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Chemistry, The Central Science, 11th edition Theodore L. Brown, H. Eugene LeMay, Jr., and Bruce E. Bursten

Lecture 1502 The Meaning of K and Heterogeneous Equilibrium

John D. Bookstaver St. Charles Community College Cottleville, MO

Equilibrium

2009, Prentice-Hall, Inc.

By convention

[products] coeff K eq coeff [reactants ]

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What Does the Value of K Mean?

If K>>1, the reaction is product-favored; product predominates at equilibrium.

Equilibrium

2009, Prentice-Hall, Inc.

What Does the Value of K Mean?

If K>>1, the reaction is product-favored; product predominates at equilibrium.

If K<<1, the reaction is reactant-favored; reactant predominates at equilibrium.

Equilibrium
2009, Prentice-Hall, Inc.

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if Keq > 1
[products]coeff > [reactants]coeff

the forward reaction proceeded to a greater extent than the reverse reaction to achieve equilibrium
Equilibrium

if Keq > 1
[products]coeff > [reactants]coeff

The products predominate at equilibrium (the numerator is greater than the denominator)
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Equilibrium

if Keq < 1
[products]coeff < [reactants]coeff

The forward reaction proceeded to a lesser extent than the reverse reaction to achieve equilibrium
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if Keq < 1
[products]coeff < [reactants]coeff

The reactants predominate at equilibrium (the denominator is greater than the numerator)
Equilibrium

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Exercise 15-3
For the reaction H2(g) + I2(g) 2 HI Kp = 794 at 298 K and Kp = 54 at 700 K. Is the formation of HI favored more at the higher or lower temperature?

Equilibrium

2009, Prentice-Hall, Inc.

Manipulating Equilibrium Constants

The equilibrium constant of a reaction in the reverse reaction is the reciprocal of the equilibrium constant of the forward reaction.
N2O4 (g) 2 NO2 (g)

2 = 0.212 at 100 C 2 NO2 (g) Kc = [N O 2 4] 2 4 N2O4 (g) Kc = [NO 2 = 4.72 at 100 C 2]

Equilibrium

[NO ]2

[N O ]

2009, Prentice-Hall, Inc.

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Manipulating Equilibrium Constants

The equilibrium constant of a reaction that has been multiplied by a number is the equilibrium constant raised to a power that is equal to that number.
N2O4(g)

2 = 0.212 at 100 C 2 NO2(g) Kc = [N O 2 4]

[NO ]2

2 N2O4(g) 4 NO2(g) Kc =

[NO2]4 = (0.212)2 at 100 C [N2O4]2

Equilibrium

2009, Prentice-Hall, Inc.

Manipulating Equilibrium Constants

The equilibrium constant for a net reaction made up of two or more steps is the product of the equilibrium constants for the individual steps.

Equilibrium

2009, Prentice-Hall, Inc.

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Multiple Equilibria
H3PO4 + 3 H2O PO43- + 3 H3O+
H3PO4 + H2O H2PO4- + H3O+ H2PO4- + H2O HPO42- + H3O+ HPO42- + H2O PO43- + H3O+
Equilibrium

Keq = K1. K2. K3 for the complete dissociation of phosphoric acid

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Exercise 15-4
Given that at 700 K, Kp = 54.0 for the reaction H2(g) + I2(g) 2 HI(g) And Kp = 1.04 x 10-4 for the reaction N2(g) + 3 H2(g) 2 NH3(g), Determine the value of Kp for the reaction 2 NH3(g) + 3 I2(g) 6 HI(g) + N2(g) at 700 K
Equilibrium

2009, Prentice-Hall, Inc.

Heterogeneous Equilibrium
Equilibrium
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The Concentrations of Solids and Liquids Are Essentially Constant

Both can be obtained by multiplying the density of the substance by its molar mass and both of these are constants at constant temperature.

Equilibrium

2009, Prentice-Hall, Inc.

The Concentrations of Solids and Liquids Are Essentially Constant

Therefore, the concentrations of solids and liquids do not appear in the equilibrium expression.
PbCl2 (s) Pb2+ (aq) + 2 Cl-(aq) Kc = [Pb2+] [Cl-]2
Equilibrium

2009, Prentice-Hall, Inc.

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

As long as some CaCO3 or CaO remain in the system, the amount of CO2 above the solid will remain the same.

Equilibrium

2009, Prentice-Hall, Inc.

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