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 AgN0 3
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 NH 3. 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 Na 2C03 in a clean large test tube add 10 drops of 0.01 M AgN0 3.
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 theAg 2C03 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 HN0 3 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) Blue 4. NiCl2 (aq) Green (Teal)
2. [Cu(NH3)4]2+(aq) Dark Blue 5. [Ni(NH3)6]2 (aq) Violet(pale)
(Almost Navy) 6. After HCl addition Green (Teal)
3. After HCl addition Blue (a little bit
dark)

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

[Cu(H:04]2+ (aq) + 4NH3(aq) = [Cu(NH3)4]2+ (aq) + 4H:0(1)

[Ni(H:0)]2+ (aq) + 6NH3(aq) = [Ni(NH3)6] (aq) + 6H2O(l)
To begin, observe that copper (II) appears blue in the chemical equation: this is the Cu(H20)4]2+, and
nickel (II) appears green (nearly like teal) in the chemical equation; this is the [Ni(H20)]2+, and the
system is already in equilibrium. When the NH3 was added, the
concentration of the reaction changed (increased), causing a stress in the equilibrium making the reaction
unbalanced, this is unbalanced due to the added reactant notice the "NH3" in the left side (reactants side),
the forward reaction will speed up to use the
additional reactant, and turn them into products, this causes the reaction to shift to the right for both the
copper and nickel solutions, and the equilibrium of both separates. Furthermore. when 1M of HCl is
added to the substances, the colors return to their original state, which is blue for copper (ll) and green
for nickel (II). Because NH3 was the reactant, this will be removed from the equilibria due to the added
HCI (This has chloride ions), causing the equilibria to shift to the left in order to restore balance to the
system.
 B. Cobalt Ions
7. Color of CoCl2 (aq) Rose Red
8. Color after the addition of HCL (aq) Dark Red (Almost Back)
9. Color after the addition of H2O Rose Red (More Slightly Light)

Account for the changes observed for the cobalt solutions in terms of LeChatelier's Principle.
Consider the following equilibrium:

Cobalt (ll) ions appear rose red (as seen in the video). Because HCL includes chloride ions, when a high
concentration of HCL is added to the solution, the hue of the solution
changes, turning it into a dark red solution. Furthermore, notice the equation:
Co + 4C1fCoC142 + 6H20, you can see "4CI" in the side (whic reactants), when we added more chloride ions, the
system changed, the equilibrium shifts to the right (from reactant to products) to get rid of some of the extra
chloride ions added. some of the chloride ions will react with [Co(H20)62+. When H20 is added to the material the
solution returns to its former state the explanation for this is because when we add water. We observe that "6H20" is
on the right side (the side of the products), this produces a fresh stress on the system, causing the equilibrium to
shift again, but this time the system shifts left, reverting to its original color (Rose Red)

PART II: Equilibria Involving Sparingly Soluble Salts

10. Sodium Carbonate (Na2C03)

11. Silver Chloride (AgCl)
Account for your observations. Consider the following equilibria::
 12. Did the precipitated AgCl dissolve? Explain.
The precipitated AgCl was indeed, dissolved. The addition of NH3 to the
solution disrupted
this dynamic equilibrium, forcing it to shift to the left and remove the Ag+ ions,
causing the AgCl precipitate to dissolve.

13. What effect did the addition of HN03 have on the contents of the test tube? Explain.
Before the addition was added, the color of the contents in the test tube is
Whitish Gray.
However, after the addition of HNO3 it has become more like a transparent liquid or a
clear
liquid with no color.

14. What effect did the addition of NH3 have on the contents of the test tube? Explain.
Before the addition of the NH3, the color of the contents in the test tube is more like
Cloudy
White. However, after the addition of NH3 it has become more like a Whitish Gray
color
having a little bit of a light blue in the top of the liquid.

15. Explain the effect of the addition of KI.

The production of the AgCl precipitate is the result of the addition of Kl. When
Kl was added,the equilibrium was disrupted and displaced to the left, whereas
Ag+ was removed.
 PART III: Effects of Temperature on Equilibria

16. Color of cool CoCl2 Rosy Red

Color of hot CoCl2 Dark Red

(Maroon-like Color)
Is the reaction exothermic? Explain.

No, for the heated CoCl2 .When a solution is heated, it will move in the direction that will
cool it down, which is the endothermic direction. Furthermore, endothermic processes absorb/gain
heat in the reactants, shifting the equlibrium system to the right from the reactants to the products.
When the CoCl2 was heated, the reactant absorbed the heat (heat + A + B = hot CoCl2), resulting
in "Dark Crimson Solution." Because it is not dipped in cold or hot water, the "Cool CoCl2
will just remain rosy red. According to Le Chatelier's principle, heating any reversible
reactioncauses it to shift to the right, whereas cooling it causes it to shift to the left.
QUESTIONS

What is meant by the term chemical equilibrium? Must amounts of

reactants and products be equal at equilibrium?

Chemical equilibrium is described as a chemical process in which the

ratio of reactants and products has no change or influence during a
reversible chemical process
Furthermore, these reversible processes are "the forward process and the
reverse process," which both run at the same pace to achieve equilibrium
and keep the
concentrations of the products and reactants constant. Furthermore, the
numbers of reactants and products do not have to be evenly matched in
terms of their
ratio/amount because once equilibrium is attained the amounts of
reactants and products remain unchanged/constant. When the
equilibrium is strained or there is stress in
the system, the system adjusts to reduce the stress, restoring balance. For
example, if more reactants are added to the system, the equilibrium will
shift right (from reactants to
products in order to produce these excess reactants and convert them
into products
Why do catalysts not alter the amounts of reactants and products present at
equilibrium?
The presence of a catalyst has no effect on the reaction's eventual equilibrium state
because doing so would violate the second law of thermodynamics, which states
that the
overall entropy of an isolated system can never be decreased, and we know that the
position of the equilibrium is dependent on the Gibbs Free Energy (AG). Catalysts
can
chang the kinetics of a reaction not amics. Thus the position of the equilibrium is
unaffected by the addition of a catalyst, it can speed up the process by
providing an alternative pathway lower energy), and by allowing the rate of reaction
to shift to a lower-enerov state the forward and reverse reaction rates () will both be
accelerated
causing the system to achieve equilibrium more efficiently Furthermore, the
amounts of reactants and products would remain the same, and at equilibrium (even
if a catalyst is
present), the catalyst cannot add anything to the product or reactant ratio.

REFERENCES

1 Silberberg, M.S., Principles of General Chemistry, The McGraw-Hill, 2007. lSBN-I 0: 0-07-

325329-4 2 From Laboratory Experiments, Tenth Edition, John H. Nelson and Kenneth C. Kemp.

Copyright
©2006 by Pearson Education, Inc. Published by Prentice Hall, Inc.