V2 ΔG = V(P2–P1)
    Or, ΔG = −nRT ln
    V1
    (b) If temperature is changed keeping pressure constant -

    dG = –SdT

    T2

    ΔG = න SdT
    T1

    Entropy as a function of temperature will be given for problem solving.


    EXAMPLE
    Calculate G (in bar-L) when pressure over 1 mole of H2O is change from
    1 bar to 10 bar.

    (i) At 4°C (ii) At 127°C


    SOLUTION

    Ans. (i) 0.162 bar–L


    (ii) 400 R ln 10
    EXAMPLE
    Calculate G (in bar-L) when a definite mass of a monoatomic ideal gas
    at 1 bar & 27oC is expanded adiabatically against vacuum from 10 L to
    20 L (ln 2 = 0.7).

    SOLUTION

    Ans : –7 bar-L
    3. For substance under going phase change

    All phase changes are considered to occur at constant pressure and


    temperature.

    All phase change at it’s boiling point, melting point or sublimation


    point are reversible in nature.

    Hence phase changes at its boiling point, melting point or sublimation


    point will have

    (G)(P,T) = 0
    EXAMPLE
    Calculate Gm for the following process:
    (i) H2O (l, 100oC, 1 atm)    H2O (g, 100oC, 1 atm)
    (ii) H2O (l, 100oC, 1 atm)    H2O (g, 100oC, 0.5
    atm)

    SOLUTION

    Ans : (i) G = 0
    (ii) G = –2149.5 J
    EXAMPLE
    5 mole H2O (l) at 373K and 1 atm is converted into H2O (g) at 373K and
    5 atm. Calculate G for this process. [Given : R = 2Cal/K-mol, ln 5 = 1.6]

    SOLUTION

    Ans : 5.968 kCal


    EXAMPLE
    A liquid freezes into a solid (H = –1000 J/mole) at 200 K and 1 atm,
    (it's normal melting point).
    (i) What is the S value at 200 K ?
    (ii) Will the freezing be spontaneous at 150 K and 1 atm ?
    (iii) What is the value of G at 250 K and 1 atm ?
    (And it is assumed that S and H do not depend on temperature)

    SOLUTION

    Ans. (i) S = – 5 J/mole.K


    (ii) Spontaneous
    iii G = + 250 J/mole
    Gibbs free Energy change (ΔG) and non-pv work

    By first law of thermodynamics


    U = q + w
    U = q + (wPV + wnon PV)
    U = q – PV – wnon PV Q S = q/T
    U = TS – PV – wnon PV
    (U + PV) – TS = – wnon PV
    H – TS = – wnon PV
    wnon PV = wuseful = – (G) (P,T)
    (G)(P,T) = – w non PV

    The decrease in Gibb’s energy of system is equal to the useful work


    or non-PV work or electrical work.
    EXAMPLE
    For reaction :
    2A(s) + B(g)  3C(l), standard entropy change of reaction is –2 kJ
    / mol-K and standard enthalpy of combustion of A(s), B(g) and C(l) are
    –100, –60, –285 kJ/mol respectively, then find maximum useful work
    that can be obtained at 27°C and 1 bar pressure from the reaction (in
    kJ/mol) .

    SOLUTION

    Ans : 1195
    Relationship between Standard Gibb's Energy Change (G°) and Equilibrium
    Constant (K) :-

    For a reaction aA + bB   cC + dD

    rG = ∆rG° + RT l n Q

    At equilibrium G = 0 and Q = Keq


    So, G° + RT ln K = 0

    ∴ ΔG° = – RT lnKeq

    G° = –2.303RT logKeq

    Q is reaction quotient which contains concentration/partial pressure


    at any instant.
    Keq is equilibrium constant which contains concentration/partial
    pressure at equilibrium (All pressure terms should be kept in bar).
    EXAMPLE
    For reaction
    N2(g) + 3H2(g)   2NH3(g)
    At equilibrium partial pressure of N2, H2 and NH3 are 2 bar, 1 bar and
    10 2 bar respectively. At 500 K calculate
    i rG° in kcal.
    (ii) If at any instant partial pressure of N2, H2 and NH3 are 2 bar, 5
    bar and 20 bar respectively. Calculate ΔrG (ln 1.6 = 0.5).

    SOLUTION

    Ans. (i) –4.6 kcal/mole


    (ii) –4.1 kcal/mole
    EXAMPLE
    The equilibrium constant of the reaction 2C3H6(g) ⇌ C2H4(g) + C4H8(g) is

    found to fit the expression lnK = – 1.04 – 1088𝐾


    𝑇
    Calculate the standard reaction enthalpy and entropy at 400 K.

    SOLUTION

    Ans. H° = 9.04 kJ/mole


    S° = –8.64 J/moleK
    EXAMPLE
    -D Glucose undergoes mutarotation to -D-Glucose in aqueous solution.
    If at 300K there is 60% conversion. Calculate G° of the reaction. (ln 2
    = 0.7, ln 3 = 1.1) -D-Glucose ⇌ -D-Glucose

    SOLUTION

    Ans : –997.68 J/mol

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