CHEM 122L General Chemistry Laboratory Revision 1.

The Synthesis of Cuprous Chloride

Learn about the element Copper and some of its compounds. Learn about Oxidation-Reduction reactions.

Salvador Dali, Medusa In this laboratory, we will synthesize Cuprous Chloride, CuCl, by direct oxidation of elemental Copper metal. Cuprous Chloride is a white Cu+ salt of Copper which will easily oxidize to the blue Cu2+ salt if allowed to come into contact with Air while moist. As we will synthesize this compound in an aqueous environment, we will need to take special precautions against its oxidation to Cu2+. Copper metal is one of nine Elements known since antiquity; carbon, sulfur, iron, tin, lead, mercury, silver and gold being the others. This is due to the fact that the smelting of Copper containing ores to isolate the pure metal was one of the first smelting processes to be discovered;

Page |2 with peoples initially smelting the Carbonate ores, and then the Sulfides. Smelting of the ore Malachite proceeds according to: Reactions Occurring During the Smelting of a Copper Carbonate Ore Cu2CO3(OH)2
(Malachite)

2 CuO + CO2 + H2O Cu + CO2 (1100oC)

(Eq. 1)

CuO + CO

(Eq. 2)

Early Romans referred to the metal as aes Cyprium; aes being a generic term for alloys of Copper and Cyprium because most of the Copper ores were mined in Cyprus. This was later shortened to cuprum and then Anglicized into Copper. Copper is a reddish-brown metal that is an excellent conductor of heat and electricity, being second only to Silver. It is alloyed as Bronze (with Tin) and Brass (with Zinc). It is a softer metal than Iron but harder than Zinc. Small amounts of Copper can be found naturally uncombined as the pure metal, particularly near Lake Superior in Michigan. Copper ores can be found worldwide: chalcopyrite (CuFeS2), a Sulfide of Copper and iron; chalcocite (Cu2S), a shiny lead-gray Copper Sulfide; bornite (Cu5FeS4), a lustrous reddish-brown Sulfide of Copper and Iron; cuprite (Cu2O), a red cuprous Oxide ore; malachite (Cu2CO3(OH)2), a bright green Carbonate ore; and azurite (Cu3(CO3)2(OH)2), a blue crystalline basic Carbonate of Copper found with other Copper ores. The chemical and physical properties of Copper, like those of the other Transition Metals, are heavily influenced by the presence of d-subshell electrons in its outer orbitals. However, Copper forms an exception to the general Aufbau electron filling scheme in that its 3d orbitals are lower in energy than its 4s orbital, resulting in an electron configuration of: Cu = = 1s2 2s22p6 3s23p63d10 4s1 [Ar] 3d10 4s1

This is consistent with Copper's placement in Group 1B of the Periodic Table of the Elements, suggesting it has but a single valence electron. In fact, Mendeleev's original Periodic Table had Copper, Silver and Gold placed within the same chemical group as the Group 1A elements (Li, Na, K, Rb, Cs). This electron configuration suggests Ionically Bonded salts of Copper should involve Cu+ ions, where the outer 4s electron is lost: Cu+ = [Ar] 3d10

And, this is frequently the case. Salts of Cu+ are reasonably common, often water insoluble and mostly white in color. However, Cu+ is readily oxidized to Cu2+ in most aqueous solution conditions. So, Cu2+ salts are much more common than the Cu+ salts. Many of these salts are water soluble and highly colored. Because Copper forms two common cations, two different names are required to identify the cation present in a given compound. These are:

Page |3 Older Naming System Cuprous Ion Cupric Ion IUPAC Naming System Copper (I) Ion Copper (II) Ion

Cu = Cu2+ =

or or

In this exercise we will convert elemental Copper into the salt Cuprous Chloride, in which the Copper is in the less common Cu+ state. This is somewhat tricky because of the tendency of the Cu+ ion to oxidize to Cu2+. Our approach will be to first Oxidize the metallic Copper into one of its Cu2+ salts, Cupric Carbonate (CuCO3), and then to Reduce this to the Cu+ containing Cuprous Chloride (CuCl) compound. In general, the oxidation process strips electrons away from the atom and Reduction adds them. The specific chemical reactions to be carried-out are:

Oxidation of Copper Metal by Nitric Acid & Ppt as Cupric Carbonate Cu(s) + 4 HNO3(aq) where the Cupric Nitrate exists as: Cu(NO3)2(aq) Cu2+(aq) + 2 NO3-(aq)
(Eq. 4)

Cu(NO3)2(aq) + 2 NO2(g) + 2 H2O (Eq. 3)

such that the Cupric Ion can be precipitated as the Carbonate salt: Cu2+(aq) + CO32-(aq) CuCO3(s)
(Eq. 5)

Reduction of Cupric Ion to form Cuprous Chloride CuCO3(s) + 2 H+(aq) + 4 Cl-(aq) CuCl42-(aq) + Cu(s) + 4 Cl-(aq) CuCl43-(aq) CuCl42-(aq) + CO2(g) + H2O
(Eq. 6)

2 CuCl43-(aq) CuCl(s) + 3 Cl-(aq)

(Eq. 7) (Eq. 8)

Now to why I began our discussion with a reproduction of Dali's Medusa. As the story goes, Dali was walking along the beach outside his home and discovered a dead octopus. He retrieved this, dipped it in Acid, and laid it out on a Copper plate. This produced an etching in the copper, providing an image for the hair of Medusa. The remainder of the plate was prepared using a technique called drypoint, in which a steel or diamond tipped needle is used to sketch an image onto the copper plate. The resulting plate is then inked and used to generate prints. Copper etchings such as this typically use Nitric Acid: Cu(s) + 4 HNO3(aq) Cu(NO3)2(aq) + 2 NO2(g) + 2 H2O
(Eq. 9)

Page |4 or Dutch Mordant, an aqueous solution of Hydrochloric Acid and Potassium Chlorate which generates chlorine gas, to oxidize the copper and bite into the metal where the ink will reside.

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Pre-lab Questions
1, If 1g of Cu is used in our synthesis, how many moles of Nitric Acid are required? (See Step 1 of the procedure.) How many moles Nitric Acid are contained in 5 mL of 15M Nitric Acid? How many moles Sodium Carbonate are contained in 5g. How is most of this being consumed during Step 5 of the procedure? Write an explicit chemical equation to account for this. Ksp = 1.9 x 10-7 for CuCl at 25oC. What is the Molar Solubility, S, for this compound in Water? Convert this to a solubility with units of grams/100mL solution. How many grams of CuCl will dissolve in 40mL of solution? How will this be affected by the presence of excess Chloride Ion, Cl-?

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Procedure
1. Obtain a 1 gram of sample of Copper metal. Weigh the sample on the analytical balance to 0.001g. In a fume hood, put the metal in a 150mL beaker and add 5mL of 15M HNO3 (Nitric Acid). Caution: Caustic brown NO2 gas will be evolved. The Merck Index reports, "One of the most insidious gases." and "Deadly poison!" A blue solution of Cupric Nitrate Cu(NO3)2 will be produced. If necessary, you may gently warm the solution . The following chemical reaction is taking place: Cu(s) + 4 HNO3(aq) 3. Cu(NO3)2(aq) + 2 NO2(g) + 2 H2O

2.

When all the copper is dissolved, add 50mL of Water and allow the solution to cool. Be sure that no more fumes of NO2 are present before you proceed to the next step. Weigh out 5g of Sodium Carbonate, Na2CO3. Add small amounts of the Sodium Carbonate to the solution, adding the solid as necessary when the evolution of CO2 subsides. Stir the solution well after each addition. When the acid is neutralized, a bluegreen precipitate of CuCO3 will begin to form. At that point, add the rest of the Na2CO3, stirring the mixture well to ensure complete precipitation of the copper carbonate. The following chemical reaction is taking place: Cu2+(aq) + CO32-(aq) CuCO3(s)

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Filter the precipitate using a Buchner Funnel. Use your rubber policeman and a spray from your wash bottle to make a complete transfer of the solid. Wash the solid well with distilled water. Transfer the solid to a 150mL beaker. Add 10mL of Water. Then, slowly, add 30mL of 6M HCl (Hydrochloric Acid), stirring continuously. The following chemical reaction is taking place: CuCO3(s) + 2 H+(aq) + 4 Cl-(aq) CuCl42-(aq) + CO2(g) + H2O

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When all the solid has dissolved, add 1.5g of Copper turnings and cover the beaker with a watch glass. Place on a hot plate in the fume hood. Heat the mixture to the boiling point and keep it at that temperature, just simmering for ~30 minutes. It may be that the dark-colored solution that forms will clear to a yellow color before that time is up, and if it does, you may stop heating and proceed with the next step. The following chemical reactions are taking place: CuCl42-(aq) + Cu(s) + 4 Cl-(aq) CuCl43-(aq) CuCl(s) + 3 Cl-(aq) 2 CuCl43-(aq)

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While the mixture is heating, put 150mL distilled water in a 400mL beaker and put the beaker in an ice-bath. Cover the beaker with a watch glass. After you are done heating the Cu-CuCl2 mixture, carefully decant the hot liquid into the beaker of chilled water, taking care not to transfer any of the excess Cu metal to the beaker. White crystals of CuCl should form. Continue to cool the beaker in the ice bath to promote crystallization and to increase the yield of solid. Cool 25mL distilled water, to which you have added five drops of 6M HCl, in an ice bath. Put 20mL Acetone into a small beaker. Filter the crystals of CuCl in a Buchner Filter. Swirl the beaker to aid in transferring the solid to the funnel. Just as the last of the liquid is being pulled through, wash the CuCl with 1/3 of the acidified cold water. Rinse the last of the CuCl into the funnel with another portion of the water and use the final 1/3 to rewash the solid. Turn off the suction and add 1/2 of the Acetone to the funnel; wait about 10 seconds and turn on the suction. Repeat this operation with the other half of the Acetone. Draw air through the sample for a few minutes to dry it. If the solid has been properly washed, it will be pure white. If the moist compound is allowed to come into contact with air, it will tend to turn pale green, due to Oxidation of Cu+ to Cu2+. Weigh the CuCl to 0.001g. Place a sample of your product in a 3 dram vial. Label the vial with the following information: Name(s) Name of Compound Formula of Compound Date Weight of Product Samples of the Copper containing ores Malachite and Azurite are available. Observe these samples. Take particular note of the color of these ores. (Azurite was one of only two blue pigments available to medieval artists.)

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Data Analysis
1. 2. 3. Calculate the Theoretical Yield of your Product. Calculate the Percentage Yield of your Product. Identify the points in the Procedure at which loss of Product is likely.

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Post Lab Questions

1. Does (Eq. 1) of the smelting process of the Copper Ore Malachite involve a Reduction of the Copper? Justify your answer by explicit assignment of the Oxidation States of the Copper. What about (Eq. 2). Show that (Eq. 3) of our synthesis involves an Oxidation of the Copper by explicit assignment of the appropriate Oxidation States. CuCl42- is an tetrahedral complex ion of Copper. (See (Eq. 6) of our synthesis.) Sketch a picture of this complex using our wedge-and-dash notation.
(Eq. 7) of our synthesis involves both an Oxidation and a Reduction of Copper. Show this

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by appropriate assignment of Oxidation States. Is this a Disproportionation reaction? Explain. 5. Gold, along with Copper, is one of the Coinage Metals that belong to Group 1B. However, Gold will not dissolve in Nitric Acid. It requires Aqua regia to dissolve Gold. What is Aqua regia and why does it dissolve Gold? Make specific reference to the appropriate chemical equilibria involved. (You will need to consult an appropriate reference in order to answer this question.) Write the electron configurations for the Group 1A (Li, Na, K, Pb, Cs) and 1B (Ag, Au) elements. (The configuration for Cu is provided in the text.)

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