Experiment 6: The Reactions of a Copper Cycle

PURPOSE AND LEARNING OBJECTIVES

During the process of this experiment, you will observe and record the chemical and accompanying physical
changes that occur when metallic copper is carried through a series of chemical reactions that produce a number of
different copper compounds before the copper is restored to its original metallic state. You will become familiar
with basic laboratory procedures employed for product separation and purification and with the concept of percent
recovery. You will balance and classify the different reactions involved in the cycle according to their type. You will
be expected to recognize and write the formula unit, total ionic and net ionic equation for the precipitation and acid-
base reactions in the cycle.

CONCEPTS
You should be familiar with the following concepts prior to the lab:
1) The Law of Conservation of Mass
2) Percent Composition
3) Writing and balancing chemical equations
4) Molarity and solution stoichiometry
5) Precipitation Reactions
6) Acid/Base Reactions

PRINCIPLES
Often it is necessary that chemists perform a series of chemical reactions in order to acquire a product which is
unobtainable from a single chemical reaction step. During these reaction processes, the product of a reaction in one
step is used as a reactant in a subsequent step in the reaction series.

Just as chemists characterize matter based on properties, they also use a system for grouping chemical reactions into
classes. The general classification system used by most chemists is to divide the chemical reactions into types. Each
one of the five reactions of the copper cycle has a reaction that can be classified as one of four types: precipitation
reactions, acid-base reactions, oxidation-reduction and decomposition reactions.

Copper belongs to a group of elements called the transition metals. Like many transition metal elements, copper is
brilliantly colored as a metal and has distinctive colors as copper compounds. During this experiment, you will
produce and observe some colorful aqueous copper (II) complexes and classify each reaction according to its
reaction type. You will begin with a sample of copper metal and will carry it through a cycle of reactions where you
begin and end with solid copper metal. In the final step of your procedure, you will recover, weigh and calculate the
percent recovery of your original sample of copper.

REACTION TYPES
I. Precipitation reactions occur when two compounds dissolved in aqueous solutions react to produce an insoluble
solid. The driving force for these types of reactions is the strong attraction between cations (positive ions) and
anions (negative ions) in the solution. The overall result of this type of reaction is the removal of ions from the
solution by the formation of a precipitate (ppt).

II. Acid-base reactions are commonly expressed as neutralization reactions, a term to that is used to describe the
reaction of an acid with a metal hydroxide base that produces a salt and water. The term is derived from the

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observation that the standard properties of the acids and the bases are neutralized when reacted with each other. The
driving force of nearly all neutralization reactions is the combination of the H+ (aq) from an aqueous acid solution
with the OH− (aq) from an aqueous base solution to form water molecules.

In our experiment today, we will encounter an acid-base reaction that involves a metal oxide. An example would be
calcium oxide reacting with sulfuric acid. During the neutralization reaction, the metal oxide is the base (a basic
anhydride) that will react with sulfuric acid (a strong acid).

Formula unit equation:

CaO (s) + H2SO4 (aq) → CaSO4 (aq) + H2O (l)

Complete ionic: (The calcium oxide is a solid and cannot be dissociated into its ions in the total ionic equation.)

CaO(s) + 2H+(aq) + SO42– (aq) → Ca2+(aq) + SO42–(aq) + H2O (l)

Net ionic:

CaO(s) + 2H+(aq) → Ca2+(aq) + H2O (l)

III. Oxidation-Reduction (Redox) reactions occur through a process of electron transfer from the element of one
reactant to the element of another reactant. That is, one of the elements in a reactant will lose one or more electrons
to an element in another reactant. This exchange of electrons between reactants results in products, which contain
elements with new oxidation states.

Oxidation States (oxidation number) is the name given to the charge on an ion or element in a covalent bond. To
assign oxidation numbers to elements in compounds, there are a few simple rules:

a. The oxidation number of any free, uncombined element is zero. The oxidation number (or charge on each atom)
is written above the atom
0 0 0 0 0

Na (s), Mg (s), Cu (s), Fe (s) and Zn (s)

b. All naturally occurring diatomic molecules have zero oxidation states.

0 0 0 0 0 0 0

Br2 I2 N2 Cl2 H2 O2 F2

Nonmetals, in their natural state, have zero oxidation states. This makes sense—no dipoles (differences in
Electronegativity) exist between the shared electrons in either the diatomic or the natural state molecules. Below are
the examples of two elements that do not exist naturally in an uncombined state.
0 0

E.g., P4 (s) and S8 (s)

c. For simple Group A binary ionic compounds (salts), the oxidation state is the charge of the element:
i. Metals (Group I A, IIA, and IIIA) are assigned a positive oxidation state – determined by the number
of electrons the element has lost.

Group IA metals
+1 (Li+, Na+, K+, Rb+, Cs+)

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Group IIA metals
+2 (Mg2+, Ca2+, Sr2+, Ba2+)

Group IIIA metals
+3 (Al3+, Ga3+, In3+)

ii. Nonmetals (Group VA, VIA, VIIA) are assigned a negative oxidation state determined by the number
of electrons the element has gained.

Group V nonmetals
– 3 (N3–, P3–, As3–, Sb3–, Bi3–)

Group VI nonmetals
–2 (O2–, S2–, Se2–, Te2–)

Group VII nonmetals
–1 (F–, Cl–, Br–, I–)

Use the periodic table to help with assigning oxidation numbers to elements. There are a few rare exceptions.

d. VA elements have oxidation numbers of –3 in binary compounds with H, metals or NH4+.

e. VIA elements below O have oxidation numbers of –2 in binary compounds with H, metals or NH4+.
f. VIIA elements have oxidation numbers of –1 in binary compounds with H, metals or NH4+.
g. In the formula for any compound, the sum of the oxidation numbers of all elements in the compound is zero.

Na2SO4 = zero charge on formula unit

h. In a polyatomic ion, the sum of the oxidation numbers of the constituent elements is equal to the charge on the
ion.
SO42- = -2 on the polyatomic ion.

i. For simple binary ionic compounds that are comprised of transition metals (with more than one possible
oxidation state), the oxidation state of the metal is determined by balancing the charge:

For our purpose, almost all transition metals in salts (except zinc and silver) have oxidation states that are
determined by the balancing the charge of the anion.

e.g. FeO vs. Fe2O3

FeO
Since the oxidation state of oxygen is −2 in the compound, the iron atom must have a charge of + 2 to
give the formula unit an overall net charge of zero.

x + (-2) = 0
x = +2

Fe2O3
Since the oxidation state of oxygen is −2 in the compound and there are three oxygen atoms, the iron
must have a charge of +3 to give the formula unit an overall net charge of zero.

2x + 3(-2) = 0
x = +3

Zinc always has an oxidation state of +2 when combined in a simple salt.

ZnCl2, ZnS, ZnSO4, Zn3(PO4)2

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Silver always has an oxidation state of +1 when combined in a simple salt.

AgCl, Ag2O, Ag2SO4, Ag3PO4

j. Fluorine has an oxidation number of –1 in its compounds.

k. Hydrogen, H, has an oxidation number of +1 unless it is combined with metals, where it has the oxidation
number -1. Examples
LiH, BaH2
l. Oxygen usually has the oxidation number –2.
Exceptions:
• In peroxides O has oxidation number of –1. Examples
H2O2, CaO2, Na2O2
• In OF2, O has oxidation number of +2. (Fluorine is the most electronegative element and has the greater
share of electrons.)

Examples: Assign oxidation numbers to each element in the following compounds:

NaNO3 K2Sn(OH)6

Na = +1 K = +1
O = –2 O = −2
N=x H = +1
Sn = x
+1 + 3(−2) + x = 0
x = +5 2(+1) + 6(−2) + 6(+1) + x = 0
x = +4
N = +5 Sn = +4

H3PO4 HCO3–

H = +1 O = −2
O = −2 H = +1
P=x C=x

3(+1) + 4(–2) + x = 0 +1 + 3(−2) + x = −1

x=+5 x = +4

P = +5 C = +4

Reactions that involve the transfer of electrons from one reactant to another reactant, regardless of the substances
involve, are collectively called oxidation-reduction reactions (redox). The reactants in these reactions will lose or
gain electrons and change their charge (oxidation number) as they form the products.
• Oxidation is the process in which a substance in a chemical reaction loses electrons.
• Reduction is the process in which a substance in a chemical reaction gains electrons.

A mnemonic that may help you remember what is oxidized and reduced is OIL RIG.
OIL
oxidation is loss of electrons
RIG
reduction is gain of electrons

Chemists often refer to these elements or compounds that are oxidized and reduced in another manner:
1) Oxidizing agents are those elements that cause loss of electrons (cause oxidation) – oxidizing agents are
reduced by gaining electrons.

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2) Reducing agents are those elements that give up electrons (cause reduction) – reducing agents are oxidized
by giving up electrons.

To determine the reactants which are undergoing oxidation and reduction as well as the oxidizing agent and
reducing agent, we will divide the redox reaction into two half reactions. One-half of the reaction represents the
oxidation reaction and the other half represents the reduction reaction. To establish which substance is oxidized and
which is reduced, we must determine the original and final oxidation states of each substance in the chemical
equation.

Example 1: Sodium metal reacts with chlorine gas to produce solid sodium chloride salt.

1) Write the balanced reaction and determine the oxidation state of each atom in the reactants and
products. Note: the oxidation number is written above the atom and only represents the oxidation state
of a single atom, not the total number of atoms in the element or compound.

0 0 +1 −1

2Na (s) + Cl2 (g)  2NaCl (s)

2) Divide the reaction of the reactants into two balanced half-reactions:

0

Oxidation: 2 Na → 2Na+ + 2e− reducing agent

0

Reduction: Cl2 + 2e− → 2Cl− oxidizing agent

3) Since we cannot either create or destroy electrons, the numbers of electrons transferred in the reaction
must be the same on both sides of the chemical equation.

Example 2: Iron metal reacts with oxygen gas to produce solid iron(III) oxide.
0 0 +3 −2

4Fe (s) + 3O2 (g)  2Fe2O3 (s)

Oxidation: 4Fe → 4Fe3+ + 12 e− reducing agent

0

Reduction: 3 O2 + 12 e− → 6 O2– oxidizing agent

Example 3: Aqueous sodium bromide reacts with liquid chlorine to produce aqueous sodium chloride and
liquid bromine.

+ − 0 + − 0

2 NaBr (aq) + Cl2 (l) → 2 NaCl (aq) + Br2(l)

We can remove the spectator ion (Na+) before we set up the half-reactions.
0

Oxidation: 2Br − → Br2 + 2e− reducing agent

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Reduction: Cl2 + 2e− → 2Cl− oxidizing agent

Example 4: An example of a solid metal reacting with the oxidizing acid, nitric acid:

Zn (s) + 2 HNO3 (aq) → Zn(NO3)2 (aq) + NO2 (g) + H2O (l)

The steps involved in solving redox reactions are as follows:

a. Assign oxidation numbers to each element in the reactants and products.

0 +1 +5 -2 +2 +5-2 +4 -2 +1 -2

Zn (s) + 2 HNO3 (aq) → Zn(NO3)2 (aq) + NO2 (g) + H2O (l)

b. Separate the reactions into two half-reactions; oxidation and reduction.

Half reactions:
0 +2

Zn → Zn(NO3)2 + 2e− (oxidation; reducing agent)

+5 +4
−
HNO3 + 1e → NO2 (reduction; oxidizing agent)

c. Balance the half-reactions, oxygen and hydrogen.

2 NO3− + Zn → Zn(NO3)2 + 2e−

d. To balance the oxygen, add one H2O for the every oxygen needed, and then add H+ to the other side to
balance the hydrogen. (This rule applies to all redox reactions that occur in acidic solution).

H+ + HNO3 + 1e− → NO2 + H2O

e. Before you sum the two balanced half-reactions, balance the charge.

2 (H+ + HNO3 + 1e− → NO2 + H2O)

2H+ + 2HNO3 + 2e− → 2NO2 + 2H2O

f. Finally, sum the two half-reactions into one balanced equation.

2NO3− + Zn → Zn(NO3)2 + 2e−

+
2H + 2HNO3 + 2e− → 2NO2 + 2H2O

4HNO3(aq) + Zn(s) → Zn(NO3)2(aq) + 2NO2 (g) + 2H2O (l)

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Example 5: Active metal oxidation-reduction. The more active metal, Al, displaces the ions of the less active metal,
Zn, from aqueous solution.

+2 0 +3 0

ZnSO4(aq) + Al(s) → Al2(SO4)3(aq) + Zn(s)

Remove the spectator ions and balance the reactants that undergo redox. The spectator ions will be added back when
the half-reactions are summed.

3 (Zn+2 + 2e− → Zn0)

2(Al0 → Al+3 + 3e−)

3Zn+2 + 6e− → 3 Zn0) (reduction; oxidizing agent)

0 +3 −
2Al → 2Al + 6e (oxidation; reducing agent)
0
3 ZnSO4(aq) + 2Al (s) → Al2(SO4)3(aq) + 3Zn(s)

IV. Decomposition reactions are those in which a compound is broken down into simpler substances. The
electrolysis of water is an example of decomposition. However, heating is the predominate method of the
decomposition of a compound.

2 H 2 O (l) electrolys
 is
→ 2 H 2 ( g ) + O2 ( g )
2 KClO3 ( s) heat
→
 2 KCl ( s) + 3 O2 ( g )

PERCENT RECOVERY
In order to determine how much of the original pure copper mass is recovered at the end of the experimental
process, it is necessary to calculate the percent recovery. This is a simple calculation that requires the weight of the
original copper used in the experiment and the weight of the final copper that is recovered at the end of the
experiment. The percent recovery represents the recovery of copper only. Any contaminants, such as water, will
cause the percent recovery to be too high and any loss of copper during the experimental procedure will cause the
percent recovery of the copper to be too low.

final weight
% Cu recovery = × 100%
original weight

LAB MATERIALS
Chemicals: 18-gauge copper wire; concentrated (16M) HNO3; 3.0 M NaOH; 6M H2SO4; 1 inch squares of
aluminum foil; 6M HCl, rubber gloves in small, medium and large.

SAFETY
Safety goggles must be worn at all times in the laboratory. Sulfuric acid is corrosive and generates much heat on
exposure to water. Concentrated nitric acid, 6 M hydrochloric acid, and 6 M NaOH are all corrosive to flesh and can
cause severe burns or blindness. In the event of skin contact, flush the affected area with copious quantities of cold
water. THE REACTION OF Cu WITH NITRIC ACID PRODUCES NO2 GAS, WHICH IS EXTREMELY
POISONOUS; CARRY OUT THIS REACTION UNDER THE FUME HOOD.

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Be careful not to discard any of the copper-containing materials during the course of the experiment. Be sure to
record all observations during each step in the series of reactions. Your observations should include the state of the
reactants and products (solid, liquid, gas, or aqueous solution), any obvious loss of reactant or product and any
changes that occur during the reactions, i.e. color, odor, precipitation (solid forms), description of the precipitate
(flakes, suspension, gel, etc.), solid dissolution (solid disappears), gas evolution (bubbles) that occurs, solutions
become cloudy or clear or a temperature change occurs. Figure 1 represents an overview of the procedures.

Cu  HNO
(1)

3
→ Cu(NO 3 ) 2  NaOH
(2)
→ Cu(OH) 2

↑ ↓
←  CuSO 4 ←  CuO ← 
Al, HCl
(5)
H 2 SO 4
(4)
heat
(3)

FIGURE 1: The Five Reactions of the Copper Cycle

Materials
Pre-cut 18-gauge copper wire 16.0 M nitric acid
2.54 cm aluminum squares 3.0 M sodium hydroxide
250 mL beaker 6.0 M sulfuric acid
10 mL graduated cylinder 6.0 M hydrochloric acid
50 mL graduated cylinder 94% ethanol
funnel Evaporating dish
Kim wipes Glass stirring rod
Utility clamp (for gas trap) Hot plate
Iron ring (for gas trap) Nitrile gloves (s, m, lg)
Rubber hose (for gas trap)

PROCEDURE: Note: Observations are a critical component of this experiment. Please leave plenty of space for
observations. It is important that any loss of copper in any of the following procedural steps in recorded in your lab
notebook.

Reaction I. Cu(s) + ? → Cu(NO3)2 (aq) + NO2 (g)

Step 1. Weigh between 0.40 - 0.60 g of pre-cut copper wire to the nearest 0.001g and place it in a clean dry 250
mL beaker. (Pre-cut 18-gauge copper wire to 10-cm lengths- should be between 0.4 and 0.6 g).

Step 2. You will use rubber gloves for the next step. Please DO NOT LEAVE the lab with your gloves on.
Before you leave the lab, you must remove your gloves to prevent the spread of contamination.

Step 3. Under the fume hood carefully add 4.0 to 5.0 mL of 16.0 M (CAUTION!) HNO3. (The reaction
produces toxic and noxious fumes of NO2.) Swirl the contents in the beaker until the copper is
completely dissolved. Once the copper appears to have dissolved, remove it from the hood and add
distilled water to bring the total volume to about 150mL (roughly half full). Record your observations.

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Reaction II. Cu(NO3)2 (aq) + ? → Cu(OH)2 (s) + NaNO3 (aq)

Step 4. Add 30.0 mL of 3.0M NaOH slowly while stirring with a glass rod. (Use the same glass stir rod
throughout the experiment and do not remove from beaker, this will prevent material loss.) Record your
observations.

Reaction III. Cu(OH)2 (s) + ? → CuO (s) + H2O (g) (Once this step is complete, you may not restart the
experiment—in other words, this is the point of no return.)

Step 5. Gently heat the solution on a hot plate, stirring frequently to prevent bumping. Do not boil the solution;
a gentle warming is all that is necessary. The reaction takes 20-25 minutes to reach completion. The
change is complete when the solid is uniform in color and the solution is colorless (or very close to
colorless). Record your observations.

Step 6. Remove the beaker from the hot plate and allow the CuO to settle. Decant (pour off) the supernatant
solution (liquid on top). The solution should be disposed of in a waste beaker (250mL beaker). Be
careful not to lose any of the solid CuO that is formed.

Step 7. Heat to just below boiling approximately 200.0 mL of deionized water on the hot plate.

Step 8. When the water is hot, turn off the hot plate and pour the hot water into the beaker with the solid
CuO. Stir briskly, allow the CuO to settle and decant the supernatant as before. Avoid losing any of the
solid. This is a washing step which will remove any unreacted NaOH solution. Record your
observations.

Reaction IV. CuO (s) + ? → CuSO4 (aq) + H2O (l)

Step 9. Add 15mL of 6.0 M H2SO4 (CAUTION!) slowly while stirring. Record your observations.

Reaction V. CuSO4 (aq) + ? → Cu (s)

Step 10. Add several 2.54 cm (1 inch) squares of aluminum foil and a several drops of 6.0 M HCl. Start with 2
aluminum squares and if necessary, add more aluminum squares until the solution is colorless. A
colorless solution indicates that all the copper ions have been removed from the solution. If the Al does
not completely dissolve, add a little more HCl.

Step 11. Prepare a steam bath. Heat 50.0 mL of water in a 100 mL beaker on a hot plate until the water boils.
Continue to step 12 while the water is heating.

Step 12. Transfer the solid copper to a pre-weighed porcelain evaporating dish. Rinse the inside of the beaker
with approximately 5.0 ml of deionized water from a water bottle and pour into the evaporating dish.
Decant the water in the evaporating dish. (Be careful not to lose any of the solid copper.) Repeat the
process until all the copper has been removed from the beaker.

Step 13. Wash the copper in the evaporating dish with two 5.0 mL portions of distilled water, decanting the wash
water between each washing.

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CH204 Experiment 6: The Cycle of Copper Reactions spring 2015

Step 14. Wash the precipitate with three 5.0 mL portions of 95% ethanol, decanting the liquid after each
individual wash. This help to hasten the drying process. Dispose of the ethanol in the “liquid waste”
container.

Step 15. Place the evaporating dish on the steam bath and heat the copper until it is completely dry (for at least 5
minutes). Note: Overheating copper during the drying process could cause the oxidation of copper with
atmospheric oxygen; therefore, a steam bath is used to prevent the overheating and oxidation of the
copper product.

Step 16. Wipe the bottom of the evaporating dish plus copper; cool it to room temperature and weigh. Be sure to
record all observations.

NOTE: If aluminum particles or salts are not completely removed during the washing steps in the procedure, the
percent mass will be too high. If the copper product is not completely dry before it is weighed or the copper is
obviously tarnished, the percent mass will be too high. The percent mass is determined by the mass of only pure
copper recovered.

Table 1. (When transcribing this table into your lab manual, be sure to leave plenty of space for observations.)
Observations During Chemical Reacations

Reactions Observations

I. Cu(s) → Cu(NO)3 (aq)

II. Cu(NO3)2 (aq) → Cu(OH)2 (s)

III. Cu(OH)2 (s) → CuO (s)

IV. CuO (s) → CuSO4 (aq)

V. CuSO4 (aq) → Cu (s)

Table 2.
Determination of Original and Experimental Mass of Copper

Weight of copper initial (g)

Weight of copper and evaporation dish (g)

Weight of evaporation dish (g)

Weight of copper final (g)

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DATA ANALYSIS

1. Record the percent recovery of your copper (show your calculation).

2. For each step of the cycle, classify and write a balanced chemical equation for the reaction.
a. If the reaction is an oxidation-reduction reaction:
i. Write the half-reactions and label each react ion as either oxidation; reducing agent or
reduction; oxidizing agent.
ii. Balance each half-reaction.
iii. Balance the half-reactions by balancing the electrons.
iv. Sum the half-reactions to obtain a balanced chemical equation for the reaction.

b. If the reaction is a precipitation or acid/base reaction, write the formula unit equation, the total ionic
and net ionic equations.

c. If the reaction is decomposition reaction, write a balanced chemical equation.

DISCUSSION (Attach written discussion to end of lab report.)

1. What was the objective of this experiment?
2. Describe each reaction that occurred in the reaction cycle. What were some of the obvious chemical
changes and the physical properties that changed as a result of the chemical reactions?
3. Were the reactions exothermic or endothermic? How do you know?
4. Why was it necessary to complete the first reaction in the fume hood?
5. In the final reaction you washed your recovered copper with water, what were you removing?
6. Why is ethanol used to wash your recovered copper?
7. Why did you use a steam bath instead of the hot plate to dry your recovered copper?
8. What is the Law of the Conservation of Mass and did your results support the law? What does percent
recovery of copper mean? What were your results? Were your results too high or too low? If so, describe
what happened to your recovered copper.
9. What does your product look like? What might have caused the change of appearance?

Be sure to upload a copy of your discussion into SafeAssign before your next lab period.

References:
Zumdahl, S. S. Chemical Principles, 5th Edition, Houghton Miffin Company, 2005, pp. 16, 97-129, 931, 934 & 942.
Atkins, P.W.; Jones, L. L. Chemical Principles: The Quest for Insight, 3rd Edition, W. H. Freeman and Company,
2005, pp. F58, F63-F78, 616-618.

Condike, G. F., “Near 100% Yields With the ‘Cycle of Copper Reactions’ Experiment,” J. Chem. Educ., 1975, v52,
p 615.

Todd, D.; Hobey, W. D. “An Improvement in the Classical Copper Cycle Experiment, “J. Chem. Educ., 1985, v62,
p 177.

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