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15.1 The Concept of Equilibrium

Most chemical reactions are reversible. p.592

Chapter 15 reversible reaction = a reaction that proceeds

simultaneously in both directions
Chemical Examples:
Equilibrium 
N2 (g ) + 3 H2 (g ) ←→ 2 NH (g )
 3


CO(g ) + 2 H2 ( g ) ←→ CH OH(g )
 3


N2O 4 ( g ) ←→ 2 NO (g )
 2


Double arrows ( ←→ ) denote an equilibrium reaction.


Equilibrium Equilibrium

Consider the reaction N2O 4 (g ) ←→ 2 NO (g )
 Let’s use 2 experiments to study the reaction
2

N2O 4 (g ) ← → 2 NO (g )
 2
At equilibrium, each starting with a different reactant(s).
the forward reaction: N2O4(g) → 2 NO2(g), and
Exp #1 Exp #2
the reverse reaction: 2 NO2(g) → N2O4(g)
proceed at equal rates.

Chemical equilibria are dynamic, not static – the
reactions do not stop.

pure N2O4 pure NO2

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Equilibrium Equilibrium
Experiment #1 
N2O 4 ( g ) ←→ 2 NO (g )
 Experiment #2 
N2O 4 ( g ) ←→ 2 NO (g )

2 2

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p.594
Equilibrium 15.2 The Equilibrium Constant

N2O 4 ( g ) ←→ 2 NO (g )
 2 At equilibrium,
rate forward = ratereverse

N2O 4 ( g ) ←→ 2 NO (g )
 2

kf [N 2O4 ]eq = kr [NO2 ]2eq

or
2
kf [NO2 ]eq
= = Kc
kr [N 2O4 ]eq

where Kc is the equilibrium constant

Are the equilibrium pressures of NO2 and N2O4
related? Are they predictable?
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p.595
The Equilibrium Constant The Equilibrium Constant
For the NO2 / N2O4 system:

N2O 4 (g ) ←→ 2 NO (g )
 2

[NO 2 ]2
K = = 0.143 at 25°C
[N2 O4 ]

equilibrium constant
equilibrium constant expression
This constant value is termed
the equilibrium constant,
Note: at 100°C, K = 6.45
Kc, for this reaction at 25°C.
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The Equilibrium Constant The Equilibrium Constant

reaction quotient = Qc = the value of the For a reaction: 
a A + bB ←→ c C + d D

“equilibrium constant expression” under
any conditions.
PCc ⋅ PDd
For, 
CO(g ) + Cl2 (g ) ←→ COCl ( g )

For gases: KP = P in atm
2 PA a ⋅ PBb
[COCl2 ]eq [COCl2 ]
Kc = Qc =
[CO]eq [Cl2 ]eq [CO][Cl2 ] [C]c [D]d
For solutions: Kc = [ ] = mol/L
[A]a [B]b

Q > K ⇒ reverse reaction favored

Q = K ⇒ equilibrium present p.595 The Law of Mass Action:
Cato Maximilian Guldberg & Peter Waage,
Q < K ⇒ forward reaction favored Forhandlinger: Videnskabs-Selskabet i
Christiana 1864, 35.
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p.599
The Equilibrium Constant 15.3 Equilibrium Expressions
c d
[C] [D] homogeneous equilibria = equilibria in which all
Note: Kc =
[A]a [B]b reactants and products are in the same phase.
• The equilibrium constant expression has products heterogeneous equilibria = equilibria in which all
in the numerator, reactants in the denominator. reactants and products are not in the same phase.
• Reaction coefficients become exponents.
Ex: 
CaCO3 (s ) ←→ CaO(s ) + CO (g )
 2
• Equilibrium constants are temperature dependent.
The equilibrium constant expression is,
• Equilibrium constants do not have units. (p.622)
K = [CO2]
• If K >>> 1, products favored (reaction goes
nearly to completion). • [CaO] and [CaCO3] are solids.
• If K <<< 1, reactants favored (reaction hardly • Pure solids and liquids are omitted from equilibrium
proceeds). constant expressions.

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Exercise: Write the expressions for Kp for the Equilibrium Expressions

following reactions: A. Reverse Equations

(a) NH4NO3 (s ) ←→ N O(g ) + 2 H O(g )
 For, 
N2O 4 (g ) ←→ 2 NO (g )
 [1]
2 2 2
→ CuCl (s) ( )
2
(b) Cu(s ) + Cl2 (g ) ← 2 PNO2
K1 = = 0.143 at 25o C
PN2O4
Solution:
For, 
2 NO2 ( g ) ←→ N O (g )
 [2]
( )
2 4
2
(a) K P = P N 2O ⋅ P H 2O PN2O4 1
( PNO )
K2 = 2 = = 6.99 at 25o C
0.143
1 2
(b) K P =
PCl2 Conclusion:
1
K2 =
K1
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Equilibrium Expressions Equilibrium Expressions

B. Coefficient Changes C. Reaction Sum (related to Hess’ Law)

For, N O (g ) ←→ 2 NO ( g )

For, 
N2O 4 (g ) ←→ 2 NO (g )
 [1] 2 4 2 [1]

( )
2
2 PNO 2 2
PNO2 K1 =
K1 = = 0.143 at 25 C
o
PN2O4
PN2O4
For, 
2 NO2 (g ) ←→ 2 NO(g ) + O ( g )
 [4]
1  → NO (g ) 2
( PNO )2 PO2
For, N2O 4 (g ) ← 2 [3]
2

( PNO )
PNO2 K4 = 2

( )
K3 = 1/2 = 0.143 = 0.378 at 25o C 2
PN2O4 Add [1] + [4],
Conclusion: N2O 4 (g ) ← → 2 NO(g ) + O (g )
 [5]
2
( PNO )2 PO2
K3 = K1 K5 = = K1 × K 4
PN 2O4
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p.601
Equilibrium Expressions Exercise: At 500ºC, KP = 2.5 × 1010 for,

2 SO2 (g ) + O2 (g ) ←→ 2 SO (g )
 3
(a) At 500ºC, which is more stable, SO2 or SO3?

Compute KP for each of the following:

(b) SO 2 (g) +
1 
O (g) ←→ SO (g)

2 2 3

(c) 3 SO 2 (g) +
3 
O (g) ←→ 3 SO (g)

2 2 3


(d) SO3 (g) ←→ SO (g) + 1 O (g)
 2 2
2

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p.606
15.4 Using Equilibrium Exercise #1: At 448°C, K = 51 for the reaction,

H (g ) + I (g ) ←→ 2 HI(g )

Expressions to Solve Problems 2 2
Predict the direction the reaction will proceed, if at
Predicting the direction of a reaction 448°C the pressures of HI, H2, and I2 are 1.3,
2.1 and 1.7 atm, respectively.
Compare the computed value of Q to K Solution:

Q > K ⇒ reverse reaction favored Q =

( PHI ) = (1.3)2 = 0.47
2

PH2 ⋅ PI2 (2.1) ⋅ (1.7)

Q = K ⇒ equilibrium present
Q < K ⇒ forward reaction favored 0.47 < 51 ⇒ system not at equilibrium
Numerator must increase and denominator must
decrease.
Consequently the reaction must shift to the right.

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Exercise #2: At 1130°C, K = 2.59 × 10−2 Exercise #3: K = 82.2 at 25°C for,
for → 2 ICl(g )
→ 2 H (g ) + S (g ) I ( g ) + Cl (g ) ←
2 2 
2 H2S(g ) ← 2 2
At equilibrium, PH2S = 0.557 atm and PH2 = 0.173 atm, Initially, PI2 = PCl2 = 2.00 atm and PICl = 0.00 atm.
calculate PS2 at 1130°C. What are the equilibrium pressures of I2, Cl2, and ICl?

( PH ) ⋅ PS Solution:
2
I2 ( g ) + 
Cl2 (g ) ←→ 2 ICl(g )

( PH S )
Solution: K = 2 2
2
= 2.59 × 10−2
Initial 2.00 atm 2.00 atm 0.00 atm
−x −x
2
Change +2x
(0.173) 2 ⋅ PS2 Equilibrium (2.00 – x) (2.00 – x) 2x
= = 2.59 × 10−2
(0.557) 2 PICl 2 (2 x )2
K = = = 82.2
PI2 ⋅ PCl2 (2.00 − x )(2.00 − x )
PS2 = 0.268 atm
perfect square
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Exercise #3: (cont.) Exercise #4: At 1280°C, Kc = 1.1 × 10−3 for

2 
Br (g ) ←→ 2 Br(g )

(2 x ) 2
= 82.2
(2.00 − x )(2.00 − x ) Initially, [Br2] = 6.3 × 10−2 M and [Br] = 1.2 × 10−2
M. What are the equilibrium concentrations of Br2
(2 x) and Br at 1280°C?
square root ⇒ = 9.066 → 2 Br(g )
(2.00 − x ) Solution: Br ( g ) ←
2 
Initial 6.3 × 10−2 M 1.2 × 10−2 M
2 x = 18.132 – 9.066 x
Change -x +2x
11.066 x = 18.132 Equilibrium (6.3 × 10−2) - x (1.2 × 10−2) + 2x
x = 18.132 / 11.066 = 1.639 [Br]2 [(1.2 × 10−2 ) + 2 x ]2
Kc = = = 1.1× 10−3
PI2 = PCl2 = 2.00 – x = 2.00 – 1.639 = 0.36 atm [Br2 ] (6.3 × 10−2 ) − x
PICl = 2x = (2)(1.639) = 3.28 atm
4x2 + 0.0491x + (7.47 × 10−5) = 0
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4x2 + 0.0491x + (7.47 × 10-5) = Exercise #5: A pure NO2 sample reacts at 1000 K,
0 
2 NO (g ) ←→ 2 NO(g ) + O (g )

quadratic equation: ax2 + bx + c = 0 2 2
KP is 158. If at 1000 K the equilibrium partial
−b ±
b2 − 4ac
solution: x = pressure of O2 is 0.25 atm, what are the equilibrium
2a
partial pressures of NO and NO2.
x = −1.779 × 10−3 and −1.050 × 10−2

Solution: 2 NO2 (g ) ←→ 2 NO(g ) + O (g)

Q: Two answers? Both negative? What’s happening? 2
Initial ? 0 atm 0 atm
Equilibrium Conc. x = −1.779 × 10−3 − 1.050 × 10−2 Change −0.50 +0.50 +0.25
[Br2] = (6.3 × 10−2) – x = 0.0648 M 0.0735 M Equilibrium PNO2 +0.50 atm 0.25 atm

( PNO ) ⋅ PO
[Br] = (1.2 × 10−2) + 2x = 0.00844 M − 0.00900 M 2
(0.50)2 (0.25)
( PNO ) ( PNO )
2
KP = = = 158
[Br2] = 6.5 × 10−2 M 2 2
impossible 2 2
[Br] = 8.4 × 10−3 M
27 rearrange and solve 28

Exercise #5: (cont.) Exercise #6: The total pressure of an equilibrium

mixture of N2O4 and NO2 at 25°C is 1.30 atm.
(0.50) 2 (0.25)
( PNO )
= 158 For the reaction:
→ 2 NO (g )
2
2
N2O 4 (g ) ← 2

( PNO ) (0.50)2 (0.25)

= 3.956 × 10−4
KP = 0.143 at 25°C. Calculate the equilibrium
2
=
2
158 partial pressures of N2O4 and NO2.

( PNO )
2
PNO2 = 3.956 × 10−4 = 0.01989
KP = 2
= 0.143
PN2O4
PNO2 = 0.020 atm
PNO = 0.50 atm PNO2 + PN2O4 = 1.30 atm

see ICE table two equations and two unknowns – BINGO!

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Exercise #6: (cont.)

p.611
15.5 Factors That Affect
( PNO ) Chemical Equilibrium
2

KP = 2
= 0.143 PNO2 + PN2O4 = 1.30 atm
PN 2O4 Le Châtelier’s Principle
PN2O4 = 1.30 atm - PNO2 “If an equilibrium system variable is changed, the
( )
2 equilibrium will shift in the direction (right or left)
PNO2
= 0.143 that tends to reduce the change.”
(1.30 − PNO2 )

PNO22 + 0.143 PNO2 − 0.1859 = 0 Example: N2, H2, and NH3 are at equilibrium in a
container at 500°C.
Use the quadratic formula, 
N (g ) + 3 H ( g ) ←→ 2 NH (g ) ∆Ho = −92kJ

2 2 3 rxn
PNO2 = +0.366 atm and −0.509 atm
(continued on next 5 slides)
PN2O4 = 1.30 atm - PNO2 = 1.30 − 0.366 = 0.934 atm
PN2O4 = 0.93 atm
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Case II: Change: compress the system

Shift: to???
the right
Case I: Change: N2 is added
Shift: to???
the right N2 H2
NH3
Q: Why?
Q: Why?
Ans: Total pressure has increased. Which
Ans: [N2] has increased. Which direction direction will decrease the total pressure?
will decrease [N2]? Recall: P ∝ n
→ 2 NH (g ) N (g ) + 3 H (g ) ← → 2 NH (g )

N2 (g ) + 3 H2 (g ) ← 3 2 2 3
right (4 moles gas) (2 moles gas)
N2 decreases
less gas
left
N2 increases less pressure
more gas
more pressure
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Case III: Change: increase the temperature

Case IV: Change: add helium at constant volume
Shift: to???
the left
Shift: none
???
Q: Why?
Q: Why?
Ans: Temperature has increased. Which
direction decreases the temperature? Ans: Helium is not a reactant or product.
Adding helium (at constant V) does not
Recall, the reaction is exothermic. change PN2, PH2 or PNH3. Hence the
∆H orxn = − 92 kJ equilibrium will not shift.

right exothermic
heat evolved
endothermic left
heat absorbed

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Case V: Change: add helium at constant Exercise: Hydrogen (used in ammonia production)
total pressure is produced by the endothermic reaction,
Shift: to
???
the left Ni

CH4 (g ) + H2O(g ) ←→ CO( g ) + 3H2 (g )

Q: Why? 750°C
Ans: If the total pressure is constant, PN2 + Assuming the reaction is initially at equilibrium,
PH2 + PNH3 must decrease. Which indicate the direction of the shift (L, R, none) if
direction increases this sum?
Recall: P ∝ n (a) H2O(g) is removed. Left

N2 (g ) + 3 H2 (g ) ←→ 2 NH (g )
 (b) The temperature is increased. Right
3
(4 moles gas) (2 moles gas) (c) The quantity of Ni catalyst is increased. None
less gas (d) An inert gas (e.g., He) is added. None
less pressure (e) H2(g) is removed. Right
more gas
more pressure (f) The volume of the container is tripled. Right

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