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General practice does not include units forthe equilibrium constant.
9
The equilibrium concentrations for the reaction between carbonmonoxide and molecular chlorine to form COCl 2 (g ) at 740C are[CO] = 0.012 M , [Cl2] = 0.054 M , and [COCl2] = 0.14 M . Calculatethe equilibrium constants K c and K p .
10
The equilibrium constant K p for the reaction
is 158 at 1000K. What is the equilibrium pressure of O2 if theP NO = 0.400 atm and P NO = 0.270 atm?
2
2NO2 (g ) 2NO (g ) + O2 (g )
11
Heterogenous equilibrium applies to reactions in whichreactants and products are in different phases.
CaCO3 (s ) CaO (s ) + CO2 (g )
[CaCO3] = constant[CaO] = constant
K c = [CO2] = K p = P CO2
[CaO][CO2]
[CaCO3]K c =′
[CaCO3]
[CaO]K c x′
12
P CO2= K p
CaCO3 (s ) CaO (s ) + CO2 (g )
P CO2does not depend on the amount of CaCO3 or CaO
The partial pressure of each gas is 0.265 atm. Calculate K p andK c for the reaction?
NH4HS (s ) NH3 (g ) + H2S (g )
14
K c =′ [C][D]
[A][B]K c =′ ′
[E][F]
[C][D]
[E][F]
[A][B]K c =
A + B C + D
C + D E + F
A + B E + F
K c ′
K c ′′
K c
K c = K c ′′ K c ′ x
If a reaction can be expressed as the sum of two or morereactions, the equilibrium constant for the overall reaction is
given by the product of the equilibrium constants of theindividual reactions.
Multiple Equilibria
15
N2O4 (g ) 2NO2 (g )
= 4.63 x 10-3K =[NO2]
2
[N2O4]
2NO2 (g ) N2O4 (g )
K =[N2O4]
[NO2]2
′ =1
K = 216
When the equation for a reversible reaction is written inthe opposite direction, the equilibrium constant becomes
the reciprocal of the original equilibrium constant.
16
Writing Equilibrium Constant Expressions
1. The concs of the reacting species in the condensed phaseare expressed in M . In the gaseous phase, theconcentrations can be expressed in M or in atm.
2. The concs of pure solids, pure liquids and solvents do not appear in the equilib constant expressions.
3. The equilib constant is a dimensionless quantity.
4. In quoting a value for the equilib constant, you must specifythe balanced eq and the T
5. If a reaction can be expressed as a sum of 2 or morereactions, the equilib constant for the overall rxn is given by
the product of the equilib constants of the individualreactions.
17
Chemical Kinetics and Chemical Equilibrium
A + 2B AB2
k f
k r
ratef = k f [A][B]2
rater = k r [AB2]
Equilibriumratef = rater
k f [A][B]2 = k r [AB2]
k f k r
[AB2]
[A][B]2= K c =
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The reaction quotient (Q c ) is calculated by substituting theinitial concentrations of the reactants and products into theequilibrium constant (K c ) expression.
IF
• Q c > K c system proceeds from right to left to reach equilibrium• Q c = K c the system is at equilibrium
• Q c < K c system proceeds from left to right to reach equilibrium
1. Express the equilibrium concentrations of all species interms of the initial concentrations and a single unknown x ,which represents the change in concentration.
2. Write the equilibrium constant expression in terms of theequilibrium concentrations. Knowing the value of theequilibrium constant, solve for x .
3. Having solved for x , calculate the equilibriumconcentrations of all species.
20
At 1280oC the equilibrium constant (K c ) 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 atequilibrium.
Br2 (g ) 2Br (g )
Br2 (g ) 2Br (g )
Let x be the change in concentration of Br2
Initial (M )
Change (M )
Equilibrium (M )
0.063 0.012
-x +2x
0.063 - x 0.012 + 2x
[Br]2
[Br2]K c = K c =
(0.012 + 2x )2
0.063 - x = 1.1 x 10-3 Solve for x
21
K c =(0.012 + 2x )2
0.063 - x = 1.1 x 10-3
4x 2 + 0.048x + 0.000144 = 0.0000693 – 0.0011x
4x 2 + 0.0491x + 0.0000747 = 0
ax 2 + bx + c =0-b ± b 2 – 4ac
2a x =
Br2 (g ) 2Br (g )
Initial (M )
Change (M )
Equilibrium (M )
0.063 0.012
-x +2x
0.063 - x 0.012 + 2x
x = -0.00178x = -0.0105
At equilibrium, [Br] = 0.012 + 2x = -0.009 M or 0.00844 M
At equilibrium, [Br2] = 0.062 – x = 0.0648 M 22
If an external stress is applied to a system at equilibrium, thesystem adjusts in such a way that the stress is partially offsetas the system reaches a new equilibrium position.