LABORATORY ACTIVITY 6

EQUILIBRIUM AND LE CHATELIER’S PRINCIPLE

EXPECTED OUTPUT

At the end of the experiment, the students should be able to:

 1. Determine the effect of an applied stress on chemical systems at equilibrium

2. Study the effects of concentration and temperature on equilibrium positions

INTRODUCTION

Chemical Equilibrium1

Many chemical reactions result in the virtually complete conversion of reactants into products. When
sodium metal reacts with chlorine gas, for example, both are entirely consumed. The sodium chloride
product is so much more stable than the reactants that once started; the reaction keeps going until it
is complete. Chemical equilibrium is an active, dynamic condition. All substances present are
continuously being made and unmade at the same rate, so their concentrations are constant at
equilibrium.

Note that it is not necessary for the concentrations of reactants and products at equilibrium to be
equal (just as it is not necessary for the numbers of people on two floors connected by escalators to
be equal). Equilibrium can be reached at any point between pure products and pure reactants. The
extent to which the forward or reverse reaction is favored over the other is a characteristic property
of a given reaction under given conditions.

Within experimental error, the ratios of product and reactant concentrations at equilibrium yield the
same result. Numerous experiments have led to a general equation that is valid for any reaction.
Consider a general reversible reaction:

𝑎𝐴 + 𝑏𝐵 + ⋯ ↔ 𝑚𝑀 + 𝑛𝑁 + ⋯

where A, B are reactants; M, N are products; and a, b, m, n are coefficients in the balanced equation.
At equilibrium, the composition of the reaction mixture obeys the following equilibrium equation,
where K is the equilibrium constant.

The equilibrium constant K is the number obtained by multiplying the equilibrium concentrations of
the products and dividing by the equilibrium concentrations of the reactants, with the concentration
of each substance raised to a power equal to its coefficient in the balanced equation.

We can summarize the meaning of equilibrium constants in the following way:

Le Chatelier’s Principle1

The effect of a change in reaction conditions on chemical equilibrium is predicted by a general rule
called Le Châtelier’s principle: “When a stress is applied to a system at equilibrium, the equilibrium
shifts to relieve the stress.”

The word stress in this context means any change in concentration, pressure, volume, or temperature
that disturbs the original equilibrium and causes the rates of the forward and reverse reactions to
become temporarily unequal.

If the concentration of any one of the reactants or products involved in a chemical equilibrium is
changed, or if the temperature is changed, the position of the equilibrium shifts to minimize the
change. Le Châtelier’s principle states that if a system at equilibrium is disturbed (by altering the
concentration of reactants or products, the temperature, or pressure) the equilibrium will shift to
minimize the disturbing influence. By this principle, if a reactant or product is added to a system at
equilibrium, the equilibrium will shift to consume the added substance. Conversely, if reactant or
product is removed, the equilibrium will shift to replenish the substance that was removed.

It is important to remember that changes in concentrations, while causing shifts in the equilibrium
positions, do not cause a change in the value of the equilibrium constant. Only changes in
temperature affect the value of equilibrium constants.

In this experiment we will observe two ways that a chemical equilibrium can be disturbed:
(1) by adding or removing a reactant or product, and
(2) by changing the temperature. Your observations and conclusions will be interpreted using
LeChatelier's principle.

PART I: Changes in Reactant or Product Concentrations2

A. Copper and Nickel Ions
Aqueous solutions of copper (II) and nickel (Il) appear blue and green, respectively. However, when
aqueous ammonia, NH3, is added to these solutions, their colors change to dark blue and pale violet,
respectively.

Ammonia substitutes for water in these two reactions because the metal ammonia bond is stronger
than the metal-water bond, and the equilibria shift to the right, accounting for the color changes. If a
strong acid such as HCl is added to these ammoniacal solutions, their colors revert back to the original
colors of blue and green. The equilibria shift left because the reactant ammonia, NH 3, is removed
from the equilibria. It reacts with the acid to form ammonium ion according to reaction
[2].

B. Cobalt Ions
Cobalt (II) ions in aqueous solution appear pale pink. In the presence of a large concentration of
chloride ions, the solution changes color, and the following equilibrium is established:

Part II. Equilibria Involving Sparingly Soluble Salts

Silver carbonate, silver chloride, and silver iodide salts are only very slightly soluble in water. They can
be precipitated from silver nitrate solutions by the addition of sodium salts containing the
corresponding anions. For example, silver carbonate will precipitate by mixing solutions of AgN03 and
Na2C03:

for which the net ionic equation is:

There is a dynamic equilibrium in the saturated solution of silver carbonate between the solid silver
carbonate and its constituent silver and carbonate ions as shown in reaction [4]. In all saturated
solutions a dynamic equilibrium exists between the solid and the ions in solution.
The silver carbonate precipitate can be dissolved by the addition of nitric acid. Protons, H +, from the
HN03 react with the carbonate ions, CO3 2-, to form unstable carbonic acid.

Removal of carbonate ions results in the dissolution of silver carbonate by a shift to the left of the
equilibrium represented by reaction [4].

Part III. Effect of Temperature on Equilibria (see procedure)

PROCEDURE2

PART I: Changes in Reactant or Product Concentrations2

A. Copper and Nickel Ions

Place about 1 mL of 0.1 M CuS04 in a small, clean test tube. Record the color of the solution on your
report sheet (1). (CAUTION: Concentrated NH3has a strong irritating odor; do not inhale. If you
come in contact with it, immediately wash the area with copious amounts of water.) Add 15 M
NH3dropwise until a color change occurs and the solution is clear, not colorless.

Record your observation on your report sheet (2). Mix the solution in the test tube by "tickling" the
test tube with your fingers as you add the NH3. Add 1 M HCl dropwise while carefully mixing the
solution in the test tube until the color changes. Note the color (3).

Repeat the same procedure using 0.1 M NiCl2 in place of the CuS04and record your corresponding
observations on your report sheet.

Dispose of the solutions in the test tubes in the designated receptacles.

B. Cobalt Ions
Place about 0.5 mL (10 drops) of 1 M CoCl2 in a clean small test tube and note the color (7). (CAUTION:
Avoid inhalation and contact with concentrated HCI. If you come in contact with it, immediately
wash the area with copious amounts of water.) Add dropwise 12 M HCl to the test tube until a
distinct color change occurs. Record the color on your report sheet (8). Slowly add water to the test
tube while mixing. Record the color change on your report sheet (9).
Dispose of the solution in the test tube in the designated receptacle.
Part II. Equilibria Involving Sparingly Soluble Salts

To 0.5 mL (10 drops) of 0.1 M Na2C03 in a clean large test tube add 10 drops of 0.01 M AgN03. Record
your observations on your report sheet (10). (CAUTION: Avoid contact with nitric acid, HN03. If you
come into contact with it, immediately wash the area with copious amounts of water.)

Cautiously add 6 M HN03 dropwise to the test tube until you observe a change in appearance of the
contents of the test tube (11). Save the contents for the next steps.

The above solution contains silver ions and nitrate ions because theAg2C03 dissolved in the nitric acid.
Addition of chloride ions to this solution, from HCI, results in the precipitation of AgCl. The
precipitated AgCI is in dynamic equilibrium with Ag+ and Cl- ions:

This dynamic equilibrium can be disturbed by removing the Ag+ ions thereby forcing the equilibrium
to shift to the left; and as a result, the AgCl dissolves. Silver ions can be removed by the addition of
NH3 because they react with NH3 to form [Ag(NH3)2]+:

Because the equilibrium of reaction [6] lies much farther to the right than that of reaction [5], the
AgCl will dissolve.

Adding acid to this ammoniacal solution will remove the NH3 by formingNH4+(see Equation (2)). This
causes equilibrium 6 to shift to the left. The released Ag+ will combine again with Cl- present to
precipitate AgCl as shown in Equation [5]. The reprecipitated AgCl can be redissolved by the addition
of excess NH3 for the same reason given above (see Equation [6]).

To the solution saved from above add 0.1 M HCI dropwise until you observe a change in the
appearance of the contents of the test tube. Record your observations on your report sheet (12).
(CAUTION: Concentrated NH3 has a strong irritating odor; do not inhale. Do not get it on your skin.
If you come into contact with it, immediately wash the area with copious amounts of water.) While
mixing the contents of the test tube, add 15 M NH3 dropwise until evidence of a chemical change
occurs (13). Acidify the solution by the dropwise addition of 6 M HN03 until there is evidence of a
chemical change. Record your observations on your report sheet (14). Again while mixing, add 15 M
NH3 dropwise until there is no longer a change in the appearance of the contents of the test tube.
Record your observations on your report sheet (15). Save the solution for the next step.

The equilibrium of Equation [6] can be disturbed by the addition of I- from KI. Silver iodide will
precipitate, removing Ag+ causing the equilibrium to shift to the left. The reason that Agl will
precipitate is because the equilibrium of Equation [7] lies much farther to the right than does the
equilibrium of Equation [6].
To the solution from above continue to add 0.1 M KI dropwise until you see evidence of a chemical
reaction. Record your observations on your report sheet (16).

Dispose of the silver salt solution in the designated receptacle.

Part III. Effect of Temperature on Equilibria

Heat about 75 ml of water to boiling in a 250 ml beaker on a ring stand. Place about 1 ml of 1.0 M
CoCl2 in a small test tube and place the test tube in the boiling water without spilling its contents.
Compare the color of the cool cobalt solution to that of the hot solution (17).

Dispose of the solution in the designated receptacle.

DATA AND RESULTS

PART I: Changes in Reactant or Product Concentrations

A. Copper and Nickel Ions

Colors:
1. CuSO4 (aq) ans: Blue 4. NiCl2 (aq) ans: Green
2. [Cu(NH3)4]2+(aq) ans: Dark blue 5. [Ni(NH3)6]2 (aq) ans: Pale Violet

3. After HCl addition ans: Original color (Blue) restored

6. After HCl addition ans: Original Color (Green) restored

Explain the effects of NH3 (aq) and HCI (aq) on the CuS04 solution in terms of Le Chatelier's Principle.
Consider the following equilibria:

B. Cobalt Ions
7. Color of CoCl2 (aq) ans: Pale Pink
8. Color after the addition of HCL (aq) ans: Dark Blue
9. Color after the addition of H2O ans: Pale Pink (Restored)
Account for the changes observed for the cobalt solutions in terms of LeChatelier's Principle. Consider
the following equilibrium:

PART II: Equilibria Involving Sparingly Soluble Salts

10. Silver carbonate precipitate observed.

11. Change in appearance after HNO3 addition.

Account for your observations. Consider the following equilibria:

12. Account for your observations. Consider the following equilibria:

Ans : AgCl dissolved.

13. Did the precipitated AgCl dissolve? Explain.

Ans: The addition of HNO3 caused the reformation of AgCl

14. What effect did the addition of HN03 have on the contents of the test tube? Explain.
Ans: The addition of NH3 caused the redissolution of AgCl.

15. What effect did the addition of NH3 have on the contents of the test tube? Explain.
Ans: No further change observed after NH3 addition.

16. Explain the effect of the addition of KI.

Ans: The addition of KI resulted in the precipitation of AgI.

PART III: Effects of Temperature on Equilibria

17. Color of cool CoCl2 Pale Pink Color

of hot CoCl2 Dark Blue
Is the reaction exothermic? Yes, the reaction is exothermic. The color change from pale pink to
dark blue indicates that heat is being released during the process. In an exothermic reaction, heat
is considered a product, and the system's temperature increases. The shift to a darker color (dark
blue) in the hot CoCl2 solution suggests that the reaction is favored in the direction that produces
heat.
QUESTIONS

What is meant by the term chemical equilibrium? Must amounts of reactants and products be equal
at equilibrium?
Chemical equilibrium is a dynamic state in a reaction where the rates of the forward and reverse
reactions are equal, and the concentrations of reactants and products remain constant over time.
The amounts of reactants and products don't need to be equal at equilibrium; they can be at any
ratio, as long as the rates are balanced.
Why do catalysts not alter the amounts of reactants and products present at equilibrium?
Catalysts facilitate the attainment of equilibrium by accelerating both the forward and reverse
reactions equally. They do not affect the position of equilibrium or the concentrations of reactants
and products but rather increase the speed at which equilibrium is reached.