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Reversible Reactions

If you recall, we mentioned that there are rxns that bounce back and forth from forming products to reforming reactants

A.K.A. reversible rxns

Reversible reactions occur simultaneously in both directions

An example of a reversible rxn involves reactants A and B producing C.

A + B

Chemical Equilibrium
o

At chemical equilibrium there is no net change in the actual amounts of the components of the system.
And although the rates of the forward & reverse rxns are equal at chemical equilibrium, the concentrations of the components on both sides of the chemical eqn are not necessarily the same.
In fact they can be dramatically different.

Consider a set of escalators as being like the double arrows in a dynamic equilibrium. The # of people using the up escalator must be the same as the # of people using the down escalator for equilibrium to have been established

However, the # of people upstairs do not have to equal the # of people downstairs Just the transfer between floors must be consistent

Which Direction is Favored?


o

The equilibrium position of a rxn is given by the concentrations of the systems components at equilibrium The equilibrium position indicates whether the components on the left or right side of a reversible rxn are at a higher concentration.

If A reacts to give B and the mixture at equilibrium contains more of B say 1% of A vs. 99% of B the formation of B is said to be favored.

Which Direction is Favored?


o On

the other hand, if the mixture contains 99% of A and 1% of B at equilibrium then the formation of A is favored.
Forward direction is favored! Reverse direction is favored!

Reversibility vs. Reality


o

In principle, almost all rxns are reversible to some extent under the right conditions In practice, one set of components is often so favored at equilibrium that the other set cannot be detected.

If one set of components has established equilibrium by converting mostly into products, the rxn has gone to completion When no products can be detected, you can say there is no rxn

Reversibility vs. Reality


o Reversible

rxns occupy a middle ground between the theoretical extremes of irreversibility and no rxn. o The addition of a catalyst will speed up forward and reverse rxns equally

By reducing the energy needed to activate the rxn in both forward and reverse directions. Does not effect the amount of reactants and products present at equilibrium; simply decreases the time it takes to establish equilibrium

Equilibrium Expression
o

Chemists can express the equilibrium position in terms of a numerical constant


The equilibrium constant shows the relationship between the amount of product and reactant at equilibrium

Consider this hypothetical rxn aA + bB cC + dD

Equilibrium Expression
o

We can write an expression to show the ratio of product concentrations to reactant concentrations called a mass action expression [C]c [D]d

[A]a [B]b
o

The conc of each substance is raised to a power equal to the # of mols of that substance in the balanced rxn eqn. The square brackets indicate concentration in Molarity (mol/L)

Equilibrium Expression
o

The resulting ratio of the equilibrium is called the equilibrium constant or Keq,
When the reactants and products amnts are in molarity the constant is called a Kc c [D]d [C] When the reactants andKeq= products amounts are in [A]a [B]b pressure units is called aK p The constant is dependent on the temp

If the temp changes so does the constant NOTE: water and solid materials are not
included in mass action

For example:
1.

Write the mass action expression for each of the following reactions: A.2SO2(g) + O2(g) <==> 2SO3(g) B.Bi2S3(s) <==> 2Bi+3(aq) + 3S2(aq)

Classwork:
Write the mass action expression for each of the following reactions: 2C4H10(g) + 13O2(g) <==> 8CO2(g) +10H2O(g) 4Al(s) + 3O2(g) <==> 2Al2O3(s)

Equilibrium Constant
o

Equilibrium constants provide valuable chemical information They show whether the products or the reactants are favored in a rxn (spontaneus or nonspontaneous)

always written as a ratio of products over reactants a value of Keq > 1 means that products are favored Keq < 1 than reactants are favored

Molarity is a measure of how much stuff is dissolved in water. The more stuff dissolved, the more concentrated the solution The higher the molarity

Classwork:
1.

2.
3.

What is the molarity of a solution that was made by dissolving 0.100 mols of sugar in 100 ml of water? How many moles of salt are contained in 300.0 mL of a 0.40 M NaCl solution? A chemist dissolves 98.4 g of FeSO4 in enough water to make 2.00 L of solution. What is the molarity of the solution?

Sample Problem 1
Dinitrogen tetroxide (N2O4), a colorless gas, and nitrogen dioxide (NO2), a brown gas, exist in equilibrium with each other according to O the following eqn: N 2NO
2 4(g) 2(g)

A 1.0 liter of gas mixture at 10C at equilibrium contains .0045 mol N2O4 & .030 mol NO2. Write the mass action expression and calculate Kc for the rxn.

Analyze: list what we know


o

Known:

[N2O4] = .0045 mol/1.0 L [NO2] = .030 mol/1.0 L

Unknown:

Mass action expression = ? Kc = ?

At equil, there is no net change in the amount of N2O4 or NO2 at any given instant

Calculate: solve for unknowns

The only product of the rxn is NO2, which has a coefficient of 2 in the balanced eqn The only reactant N2O4 has a coefficient of 1 in the balanced eqn

o
o

The mass action 2 expression is: [NO ] [.030M]2 2 Kc = Kc= [.0045M]1 [N2O4]1 Kc is equal to: Kc = 0.20 Kc < 1, therefore rxn doesnt favor products

Classwork:
1.

2.

Find the equilibrium constant if [SO2] = 1.0 M; [O2]=1.0 M; [SO3]=2.0 M; using the mass action expression written in the examples Find the equilibrium constant if [Bi+3] = 0.00058 M; [S-2] = 0.00087 M; using the mass action expression written in the examples

Reaction Quotient
o

We can also determine if a reaction has reached equilibrium by calculating a reaction quotient (Q).

Its like taking a snapshot of a reaction at a given time and interpreting how far along the reaction is.

Once the reaction quotient is solved, it is compared to the equilibrium constant

The following picture helps us decide how to interpret the direction the reaction will continue.

Sample Problem 2
At a certain temperature Keq = 55 and a reaction vessel contains a mixture with the following concentrations : [SO3] = 0.85 M, [NO] = 1.2 M , [SO2] = 1.5 M and [NO2] = 2.0 M.

SO3(g) + NO(g) SO2(g) + NO Is the reaction at equilibrium and if not 2(g)


which direction will the rxn proceed?

Solve just as if you were solving for the equilibrium constant. Then analyze the resulting quotient with the given Keq

[SO2 ][NO 2 ] (1.5M)(2.0M) Q Q [SO3 ][NO] (.85M)(1.2M)


o o

Q = 2.94 which is < Keq (55) If Q < Keq then the numerator of our quotient must increase

therefore the rxn continues in order to increase [products] until it reaches

Classwork:
1.

0.035 moles of SO2, 0.500 moles of SO2Cl2, and 0.080 moles of Cl2 are combined in an evacuated 5.00 L flask and heated to 100C. What is Q before the reaction begins? Which direction will the reaction proceed in order to establish equilibrium? SO2Cl2(g) <==> SO2(g) + Cl2(g) Kc = 0.078 at 100C

Manipulating the o Equilibrium There is a principle that can be studied


o

to govern changes in equilibrium Le Chateliers Principle. Le Chateliers Principle states:

If a stress is applied to a system in dynamic equilibrium, the system changes to relieve the stress. Stresses are changes in temperature, pressure, concentration of reactants, or concentration of products

Concentration & Equilibrium


o

Adjusting the concentrations of either reactants or products can have dramatic impact on the equilibrium If we add more of reactant A to a system at equilibrium the system will strive to reestablish equilibrium at a new equilibrium position. The reaction will push to use up the extra A and generate more C

A + 2B

H= - 250 kJ

[A], rxn will shift toward products

Concentration & Equilibrium


o

Adjusting the concentrations of either reactants or products can have dramatic impact on the equilibrium If we add more of product C to a system at equilibrium the system will strive to reestablish equilibrium at a new equilibrium position. The reaction will push to use up the extra C and generate more A and B

A + 2B

H= - 250 kJ

[C], rxn will shift toward reactants

Temp effects on Equilibrium


o The

impact of temperature changes on an equilibrium is dependent on if the process is endothermic or exothermic

Endothermic processes use energy as a reactant, while exothermic processes produce energy Keq is temperature dependent
250 kJ is a product

A + 2B

H= - 250 kJ

If T, the equilibrium shifts left

Temp effects on Equilibrium


o The

impact of temperature changes on an equilibrium is dependent on if the process is endothermic or exothermic

Endothermic processes use energy as a reactant, while exothermic processes produce energy
energy is a reactant

A + 2B

H= + 250 kJ

If T, the equilibrium shifts right

Pressure & Equilibrium


o

If A, B, and C are all gases, then the equil they establish is pressure dependent When the pressure is increased, the system relieves the pressure by favoring the direction that produces fewer gas molecules.

Pressure is # of particles dependent, the more particles the higher the pressure Fewer gas molecules will exert less pressure.

Pressure & Equilibrium


o

Conversely, a decrease in pressure will favor the rxn that produces the most molecules So we have a shift to the left
P, this equilibrium shifts right

A + 2B

H= - 250 kJ

If P, this equilibrium shifts left

Classwork
Predict the effect of the following changes on the reaction in which SO3 decomposes to form SO2 and O2. 2SO3(g) <=> 2SO2 (g) + O2 (g) Ho = 197.78 kJ (a) Increasing the temperature of the reaction. (b) Increasing the pressure on the reaction. (c) Adding more O2 when the reaction is at equilibrium. (d) Removing O2 from the system when