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Chang, 7th Edition, Chapter 14, Worksheet #1 S. B.

Piepho, Fall 2002

How to Solve Equilibrium Problems

Equilibrium problems are a common type of problem in Chemistry which involve the
equilibrium constant K. More specifically, Kc is used when the equilibrium constant is written in
terms of concentrations, and Kp is appropriate for a gas reaction if partial pressures of gases are
given.
For a reaction

aA +bB ↔ cC + dD

Kc is defined to be
 [C]c [D]d 
Kc = 
 [A]a[B]b  (at equilibrium)

where all concentrations are equilibrium concentrations. The double arrow in the equation
indicates the reaction goes in both directions (and never reaches completion). At equilibrium,
the rates of the forward and reverse reactions are equal, and there is no further change in
concentration. Kc is a constant for a given reaction at a given temperature.

Methods for solving equilibrium problems are best shown with examples.
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Example 1 [Similar problems: Chang, #14.76 and 14.82.]

Calculate the equilibrium constant Kc at 25 oC for the reaction

2 NOCl(g) ↔ 2 NO(g) + Cl2(g)

using the following information. In one experiment 2.00 mol of NOCl is placed in a 1.00 -L
flask, and the concentration of NO after equilibrium is achieved is 0.66 mol/L.

Method:
(a) Calculate the initial concentration of NOCl from the information given.
(b) Form an equilibrium table and fill in all known quantities. Represent unknown quantities
with variables. Use the information in the table to calculate the concentration of NOCl and Cl2 at
equilibrium.
(c) Form the Kc equation and fill in all known information. Calculate Kc.

Solution:
Step(a): The initial concentration of NOCl is

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Chang, 7th Edition, Chapter 14, Worksheet #1 S. B. Piepho, Fall 2002

2.0 mol
[NOCl]0 = = 2.00 M
1.00 L

Step(b): The equilibrium table is:

Balanced Equation 2 NOCl(g) ↔ 2 NO(g) + Cl2(g)


Initial Concentrations (M) 2.00 0 0
Change (M) - 2x 2x x
Equilibrium Concentrations (M) (2.00 - 2x) 2x = 0.66 x

From the table we have

[NO] = 2x = 0.66 M
x = 0.33 M
Thus

[NOCl] = (2.00 - 2x) M = (2.00 - 2(0.33)) M = 1.34 M

[Cl2] = x = 0.33 M

Step(c): We now have the information we need to calculate Kc:

 [NO]2 [Cl 2 ] 2
(0.66) (0.33)
Kc = = = 0.080
 [NOCl]2  (at equilibrium ) (1.34)2

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Example 2 [Related problem: Chang, #14.40.]

When solid ammonium carbamate sublimes, it dissociates completely into ammonia and carbon
dioxide according to the equation

N2H6CO2(s) ↔ 2 NH3(g) + CO2(g)

At 25 oC, experiment shows that the total pressure of the gases in equilibrium with the solid is
0.116 atm. What is the equilibrium constant Kp?

Method:
The steps are:
(a) Form an equilibrium table and fill in all known quantities. Represent unknown quantities
with variables.
(b) Use the table together with the rule that the sum of the partial pressures equals the total
pressure to find the partial pressures of NH3 and CO2 at equilibrium.
(c) Form the Kp equation and fill in all known information. Calculate Kp.

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Chang, 7th Edition, Chapter 14, Worksheet #1 S. B. Piepho, Fall 2002

Solution:
Step (a): The equilibrium table is:

Balanced Equation N2H6CO2(s) ↔ 2 NH3(g) + CO2(g)


Initial Partial Pressures (atm) (solid!) 0 0
Change (atm) not applicable 2x x
Equilibrium Partial Pressures (atm) not applicable 2x = p(NH3) x = p(CO2)

Step (b): The total pressure at equilibrium (given as 0.116 atm) equals the sum of the partial
pressures. The last line of the equilibrium table allows us to express p(NH3) and p(CO2) in terms
of x. Thus we have

pTotal = p(NH3) + p(CO2)

0.116 atm = 2x + x = 3x

x = 0.03867 atm

It follows that
p(NH3) = 2 x = 2 (0.0387 atm) = .07734 atm
p(CO2) = x = 0.03867 atm

Step (c): Now we have the information needed to calculate Kp:

(
K p = p2NH 3 pCO 2 )
( at equilibrium )
= ((0.07734) 2(0.03867)) = 2.31×10 −4

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Example 3 [Similar problems: Chang, #14.42 and 14.46.]

A sample of 0.0020 moles of F2 was sealed into a 2.0 L reaction vessel and heated to 1000 K to
study the dissociation into F atoms:
F2 ↔ 2 F

At this temperature, Kc = 1.2 × 10-4. What are [F2] and [F] at equilibrium? What is the percent
dissociation of F2?

Method:
The steps are:
(a) Calculate the initial concentration of F2 from mole and volume information given.
(b) Form an equilibrium table and fill in all known quantities.
(c) Form the Kc equation and fill in all known information. Solve for the unknown.
(d) Calculate results asked for in the problem.

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Chang, 7th Edition, Chapter 14, Worksheet #1 S. B. Piepho, Fall 2002

Solution:
Step (a): The initial concentration of F2 is

 0.0020 mol
[F2]0 =  = 0.0010 M
2.0 L 

Step (b): The equilibrium table is given below. Note that as the reaction proceeds, reactants are
consumed and products are formed in proportion to their stoichiometric coefficients.

Balanced Equation F2 ↔ 2F
Initial Concentration (M) 0.0010 0
Change (M) -x 2x
Equilibrium Concentration (M) 0.0010 - x 2x

Step (c): Next we form the Kc equation and fill in equilibrium values. Note that [F] = (2x) and
that the entire quantity is squared:

 [F]2  (2x)2 4x 2
Kc = 1.2 ×10 −4
=   = =
 [F2 ]  (at eq) (0.0010 − x ) (0.0010 − x )

(0.0010 - x)(1.2 × 10-4) = 4 x2

Next we rearrange the equation above to quadratic form, a x2 + b x + c = 0:

4 x2 + 1.2 × 10-4 x - 1.2 × 10-7 = 0

In our case,

a = 4, b = 1.2 × 10-4, and c = - 1.2 × 10-7

and, using the quadratic formula, we have:

−b ± b 2 − 4ac −(1.2 ×10 −4 ) ± (1.2 ×10 −4 )2 − 4(4)( −1.2 ×10 −7 )


x± = =
2a 2(4)

−1.2 × 10 −4 ± 1.934 ×10 −6


x± =
8

This gives x+ = 1.59 × 10-4 and x- = - 1.89 × 10-4. Clearly, only the positive root makes sense
physically; there is no such thing as a (-) concentration! Thus x = x+ = 1.59 × 10-4.

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Chang, 7th Edition, Chapter 14, Worksheet #1 S. B. Piepho, Fall 2002

Step (d): Now we are ready to calculate the results asked for in the problem. For this we go
back to the last line of our equilibrium table, and use the value of x calculated above to obtain

[F2] = (0.0010 - x) = (0.0010 - 1.59 × 10-4) = 8.4 × 10-4

[F] = 2 x = 2 (1.59 × 10-4) = 3.2 × 10-4

The equation for percent dissociation is:

 quantity dissociated
% dissociation =  × 100%
initial am ount 

In this case,
 x   1 .5 9× 1 0-4 
% dissociation of F2 =   × 1 0 0 %= × 100%
 [F2 ]0   0.0 0 1 0 

= 15.9 %

≈ 16 %

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Approximate Methods
In many cases calculations may be simplified by making approximations. For example, if Kc
is very small (i.e., < 5.0 × 10-5) and the initial reactant concentration c0 is fairly large (i.e., c0 >
1000 × Kc ), to a good approximation

(c0 ± x) ≈ c 0

Use of this type of approximation eliminates the need to solve quadratic equations in many cases.

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