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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 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.
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 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)
3. 4. 5. 6.
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.
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.
i)
Net-ionic equation:
b.
i)
Observation:
ii)
Net-ionic equation:
c.
i)
Observation:
ii)
Net-ionic equation:
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.
i)
Net-ionic equation:
ii)
Observation:
iii)
Net-ionic equation:
b.
i)
Observation:
ii)
Net-ionic equation: Note: You should get a new net-ionic here (Its not the Cl ion!).
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.
i)
Net-ionic equation:
b.
ii)
Net-ionic equation:
c.
ii)
Net-ionic equation:
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.
Observation:
Net-ionic equation:
ii)
Reactants:
Observation:
Net-ionic equation:
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: