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Chemical Equilibrium
Chapter 14 Module 1 Sections 14.1, 14.2, and 14.3
Chemical Equilibrium
When compounds react, they eventually form a mixture of products and unreacted reactants, in a dynamic equilibrium.
A dynamic equilibrium consists of a forward reaction, in which substances react to give products, and a reverse reaction, in which products react to give the original reactants. Chemical equilibrium is the state reached by a reaction mixture when the rates of the forward and reverse reactions have become equal.
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Chemical Equilibrium
Much like water in a U-shape tube, there is constant mixing back and forth through the lower portion of the tube.
reactants products
Its as if the forward and reverse reactions were occurring at the same rate. The system appears to static (stationary) when, in reality, it is dynamic (in constant motion). (see Figure 14.2)
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Chemical Equilibrium
Consider the gaseous reaction of carbon monoxide and hydrogen to produce methane and steam.
CO(g ) 3H 2 (g )
Suppose you put 1.000 mol CO and 3.000 mol H2 into a 10.00-L container at 1200 K.
The rate of the forward reaction, which depends on reactant concentrations, is large at first but steadily decreases.
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Chemical Equilibrium
Consider the gaseous reaction of carbon monoxide and hydrogen to produce methane and steam.
CO(g ) 3H 2 (g )
Suppose you put 1.000 mol CO and 3.000 mol H2 into a 10.00-L container at 1200 K.
The rate of the reverse reaction starts at zero but steadily increases.
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Chemical Equilibrium
Consider the gaseous reaction of carbon monoxide and hydrogen to produce methane and steam.
CO(g ) 3H 2 (g )
Suppose you put 1.000 mol CO and 3.000 mol H2 into a 10.00-L container at 1200 K.
The forward rate decreases and the reverse rate increases until they eventually become equal and the reaction mixture has reached equilibrium.
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Chemical Equilibrium
Consider the gaseous reaction of carbon monoxide and hydrogen to produce methane and steam.
CO(g ) 3H 2 (g )
Suppose you put 1.000 mol CO and 3.000 mol H2 into a 10.00-L container at 1200 K.
Figure 14.2
The experiment begins with 1.00 mol CO and 3.000 mol H2 in a 10.00-L vessel. Note that the amounts of substances become constant at equilibrium.
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Figure 14.2
The forward rate is large at first but steadily decreases, whereas the reverse rate starts at zero and steadily increases. Eventually, both rates become equal (at equilibrium).
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Chemical Equilibrium
Another example is the Haber process for producing ammonia from N2 and H2 which does not go to completion.
N 2 ( g ) 3H 2 ( g )
2NH3 (g)
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Chemical Equilibrium
Another example is the Haber process for producing ammonia from N2 and H2 which does not go to completion.
N2 + 3 H2
2 NH3
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A Problem To Consider
Applying Stoichiometry to an Equilibrium Mixture.
Suppose we place 1.000 mol N2 and 3.000 mol H2 in a reaction vessel at 450 oC and 10.0 atmospheres of pressure. The reaction is:
N 2 ( g ) 3H 2 ( g )
2NH3 (g)
What is the composition of the equilibrium mixture if it contains 0.080 mol NH3?
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A Problem To Consider
Using the information given, set up the following table.
N 2 ( g ) 3H 2 ( g )
Starting 1.000 Change -x Equilibrium 1.000-x
2NH3 (g)
0 +2x 2x = 0.080 mol
The equilibrium amount of NH3 was given as 0.080 mol. Therefore, 2x = 0.080 mol NH3 (x = 0.040 mol).
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A Problem to Consider
Using the information given, set up the following table.
N 2 ( g ) 3H 2 ( g )
Starting 1.000 Change -x Equilibrium 1.000-x
2NH3 (g)
0 +2x 2x = 0.080 mol
A Problem to Consider
Using the information given, set up the following table.
N 2 ( g ) 3H 2 ( g )
Starting 1.000 Change -x Equilibrium 1.000-x
2NH3 (g)
0 +2x 2x = 0.080 mol
A Problem to Consider
Using the information given, set up the following table.
N 2 ( g ) 3H 2 ( g )
Starting 1.000 Change -x Equilibrium 1.000-x
2NH3 (g)
0 +2x 2x = 0.080 mol
aA bB
cC dD
[C] [D] Kc a b [ A ] [B ]
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For the general equation above, the equilibriumconstant expression would be:
aA bB
cC dD
[C] [D] Kc a b [ A ] [B ]
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The molar concentration of a substance is denoted by writing its formula in square brackets.
N 2 ( g ) 3H 2 ( g )
2NH3 (g)
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[NH 3 ] Kc 3 [N 2 ][H 2 ]
Note that the stoichiometric coefficients in the balanced equation have become the powers to which each concentration is raised.
N 2 ( g ) 3H 2 ( g )
2NH3 (g)
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A Problem To Consider
Write the equilibrium-constant expression Kc for catalytic methanation.
CO(g ) 3H 2 (g )
Write the concentrations of products in the top (numerator) of the equilibrium constant expression, and write the concentrations of reactants in the bottom (denominator).
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A Problem To Consider
Write the equilibrium-constant expression Kc for catalytic methanation.
CO(g ) 3H 2 (g )
Raise each concentration term to the power equal to the coefficient of the substance in the chemical equation.
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A Problem To Consider
Write the equilibrium-constant expression Kc for catalytic methanation.
CO(g ) 3H 2 (g )
A Problem To Consider
Write the equilibrium-constant expression Kc for the reverse of the previous reaction.
CO(g ) 3H 2 (g )
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A Problem To Consider
Our previous look at the Haber process led us to the equilibrium-constant expression below.
N 2 ( g ) 3H 2 ( g )
[NH 3 ] Kc 3 [N 2 ][H 2 ]
2
2NH3 (g)
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A Problem To Consider
Write the equilibrium-constant expression Kc when the equation for the previous reaction is written.
1 N (g ) 3 H (g ) 2 2 2 2
NH 3 (g)
Whether coefficients are fractional or not, they still become exponents in the equilibrium-constant expression.
[NH 3 ] Kc [N 2 ] [H 2 ]
1 2
3 2
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N 2O 4 ( g )
2NO2 (g)
If we start with some dinitrogen tetroxide and heat it, it begins to decompose to produce NO2.
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N 2O 4 ( g )
2NO2 (g)
2NO2 (g)
Call the decomposition of N2O4 the forward reaction and the formation of N2O4 the reverse reaction. These are elementary reactions, and you can immediately write the rate law for each.
Rate(forward) k f [N 2O4 ]
Rate(reverse) k r [NO 2 ]
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2NO2 (g)
Ultimately, this reaction reaches an equilibrium state where the rate of the forward and reverse reactions are equal, therefore:
k f [N 2O4 ] k r [NO2 ]
2NO2 (g)
Combining the constants you can identify the equilibrium constant Kc, as the ratio of the forward and reverse rate constants.
kf [NO2 ] Kc kr [ N 2O 4 ]
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CO(g ) 3 H 2 (g)
Suppose we started with initial concentrations of CO and H2 of 0.100 M and 0.300 M, respectively.
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CO(g ) 3 H 2 (g)
When the system finally settled into equilibrium we determined the equilibrium concentrations to be as follows.
Reactants [CO] = 0.0613 M [H2] = 0.1893 M Products [CH4] = 0.0387 M [H2O] = 0.0387 M
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CO(g ) 3 H 2 (g)
CO(g ) 3 H 2 (g)
CO(g ) 3 H 2 (g)
Note that regardless of initial concentrations (whether they be reactants or products) the law of mass action dictates that the reaction will always settle into an equilibrium where the equilibrium-constant expression equals Kc.
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CO(g ) 3 H 2 (g)
For example, if we repeat the previous experiment, only this time, starting with initial concentrations of products:
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CO(g ) 3 H 2 (g)
We find that these initial concentrations result in the following equilibrium concentrations.
Reactants Products
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CO(g ) 3 H 2 (g)
Substituting these values into the equilibriumconstant expression, we obtain the same result.
CO(g ) 3 H 2 (g)
Substituting these values into the equilibriumconstant expression, we obtain the same result.
n P ( )RT MRT V
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CO(g ) 3 H 2 (g)
Kp
PCH PH O
4 2
PCO PH
3
2
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K p K c ( RT)
Dn
where Dn is the sum of the moles of gaseous products in a reaction minus the sum of the moles of gaseous reactants.
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A Problem To Consider
Consider the reaction
2SO 2 (g ) O 2 (g )
2 SO 3 (g)
The Kc for the reaction is 2.8 x 102 at 1000 K. Calculate the Kp for the reaction at this temperature.
Therefore, Dn = -1
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A Problem To Consider
Consider the reaction
2SO 2 (g ) O 2 (g )
Since
2 SO 3 (g)
Dn
K p K c ( RT)
and from the equation we see that Dn = -1, we can simply substitute the given reaction temperature and the value of R (0.08206 L.atm/mol.K) to obtain Kp.
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A Problem To Consider
Consider the reaction
2SO 2 (g ) O 2 (g )
Since
2 SO 3 (g)
Dn
K p K c ( RT)
2
K p 2.8 10
1000 K)
-1
K p 3.4
aA bB
[C] [D] a b [ A ] [B ]
c d
cC dD
K forward
If we reverse :
cC dD
1 K forward
a
aA bB
b
K reverse
[ A ] [B ] c d [C] [D]
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For example,
AB
C D
K initial
[C][D] [ A][B]
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3A 3B
3 3
3C 3D
K tripled
For example,
AB
C D
K initial
[C][D] [ A][B]
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1A 1B 2 2
1 2 1 2
1C 1D 2 2
1 2
K halved
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AB C D
AB
C D EF
EF
K1 K2
K overall
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K overall K overall
(1) N 2 (g ) O 2 (g )
(2)
2 NO(g)
Kc = 4.1 x 10-31
N 2 (g ) 1 2 O 2 (g )
Using these two equations, we can obtain the Kc for the formation of NO(g) from N2O(g) (3) N 2O(g ) 1 2 O 2 (g )
2 NO(g)
Kc = ?
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(1) N 2 (g ) O 2 (g )
(2)
2 NO(g)
1 O (g ) 2 2
Kc = 4.1 x 10-31 Kc =
1 2.4 10-18
N 2O(g)
N 2 (g)
(3)
N 2O(g ) 1 2 O 2 (g )
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2 NO(g)
1 13 ) 1 . 7 10 2.4 1018
K c (overall) (4.1 10
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Heterogeneous Equilibria
A heterogeneous equilibrium is an equilibrium that involves reactants and products in more than one phase.
The equilibrium of a heterogeneous system is unaffected by the amounts of pure solids or liquids present, as long as some of each is present. The concentrations of pure solids and liquids is considered to be 1 and therefore, do not appear in the equilibrium expression.
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Heterogeneous Equilibria
Consider the reaction below.
C(s) H 2O(g )
CO(g) H 2 (g)
The equilibrium-constant expression contains terms for only those species in the homogeneous gas phaseH2O, CO, and H2.
[CO][H 2 ] Kc [ H 2O ]
Homework
Chapter 14 Homework: To be collected at the first exam. Review Questions: 4, 6 Problems: 15, 21, 25, 29, 31, 39, 41, 45
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Operational Skills
Applying stoichiometry to an equilibrium mixture Writing equilibrium-constant expressions Obtaining the equilibrium constant from reaction composition Determining equilibrium constants for sums of reactions
Time for a few review questions.
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