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Verdigris

Copper acetates

Science and Art Initiative supported by
the cogito foundation

Pigments sorted by:     Colour   |   Type   |  First date of use   |  Elements  | |  Timelines

painted swatch

crystals

Raphael, Saint John Preaching, ca 1505

Verdigris is not a unique chemical substance but is a collective name for various copper acetates. Their color varies from blue to green.

It reacts with binding media such as oils and resins and forms transparent oleates or resinates. This property has been utilized for preparing transparent green glazes called copper resinates by dissolving verdigris in warm turpentine resin mixed with mastic and wax.

Neutral verdigris is neutral copper acetate with the formula Cu(CH3COO)2·H2O. It can be prepared by solving basic verdigris in acetic acid.

Basic verdigris can contain several forms of copper acetates such as [Cu(CH3COO)2]2·Cu(OH)2·5 H2O or Cu(CH3COO)2·Cu(OH)2·5 H2O which are both blue. The following copper acetate shows green color: Cu(CH3COO)2·[Cu(OH)2]3·2 H2O.

German: Grünspan  |  French: vert-de-gris  |  Italian:verderame  |  Spanish: cardenillo, verdete

Colour Index: Pigment green 20 (PG 20), 77408

Verdigris
Image courtesy of Technisches Museum Wien

References

(1) H. Kühn, Verdigris and Copper Resinate, in Artists’ Pigments. A Handbook of Their History and Characteristics, Vol. 2: A. Roy (Ed.) Oxford University Press 1993, p. 131 – 158. Available as pdf from the National Gallery of Art. Buy this book at Amazon US, Amazon UK, Amazon DE.

(2) Schweizer, F. und Mühletaler, B. Einige Grüne und Blaue Kupferpigmente, Farbe und Lack, 74 1968, p. 1159-73

(3) Kühn, H., Grünspan und seine Verwendung in der Malerei, Farbe und Lack, 70, 1964, p. 703-711.

Chemical stability:

Verdigris, in general, is not very stable and decomposes on heating, they are soluble in dilute acids and react with alkalis forming copper hydroxide.

Stability to light:

Verdigris painting materials change their color from blue-green to green with time for approximately one month. Verdigris had also a bad reputation for insufficient lightfastness but newer experiments do not confirm this fact.

Compatibility with other pigments: Verdigris darkens when mixed with sulfur containing pigments such as ultramarine or orpiment.

References

(1) H. Kühn, Verdigris and Copper Resinate, in Artists’ Pigments. A Handbook of Their History and Characteristics, Vol. 2: A. Roy (Ed.) Oxford University Press 1993, p. 131 – 158. Available as pdf from the National Gallery of Art. Buy this book atAmazon US, Amazon UK, Amazon DE.

Basic verdigris can be prepared by bringing copper in contact with acetic acid vapor, water vapor and air. Neutral pigment is formed by solving basic verdigris in acetic acid. It also occurrs naturally as the rare mineral hoganite.

Historic Chemistry: Verdigris

AlchemicalGarden’s channel

References

(1) Sally D. Solomon, Susan A. Rutkowsky, Megan L. Mahon, and Erica M. Halpern, Synthesis of Copper Pigments, Malachite and Verdigris: Making Tempera Paint, J. Chem. Educ., 2011, 88 (12), pp 1694–1697, DOI: 10.1021/ed200096e

Microphotography

(image © Volker Emrath)

Spectroscopy

Fiber optics reflectance spectra (FORS)

 Spectra by A. Cosentino, Cultural Heritage Science Open Source (CHSOS)

IR Spectroscopy

1. IR-Spectrum in the ATR-FT-IR spectra of different pure inorganic pigments, University of Tartu, Estonia

2. Spectrum of verdigris in linseed oil by S. Vahur, Database of ATR-IR spectra of materials related to paints and coatings, University of Tartu, Estonia

Raman Spectroscopy

Spectrum by Ian M. Bell, Robin J.H. Clark and Peter J. Gibbs, Raman Spectroscopic Library
University College of London

X-Ray Fluorescence Spectroscopy (XRF)

XRF Spectrum in the Free XRF Spectroscopy Database of Pigments Checker, CHSOS website.

Verdigris has been in use since prehistoric times until the present day. It was employed for green tones in landscape or interior paintings as it was the most intense green pigment at the time of the renaissance. With the arrival of the modern green pigments such as emerald green and viridian the use of verdigris ceased. The following graph gives the frequency of its use in the paintings of the Schack Collection in the Bavarian State Art Collections in Munich (1).

Examples of use

Raphael, ‘Saint John the Baptist Preaching‘, ca 1505

References

(1) Kühn, H., Die Pigmente in den Gemälden der Schack-Galerie, in: Bayerische Staatsgemäldesammlungen (Ed.) Schack-Galerie (Gemäldekataloge Bd. II), München 1969.

(1) H. Kühn, Verdigris and Copper Resinate, in Artists’ Pigments. A Handbook of Their History and Characteristics, Vol. 2: A. Roy (Ed.) Oxford University Press 1993, p. 131 – 158. Available as pdf from the National Gallery of Art. Buy this book at Amazon US, Amazon UK, Amazon DE.

(2) Schweizer, F. und Mühletaler, B. Einige Grüne und Blaue Kupferpigmente, Farbe und Lack, 74 1968, p. 1159-73.

(3) Kühn, H., Grünspan und seine Verwendung in der Malerei, Farbe und Lack, 70, 1964, p. 703-711.

(4) Renate Woudhuysen-Keller, Aspects of Painting Technique in the Use of Verdigris and Copper Resinate, in Historical Painting Techniques, Materials, and Studio Practice, Symposium of Getty Conservation Institute at the University of Layden, 1995, pp. 65 – 69. Available as pdf.

Examples of use

Titian, Death of Actaeon

Titian, Diana and Actaeon

Titian, Diana and Callisto

Hieronymus Bosch, The Crowning with Thorns

Hieronymus Bosch, The Haywain Triptych

Rogier van der Weyden, The Magdalen Reading

Van Dyck, The Balbi Children

Titian, The Holy Family with a Shepherd

Titian, Noli me tangere

Bellini, Pesaro Altarpiece

Michelangelo, Doni Tondo

Bruegel, Mad Meg

Raphael, Mond Crucifixion

Raphael, Ansidei Madonna

Raphael, Saint John Preaching

Raphael, Madonna of the Pinks

Raphael, An Allegory

El Greco, Disrobing of Christ

Titian, Venus and Adonis

Tintoretto, Portrait of Vincenzo Morosini

Tintoretto, St George and the Dragon

Bellini, Feast of the Gods

Cima, The Incredulity of Saint Thomas

Titian, The Aldobrandini Madonna

Titian, Bacchus and Ariadne

Green pigments

Cobalt titanate green

Verdigris

Green earth

Malachite

Viridian

Emerald green

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