Download as ppt, pdf, or txt
Download as ppt, pdf, or txt
You are on page 1of 66

Chapter 17

Equilibrium: The Extent of Chemical Reactions

17-1
Chemical Equilibrium

Eq Concept Solving Eq Le Chatelier’s


Problem Principle
- Explain on how rxn
ICE condition affect eq
% change
Rxn table state
Quotient
(Q) Change in [ ]
Eq Constant Relationship
(K) btw Kc and Kp Change in P

Change in T
Magnitude K
Effect of catalyst
Homo&Hetero Eq Multistep Rxn

Variation of K Reverse Rxn

Rxn with diff coefficient

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:

At one time, evaporation


occurs as fast as
1 Evaporation will happen
condensation. Thus the
system is said to be at
2 Condensation happen
“equilibrium”
at the walls
3 Liquid will return to the
source

Rate forward = Rate reverse

H2O (l) ⇌ H2O (g)


Conc. of reactants &
products are constant
17-4
WHAT IS….?
 Irreversible Rxn  Rxn that proceeds in only one direction

 Reversible Rxn  Rxn that proceeds in both direction

 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

Consist mostly of •As rxn proceed, N2O4 •When N2O4decomposes as


colorless N2O4 decomposes into NO2(pale as NO2 combine & re-form
brown) N2O4 , the system is at
•When NO2 , they tend to collide equilibrium
17-6
If rateforward = ratereverse then
kforward[reactants]m = kreverse[products]n

kforward [products]n
= = K the equilibrium constant
kreverse [reactants]m

This is also known as the LAW OF MASS ACTION.

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)

 CH3OH(l) + CH3COOH(l) ⇌ CH3OCOCH3(l) + H2O(l)

17-12
Figure 17.4 The equilibrium constant for a heterogeneous system.

CaCO3(s)⇌ CaO(s) + CO2(g)

 Since we only concern


on [ ] that changes as
they approach eq, thus
term of SOLID and
LIQUID are neglected
from K expression

 Kc = [CO2]
17-13
HETEROGENOUS EQUILIBRIUM
Write equilibrium constant expression in terms of Kc
 AgCl(s) ⇌ Ag+(aq) + Cl- (aq)

 Ni(s) + 4CO(g)⇌ Ni(CO)4(s)

17-14
VARIATION FORMS OF K

Multistep Rxn

 If an overall is the sum of 2/more reactions, the overall K is


product of multiplication of the individual K

Kc overall = Kc1 x Kc2 x Kc3 x…

 Ex: N2(g) + O2(g) ⇌ 2 NO(g) Kc1=4.3 x 10-25


+ 2 NO(g) + O2(g) ⇌ 2 NO2(g) Kc2=6.4 x 109
N2(g) + 2O2(g) ⇌ 2 NO2(g) Kc overall = Kc1 X Kc2 = 2.8 x 10-15

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

(2) 2NO(g) + O2(g) 2NO2(g) Kc2 = 6.4x109

(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

[NO]2 [NO2]2 [NO2]2


Kc1 x Kc2 = =
[N2][O2] [NO]2[O2] [N2] [O2] 2

(b) Kc overall = Kc1 x Kc2 = (4.3x10-25) x (6.4x109) = 2.8x10-15

17-17
VARIATION FORMS OF K

Reversed Rxn

 Kc for reverse rxn is the reciprocal of Kc for forward reaction

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

Rxn with Different Coefficient

 When an equation is multiplied by a factor, that factor will be


raised as “power” for the K

 Ex: 2SO2(g) + O2(g) ⇌ 2 SO3(g) x 1/2 Kc =261


1/2
K
SO2(g) + ½O2(g) ⇌ SO3(g) Kc’=? c

Kc =√261 = 16.2

17-19
Sample Problem 17.3 Finding the Equilibrium Constant for an Equation
Multiplied by a Common Factor

PROBLEM: For the ammonia formation reaction N2(g) + 3H2(g) 2NH3(g)


the equilibrium constant, Kc, is 2.4x10-3 at 1000 K. If we change the
coefficients of the equation, which we’ll call the reference (ref) equation, what
are the values of Kc for the following balanced equations?
(a) 1/3N2(g) + H2(g) 2/3NH3(g) (b) NH3(g) 1/2N2(g) + 3/2H2(g)

PLAN: Compare each equation to the reference. Keep in mind that


changing the coefficients will be reflected in a power change in Kc
and a reversal of the equation will show up as an inversion of Kc.
SOLUTION:

(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.

Kc‘ = [Kc(ref)]-1/2 = (2.4x10-3)-1/2 = 20.

17-20
Follow up Problem 17.3A pg 739

H2(g) + Cl2(g) ⇌ 2HCl(g) Kc= 7.6 × 108

ANS: (a) 2.8 x 104


(b) 1.2 x 10-6

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).

 Q adopts the same expression as K, but the amount that we consider is


not at equilibrium

 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]oc[D]od
Qc =
[A]oa[B]ob
 Q can tell us whether the system is at equilibrium or not. If not, to which
direction the rxn will proceed in order to establish the equilibrium

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

 To do so, [product]  This can happen by  The system is already


must be increased and decreasing [product] and at equilibrium
[reactant] must decrease increasing [reactant]

 Thus system must  System must progress


lies/progress towards to the reactants side
product

[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

Reactants Products Equilibrium: reactants products


no net change

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)

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

SOLUTION:
[NO2]o4[O2]o
(a) 2 N2O5(g) 4NO2(g) + O2(g) Qc =
[N2O5]o2

(b) C3H8(g) + 5 O2(g) 3 CO2(g) + 4H2O(g)

[CO2]o3[H2O]o4
Qc =
[C3H8]o[O2]o5

17-27
Sample Problem 17.6 Comparing Q and K to Determine Reaction Direction

PROBLEM: For the reaction N2O4(g) 2NO2(g), Kc = 0.21 at 100oC. At


a point during the reaction, [N2O4] = 0.12 M and [NO2] = 0.55 M.
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.

17-28
Follow up Problem 17.6A pg 744

CH4(g) + Cl2(g) ⇌ CH3Cl(g) + HCl(g) Kp= 1.6×104

In the reaction mixture, PCH4=0.13 atm, PCl2=0.035 atm, PCH3Cl=0.24 atm


and PHCl=0.47atm. Is CH3Cl or CH4 forming?

ANS: Qp = 25 (24.8)
Direction to achieve equilibrium = to the products side
So, CH3Cl is forming
17-29
RELATIONSHIP BETWEEN KC AND KP

 Generally, Kc is not equal to Kp

 Relationship between Kc and Kp can be derived


using ideal gas law

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.

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

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)(0.0821x1000)-1 = 2.6x10-6

17-31
Follow up Problem 17.4A pg 742

ANS: 4.07 x 10-2

17-32
EQUILIBRIU
M PROBLEM
TYPES OF EQUILIBRIUM PROBLEM
 There are 2 types of equilibrium problem;

1. Equilibrium quantities are given and solve for K

 Substitute the equilibrium quantities given into


correct K expression

2. Initial quantities and K are given and solve the equilibrium


quantities
 Use ICE table to relate initial, changes and
equilibrium info

17-34
Sample Problem 17.7 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 453oC.
2HI(g) H2(g) + I2(g)

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

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 = 0.011 M

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


Kc = = = 0.020
[HI]2 (0.078)2

17-36
Follow up Problem 17.7A pg 747

ANS: Kp = 1.3 x 104

17-37
Sample Problem 17.8 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 0.28 mol of CO, 0.084 mol
of H2, and 0.045 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 K expression and then
substitute values for each component.
[CO][H2]3
SOLUTION: CH4(g) + H2O(g) CO(g) + 3H2(g) Kc =
[CH4][H2O]
0.041 mol [CO][H2]3
[CH4]eq = = 0.13 M
0.32 L [H2O] =
[CH4] Kc
0.26 mol
[CO]eq = = 0.81 M
0.32 L (0.81)(0.28)3
= = 0.53 M
0.091 mol (0.13)(0.26)
[H2]eq = = 0.28 M
0.32 L
17-38
Follow up Problem 17.8A pg 747

ANS: PNO = 2.7 x 10-16 atm

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)

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] = 0.250/0.125 L

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

17-40
Sample Problem 17.9 Determining Equilibrium Concentrations from Initial
Concentrations and Kc

[CO2][H2] (x) (x) (x)2


Q c = Kc = = =
[CO][H2O] (2.00 - x) (2.00 - x) (2.00 - x)2

x
1.56 = = +/-1.25
2.00-x

x = 1.11 M [CO] = [H2O] = 0.89 M

[CO2] = [H2] = 1.11 M


2.00 - x = 0.89 M

17-41
Follow up Problem 17.9A pg 749

ANS: [H2]eq= 8.02 x 10-3 M

17-42
Calculating Equilibrium Concentrations with a
Sample Problem 17.10 Simplifying Assumption
(K expression is not in Perfect square)

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 360oC)
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 simplify the calculating by ignoring
the solution to a quadratic equation.

SOLUTION: (a) 5.00 mol/10.0 L = 0.500 M (b) 0.100 mol/10.0 L = 0.0100 M

Let x = [CO]eq = [Cl2]eq and 0.500 - x and 0.0100 - x = [COCl2]eq,


respectively, for (a) and (b).

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-x0.500
[COCl2]

(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 = 2.9x10-3 M. (0.010 - x) ≈ 0.0071 M

CHECK: 0.0029/0.010 = 0.29 or 29% percent error


Using the quadratic formula produces x = 2.5x10-3 and
0.0100 - x = 7.5x10-3 M

17-44
Predicting when the assumption can be justified

The benchmark:

•If [A]initial/Kc > 400


- the assumption is justified
- can neglect x
- error will be <5%

•If [A]initial/Kc < 400


- means K is large
- the assumption is not justified
- cannot neglect x
- error will be >5%

*refer sample problem 17.10 as example


17-45
Sample Problem 17.11 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 2.00 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

[H2S]initial = 2.00 mol/0.25 L = 8.0 M [H2]initial = 2.00 mol/0.25 L = 8.0 M

17-46
Sample Problem 17.11 Predicting Reaction Direction and Calculating
Equilibrium Concentrations

[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.

Concentration (M) 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] = 5.56 M, so 5.56 = 4.0 + x and x = 1.56 M

Therefore - [H2S] = 8.0 + 2x = 11.12 M


[CS2] = 4.0 - x = 2.44 M
[H2] = 8.0 - 4x = 1.76 M
17-47
Follow up Problem 17.11A pg 753

ANS: Qc = 3.86 x 10-2


Direction: Qc < Kc ;Proceeds to the right(products)

17-48 Since x = 3.50 x 10-3 M so [PCl3]=[Cl2]= 9.35 x 10-2 M


LE
CHATELIER’
S PRINCIPLE
Le Chatelier’s Principle
When a chemical system at equilibrium is subjected to a stress,
the system will counteract by shifting to a new direction to offset
the stress applied and re-attains the equilibrium

If the concentration increases, the system reacts to consume some of it.

If the concentration decreases, the system reacts to produce some of it.

17-50
CHANGES IN CONCENTRATION
Consider the following equilibrium ;
PCl3(g) + Cl2(g) ⇌ PCl5(g)

 What happens if we inject some Cl2(g)?


 Conc. of Cl2 will increase, the system is no longer at equilibrium

 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

 What happens if we remove PCl5(g)?


 Conc. of PCl5 will decrease, the system is no longer at
equilibrium

 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)

 What happens if we remove PCl3(g)?


 Conc. of PCl3 will decrease, the system is no longer at
equilibrium

 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?

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.
17-54
Sample Problem 17.12 Predicting the Effect of a Change in Concentration
on the Equilibrium Position

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] increases.
(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.

Follow-up Problem
17.12(A)

17-55
CHANGES IN PRESSURE
 Changes in pressure have significant effect only on
equilibrium with gaseous components.

 Changing the P can occur in 2 ways

Change volume of
container

Addition of inert gas

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

Consider the following equilibrium ;


2 mol gas 1 mol gas

PCl3(g) + Cl2(g) ⇌ PCl5(g)


 What happens if P of the system is increased by decreasing
the volume of container?

•If volume becomes smaller (pressure is higher), the rxn


shifts so that the total no. of gas molecules decreases
•So, the equilibrium position will be shifted to the side with
less no. of gas molecules (right side)

17-58
CHANGES IN PRESSURE

Consider the following equilibrium ;


2 mol gas 1 mol gas

PCl3(g) + Cl2(g) ⇌ PCl5(g)

P , V ; the rxn will be shifted to the side with FEWER


gas molecules

P , V ; the rxn will be shifted to the side with MORE


gas molecules

17-59
CHANGES IN PRESSURE

Consider the following equilibrium ;

PCl3(g) + Cl2(g) ⇌ PCl5(g)


 What happens if P is increased by the addition of inert gas?

PCl3(g) PCl5(g)
Pressure of
Argon
system Cl2(g)

Partial pressure of existing gas


remain constant
Ptotal = PPCl3 + PCl2 +PPCl5 +PArgon

Since Kp does not affected so, the equilibrium remain


17-60 unchanged.
Sample Problem 17.13 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.

17-61
Follow-up Problem
17.13B

17-62
CHANGES IN TEMPERATURE

 Only change in temperature will alter the K

 Because energy content of each components changing as


well.

 Consider heat as a reactant or product in the equation

In an exothermic reaction, heat is a product.


In an endothermic reaction, heat is a reactant.

17-63
CHANGES IN TEMPERATURE
Consider the following equilibrium ;

PCl3(g) + Cl2(g) ⇌ PCl5(g) + Heat H=-111kJ

 When heat is supplied,

 The equilibrium will be shifted in “endothermic


direction” (to the left side) ; K

 When heat is released,

 The equilibrium will be shifted in “exothermic


direction” (to the right side) ; K

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

(b) CaCO3(s) CaO(s) + CO2(g) Ho = 178 kJ

(c) SO2(g) S(s) + O2(g) Ho = 297 kJ


PLAN: Express the heat of reaction as a reactant or a product. Then consider
the increase in temperature and its effect on K.

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 K.
(b) CaCO3(s) + heat CaO(s) + CO2(g)
The reaction will shift right resulting in an increase in [CO2] and increase in K.
(c) SO2(g) + heat S(s) + O2(g)
The reaction will shift right resulting in an decrease in [SO2] and increase in K.

17-65
EFFECT OF CATALYST

 Catalyst shortens the time it takes to reach equilibrium


(by lowering the Ea)

 Increasing forward and reverse rates to the same extent

 But catalyst has no effect on the equilibrium position

17-66

You might also like