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Honors Chemistry-B
Equilibrium
Chapter Objectives
After students have completed they will be able to:
1. Explain the collision theory of reactions.
2. Describe what is meant by a reaction mechanism, a rate-determining step, an activated
complex, and activation energy.
3. Account for the effect on reaction rates of the nature of the reactants, their surface area,
their concentrations, the temperature of the reaction system, and the presence of a
catalyst.
4. Interpret potential energy diagrams and energy distribution diagrams. Recognize the
characteristics of chemical equilibrium.
5. Distinguish between a reversible reaction that is in equilibrium and one that is not.
6. Derive mass action expressions.
7. Write equilibrium expressions for systems that are at equilibrium.
8. Calculate equilibrium constants from concentration data and apply them to reversible
reactions.
9. Calculate equilibrium constants and equilibrium concentrations using the ICE box
method and apply them to reversible reactions.
10. Explain and apply Le Chateliers principle.
11. Describe how various factors affect chemical equilibrium.
Chemical Kinetics Chemical kinetics is the branch of chemistry concerned with the rate and
mechanisms of chemical reactions.
What two factors determine the rate of a reaction by the collision theory?
a. ________________of collisions
b. ________________of collisions
http://www.youtube.com/watch?v=OkGzaSOkyf4
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In general, what 6 factors influence the rate of a chemical reaction?
An increase in temperature means that the kinetic energy of the reacting particles
has increased. The faster moving particles _____________________, and their
_______________________ increases the effectiveness of these collisions.
PLUS..an increase in temperature means there are more overall collisions and
therefore more effective collisions!
Boltzman Distribution
The boltzman distribution shows how at
any given temperature there are a fraction
of molecules with enough energy to react
if they collide with correct orientation.
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3. Concentration of Reactants & Reaction Rate
How does increasing the concentration of the reactants affect the rate of a chemical reaction?
An increase in the concentration of any one or more of the reactants usually, but not always
increases the rate of a reaction.
Why does increasing the concentration increase the rate of a chemical reaction?
An increase in concentration means that the particles that need to collide are __________________
and that there are____________________ to collide. With less distance to travel between collisions,
more collisions will take place during any given unit of time. Therefore, an increase in concentration
______________ the _______________ of the collisions, which will usually, but not always,
increase the rate of the reaction.
4. Pressure and Reaction Rate
Pressure changes __________affect reactions that use ______________ reactants.
What are two ways to increase the pressure of a reactant?
a. Change the volume of the reaction chamber (_____________ )
b. Change the number of moles of gas ( ___________ )
As the pressure of reactants increases the rate of the reaction will increase because there are more
collisions between the molecules. More collisions means that more reactions will take place.
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5. Catalysts and Reaction Rate
Catalyst A catalyst is a substance that speeds up a chemical reaction without itself being
permanently altered. A catalyst always ____________________ of the activated complex.
Inhibitors - Inhibitors are substances that slow down chemical reactions by causing reactants to
become tied-up inside reactions.
6. The amount of surface area of each reactant that is exposed to the other reactants
How does the amount of surface area affect the concentration of a solid reactant?
While increasing the amount of surface area does not change the concentration of the solid it does
allow for more contact between the solid and any other reactants therefore increasing the
rate of the reaction.
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Activation Energy and the Activated Complex
Activation energy The activation energy is the minimum amount of energy needed to form an
activated complex. This is the energy barrier to the reaction. If the molecules collide with less energy
then the activation energy the reaction will not go to completion. (__________________________)
Exothermic There is a _____________ of energy from the reaction to the surroundings. The
energy of the reactants is greater than that of the products. The energy that is lost during the
reaction is given off as heat. (More heat exiting the system) rxn (usually observe a temp
increase)
(H rxn = ______________- ________________)
Endothermic - There is a ______ ___________ of energy by the system (chemical reaction) from
the surroundings. The energy of the products is greater than that of the reactants. The energy
gained during the reaction causes a decrease in the temperature of the surroundings. + H rxn
(H rxn = E of Products- E of Reactants)
__________
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1) Sketch a potential energy diagram:
a. Reactant Energy is 50 kJ
b. Has an activated complex of 90 kJ
c. Has an activation energy of 40 kJ
d. Has an energy of Products of 70 kJ
e. Has a catalyst that lowers the activation energy by 10 kJ
( represent with a dotted line)
Time
_______________________________________________________________________________
2) Sketch a potential energy diagram:
a. Reactant Energy is 40 kJ
b. Has an activated complex of 90 kJ
c. Has an activation energy of _______ kJ
d. Has an energy of Products of 30 kJ
e. Has a catalyst that lowers the activation energy by 15 kJ
( represent with a dotted line)
Potential Is the reaction endothermic or
Energy exothermic?
What is the H of the reaction
(KJ) forward?
What is the H of the reverse
reaction?
Time
How does a catalyst increase the rate of a reaction, that is what does it actually do that will
increase the reaction rate?
A catalyst increases the speed of a reaction by changing the reaction mechanism. The new
mechanism will provide steps with lower activation energies. Because more molecules will have the
lower activation energies required for the catalyzed reaction, more molecules will react during a unit
of time. The rate of the catalyzed reaction will be greater.
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2A + B A2B
After some time the [A2B] will increase, and the concentrations of A and B will decrease.
What would the collision theory predict?
A2B begins to collide and form some A + B
A2B 2A + B
So there is both a ___________ and a _____________ reaction taking place at the same time !
We represent this with a double arrow , .
2A + B A 2B
As the forward reaction continues, it makes more A 2B, which will in turn react to make more A + B
Lets look at an example of this process using the following reaction: A B
Expressing Equilibrium:
Equilibrium Equations (Expressions) are unique for each reaction. The value we set them equal to is
called K or sometimes Keq. This calculation is done to allow us to determine if the [reactants] or the
[products] is favored at equilibrium.
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What does the size of K mean?
K is expressed as [ products ] / [ reactants ]. As such it lets us know which side of the reaction
the equilibrium favors.
When K > 1 the numerator is greater than the denominator. Eq favors _____________
When K < 1 the denominator is greater than the numerator. Eq favors _____________
When K 1 the denominator and numerator are approximately equal. ________________________
Keq =
If at equilibrium the concentration of N 2 was 0.45 M, H2 was 0.12M and NH3 was 0.800 M we could
determine the value of K.
K=
Your Turn:
1. Write K equations..
Rxn 1: aA(g) + bB(g) cC(g) + dD(g)
2. For the reaction: H2 (g) + I2 (g) 2 HI (g), at a certain temperature the equilibrium
concentrations of H2 and I2 are both 0.15 M and that of HI is 0.50 M. Write an equilibrium
expression first. Then calculate the equilibrium constant at this temperature? Are reactants or
products favored?
3. Analysis of the concentrations at equilibrium in a 2 L flask yields the following results: [NOCl]
= 0.30 mol, [NO ] = 1.2 mol, and [Cl2] = 0.60 mol. Write an equilibrium expression. Then
calculate the equilibrium constant at this temperature? Are reactants or products favored?
2 NOCl (g) 2 NO (g) + Cl2 (g)
change -.02 ( ) ( )
change -.02 ( ) ( )
t2 [ ] 0.160 ______ _______
change 0 ( ) ( )
concentrations at eq
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K= Calculate K =
Example 2: A 2.00-L container contains 6.00 mole each of H2 and I2 gases. When the system reached
equilibrium, the concentration of I2 is 1.1 M.
a) What is the initial molarity of the H2 in the container? (Remember M= Moles/L) _________
b) What is the initial molarity of the I2 in the container?
What is the value of K for this reaction? (Set up K expression first). What is favored?
Example 3:
For the equation at 200K: 2HI (aq) H2 (g) + I2 (g) the concentrations at equilibrium are 0.34 M HI, 0.0234
M H2 and 0.0234 M I2. Calculate K.
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Solve for x. At equilibrium, Pressure HBr = __________, P of H2 = __________, P Br2 = __________
b. Calculate the pressures of each of these gases at equilibrium:
HI H2 (g) + I2
A reaction that is______ at equilibrium can have the direction it is moving to reach equilibrium
expressed by the calculation of Q. Note a Q calculation is mathematically the same as K but will be
compared to the K value to determine what way the reaction will move (or if it is at equilibrium).
For example,
The current concentrations (not at EQ) of the chemicals are 0.333 M COCl2, 0.233M CO
and 0.233 M Cl2. Is this solution at equilibrium and if not what way is it moving to achieve equilibrium?
Q= [ CO ] [Cl2] =
[COCl2]
K _____ Q so the reaction is ______at equilibrium and the values of products must increase
(and reactants decrease) so that the fraction will = 2.33 and be at equilibrium.
This means the forward reaction is going faster than the reverse. The reaction is shifting to the
right to achieve equilibrium.
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Keq ______ then the solution is at equilibrium and will have equal rates and no net change in
concentrations. _________________
Keq ______ then the solution has more products than it should at equilibrium (so more reactant
needs to be made). The __________ reaction must be going faster than the forward
reaction and the reaction is proceeding to the left. ___________
Keq _______ then the solution has more reactants than it should at equilibrium (so more product
needs to be made). The _________ reaction must be going faster than the reverse
react and the reaction is proceeding to the right. __________
If the concentration of the HC2H3O2 is .0123 M and the concentrations of H+ is 0.0334 and the
C2H3O2- is 0.00124, are we at equilibrium? If not which way is the reaction shifting?
Q =
K____ Q reaction will shift __________to make more reactants and achieve equilibrium.
Another Example:
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Le Chateliers Principle- Ways to stress out a reaction and make it shift
Once a reaction reaches equilibrium, stress (an outside force) can be applied to shift the equilibrium
rates. The reaction will shift to achieve a new equilibrium by reducing the stress.
Types of Stresses
1.
2.
3. V (____________)
4.
5.
6.
INCREASING CONCENTRATION:
Example: A + B C + D
For example, if A were added to the above reaction than more collisions would occur between A and
B. This___________ the reaction rate of the ___________ reaction and results in the production of
more C and D. The reaction is said to have ________________to reduce the stress.
In terms of concentrations:
[C] and [D] will be increased above their initial equilibrium concentrations at the new equilibrium.
[B] will be used up by the increased [A] and will show a decreased [B] at the new equilibrium.
[A] will show a slight increase overall because even though it is used up in the forward reaction,
not all of the [A] that was added will be used up to reach the new equilibrium.
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Initially it is at EQUILIBRIUM:
When H2 is added:
The system is no longer in
equilibrium. The rate of the forward
reaction is now _________because
there are more collisions between N2
and H2. This results in an increasing
concentration of NH3. This continues
to occur until the rates of the forward
and reverse reaction are equal.
New Equilibrium:
At the new equilibrium rate of the
forward reaction = rate of the reverse
reaction and concentrations of
reactants and products are constant.
Notice that the reaction shifts to the right and more NH 3 is produced, N2 is used up, and H2 is higher
than its previous equilibrium value but has decreased from the amount that was added.
DECREASING CONCENTRATION
This has the opposite effect of adding a chemical. When a chemical is removed it slows the rate of
the reaction that the chemical is involved in. This results in more of that chemical being produced
until the rates of forward and reverse reactions are again equal.
If NH3 is removed the reverse reaction ______________, but the forward reaction is still
producing the same amount of NH3. As a result when a new equilibrium is established the reaction
has generated ______________. (Not as much as it had at the first equilibrium, but more than it had
after the removal of some of the NH3)
Only affects gaseous reactants or products. The equilibrium shifts to the side with the fewest moles
of gas as pressure is increasing, and shifts to create more moles of gas as pressure is decreasing.
Both of these ameliorate, or minimize, the change in pressure.
Increase Pressure:
Causes shift to __________ to decrease pressure.
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Example 2: 2 A(g) + 3 B(g) <===> 2 C(l)
Increase Pressure:
Causes shift to __________ to decrease pressure.
Increase Pressure:
Adding solvent (like water) decreases the concentration of ALL solutions in the equilibrium.
The amount of mols of each chemical remains constant while the total volume increases. (Just like
gas pressure shifts)
M = _______________
Add volume = shift toward side with more moles in the K equation (only gas and aq)
Decrease volume = shift toward the side with less moles in the K equation. (only gas and aq)
If moles are equal on both sides of the equation = NO SHIFT
Shift will depend on if the reaction is endothermic or exothermic. The equilibrium shifts to minimize
the change in heat. The best way to think of this is that heat is a reactant in either the forward or
the reverse reaction. Additional heat will fuel the reaction it is being used in, a decrease in heat
will hinder the reaction that heat is being used up in. Heat is always used in an endothermic
reaction.
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1. Increasing Temperature shifts the equilibrium ______________ the __________
2. Decreasing Temperature shifts the equilibrium toward the __________
Equilibrium constants "K" values are changed if you change the __________________ of the
system. (This is the only stress that will change K)
If the forward reaction is ____________, increasing the temperature __________ the value of the
equilibrium constant.
Why? Increasing temperature causes shift _______so [reactant] ___________ and [product]
___________ resulting in a decreased [product] / [reactant] ratio.
A B + Heat
If the forward reaction is ____________, increasing the temperature __________ the value of the
equilibrium constant.
Heat + A B
Why? Increasing temperature causes shift ______ so [reactant] _____________ and [product]
_____________ resulting in an increased [product] / [reactant] ratio.
Equilibrium Shifts and LeChateliers Principle- How does shift effect ALL values at equilibrium?
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1. Adding a reactant or product- Reaction shifts to reduce the stress but the reaction can NOT eliminate
the stress. Example: A (g) + B (g) C (aq) + Heat(Energy)
a. adding A: Causes shift to __________ In New Equiilibrium: A ________, B _________ C
__________
b. removing B: Causes shift to _________ In New Equiilibrium: A _________, B _________ C
__________
c. removing C: Causes shift to _________ In New Equilibrium: A __________, B _________ C
__________
2. Changes in Pressure- When Pressure of REACTION is increased, the reaction will shift to the side with
LESS moles of GAS. A (g) + B (g) C (aq) + Heat(Energy)
d. Increasing Pressure: Causes shift to ______ In New Equilibrium: A _______, B ________ C ________
e. Decreasing Pressure: Causes shift to ______ In New Equilibrium: A ________, B ________ C _______
3. Changes in Temperature- Treat Heat or Energy as a reactant or product. Fill in heat as a reactant when
a reaction is ________________ and as a product when a reaction is ______________. Remember that
endothermic reactions have a ______ H and exothermic reactions have a ______ H.
A (g) + B (g) C (aq) + Heat(Energy)
f. Increasing Temperature will cause shift to _______ In New Equilibrium: A ______, B ______ C ______
g. Cooling the reaction will cause shift to ________ IN New Equilibrium: A _______, B ______ C _______
**Changing Temperature is the only stress that also CHANGES the value of K! A shift to the right makes
more products so K ____________. A shift to the left makes more reactants so K will _______________.
4. Adding a catalyst when the reaction is at equilibrium is NEVER a stress. A catalyst only shortens the
time for the reaction to reach the original equilibrium.
5. Adding anything that does not appear in the K expression will not cause a shift unless it reacts with
something in the equation. This applies to solids! They will be effected by a shift but adding more of them
when a reaction is at equilibrium will not cause a shift. This is because for a reaction to be at equilibrium,
some solid must already be present in the equilibrium conditions. Adding more will not have an effect.
h. adding C will _________________. The effect is in the New Equilibrium: A _____, B _____ C ______
i. adding A will cause shift to ____________. In New Equilibrium: A _______, B _______ , C _________
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reactant Forward reaction rate increases. Increase in the concentration of the
concentration products of the forward reaction.
(shifts right)
The rate of the reaction with the Increased concentration for the products of
pressure most moles of gas will increase. the reaction (forward or reverse) with the
most moles of gas.
The rate of reaction with the Increased concentration for the products of
pressure least moles of gas will increase. the reaction (forward or reverse) with the
least moles of gas.
Increase concentration for the products of
temperature Endothermic reaction rate the endothermic reaction.
increases
Increase concentration for the products of
temperature Exothermic reaction rate the exothermic reaction.
increases
Increase the reaction rate for No change in equilibrium concentrations
Add a Catalyst both forward and reverse
reactions
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