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Unit 16

Chemical Equilibrium:
Gases & Heterogeneous
Dr. Kamyar Shameli,
Textbook Reference:
MJIIT-UTM •Chapter # 17
KL •Module # 5 (& Appendix
Equilibrium
2)
The Concept of Equilibrium
{Non-Equilibrium Reactions}: proceed in one direction, A  B
2 NO (g) + O2 (g) 2 NO2 (g)
(clear gases) (red-brown gas)
{Equilibrium Reactions}: proceed in both directions, A ↔B

N2O4 (g) 2 NO2 (g)
(clear gas) (red-brown
2X
gas)
Chemical equilibrium occurs when a
reaction and its reverse reaction proceed
at the same rate.

Equilibrium
This does not mean chemicals are found
in same concentration!
The Equilibrium Constant (Keq)
N2O4 (g) 2 NO2 (g)
• Therefore, at equilibrium
Ratef = Rater
kf [N2O4] = kr [NO2]2
• Rewriting this, it becomes
kf [NO2]2
Keq = =
kr [N2O4]
The Equilibrium Constant is the ratio of theEquilibrium

rate constants at a particular temperature.


The Equilibrium Constant (K)
• To generalize this expression, consider
the reaction
aA(aq) + bB(aq) cC(aq) + dD(aq)
• The equilibrium expression for this
reaction would be
[C]c[D]d
Kc =
[A]a[B]b
Equilibrium
where [X] = concentration of each chemical
in moles/ liter (M).
What Does the Value of K Mean?
10 x
aA + bB cC + dD
[C]c[D]d 10 = 10
Kc = [A]a[B]b Kc =
1
• If K >> 1, the reaction is product-favored; product
predominates at equilibrium.
aA + bB 10 x cC + dD
[C]c[D]d Kc = 1 = 0.1
Kc = [A]a[B]b 10

• If K << 1, the reaction is reactant-favored; reactant


Equilibrium

predominates at equilibrium.
The Equilibrium Constant for Gases
[C]c[D]d
Kc =
[A]a[B]b
aA(g) + bB(g) cC(g) + dD(g)
Partial press: (75 torrs) (150 torrs) (300 torrs) (600 torrs) = total (1125 torrs)

Because pressure is proportional to


concentration for gases in a closed
system, the equilibrium expression can
also be written
(PC)c (PD)d
Kp =
(PA)a (PB)b
where Kp = equilibrium constant for gases, and Equilibrium

Px = partial pressure of each gas.


Relationship between Kc and Kp
• ideal gas law:

[C]c[D]d PV = nRT
Kc = n
[A]a[B]b P= RT
V
n n
(PC)c (PD)d ( V RT )c
( V RT )d
Kp = =
( n ) a ( n ) b
(PA)a (PB)b V RT V RT
Plugging this into the expression for Kp

Where
Kp = Kc (RT)n ☺ Equilibrium

n = (moles of gaseous product) − (moles of gaseous reactant)


Equilibrium Can Be Reached from
Either Direction
@ 100°C

KC
[NO2]2
=
[N2O4]
2
2
[0.0172] [0.0243] [0.0310]2 [0.0310]2
Kc      0.212
[0.0014] [0.0028] [0.0045] [0.0045]
The ratio of [NO2]2 to [N2O4] remains constant at this temperature noEquilibrium
matter
what the initial concentrations of NO2 and N2O4 are.
Equilibrium Can Be Reached from
Either Direction
N2O4 (g) 2 NO2 (g)

2
[ NO 2 ] [0.0172 ] [0.0243] [0.0310 ]2 Equilibrium
2 2

Kc      0.212
[ N 2O4 ] [0.0014 ] [0.0028] [0.0045]
Manipulating Equilibrium Constants
RULE #1: Reciprocal Rule

The equilibrium constant of a reverse reaction is


the reciprocal of the equilibrium constant of the
forward reaction.

I [NO2]2
N2O4 (g) 2 NO2(g) K =
[N2O4]
= 0.212 at 100C

1
2 NO2 (g) N2O4(g) II
K =
[N2O4]
[NO2]2 =
0.212
Equilibrium
= 4.72 at 100C
Manipulating Equilibrium Constants
RULE #2: Coefficient Rule
If the coefficients of a chemical equation are
changed (increased or decreased) by a factor
n, then the value of K is raised to that power.
[NO ] 2
2
N2O4 (g) 2 NO2 (g) KI =
[N2O4]
= 0.212 at 100C

[NO2]4
2 N2O4 (g) 4 NO2 (g) KIII =
[N2O4]2
= (0.212) 2 at 100C

[ NO 2 ]2 Equilibrium
½N2O4(g) NO2(g) KIV =  0.212 at 100C
[N 2 O 4 ]
Manipulating Equilibrium Constants
RULE #3: Multiple Equilibria Rule

When two or more equations are added to


obtain a final resultant equation, the equilibrium
constant for the resultant equation is product of the
constants of the added equations.
4
[ C]
2 A(aq) + B(aq) ↔ 4 C(aq) KV 
[A]2 [ B]
[ F]2
4 C(aq) + E(aq) ↔ 2 F(aq) K  VI

[C]4 [ E]

[ F]2
2 A(aq) + B(aq) + E ↔ 2 F(aq) K VII  Equilibrium

[A]2 [ B][ E]
Homogeneous
Reactions involving only gasses or only solutions
[NO2]2
N2O4 (g) 2 NO2(g) Kc = = 0.212 at 100C
[N2O4]

vs.
Heterogeneous
Reactions involving different phases (s, l, g, aq) of matter

CaCO3 (s) CO2 (g) + CaO(s) K C  [CO2 ]

Equilibria Equilibrium
The Concentrations of Solids and
Liquids Are Essentially Constant
PbCl2 (s) Pb2+ (aq) + 2 Cl−(aq)
Write the equilibrium expression!

Kc = [Pb2+] [Cl−]2
The concentrations of solids and liquids do not appear in
equilibrium expressions because their concentration does not
change.
Concentration of both solids and liquids can be obtained by
dividing the density of the substance by its molar mass—and
both of these are constants at constant temperature.
g g
D MM  mol Equilibrium
Concentration ( M )   L 
MM MM L L
What are the Equilibrium
Expressions for these
Heterogeneous Equilibria?

Kp 
P CO2
2

PCO  2


K p  PCO2 
2
[Zn ]
Kc  2
[Cu ]
Equilibrium
CaCO3 (s) CO2 (g) + CaO(s)


K p  PCO2 

How does the concentration of CO2 differ in the two bell jars?
As long as some CaCO3 or CaO remain in the system, the
Equilibrium

amount of CO2 above the solid will remain the same.


Equilibrium Calculations
(1) Calculating Kc from experimental data: [ ]i & [ ]e

(2) Calculating Equilibrium Concentrations [ ]e


when Kc & [ ]i are known

ICE Tables:
[A] + [B] [C] + [D]
Initial I [A]i [B]i 0 0
- - + +
Change C change change change change

Equilibrium E [A]e [B]e [C]e [D]e

[C ]cequi[ D]equi
d
[C ]cequi[ D]equi
d

Kc   Equilibrium
a
[ A]equi [ B]bequi [[ A]i  change]equi
a
[[ B]i  change]bequi
(1) Calculating Kc from experimental data: [ ]i & [ ]e
[HI]2
H2 (g) + I2 (g) 2 HI (g) Kc =
[H2] [I2]
A closed system initially containing 1.000 x 10−3 M H2 and 2.000 x 10−3 M
I2 at 448C is allowed to reach equilibrium. Analysis of the equilibrium
mixture shows that the concentration of HI is 1.87 x 10−3 M. Calculate Kc at
448C for the reaction taking place, which is

[H2], M + [I2], M  2 [HI], M


Initially 1.000 x 10-3 2.000 x 10-3 0
Change -9.35 x 10-4 -9.35 x 10-4 +1.87 x 10-3
At Equilibrium 6.5 x 10-5 1.065 x 10-3 1.87 x 10-3

[HI] Increases by 1.87 x 10-3 M


Equilibrium
Stoichiometry tells us [H2] and [I2] decrease by half as much
…and, therefore, the equilibrium constant
[H2], M + [I2], M  [HI], M
Initially 1.000 x 10-3 2.000 x 10-3 0
Change -9.35 x 10-4 -9.35 x 10-4 +1.87 x 10-3
At Equilibrium 6.5 x 10-5 1.065 x 10-3 1.87 x 10-3

[HI]2
Kc =
[H2] [I2]
(1.87 x 10-3)2
=
(6.5 x 10-5)(1.065 x 10-3)
Equilibrium

= 51
Calculating Kc from experimental data: [ ]i & [ ]e
@
100°C
+x - 2x x
+x - 2x
+x - 2x
-x + 2x

N2O4 (g) 2 NO2 (g)


I 0.0 0.0200 [NO2]2
C +x - 2x
Kc = [N O ]
2 4
E 0.0014 0.0200-2x

([0.02]i  2 x) 2 ([0.03]i  2 x) 2 ([0.04]i  2 x) 2 ([.00]i  2 x) 2


Kc      0.212
[0.0014] [0.0028] [0.0045] [0.0045]
Equilibrium
The ratio of [NO2]2 to [N2O4] remains constant at this temperature no matter
what the initial concentrations of NO2 and N2O4 are.
2006B Q5

Practice Problem

{ }

Equilibrium
Equilibrium
Equilibrium
Equilibrium Calculations
(1) Calculating Kc from experimental data: [ ]i & [ ]e
[H2], M + [I2], M  [HI], M
Initially 1.000 x 10-3 2.000 x 10-3 0
Change
At Equilibrium 1.87 x 10-3

(2) Calculating Equilibrium Concentrations


when K & [ ]i are known
H2(g) + I2(g) ↔ 2HI(g)
I 0.00623 0.00414 0.0224 [HI ]2e
C -x -x + 2x K  51 =
[H 2 ]eEquilibrium
[I 2 ]e
E 0.00632- x 0.00414- x 0.0224 + 2x
(2) Calculating Equilibrium
Concentrations [ ]e when K & [ ]i are known
aA + bB cC + dD
I [A]i [B]i 0 0
C - ax - bx + cx + dx
E [A]i- ax [B]i- bx cx dx

[C ]cequi[ D]eequi (cx)c  (dx) d


K 
[ A] a
equi
b
[ B]
equi ([ A]i  ax)  ([ B]i  bx)
a b

Solve for x by using the quadratic equation:

ax  bx  c  0
2  b  b Equilibrium
 4ac 2
x 
2a
Calculating Equilibrium Concentrations
when K & [ ]i are known
Problem: for the reaction H2(g) + I2(g) 2HI(g) , K= 54.3 @
430ºC. Suppose that the initial concentrations of H2, I2, and HI
are 0.00623 M, 0.00414 M, and 0.0224 M, respectively.
Calculate the concentrations of these species at equilibrium.
H2(g) + I2(g) 2HI(g)

I 0.00623 0.00414 0.0224 [HI ]2e


K
C -x -x + 2x [H 2 ]e [I 2 ]e
E 0.00632- x 0.00414- x 0.0224 + 2x
ax 2  bx  c  0
(0.0224  2 x) 2
Deciding if x is negligible: 54.3 
([0.00632] - x)  ([0.00414] - x)
54.3(2.58 x 1015  0.0104 x  x 2 )  5.02 x 10-4  0.0896 x  4 x 2 Equilibrium

50.3x  0.654 x  8.98 x 10  0


2 -4
x 
 b  b 2  4ac
2a
Problem: for the reaction H2(g) + I2(g) 2HI(g) , K= 54.3 @
430ºC. Suppose that the initial concentrations of H2, I2, and HI
are 0.00623 M, 0.00414 M, and 0.0224 M, respectively.
Calculate the concentrations of these species at equilibrium.
Deciding if x is negligible:
(0.0224  2 x) 2
54.3  [A]i
 K  [A]i x 100
([0.00632] - x)  ([0.00414] - x) 100
0.000224  54.3  2.24
ax 2  bx  c  0 1. Take the largest [A]i and multiply it by
100 and also divide it by 100.
2. Compare the answers of above to
50.3x 2  0.654 x  8.98 x 10-4  0 the value of K
YOU MUST USE QUADRATIC! 3. If comparison are not significant as
50.3x 2  8.98 x 10-4 compared to K, then x is negligible
 and you can delete the x that is
50.3 50.3 subtracted from [A]I
4. If these calc values are significant
x 2  1.79 x 10 -5 compared to K, then x is notEquilibrium
negligible and you must use the
x  0.00423 quadratic to solve for x.
Calculating Equilibrium Concentrations
when K & [ ]i are known
ax 2  bx  c  0  b  b  4ac 2
x 
50.3x 2  0.654 x  8.98 x 10-4  0 2a
0.654  (0.654) 2  4(50.3)(8.98 x 10-4 )
x 
2(50.3)
x  0.0114 M or x  0.00156 M
[H2]i = 0.00623
[I2]i = 0.00414 E 0.00632- x 0.00414- x 0.0224 + 2x

First answer is physically impossible, since conc. of H2 and I2


would be more than original conc. x calc without quadratic:
[H2]e = 0.00623 – 0.00156) = 0.00467 M x  0.00423M

[I2]e = (0.00414 – 0.00156) = 0.00258 M Equilibrium

[HI]e = (0.0242 + 2 x 0.00156) = 0.0255 M


Equilibrium Calculations
(1) Calculating Kc from experimental data: [ ]i & [ ]e
[H2], M + [I2], M  2 [HI], M
Initially 1.000 x 10-3 2.000 x 10-3 0
Change
At Equilibrium 1.87 x 10-3
[ HI ]2
K
e

(2) Calculating Equilibrium Concentrations [ H 2 ]e [I 2 ]e


when K & [ ]i are known
H2(g) + I2(g) 2HI(g) [HI ]2e
I 0.00623 0.00414 0.0224 K  51 =
[H 2 ]e [I 2 ]e
C -x -x + 2x
E 0.00632- x 0.00414- x 0.0224 + 2x Deciding if x is negligible:
Equilibrium
 b  b  4ac
2 [A]i
ax 2  bx  c  0 x   K  [A]i x 100
2a 100
Le Châtelier’s Principle
{Equi.Intro1}

{Equi.Intro2}

“If a system at equilibrium is disturbed


by a change in temperature, pressure, or the
concentration of one of the components, the
system will shift its equilibrium position so
as to counteract the effect of the
disturbance.” [N2O4]
KC = [NO ]2
The effect of (1) Concentration 2
Henri Louis Le Chatelier
1850-1936

2 NO2 (g) 
N2O4 (g)
(red-brown gas) (clear gas)
Equilibrium
The effect of (2) Pressure & Volume (3) Temperature
{L.C.&PressVol}
Le Châtelier’s Principle
The effect of (3) Temperature

2 NO2 (g) 
N2O4 (g) + HEAT
(red-brown gas) (clear gas) H = -58.0 kJ
Why does heat
favor the formation
of NO2 over N2O4?
{Le Châtelier’s&Temp}
{Molecular Explanation}

Keq at different Temp:


Equilibrium
The Effect of Temperature Changes
Add heat (), which way will the equlibrium be shifted?

Co(H2O)62+(aq) + 4 Cl(aq) CoCl4 (aq) + 6 H2O (l)
(pink) + HEAT (blue) H= +

{CoCl}
Equilibrium
Briggs-Rauscher reaction

{ClockReaction}

Equilibrium

IO3− + 2H2O2 + CH2(COOH)2 + H+ → ICH(COOH)2 + 2O2 + 3H2O


Le Châtelier’s Principle & the Haber Process
It was not until the early 20th century that this method was
developed to harness the atmospheric abundance of nitrogen
to create ammonia, which can then be oxidized to make the
nitrates and nitrites essential for the production of fertilizers and
ammunitions.

∆H = -92.4 kJ/n
@ 250 C

Equilibrium

NH3 + HNO3  NH4NO3 (explosives & fertilizers)


Le Châtelier’s Principle & the Haber Process
Shift equilibrium to the right
Fe
N2 (g) + 3H2 (g) 2NH3 (g) by increasing press & conc. of
N2 + H2 and by removing NH3
from system
This apparatus helps
push the equilibrium to the
right by removing the
ammonia (NH3) from the
system as a liquid

Removed by liquefaction

Fe
Subs b. pt.
NH3 -33°C
N2 -196°C
Equilibrium
H2 -253°C
The Effect of Catalysts on Equilibrium

How does the


addition of a catalyst
catalyst affect
the equilibrium
between subs. A
and B?

• Increase the rate of both the forward and reverse reactions.


• Equilibrium is achieved faster, but the equilibrium Equilibrium
composition remains unaltered.
Equilibrium Constant (K)
vs. Reaction Quotient (Q)
aA(aq) + bB(aq) cC(aq) + dD(aq)
At Equilibrium: At Non-Equilibrium:

[C]c[D]d [C]ic[D]id
K= Q=
[A]a[B]b [A]ia[B]ib
• To calculate Q, one substitutes the initial
concentrations on reactants and products into the
equilibrium expression.
• Q gives the same ratio the equilibrium expression Equilibrium
gives, but for a system that is not at equilibrium.
aA(aq) + bB(aq) cC(aq) + dD(aq)

[C]c[D]d [C] c[D] d


K= Q= i i

[A]a[B]b [A] a[B] b


i i

If Q = K, the system is at equilibrium.


If Q < K? If Q < K, there is too much reactant, and the
equilibrium shifts to the right.
If Q > K? If Q > K, there is too much product and the Equilibrium
equilibrium shifts to the left.
Kc, Q and Spontaneity (ΔG)
[NH ] 2
[NH3]2eq Q= 3 i
KC =
[N2]eq[H2]eq [N2]i[H2]i

N2(g) + 3H2(g) 2NH3(g)


ΔG= -
Reverse Process

ΔG = + ΔG= -
Reverse Process

ΔG = +

Equilibrium
@ Equilibrium
K = Q, ΔG = 0
Free Energy (G) & Reaction Quotient
(Q) under non-Standard Conditions

☺ G = G + RT ln Q = G + RT 2.303 log Q


Non-standard
conditions Non-standard conditions

G = - (spontaneity), implies COMPLETE conversion of all reactants to →


products @ standard conditions (25ºC, 1 atm, 1M).

G implies DIFFERENT CONCENTRATIONS of both reactants ↔ products


and under non-standard conditions of concentration, temperature and
pressure.
• If [Reactants]↑, then G = -
[ Products]p
• If [Products]↑, then G = + Q
[ Reactants]r
• If at Equilibrium , then G = 0 Equilibrium
Free Energy (G) & Equilibrium Constant (K)
at Equilibrium
At equilibrium, G = 0 and Q = K so……

G = G + RT ln Q
0 = G + RT ln K
Rearranging ……
K = eG/RT

G = - RT ln K = - 2.303 RT log K ☺


G K Product formation
– >1 Product-favored @ Equilibrium
0 =1 [Products] = [Reactants] @ Equilibrium (RARE)
Equilibrium

+ <1 Reactant-favored @ Equilibrium


Free Energy (ΔG), the Equilibrium
Constant (ΔK),and Temperature
Low Temp. How would T ↓or ↑ affect K?
2 NO2 (g) High Temp.
N2O4 (g) H = -58.0 kJ
(red-brown gas) (clear gas)
[ Products]p @ T ↓, K ↑ G°= -
K
G = - RT ln K [ Reactants]r @ T ↑, K ↓ G°= +
Low Temperature: High Temperature:

G°= - G°= +

Q=K

Reactants Equilibrium Products


only mixture only Equilibrium

{G, Q & T↓ NO2 → N2O4}LowT {G, Q & T↑NO2 ← N2O4}HighT


2003B Q1
2 HIH2 + I2

Equilibrium
2003B Q1 Kp = Kc(RT)Δn

Equilibrium
2000A Q1

Equilibrium
2000A Q1

Equilibrium
Equilibrium
Equilibrium
2004B Q1

Equilibrium
Equilibrium
2007B Q1

Equilibrium
2000 1

Equilibrium
Equilibrium
Equilibrium
2003 B

Equilibrium
Equilibrium
2004 B

Equilibrium
Equilibrium
2006 A

Equilibrium
Equilibrium
2006 (B)

Equilibrium
Equilibrium
Equilibrium
Equilibrium
Equilibrium
Equilibrium
Equilibrium
2007 (B)

Equilibrium
Equilibrium