Le Chateliers Principle

Le Chateliers Principle (Chemical Equilibria) Introduction

We will investigate Le Chateliers Principle in several systems by shifting the equilibrium concentrations of reactants and products by applying a stress to the equilibrium. This experiment will demonstrate some observable equilibrium concentration shifts and give you a chance to relearn the technique of writing net-ionic equations. Le Chateliers Principle states: When a stress is applied to a chemical system at equilibrium, the equilibrium concentrations will shift in a direction that reduces the effect of the stress. The stress that will be applied in our investigation will be either: the addition of more reactant or product to the equilibrium mixture, increasing their concentration. the addition of a species that chemically reacts with either a reactant or product in the equilibrium mixture, lowering their concentration. The systems will involve equilibriums that you may have already studied: weak acid and base, (Ka and Kb), solubility, (Ksp), and complex ion formation, (Kf). Although no calculations will be done, you should be able to recognize the type of equilibrium under investigation. The following is an example of an equilibrium system similar to the five you will investigate. The first step in the process is to establish the equilibrium given the allowed reagents. The equilibrium concentrations are shifted (to the left or right) by applying a stress to the equilibrium system by adding one of the given reagents. Changes in the appearance of the system are recorded. Finally, a net-ionic equation is written to understand the chemistry behind the change in equilibrium concentrations. An example equilibrium Consider the following equilibrium between aluminum ions and ammonia: Al3+(aq) + 3 NH3(aq) + 3 H2O(aq) Al(OH)3(s) + 3 NH4+(aq) Reagents To establish equilibrium: To shift equilibrium concentrations: 1. aluminum nitrate, 0.1 M hydrochloric acid, 1 M ammonia, 0.1 M

Al(OH)3(s) might be produced by: Adding aluminum nitrate with ammonia a) b) Observation: When the two clear and colorless solutions were mixed, a white precipitate formed. Net-ionic equation: Al3+(aq) + 3 NH3(aq) + 3 H2O(l) Al(OH)3(s) + 3 NH4+(aq)

2.

The equilibrium concentrations can be shifted left by adding: HCl a) b) Observation: The precipitate dissolved. Net-ionic equation: Al3+(aq) + 3 H2O(l) < Al(OH)3(s) + 3 H+(aq)

Le Chatelier's Principle.doc Daley/Larson

April 26, 2008

Le Chateliers Principle Writing net-ionic equations This will be the troublesome part for most students. There are two different methods to use when writing the net-ionic equations depending on the type of stress applied to the equilibrium. Method 1 for writing the net-ionic equations. If the stress applied to the equilibrium system is simply an increase in concentration of a reactant or product, without any new chemistry, then the net-ionic equation is given by the original equilibrium net-ionic equation. In the aluminum example, the original equilibrium equation indicated how the precipitate would form based on the reagents needed to establish the equilibrium, Al3+ and NH3. Method 2. This is used when NEW chemistry takes place. This method is somewhat more complicated and requires some thought about chemical reactions. If the addition of a species to the equilibrium system results in a chemical reaction with either a reactant or product then the stress applied to the equilibrium lowers the concentration of a reactant or product. The equilibrium concentrations will shift accordingly. To write the overall net-ionic equation several steps are involved. This method will work with all the systems you will study today. In the previous example H+ was added to shift the equilibrium concentrations to the left. To write the final net-ionic equation follow these steps (in order!). 1. 2. Start with the original equilibrium net-ionic equation: Al3+(aq) + 3 NH3(aq) + 3 H2O(l) Al(OH)3(s) + 3 NH4+(aq) Since the equilibrium is shifting to the left, a reactant in the original equilibrium must be reacting with the added acid, THIS is LE CHATELIERS PRINCIPLE! The two possible reactants are Al3+(aq) and 3 NH3(aq). Your chemical knowledge should tell you H+ ions are reacting with the ammonia in an acid-base reaction. We now add enough H+ ions to both sides of the original equilibrium equation to react all the ammonia: Al3+ + 3 NH3 + 3 H2O Al(OH)3(s) + 3 NH4+ 3 H+ 3 H+ 3+ Al + 3 NH4+ + 3 H2O Al(OH)3(s) + 3 NH4+ + 3 H+ (original equilibrium) (acid added) (result of chemical rxn)

3. 4.

We now cancel any species that appear on both sides of the new equation, NH4+ in this example: Al3+(aq) + 3 H2O(l) < Al(OH)3(s) + 3 H+(aq) Since the original equilibrium concentrations were being shifted to the left it is good practice to write the new equation and replace the equilibrium double arrow with a single arrow to the left as shown. Also include all phase symbols.

Ammonia as a reagent many uses.

Ammonia will be used in this lab to do three things for us: 1) form hydroxide precipitates, 2) neutralize acids, and 3) form complex ions. The chemistry of each is discussed in more detail below. 1. Using Ammonia in net-ionic equations as a source of hydroxide ions.

When a few drops of 6 M ammonia is added to a 0.10 M solution of aluminum nitrate a precipitate forms. The precipitate is aluminum hydroxide. The small concentration of hydroxide ions in the ammonia solution is enough to precipitate some Al3+ ions. Remember ammonia is a weak base and maintains an equilibrium with water that produces hydroxide ions: NH3 + H2O NH4+ + OH Kb = 1.8x105. Thus, whenever you add ammonia to an equilibrium system you are also adding about 1% hydroxide ions. Since there is already a Kb equilibrium present in the ammonia solution the net-ionic equation for the precipitation is written according to method 2 with the chemistry being the reaction of Al3+ with the hydroxide ions. Thus we use the Kb equilibrium of ammonia to obtain the hydroxide ions needed for the chemical reaction.

Le Chatelier's Principle.doc Daley/Larson

April 26, 2008

Le Chateliers Principle First the coefficients in the ammonia equilibrium are tripled to provide 3 hydroxide ions for reaction with the Al3+. 3 NH3 + 3 H2O 3 NH4+ + 3 OH Al3+ Al3+ Al3+ + 3 NH3 + 3 H2O Al(OH)3(s) + 3 NH4+ 2. Using ammonia to neutralize acids. (equilibrium already present) (species added) (result of chemical reaction on product side)

Often ammonia is used as a base to consume extra acid in solution and therefore shift an equilibrium. In this case it is the ammonia directly reacting with the hydronium ions, not the hydroxide ions present in the ammonium solution. When writing net ionic equations using ammonia as a base to simply neutralize hydronium ions use the following procedure to write a net-ionic equation: BaC2O4(s) + H3O+ HC2O4 + Ba2+ + H2O NH3 NH3 BaC2O4(s + NH4+ HC2O4 + Ba2+ + NH3 (original equilibrium) (ammonia added) (result of chemical rxn, waters cancel)

3. Using Ammonia in net-ionic equations as to form complex ions. Cd(OH)2(s) can be dissolved by adding excess ammonia. For many cations, excess ammonia forms a complex ion. The ammonia is in high enough concentration to act as a Lewis base, replacing the OH on the cadmium. The complex ion Cd(NH3)42+ is formed. Use method 2 to write the net-ionic equation realizing Cd2+ is reacting with excess NH3. Cd2+ + 2 OH Cd(OH)2(s) 4 NH3 4 NH3 (original equilibrium) (ammonia added) (result of chemical rxn)

Cd(NH3)42+ + 2 OH < Cd(OH)2(s) + 4 NH3

Overview of the Procedure

To prepare your notebook, copy each equilibrium system, numbers 1 to 5, onto a separate page in your notebook. Make sure to list all reagents with concentrations. DO NOT USE THE REPORT SHEET IN LAB! For each equilibria you investigate, use only the reagents listed to set-up the equilibrium. Use small test tubes. After the equilibrium is established, again use only the reagents listed and/or a temperature change to shift the equilibrium concentrations to the left or right. Record all observations that indicate the equilibrium concentrations have shifted and then write the net-ionic equation that produced the shift in equilibrium concentrations. Other notes: 1. Use one ml quantities to establish the initial equilibrium in the test tube. Reagents are then added drop wise to shift the equilibrium. 2. Do not add more reagent than the minimum needed to produce the desired effect. If the concentration of a reagent becomes too high, you may not be able to shift the equilibrium concentrations back again or an unexpected side-reaction may occur. If you carefully add reagents drop-wise you should be able to shift the equilibrium concentrations back and forth several times. When needed, heat test tubes in a hot water bath. Use an ice bath for cooling. Rinse your test tubes thoroughly with de-ionized water between investigations to avoid contamination. All reagents should be disposed of in a proper Hazardous Waste container, not in the sink. All species are aqueous unless otherwise noted.

3. 4. 5. 6.

Le Chatelier's Principle.doc Daley/Larson

April 26, 2008

Chem. 1C Lab section: MW or TTh 1. Locker #

Name Partner

CoCl42 (aq) (blue) + 6 H2O (l) Co(H2O)62+ (aq) (pink) + 4 Cl (aq) CoCl2 in 95% ethanol, 0.1 M (Measure 3 mL into a clean dry test tube) Caution: CoCl2 in ethanol is flammable, toxic and irritating! hydrochloric acid, 12 M, use drop wise (Caution: Use in the hood with gloves!) deionized water, use drop-wise

Reagents:

Prepare the equilibrium by adding deionized water, 1 drop at a time and mixing well after each drop, to 3 mL of the CoCl2 solution until you see a light purple color. a. Equilibrium concentrations in equation (1) are shifted left by adding: i) ii) Observation: Net-ionic equation:

b.

Equilibrium concentrations in equation (1) are shifted back to the right by adding: i) ii) Observation: Net-ionic equation:

c.

Prepare a fresh 3 mL sample as instructed above. Separate this sample into two different test tubes. Place one test tube in hot water and the other in ice water. Wait five minutes. i) Observation:

ii)

Is the reaction in equation (1) exothermic or endothermic as written? How do you know?

iii)

Rewrite the equilibrium reaction by adding heat to the appropriate side of the equation.

Le Chatelier's Principle.doc Daley/Larson

April 26, 2008

Chem. 1C Lab section: MW or TTh 2. Locker #

Name Partner

BaC2O4 (s) + H3O+ (aq) HC2O4 (aq) + Ba2+(aq) + H2O (l) barium chloride, 0.1 M, use 1 ml hydrochloric acid, 1 M, use drop-wise ammonium oxalate, 0.1 M, use 1 ml ammonia solution, 6 M, use drop-wise

Reagents a.

BaC2O4(s) is produced by mixing:

i)

Net-ionic equation:

b.

The equilibrium in equation (2) is shifted right by adding:

i)

Observation:

ii)

Net-ionic equation:

c.

The equilibrium in equation (2) is shifted back left by adding:

i)

Observation:

ii)

Net-ionic equation:

Le Chatelier's Principle.doc Daley/Larson

April 26, 2008

Chem. 1C Lab section: MW or TTh 3. Locker #

Name Partner

AgCl (s) (white) + 2 NH3 (aq) [Ag(NH3)2]+ (aq) (colorless) + Cl (aq) silver nitrate, 0.01 M, use 1 ml ammonia solution, 6 M, use drop-wise hydrochloric acid, 1 M, use drop-wise

Reagents: a.

AgCl(s) is produced by mixing:

i)

Net-ionic equation:

The equilibrium in equation (3) is shifted right by adding:

ii)

Observation:

iii)

Net-ionic equation:

b.

The equilibrium in equation (3) is shifted back left by adding:

i)

Observation:

ii)

Net-ionic equation: Note: You should get a new net-ionic here (Its not the Cl ion!).

Le Chatelier's Principle.doc Daley/Larson

April 26, 2008

Chem. 1C Lab section: MW or TTh 4. 4a. 4b. Locker #

Name Partner

Copper ions and ammonia produce multiple equilibria. 2 H2O (l) + Cu2+ (aq) (pale blue) + 2 NH3 (aq) Cu(OH)2 (s) (light blue solid) + 2 NH4+ (aq) Cu(OH)2 (s) + 4 NH3 (aq) [Cu(NH3)4]2+ (aq) (deep blue) + 2 OH (aq) copper (II) nitrate, 0.1 M, use 1 ml ammonia solution, 6 M, use drop-wise hydrochloric acid, 1 M, use drop-wise

Reagents: a.

Cu(OH)2 (s) is produced by mixing:

i)

Net-ionic equation:

b.

The equilibrium in equation (4a) is shifted left by adding: i) Observation:

ii)

Net-ionic equation:

c.

The equilibrium in equation (4b) is shifted right by adding: i) Observation:

ii)

Net-ionic equation:

Le Chatelier's Principle.doc Daley/Larson

April 26, 2008

Chem. 1C Lab section: MW or TTh 5. 5a. 5b. 5c. Locker #

Name Partner

Zinc ions and bases produce multiple equilibria. Zn2+ (aq) + 2 OH (aq) Zn(OH)2(s) Zn2+ (aq) + 4 OH (aq) [Zn(OH)4]2 (aq) Zn2+ (aq) + 4 NH3 (aq) [Zn(NH3)4]2+ (aq) zinc nitrate, 0.1 M, use 1 ml sodium hydroxide, 1 M, use drop-wise hydrochloric acid, 1 M, use drop-wise ammonia solution, 6 M, use drop-wise

Reagents: a.

Produce Zn(OH)2(s) two ways: i) Reactants:

Observation:

Net-ionic equation:

ii)

Reactants:

Observation:

Net-ionic equation:

Le Chatelier's Principle.doc Daley/Larson

April 26, 2008

Chem. 1C Lab section: MW or TTh b. Locker #

Name Partner

Dissolve Zn(OH)2(s) three possible ways. Use the Zn(OH)2(s) Zn2+ (aq)+ 2 OH (aq) equilibrium as the starting point for your net ionic equations. i) Reactants: Observation:

Net-ionic equation:

ii)

Reactants: Observation:

Net-ionic equation:

iii)

Reactants: Observation:

Net-ionic equation:

Le Chatelier's Principle.doc Daley/Larson

April 26, 2008