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

Lecture 1501 Introduction to Chemical Equilibrium

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

Equilibrium

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There are Essentially Two Types of Reactions 1. one way (goes to completion) NaOH(s) Na+(aq) + OH-(aq)
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Types of Reactions
2. Equilibrium (two opposite reactions at same time) a. dimerization 2NO2(g) N2O4(g)

Equilibrium

Figure 15.01

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b. dissociation of a weak electrolyte

CH3COOH + H2O CH3COO- + H3O+

Equilibrium

c. saturated aqueous solutions

AgCl(s) Ag+(aq) + Cl-(aq) C6H12O6(s) C6H12O6(aq)
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The Concept of Equilibrium

As a system approaches equilibrium, both the forward and reverse reactions are occurring. At equilibrium, the forward and reverse reactions are proceeding at the same rate.
Equilibrium

N2O4 2 NO2

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A System at Equilibrium
Once equilibrium is achieved, the amount of each reactant and product remains constant.

Equilibrium

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Depicting Equilibrium
Since, in a system at equilibrium, both the forward and reverse reactions are being carried out, we write its equation with a double arrow. N2O4 (g) 2 NO2 (g)

Equilibrium

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The Equilibrium Constant

Equilibrium
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EQUILIBRIUM
Dynamic chemical system in which two reactions, equal and opposite, occur simultaneously

Equilibrium

Properties
1. Appear from outside to be inert or not functioning 2. Can be initiated from either direction
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Equilibrium Can Be Reached from Either Direction

As you can see, the ratio of [NO2]2 to [N2O4] remains constant at this temperature no matter what the initial concentrations of NO2 and N2O4 are.

Equilibrium

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Equilibrium Can Be Reached from Either Direction

This is the data from the last two trials from the table on the previous slide.

Equilibrium

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N2 + 3 H 2

2 NH3

It doesnt matter whether we start with N2 and H2 or whether we start with NH3: we will have the same proportions of all three substances at equilibrium.
Equilibrium
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Kinetic Definition of Equilibrium

Rf = Rr

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At equilibrium, the rates of the forward and reverse reactions are equal.
Equilibrium

How are kf and kr related to temperature? kf and kr are temperature dependent thus, Keq is temperature dependent
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N2O4 + heat 2 NO2 (colorless) Ho = + 57.2 kJ (brown)

[NO2 ]2 KC [ N 2O 4 ]

Effect of Temperature

Kc (273 K) = 0.00077 Kc (298 K) = 0.0059

Equilibrium

The Equilibrium Constant

Forward reaction:
N2O4 (g) 2 NO2 (g)

Rate Law:
Rate = kf [N2O4]

Equilibrium

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The Equilibrium Constant

Reverse reaction:
2 NO2 (g) N2O4 (g)

Rate Law:
Rate = kr [NO2]2

Equilibrium

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The Equilibrium Constant

Therefore, at equilibrium Ratef = Rater kf [N2O4] = kr [NO2]2 Rewriting this, it becomes

kf [NO2]2 = kr [N2O4]
Equilibrium
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The Equilibrium Constant

The ratio of the rate constants is a constant at that temperature, and the expression becomes

k Keq = f kr

[NO2]2 = [N2O4]
Equilibrium

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The Equilibrium Constant

Consider the generalized reaction
aA + bB cC + dD

The equilibrium expression for this reaction would be

[C]c[D]d Kc = [A]a[B]b

Equilibrium

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Exercise 15-1
Write the equilibrium-constant expressions for
a. H2 + I2 2 HI b. Cd2+ (aq) + 4 Br- CdBr42-

Equilibrium

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The Equilibrium Constant

Since pressure is proportional to concentration for gases in a closed system, the equilibrium expression can also be written

Kp =

(PC) c (PD) d (PA) a (PB) b

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Relationship Between Kc and Kp

From the Ideal Gas Law we know that

PV = nRT
Rearranging it, we get

P=

n RT V
Equilibrium

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Relationship Between Kc and Kp

Plugging this into the expression for Kp for each substance, the relationship between Kc and Kp becomes

Kp = Kc (RT)n
where
n = (moles of gaseous product) - (moles of gaseous reactant)
Equilibrium

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Exercise 15-2
When 2.0 moles of HI(g) are placed in a 1.0 L container and allowed to come to equilibrium with its elements, it is found that 20% of the HI decomposes. What is KC and KP?

Equilibrium

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Exercise 5.2b A mixture of 0.10 mol of NO, 0.050 mol H2, and 0.10 mol of H2O is placed in a 1.0-L vessel at 300K. 2 NO(g) + 2 H2(g)

Equilibrium

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