Preparation of Tetraamminecopper (II) Sulfate Monohydrate: [Cu

(NH3)4] SO4. H2O

The Chemistry of Copper
The two most important oxidation states of copper are the +1 (cuprous) and +2
(cupric). The +2 ion is more stable and by far the most common. Commonly
encountered copper salts include copper sulfate pentahydrate and copper
chloride dehydrated, which have the formulas CuSO4 •5H2O and CuCl 2 •2H2O.
The former is pale blue in color, and the latter is blue-green in color.
Copper sulfate pentahydrate contains copper (II) in a geometry best described
as distorted octahedral. The copper (II) is bound to four water molecules in a
square-planar geometry and two oxygen atoms from two sulfate ions. This salt
dissolves in water to produce the pale-blue [Cu (H2O)6]2+ ion, in which two of
the water molecules are less tightly held and have longer bond distances. The
blue-green color of copper chloride dihydrate is due to the presence of some
CuCl4 2- , which is yellow in color and has a square planar geometry.
Concentrated solutions of copper chloride may appear blue-green in color, but
dilution results in the formation of the pale-blue [Cu (H2O)6 ] 2+ ion.
Addition of NH3 to solutions containing the [Cu (H2O)6 ] 2+ ion results in
successive replacement of the first four H2O molecules. Replacement of the fifth
and six water molecules does not occur to an appreciable extent in aqueous
solution, and replacement of the sixth only occurs in liquid ammonia

A similar series of reactions occur when ethylene diamine is added to a solution

containing the [Cu(H2O)6 ]2+ ion. Addition of the first two ethylene diamine
molecules occurs readily, but addition of a third only occurs when the
concentration is very high.

Addition of HCl to a solution containing the [Cu (H2O)6]2+ ion results in the
formation of [CuCl4 ] 2- which, as previously mentioned, is yellow in color and
has square planar geometry. Salts containing this ion may be isolated with
bulky cations, as in (NH4)2 [CuCl4]. Addition of OH-to [Cu (H2O)6]2+ results in
the initial formation of solid Cu(OH)2 , but with further additions the solid
dissolves to form the complex ion [Cu(OH)4 ]2- . Addition of NO2 - to a solution
containing the [Cu (H2O)6]2+ ion results in the formation of a solution which
probably contains the [Cu(NO2)4 ]2- ion.
In this experiment, you will prepare tetraaminecopper (II) sulfate
monohydrate, [Cu (NH3)4] SO4. H2O from a reaction of Cu SO4. 5H2O (The fifth
water molecules are not part of the complex ion, but is hydrogen bonded to the
sulfate ion (SO4 2-) in the solid) and NH3 in aqueous solution. . The chemical
reaction described above is shown the following equation:

[Cu (H2O)4] SO4. H2O(aq) + 4NH3 (aq) →[Cu (NH3)4] SO4. H2O (aq) + 4H2O (l) .

This is a single replacement reaction in which NH3 molecule replace the water
molecules originally bonded to the copper (II) ion.

The Structure of Complexes

• Contain coordinate covalent bonds
• Unusual composition: Central metal ion or atom +
ligands + counter ion
• Called complex ion if charged

Procedure
The strategy you will employ in this synthesis is to add a large excess of NH3
solution to an aqueous solution of [Cu (H2O)4]2+ ion in order to achieve a
complete replacement of H2O by NH3. At this point, you will have the product in
solution, where it exists as discrete tetraamminecopper (II) ions, [Cu (NH3)4]2+,
and SO4 2- ions.

1) Weigh about 6.5 grams (CuSO4•5H2O) into a clean 250 ml beaker.

2) Add 6 mL of hot distilled water to the solid in the beaker

CuSO4. 5H2O(s) +H2O → Cu 2+(aq) + SO4 2- (aq)

[Cu (H2O)4] SO4.H2O + H2O → [Cu (H2O) 4] 2+ (aq) + SO4 2- (aq)

3) In the fume hood, measure 10ml of concentrated NH3 solution (NH4OH (aq)
25%) into a 100ml graduated cylinder. after all of the solid in the beaker has
dissolved, slowly add the NH3 solution to the solution in the beaker. stir the
reaction mixture with a glass stirring rod after each 1-2ml addition of NH3
solution.
4) To isolate the product as a solid, you must crystallize it. To do this, you will evaporate a
portion of the water; add some ethanol (10ml).
5) Cool the mixture solution in ice bath during 30min, When the complex ion salt
precipitates, it carries one molecule of water with it, so that the solid crystals have the
formula: [Cu (NH3)4] SO4·H2O. Each of these steps reduces the solubility of the product and
is therefore important in maximizing your yield.
6) Collect the crystals that deposit by suction filtration using a Buchner funnel. 7) Wash the
product with an equal volume mixture (1:1) of concentrated ammonia (5ml) and ice cold
ethanol (5ml); followed by 10 ml ethanol (using ethanol in order to maximize the formation
of complex, to prevent any redissolving of the product).
8) Dry the precipitate in an oven for 10 min at 110°C.

Notes:

4. Ethanol is less polar than water; ethanol is a poor solvent for ionic compounds. Addition
of ethanol to the solution reduces the solubility of [Cu (NH3)4] SO4. H2O in the mixture,
causing the product to crystallize. Very little, if any, solid (NH3)4] SO4. H2O will form if you do
not add ethanol. If you fail to reduce the water volume or to cool the solution sufficiently,
your yield will also be reduced, because some of the (NH3)4]SO4. H2O will remain dissolved
in solution.

You can also help maximize your yield by using proper experimental technique. You must be
particularly careful to prevent loss of product during certain steps in the synthesis. First,
when evaporating the water, you must heat the CuSO4-NH3 solution gently. Some of the
(NH3)4]SO4. H2O. H2O may decompose if you heat the reaction mixture too vigorously. If some
decomposition does occur, you will see a brown film on the bottom of your beaker and a
blackish brown tinge in the solid product.

Answer the following question:

1. What is the difference between tetraaminecopper (II)sulfate monohydrate and
copper (II) ammonium sulfate?
2. What is the geometric structure of the obtained substance?
3. Measure the weight of the product and calculate the % yield