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Quick Equilibrium review
The Concept of Equilibrium• As the substance warms it begins to
decompose: N2O4(g) 2NO2(g)
• When enough NO2 is formed, it can react to form N2O4:
2NO2(g) N2O4(g).
• At equilibrium, as much N2O4 reacts to form NO2 as NO2 reacts to re-form N2O4
• The double arrow implies the process is dynamic.
N2O4(g) 2NO2(g)
The Concept of EquilibriumAs a system
approaches equilibrium, both the forward and reverse reactions are occurring.
At equilibrium, the forward and reverse reactions are proceeding at the same rate.
A System at Equilibrium
Once equilibrium is achieved, the amount of each reactant and product remains constant.
The Equilibrium Constant
To generalize this expression, consider the reaction
• The equilibrium expression for this reaction would be
Kc = [C]c[D]d
[A]a[B]b
aA + bB cC + dD
The Equilibrium Constant
Because pressure is proportional to concentration for gases in a closed system, the equilibrium expression can also be written
Kp =(PC)c (PD)d
(PA)a (PB)b
Relationship between Kc and Kp
Plugging this into the expression for Kp for each substance, the relationship between Kc and Kp becomes
Where
Kp = Kc (RT)n
n = (moles of gaseous product) − (moles of gaseous reactant)
What Does the Value of K Mean?
If K >> 1, the reaction is product-favored; product predominates at equilibrium.
• If K << 1, the reaction is reactant-favored; reactant predominates at equilibrium.
Manipulating Equilibrium Constants
The equilibrium constant of a reaction that has been multiplied by a number is the equilibrium constant raised to a power that is equal to that number.
Kc = = 0.212 at 100C[NO2]2
[N2O4]N2O4 (g) 2 NO2 (g)
Kc = = (0.212)2 at 100C[NO2]4
[N2O4]22 N2O4 (g) 4 NO2 (g)
Manipulating Equilibrium Constants
The equilibrium constant of a reaction in the reverse reaction is the reciprocal of the equilibrium constant of the forward reaction.
10.212=
Kc = = 0.212 at 100C[NO2]2
[N2O4]N2O4 (g) 2 NO2 (g)
Kc = = 4.72 at 100C
[N2O4][NO2]2N2O4 (g)2 NO2 (g)
Applications of Equilibrium ConstantsPredicting the Direction of Reaction• We define Q, the reaction quotient, for a
reaction at conditions NOT at equilibrium
as
where [A], [B], [P], and [Q] are molarities at any time.
• Q = K only at equilibrium.
aA + bB(g) pP + qQ
ba
qpQ
BA
QP
The Reaction Quotient (Q)
To calculate Q, one substitutes the initial concentrations on reactants and products into the equilibrium expression.
Q gives the same ratio the equilibrium expression gives, but for a system that is not at equilibrium.
Applications of Equilibrium ConstantsPredicting the Direction of Reaction• If Q > K then the reverse reaction
must occur to reach equilibrium (go left)
• If Q < K then the forward reaction must occur to reach equilibrium (go right)
Applications of Equilibrium ConstantsPredicting the Direction of Reaction• If Q > K then the reverse reaction
must occur to reach equilibrium (go left)
• If Q < K then the forward reaction must occur to reach equilibrium (go right)
Le Châtelier’s PrincipleChange in Reactant or Product
Concentrations• Adding a reactant or product shifts the
equilibrium away from the increase.• Removing a reactant or product shifts the
equilibrium towards the decrease.• To optimize the amount of product at
equilibrium, we need to flood the reaction vessel with reactant and continuously remove product (Le Châtelier).
• We illustrate the concept with the industrial preparation of ammoniaN2(g) + 3H2(g) 2NH3(g)
Le Châtelier’s PrincipleEffects of Volume and Pressure• The system shifts to remove gases and
decrease pressure.• An increase in pressure favors the
direction that has fewer moles of gas.• In a reaction with the same number of
product and reactant moles of gas, pressure has no effect.
• Consider N2O4(g) 2NO2(g)
Le Châtelier’s PrincipleEffect of Temperature Changes• Removing heat (i.e. cooling the vessel),
favors towards the decrease:– if H > 0, cooling favors the reverse
reaction,– if H < 0, cooling favors the forward
reaction.• Consider
for which DH > 0.– Co(H2O)6
2+ is pale pink and CoCl42- is blue.
Cr(H2O)6(aq) + 4Cl-(aq) CoCl42-(aq) + 6H2O(l)
CATALYST—EQUILIBRIUM is achieved faster, but the equilibrium composition remains unaltered.
Manipulating Equilibrium Constants
The equilibrium constant for a net reaction made up of two or more steps is the product of the equilibrium constants for the individual steps.
EQUILIBRIUM INVOLVING THE SOLUBILITY AND PRECIPITATION OF
COMPOUNDSEquilibrium and Solubility
Saturated solutions
A saturated solution is a solution that is in equilibrium with undissolved solute
Example: BaSO4 (s)
D Ba+2 (aq)+ SO4-2 (aq)
Solubility Products
The equilibrium constant expression for this equilibrium is
Ksp = [Ba2+] [SO42-]
where the equilibrium constant, Ksp, is called the solubility product.
Solubility Products
The equilibrium constant expression for this equilibrium is
Ksp = [Ba2+] [SO42-]
where the equilibrium constant, Ksp, is called the solubility product.
Solubility Products
Ksp is not the same as solubility.Solubility is generally expressed as the
mass of solute dissolved in 1 L (g/L) or 100 mL (g/mL) of solution, or in mol/L (M).
Will a Precipitate Form?
In a solution, If Q = Ksp, the system is at equilibrium and
the solution is saturated. If Q < Ksp, more solid will dissolve until Q
= Ksp. If Q > Ksp, the salt will precipitate until Q
= Ksp.
Selective Precipitation of Ions
One can use differences in solubilities of salts to separate ions in a mixture.
Common Ion Effect
If a solution containing two dissolved substances share a common ion, then the solubility of the salt is more difficult to determine
Adding “common ion” will cause the solubility to be less in the presence of the common ion
Causes less of the substance with the smaller Ksp
will dissolve.