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Chemical Equilibrium

Equilibrium
Equilibrium is a state in which there are no observable changes as time goes by. Chemical equilibrium is achieved when: 1.) the rates of the forward and reverse reactions are equal and 2.) the concentrations of the reactants and products remain constant

Equilibrium
There are two types of equilibrium: Physical and Chemical.
Physical Equilibrium H20 (l) H20 (g) Chemical Equilibrium N2O4 (g) 2NO2

Physical Equilibrium

Chemical Equilibrium

Chemical Equilibrium
N2O4 (g) 2NO2 (g)

Law of Mass Action


Law of Mass Action- For a reversible reaction at equilibrium and constant temperature, a certain ratio of reactant and product concentrations has a constant value (K). The Equilibrium Constant (K)- A number equal to the ratio of the equilibrium concentrations of products to the equilibrium concentrations of reactants each raised to the power of its stoichiometric coefficient.

Law of Mass Action


For the general reaction:
aA (g) + bB (g) cC (g) + dD (g)

K=

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

Equilibrium Constant
N2O4 (g) 2NO2 (g)

Chemical Equilibrium
Chemical equilibrium is defined by K. The magnitude of K will tell us if the equilibrium reaction favors the reactants or the products. If K 1..favors products If K 1..favors reactants

Equilibrium Constant Expressions


Equilibrium constants can be expressed using Kc or Kp. Kc uses the concentration of reactants and products to calculate the eq. constant. Kp uses the pressure of the gaseous reactants and products to calculate the eq. constant.

Equilibrium Constant Expressions


Equilibrium Constant Equations
aA (g) + bB (g) cC (g) + dD (g)
2 PNO 2

Kc =

[NO2

]2

[N2O4]

Kp =

P N2O4

Homogeneous Equilibrium
Homogeneous Equilibrium- applies to reactions in which all reacting species are in the same phase. N2O4 (g) 2NO2 (g)
Kc = [NO2]2 [N2O4] Kc Kp
2 PNO 2

Kp = In most cases

P N2O4

Equilibrium Constant Expressions


Relationship between Kc and Kp Kp = Kc(RT)Dn
Dn = moles of gaseous products moles of gaseous reactants = (c + d) (a + b)

Equilibrium Constant Calculations


The equilibrium concentrations for the reaction between carbon monoxide and molecular chlorine to form COCl2 (g) at 740C are [CO] = 0.012 M, [Cl2] = 0.054 M, and [COCl2] = 0.14 M. Calculate the equilibrium constants Kc and Kp.

CO (g) + Cl2 (g)

COCl2 (g)

[COCl2] 0.14 = 220 = Kc = [CO][Cl2] 0.012 x 0.054


Kp = Kc(RT)Dn

Dn = 1 2 = -1

R = 0.0821

T = 273 + 74 = 347 K

Kp = 220 x (0.0821 x 347)-1 = 7.7

Equilibrium Constant Calculations


The equilibrium constant Kp for the reaction is 158 at 1000K. What is the equilibrium pressure of O2 if the PNO = 0.400 atm and PNO = 0.270 atm? Kp =
2 PNO PO2 2 PNO 2 2 PNO 2

PO2 = Kp

PNO

PO2 = 158 x (0.400)2/(0.270)2 = 347 atm

Heterogeneous Equilibrium
Heterogeneous Equilibrium- results from a reversible reaction involving reactants and products that are in different phases. Can include liquids, gases and solids as either reactants or products. Equilibrium expression is the same as that for a homogeneous equilibrium. Omit pure liquids and solids from the equilibrium constant expressions.

Heterogeneous Equilibrium Constant


CaCO3 (s)
[CaCO3] = constant [CaO] = constant

CaO (s) + CO2 (g)


Kp = PCO2

The concentration of solids and pure liquids are not included in the expression for the equilibrium constant.

Heterogeneous Equilibrium Constant

Equilibrium Constant Calculations


Consider the following equilibrium at 295 K:

NH4HS (s) NH3 (g) + H2S (g) The partial pressure of each gas is 0.265 atm. Calculate Kp and Kc for the reaction. P = 0.265 x 0.265 = 0.0702 Kp = P NH H S
3 2

Kp = Kc(RT)Dn Kc = Kp(RT)-Dn

Dn = 2 0 = 2

T = 295 K

Kc = 0.0702 x (0.0821 x 295)-2 = 1.20 x 10-4

Multiple Equilibria
Multiple Equilibria- Product molecules of one equilibrium constant are involved in a second equilibrium process.

A+B C+D A+B

C+D E+F E+F

Kc Kc Kc

[C][D] Kc = [A][B]

[E][F] Kc = [C][D]
[E][F] Kc = [A][B]

Kc = Kc x Kc

Writing Equilibrium Constant Expressions


The concentrations of the reacting species in the condensed phase are expressed in M. In the gaseous phase, the concentrations can be expressed in M or in atm. The concentrations of pure solids, pure liquids and solvents do not appear in the equilibrium constant expressions. The equilibrium constant is a dimensionless quantity. In quoting a value for the equilibrium constant, you must specify the balanced equation and the temperature. If a reaction can be expressed as a sum of two or more reactions, the equilibrium constant for the overall reaction is given by the product of the equilibrium constants of the individual reactions.

14.2

What does the Equilibrium Constant tell us?


We can:
Predict the direction in which a reaction mixture will proceed to reach equilibrium Calculate the concentration of reactants and products once equilibrium has been reached

Predicting the Direction of a Reaction


The Kc for hydrogen iodide in the following equation is 53.4 at 430C. Suppose we add 0.243 mol H2, 0.146 mol I2 and 1.98 mol HI to a 1.00L container at 430C. Will there be a net reaction to form more H2 and I2 or HI? H2 (g) + I2 (g) 2HI (g) [HI]02 Kc = [H2]0 [I2]0

[1.98]2 Kc = [0.243] [0.146]

Kc = 111

Reaction Quotient
The reaction quotient (Qc) is calculated by substituting the initial concentrations of the reactants and products into the equilibrium constant (Kc) expression.

IF Qc > Kc system proceeds from right to left to reach equilibrium Qc = Kc the system is at equilibrium Qc < Kc system proceeds from left to right to reach equilibrium

Reaction Quotient

Calculating Equilibrium Concentrations


If we know the equilibrium constant for a reaction and the initial concentrations, we can calculate the reactant concentrations at equilibrium. ICE method Reactants Products Initial (M): Change (M): Equilibrium (M):

Calculating Equilibrium Concentrations


At 1280C the equilibrium constant (Kc) for the reaction is 1.1 x 10-3. If the initial concentrations are [Br2] = 0.063 M and [Br] = 0.012 M, calculate the concentrations of these species at equilibrium. Br2 (g) 2Br (g) Let x be the change in concentration of Br2 Br2 (g) 2Br (g) 0.012 0.063 Initial (M) Change (M) Equilibrium (M)

-x 0.063 - x

+2x 0.012 + 2x

Calculating Equilibrium Concentrations


[Br]2 Kc = [Br2] (0.012 + 2x)2 = 1.1 x 10-3 Kc = 0.063 - x

4x2 + 0.048x + 0.000144 = 0.0000693 0.0011x


4x2 + 0.0491x + 0.0000747 = 0 -b b2 4ac x= 2a

ax2

+ bx + c = 0

x = -0.0105
x = -0.00178

Calculating Equilibrium Concentrations


Br2 (g)
Initial (M) Change (M) 0.063 -x

2Br (g)
0.012 +2x

Equilibrium (M)

0.063 - x

0.012 + 2x

At equilibrium, [Br] = 0.012 + 2x = -0.009 M or 0.00844 M At equilibrium, [Br2] = 0.063 x = 0.0648 M

Calculating Equilibrium Concentrations


Express the equilibrium concentrations of all species in terms of the initial concentrations and a single unknown x, which represents the change in concentration. Write the equilibrium constant expression in terms of the equilibrium concentrations. Knowing the value of the equilibrium constant, solve for x. Having solved for x, calculate the equilibrium concentrations of all species.

Factors that Affect Chemical Equilibrium


Chemical Equilibrium represents a balance between forward and reverse reactions. Changes in the following will alter the direction of a reaction:
Concentration Pressure Volume Temperature

Le Chtliers Principle
Le Chtliers Principle- if an external stress is applied to a system at equilibrium, the system adjusts in such a way that the stress is partially offset as the system reaches a new equilibrium position. Stress???

Changes in Concentration
Increase in concentration of reactants causes the equilibrium to shift to the ________. Increase in concentration of products causes the equilibrium to shift to the ________.

Changes in Concentration
Change Increase in [Products] Decrease in [Products] Increase in [Reactants] Decrease in [Reactants] Shift in Equilibrium left right right left

Changes in Concentration
FeSCN2+(aq) Fe3+(aq) + SCN-(aq) a.) Solution at equilibrium b.) Increase in SCN-(aq) c.) Increase in Fe3+(aq) d.) Increase in FeSCN2+(aq)

Changes in Volume and Pressure


Changes in pressure primarily only concern gases. Concentration of gases are greatly affected by pressure changes and volume changes according to the ideal gas law. PV = nRT P = (n/V)RT

Changes in Pressure and Volume


Change Increase in Pressure Decrease in Pressure Increase in Volume Decrease in Volume Shift in Equilibrium Side with fewest moles Side with most moles Side with most moles Side with fewest moles

Changes in Pressure and Volume

Changes in Temperature
Equilibrium position vs. Equilibrium constant A temperature increase favors an endothermic reaction and a temperature decrease favors and exothermic reaction.
Change Increase T Decrease T Endo. Rx K decreases K increases Exo. Rx K increases K decreases

Changes in Temperature
Consider: N2O4(g) 2NO2(g)
The forward reaction absorbs heat; endothermic heat + N2O4(g) 2NO2(g) So the reverse reaction releases heat; exothermic 2NO2(g) N2O4(g) + heat Changes in temperature??

Effect of a catalyst
How would the presence of a catalyst affect the equilibrium position of a reaction?