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Le Chatelier’s Principle
Before watching these videos, review Chapter 14 slides #50 - #57.

Equilibrium #1

Co(H2O)62+(aq) + 4Cl-(aq) <-> CoCl42-(aq) + 6H2O(l)

What would happen if you added AgNO3 to test tube #3 (her control)? Would it turn pink or
would it turn blue? Explain your choice. If you are unsure of your answer, watch the video
below.
It turns pink .

Demonstration:

Co(H2O)62+ is formed by dissolving CoCl2*H2O in water.

1. The first sample of the solution is heated to boiling.


2. The first sample now contains a hot CoCl42- solution. AgNO3 is added to produce
Co(H2O)62+ again. A second sample is used as a reference.
3. HCl is added to a third sample at room temperature.

Observations:

When the solution is heated to boiling, it turns from pink to blue. This blue
solution shifts back to pink as the AgNO3 is added. When HCl is added to a pink
solution, it turns blue.

Explanations (including important chemical equation):

The following equilibrium is observed:

Co(H2O)62+(aq) + 4 Cl-(aq) <=> CoCl42-(aq) + 6 H2O(g)

The Co(H2O)62+ complex is pink, and the CoCl42- complex is blue.


This reaction is endothermic as written, so adding heat causes the equilibrium
constant to shift to the right. This, correspondingly, makes the solution blue.

When the AgNO3 is added, Cl- is removed from solution. This shifts the
equation back to the left, and the solution turns pink again.

When HCl is added, there is more Cl- in solution, so the equilibrium is shifted to
the right, and the solution turns blue.

All of the above effects are variations of LeChatelier's principle

Equilibrium #2

Fe3+(aq) + SCN-(aq) <-> FeSCN2+(aq)

In test tube #4, the following reaction took place.

Fe3+(aq) + 4Cl-(aq) <-> FeCl4-(aq)

The equilibrium position of this reaction lies way to the right side. So by adding Cl-(aq), we
effectively remove Fe3+ from solution by turning it into FeCl4-.

Suppose he had Test Tube #7 and added HNO3 to it. Would you see the solution get darker red
or would you see the color of solution lighten? Hint: We have already learned about the
relationship between conjugate acids and conjugate bases. What is the conjugate acid of SCN -.
Is it a strong acid or a weak acid? Is SCN- a neutral ion, an acidic ion, or a basic ion? Use these
answers to predict what happens when HNO3 is added to Test Tube #7.
ANSWER:
Enthalpy is negative. Thiocyanate (also known as rhodanide) is the anion [SCN]−. It is
the conjugate base of thiocyanic acid.

In test tube 7, as the temperature increased, the red color of the products faded,
indicating an equilibrium shift to the left as more reactants were formed. This
observation leads to the conclusion that the reaction is exothermic. For an exothermic
reaction, the heat generated by the reaction resides on the product side of the equation:

Fe3+ + SCN- FeSCN2+ + heat


Equilibrium #3

2CrO42-(aq) + 2H+(aq) <-> Cr2O72-(aq) + H2O(l)

yellow orange

You have a test tube which contains an equilibrium mixture of chromate and dichromate ions.
It is not quite yellow (bit too dark) but not quite orange (a bit too light).

What color change will you see if you add HNO3 to this test tube? Explain.

What will happen if you add NaOH to the test tube you just added nitric acid to? Explain.
Equilibrium #4

You are studying the following equilibrium.

Ni(s) + 4CO(g) <-> Ni(CO)4(g)

You have an equilibrium mixture of Ni, CO, and Ni(CO)4 contained in a sealed container with a
moveable piston, gas valve, pressure gauge, and heating element.

You want to remove more Ni from the surface of the piece of Ni metal in the container. Give
two different ways to do this?

1. An electrochemical technique was used to remove nickel from aqueous solutions on a laboratory
scale using a self-made Plexiglas cell. Electrodes comprising a stainless steel net coated with
single-walled carbon nanotubes were used as both the anode and the cathode.

2. For stubborn stains, soak Ni plated piece instead of simply wiping it down. Combine four parts
water with one part vinegar in a container large enough to soak the piece in. Do not use straight
vinegar, since it is often too abrasive to expose to thin Ni coatings for extended periods. Soak the Ni
plated item in the solution for several hours to overnight. Upon pulling it out, wipe the dirt and tarnish
off with a cloth and rinse the Ni under clean water to remove any traces of vinegar.

When you turn on the heating element inside the container, you see Ni metal being formed on
the element. Is the above reaction exothermic or endothermic? Would you see the pressure
gauge go up or go down when you turned on the heating element (assume the volume inside
the container stays constant)?

The rection is exothermic.


The pressure gauge will go up when we turned the heating element.

Equilibrium #5
Actually, the video below shows an experiment being performed which links together three
different equilibria.

Cu(OH)2(s) <-> Cu2+(aq) + 2OH-(aq) #1

NH3(aq) + H2O(l) <-> NH4+(aq) + OH-(aq) #2

Cu2+(aq) + 4NH3(aq) <-> Cu(NH3)42+(aq) #3

To begin with, the person dissolves CuSO4.5H2O in tap water. Cu2+(aq) is light blue. In tap
water, the [OH-] is low. Eq #1 is shifted to the right due to the low [OH-], and you do not see a
precipitate.

Next, the person starts adding NH3. As the amount of NH3 increases, eq#2 shifts to the right,
causing more [OH-] to be produced. This increase in [OH-] causes eq#1 to shift back to the left,
and you see a light blue precipitate of Cu(OH)2 form.

As he adds more NH3, its concentration keeps increasing. This causes eq#3 to shift the right.
The darker blue color you see is due to the formation of the complex ion Cu(NH3)42+. As eq#3 is
shifted to the right, Cu2+(aq) is used up. In eq#1, as Cu2+ is used up, eq#1 shifts to the right and
the Cu(OH)2 is seen to dissolve.

He adds some vinegar, which as an acid, is a source of H+. Increasing [H+] by adding more
vinegar uses up the OH- in eq#2. As the OH- in eq#2 is used up, eq#2 shifts to the right, causing
NH3 to decrease. As the [NH3] decreases, eq#3 shifts back to the left, and we see the dark blue
color disappear, due to the decrease in Cu(NH3)42+. As equation #3 shifts back to the left, we
get more Cu2+ which causes eq#1 to shift to the left and we see Cu(OH)2 form. As more vinegar
is added, the additional H+ uses up the OH- in eq#1, causing eq#1 to shift to the right. The
result is that we see the Cu(OH)2 precipitate re-dissolve.

You have a solution that contains both Al(NO3)3 and Ni(NO3)2. Al3+(aq) is colorless while Ni2+(aq)
is a light green/blue. You start adding NH3 dropwise to this solution and you see first a white
precipitate form. After a few more drops you start seeing a light green/blue precipitate form.

What are the formulas of these precipitates and how did they form (what has adding NH 3 got to
do with their formation)?
2Al(NO3)3 + 3Ni → 2Al + 3Ni(NO3)2

NH3(aq) + H2O(l) <-> NH4+(aq) + OH-

As you add more NH3, you start to see the light green/blue solid dissolve and the solution turns
to a dark blue color. Nothing happens to the white precipitate. Provide an explanation for
what might be occurring.
Could you use what you just learned to separate a mixture and Al(NO3)3 and Ni(NO3)2?
Describe what would you do to separate the two from each other?
Vinegar can be used.