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    Ghada El-Zakhem Naous

    Chemistry preparatory course


    Chemical Equilibrium

    Topic 7
    Equilibrium is a state in which there are no observable
    changes as time goes by.

    Chemical equilibrium is achieved when:


    • the rates of the forward and reverse reactions are equal
    • the ratio of the concentrations of the reactants and products
    remain constant

    Physical equilibrium
    NO2
    H2O (l) H2O (g)

    Chemical equilibrium
    N2O4 (g) 2NO2 (g)
    N2O4 (g) 2NO2 (g)

    equilibrium equilibrium

    equilibrium

    Start with NO2 Start with N2O4 Start with NO2 & N2O4
    N2O4 (g) 2NO2 (g)

    [NO2]2
    K= = 4.63 x 10-3
    [N2O4]

    aAaq + bBaq cCaq + dDaq

    [C]c[D]d
    K= Law of Mass Action
    [A]a[B]b
    [C]c[D]d
    K= aA + bB cC + dD
    [A]a[B]b

    Equilibrium Will
    K >> 1 Lie to the right Favor products
    K << 1 Lie to the left Favor reactants

    6
    Equilibrium expression

    CH3COOH (aq) + H2O (l) CH3COO- (aq) + H3O+ (aq)

    [CH3COO-][H3O+]
    Kc =
    [CH3COOH]

    The concentration of solids and pure liquids are not


    included in the expression for the equilibrium constant.

    General practice not to include units for the equilibrium


    constant.
    Application on K or Kc

    The following equilibrium process has been studied at 230°C:


    2NO(g) + O2(g) 2NO2(g)

    In one experiment, the concentrations of the reacting species


    at equilibrium are found to be [NO] = 0.0542 M, [O2] = 0.127
    M, and [NO2] = 15.5 M.
    Calculate the equilibrium constant (Kc) of the reaction at this
    temperature.
    Strategy The concentrations given are equilibrium
    concentrations. They have units of mol/L, so we can calculate
    the equilibrium constant (Kc) using the law of mass action

    Solution The equilibrium constant is given by

    [NO2 ]2
    Kc =
    [NO]2 [O 2 ]
    Substituting the concentrations, we find that

    (15.5)2 5
    Kc = = 6.44 × 10
    (0.0542)2 (0.127)
    Kc versus Kp, Kp could be used in gaseous equilibrium

    N2O4 (g) 2NO2 (g)

    2
    PNO
    [NO2]2
    Kc = Kp =
    2

    [N2O4] PN2O4
    In most cases
    Kc  Kp
    Application on Kp
    The equilibrium constant KP for the decomposition of
    phosphorus pentachloride to phosphorus trichloride and
    molecular chlorine

    PCl5(g) PCl3(g) + Cl2(g)

    is found to be 1.05 at 250°C.


    If the equilibrium partial pressures of PCl5 and PCl3 are
    0.875 atm and 0.463 atm, respectively, what is the
    equilibrium partial pressure of Cl2 at 250°C?
    Solution
    First, we write KP in terms of the partial pressures of the
    reacting species
    PPCl3 PCl2
    Kp =
    PPCl5
    Knowing the partial pressures, we write

    (0.463)(PCl2 )
    1.05 =
    (0.875)

    (1.05)(0.875)
    PCl2 = = 1.98 atm
    (0.463)
    Writing Equilibrium Constant Expressions

    1.The concentrations of the reacting species in the condensed


    phase are expressed in M.

    2.In the gaseous phase, it could be expressed in M or in atm,


    so it could be expressed as Kc or Kp.

    3.The concentrations of pure solids, pure liquids and solvents


    do not appear in the equilibrium constant expressions
    Heterogenous equilibrium applies to reactions in which
    reactants and products are in different phases.

    CaCO3 (s) CaO (s) + CO2 (g)

    [CaCO3] = constant
    [CaO] = constant

    Kc = [CO2] Kp = PCO
    2

    The concentration of solids and pure liquids are not


    included in the expression for the equilibrium constant.
    Relation between Kc and Kp

    aA (g) + bB (g) cC (g) + dD (g)

    Kp = Kc(RT)Dn

    Dn = moles of gaseous products – moles of gaseous reactants

    = (c + d) – (a + b)
    Write expressions for Kc, and KP if applicable, for the following
    reversible reactions at equilibrium:

    (a) HF(aq) + H2O(l) H3O+(aq) + F-(aq)

    (b) 2NO(g) + O2(g) 2NO2(g)

    (c) CH3COOH(aq) + C2H5OH(aq ) CH3COOC2H5(aq) +


    H2O(l)
    (d) (NH4)2Se(s) 2NH3(g) + H2Se(g)

    (e) AgCl(s) Ag+(aq) + Cl-(aq)

    (f) P4(s) + 6Cl2(g) 4PCl3(l)


    Solution

    (a)
    HF is a weak acid, so that the amount of water consumed
    in acid ionizations is negligible compared with the total
    amount of water present as solvent. Thus, we can rewrite
    the equilibrium constant as

    [H 3O + ][F - ]
    Kc =
    [HF]
    2 2
    [NO2 ] PNO
    (b) Kc = Kp = 2

    [NO]2 [O 2 ] 2
    PNO PO2

    (c) The equilibrium constant Kc is given by

    [CH 3COOC2 H5 ]
    Kc =
    [CH 3COOH][C2 H 5OH]
    Solution

    (d) Because (NH4)2Se is a solid, the equilibrium constant Kc


    is given by
    Kc = [NH3]2[H2Se]

    Alternatively, we can express the equilibrium constant KP in


    terms of the partial pressures of NH3 and H2Se:
    2
    K p = PNH 3
    PH 2Se
    (e) Here AgCl is a solid so the equilibrium constant is given
    by
    Kc = [Ag+][Cl-]
    Because no gases are present, there is no KP expression

    (f) We note that P4 is a solid and PCl3 is a liquid, so they


    do not appear in the equilibrium constant expression.
    Thus, Kc is given by
    1
    Kc = 6
    [Cl 2 ]
    We can express also as Kp
    K net equation

    [C][D] [E][F]
    A+B C+D Kc′ Kc′ = Kc′′=
    [A][B] [C][D]
    C+D E+F Kc′′
    [E][F]
    A+B E+F Kc Kc =
    [A][B]

    Kc = Kc′ x Kc′′

    If a reaction can be expressed as the sum of two or more


    reactions, the equilibrium constant for the overall reaction is
    given by the product of the equilibrium constants of the
    individual reactions.
    N2O4 (g) 2NO2 (g) 2NO2 (g) N2O4 (g)

    [NO2]2 [N2O4] 1
    K= = 4.63 x 10-3 K′ = = = 216
    [N2O4] [NO2] 2 K

    When the equation for a reversible reaction is written in


    the opposite direction, the equilibrium constant becomes
    the reciprocal of the original equilibrium constant.
    The reaction quotient (Qc) is calculated by substituting the
    initial concentrations of the reactants and products into the
    equilibrium constant (Kc) expression.
    IF
    • Qc < Kc system proceeds from left to right to reach equilibrium
    • Qc = Kc the system is at equilibrium
    • Qc > Kc system proceeds from right to left to reach equilibrium
    Application

    At the start of a reaction, there are 0.249 mol N2, 3.21 x 10-2
    mol H2, and 6.42 x 10-4 mol NH3 in a 3.50-L reaction vessel
    at 375°C. If the equilibrium constant (Kc) for the reaction
    N2(g) + 3H2(g) 2NH3(g)

    is 1.2 at this temperature, decide whether the system is at


    equilibrium. If it is not, predict which way the net reaction will
    proceed.
    The initial concentrations of the reacting species are

    0.249 mol
    [N 2 ]o = = 0.0711 M
    3.50 L
    3.21  10 −2 mol
    [H 2 ]o = = 9.17  10−3 M
    3.50 L
    6.42  10−4 mol
    [NH3 ]o = = 1.83  10 −4 M
    3.50 L
    [NH 3 ]o2 (1.83 × 10-4 ) 2
    Qc = 3
    = -3 3
    = 0.611
    [N 2 ]o [H 2 ]o (0.0711)(9.17 × 10 )

    Because Qc is smaller than Kc (1.2), the system is not at


    equilibrium. The net result will be an increase in the
    concentration of NH3 and a decrease in the concentrations of
    N2 and H2. That is, the net reaction will proceed from left to
    right until equilibrium is reached.
    Calculating Equilibrium Concentrations

    1.Express the equilibrium concentrations of all species in


    terms of the initial concentrations and a single unknown x,
    which represents the change in concentration.
    2.Write the equilibrium constant expression in terms of the
    equilibrium concentrations. Knowing the value of the
    equilibrium constant, solve for x.
    3.Having solved for x, calculate the equilibrium concentrations
    of all species.
    Application

    A mixture of 0.500 mol H2 and 0.500 mol I2 was placed in a


    1.00-L stainless-steel flask at 430°C. The equilibrium constant
    Kc for the reaction

    H2(g) + I2(g) 2HI(g)


    is 54.3 at this temperature.

    Calculate the concentrations of H2, I2, and HI at equilibrium.


    Solution

    We follow the preceding procedure to calculate the


    equilibrium concentrations.
    Step 1: The stoichiometry of the reaction is 1 mol H2 reacting
    with 1 mol I2 to yield 2 mol HI. Let x be the decrease in
    concentration (mol/L) of H2 and I2 to reach equilibrium. It
    follows that the equilibrium concentration of HI must be 2x. We
    summarize the changes in concentrations as follows:
    H2 + I2 2HI
    Initial (M): 0.500 0.500 0.000
    Change (M): -x -x + 2x
    Equilibrium (M): (0.500 - x) (0.500 - x) 2x
    Step 2: The equilibrium constant is given by

    [HI]2
    Kc =
    [H 2 ][I 2 ]

    Substituting, we get

    (2x) 2
    54.3 =
    (0.500 - x)(0.500 - x)

    Taking the square root of both sides, we get


    2x
    7.37 =
    0.500 - x
    x = 0.393 M
    Thank You

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