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Chemical Equilibrium
Chemical Equilibrium
17-1
Chemical Equilibrium
Change in T
Magnitude K
Effect of catalyst
Homo&Hetero Eq Multistep Rxn
17-2
EQUILIBRIU
M CONCEPT
EQUILIBRIUM CONCEPT
Equilibrium is a state where there is no observable changes
Only occur in closed system where the rxn is reversible
Ex:
Dynamic Equilibrium
A state of balanced in which forward and reverse rxn
proceed at equal rates & the concentrations of reactants and
products remain constant over time
At equilibrium;
Ratefwd = Raterev
[Reactants]&[Products]=CONSTANT
17-5
Figure 17.1 pg 732
Reaching equilibrium on the macroscopic and molecular levels of
the reaction: N O (g) 2NO (g).
2 4 2
Colorless Brown
kforward [products]n
= = K the equilibrium constant
kreverse [reactants]m
Kc expression;
[C]c[D]d
aA + bB ⇌ cC + dD Kc=
[A]a[B]b
17-7
MAGNITUDE OF EQUILIBRIUM
CONSTANT(K)
According to equilibrium law, K is expressed in terms of ratio
products to reactants
Kc = [Products]p
K = Products [Reactants]r
Reactants
Kp =(Pproducts)p
(Preactants)r
K is used to measure/know how rxn proceeds toward products.
Magnitude of K can tell us whether a rxn favors the products or
reactants formation at equilibrium.
K is unitless.
17-8
MAGNITUDE OF EQUILIBRIUM
CONSTANT(K)
17-9
Figure 17.2 The range of equilibrium constants.
small K
large K
intermediate K
17-10
TYPES OF EQUILIBRIUM
17-11
HOMOGENOUS EQUILIBRIUM
Write equilibrium constant expression in terms of Kc
N2(g) + 3H2(g)⇌ 2NH3(g)
17-12
Figure 17.4 The equilibrium constant for a heterogeneous system.
Kc = [CO2]
17-13
HETEROGENOUS EQUILIBRIUM
Write equilibrium constant expression in terms of Kc
AgCl(s) ⇌ Ag+(aq) + Cl- (aq)
17-14
VARIATION FORMS OF K
Multistep Rxn
17-15
Sample Problem 17.2 Writing the Equilibrium constant and Finding K for an
Overall Reaction
PROBLEM: Understanding reactions involving N2 and O2, the most abundant
gases in air, is essential for solving problems dealing with
atmospheric pollution. Here is a reaction sequence between N2 and
O2 to form nitrogen dioxide, a toxic pollutant that contributes to
photochemical smog.
(1) N2(g) + O2(g) 2NO(g) Kc1 = 4.3x10-25
(a) Show that the Kc for the overall reaction sequence is the same as the
product of the Kcs of the individual reactions.
(b) Calculate the Kc for the overall reaction.
PLAN: Write the sum of the overall reactions; write the Kc. Write the Kcs for
the individual reactions and then multiply the expressions.
We are given the Kcs for the individual reactions, so we multiply those
values.
17-16
Sample Problem 17.2 Writing the Equilibrium constant for an Overall
Reaction
SOLUTION: Kc1 = [NO]2
(a) (1) N2(g) + O2(g) 2NO(g)
[N2][O2]
(2) 2NO(g) + O2(g) 2NO2(g)
Kc2 = [NO2]2
N2(g) + 2O2(g) 2NO2(g)
[NO]2[O2]
[NO2]2
Kc =
[N2][O2]2
17-17
VARIATION FORMS OF K
Reversed Rxn
Kc reverse = 1
Kc foward
Ex: 2SO2(g) + O2(g) ⇌ 2 SO3(g) Kc fwd=261
2 SO3(g) ⇌ 2SO2(g) + O2(g) Kc rev=?
Kc reverse = 1 = 1
Kc forward 261
= 3.83 x 10-3
17-18
VARIATION FORMS OF K
Kc =√261 = 16.2
17-19
Sample Problem 17.3 Finding the Equilibrium Constant for an Equation
Multiplied by a Common Factor
(a) The reference equation is multiplied by 1/3, so Kc(ref) will be to the 1/3 power.
Kc‘ = [Kc(ref)]1/3 = (2.4x10-3)1/3 = 0.13
(b) The reference equation is reversed and halved, so Kc(ref) is to the -1/2 power.
17-20
Follow up Problem 17.3A pg 739
17-21
17-22
Q - The Reaction Quotient
At any time, t, the system can be sampled to determine the amounts of
reactants and products present. A ratio of products to reactants,
calculated in the same manner as K tells us whether the system has come
to equilibrium (Q = K) or whether the reaction has to proceed further from
reactants to products (Q < K) or in the reverse direction from products to
reactants (Q > K).
17-23
Figure 17.3 The change in Q during the N2O4-NO2 reaction.
17-24
THERE ARE 3 POSSIBILITIES FOR CONDITION
OF Q
Q<K Q>K Q=K
Q need to increase Q need to decrease No further net changes
until it equals to K until it equals to K occur
[Product]p [Product]p
Q = Q =
[Reactant] r
[Reactant]r
17-25
Figure 17.5 Reaction direction and the relative sizes of Q and K.
Reaction Reaction
Progress Progress
17-26
Sample Problem 17.1 Writing the Reaction Quotient from the Balanced
Equation
PROBLEM: Write the reaction quotient, Qc, for each of the following reactions:
(a) The decomposition of dinitrogen pentoxide, N2O5(g) NO2(g) + O2(g)
(b) The combustion of propane gas, C3H8(g) + O2(g) CO2(g) + H2O(g)
SOLUTION:
[NO2]o4[O2]o
(a) 2 N2O5(g) 4NO2(g) + O2(g) Qc =
[N2O5]o2
[CO2]o3[H2O]o4
Qc =
[C3H8]o[O2]o5
17-27
Sample Problem 17.6 Comparing Q and K to Determine Reaction Direction
17-28
Follow up Problem 17.6A pg 744
ANS: Qp = 25 (24.8)
Direction to achieve equilibrium = to the products side
So, CH3Cl is forming
17-29
RELATIONSHIP BETWEEN KC AND KP
PV=nRT
P=(n/V)RT
Kp = Kc (RT)n (gas only!!)
n= mol of gaseous product – mol of gaseous reactant
17-30
Sample Problem 17.4 Converting Between Kc and Kp
PROBLEM: A chemical engineer injects limestone (CaCO3) into the hot flue
gas of a coal-burning power plant for form lime (CaO), which
scrubs SO2 from the gas and forms gypsum. Find Kc for the
following reaction, if CO2 pressure is in atmospheres.
17-31
Follow up Problem 17.4A pg 742
17-32
EQUILIBRIU
M PROBLEM
TYPES OF EQUILIBRIUM PROBLEM
There are 2 types of equilibrium problem;
17-34
Sample Problem 17.7 Calculating Kc from Concentration Data
PLAN: First find the molar concentration of the starting material and then find
the amount of each component, reactants and products, at equilibrium.
At equilibrium, [HI] = 0.078 M. Calculate Kc?
SOLUTION:
0.200 mol
[HI] = = 0.100 M
2.00 L
Let x be the amount of [H2] at equilibrium. Then x will also be the
concentration of [I2] and the change in of [HI] will be the original
concentration minus the stoichiometric amount that reacted, 2x, or
0.078 M.
17-35
Sample Problem 17.7 Calculating Kc from Concentration Data
initial 0.100 0 0
change -2x +x +x
equilibrium 0.100 - 2x x x
17-36
Follow up Problem 17.7A pg 747
17-37
Sample Problem 17.8 Determining Equilibrium Concentrations from Kc
17-39
Determining Equilibrium Concentrations from Initial
Sample Problem 17.9 Concentrations and Kc
(Perfect square of K expression)
PROBLEM: Fuel engineers use the extent of the change from CO and H2O to
CO2 and H2 to regulate the proportions of synthetic fuel mixtures. If
0.250 mol of CO and 0.250 mol of H2O are placed in a 125-mL flask
at 900 K, what is the composition of the equilibrium mixture? At this
temperature, Kc is 1.56 for the equation
CO(g) + H2O(g) CO2(g) + H2(g)
17-40
Sample Problem 17.9 Determining Equilibrium Concentrations from Initial
Concentrations and Kc
x
1.56 = = +/-1.25
2.00-x
17-41
Follow up Problem 17.9A pg 749
17-42
Calculating Equilibrium Concentrations with a
Sample Problem 17.10 Simplifying Assumption
(K expression is not in Perfect square)
PLAN: After finding the concentration of starting material, write the expressions
for the equilibrium concentrations. When solving for the remaining
amount of reactant, see if you can make an assumption about the initial
and final concentrations which could simplify the calculating by ignoring
the solution to a quadratic equation.
17-43
Sample Problem 17.10 Calculating Equilibrium Concentrations with a
Simplifying Assumption
(x)(x) Since K is small, assume
[CO][Cl2] (a) Kc = 8.3x10-4 = x is << 0.500 so when
Kc = (0.500 - x) 0.500-x0.500
[COCl2]
(x)(x)
(b) Kc = 8.3x10 =
-4
(0.010 - x)
Dropping the -x will give a value for x = 2.9x10-3 M. (0.010 - x) ≈ 0.0071 M
17-44
Predicting when the assumption can be justified
The benchmark:
In one experiment, 1.00 mol of CH4, 1.00 mol of CS2, 2.00 mol of H2S, and 2.00 mol
of H2 are mixed in a 250-mL vessel at 960oC. At this temperature, Kc = 0.036.
(a) In which direction will the reaction proceed to reach equilibrium?
(b) If [CH4] = 5.56 M at equilibrium, what are the equilibrium concentrations of the
other substances?
PLAN: Find the initial molar concentrations of all components and use these to
calculate a Qc. Compare Qc to Kc, determine in which direction the
reaction will progress, and draw up expressions for equilibrium
concentrations.
SOLUTION: [CH4]initial = 1.00 mol/0.25 L = 4.0 M [CS2]initial = 1.00 mol/0.25 L = 4.0 M
17-46
Sample Problem 17.11 Predicting Reaction Direction and Calculating
Equilibrium Concentrations
17-50
CHANGES IN CONCENTRATION
Consider the following equilibrium ;
PCl3(g) + Cl2(g) ⇌ PCl5(g)
To offset this stress, PCl3 reacts with the added Cl2 and causes
the equilibrium position to shift to the right producing more PCl5
until equilibrium is re-established
To reduce this stress, PCl3 must react with Cl2 to produce PCl5
again and causes the equilibrium position to shift to the right until
equilibrium is re-established
17-51
CHANGES IN CONCENTRATION
Consider the following equilibrium ;
PCl3(g) + Cl2(g) ⇌ PCl5(g)
To reduce this stress, PCl5 must react to produce PCl3 again and
causes the equilibrium position to shift to the left until equilibrium
is re-established
17-52
Figure 17.7 The effect of a change in concentration.
17-53
Sample Problem 17.12 Predicting the Effect of a Change in Concentration
on the Equilibrium Position
PROBLEM: To improve air quality and obtain a useful product, chemists often
remove sulfur from coal and natural gas by treating the fuel
contaminant hydrogen sulfide with O2:
2H2S(g) + O2(g) 2S(s) + 2H2O(g)
What happens to
(a) [H2O] if O2 is added? (b) [H2S] if O2 is added?
(c) [O2] if H2S is removed? (d) [H2S] if sulfur is added?
SOLUTION: Q = [H2O]2
[H2S]2[O2]
Q= [H2O]2
[H2S]2[O2]
Follow-up Problem
17.12(A)
17-55
CHANGES IN PRESSURE
Changes in pressure have significant effect only on
equilibrium with gaseous components.
Change volume of
container
17-56
Figure 17.9 The effect of pressure (by volume changes) on a system at
equilibrium.
+
lower P
(higher V)
more moles
of gas
higher P
(lower V)
fewer moles
of gas
17-57
CHANGES IN PRESSURE
17-58
CHANGES IN PRESSURE
17-59
CHANGES IN PRESSURE
PCl3(g) PCl5(g)
Pressure of
Argon
system Cl2(g)
PROBLEM: How would you change the volume of each of the following
reactions to increase the yield of the products.
(a) CaCO3(s) CaO(s) + CO2(g)
SOLUTION: (a) CO2 is the only gas present. To increase its yield, we
should increase the volume (decrease the pressure).
(b) There are more moles of gaseous reactants than products, so we should
decrease the volume (increase the pressure) to shift the reaction to the right.
(c) There are an equal number of moles of gases on both sides of the
reaction, therefore a change in volume will have no effect.
17-61
Follow-up Problem
17.13B
17-62
CHANGES IN TEMPERATURE
17-63
CHANGES IN TEMPERATURE
Consider the following equilibrium ;
17-64
Sample Problem 17.14 Predicting the Effect of a Change in Temperature
on the Equilibrium Position
PROBLEM: How does an increase in temperature affect the concentration of
the underlined substance and K for the following reactions?
(a) CaO(s) + H2O(l) Ca(OH)2(aq) Ho = -82 kJ
17-65
EFFECT OF CATALYST
17-66