1. Chapter 18 Reaction Rates and Equilibrium
18.1 Rates of Reaction
18.2 The Progress of Chemical
Reactions
18.3 Reversible Reactions
and Equilibrium
18.4 Solubility Equilibrium
18.5 Free Energy and Entropy
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2. Rate Laws
rate = = k × [A] ΔA Δt
This equation is a rate law, an expression for the rate of a reaction in terms of the concentration of the reactants.
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3. Rate Laws
rate = = k × [A] ΔA Δt
This equation is a rate law, an expression for the rate of a reaction in terms of the concentration of the reactants.
The specific rate constant (k) for a reaction is a proportionality constant relating the concentrations of reactants to the rate of the reaction.
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4. Rate Laws
The value of the specific rate constant, k, in a rate law is large if the products form quickly; the value is small if the products form slowly.
rate = = k × [A] ΔA Δt
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5. First-Order Reactions
Rate Laws
First-Order Reactions
The order of a reaction is the power to which the concentration of a reactant must be raised to match the experimental data on concentration and rate.
In a first-order reaction, the rate is directly proportional to the concentration of only one reactant.
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6. Interpret Graphs
Over time, the rate of reaction decreases because the concentration of the reactant is decreasing.
The reaction A  B is a first-order reaction.
If [A] is reduced by one half, the reaction rate is reduced by one half.
The rate (ΔA/Δt) at any point on the graph equals the slope of the tangent to the curve at that point.
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7. Higher-Order Reactions
Rate Laws
Higher-Order Reactions
In some reactions, two substances react to produce products.
In the general equation for a double-replacement reaction below, the coefficients are represented by lowercase letters.
aA + bB  cC + dD
For the reaction of A with B, the rate of reaction is dependent on the concentrations of both A and B.
rate = k[A]x[B]y
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8. Higher-Order Reactions
Rate Laws
Higher-Order Reactions
rate = k[A]x[B]y
When each exponent in the rate law equals 1 (that is, x = y = 1) the reaction is said to be first order in A and first order in B.
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9. Higher-Order Reactions
Rate Laws
Higher-Order Reactions
The overall order of a reaction is the sum of the exponents for the individual reactants.
A reaction that is first order in A and first order in B is thus second order overall.
The actual order of a reaction must be determined by experiment.
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10. Finding the Order of a Reaction from Experimental Data
Sample Problem 18.1
Finding the Order of a Reaction from Experimental Data
Consider the reaction aA  B. The rate law for this reaction is Rate = k[A]x. From the data in the table, find the order of the reaction with respect to A and the overall order of the reaction.
Trial
Initial concentration of A (mol/L)
Initial rate (mol/(L·s)) 1
0.050
3.0  10–4 2
0.10
12  10–4 3
0.20
48  10–4
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11. Analyze List the knowns and the unknowns.
Sample Problem 18.1
Analyze List the knowns and the unknowns. 1
Use the first two trials to calculate the order and the third to evaluate your answer.
KNOWNS
[A]1 = mol/L
[A]2 = 0.10 mol/L
Rate1 = 3.0  10–4 mol/(L·s)
Rate2 = 12  10–4 mol/(L·s)
UNKNOWN
Order of reaction with respect to A = ?
Overall order of the reaction = ?
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12. Calculate Solve for the unknowns.
Sample Problem 18.1
Calculate Solve for the unknowns. 2
Start with the rate law for each initial concentration of A.
The rate law of the reaction and the specific rate constant, k, is the same for any initial concentration of A.
Rate1 = k [A1]x
Rate2 = k [A2]x
Divide the second expression by the first expression.
= = ( )
Rate k [A1]x
Rate k [A2]x
[A2]
[A1] x
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13. Calculate Solve for the unknowns.
Sample Problem 18.1
Calculate Solve for the unknowns. 2
Substitute the known quantities into the equation.
= ( )
3.0  10–4 mol/(L·s)
12  10–4 mol/(L·s)
0.10 mol/L
0.050 mol/L x
4.0 = 2.0x
Determine the value of x.
x = 2
The reaction is second order in A.
Since A is the only reactant, the reaction must be second order overall.
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14. aA  bB + cC The following reaction is a second-order reaction.
If the initial concentration of A is 2.0 mol/L and the initial rate is 9.6  10–7 mol/(L·s), what is the concentration when the rate is 1.2  10–7 mol/(L·s)?
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15. aA  bB + cC The following reaction is a second-order reaction.
If the initial concentration of A is 2.0 mol/L and the initial rate is 9.6  10–7 mol/(L·s), what is the concentration when the rate is 1.2  10–7 mol/(L·s)?
1.2  10–7 mol/(L·s)
9.6  10–7 mol/(L·s)
= ( )
[A2]
2.0 mol/L 2
[A2] = 0.71 mol/L
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16. One-Step and Multistep Reactions
Reaction Mechanisms
One-Step and Multistep Reactions
An elementary reaction is a reaction in which reactants are converted to products in a single step.
This type of reaction has only one activation-energy peak and one activated complex.
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17. One-Step and Multistep Reactions
Reaction Mechanisms
One-Step and Multistep Reactions
Most chemical reactions consist of two or more elementary reactions.
The series of elementary reactions or steps that take place during the course of a complex reaction is called a reaction mechanism.
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18. One-Step and Multistep Reactions
Reaction Mechanisms
One-Step and Multistep Reactions
An intermediate is a product of one step in a reaction mechanism and a reactant in the next step.
An intermediate has a more stable structure and longer lifetime than an activated complex.
Intermediates do not appear in the overall chemical equation for a reaction.
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19. Rate-Determining Steps
Reaction Mechanisms
Rate-Determining Steps
In a multistep chemical reaction, the steps do not all progress at the same rate.
One step will be slower than the others.
The slowest step will determine, or limit, the rate of the overall reaction.
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20. Rate-Determining Steps
Reaction Mechanisms
Rate-Determining Steps
Consider the reaction mechanism for the decomposition of nitrous oxide (N2O). Experiments have shown that the mechanism consists of the two steps shown below.
N2O(g) N2(g) +O(g)
N2O(g) + O(g) N2(g) + O2(g)
2N2O (g) 2N2(g) + O2(g)
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21. Rate-Determining Steps
Reaction Mechanisms
Rate-Determining Steps
N2O(g) N2(g) +O(g)
N2O(g) + O(g) N2(g) + O2(g)
2N2O (g) 2N2(g) + O2(g)
In the first step, nitrous oxide decomposes into nitrogen gas and oxygen atoms.
The oxygen atoms are an intermediate.
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22. Rate-Determining Steps
Reaction Mechanisms
Rate-Determining Steps
N2O(g) N2(g) +O(g)
N2O(g) + O(g) N2(g) + O2(g)
2N2O (g) 2N2(g) + O2(g)
For the decomposition of nitrous oxide, the first step is the rate-determining step.
To increase the rate of the overall reaction, you would need to increase the rate of the first step.
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23. In the following reaction mechanism, which is an intermediate?
A2 2A
2A + B2 2AB
A2 + B2 2AB
A. A2 C. A
B. B2 D. AB
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24. In the following reaction mechanism, which is an intermediate?
A2 2A
2A + B2 2AB
A2 + B2 2AB
A. A2 C. A
B. B2 D. AB
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25. Key Concepts and Key Equations
The value of the specific rate constant, k, in a rate law is large if the products form quickly; the value is small if the products form slowly.
Most chemical reactions consist of two or more elementary reactions.
Rate = = k  [A] DA Dt
Rate = k[A]x[B]y
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26. Glossary Terms
rate law: an expression relating the rate of a reaction to the concentration of the reactants
specific rate constant: a proportionality constant relating the concentrations of reactants to the rate of the reaction
first-order reaction: a reaction in which the reaction rate is proportional to the concentration of only one reactant
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27. Glossary Terms
elementary reaction: a reaction in which reactants are converted to products in a single step
reaction mechanism: a series of elementary reactions that take place during the course of a complex reaction
intermediate: a product of one of the steps in a reaction mechanism; it becomes a reactant in the next step
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