Additional file 1 of Illuminating the problem of blue verditer synthesis in the early modern English period: chemical characterisation and mechanistic understanding
Creators: name: Purdy, Ellen H.
name: Critchley, Sarah
name: Kirkham, Andrea
name: Casford, Michael
Publisher: name: figshare
Year: 2024
Subjects: subject: Biochemistry
subject: Biotechnology
subject: Chemical Sciences not elsewhere classified
subject: Ecology
subject: FOS: Biological sciences
subject: Inorganic Chemistry
subject: FOS: Chemical sciences

description: Additional file1: Figure S1. Raman spectra (532 nm excitation) are presented for modern synthetic green verditer (red) and natural malachite pigment (blue). A reference spectrum for malachite is presented for comparison (black).[1] Table S1. Integrated areas and ratios of integrated areas A(rou.)/A(az.) from PXRD data collected from Rx_Air_4_int after one wash, two washes, and three washes. Table S2. Colorimetry values collected from reaction products. Figure S2. Two representative Raman spectra for samples synthesized at low [Cu2+] (black, red) are shown, with reference malachite (green) and calcite (grey) spectra provided for comparison. Significant peaks corresponding to malachite are marked by a circle (•), while significant calcite peaks are marked by a diamond (•). Figure S3. The PXRD pattern for one sample synthesized at low [Cu2+] is shown (black), with reference malachite (green) and calcite (grey) data provided for comparison. Significant peaks corresponding to malachite are marked by a circle (•), while significant calcite peaks are marked by a diamond (•). This confirms the presence of calcite and malachite and the absence of detectable azurite in low concentration samples. Figure S4. a) SEM image of low concentration product, boxed area is shown at higher magnification in b); c) EDX map of low concentration sample, showing Cu (red) and Ca (green) intensities. Particles of high Ca intensity suggest incomplete reaction of CaCO3. SEM images similarly show varied morphologies, including a fine, feathery structure in b). Figure S5. Representative Raman spectra for Rx_Air_20_S2 are presented, compared to literature spectra. Significant bands of rouaite (*), azurite (+), and malachite (•) are marked. Rouaite forms after the first wash (Unstirred 1, black). After the second wash rouaite (Unstirred 2, red), azurite (Unstirred 3, orange) and malachite (Unstirred 4, gold) are formed. Note that the gold spectrum for Unstirred 4 is a superposition of the azurite and malachite spectra, evident in the peaks around 400-430 cm-1. Figure S6. Rx_Air_20_S2, allowed to react for several days without any disruption or mixing, &lt;12 C. Distinct layers of green and blue are apparent, enclosed by white box. Figure S7. PXRD spectra of product resulting from reaction of Rx_Air_20_S5, CuSO4 starting material (1); reference spectra for devilline (2), posnjakite (3), gypsum (4), calcite (5). Figure S8. a) pH measurements over time recorded for DI H2O (black, red) and continuously stirred CaCO3 (blue, green) at room temperature and when heated. Note that room temperature sample experienced small increase in temperature generated from magnetic stirring action. b) pH measurements over time recorded for three samples of continuously stirred CaCO3 in Cu(NO3)2 solution, at room temperature (red), heated (black), and with increased total sample volume (blue). Elevated temperature does not significantly perturb pH for these samples.