1 AP Chem Gen.

Equilibrium notes:
Chapter 16 in Tro

I. Chemical Equilibrium = the concentrations of all reactants and products remain constant
with time. Equilibrium predicts the direction that a reaction will go to establish dynamic
equilibrium. Please note that the concentration of the products may not equal to the
concentration of the reactants at equilibrium. The higher the K the more products you will
form when you have reached equilibrium
A. The equilibrium of a reaction is determined by
1. Initial concentration of your reactants
2. Relative energies of the reactants and products (remember KE and Ea)
3. Relative degree of “organization” or “orientation” of the reactants and
products.
B. Please read and answer the following questions

1. What is dynamic equilibrium?

2. What is true about the initial rate (this is kinetics!) of forward and reverse
reactions in a system where only reactants are present?

3. What is true about the rates of forward and reverse reactions at

equilibrium?

4. Why does equilibrium occur?

C. The Law of Mass Action = expresses the relationship between the concentrations
of the reactants and products at equilibrium in any reaction

1. For the reaction:

nA + mB ↔ pC + qD

The equilibrium constant K is given by = K is the ratio of the forward reaction to the
reverse reactions) raised to the proper coefficients ( DO NOT INCLUDE SOLIDS OR
LIQUIDS)

K=[C]p[D]q
[ A] n [ B]m

Note: There are different types of K’s you can have a Kc. Kp, Ksp, Ka, Kb

2. Write the equilibrium expression for each of the following reactions

a. PCl 5 (g) ↔PCl3 (g) + Cl2 (g)

b. S 8 (g) ↔8 S(g)
2 AP Chem Gen. Equilibrium notes:
Chapter 16 in Tro
c. Cl 2O7 (g) + 8 H2 (g) ↔2 HCl(g) + 7 H2O(g)

3. Types of equilibrium problems

a. Solving for K (knowing equilibrium concentrations)

b. Predicting the equilibrium position if you know Q

c. Solving for equilibrium concentrations (knowing K and only initial

concentrations) You will have to use Q !

D. Type I Calculating an Equilibrium Constant (K) (Solving for K)

a. Rules that Summarize of Equilibrium Expressions

1). The equilibrium expression for a reaction is the reciprocal of that for the reaction
written in reverse. If you reverse an equation, you must take the reciprocal of K. ( 1/K)
Ex. If the K for the equation: 2 NH3(g) ↔N2 (g) + 3 H2 (g) is 1.7
Then the K for: N2 (g) + 3 H2 (g) ↔2 NH3(g) is 1/1.7 =.59

2). When the balanced equation for a reaction is multiplied by a factor n, the equilibrium
expression ( K) for the new reaction is the original expression raised to the nth power and
Knew = (K original) n
Ex: 2NO (g) ↔N2 (g) + O2 (g) and K = 2.4 x 10 3
You rewrite the equation by multiplying by 2 to read:
4NO (g) ↔ 2N2 (g) + 2O2 (g) then K' = K 2 = (2.4 x10 3) 2 = 5.8 x 10 6

3). The units for K are dimensionless because the units cancel out.
4). The K over all rxn = K1 x K2

Examples to practice the rules

Ex.1 Calculate the K for the following reaction at 25 degrees Celsius

H2 (g) + I2 (g) ↔ 2 HI (g)

if the equilibrium concentration are [H2] = 0.106 M, [I 2] = 0.022M, and [HI] = 1.29 M
3 AP Chem Gen. Equilibrium notes:
Chapter 16 in Tro
Using the same reaction as in the previous problem (with K = 7.1 x 10 2 at 25 0C) , if the
equilibrium concentrations of H2 and I 2 are 0.81 M and 0.035 M respectively, calculate the
equilibrium concentration of HI.

Using the same information of example 1, calculate the value of K for the following
reactions.

a). The equation is the reverse of the original.

b). The equation is 1/3 of the original

c). The equation is reversed and is four times the original

2. The equilibrium for gases can be expressed either in concentrations or in

pressure terms. We use K or Kc for the equilibrium constant when
concentrations are known ( mols/liter) but for a gas, we use K p which is
calculated by using the pressures of gasses instead of concentrations

Please note you may not just interchange the values for Kc for Kp but they can
be related by an expression stated below!!

1. Kc and Kp can be related by the expression

Kp = Kc (R T)  n
R = 0.0821 L● atm/ K  mol
T = Kelvin
n = total moles of gas produced minus total moles of gas reacted
4 AP Chem Gen. Equilibrium notes:
Chapter 16 in Tro
Example: Calculate Kp and K for the following reaction
CH3OH(g) ↔ CO (g) + 2 H2 (g) at 25 degrees Celsius
given the equilibrium pressures as follows:
P CH3OH = 6.10 x 10 ─4 atm
PCO = 0.387 atm
PH2 = 1.34 atm

c. What does K mean? Remember it only compare the ratio of forward and
reversible reactions at equilibrium. It only tells you what concentrations are at
equilibrium
1). It does not mean how fast a reaction is going (that is kinetics
and rate) It only tells you the direction that the reaction is
favoring!!
2). It does not tell you whether or not a given set of
concentrations represents an equilibrium condition
3) It does tell you if more products or reactants are present
when you do reach equilibrium

Very important to remember!!!

If the value of K is: Equal to 1 then reaction is at equilibrium
If the K greater than 1 then goes to right and products favored or
there are more products present at equilibrium.
If the K less than 1 goes to left and reactants more favored at
equilibrium or there are more reactants present at equilibrium.

d. Remember when you have

a) Pure solids = do not include in equilibrium expression
b) Pure liquids = do not include in equilibrium expression
c) Water as a liquid= do not include in equilibrium
expression
d) Why? Pure substances only change in amount but not
in concentration!!!
5 AP Chem Gen. Equilibrium notes:
Chapter 16 in Tro

Examples: Write the equilibrium expressions ( K or K p )of the following equations:

1. CaCO3 (s) ↔ CaO (s) + CO2 (g)

2. 2 H2O (l) ↔2 H2 (g) + O2(g)

Practice the following. Write the equilibrium expressions for each of the following
reactions.

a). Ba(OH)2 (s) ↔Ba 2(aq) + 2OH(aq)

b). NH4NO2(s) ↔N2(g) + 2 H2O(g)

c). HCl(g) + NH3(g) ↔NH4 Cl(s)

d). Zn(OH)2(s) + 2 OH −(aq) ↔Zn(OH)4─2 (aq)

e). CH3CO2H(aq) ↔H+ (aq) + CH3CO2 -(aq)

f). Al(NO3)3 (s) + 6 H2O (l) ↔[Al(H2O)6] + 3(aq) + 3 NO3-(aq)

6 AP Chem Gen. Equilibrium notes:
Chapter 16 in Tro

E. TYPE II – PREDICTING THE EQUILIBIRUM POSITION BY LOOKING AT Q. A

second use of equilibrium K involves finding one or more equilibrium concentrations
and you must be able to predict the direction of the chemical reactions toward
equilibrium. To do this you must use the REACTION QUOTIENT (Q).

THE REACTION QUOTIENT IS USED FOR REACTIONS THAT ONLY THE

INITIAL CONCENTRATIONS OR PRESSURES OF THE REACTION
SUBSTANCES ARE KNOWN. You can calculate Q by using the Law of Mass Action
on initial, not equilibrium, concentrations (or pressures) of the reaction substances.

LEARN!!!!! REMEMBER ALLIGATOR MOUTH!

REMEMBER Q = INITIAL CONCENTRATION
 If Q is equal to K, the system is at equilibrium
 If Q greater than K, the system will shift to the left to reach equilibrium (too much
product present) Get more reactants present to reach equilibrium
 If Q less that K, the system will shift to right to reach equilibrium (too much reactant
present) Must form more product to reach equilibrium
Q IS LIKE A 1 AND USE THE OLD ALLIGATOR MOUTH TO CLOSE IT

K< Q < 1 GOES TO LEFT

K = Q =1 EQUILIBRIUM
K > Q >1 GOES TO RIGHT

1. Example: Suppose H2 (g) + I2(g) ↔ 2 HI (g)

K = 7.1 x 10 2 at 25 degrees Celsius
Predict the direction that the system will shift in order to reach equilibrium given each of
the following initial conditions.

(1) Q = 427

(2) Q = 1522

(3) [H2] 0 = 0.81M , [I 2] 0 = 0.44 M , [HI]0 = 0.58M

(4) [H2] 0 = 0.078M , [I 2] 0 = 0.033M, [HI]0 = 1.35M

(5) [H2] 0 = 0.034M , [I 2] 0 = 0.035M , [HI]0 = 1.50M

7 AP Chem Gen. Equilibrium notes:
Chapter 16 in Tro
F. Type III Problems Calculating equilibrium concentrations if you know the K You
are using the Q because you are not at equilibrium

1. Large value for K = means reaction will shift to right (forms

products)in order to reach equilibrium = large K means over 100
Example 1. Suppose your have the reaction
H2 (g) + I2(g)  2 HI (g)
K = 7.1 x 10 2 at 25 degrees Celsius.
Calculate the equilibrium concentrations if a 5.00 L vessel initially contains 15.7 g of
hydrogen and 294 g of iodine.
Step 1: Write a balanced equation AND DO THE STOICHIOMETRY FIRST =
Initial concentrations of each reactant

When you first start a reaction, there is no product!! Therefore initial concentration
is 0M of the product!

Looking at the reaction, iodine will be the limiting reactant and hydrogen will be in
excess. (Try to calculate that iodine is the limiting reagent below) You only have to
worry about limiting reactions if the reaction goes to completion and large value of k

Step 2 Set up equilibrium expression (no numbers yet!)

Step 3 Determine the direction of the reaction by comparing Q to K (note: Q must

be calculated from initial conc. of mol/L)

Step 4 Set up table of initial and final conditions. This is called the RICE Table.
You must take K into account. Remember K= 710

(SEE IF YOU CAN FIGURE OUT WHAT RICE STANDS FOR!!)

We assume reaction will go to completion but keep in mind that there will be some
small amount of the reactant that will not be reacted. THE LIMITING
REACTION WILL PLAY AN IMPORTANT PART IN THIS REACTION BUT
YOU WILL NEVER REACH 0 even in the limiting reagent!
8 AP Chem Gen. Equilibrium notes:
Chapter 16 in Tro
Since the reaction does not go all the way, there will be some iodine left over called amount
+x. Also an identical amount of hydrogen will be left over, +x, and twice the amount of HI
that you predict will not be formed or -2X.

Summarizing all of this in a Rice Table. (Note that the moles of HI is calculated by using
the limiting reagent amount= in this case that will be the I2 moles)

Reaction H2 (g) + *I2(g)  2 HI (g)

Initial
Change
At Equilibrium

Assume reaction is fairly complete and we can neglect x relative to 1.328 and .464 moles. We
must use 5% rule to check it we can neglect X (watch in step 6 how we check!!)
Step 5 Substitute final concentrations into the equilibrium expression and solve
for X ( this is the small amount of iodine that did not react!)

Step 6 Check for logic = using the 5% rule.

Testing assumption: 5 % rule

9 AP Chem Gen. Equilibrium notes:
Chapter 16 in Tro
2. Small value of K (reaction will stay far to the left -more reactant) =
small K is less than .01
Example 1: Suppose nitrogen gas and oxygen gas react to form nitrogen monoxide
N2(g) + O2(g) 2NO(g)

The equilibrium constant at 250C = 4.1 x 10-4.

If 0.50 moles of nitrogen and 0.86 moles of oxygen are put in a 2.0L container at
250C, what would the equilibrium concentration of all species be?

1. Write balanced equation and do stoichiometry of reaction

2. K less than .01 and reactions stay far to left. Only a small amount of N2 and O2
will react. The small amount that will be formed will be 2 X because of 2:1 ratio NOTE: WE
ARE ASSUMING THAT THE SAME CONCENTRATIONS OF N2 AND O2 WILL REMAIN
AT THE END OF THE REACTION SO THE LIMITING REACTION DOES NOT PLAY AN
IMPORTANT PART TO EVEN CONSIDER

3. RICE TABLE
N2(g) + O2(g)  2NO(g)
Reaction
Initial
Change
Equilib.

Because x is so small and reactants are favored, x is negligible for .25 and .43

4. Equilibrium reaction =

[NO] =
[N2] = [O2] = .
Remember K was so small that reaction essentially did not occur to any significance

Test : 5% rule
10 AP Chem Gen. Equilibrium notes:
Chapter 16 in Tro
3. Intermediate value of K (between 0.01 and 100) you can not make
assumptions based on the extent of the reaction. It is too uncertain. The
trade off is that you must explicitly solve for X, often using the quadratic
formula
Always follow the same steps
a) Write a balanced equation and work out the
stoichiometry first!! Then write the equilibrium constant
expression (no numbers yet!)
b) If can not tell which way the reaction is going to shift,
solve for Q
c) Set up a chart (RICE chart) the includes reaction , initial
concentrations, changes in concentration in terms of x,
final or equilibrium concentrations.
d) Substitute these final concentration into the
equilibrium expression and solve for X
e) Check your final answer to be sure it is logical

Example1 : Sulfurous acid dissociates in water as follows:

H2(SO3)(aq) → H+ (aq) + HSO3- (aq)

If [H2SO3] 0= 1.50 M and [H+] = [HSO3-] = 0 M , calculate the equilibrium concentration of

all species at 25 degrees C if Ka1 = 1.20 x 10 -2 and you are in a 1 L container
Thought process = Value of K is very small and you assume that you neglect x in
relationship to H2(SO3) which is the reactant.

Equilibrium expression in general

Reaction H2(SO3)(aq) ↔ H+ (aq) + HSO3- (aq)

Initial
Change
Equilib

Solving for x ( 1st assumption is to ignore x for reactant because stays to left)
K =

Test (5%)
11 AP Chem Gen. Equilibrium notes:
Chapter 16 in Tro
So must be explicit!!! (Must take into account small amount of reactant that does form the
product) ( hint use program in calculator!!!)

Have quadratic formula -b +- √ b2 - 4 ac

2a

Example 2 : Consider the reaction 2HF (g) ↔H2 (g) + F2 (g) where K = 1.0 x 10 -2 at
500 K. In an experiment 5.00 moles of HF(g), 0.500 moles of H2(g), and 0.750 moles
of F2 (g) are mixed in a 5.00 liter flask and allowed to react to equilibrium. Solve for
the equilibrium concentrations. In terms of Kc and change into Kp

You need to practice more RICE problems!!!! I will give you a sheet to practice. Remember
to look at K ASK YOURSELF
IS THE K OVER 100?
IS THE K UNDER .01?
IS THE K IN BETWEEN?
This will give you an idea of how the reaction is shifting (product side or reactant side) if not
at equilibrium
12 AP Chem Gen. Equilibrium notes:
Chapter 16 in Tro
THIS CONTENT IS NOT AN OPTION TO BE FORGOTTEN = IT WILL BE THE FIRST
PART OF THE 1ST FREE RESPONSE OF YOUR AP EXAM. THIS AND THERMO
MAKE UP A GREAT DEAL OF YOUR AP EXA

G. Le Chatelier Principle = a change in one of the variables that describe a system at

equilibrium produces a shift in the position of the equilibrium that counteracts the effect of
the change.
1. How to predict the direction of the shift in the reaction
a. Change in concentration = shift to opposite side
1) Increase in reactant = shift to make product
2) Increase in product =shift to make more reactant
3) Decrease reactant = shift to make more reactant
4) Decrease product = shift to make more product
b. Change in pressure (only affects systems having gaseous products
and /or reactants)
1) Increasing pressure will cause system to shift to side with fewer gas
particles
2) Decrease pressure will cause system to shift to side with more gas
particles
3) If have same number of moles of gas on each side, changes in
pressure does not affect equilibrium
4) Adding inert gas does not affect equilibrium because the partial
pressures of the other gases are not changed. Total pressure
increases but individual partial pressures do not change.
c. Change in temperature = watch where you put delta H in an equation!
1). An increase in temperature (heat a product in exothermic and heat
is a reactant in endothermic)
a) if endothermic + H shifts right to products

b) if exothermic -H shifts left to reactants

2). A decrease in temperature

a). If endothermic = shifts to left

b). If exothermic = shifts to right

d. Adding a catalyst = does not affect just get to equilibrium faster

e. Removing a product shifts to make more products

f. Increasing volume = shifts to products

Practice = Tell what would happen to the following reaction
2NO2 (g) ↔ N2 (g) + 2 O2 (g) which is exothermic

a. NO2 is added d. He (g) is added

b. N2 is removed e. The temperature is increased

c. The volume is halved f. A catalyst is added

13 AP Chem Gen. Equilibrium notes:
Chapter 16 in Tro