LABORATORY EXPERIMENT

pubs.acs.org/jchemeduc

Synthesis of Copper Pigments, Malachite and Verdigris: Making

Tempera Paint
Sally D. Solomon,* Susan A. Rutkowsky, Megan L. Mahon, and Erica M. Halpern
Department of Chemistry, Drexel University, Philadelphia, Pennsylvania 19104, United States
bS Supporting Information
ABSTRACT: Malachite and verdigris, two copper-based pigments, are
synthesized in this experiment intended for use in a general chemistry
laboratory. The preparation of egg tempera paint from malachite is also
described. All procedures can be done with a magnetic stir plate, standard
glassware present in any first-year laboratory, and household chemicals. Yields
for the synthesis of malachite are about 95% making this an ideal activity for
courses emphasizing green chemistry. Typical results from students enrolled in
a general chemistry course are reported. While introducing the students to the
composition of artists’ paints, performing this experiment provides students an
opportunity to apply concepts in topics such as stoichiometry (excess reactants and yields), solubility, precipitation, and properties
of emulsions. The importance of reading the experiment before coming to the laboratory is emphasized as students must come up
with timesaving strategies to finish both pigment syntheses in the time allotted.
KEYWORDS: First-Year Undergraduate/General, High School/Introductory Chemistry, Laboratory Instruction, Physical
Chemistry, Dyes/Pigments, Green Chemistry, Precipitation/Solubility, Stoichiometry, Synthesis

A ll paints contain pigment, which provides color, and a binder

(or medium), which suspends the pigments and binds them
to the surface of the object to be painted. Two paint pigments,
synthesis, done at room temperature with household materials
and a yield of 95%, is suitable for a laboratory course emphasizing
green chemistry. Although verdigris is also made at ambient
malachite and verdigris, are synthesized in this general chemistry temperature from similar household chemicals, their incorpora-
laboratory experiment and then a tempera paint is made using tion into the final product is reduced because the yields are much
malachite. While introducing the students to the composition of lower (30
50%). Further, the copper acetate product is not as
artists’ paints, performing this experiment exposes students to safe to handle, making this synthesis less “green”.
chemical concepts such as stoichiometry (excess reactants and
yields), solubility, precipitation, and properties of emulsions.
’ BACKGROUND
Copper sulfate is the starting material for the one-step
synthesis of malachite and the three-step synthesis of verdigris. Pigments: Malachite and Verdigris
Both syntheses can be done with a magnetic stir plate, standard Up until the 1800s when synthetic materials became available,
glassware, and chemicals purchased from hardware stores and pigments were made from natural minerals or from corrosion of
supermarkets. The products are dried and weighed to determine metals. Copper-based pigments were used as early as the
percent yields. Malachite pigment is combined with egg yolk Egyptian fourth dynasty in 3000 B.C.E. when artifacts were
binder to make tempera paint. A version of the student write-up shown to contain Egyptian blue (CaCuSi4O10). By this time,
for this experiment can be found in a laboratory manual that malachite was also in use, and by 1300 B.C.E., verdigris was on
contains standard first-year general chemistry experiments, all of the list of pigments available to artists.2
which can be done with household chemicals.1 Greenish malachite, copper(II) carbonate hydroxide, CuCO3Cu-
The experiment was tested by students enrolled in a general (OH)2, occurs with copper ore deposits in many parts of the world.
chemistry course. Knowing they would be required to finish both Malachite is a secondary mineral, created by a chemical reaction with
syntheses in one lab period was a strong motivation for students minerals that have already formed, for instance, by the action of
to read the experiment before coming to class to devise time- water containing carbon dioxide or dissolved carbonate minerals on
saving strategies. Results obtained from the class include time primary copper-containing rocks. Verdigris (“green of Greece”) can be
required to finish both syntheses, yields of both pigments, as well collected by scraping the colored crust from sheets of copper exposed
as the ideas used by students to make best use of their time. to vapors from vinegar, wine, or urine with addition of other sub-
This experiment can also be used to explore green chemistry. stances such as NaCl, ammonium salts, and honey. If a copper
Among the principles to classify a reaction as “green” are the use penny (pre-1982) is placed in vinegar, a green solution of copper
of nonhazardous starting materials, their maximum incorpora-
tion into products, use of ambient temperature for energy
efficiency, and production of nontoxic products. The malachite Published: July 12, 2011

Copyright r 2011 American Chemical Society and

Division of Chemical Education, Inc. 1694 dx.doi.org/10.1021/ed200096e | J. Chem. Educ. 2011, 88, 1694–1697
Journal of Chemical Education LABORATORY EXPERIMENT

Table 1. Chemicals for Synthesis of Pigments

Chemical Formula Molar Mass/(g mol
1) Source CAS No.

Copper(II) sulfate pentahydrate CuSO4 3 5H2O 249.70 root killer 7758-99-8

Sodium carbonate Na2CO3 105.99 Arm & Hammer washing soda 497-19-8
Sodium hydroxide(aq) NaOH 39.99 lye; oven cleaner 1310-73-2
Acetic acid(aq) C2H4O2 60.05 vinegar 64-19-7
Ammonia(aq) NH3 17.03 ammonia cleaner 5
10% 1336-21-6
Malachite: copper(II) carbonate hydroxide CuCO3Cu(OH)2 221.12 synthesis product 12069-69-1
Verdigris: copper(II) acetate monohydrate Cu(CH3COO)2 3 H2O 199.65 synthesis product 6046-93-1

acetate is visible after a few weeks. However, the verdigris produced (i) basic copper(II) sulfate, CuSO4 3 3Cu(OH)2, is formed upon
using methods similar to this can lead to a mixture of chemical addition of ammonia, (ii) followed by conversion to copper
compositions and different colors, particle sizes, and morpholigies.3,4 hydroxide using sodium hydroxide, and (iii) then addition of
The synthetic methods described here for both copper- acetic acid to form the verdigris product.9 Vinegar (5% acetic acid)
containing pigments start with copper sulfate and use readily is substituted for pure glacial acetic acid, which has an over-
available materials and simple techniques. Methods used to whelmingly powerful pungent odor. This makes the isolation of
prepare other pigments, including chrome yellow, PbCrO4,5,6 the somewhat water-soluble copper acetate (7.2 g/100 mL cold
Prussian blue,5,7 thalo blue,5 iron(III) oxide,7 titanium and 20 g/100 mL hot) more difficult, but allows the reaction to be
dioxide,7,8 and charcoal5 have appeared in this Journal. performed on the bench top. As in the synthesis of malachite, a
magnetic stir plate and standard glassware will suffice for all steps.
Binders: Types of Paint
Step i: A precipitate of basic copper sulfate, CuSO4 3 3Cu-
Paints are generally named from the binder used. Oil paint is
(OH)2, is produced upon addition of ammonia solution:
made with linseed oil, egg tempera with egg yolk, and acrylic
paint with acrylic polymers. Watercolor, however, is named for 4CuSO4 3 5H2 OðaqÞ
water, the diluent added to make the paint spreadable, rather þ 6NH 3 ðaqÞ f CuSO4 3 3CuðOHÞ2 ðsÞ
than the binder, which is gum arabic or some other gum or starch. þ 3ðNH 4 Þ2 SO4 ðaqÞ þ 14H2 OðlÞ
Although any pigment can be used with any binder, in some cases
a particular binder may produce superior paint. For example, Household ammonia (5
10% w/v) is added dropwise to a
malachite gives brighter colors with egg tempera than with oil. solution of 4.2 g of CuSO4 3 5H2O (0.017 mol) in 25 mL of
In the second part of this laboratory exercise, the synthetic distilled water with vigorous stirring. As each drop of NH3(aq)
malachite pigment is dried, ground to remove lumps, then touches the liquid surface, the characteristic deep blue of the
mixed with egg yolk/water emulsion to make egg tempera paint. copper ammonium complex, [Cu(NH3)4]2+, is seen for an
A method used to prepare egg tempera paint has been described instant, then disappears. The dropwise addition of ammonia
in a classroom activity on making artist’s paints.7 solution is continued until the blue color of the complex remains
throughout the reaction mixture. This will require 25
35 mL of
’ EXPERIMENTAL DETAILS NH3(aq). After the mixture is stirred for a few minutes, the solid
Sources and CAS numbers for all chemicals involved are listed precipitate of light blue CuSO4 3 3Cu(OH)2 is collected by
in Table 1. gravity filtration and washed once with a small volume,
1
2 mL, of distilled water. The damp precipitate can be used
Synthesis of Malachite for the next step.
Malachite is synthesized according to the reaction Step ii: In the second step, basic copper sulfate is converted to
copper(II) hydroxide by reaction with sodium hydroxide:
2CuSO4 3 5H2 OðaqÞ
þ 2Na2 CO3 ðaqÞ f CuCO3 CuðOHÞ2 ðsÞ CuSO4 3 3CuðOHÞ2 ðsÞ þ 2NaOHðaqÞ f 4CuðOHÞ2 ðsÞ
þ 2Na2 SO4 ðaqÞ þ CO2 ðgÞ þ 9H2 OðlÞ þ ðNaÞ2 SO4 ðaqÞ
The damp precipitate of basic copper sulfate removed from the
in which hydrated copper(II) sulfate reacts with aqueous sodium filter paper is mixed with 40 mL of distilled water in a beaker and
carbonate to produce copper(II) carbonate hydroxide.9,10 In a stirred vigorously while 8.5 mL of 2.0 M sodium hydroxide is
150 mL beaker, 6.2 g (0.025 mol) of CuSO4 3 5H2O is dissolved added all at once. Once the resulting precipitate of bright blue
in 25 mL of distilled water. With vigorous stirring on a magnetic copper hydroxide, Cu(OH)2, is filtered, a paper towel can be
stir plate, a small excess of carbonate solution, 2.9 g (0.027 mol) used to absorb as much excess liquid as possible. The copper
of Na2CO3 in 25 mL distilled water, is added gradually to the hydroxide should be used for the next step as soon as possible,
copper solution accompanied by the evolution of carbon dioxide. because when it is moist it can slowly turn from blue to black
After the reaction mixture is cooled in an ice bath for about 30 min, owing to the formation of black copper(II) oxide, CuO:
the precipitate of insoluble greenish-blue colored malachite is
filtered, dried (about a week), and then stored in a covered vial CuðOHÞ2 ðsÞ f CuOðsÞ þ H2 OðlÞ
until used to prepare paint.
However, the blue hydroxide is more stable when precipitated
Synthesis of Verdigris from a dilute solution of a basic copper salt12 as done in this
Copper(II) acetate monohydrate is synthesized starting with procedure. No students who performed the reaction noticed any
hydrated copper(II) sulfate according to a three-step procedure:11 color change during the 20 min filtration.
1695 dx.doi.org/10.1021/ed200096e |J. Chem. Educ. 2011, 88, 1694–1697
Journal of Chemical Education LABORATORY EXPERIMENT

Table 2. Yields of Synthetic Pigments

Malachite (%) Verdigris (%)

98.0a 74.0a
98.0 66.1
97.9 51.8
97.7 47.3
96.2 46.8
94.0 42.5
Figure 1. Malachite egg tempera paint applied to 6 in.  8 in. clay board. 94.9 36.3
93.5 33.2
Step iii: Finally, the blue copper(II) hydroxide is reacted with 93.5 30.8
40 mL of vinegar (5% acetic acid) to form the copper(II) acetate
93.0 23.5
monohydrate product, verdigris:
92.1 21.8
CuðOHÞ2 ðsÞ a
The values were obtained by an experienced chemist.
þ 2CH 3 COOHðaqÞ f CuðCH 3 COOÞ2 3 H2 OðaqÞ
þ H2 OðlÞ
solutions of sodium hydroxide should be handled with care.
The conversion takes place almost instantly forming a blue-green Although the students wear gloves, it is still recommended that
solution. The reaction is allowed to proceed with stirring for students who are allergic to eggs take special precautions to avoid
about 5 min or until all of the copper hydroxide comes into letting egg touch their skin by allowing their lab partners to
contact with the vinegar and disappears. The solution is evapo- perform steps such as separating the egg, making the egg water
rated to dryness, which takes about a week. After a day or two, emulsion, and mixing the emulsion with pigment.
dark green crystals begin to appear. When crushed, the color of
the crystals is blue-green. From the mass of dry product, the
percent yield is calculated given that acetic acid is the excess ’ CLASS TESTING
reactant. The pigment is stored in a covered vial. Both the synthesis of malachite and verdigris were performed
Making Paint in a single 3-h laboratory period by 20 general chemistry students
Oil paint can be made by mixing linseed oil with pigment, and working in pairs.
egg tempera paint can be made using egg yolk/water emulsion.
For this experiment, the decision to make egg tempera paint and Time
to use malachite as the pigment was made for several reasons. Students had been advised to read the experiment carefully
Making tempera paint is easy to do and, unlike oil paint, can before lab to make best use of their time. They all noted that
readily be cleaned using water. Malachite egg tempera produces working on both experiments at once would minimize idle time
vibrant color. No dust is produced from the minimal grinding during the filtering steps, each of which was expected to require
needed to remove lumps from malachite. Making verdigris into a about 15
20 min to complete. Specific plans included measuring
powder suitable for a pigment is more difficult and its dust is reagents, making solutions, and preparing an ice bath while
harmful upon inhalation (see Hazards). Unlike malachite, verdigris waiting for copper sulfate to dissolve or for a filtering step to
produces better color when mixed with oil binder rather than finish. The first pair of students was done in 1 h and 40 min
egg yolk. followed by three more pairs of students 15 min later. Everyone
The malachite sample is ground using a mortar and pestle or a else finished within 2 h and 15 min.
spatula until the visible lumps are removed, which takes 1
2 min.
A fresh egg yolk is carefully separated from the egg white, then Yield
made as dry as possible by transferring from hand to hand or by Measuring yields was delayed for a week to allow the pigments
using a paper towel. The yolk is poured into a small container. to dry. The yield obtained for the one-step malachite synthesis
The malachite is first made into a paste by adding about 1 mL of was high for all students, averaging 95% (SD 2). An experienced
water for every gram of pigment. To the malachite paste is added chemist was able to obtain a yield of verdigris exceeding 70%;
1
1.5 mL of egg yolk for every milliliter of water that was used to however, student yields for the multistep verdigris synthesis were
make the paste. A spatula or glass rod is used to grind the pigment lower, averaging 40% (SD 14). Values are listed from highest to
paste and yolk together to form paint, which should have the lowest in Table 2. Yields for all three steps of the verdigris
consistency of mayonnaise. Egg tempera paint must be tightly reaction were measured independently in the laboratory, to see
covered until used. Applied paint should dry within 1
2 min and which step or steps caused the yield to be lowered (for a detailed
once dried, should not flake off. A sample of malachite egg description of this study refer to the instructor’s guide in the
tempera paint produced from 5 g of pigment was used to create Supporting Information).
the image in Figure 1.
Paint
’ HAZARDS Rather than devoting a full two weeks for this experiment,
Dilute ammonia and all of the copper compounds are irritating the paint making could be eliminated or could be done in the
to the eyes, respiratory tract, and the skin. Copper(II) acetate first 30 min of a lab period before beginning another scheduled
monohydrate (verdigris) is also harmful by inhalation. Dilute 2 M experiment.
1696 dx.doi.org/10.1021/ed200096e |J. Chem. Educ. 2011, 88, 1694–1697
Journal of Chemical Education LABORATORY EXPERIMENT

’ SUMMARY
Two artists’ pigments, malachite and verdigris, were synthe-
sized in a 3-h general chemistry laboratory class using household
chemicals. The students were able to make use of basic principles
such as stoichiometry, precipitation, and solubility as well as time
management skills.

’ ASSOCIATED CONTENT

bS Supporting Information
Two versions of the lab write-up for students are given, the
step-by step version I as well as an alternative write-up, version II,
similar to those used in organic laboratory manuals; a guide
giving quantities of material needed as well as typical results for
instructors. This material is available via the Internet at http://
pubs.acs.org.

’ AUTHOR INFORMATION
Corresponding Author
*E-mail: [email protected].

’ ACKNOWLEDGMENT
We wish to thank the Drexel University General Chemistry
students who helped to determine the average yields for each
pigment and who made many useful suggestions that improved
the student laboratory write-ups. We also acknowledge Tina
Lewinski for assisting with the photograph.

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1697 dx.doi.org/10.1021/ed200096e |J. Chem. Educ. 2011, 88, 1694–1697