molecules
Article Water-Based Aerosol for Book Deacidification: Experimental Apparatus and Theoretical Interpretation of Results
Giuseppe Chidichimo, Alessandra Crispini, Antonio Tursi *, Maria Rita Basile, Ilaria Lania, Giovanni De Filpo , Cesare Oliviero Rossi and Francesca Scarpelli
Department of Chemistry and Chemical Technologies, University of Calabria, 87036 Rende, Italy; [email protected] (G.C.); [email protected] (A.C.); [email protected] (M.R.B.); [email protected] (I.L.); giovanni.defi[email protected] (G.D.F.); [email protected] (C.O.R.); [email protected] (F.S.) * Correspondence: [email protected]; Tel.: +39-098-449-3501
Abstract: One of the major problems in book conservation is the long-term deconstructive effect of acidity introduced into the paper by several additives, which, in the presence of humidity, generates a hydrogen cation with a strong catalytic role in cellulose depolymerization. Many types of treatment have been used in the past, but up to now, research for less-invasive, fast and cheap methods is still vividly ongoing. In this study, an approach to book deacidification is presented, where alkaline water solutions are administered to bound books in the form of micrometer-sized aerosol droplets, without using vacuum apparatus accessories. Alkaline clouds treatments were alternated with gentle air fluxes of drying steps. Few cycles are required to achieve uniform deacidification of books. The treatment could be conducted with proper apparatus on large volumes, resulting in rapid Citation: Chidichimo, G.; Crispini, treatment time and low cost. The titration curve reporting the variation of book pH, with respect A.; Tursi, A.; Basile, M.R.; Lania, I.; De to the amount of absorbed alkaline aerosol, was built and interpreted in terms of a chemical model Filpo, G.; Rossi, C.O.; Scarpelli, F. Water-Based Aerosol for Book for the neutralization process. FTIR, PXRD and XRF spectroscopies were used to characterize the Deacidification: Experimental book chemistry. The effects of the treatment on the book were evaluated by measuring the degree of Apparatus and Theoretical polymerization (DP) of the paper and the colorimetric coordinates of the paper and ink. Artificial Interpretation of Results. Molecules aging tests revealed a general increase in the aging stability of the deacidified paper samples with 2021, 26, 4249. https://doi.org/ respect to the untreated samples. Finally, the alkaline reserve data are discussed. 10.3390/molecules26144249 Keywords: paper deacidification; pH; X-ray fluorescence; FTIR spectroscopy; PXRD; alkaline reserve Academic Editor: Maria Luisa Saladino
Received: 16 May 2021 1. Introduction Accepted: 9 July 2021 Published: 13 July 2021 The mass deacidification of paper works and library archives is currently a problem of considerable importance. Every year, tens of tons of books are treated in order to facilitate
Publisher’s Note: MDPI stays neutral their conservation and usability and improve the appearance of the paper [1,2]. with regard to jurisdictional claims in Millions of tons of acid paper have been produced over the past two centuries, and published maps and institutional affil- acid paper is still mainly produced in Asia. It is estimated that 30% of Indian publications iations. and about 5–10% of paper in Europe and the United States require deacidification processes. Several studies have evaluated the consequences of the hydrolysis and oxidation processes of hundreds of millions of bound and unbound paper documents in different collections around the world [2,3]. Cunha (1987) [4] estimated that a typical library loses about 5% of the value of books each year, while Smith (1987) [5] calculated that the Library of Congress Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland. has losses of around USD 200,000 each day due to hydrolysis processes occurring during This article is an open access article book storage. distributed under the terms and The raw material usually used for the production of paper is cellulose, the most abun- conditions of the Creative Commons dant organic polymer in nature, formed by glucose monomers organized in chains and Attribution (CC BY) license (https:// linked together by hydrogen bonds [6,7]. Several past paper production techniques (espe- creativecommons.org/licenses/by/ cially those from the 19th century with the addition of alum rosin sizing and industrial paper 4.0/). production from wood) introduced conservation problems related to its acidity, including
Molecules 2021, 26, 4249. https://doi.org/10.3390/molecules26144249 https://www.mdpi.com/journal/molecules Molecules 2021, 26, x 2 of 20
linked together by hydrogen bonds [6,7]. Several past paper production techniques (espe- cially those from the 19th century with the addition of alum rosin sizing and industrial Moleculespaper2021, 26 production, 4249 from wood) introduced conservation problems related to its acidity, in- 2 of 20 cluding the acid-catalyzed depolymerization of cellulose and oxidative processes [8,9]. In particular, ancient paper artifacts have high acidity from their production due to the many substances added duringthe acid-catalyzed the production depolymerization process of(alum, cellulose metal and oxidativeions, rosin processes and [additives)8,9]. In particular, [1,10]. The presenceancient of these paper substances artifacts have and high high acidity levels from of their relative production humidity due to dramatically the many substances added during the production process (alum, metal ions, rosin and additives) [1,10]. The promotes the acid hydrolysispresence of theseof cellulose substances [11]. and highThe levelsbonds of between relative humidity the different dramatically glucose promotes units (1,4 glycosidicthe bond acid of hydrolysis cellulose) of celluloseare broken [11]. due The to bonds the betweeninsertion the of different water molecules, glucose units (1,4 leading to the cleavageglycosidic of the bond glycosidic of cellulose) bond are broken(which due results to the in insertion a decrease of water in molecules,the degree leading of polymerization ofto cellulose), the cleavage as of illustrated the glycosidic in bondFigure (which 1 [1,12]. results In in addition a decrease to in acid the degreehydrol- of poly- merization of cellulose), as illustrated in Figure1[ 1,12]. In addition to acid hydrolysis ysis processes, oxidationprocesses, reactions oxidation take reactions place takeat the place reducing at the reducing end of end polymer of polymer chains chains in inthe the C1, C1, C2 and C3 positionsC2 and of C3 the positions glycosidic of the ring glycosidic generating ring generating acid species acid species [13–15]. [13– 15].
Figure 1. Hydrolysis of cellulose. Figure 1. Hydrolysis of cellulose. Concerning book preservation, an important common goal is to neutralize the acids Concerning bookalready preservation, present in the an paper importan and introducet common an alkaline goal is reserve to neutralize to protect the books acids from the already present in thepossible paper formation and introduce of further an acidic alkaline compounds reserve during to protect natural aging. books In from order the to inhibit possible formation ofthe further acid-catalyzed acidic cleavage compounds reactions during of the cellulose natural chains aging. of theIn paper,order the to useinhibit of alkaline + the acid-catalyzed cleavagecompounds reactions allows neutralizing of the cellulose the protons chains (H ) of responsible the paper, for thethe acidic use of pH. alka- Currently, several conservation and restoration methods are employed in order to deacidify the paper + line compounds allowsof books neutralizing [2,16]. The mostthe protons commonly (H used) responsible deacidification for treatments, the acidic also pH. carried Cur- out on rently, several conservationentire volumes, and restoration are divided into methods two classes: are employed non-aqueous in and order aqueous to deacidify processes. The the paper of books main[2,16]. non-aqueous The most processescommonly involve used the deacidification use of carrier fluids treatments, such as fluorinated also car- liquids ried out on entire volumes,or hexamethyldisiloxane are divided into in combination two classes: with non-aqueous alkoxides ofalkali and metalsaqueous (non-aqueous pro- solution) or fluorinated liquid or heptane as carrier fluids with MgO or other alkaline cesses. The main non-aqueous processes involve the use of carrier fluids such as fluori- particles (non-aqueous dispersion) [2,17,18]. Some of the most accredited methods for nated liquids or hexamethyldisiloxanedeacidification, still in use in andcombination not, which canwith also alkoxides be used for of the alkali treatment metals of entire (non-aqueous solution)volumes, or fluorinated are presented below:liquid or heptane as carrier fluids with MgO or other alkaline particles1. The(non-aqueous “Vienna process”, dispersi conceivedon) [2,17,18]. in the 1970s, Some involves of immersingthe most the accredited entire volume in methods for deacidification,vacuum still in in a solution use and of calciumnot, which hydroxide can also and methylcellulosebe used for the as atreatment consolidant [19]. of entire volumes, are presentedThe system below: is still used for the deacidification of newspapers [20]; 2. The “Sablè” method is a French variation of the Wei T’o system invented by Richard 1. The “Vienna process”,D. Smith conceived and developed in the by1970 thes, National involves Archive immersing in Canada. the It entire was adopted volume between in vacuum in a solution1987 and of 1989.calcium The system hydroxide consists and of the methylcellulose insertion of open volumes,as a consolidant kept in a vertical ◦ [19]. The system is positionstill used inside for metalthe deacidification baskets, into an autoclave. of newspapers The volumes [20]; are first dried at 45 C and then impregnated for 10 min with a mixture consisting of ethoxy-magnesium
2. The “Sablè” methodcarbonate is a French and ethanolvariation [21,22 of]; the Wei T’o system invented by Richard D. Smith and developed by the National Archive in Canada. It was adopted between 1987 and 1989. The system consists of the insertion of open volumes, kept in a vertical position inside metal baskets, into an autoclave. The volumes are first dried at 45 °C
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3. The Bookkeeper® method, devised in 1985, is based on the use of magnesium oxide microparticles dispersed in perfluoroheptane and the addition of a surfactant. The volumes are placed on vertical supports and opened at an angle of 90◦ and then placed inside four reactors that operate sequentially and can treat 32 volumes in 2 h. The deacidifying product is inserted, after establishing vacuum conditions. This is one of the most popular methods for its speed of execution and relatively low costs. The Bookkeeper® method provides a considerable reduction of paper degradation and does not affect inks and book ligatures. However, it is reported in the literature that this method appears less efficient for the treatment of large-sized books due to the fact that the alkaline reserve is low and the deacidification is not very uniform. The solvent seems to have a low penetration capacity into the paper fibers, and some white patina appears on the surface [2,21,23,24]; 4. The “CSC Booksaver” method, developed in 2001, involves the use of n-propylated magnesium carbonate dispersed in heptafluoropentane. The volumes are first dehy- drated and then impregnated with the deacidifying substance [20,25]; 5. The “ZFB:2” method, devised in 2011, uses calcium carbonate and magnesium oxide dispersed in heptane. The volumes are not opened, and the process takes about four weeks [26]; 6. The “Papersave” method from Battelle Ingenieurtechnik GmbH and the “Papersave Swiss” method use magnesium and titanium ethyloxides dissolved in hexa-dimethyl siloxane and provide good penetration and an alkaline reserve, reducing the degra- dation of cellulose with aging. However, the treatment cannot be applied to leather covers, pergamene covers, patinated papers and newspapers. Inconvenient decreases in paper mechanical strength, discoloration, white deposits and ink bleeding have been observed [27]. In general, it is asserted that the non-aqueous methodologies mentioned above have disadvantages and limitations such as the accumulation of by-products on the surface of the paper during the treatment process, the use of compounds that alter the appearance of the treated documents (non-aqueous treatments with magnesium compounds) and the use of solvents that are not environmentally friendly and/or that could also solubilize the inks, as well as the absence of the washing action of the water, which prevents the solubilized products from moving away [28–30]. Ultimately, all these methodologies require improvements to further facilitate the penetration of the deacidifying solution between the pages, increase the alkaline reserve and avoid the mentioned problems. In non-aqueous solvents, the alkaline medium remains at the state of micrometer-sized particles, and for this reason, they cannot easily penetrate into the paper fibers. In fact, there is evidence that they mostly remain on the external surfaces of paper sheets, rather than in the interior of the sheets [31], and that treatment applied to one side of paper by spray application does not affect the opposite sides [32]. On the other hand, the processes based on the use of aqueous solutions ensure good penetration of the solvent in the paper due to the hydrophilic character of cellulose. These should give, in principle, better spatial homogeneity and bigger alkaline reserves. Further, certain biocide protection should be given by the aqueous solution containing appropriate compounds, which, indeed, are very soluble in water [33]. One of the most used aqueous methodologies [34] consists of their complete disassem- bly and the immersion of single pages in two solutions: one of Ca(OH)2, which counteracts the acidity present, and one of Ca(HCO3), which deposits an alkaline reserve. The sheets are then left to dry, and the book is stitched back. However, this process is very expensive both in terms of time and money and allows treating only one book at a time [6,30,35]. Since the beginning of the 21st century, up to now, several patents [36–41] have appeared on book deacidification by means of a basic water solution fed to book pages in the form of aerosol droplets. These patented methods [36–41] make use of vacuum techniques at least in one of the process steps such as droplet injection or the subsequent drying of books. This condition introduces a certain degree of complexity to the treatment Molecules 2021, 26, x 4 of 20
Molecules 2021, 26, 4249 the form of aerosol droplets. These patented methods [36–41] make use of vacuum4 tech- of 20 niques at least in one of the process steps such as droplet injection or the subsequent dry- ing of books. This condition introduces a certain degree of complexity to the treatment apparatusapparatus andand representsrepresents aa sortsort ofof limitationlimitation factorfactor withwith respectrespect toto thethe diffusiondiffusion ofof thisthis interestinginteresting methodology.methodology.
2.2. MaterialsMaterials andand MethodsMethods 2.1.2.1. AerosolAerosol SystemSystem TheThe bookbook deacidificationdeacidification experimentsexperiments werewere performedperformed byby meansmeans ofofthe thehomemade homemade experimentalexperimental apparatusapparatus shownshown inin FigureFigure2 .2.
FigureFigure 2.2. DeacidificationDeacidification homemade homemade apparatus: apparatus: (a ()a )chamber chamber hosting hosting the the book book during during treatment treatment cy- cycles;cles; (b ()b book;) book; (c ()c )nuzzle nuzzle nebulizer; nebulizer; (d (d) )valve valve for for dry dry air air inlet; inlet; ( (ee)) valve valve for the exit ofof thethe dryingdrying air;air; ((ff)) steelsteel vesselvessel alkalinealkaline solutionsolution container;container; ((gg)) inletinlet compressedcompressed air;air; ((hh)) T-valveT-valve connector; connector; (i()i) steel steel desiccator; (j) temperature control device; (k–n) flux control valves. desiccator; (j) temperature control device; (k–n) flux control valves.
TheThe chamber (Figure (Figure 2a)2a) hosting hosting the the book book (Figure (Figure 2b)2b) during during the the deacidification deacidification treat- treatmentment was was a polypropylene a polypropylene flask flask made made by by tw twoo airtight airtight hemispheric hemispheric sectors overlappingoverlapping alongalong thethe equatorialequatorial circumferencecircumference with with a a volume volume of of 6565 L.L. TheThe bookbook waswas suspendedsuspended belowbelow thethe equatorialequatorial planeplane ofof thethe flaskflask byby meansmeans ofof anan appropriateappropriate grid. grid. AnAn IKEUCHIIKEUCHI BIMK6004BIMK6004 S303S303 nozzlenozzle nebulizernebulizer (TKK(TKK Corporation,Corporation, Thailand)Thailand) (Figure(Figure2 c),2c), able able to to uniformly uniformly spread spread aa basicbasic solutionsolution cloudcloud inin thethe formform ofof 20–3020–30 µµmm dropletsdroplets onon thethe openopen bookbook pages,pages, waswas mountedmounted on the the superior superior hemisphere hemisphere of of the the flask. flask. On Onthe same the same superior superior hemisphere hemisphere of the offlask, the a flask, connector a connector carrying carrying a valve a for valve dry for air dry inlet air (Figure inlet (Figure 2d) was2d) placed. was placed. The bottom The bottomhemisphere hemisphere was fitted was with fitted an with additional an additional valve (Figure valve (Figure 2e) to allow2e) to allowthe exit the of exitthe ofdrying the dryingair to the air toexternal the external environment environment and maintain and maintain the inner the inner of the of theflax flax at room at room pressure. pressure. A ACa(OH) Ca(OH)2 saturated2 saturated water water solution solution with with a apH pH equal equal to 12.24 (molar(molar concentrationconcentration ofof −−3 3 −1 −1 Ca(OH)Ca(OH)22 equal to 8.7 × 1010 molmol L·L) was) was provided provided for fordeacidification deacidification means means by byusing using the thesteel steel vessel vessel (Figure (Figure 2f).2f). The The basic basic solution solution wa wass fed fed into into the the flaskflask fromfrom thethe bottombottom of of this this containercontainer byby pressurizingpressurizing thethe surfacesurface ofof thethe solutionsolution atat aa pressurepressure ofof 1.51.5 atmatm byby meansmeans ofof anan airair compressorcompressor (not(not shownshown inin thethe figure)figure) connectedconnected throughthrough aa valve valve (Figure (Figure2 g).2g). The The compressor,compressor, byby meansmeans ofof thethe T-connectorT-connector (Figure(Figure2 h),2h), further further fed fed the the air air required required by by the the nozzle.nozzle. Once a a humidification humidification stage stage of of the the book book pages pages was was completed, completed, warm warm and and dry dry air, air,coming coming from from the thesteel steel desiccator desiccator (Figure (Figure 2i), fi2lledi), filled with with silica silica gel, and gel, thermostated and thermostated by the bypower the powersupply supply and controller and controller (Figure (Figure 2j), was2j), passed was passed through through the flask the (Figure flask (Figure 2a). During2a). Duringthe drying the dryingstages, stages,the bottom thebottom valve of valve the flas of thek (Figure flask (Figure 2e) was2e) kept was open, kept open,and all and valves all valves (Figure2h,k–n) were manually settled to cut the fluxes in and from the steel vessel (Figure2f) and maintain the fluxes in and from desiccator (Figure2i). In order to ensure a uniform spread of the nebulized solution, pages were maintained well and separated from Molecules 2021, 26, x 5 of 20
Molecules 2021, 26, 4249 5 of 20 (Figure 2h,k–n) were manually settled to cut the fluxes in and from the steel vessel (Figure 2f) and maintain the fluxes in and from desiccator (Figure 2i). In order to ensure a uniform spread of the nebulized solution, pages were maintained well and separated from each eachother other by using by using a grid a grid holder, holder, where where appropriat appropriatee tin tin wood wood rods rods could could be be inserted inserted as as page pagespacers, spacers, as indicated as indicated in Figure in Figure 3. 3.
FigureFigure 3. 3.Details Details of of the the book book holder holder grid grid with with page page spacers. spacers.
DeacidificationDeacidification experiments experiments were were performed performed according according to the to followingthe following steps: steps: 1.1. TheThe bookbook “Studi“Studi di di Enologia” Enologia” del del cav. cav. Angelo Angelo Mona Mona (Brescia—Pio (Brescia—Pio Istituto Istituto Pavoni— Pavoni— 1875),1875), the the title title page page of whichof which is shown is shown in Figure in Figure4, after being4, after weighed, being weighed, was supported was sup- onported the holder,on the asholder, indicated as indicated in Figure 2inb, Figure and inserted 2b, and into inserted the flask. into At the the flask. actual At the developmentactual development stage of stage our homemade of our homemade apparatus, apparatus, only a limited only numbera limited of number pages of could be homogeneously treated with the alkaline droplets. For this reason, only pages could be homogeneously treated with the alkaline droplets. For this reason, 12 (from 1 to 6 and from 91 to 96 pages) of the almost 200 pages of the book were only 12 (from 1 to 6 and from 91 to 96 pages) of the almost 200 pages of the book were kept wide open to facilitate a uniform deposition of the aerosol through a single nozzle.kept wide The open other to pages facilitate were a keptuniform firmly deposition closed in of order the toaerosol exclude through them froma single the noz- deacidificationzle. The other process;pages were kept firmly closed in order to exclude them from the dea- 2. Thecidification book, placed process; into the flask, was exposed to a dry air flux at the temperature of 2. 45The◦C book, for 15 placed min. Then, into itthe was flask, extracted was exposed from the to chamber a dry air and flux weighed. at the Thetemperature weight of variation45 °C for was15 min. 3.45%; Then, it was extracted from the chamber and weighed. The weight 3. Thevariation book was replaced3.45%; in the chamber. A cloud of nebulized solution was fluxed 3. aboveThe book the openwas pagesreplaced through in the the chamber. nozzle placed A cloud on the of topnebulized hemisphere. solution The aerosolwas fluxed inletabove was the left open to flowpages for through 3 min, while the nozzle the valve placed on theon bottomthe top ofhemisphere. the flask was The kept aerosol openinlet towas ensure left to a constantflow for pressure3 min, while in the the flask; valve on the bottom of the flask was kept 4. Theopen book to ensure was removed a constant from pressure the flask in and the weighed flask; in order to measure the amount 4. ofThe the book absorbed was removed basic solution from and the insertedflask and back weighed into the in treatment order to chamber;measure the amount 5. Dry air at the temperature of 45 ◦C was let gently fluxed into the flask for 3 min, enter- of the absorbed basic solution and inserted back into the treatment chamber; ing with the help of a small pressure gradient (around 0.05 atm) and exiting through 5. Dry air at the temperature of 45 °C was let gently fluxed into the flask for 3 min, the bottom open valve. The rehydration of the air gradually removed the absorbed entering with the help of a small pressure gradient (around 0.05 atm) and exiting humidity from the book. After the above dehydration cycle, the book was weighed. Thisthrough step wasthe bottom repeated open 5 times valve. in order The torehydr bringation the book of the to aair constant gradually weight; removed the 6. Theabsorbed pH on humidity every treated from page the wasbook. measured After the in above six different dehydration points, cycle, as described the book in was Sectionweighed. 2.4 ,This and thestep average was repeated value was 5 times recorded; in order to bring the book to a constant 7. Theweight; procedure described above, as defined in Steps 3 to 6, was repeated 8 times in 6. orderThe pH to reachon every a satisfactory treated page pH value.was measured in six different points, as described in Section 2.4, and the average value was recorded; 7. The procedure described above, as defined in Steps 3 to 6, was repeated 8 times in order to reach a satisfactory pH value.
MoleculesMolecules 20212021, 26, 26, x, 4249 6 of 20 6 of 20
FigureFigure 4. 4.Photography Photography of the of titlethe pagetitle ofpage the analyzedof the analyzed book. book.
2.2. X-ray Fluorescence (XRF) 2.2. X-ray Fluorescence (XRF) Analysis was performed by a Bruker Tracer III with an Rh/Pd X-ray source under the followingAnalysis conditions: was performed voltage, 40 kV; by current, a Bruker 11 µTracerA; acquisition III with time, an Rh/Pd 15 s. Measurements X-ray source under the werefollowing taken inconditions: six different voltage, points of 40 the kV; pages current, in all 12 11 pages µA; investigated.acquisition time, XRF data 15 s. were Measurements evaluatedwere taken by Artaxin six software different from points Bruker. of the The pages software in provides all 12 pages qualitative investigated. and partially XRF data were semi-quantitativeevaluated by Artax information software with from respect Bruker. to the The elements software detected. provides These dataqualitative represent and partially the values of the integrals subtended by the characteristic peaks of the emitted fluorescence semi-quantitative information with respect to the elements detected. These data represent by the different detectable elements. They depend in principle on many factors, but when measurementsthe values ofare the appropriately integrals subtended made, it can by be the assumed characteristic that XRF intensitiespeaks of arethe in emitted the fluores- firstcence approximation by the different proportional detectable to the elements. density of They the chemical depend elements in principle dispersed on many into factors, but thewhen sampled measurements volume and are to a specificappropriately emission made, constant, it can which be is assumed different for that each XRF of the intensities are elements.in the first Thus, approximation significant information proportional on the chemistryto the density of the bookof the could chemical be derived elements from dispersed XRFinto signals. the sampled volume and to a specific emission constant, which is different for each 2.3.of the FTIR elements. Spectroscopy Thus, significant information on the chemistry of the book could be de- rivedFTIR-ATR from XRF analysis signals. was performed by using the FTIR ATR BRUKER ALPHA II spec- trophotometer equipped with the accessory for attenuated total reflectance (ATR) with a diamond2.3. FTIR and Spectroscopy crystal window. Analysis was carried out with a resolution of 4 cm−1 in the −1 regionFTIR-ATR between 4000 analysis and 375 was cm performed, setting 48 by scans using for the a single FTIR analysis. ATR BRUKER The recorded ALPHA II spec- spectra were interpreted using the Bruker OPUS software. trophotometer equipped with the accessory for attenuated total reflectance (ATR) with a 2.4.diamond Powder X-rayand crystal Diffraction window. (PXRD) Analysis was carried out with a resolution of 4 cm−1 in the regionPXRD between patterns 4000 were acquiredand 375 on cm a− Bruker1, setting D2-Phaser 48 scans equipped for a withsingle Cu Kanalysis.α radiation The recorded (spectraλ = 1.5418 were A) andinterpreted a Lynxeye using detector, the Bruker at 30 kV OPUS and 10 software. mA, with a step size of 0.01◦ and a step time of 1.5 s (acquisition time: 11,250 s), over an angular range of 5–80◦ 2θ. 2 A2.4. 1 cmPowderarea X-ray of the bookDiffraction was sacrificed (PXRD) to perform the PXRD analysis before and after deacidification treatment. Small pieces of paper sheets, as they were, were placed on a zero-backgroundPXRD patterns sample were holder. acquired Slight 2 onθ displacements a Bruker D2-Phaser of some reflection equipped peaks, with which Cu Kα radiation did(λ = not 1.5418 exceed A)± 0.3and◦, witha Lynxeye respect todetector, the reference at 30 patterns kV and reported 10 mA, in with the Crystallography a step size of 0.01° and a step time of 1.5 s (acquisition time: 11,250 s), over an angular range of 5–80° 2θ. A 1 cm2 area of the book was sacrificed to perform the PXRD analysis before and after deacidifi- cation treatment. Small pieces of paper sheets, as they were, were placed on a zero-back- ground sample holder. Slight 2θ displacements of some reflection peaks, which did not exceed ±0.3°, with respect to the reference patterns reported in the Crystallography Open Database (COD) and in the RRUFF database, could be ascribed to both the sample prepa- ration and the instrumental set-up.
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Open Database (COD) and in the RRUFF database, could be ascribed to both the sample preparation and the instrumental set-up.
2.5. Contact pH Meter The surface pH method (TAPPI T 529 om99) [42] was used for the pH measurement. Measurements of pH in standard conditions were made by placing a polypropylene plastic sheet beneath the investigated page. On each of the measurement points, a 40 µg drop of MilliQ water (HANNA HI70960 conductive electrolyte solution) was added dropwise by a droplet-dosing cup bottle. The surface electrode was then set on the water droplet. Both these operations were performed in rapid succession in a time lower than 1 s. The pH was measured by a HANNA—Leather and Paper HI 99171 pH meter with a surface glass. Reported pH values are the mean values calculated from the pH measurements, taken from six test points, in each of the twelve pages investigated.
2.6. Artificial Aging Artificial aging tests were performed according to the methods developed by the Conservation Processes and Materials Research Division of the Canadian Conservation Institute (CCI) in Ottawa (Canada) and the Preservation Research a Testing Office of the U.S. Library of Congress (LOC) in Washington (USA) [43]. Six strips of about 0.2 g, taken from all of the deacidified book pages (from 1 to 6 and from 91 to 96), and six analogous strips, cut from 41 to 46 and from 107 to 112 pages (taken out from the book before any treatment), were aged. All paper samples were conditioned at 23 ◦C and 50% RH for ≥24 h both immediately prior to and following the accelerated aging period. The preconditioned paper samples were inserted inside closed glass bottles with a proportion of paper weight/bottle volume of 1 g/36 mL and introduced into the heated oven at 100 ◦C for 120 h in one continuous period.
2.7. Colorimetry and Optical Microscopy Colorimetric measurements CIE L*a*b* were performed to ascertain the effect of the deacidification treatments on paper and ink color before and after aging. The ARW-265 portable colorimeter (Arroweld Italia Spa, Italy) with a measurement caliber of 8 mm was used in the D65/10◦ (light source) mode. The paper colorimetric coordinates were measured, for all sample types (untreated: Pages 41, 44, 45, 107, 109, 112; deacidified: Pages 1, 4, 5, 92, 93 and 95; untreated and aged: corresponding aged strips of Pages 41, 44, 45, 107, 109 and 112; deacidified and aged: corresponding aged strips of Pages 1, 4, 5, 92, 93 and 95), on six different testing points, opportunely chosen on each of the above- mentioned book pages. In particular, the colorimetric ink investigations were performed, according to Sequeira et al. (2006) [1], on six “a” letters for each of the different page samples. The total color difference (∆E*) and the whiteness parameter (W) were calculated according to Brainard (2003) [44] and Gooch (2011) [45], respectively. The averaged values and standard deviations were determined. The script character was observed by a Zeiss Telaval 31 inverted phase contrast optical microscope (Zeiss, Oberkochen, Germany) with an S5A-6V halogen lamp (25 W) as a light source in order to detect the presence of eventual bleeding effects.
2.8. Determination of the Degree of Polymerization (DP) The polymerization degree for each of the different paper sample types, as in the case of the colorimetric measurement (untreated, deacidified, untreated and aged, deacidified and aged), was determined according to the UNI 8282 standard test [46] by measuring the viscosity limit of cellulose solutions in bis-(ethylenediamine)-copper (II) hydroxide (CED) 0.5 M. The CED solution was prepared by diluting the Aldrich® 1M CED solution in water. A 10 mg amount of paper for each paper sample was dissolved in 20 mL of CED at 25 ◦C by stirring the system for at least 30 min. In order to obtain the required limit viscosities, 5 solutions for each of the investigated paper samples were analyzed: Molecules 2021, 26, 4249 8 of 20
the base solutions, obtained as described above, and 4 solutions, obtained by diluting the base solution with 0.5 M CED. Four dilution ratios, 2, 4, 8 and 16, were used. Viscosity measurements were carried out at room temperature (25 ◦C) using an RFS III shear-strain- controlled rheometer (Rheometrics Co. Ltd., Piscataway, NJ, USA) equipped with parallel plate geometry (gap, 1.000 ± 0.001 mm; diameter, 50 mm) for the samples analyzed and a Peltier system (±0.1 ◦C) for temperature control. Steady flow experiments were performed, and the viscosity was measured at different shear rate values. The variation of viscosity versus shear rates for all samples was measured. It was observed that all samples had Newtonian rheological behaviors, which meant the viscosity was independent of the shear rates. Specific [η] viscosity was obtained according to Equation (1):
ηsp [η] = lim (1) c→0 c where c is the solution concentration, and ηsp = (η − ηs)/ηs, where ηs is the viscosity of the CED solvent by determining the vertical intercept of the ηsp plot versus the con- centration. Finally, the degree of polymerization (DP) was calculated according to the equation: DP = 1.33[η]0.905, according to UNI 8282:1994 [46]. Mean values, obtained by averaging those measured from Pieces 41/42, 43/44, 45/46, 107/108, 109/110 and 111/112 of untreated and untreated-aged book pages and those measured from Pieces 1/2, 3/4, 5/6, 91/92, 93/94 and 95/96 of deacidified and deacidified-aged book pages, were reported.
2.9. Alkaline Reserve Determination The alkaline reserve was determined according to the TAPPI 533 pm-92 method [47]. A 1 g amount of dry small paper pieces, taken in equal amounts from the untreated book pages and analogous quantities of paper taken from the deacidified pages, were used to investigate the original (before treatment) and final (after treatment) alkaline reserve, respectively. Each gram of the two of these paper samples was inserted into 25 mL of distilled water. A 20 mL volume of HCl 0.1 N solution was added to the suspension, which was then left for about 1 min at boiling temperature. After cooling, the suspension was titrated with a NaOH 0.1 N solution monitoring the color change of the indicator (close to pH = 7) previously added.
3. Results and Discussion Before discussing the deacidification process and the related model, FTIR, PXRD and XRF data will be presented in order to obtain a useful indication of the book chemistry. Spectral data were taken from the pages of the book kept open during the acidification process before and at the end of the deacidification treatment. pH values were measured, on the same pages, before the treatment and after each of the eight used aerosol/drying cycles. After discussing the deacidification process data, the effect of treatment on the degree of polymerization (DP) of the paper and the colorimetric coordinates of paper and ink, the variation of these parameters with aging and, finally, the alkaline reserve data will be discussed.
3.1. FTIR Results FTIR spectra are substantially equal for all the 12 pages investigated. Two copies of these spectra, precisely those recorded from Page 1, in pre- and post-treatment conditions, are reported in Figure5, together with the transition wavenumbers. Those related to cellulose are reported in blue [48–50]. The identification of vibrational bands is reported in Table1. MoleculesMolecules 20212021, ,2626, ,x 4249 9 9of of 20 20
Figure 5. FTIR spectra before (black) and after (red) deacidification treatment recorded from page 1. Figure 5. FTIR spectra before (black) and after (red) deacidification treatment recorded from page 1.Frequency Frequency values values in in blue blue are are identified identified as as cellulose cellulose peaks. peaks.
TableThose 1. FTIR related wavenumbers, to cellulose vibrational are reported mode and in related blue [48–50]. chemical compoundsThe identification (cellulose of bands vibra- are tionalin blue) bands (Miller is andreported Wilkins in 1952; Table Garside 1. and Wyeth 2003; Sequeira et al., 2006; Librando et al., 2011).
Wavenumber (cm−1) Functional Chemical Groups Chemical Compound Table 1. FTIR wavenumbers, vibrational mode and related chemical compounds (cellulose bands are in blue)3680–3000 (Miller and Wilkins 1952; Garside OH stretching and Wyeth 2003; Sequeira et al., Cellulose2006; Librando et al., 2011). 2900 CH stretching Cellulose 2740–2700 CH stretching Cellulose −1 Wavenumber2540–2510 (cm ) Functional Chemical CO stretching Groups Chemical CaCO Compound3 3680–30002230–2130 OH COstretching stretching Cellulose CaCO3 29001735 CH C=O stretching stretching Cellulose Cellulose 1650–1635 OH bending/adsorbed water Cellulose and others 2740–2700 CH stretching Cellulose 1430 CO stretching CaCO3 2540–25101372 CO stretching CH bending CaCO Cellulose3 2230–21301340 CO stretching CH bending CaCO Cellulose3 17351320 C=O CHstretching bending Cellulose Cellulose 1280 CH2 twisting Cellulose 1650–16351174 OH bending/adsorbed C-C stretching water Cellulose Cellulose and (and others others) 14301130 CO SO stretching stretching asym Ca(SO CaCO4)·2H3 2O 13721090 CH CO stretchingbending asymCellulose CaCO3 13401050–1015 CH SO bending stretching Ca(SO Cellulose4)·2H 2O 870–880 CO stretching asym CaCO 1320 CH bending Cellulose3 715 CO stretching asym CaCO3 1280 CH2 twisting Cellulose 670 Ca-OH bending Ca(SO4)·2H2O 1174640–610 C-C Ca-OH stretching bending Cellulose CaCO (and 3others) 1130460–430 SO stretching Ca-OH stretching asym Ca(SO CaCO4)·2H3 2O 1090 CO stretching asym CaCO3 − An1050–1015 intense band, between 3680SO stretching and 3000 cm 1, is related to theCa(SO OH4 stretchings)·2H2O of cel- −1 lulose [870–88046] and absorbed water, CO while stretching the bending asym of this species appears CaCO at 16353 cm [48]. The intensity715 of these bands is, CO of stretching course, related asym with the degree of the CaCO paper3 hydration. −1 Cellulose670 CH stretchings appearCa-OH betweenbending 2900 and 2740–2700Ca(SO cm 4)·2H[482],O while CH −1 bendings640–610 are at 1372, 1340 andCa-OH 1320 cm bending[49]; CH2 twistings and C=OCaCO stretchings3 are, respectively, at 1280 and 1735 cm−1 [48,49]. The band between 610 and 640 cm−1 can 460–430 Ca-OH stretching CaCO3
Molecules 2021, 26, x 10 of 20
An intense band, between 3680 and 3000 cm−1, is related to the OH stretchings of cellulose [46] and absorbed water, while the bending of this species appears at 1635 cm−1 [48]. The intensity of these bands is, of course, related with the degree of the paper hydra- tion. Molecules 2021, 26, 4249 10 of 20 Cellulose CH stretchings appear between 2900 and 2740–2700 cm−1 [48], while CH bendings are at 1372, 1340 and 1320 cm−1 [49]; CH2 twistings and C=O stretchings are, respectively, at 1280 and 1735 cm−1 [48,49]. The band between 610 and 640 cm−1 can be attributedbe attributed to Ca-OH to Ca-OH bending bending [1]. On [1 ].the On other the hand, other spectra hand, spectrashow the show presence the presence of calcium of ⋅ sulfatecalcium (CaSO sulfate4 2H (CaSO2O) and4·2H calcium2O) and carbonate calcium carbonate (CaCO3), (CaCOthe bands3), the of bandswhich offall which at 1130, fall 1050–1015at 1130, 1050–1015 and 670 andcm−1 670[50] cm and−1 2510–2540,[50] and 2510–2540, 2230–2130, 2230–2130, 1430, 870–880, 1430, 870–880,715 and 460–430 715 and cm460–430−1 [51], cm respectively.−1 [51], respectively. These substances These substanceswere used as were fillers used of asthe fillers paper of to the improve paper its to mechanicalimprove its properties. mechanical Ultimately, properties. Ultimately,FTIR spectr FTIRa shown spectra in Figure shown 5, in taken Figure before5, taken and before after treatment,and after treatment, do not show do notappreciable show appreciable variation, variation, confirming confirming that our thattreatment our treatment does not does in- troducenot introduce a valuable a valuable modification modification in the in number the number of significant of significant functional functional groups groups (i.e., (i.e.,hy- droxylshydroxyls and and carbonyls). carbonyls).
3.2.3.2. PXRD PXRD Results Results TheThe untreated untreated paper paper PXRD PXRD pattern pattern is reported reported in Figure 66.. TheThe distinctivedistinctive diffractiondiffraction ◦ ◦ ◦ peakspeaks of of cellulose are visible at 2θ == 15.115.1°,, 16.816.8° and 22.922.9° [[52].52]. Several other reflections reflections cancan be be observed observed in in Figure Figure 66 (see(see insets),insets), provingproving thethe presencepresence ofof otherother crystallinecrystalline species.species.
Figure 6. Untreated paperpaper PXRDPXRD and and related related magnifications magnifications in in the th angulare angular ranges ranges 5–28 5–28°◦ (red (red inset), inset), 28–50 28–50°◦ (blue (blue inset) inset) and and 50–80° (green inset). 50–80◦ (green inset).
These compounds were identified by comparison with reference patterns reported in the Crystallography Open Database (COD) and in the RRUFF database (Table2).
Molecules 2021, 26, x 11 of 20
These compounds were identified by comparison with reference patterns reported in Molecules 2021, 26, 4249 the Crystallography Open Database (COD) and in the RRUFF database (Table 2). 11 of 20
Table 2. Crystalline compound identified in PXRD spectra of the book paper (before and after deacidification).
PXRD IdentifiedTable 2. Crystalline Compound compound Common identified Name in PXRD spectra of the book paper2θ (°) (before and after deacidification). N.° Ref. ⋅ PXRDKAl(SO Identified4)2 12H Compound2O K-alum Common Name 12.6; 17.9; 20.4; 31.2; 32.3; 2θ (◦ )34.7; 44.7 R040134 N.◦ Ref. KAl3(SO4)2(OH)6 Alunite 17.9; 25.7; 29.6; 39.4; 47.8 R060430 KAl(SO ) ·12H O K-alum 12.6; 17.9; 20.4; 31.2; 32.3; 34.7; 44.7 R040134 FeO(OH)4 2 2 Goethite 21.0; 33.6; 34.7; 36.8 R050142 KAl3(SO4)2(OH)6 Alunite 17.9; 25.7; 29.6; 39.4; 47.8 R060430 Ca4FeO(OH)Al6O12(SO4) Ye’elimite Goethite 23.5; 33.6; 36.3; 50.5; 21.0; 56.6; 33.6; 58.4; 34.7; 60.5; 36.8 62.4 COD R0501429009938 Ca4AlTiO6O122 (SO4) Anatase Ye’elimite 23.5; 25.1;33.6; 36.3;37.7; 50.5; 47.8 56.6; 58.4; 60.5; 62.4 R060277 COD 9009938 TiO Anatase 25.1; 37.7; 47.8 R060277 CaCO2 3 Calcite 29.6; 39.4; 48.5 R040070 CaCO Calcite 29.6; 39.4; 48.5 R040070 NiO 3 Bunsenite 37.7; 43.5; 63.5; 75.5 R080121 NiO Bunsenite 37.7; 43.5; 63.5; 75.5 R080121
Finally, no differences between the diffractograms obtained after deacidification of the bookFinally, were no observed differences with between respect to the those diffractograms obtained before obtained the treatment. after deacidification The presence of ofthe K-alum book wereand alunite observed confirms with respect the historical to those tradition obtained of before paper the manufacturing treatment. The of presence adding K-alumof K-alum and and other alunite similar confirms compounds the historical into the ligno-cellulosic tradition of paper paste, manufacturing together with of animal adding gelatinK-alum [53,54]. and other While similar FTIR compounds spectra show into eviden the ligno-cellulosicce of the presence paste, of together calcium with sulfate animal bi- hydrategelatin and [53,54 calcium]. While hydroxide, FTIR spectra PXRD show spectra evidence do not of show the presenceevidence of these calcium compounds, sulfate bi- athydrate least in and the calciumcrystalline hydroxide, phase. This PXRD is an spectra interesting do not point show that evidence requires of thesea deeper compounds, investi- at least in the crystalline phase. This is an interesting point that requires a deeper investi- gation, which is beyond the aim of this work. At the moment, we can only hypothesize gation, which is beyond the aim of this work. At the moment, we can only hypothesize that both calcium hydroxide and calcium sulfate may exist in the system as amorphous that both calcium hydroxide and calcium sulfate may exist in the system as amorphous material dispersed on the cellulose surface. It is worth mentioning that iron appears to be material dispersed on the cellulose surface. It is worth mentioning that iron appears to present only as crystalline goethite. It is known [54] that epta-hydrate ferrous sulfate, tra- be present only as crystalline goethite. It is known [54] that epta-hydrate ferrous sulfate, ditionally defined as green vitriol, was often added to alum to partially substitute this traditionally defined as green vitriol, was often added to alum to partially substitute this much costly component. Further, ferric alum, a less pure form of alum, obtained by the much costly component. Further, ferric alum, a less pure form of alum, obtained by the sulfuric acid treatment of natural bauxite raw materials, could also have been used by sulfuric acid treatment of natural bauxite raw materials, could also have been used by paper paper manufacturing to replace part of alum. Goethite could be derived from bauxite, as manufacturing to replace part of alum. Goethite could be derived from bauxite, as this this mineral represents one of the major sources of iron in bauxite [55]. Finally, no differ- mineral represents one of the major sources of iron in bauxite [55]. Finally, no differences ences between the diffractograms obtained after deacidification of the book were ob- between the diffractograms obtained after deacidification of the book were observed with servedrespect with to those respect obtained to those before obtained the treatment. before the treatment.
3.3.3.3. X-ray X-ray Fluorescence Fluorescence Results Results SixSix spectra spectra were were recorded recorded for for each each of of the the analyzed analyzed pages. pages. Spectra Spectra were were all all similar similar to to thosethose reported reported in in Figure Figure 7.7.
FigureFigure 7. 7. XRFXRF spectra spectra after after treatment treatment of of Page Page 1. 1.
The averaged XRF intensity of each of the detected chemical elements, expressed in the scale applied by the instrument (count/s), is summarized in Figure8. The aver- age was taken on all data recorded from the 12 analyzed pages. The bars represent the standard deviations. Molecules 2021, 26, x 12 of 20 Molecules 2021, 26, x 12 of 20
TheThe averaged averaged XRF XRF intensity intensity of of each each of of the the detected detected chemical chemical elements, elements, expressed expressed in in the scale applied by the instrument (count/s), is summarized in Figure 8. The average was Molecules 2021, 26, 4249 the scale applied by the instrument (count/s), is summarized in Figure 8. The average12 was of 20 takentaken on on all all data data recorded recorded from from the the 12 12 anal analyzedyzed pages. pages. The The bars bars represent represent the the standard standard deviations.deviations.
FigureFigureFigure 8. 8.Intensity 8. IntensityIntensity of of the ofthe chemical the chemical chemical species species species detected detected detected in in the the inpaper paper the paperthrough through through XRF XRF before before XRF and before and after after and dea- dea- after cidifyingcidifyingdeacidifying treatment. treatment. treatment. The The error Theerror bars error bars are bars are the the are standard thestandard standard deviation deviation deviation as as obtained obtained as obtained from from from all all measurements. allmeasurements. measurements.
TheTheThe elements elements elements detected detected detected through through through XRF XRF XRF analysis analysis analysis ar are are Al,e Al, Al, Si, Si, Si,S, S, K, S, K, K,Ca, Ca, Ca, Ti, Ti, Ti,Fe, Fe, Fe, Ni, Ni, Ni, Cu CuCu and and and Sr, Sr, Sr, fromfromfrom which which which those those those found found found with with with the the the highest highest highest intensity intensity intensity are are are calcium, calcium, calcium, iron, iron, iron, potassium potassium potassium and and and sulfur, sulfur, sulfur, confirmingconfirmingconfirming the the the findings findings findings obtained obtained obtained by by byFTIR FTIR FTIR and and and PXRD PXRD PXRD spectroscopies. spectroscopies. spectroscopies. The The The low low low aluminum aluminum aluminum intensityintensityintensity in in inthe the the XRF XRF XRF spectra spectra spectra can can can be be beattributed attributed attributed to to tothe the the low low low sensitivity sensitivity sensitivity of of ofthis this this element element element in in inthe the the XRFXRFXRF technique. technique. technique. The The The XRF XRF XRF signal signal signal in in inFigure Figure Figure 8 8sh8 shshows,ows,ows, as as expected expected from from the the beginning, beginning, that that calciumcalciumcalcium is is the is the the only only only element element element increased increased increased by by bythe the the deacidification deacidification deacidification process; process; process; the the the differences differences differences before before before andandand after after after treatment treatment treatment are are are far far far from from from the the the experimental experimental experimental error. error. error. InIn Inorder order order to to toshow show show the the the uniformity uniformity uniformity level level level of of ofcalcium calcium calcium deposition deposition deposition in in inthe the the several several several analyzed analyzed analyzed pages,pages,pages, the the the intensity intensity intensity of of the of the thecalcium calcium calcium “seen” “seen” “seen” by by the by the XRF the XRF XRF spectra spectra spectra for for all forall pages allpages pages is is reported reported is reported in in in Figure9, where the black line represents the pre-treatment-averaged (on the page) FigureFigure 9, 9, where where the the black black line line represents represents the the pre-treatment-averaged pre-treatment-averaged (on (on the the page) page) cal- cal- calcium spectral intensity, while the red line shows the trend of the calcium signal after the ciumcium spectral spectral intensity, intensity, while while the the red red line line sh showsows the the trend trend of of the the calcium calcium signal signal after after the the treatment. An average difference of the order of about 50% can be observed. treatment.treatment. An An average average difference difference of of th the eorder order of of about about 50% 50% can can be be observed. observed.
Figure 9. Average of the intensity values, per page, of Ca (before and after treatment). The pages are Figure 9. Average of the intensity values, per page, of Ca (before and after treatment). The pages are Figureshown 9. on Average the abscissa of the axis,intensity while values, the intensity per page, is shown of Ca (before on the ordinateand after axis.treatment). The pages are shownshown on on the the abscissa abscissa axis, axis, while while the the inte intensitynsity is isshown shown on on the the ordinate ordinate axis. axis. 3.4. pH Results Figure 10 reports the values of averaged pH values measured on the book pages before
treatment and after each nebulization/drying cycle. pH was also measured even on the book pages kept closed during the deacidification treatment. Molecules 2021, 26, x 13 of 20
3.4. pH Results
Molecules 2021, 26, 4249 Figure 10 reports the values of averaged pH values measured on the book pages be-13 of 20 fore treatment and after each nebulization/drying cycle. pH was also measured even on the book pages kept closed during the deacidification treatment.
Figure 10. Trend of the average pH value measured after each complete deacidification treatment. Figure 10. Trend of the average pH value measured after each complete deacidification treatment. No pH variation was observed, confirming that the nebulized solution did not pen- etrateNo pH on variation these pages. was observed, On the abscissa confirming axis, thethat total the nebulized amount of solution basic solution did not absorbed pen- etrateby on the these book pages. at the On end the of abscissa every cycleaxis, th ise reported. total amount This of quantity basic solution was calculated absorbed by the the bookfollowing at the Equation end of every (2): cycle is reported. This quantity was calculated by the follow- ing Equation (2): J W = ∆P (2) J ∑ i i=1 W = ∆P (2) where ∆Pi is the variation of the book weight between the i-esimo nebulization stage and the (i − 1)-esimo drying stage. The hypothesis that WJ is proportional to the average wherecalcium ΔPi is concentrationthe variation of added the book to the weight book be attween the J-esimo the i-esimo nebulization nebulization stage stage will beand used the (iin − the 1)-esimo following. drying If this stage. increment The hypothesis of the calcium that W concentrationJ is proportional is definedto the average as bJ, then cal- the ciumproposed concentration hypothesis added canto the be book expressed at the byJ-esimo the equation nebulization bJ = stageβWJ. will The be trend used ofin thethe pH following.values If against this increment WJ can be of considered the calcium as concentration a titration curve is defined of the book as bJ, pages.then the The proposed continuous hypothesisline is the can interpolation be expressed of by the the titration equation curve bJ = β byW theJ. The simple trend chemical of the pH model values illustrated against in WJ canthe following.be considered Taking as a into titration consideration curve of thethe spectroscopicbook pages. The results continuous shown above, line is it the can be interpolationhypothesized of the that titration the acidity curve of by the the book simple is linked chemical to the model hydrolysis illustrated of some in the acid follow- cationic ing. species.Taking into To simplifyconsideration the problem, the spectroscopic the dominating results shown effect of above, a single it can species be hypothe- was taken sizedinto that consideration. the acidity of the The book identification is linked to of the this hydrolysis acid species of some will be acid discussed cationic next,species. taking To simplifyinto consideration the problem, the the acid dominating constant of effect the involvedof a single hydrolysis species was process taken coming into consid- from the eration.titration The curve,identification as well asof thethis information acid species obtained will be discussed from spectroscopic next, taking and into X-ray consider- diffraction ationdata. the acid The constant starting pointof the is involved then the hydrolysis general assumption process coming of the from presence the titration of a water-soluble curve, as wellcompound as the information CnAm, where obtained C is hypothesized from spectroscopic to be the and cation X-ray species diffraction responsible data. The for the startingbook point acidity, is then while the A general is its anionic assumption counterpart of the (Apresence could indeedof a water-soluble correspond compound to more than a CnAsinglem, where anionic C is hypothesized species, but this to be aspect the cation would species not affect responsible at all the model).for the book The presenceacidity, of whilehumidity A is its anionic leads to counterpart the electrolytic (A could dissociation indeed of correspond CnAm, according to more to than Equation a single (3): ani-
onic species, but this aspect would not affect at alln +the model).m− The presence of humidity CmAn → mC + nA (3) leads to the electrolytic dissociation of CnAm, according to Equation (3):