Equilibrium

EQUILIBRIUM
THEEXTENTOFCHEMICAL
REACTIONS
ASEPMUHAMADSAMSUDIN,S.T,M.T.
Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Chapter 17
Equilibrium:
The Extent of Chemical Reactions
17-2
Equilibrium: The Extent of Chemical Reactions
17.1 The Equilibrium State and the Equilibrium Constant
17.2 The Reaction Quotient and the Equilibrium Constant
17.3 Expressing Equilibria with Pressure Terms: Relation between Kc and Kp
17.4 Reaction Direction: Comparing Q and K
17.5 How to Solve Equilibrium Problems
17.6 Reaction Conditions and the Equilibrium State: Le Chteliers Principle
17-3
Introduction
Kinetics applies to the speed of a reaction, the concentration of

product that appears (or of reactant that disappears) per unit time.
Equilibrium applies to the extent of a reaction, the concentration

of product that has appeared after an unlimited time, or once no
further change occurs.
Just as reactions vary in their speed, they also vary in their extent. e.g.
dissociation acid in water.
Knowing the extent of a given reaction is crucial.
How much product can you obtain? How can you adjust condition to obtain
more? If a reaction is slow but has a good yield, will a catalyst speed it up
enough to make it useful?
17-4
The Equilibrium State and The Equilibrium Constant
Countless experiments with chemical systems have shown that, In

a state of equilibrium, the concentrations of reactants and products
nolongerchangewithtime.
This apparent cessation of chemical activity occurs because reactions are

reversible.
17-5
Figure17.1
Reaching equilibrium on the macroscopic and molecular levels.
N2O4(g) 2NO2(g)
colorless brown
17-6
The system has reached equilibrium: reactant and product

concentrations stop changing because the forward and reverse rates
hare become equal:
Thus, a system at equilibrium continues to be dynamic at the molecular

level, but we observe no further net change because changes in
one direction are balanced by changes in the other.
At equilibrium: rateforward = ratereverse
17-7
If rateforward = ratereverse then

kforward[reactants]m = kreverse[products]n
kforward [products]n
= = K the equilibrium constant
kreverse [reactants]m
The equilibrium constant K is a number equal to a particular ratio of

equilibrium concentrations of product and reactant at a particular temperature.
This is also known as the LAW OF MASS ACTION.
The values of m and n are those of the coefficients in the balanced

chemical equation. Note that this is equilibrium, not kinetics. The rates of
the forward and reverse reactions are equal, NOT the concentrations of
reactants and products.
17-8
The magnitude of K is an indication of how' far a reaction proceeds toward

product at a given temperature.
17-9
Figure17.2 The range of equilibrium constants.
small K
K = 1/49 = 0.020
large K
K = 49/1 = 49
intermediate K
K = 25/25 = 1
17-10
Q - The Reaction Quotient and the Equilibrium Constant
In 1864, two Norwegian chemists, Cato Guldberg and Peter Waage,

observed that at a given temperature, a chemical system reaches a state
in which a particular ratio of reactant and product concentrations has a
constant value.
They found that, for a particular system and temperature, the same
equilibrium state is attained regardless of how the reaction is run.
The particular ratio of concentration terms that we write for a given
reaction is called the reaction quotient (Q, or mass-action expression).
For a general reaction aA + bB cC + dD where a, b, c, and d

are the numerical coefficients in the balanced equation, Q (and K) can be
calculated as
[C]c[D]d
Q=
[A]a[B]b
17-11
Q - The Reaction Quotient and the Equilibrium Constant
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).
17-12
Table 17.1 Initial and Equilibrium Concentration Ratios for

the N2O4-NO2 System at 2000C(473 K)
Ratio(Q) Ratio(K)
Initial [NO2]2 Equilibrium [NO2]eq2
Experiment [N2O4] [NO2] [N2O4] [N2O4]eq [NO2]eq [N2O4]eq
1 0.1000 0.0000 0.0000 3.57x10-3 0.193 10.4
2 0.0000 0.1000 9.24x10-4 9.83x10-3 10.4

3 0.0500 0.0500 0.0500 2.04x10-3 0.146 10.4
4 0.0750 0.0250 0.00833 2.75x10-3 0.170 10.5
17-13
Figure17.3 The change in Q during the N2O4-NO2 reaction.
K is a special value of Q that occurs when the reactant and product terms
have their equilibrium values.
17-14
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)
PLAN: Be sure to balance the equations before writing the Qc expression.
SOLUTION:
[NO2]4[O2]
(a) 2 N2O5(g) 4NO2(g) + O2(g) Qc =
[N2O5]2
[CO2]3[H2O]4
(b) C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(g) Qc =
[C3H8][O2]5
17-15
Calculating Variations on Q and K
[C]c[D]d
aA + bB cC + dD Qc =
[A]a[B]b
cC + dD aA + bB Q = 1/Qc
n aA + bB cC + dD Qc = (Qc)n
For a sequence of equilibria, Koverall = K1 x K2 x K3 x
17-16
17-17
17-18
Form of Q for a Forward and Reverse Reaction
The form of the reaction quotient depends on the direction in which the
balanced equation is written.
Consider, for example, the oxidation of sulfur dioxide to sulfur trioxide. This
reaction is a key step in acid rain formation and sulfuric acid production.
The balanced equation is
17-19
17-20
Form of Q for a Reaction with Coefficients Multiplied by a

Common Factor
17-21
17-22
Form of Q for a Reaction Involving Pure Liquids and Solids
17-23
17-24
17-25
Expressing Equilibria with Pressure Terms

Kc and Kp
n P n
PV = nRT P= RT = =M
V RT V
P M so for 2NO(g) + O2(g) 2NO2(g)
p(NO2)2 [NO2]2
Qp = Qc =
p(NO) x p(O2)
2
[NO]2 x [O2]
Kp = Kc (RT)n(gas)
17-26
Sample Problem 17.2 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.
CaCO3(s) CaO(s) + CO2(g) Kp = 2.1x10-4 (at 1000K)
PLAN: We know Kp and can calculate Kc after finding ngas. R = 0.0821

L*atm/mol*K.
SOLUTION: ngas = 1 - 0 since there is only a gaseous product and no
gaseous reactants.
Kp = Kc(RT)n Kc = Kp/(RT)n = (2.1x10-4)(0.0821 x 1000)-1 = 2.6x10-6
17-27
REACTION DIRECTION: COMPARING Q AND K
Reaction Reaction
Progress Progress
reactants products Equilibrium: reactants products

no net change
17-28
REACTION DIRECTION: COMPARING Q AND K
17-29
Sample Problem 17.3 Comparing Q and K to Determine Reaction Direction
PROBLEM: For the reaction N2O4(g) 2NO2(g), Kc = 0.21 at 1000C. At

a point during the reaction, [N2O4] = 0.12M and [NO2] = 0.55M.
Is the reaction at equilibrium. If not, in which direction is it
progressing?
PLAN: Write an expression for Qc, substitute with the values given, and
compare the Qc with the given Kc.
SOLUTION: [NO2]2 (0.55)2

Qc = = = 2.5
[N2O4] (0.12)
Qc is > Kc, therefore the reaction is not at equilibrium and will

proceed from right to left, from products to reactants, until Qc = Kc.
17-30
HOW TO SOLVE EQUILIBRIUM PROBLEMS
Many kinds of equilibrium problems arise in the real world, as well as on

chemistry exams. but we can group most of them into two types:
1. In one type, we are given equilibrium quantities (concentrations or

partial pressures) and solve for K.
2. In the other type, we are given K and initial quantities and solve for the
equilibrium quantities.
17-31
Sample Problem 17.4 Calculating Kc from Concentration Data
PROBLEM: In order to study hydrogen halide decomposition, a researcher fills

an evacuated 2.00-L flask with 0.200 mol of HI gas and allows the
reaction to proceed at 4530C.
2HI(g) H2(g) + I2(g)
At equilibrium, [HI] = 0.078 M. Calculate Kc.
PLAN: First find the molar concentration of the starting material and then find
the amount of each component, reactants and products, at equilibrium.
SOLUTION: [HI] = 0.200 mol = 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
0.078M.
17-32
Sample Problem 17.4 Calculating Kc from Concentration Data
continued
concentration (M) 2HI(g) H2(g) + I2(g)
initial 0.100 0 0
change -2x + x + x
equilibrium 0.100 - 2x x x
[HI] = 0.078 = 0.100 - 2x ; x = 0.011M
[H2] [I2] [0.011][0.011]

Qc = = = 0.020 = Kc
[HI]2 (0.078)2
17-33
Sample Problem 17.5 Determining Equilibrium Concentrations from Kc
PROBLEM: In a study concerning the conversion of methane to other fuels, a

chemical engineer mixes gaseous CH4 and H2O in a 0.32-L flask at
1200 K. At equilibrium the flask contains 0.26 mol of CO, 0.091 mol
of H2, and 0.041 mol of CH4. What is the [H2O] at equilibrium? Kc =
0.26 for the equation
CH4(g) + H2O(g) CO(g) + 3H2(g)
PLAN: Use the balanced equation to write the reaction quotient and then
substitute values for each component.
[CO][H2]3
SOLUTION: CH4(g) + H2O(g) CO(g) + 3H2(g) Qc =
[CH4][H2O]
0.041mol
[CH4]eq = = 0.13 M [CO][H2]3
[H2O] =
0.32 L [CH4] Kc
0.26mol
[CO]eq = = 0.81 M
0.32 L (0.81)(0.28)3
= = 0.53 M
0.091mol (0.13)(0.26)
[H2]eq = = 0.28 M
0.32 L
17-34
Sample Problem 17.6 Determining Equilibrium Concentrations from Initial

Concentrations and Kc
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 900K, 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)
PLAN: We have to find the concentrations of all species at equilibrium and

then substitute into a Kc expression.
SOLUTION: All concentrations must be recalculated as M, so [CO] = 0.250/0.125L
concentration CO(g) + H2O(g) CO2(g) + H2(g)
initial 2.00 2.00 0 0

change -x -x +x +x
equilibrium 2.00-x 2.00-x x x
17-35
Sample Problem 17.6 Determining Equilibrium Concentrations from Initial

Concentrations and Kc
continued
[CO][H2] (x) (x) (x)2

Qc = K c = = =
[CO2][H2O] (2.00-x) (2.00-x) (2.00-x)2
x
1.56 = = +/- 1.25
2.00-x
x = 1.11M [CO2] = [H2O] = 0.89M
[CO] = [H2] = 1.11M

2.00 - x = 0.89M
17-36
Sample Problem 17.7 Calculating Equilibrium Concentration with

Simplifying Assumptions
PROBLEM: Phosgene is a potent chemical warfare agent that is now outlawed by

international agreement. It decomposes by the reaction
COCl2(g) CO(g) + Cl2(g) Kc = 8.3x10-4 (at 3600C)
Calculate [CO], [Cl2], and [COCl2] when the following amounts of phosgene
decompose and reach equilibrium in a 10.0-L flask.
(a) 5.00 mol COCl2 (b) 0.100 mol COCl2
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 simplifying the calculating by
ignoring the solution to a quadratic equation.
SOLUTION: (a) 5.00 mol/10.0 L = 0.500M (b) 0.100 mol/10.0 L = 0.0100M
Let x = [CO]eq = [Cl2]eq and 0.500-x and 0.0100-x = [COCl2]eq,

respectively, for (a) and (b).
17-37
Sample Problem 17.7 Calculating Equilibrium Concentration with

Simplifying Assumptions
continued
(x) (x)
[CO][Cl2] (a) Kc = 8.3x10-4 =
Kc = (0.500-x)
[COCl2]
assume x is << 0.500 so that we can drop x in the denominator
(x) (x) 4.15x10-4 = x2 x 2 x 10-2
8.3x10 = -4
(0.500) (0.500 - x) = 4.8x10-2

CHECK: 0.020/0.500 = 0.04 or 4% percent error
(x) (x)
(b) Kc = 8.3x10 =-4
(0.010 - x)
Dropping the -x will give a value for x = 2.9x10-3M. (0.010 - x) 0.0071M
CHECK: 0.0029/0.010 = 0.29 or 29% percent error

Using the quadratic formula produces x = 2.5x10-3 and 0.0100-x = 7.5x10-3M
17-38
Sample Problem 17.8 Predicting Reaction Direction and Calculating

Equilibrium Concentrations
PROBLEM: The research and development unit of a chemical company is studying

the reaction of CH4 and H2S, two components of natural gas.
CH4(g) + 2H2S(g) CS2(g) + 4H2(g)
In one experiment, 1.00 mol of CH4, 1.00 mol of CS2, 2.00 mol of H2S, and 2.00mol
of H2 are mixed in a 250-mL vessel at 9600C. 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 = 1.00mol/0.25 L = 4.0M [CS2]initial = 1.00mol/0.25 L = 4.0M
[H2S]initial = 2.00mol/0.25 L = 8.0M [H2]initial = 2.00mol/0.25 L = 8.0M
17-39
Sample Problem 17.8 Predicting Reaction Direction and Calculating

Equilibrium Concentrations
continued
[CS2][H2]4 [4.0][8.0]4 A Qc of 64 is >> than Kc = 0.036

Qc = = = 64
[CH4][H2S] 2
[4.0][8.0] 2
The reaction will progress to the
left.
concentrations CH4(g) + 2H2S(g) CS2(g) + 4H2(g)
initial 4.0 8.0 4.0 8.0
change +x + 2x -x - 4x
equilibrium 4.0 + x 8.0 + 2x 4.0 - x 8.0 - 4x
At equilibrium [CH4] = 5.56M, so 5.56 = 4.0 + x and x = 1.56M
Therefore - [H2S] = 8.0 + 2x = 11.12M

[CS2] = 4.0 - x = 2.44M
[H2] = 8.0 - 4x = 1.76M
17-40
Figure17.5 Steps in solving equilibrium problems
PRELIMINARY SETTING UP WORKING ON A REACTION TABLE
1. Write the balanced equation. 4. When reaction direction is not

2. Write the reaction quotient, Q. known compare Q with K.
3. Convert all of the amounts into 5. Construct a reaction table.
the correct units (M or atm). Check the sign of x, the change
in the quantity.
SOLVING FOR X AND EQUILIBRIUM QUANTITIES
6. Substitute the quantities into Q. Check that assumption is

7. To simplify the math, assume that x is justified (<5% error). If not,
negligible. solve quadratic equation for
x.
8. [A]ini - x = [A]eq = [A]ini
Check to see that calculated
9. Solve for x.
values give the known K.
10. Find the equilibrium quantities
17-41
Le Chteliers Principle
When a chemical system at equilibrium is disturbed, it

reattains equilibrium by undergoing a net reaction that
reduces the effect of the disturbance.
At equilibrium, Q equals K. When a change in conditions forces

the system temporarily out of equilibrium (QK), we say that the
system has been stressed, or disturbed.
Three common disturbances are a change in concentration of
a component, a change in pressure (caused by a change in
volume), or a change in temperature.
"net reaction," is often referred to as a shift in the equilibrium
position of the system to the right or left.
The equilibrium position shifts means concentrations (or
pressures) change in a way that reduces the disturbance, and
the system attains a new equilibrium position (Q = K again).
17-42
The Effect of a Change in Concentration
If the concentration increases, the system reacts to consume some of it.
If the concentration decreases, the system reacts to produce some of it.
17-43
The Effect of a Change in Concentration
What happens if we now inject some Cl2 gas, one of the reactants?
The equilibrium position shifts to the right when a

component on the left is added:
What happens if we remove some PCl3, the other reactant?

The equilibrium position shifts to the right when a
component on the left is added:
The equilibrium position shifts to the right if a reactant is added or a

product is removed: [reactant] increases or [product] decreases.
The equilibrium position shifts to the left if a reactant is removed or a
product is added: [reactant] decreases or [product] increases.
17-44
Table 17.3 The Effect of Added Cl2 on the PCl3-Cl2-PCl5 System
Concentration (M) PCl3(g) + Cl2(g) PCl5(g)
Original equilibrium 0.200 0.125 0.600
Disturbance +0.075
New initial 0.200 0.200 0.600
Change -x -x +x
New equilibrium 0.200 - x 0.200 - x 0.600 + x

(0.637)*
*Experimentally determined value.
17-45
Figure17.7 The effect of added Cl2 on the PCl3-Cl2-PCl5 system.
PCl3(g) + Cl2(g) PCl5(g)
17-46
Sample Problem 17.9 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?
PLAN: Write an expression for Q and compare it to K when the system is

disturbed to see in which direction the reaction will progress.
SOLUTION: Q = [H2O]2
[H2S]2[O2]
(a) When O2 is added, Q decreases and the reaction progresses

to the right to come back to K. So [H2O] increases.
17-47
Sample Problem 17.9 Predicting the Effect of a Change in Concentration

on the Equilibrium Position
continued
Q= [H2O]2
[H2S]2[O2]
(b) When O2 is added, Q decreases and the reaction progresses

to the right to come back to K. So [H2S] decreases.
(c) When H2S is removed, Q increases and the reaction
progresses to the left to come back to K. So [O2] decreases.
(d) Sulfur is not part of the Q (K) expression because it is a solid.
Therefore, as long as some sulfur is present the reaction is
unaffected. [H2S] is unchanged.
17-48
The Effect of a Change in Pressure (Volume)
Pressure changes can occur in two ways:

1. Changing the concentration of a gaseous component
2. Changing the volume of the reaction vessel
If we press down on the piston to halve the volume: the gas pressure
immediately doubles. To reduce this increase in gas pressure, the
system responds by reducing the number of gas molecules by shifting
the reaction toward the side with fewer moles of gas.
PCl3(g) + Cl2(g) PCl5(g)
2 mol gas 1 mol gas
If the volume becomes smaller (pressure is higher), the reaction

shifts so that the total number of gas molecules decreases.
If the volume becomes larger (pressure is lower), the reaction shifts
so that the total number of gas molecules increases.
17-49
Figure17.8 The effect of pressure (volume) on an equilibrium system.
lowerP
(higherV)
more moles
of gas
higherP
(lowerV)
fewer moles
of gas
17-50
The Effect of a Change in Pressure (Volume)
PCl3(g) + Cl2(g) PCl5(g) Q= [PCl5]

[PCl3][Cl2]
a change in volume results in a change in concentration: a

decrease in container volume raises the concentration, and an
increase in volume lowers the concentration.
When the volume is halved, the concentrations double, but the
denominator of Qc is the product of two concentrations, so it
quadruples while the numerator only doubles. Thus, Qc becomes
less than Kc. As a result, the system forms more PCl 5 and a new
equilibrium position is reached.
17-51
Sample Problem 17.10 Predicting the Effect of a Change in Volume

(Pressure) on the Equilibrium Position
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)
(b) S(s) + 3F2(g) SF6(g)
(c) Cl2(g) + I2(g) 2ICl(g)

PLAN: When gases are present a change in volume will affect the
concentration of the gas. If the volume decreases (pressure
increases), the reaction will shift to fewer moles of gas and vice versa.
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.
17-52
The Effect of a Change in Temperature
Only temperature changes can alter K.
Consider heat as a product or a reactant, In an exothermic reaction,

heat is a product, In an endothermic reaction, heat is a reactant.
A temperature increase (adding heat) favors the endothermic (heat-

absorbing) direction, and a temperature decrease (removing heat)
favors the exothermic (heat-releasing) direction.
AtemperaturerisewillincreaseKcforasystemwithapositiveH0rxn
AtemperaturerisewilldecreaseKcforasystemwithanegativeH0rxn
17-53
Sample Problem 17.11 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 Kc for the following reactions?
(a) CaO(s) + H2O(l) Ca(OH)2(aq) H0 = -82kJ
(b) CaCO3(s) CaO(s) + CO2(g) H0 = 178kJ
(c) SO2(g) S(s) + O2(g) H0 = 297kJ

PLAN: Express the heat of reaction as a reactant or a product. Then consider
the increase in temperature and its effect on Kc.
SOLUTION: (a) CaO(s) + H2O(l) Ca(OH)2(aq) heat

An increase in temperature will shift the reaction to the left, decrease
[Ca(OH)2], and decrease Kc.
(b) CaCO3(s) + heat CaO(s) + CO2(g)
The reaction will shift right resulting in an increase in [CO2] and increase in Kc.
(c) SO2(g) + heat S(s) + O2(g)
The reaction will shift right resulting in an decrease in [SO2] and increase in Kc.
17-54
The vant Hoff Equation

The Effect of T on K
R = universal gas constant

K2 H 0
rxn 1 1
ln = - - = 8.314 J/mol*K
K1 R T2 T1 K1 is the equilibrium constant at T1
Temperature Dependence
k2 Ea 1 1 P2 Hvap 1 1
ln = - - = - -
ln
k1 R T2 T1 P1 R T2 T1
K2 H0rxn 1 1
ln = - -
K1 R T2 T1
17-55
17-56
Sample Problem 17.12 Determining Equilibrium Parameters from

Molecular Scenes
PROBLEM: For the reaction X(g) + Y2(g) XY(g) + Y(g) H>0
the following molecular scenes depict different reaction mixtures.
(X = green, Y = purple)
(a) If Kc = 2 at the temperature of the reaction, which scene represents the

mixture at equilibrium?
(b) Will the reaction mixtures in the other two scenes proceed toward
reactant or toward products to reach equilibrium?
(c) For the mixture at equilibrium, how will a rise in temperature affect [Y2]?
[XY][Y]
SOLUTION: The equilibrium constant, K, is .
[X][Y2]
scene 1: Qc = (5)(3)/(1)(1) = 15
scene 2: Qc = (4)(2)/(2)(2) = 2.0 scene 3: Qc = (3)(1)/(3)(3) = 0.33
17-57
Sample Problem 17.12 Determining Equilibrium Parameters from

Molecular Species
continued
Qc = 15 Qc = 2.0 Qc = 0.33
(a) In scene 2 Qc = Kc, so it represents the system at equilibrium.
(b) In scene 1 Qc > Kc, so the system will proceed to reactants to

reach equilibrium while in scene 3 Qc < Kc, so the system will proceed
to products.
(c) If H > 0, heat is a reactant (endothermic). A rise in temperature
will favor products and [Y2] will decrease as the system shifts to
products.
17-58
Table 17.5 Effect of Temperature on Kc for Ammonia Synthesis
T (K) Kc
200. 7.17 x 1015
300. 2.69 x 108
400. 3.94 x 104
500. 1.72 x 102
600. 4.53 x 100
700. 2.96 x 10-1
800. 3.96 x 10-2
17-59
Figure17.9 Percent yield of ammonia vs. temperature (0C) at

five different operating pressures.
17-60
17-61
1. Theoxidationofnitrogenmonoxide,NO(g)+O2(g)NO2wasstudiedat184C
withinitialpressuresof2atmofNOand2atmofO2,atequilibrium,PO =0.126 2
atm.CalculateKp!
2. Aninorganicchemiststudyingthereactionsofphosphorushalidesmixes0.205mol
ofPCI5with0.095molofCl2and0.095molofPCl3ina0.5Lflaskat250C:Kc=
4.2x102
a) Inwhichdirectionwillthereactionproceed?
b) If[PCI5]=0.4175Matequilibrium,whataretheequilibriumconcentrationsoftheother
components?
3. Forthereaction
A2(g)+B2(g)AB(g)H>0
thesemolecularscenesdepictdifferentreactionmixtures(A=redandB=blue):

(a) CalculatethevalueofKp.
(b) Inwhichdirectionwillthereactionproceedforthemixturesnotatequilibrium?
(c) Forthemixtureatequilibrium,whateffectwillariseinThaveonthetoral
17-62 molesofgas(increase,decrease,noeffect)?Explain.

Equilibrium

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Equilibrium

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EQUILIBRIUM

Equilibrium: The Extent of Chemical Reactions

17.1 The Equilibrium State and the Equilibrium Constant

17.2 The Reaction Quotient and the Equilibrium Constant

17.3 Expressing Equilibria with Pressure Terms: Relation between Kc and Kp

17.4 Reaction Direction: Comparing Q and K

17.5 How to Solve Equilibrium Problems

17.6 Reaction Conditions and the Equilibrium State: Le Chteliers Principle

Kinetics applies to the speed of a reaction, the concentration of

Equilibrium applies to the extent of a reaction, the concentration

Knowing the extent of a given reaction is crucial.

The Equilibrium State and The Equilibrium Constant

Countless experiments with chemical systems have shown that, In

This apparent cessation of chemical activity occurs because reactions are

The system has reached equilibrium: reactant and product

Thus, a system at equilibrium continues to be dynamic at the molecular

At equilibrium: rateforward = ratereverse

If rateforward = ratereverse then

The equilibrium constant K is a number equal to a particular ratio of

This is also known as the LAW OF MASS ACTION.

The values of m and n are those of the coefficients in the balanced

The magnitude of K is an indication of how' far a reaction proceeds toward

Figure17.2 The range of equilibrium constants.

Q - The Reaction Quotient and the Equilibrium Constant

In 1864, two Norwegian chemists, Cato Guldberg and Peter Waage,

For a general reaction aA + bB cC + dD where a, b, c, and d

Q - The Reaction Quotient and the Equilibrium Constant

At any time, t, the system can be sampled to determine the amounts of

Table 17.1 Initial and Equilibrium Concentration Ratios for

1 0.1000 0.0000 0.0000 3.57x10-3 0.193 10.4

2 0.0000 0.1000 9.24x10-4 9.83x10-3 10.4

Figure17.3 The change in Q during the N2O4-NO2 reaction.

PLAN: Be sure to balance the equations before writing the Qc expression.

Calculating Variations on Q and K

For a sequence of equilibria, Koverall = K1 x K2 x K3 x

Form of Q for a Forward and Reverse Reaction

The balanced equation is

Form of Q for a Reaction with Coefficients Multiplied by a

Form of Q for a Reaction Involving Pure Liquids and Solids

Expressing Equilibria with Pressure Terms

P M so for 2NO(g) + O2(g) 2NO2(g)

Sample Problem 17.2 Converting Between Kc and Kp

CaCO3(s) CaO(s) + CO2(g) Kp = 2.1x10-4 (at 1000K)

PLAN: We know Kp and can calculate Kc after finding ngas. R = 0.0821

Kp = Kc(RT)n Kc = Kp/(RT)n = (2.1x10-4)(0.0821 x 1000)-1 = 2.6x10-6

REACTION DIRECTION: COMPARING Q AND K

reactants products Equilibrium: reactants products

REACTION DIRECTION: COMPARING Q AND K

Sample Problem 17.3 Comparing Q and K to Determine Reaction Direction

PROBLEM: For the reaction N2O4(g) 2NO2(g), Kc = 0.21 at 1000C. At

SOLUTION: [NO2]2 (0.55)2

Qc is > Kc, therefore the reaction is not at equilibrium and will

HOW TO SOLVE EQUILIBRIUM PROBLEMS

Many kinds of equilibrium problems arise in the real world, as well as on

1. In one type, we are given equilibrium quantities (concentrations or

Sample Problem 17.4 Calculating Kc from Concentration Data

PROBLEM: In order to study hydrogen halide decomposition, a researcher fills

At equilibrium, [HI] = 0.078 M. Calculate Kc.

Let x be the amount of [H2] at equilibrium. Then x will also be the

Sample Problem 17.4 Calculating Kc from Concentration Data

concentration (M) 2HI(g) H2(g) + I2(g)

[HI] = 0.078 = 0.100 - 2x ; x = 0.011M

[H2] [I2] [0.011][0.011]

Sample Problem 17.5 Determining Equilibrium Concentrations from Kc