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Chemical Equilibrium
Brown, LeMay Ch 15 AP Chemistry Monta Vista High School
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15.1: Chemical Equilibrium

Occurs when opposing reactions are proceeding at the same rate

Forward rate = reverse rate of reaction Ex: Vapor pressure: rate of vaporization = rate of condensation Saturated solution: rate of dissociation = rate of crystallization

Expressing concentrations:
Gases: partial pressures, PX Solutes in liquids: molarity, [X]

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Forward reaction: Reverse reaction: or

AB BA

Rate = kforward [A] Rate = kreverse [B]

PV nRT
[ A]

M PA RT

n P V RT [ B] PA RT PB RT PB RT
R = 0.0821 Latm molK

Forward reaction: Reverse reaction:

Rate k f Rate k r

http://www.kentchemistry.com/links/Kinetics/Equilibrium/equilibrium .swf

k f [A] k r [B]

or

kf

PA P kr B RT RT

[B] k f [A] k r

or

PB k f constant K eq PA k r

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Kc= kf/kr, at equilibrium, if K> 1, then

more products at equilib. And if k<1, then reactants favored at equilb. K=1 (conc. Of reactants and products nearly same at equilibrium) The magnitude of Kc gives us an indication of how far the reaction has proceeded toward the formation of products, when the equilibrium is achieved. The larger the value of K, the further the reaction will have proceeded towards completion when equilibrium is reached. 5

Equilibrium
Equilibrium is dynamic. The forward and reverse rxns occur at the same rate. There is a spontaneous tendency towards equilibrium. This does not mean that equilibrium will occur quickly, it simply means that there is always a drive TOWARD the equilibrium state. The amount of drive is measured as Free Energy (D G) The driving force towards equilibrium diminishes as equilibrium is approached. Thus the appearance of products actually decreases the forward impetus of the reaction, making the free energy change less negative. http://www.youtube.com/watch?v=CMs2WhGY3NE 6

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Equilibrium
The equilibrium position is the same at a given temperature, no matter from which direction it is approached. It is possible to force an equilibrium one way or the other temporarily by altering the reaction conditions, but once this stress is removed, the system will return to its original equilibrium.

Figure 1: Reversible reactions

[A]0 or PA0 / RT [A] or PA / RT PX or [X] [B] or PB / RT Equilibrium is established

Time
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Reversible Reactions and Rate

Forward rate Reaction Rate Equilibrium is established: Forward rate = Backward rate

Backward rate Time When equilibrium is achieved: [A] [B] and kf/kr = Keq
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15.2: Law of Mass Action

Derived from rate laws by Guldberg and Waage (1864)

For a balanced chemical reaction in equilibrium:

aA+bBcC+dD

Equilibrium constant expression (Keq):

Cato Guldberg (1836-1902)

Peter Waage (1833-1900)

[C]c [D]d Kc [A]a [B]b

or

(PC ) c (PD ) d Kp (PA ) a (PB ) b

Keq is strictly based on stoichiometry of the reaction (is independent of the mechanism). Units: Keq is considered dimensionless (no units)
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Relating Kc and Kp
Convert [A] into PA:

n P V RT

PA [ A]RT

(PC ) c (PD ) d ([C]RT) c ([D]RT) d [C]c [D]d (RT) c d Kp (PA ) a (PB ) b ([A]RT) a ([B]RT) b [A]a [B]b (RT) a b

K p K c (RT) (c d) - (a b) K c (RT) n
where n = = change in coefficents of products reactants (gases only!) = (c+d) - (a+b)
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Magnitude of Keq
Since Keq [products]/[reactants], the magnitude of Keq predicts which reaction direction is favored:

If Keq > 1

then [products] > [reactants] and equilibrium lies to the right then [products] < [reactants] and equilibrium lies to the left

If Keq < 1

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Relationship Between Q and K

Reaction Quotient (Q): The particular ratio of concentration terms that we write for a particular reaction is called reaction quotient. For a reaction, A B, Q= [B]/[A] At equilibrium, Q= K Reaction Direction: Comparing Q and K Q<K, reaction proceeds to right, until equilibrium is achieved (or Q=K) Q>K, reaction proceeds to left, until Q=K
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Value of K
For the For the For the reference reverse rxn, reaction, rxn, A>B, B >A, 2A > 2B For the rxn, A > C C > B

K(ref)= [B]/[A]

K= 1/K(ref)

K= K(ref)2

K (overall)= K1 X K2

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15.3: Types of Equilibria

Homogeneous: all components in same phase (usually g or aq) 1 N2 (g) + 3 H2 (g) 2 NH3 (g)

(PC ) c (PD ) d KP (PA ) a (PB ) b

Fritz Haber (1868 1934)

KP

(PNH 3 ) 2 (PN 2 )1 (PH 2 )3

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Heterogeneous: different phases CaCO3 (s) CaO (s) + CO2 (g) Definition: What we use:

K eq

[CaO] (PCO 2 ) [CaCO 3 ]

K p PCO 2

Concentrations of pure solids and pure liquids are not included in Keq expression because their concentrations do not vary, and are already included in Keq (see p. 548). Even though the concentrations of the solids or liquids do not appear in the equilibrium expression, the substances must be present to achieve equilibrium.
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15.4: Calculating Equilibrium Constants

Steps to use ICE table: 1. I = Tabulate known initial and equilibrium concentrations of all species in equilibrium expression 2. C = Determine the concentration change for the species where initial and equilibrium are known Use stoichiometry to calculate concentration changes for all other species involved in equilibrium 3. E = Calculate the equilibrium concentrations

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Ex: Enough ammonia is dissolved in 5.00 L of water at 25C to produce a solution that is 0.0124 M ammonia. The solution is then allowed to come to equilibrium. Analysis of the equilibrium mixture shows that [OH1-] is 4.64 x 10-4 M. Calculate Keq at 25C for the reaction:

NH3 (aq) + H2O (l) NH41+ (aq) + OH1- (aq)

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NH3 (aq) + H2O (l) NH41+ (aq) + OH1- (aq)

NH3 (aq)
Initial Change Equilibrium

H 2O (l)

NH41+ (aq)

OH1- (aq)

0.0124 M
-x

0.0119 M

X X X

0M
+x 4.64 x 10-4 M

0M
+x 4.64 x 10-4 M

x = 4.64 x 10-4 M

[NH 4 ][OH1- ] (4.64 10-4 ) 2 Kc 1.81x 10 -5 [NH 3 ] 0.0119

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Ex: A 5.000-L flask is filled with 5.000 x 10-3 mol of H2 and 1.000 x 10-2 mol of I2 at 448C. The value of Keq is 1.33. What are the concentrations of each substance at equilibrium?

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

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

H2 (g)
Initial Change Equilibrium

I2 (g)

HI (g)

1.000x10-3 M
-xM
2

2.000x10-3 M
-xM

0M
+ 2x M 2x M

(1.000x10-3 x) M (2.000x10-3 x) M

Kc

[HI] (2x) 2 1.33 [H 2 ][I 2 ] (1.000 10-3 - x)(2.000 10-3 - x)

4x2 = 1.33[x2 + (-3.000x10-3)x + 2.000x10-6] 0 = -2.67x2 3.99x10-3x + 2.66x10-6 Using quadratic eqn: x = 5.00x10-4 or 1.99x10-3; x = 5.00x10-4 Then [H2]=5.00x10-4 M; [I2]=1.50x10-3 M; [HI]=1.00x10-3 M
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15.6: Le Chteliers Principle

If a system at equilibrium is disturbed by a change in:
Concentration of one of the components, Pressure, or Temperature

Henri Le Chtelier (1850 1936)

the system will shift its equilibrium position to counteract the effect of the disturbance.
http://www.mhhe.com/physsci/chemistry/essentialchemistry /flash/lechv17.swf
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4 Changes that do not affect Keq:

1. Concentration Upon addition of a reactant or product, equilibrium shifts to re-establish equilibrium by consuming part of the added substance. Upon removal of reactant or product, equilibrium shifts to re-establish equilibrium by producing more of the removed substance. Ex: Co(H2O)62+ (aq) + 4 Cl1- CoCl42- (aq) + 6 H2O (l) Add HCl, temporarily inc forward rate Add H2O, temporarily inc reverse rate
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2. Volume, with a gas present (T is constant)

Upon a decrease in V (thereby increasing P), equilibrium shifts to reduce the number of moles of gas. Upon an increase in V (thereby decreasing P), equilibrium shifts to produce more moles of gas.

Ex: N2 (g) + 3 H2 (g) 2 NH3 (g) If V of container is decreased, equilibrium shifts right.

XN2 and XH2 dec XNH3 inc

KP

(PNH3 ) 2 PN 2 (PH 2 ) 3

(X NH 3 PT ) 2 (X N 2 PT )(X H 2 PT ) 3

(X NH3 ) 2 PT

2 4

X N 2 (X H 2 ) 3 PT

(X NH3 ) 2 X N 2 (X H 2 ) 3 PT
2

Since PT also inc, KP remains constant. K P

( NH 3 ) 2 N 2 ( H 2 ) 3 2
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3. Pressure, but not Volume

Usually addition of a noble gas, p. 560

Avogadros law: adding more non-reacting particles fills in the empty space between particles. In the mixture of red and blue gas particles, below, adding green particles does not stress the system, so there is no Le Chtelier shift.

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4. Catalysts
Lower the activation energy of both forward and reverse rxns, therefore increases both forward and reverse rxn rates. Increase the rate at which equilibrium is achieved, but does not change the ratio of components of the equilibrium mixture (does not change the Keq) Ea, uncatalyzed
Energy

Ea, catalyzed

Rxn coordinate

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1 Change that does affect Keq:

Temperature: consider heat as a part of the reaction Upon an increase in T, endothermic reaction is favored (equilibrium shifts to consume the extra heat) Upon a decrease in T, equilibrium shifts to produce more heat. Effect on Keq 1. Exothermic equilibria: Reactants Products + heat Inc T increases reverse reaction rate which decreases Keq 2. Endothermic equilibria: Reactants + heat Products Inc T increases forward reaction rate increases Keq
Ex: Co(H2O)62+ (aq) + 4 Cl1- CoCl42- (aq) + 6 H2O (l); H=+? Inc T temporarily inc forward rate Dec T temporarily inc reverse rate

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Vant Hoffs Equation

Vant Hoffs equation shows mathematically how the equilibrium constant is affected by changes in temp.

ln K2 = -d H0 K1 R

rxn

(1 1) T 2 T1

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Effect of Various Changes on Equilibrium

Disturbance
Concentration Increase (reactant)

Net Direction of Rxn

Towards formation of product Towards formation of reactant Towards formation of reactant Towards formation of product

Effect of Value of K
None

Decrease(reactant) Increase (product) Decrease (product)

None None None

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Effect of Pressure on Equilb.

Pressure Increase P (decrease V) Decrease P (Increase V) Towards formation of fewer moles of gas Towards formation of more moles of gas None, concentrations unchanged None

None

Increase P ( Add inert gas, no change in V)

None

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Effect of Temperature on Equilb

Temperature Increase T Towards absorption of heat Increases if endothermic Decreases if exothermic Increases if exothermic Decreases if endothermic None

Decrease T

Towards release of heat

Catalyst Added

None, forward and reverse equilibrium attained sooner

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