copyright©2000 by houghton mifflin company. all rights reserved. 1 figure 13.1 a molecular...

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Copyright©2000 by Houghto n Mifflin Company. All ri ghts reserved. 1 Figure 13.1 A Molecular Representation of the Reaction 2NO 2 (g) g) Over Time in a Closed Vessel

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Copyright©2000 by Houghton Mifflin Company. All rights reserved.

1

Figure 13.1A Molecular Representation of the Reaction 2NO2(g) g) Over

Time in a Closed Vessel

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2

Chemical Equilibrium

The state where the concentrations of all reactants and products remain constant with time.

On the molecular level, there is frantic activity. Equilibrium is not static, but is a highly dynamic situation.

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3

Figure 13.2Changes in Concentrations

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4

Figure 13.3H20 and CO Begin to React and

Reach Equilibrium

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5

Figure 13.4The Changes with Time in the Rates of

Forward and Reverse Reactions

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6

The Haber Rxn

N2 + 3H2 → 2NH3 all (g);

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7

Figure 13.5 The Ammonia Synthesis Equilibrium

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8

The Law of Mass Action

For

jA + kB lC + mD

The law of mass action is represented by the equilibrium expression:

Kl m

j k C DA B

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9

Equilibrium Expression

4NH3(g) + 7O2(g) 4NO2(g) + 6H2O(g)

K NO H O

NH O2

2

24 6

34 7

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10

Notes on Equilibrium Expressions

The Equilibrium Expression for a reaction is the reciprocal of that for the reaction written in reverse.

When the equation for a reaction is multiplied by n, EEnew = (EEoriginal)n

The units for K depend on the reaction being considered. So, we will omit them!

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11

K v. Kp

For

jA + kB lC + mD

Kp = K(RT)n

n = sum of coefficients of gaseous products minus sum of coefficients of gaseous reactants.

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12

Heterogeneous Equilibria

. . . are equilibria that involve more than one phase.

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

K = [CO2]

The position of a heterogeneous equilibrium does not depend on the amounts of pure solids or liquids present.

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13

Figure 13.6CaCO3(s) CaO(s) + CO2(g)

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14

Figure 13.7The Difference between Thermodynamic and Kinetic Stabilities

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15

Reaction Quotient

. . . helps to determine the direction of the move toward equilibrium.

The law of mass action is applied with initial concentrations.

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16

Reaction Quotient (continued)

H2(g) + F2(g) 2HF(g)

Q HF

H F2 2

02

0 0

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17

Solving Equilibrium Problems

1. Balance the equation.

2. Write the equilibrium expression.

3. List the initial concentrations.

4. Calculate Q and determine the shift to equilibrium.

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18

Solving Equilibrium Problems(continued)

5. Define equilibrium concentrations.

6. Substitute equilibrium concentrations into equilibrium expression and solve.

7. Check calculated concentrations by calculating K.

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19

Le Châtelier’s Principle

. . . if a change is imposed on a system at equilibrium, the position of the equilibrium will shift in a direction that tends to reduce that change.

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20

Figure 13.8A Mixture of N2, H2, and NH3

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21

Effects of Changes on the System

1. Concentration: The system will shift away from the added

component.

2. Temperature: K will change depending upon the temperature (treat the energy change as a reactant).

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22

Effects of Changes on the System (continued)

3. Pressure:

a. Addition of inert gas does not affect the equilibrium position.

b. Decreasing the volume shifts the equilibrium toward the side with fewer moles.

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23

Figure 13.9The Effect of Decreased Volume on the

Ammonia Synthesis Equilibrium