eS seuSE GALLERIES COMMISSION utledgeCLEANING For over a decide, the Science for Conservators volumes have been the key basic texts for conservators throughout the world. Scientific concepts are fundamental to the conservation of artefacts of every type yet many conservators have litle or no scent training, These invoductory volumes provide non-scienists withthe essential theor- ‘tial background to their work,The Heritage: Care-Preseroaion-Management programme has been designed to serve the needs of the museum and heritage community worldwide. It publishes ‘books and information services for professional museum and heritage workers, and forall the organizations that service the museum community. itor chet Andree Whestoft ‘The Development of Costume ‘Neo Taran Forward Planning: hint ofbusnss, copa at “ewlopment plang for mate ond slo Edited by Temoty Ambrose sn Sue Ruayard | ‘The Handbook for Museums ‘Gary Eason and David Dean Hevtage Gardens: Car, omsreton and magenint ‘Sheena Mackall Couly eritage and Tourism: the loa lige Prslla Boniface and Pte. Power ‘The Industral Heritage: Managing sources ma ses Tats fey and Tn Funan Managing Quality Cultural Torin Priscila Boniface “Timothy Ambrove nd Crispin Pine Museum Exhibition: Toy an practice ‘David Dean Museuay, Media, Message cited by Eilean Hooper Gree Museum Security and Protection: hindbat er eltaral heritage isitions TCOM and ICS “Maseurns 200: Pats, people, prfesion "lite by Fat Boyan “Maseums and the Shaping of Knowledge lean Hooper Greenil “Museums and thei Visitors lean Hooper reel ‘Museums without Baier: A nw da fr dad pape Foundation de France end ICOM “The Fastin Contemporary Society: Thennxe Peter] Fowler ‘The Representation of the Pst Musume and ritagein he postmen werd ‘Kevin Wale ‘Towards the Museum ofthe Future: New Europea perspectives ited by Roger Miles and Lauro Zaval “Maseuans A Place o Work: Plnning mse careers Have Glaser and Artemis Zena Marketing the Museum "Bona MeLesn| ‘Managing Museums and Galleries ‘chal A Kopp ‘Museum Bthice ited by Gary Eaton and profit ‘SCIENCE FOR CONSERVATORS Volume 2 CLEANING Conservation Science Teaching Series MUSEUMS & GALLERIES COMMISSION in conjunction with Routledge London and New YorkIona ey Sth eve Monat na eer Conenton Cone Ofer Somer She telsematode ry | [toler ‘Ue Calle Landon one Scorer Scam Kene Deputect of Mat see eat Cont Sri Gg ‘Advuer Fro Tekin Somer Mlscan rtm Were Ope ey ie Medd Org ‘ees Pde pe ty Ft pulse bythe Cre Con 18 bse The Cameron Ut the Dy hontee 2h Spr Non Pak Angora OXILARN 2BUBadon Ave New Yo, NY Repine 4 196 1992, 202 nt 208 ‘Trstened Digit Pring 205 oie rit f tr Fr Crap seo ty Berlin Dsin Deter Up nil Ce and en rN pe fh ky pi Inch oer mene ow nw ean Incudng petri sd mmo myers ‘ep nwa rein mg on rie ry Cig Pain Dt cep rb ae rary of Con Can eno ae ‘Newloge fr so nae. Prin nd Rony Anny Rave Ll East Contents Introduction Chapter 1 The nature of dirt Chapter 2. Mechanical cleaning Chapter 3. Liquids and solutions Chapter 4 Organic solvents Chapter 5 Cleaning with water Chapter 6 Water, acidity and alkalinity Chapter 7 Cleaning by chemical reaction Recommended reading Index 7 10 24 42 58 72 86 104 127 135Preface to the 1992 edition The science of conserving artworks and other tems of cla sigriicance has undergone considerable change since 1982 when ths serie was instigated, mostly Involving the development or application of new materi or techniques. Their understanding by conservators, restorers and stants ‘continues nonetheless, to depend on famillaty with the underying sient Principles which do not ehange and sehich ar lesly explained in theve books. In response to continued intemationa demand forth series, The Conservation Unt is pleased t be associated with Routledge in presenting ‘hese ner etions as part of The Heritage: Care-Preservaton- Management programme. The volumes are now enhanced by lt of recommended reading ‘vic wll lead the rear to further hepfl texts, developing scientific ese Ina conservation sling and bringing thes aplicaion uptodate, Introduction Alice thought she had never seen such a curlous croquet-ground in all thr life; it a8 all ridges and furrows; the balls were live hedgehogs the ‘mallets Ive lamingocs, andthe soldiers had to double themselves up Sd to stand upon their hands and fet, to make the arches ‘The chief difiatty Alice found at first was in managing her ‘amingo: she sucteeded in geting is Body tucked away, comfortably fenough, under her arm, with Is legs hanging down, but generally, just fs she had got itsneck nicely straightened ott, and was going to give ‘he hedgehog a blow with is head, it would tis iself round and look lupin her face, wah such a puzzled expression that she could not help bursting out laughing: and when she had got its head down, and was Going to begin spun, was very provoking to find tht the hedgehog Fad wngolled ite, and sas in the act of erwling away: besides all ths, there was generaly a ridge or a fureow inthe way wherever she wanted tosend the hedgeiog to, and, as the doubled-up soldiers were always getting up and walking ff to other parts of the ground, Alice soon came fo the conclusion that it was a very dificult gamse indeed. Alice's Adventures in Wonderland Lewis Carol, 1865, Cleaning treatments used in conservation are, of course, no game ‘but many of the problems Alice has to cope with are analogous to the conservator’, Essentially, all cleaning might be described as. hitting away (using many different methods and on widely differing scales) unwanted material from an object that is often flawed and fragile. Although the reasons for cleaning can vary, ‘once the decision to clean has been taken, the conservator's problems are fundamentally ones of control I is here that this book (and the others in the series) will help you. By learning the scientific principles governing the cleaning methods you use, its possible to systematise and understand more fully what controls their effectiveness and applicability.cloning Irian "As with all the books in the series, this, the second of six, has been designed for conservators working om all kinds of material, and there is much scientific interrelation between many of the ‘methods used. Do remember, however, that this book is not Intended a¢ a conservation handbook or manual and will not help {you to solve all the ethical questions of whether or not to clea, ‘What itcan do, however, is to inform you of the possible risks and the extent of damage that might be caused through using one ‘method rather than another. ‘The Crafts Council and the team who have worked on these books hope that their publication will provide you with a useful scientific base whic will enable you to go on to read with some confidence the specialist papers and books on conservation which are already available, It is hoped, to, that the series as a whole will form & useful text for conservation courses, Using This Book [As the second book inthe series sasumed fom Chapter 1 ware that you will ave steady rend and become far wth the contents of Bok I, An Intaduction o Matra. This Ineans hat you will ow thiok of scence systematic and rvctred discipline and will have an understanding of base Shemingy. eis tsumed, therefore, that you wil be able to ead Chemical names, structural formula and chemical equations that ‘ou ate familar with atomle suture and chemical bonding, and otce how chemi stuctre rts to the physi and hes Droperisdiplayed by some common tattle wed r worked On by conservator Book 2 covers much ofthe scence involv ina wide variety of ceasing proedures, both nechanial and chemi. expe what holds drm pace and discusses, amongst other ting, the ‘ince underlying the properties of iguids andthe use of Solvents, finches on explanation of pi and inteduse he Schntic concepts of energy and colour Because these books have been specally prepared for practising conservator, some readers may nd that the order ‘ich Be stone in might varies quite considerably fom other Imote standard textbooks. Is especially important, therefore, that you read this book ints proper sequence. Remember that Books | and 2 wil not fra compete scene slabs in ‘hemslves: you wil eed to goon fo read Book 3 (where you wll lear far more about polymers) and the subsequent books before & Commpechersive plats but up Do not ty to read this bok to qulcly, often the since consis eke wich ake time to sb propery. Ask someone toh slentife traning to help you if ay part sil seme acu after several readings. Some simple demonsatons have been inched to istate cay certain points nthe text ‘evr slentife words and terme ate printed in bold type and are {cpus inthe outer angi for ary reference, Crom rlrencs Gre also made a certain points in the text where fr may be useful for you to refer back to a previous passage (ar to Book 1). A full index is included at the end of the book. Acknowledgements ‘This series is belag prepared by a team of conservation scientists, conservators ané sclence teachers. The Crafts Council is deeply frateful to the conservators and in particular the conservation Scientist, who, asthe joint author ofthis book has given an fenormous amount of her own time to its preparation over the last three years. The Council also wishes to acknowledge the generosity of the institutions and private workshops (in particular {he Victoria & Albert Museum and the Open University) who have lent their sapport through allowing ther staff to work with us, The contributions made to such a complex and difficult ‘educational taskchave been necessarily varied, but each has been Of great value ard importance. The Council is especially indebted fo Jonathan Ashley-Smaith for his contribution as scientific editor. (October 1982The nature of dirt A What dirt is and why you clean What holds dirt in place? Chemically bonded dirt Cleaning techniques vobThe nature of dirt ‘This chapter deals with some of the general features of dist and points to ome ofthe factor that need to be considered when carry {ng out cleaning in conservation work. Physical and chemical reasons for the adherence of dirt to objects are discussed and the buasie principles behind cleaning techniques are outlined. A What dirt is and why you clean Dirt can be defined as material which is inthe wrong place, rather asa weed is thought of asa plant growing in the wrong place. The evidence of blood on textiles oF the remains of food in a vessel may be considered “ire” on modern objects but may haveto be carefully preserved on arcient artefacts. As a conservator, you often need t0 beable to remove material which isin the vrong place (fora variety ‘of reasons) without removing material which is in the right place. ‘This process is frequently complicated by the fact thatthe substance of the object may be very similar to the dirt 'A major objective of all conservation treatment isto increase the chemical stability of the object being treated. Cleaning often cleaning forms an important part of the stabilizing process. This is because dirt on an object can be a potent source of deterioration (as, for ‘example, when chloride salts set up corrosion reactions on bronze, ‘or moulds grow on organic materials like paper or textiles). Atother times, cleaning may be a necessary preliminary to a further treat- ‘ment, as when preparing a surface before coating or joining, Inmany instances cleaning requires delicate judgement and experience on ee eeleaning foreign matter Product of alteration dust ‘the part ofthe conservator, In deciding what the Bnalappearance of the object being cleaned should be and how much “ditt” should be kept (patina, historical evidence, ete). It isn'teasy to choose clean ing method when you want to remove only part of the dit ‘tis helpful to begin by classifying dirt into two categories: Foreign matter which is not part of the original object. Examples: soot, grease, stains, adhesives and fillings from old repairs Products of alteration of the original material ofthe object. Examples: metal corrosion products, yellowed varnish, decayed timber or stone. ‘The scientific bass ofthis classification of dirt isto be seen in the distinction between physical mixtures and chemical compounds Skeroahgmdatpacnre = ag = 6 Sey repelae byte cog on the = pul push. Surtace melon fe dst pte = oat chang stenfor ene figuret.2 ind the + end of the dust ‘The attraction between the surface and the + he ds parce ie tongs than the repulsion Beween the ~ endand Firface because the + end is nearer. the dst moves tothe sure ond Sales Under te con ese 7 See Figure 12 ‘Once an lectcaly charged surface has ben produced tee i acy tevin ed moving not Ateneo thet by wiping st werk ce mor ined ae orcs the ate charge, The dust wl ump Sra tek onthe dst he changed sure, The ner arya atthe charge o I osble nt fo generate at al. To Sfrtand ths maser ou ned 0 Kw re sos he Sinan eral per of mae he onions i belng cer contucor or insulator, ere arc at meals conductlercy wile mos ober inter do no Tals observation son ofthe pies of evidence sae oe detaodcofstmic bonding ae based Inmcals some Sean thued among some andar realy abe fo move Shounen ae of Clecrons ‘conaites_ an electric cient. “Thoteonysolimaterial in which te electrons aeied up toone lon reesei thug onic o covalent tondig) doesnot allow is cep att of ceeons, As thesis no movement of cage. no Set beech miter li ee n istuors senor thconly agents by whichan lr charge ae aero. tns canals ary charge they are made fee Sere nas congregate ine cosa alll with + and ‘Sndsttermatigin the structure If sucha solid melted or dsolved The matoreof it conductors and insulatorslening earthed charges in a liquid, the ions are mobile and will therefore transport the charge with them, Gas molecules can also become ionized and com, duct current as, for instance, ina fluorescent light tube ‘When.a metal wire is connected across a batery the positive plate of the battery attracts electrons (being short of them) while the negative end is pumping excess electrons into the wire. The voltage of the battery indicates the strength of the force that pushes electrons through the wire. The battery is run down, or flat, when the excess and defi of electrons onthe negative and positive plates hhave been removed and a balance has been achieved. When you polish an object and generate static electricity you have effectively charged up a battery. The object forms ‘the equivalent ofa negative plate (with excess electrons) and the polish. {ng cloths the positive plate. What happens after you take the cloth away depends on what electrical connections are made with the charged object. Both insulators and conductors can become charged. If an in- sulator (a Perspex display case, for example) has been charged by polishing the charge will stay exactly where itis, However, ¢ metal ‘object similarly charged can redistribute the charge all over its sur- face by conduction, so the charges are as far from cach other as ‘pessble, The Earth is a good conductor, on the whole (having a lot Of solutions of ions on its surface). and so if the metal object is connected electrically to Farth the charge will disperse so thisly as fo be unnoticeable and the object is described as having been ccarthed. Where the metal is insulated from Earth the charge remains on the metal Though static charge on metal is easily diffused by conduction, ‘that on insulators isnot. The difficulty comes from the inability of the stale charge to move across the surface. This means thet edery Point of the object needs to be earthed, not just one. So, to be effective, a conductor has to cover the entire surface. Obviously, in the case of a Perspex display case, placing a sheet of metal over its entire surface isnot on, so another means of dispersing the static charge must be found. You are probably aware that static is less ofa problem in humid conditions. This is because a layer of water {if only one molecule thick) om a surface connecting it tothe earth is sufficient to conduct away the static charge. Although pure water is not good electrical ‘conductor, a thin layer of water exposed to the ar om one side and touching an object on the other will not be pure, and will contain enough ions to conduct away the offending charge C Chemically bonded dirt ‘The mechanisms of bonding between atoms to form molecules were dlealt with in detail in Book I (Chapter 4). Three main types were Sdentified, characterised by electrons being exchanged between atoms (lone) shared between wo atoms (covalent), or shared among Toms (mel) Collectively these are known as primary onde and al produce song forces holding stoms together to fo efocules or crystals, Chena reactions involve changes in the ras rina bonds etwecn tome However, tases hick ad lee tgs Thse feces led secondary Bond and teem pls, thy represent mich eke fre thn primary beds hese onde whch epi ow material Ck git without renting and n prs how i ks Sbjct, fou wl remeber th the demarcation between oni tnd and covakt bondele not sharp An parca, atoms sul mygen which veceive electrons in aking lnle bonds veil also fake covalent bonds in which they get the greater share of the Clcerons, The negative charge ofthe clctrone i displaced reltve Stn pte cng one mcs, he dso of hares the molecule i ot even, Most kings of secondary bonds have tie triginin uneven charge distibtion Gece Figure 1.3. The aostve and negative charge dismbution on an electric pole Yoo wllsce ta the imbalance of hag shown inthis dlagram as5* and 5~. The Greek letter deta, 5, is conventionally used to ‘denote “a litle bi, im this ease rather less than a whole electron’s- worth of charge. Molecules charged like this are known as electric dipoles (di=two, poles=ends}. A substance is called polar if its molecules aredizoles and non-polar if they are not. Dipolar molecules Dbehave rather like bar magnets, unlike ends sticking together in patterned arrays, as shown in Figure 1.4 — a —— a) = + —— a) —=" + Figure 14 An ary fino moles iasrating schematic the Sisibuineofpecive ae negate chore Book “his arrangement i similar to thos of lone crystal (se Boo Chapter 4) wher the charge involved has the strength of atleast one The natur of de primary bonds secondary bonds dipolesleaning polar and non-polar ‘materials hydrogen bonding ‘whole electron and the shapes of the ions allow ght packing. The electrostatic forces in onic crystals can thus be very strong. Dipolar molecules, on the other hand, with a smaller charge which is often, ‘onan irregular shape, can interact only weakly. This weak attraction is present in the solid, liquid and gaseous states and is one of the cauises of the noticeable differences between polar and non-polar materials 2 Hydrogen bonds {A stronger type of dipole bond occurs when the atom from which ‘oxygen Is drawing electrons isa hydrogen atom, Water isthe classic ‘ase. The hydrogen atoms are slightly positive and are therefore attracted by the negative charge on the oxygen atoms in neighbour- Ing molecules. The molecules tend to forma regular array (Figure 1.3) Figure 1.6 Jn which some of the O-H bonds are strong and some weaker, and the hydrogen atoms become like bridges between the oxygen atoms When hydrogen atoms make bridges in this way it is called hydrogen bonding. Hydrogen bonding is common (because water 's common) and accounts for a host of phenomena of importance in conservation, which will be dealt with in this book and in Book 3. ‘Thus, for example, cellulose bres in cotton and linen textiles and in wood are very strong. This is because there are hydrogen bonds between the many “OH groups on the cellulose molecules. (See Book 1, Chapter 4 for the structure of cellulose.) 3 Van der Waals bonds ‘The final, and weakest, type of secondary bond to be discussed here was frst explained by the scientist Van der Waals. When two atoms are close together there are three sets of electrostatic forces acting! Figure 1.6 There are atwacuive forces benwoen th postive and negative 27068 ofthese to ator. 7 he postive nuclei repel one another. «+ ‘The two clouds of electrons repel one another. + Bach nucleus cttracts the electrons of the other atom, Figure 1.2 showsd how an imbalance of charge was induced in a particle of dust, causing It to be attracted to 2 charged surface. The [orces acting onthe electron cloud of one atom tend to distort itand fo induce an imbalance of eharge (dipole) inthe atom, if only for a Short time. Such dipoles are constantly appearing and disappearing but there is an overall attractive force between the induced dipoles. ‘This means that there is a weak attractive force acting between ail atoms and moleceles at all times, The emphasised words are really all {you need to know about Van der Waals forces. It is important Bhat these forces act between all atoms because this means that ‘molecules will stick together, even when there are no attractive forces due to permanent charge separation in the molecules them selves. For exanple, paraffin wax is held together by these forces fand many thing will in turn stick to wax. AS wax will stick on the ‘surface of objects, dust sticks in the wax producing typical “Toreign matter” dirt, Chapter 3 shows just how solvents work in terms of these forces. The slippery nature of most waxes shows that their ‘molecules are not held together strongly, in contrast with erystalline solids like sugar hydrogen bonded) and sal (ionic bonds) where the electrostatic forces are much stronger. Generally speaking, dict is held to the surface of objects by one or other of these secondary bonds. The problems of cleaning can be ‘usefully looked at as comparisons ofthe strength of the adhesion of the dirt to the otject and the cohesion ofthe molecules ofthe object, to one another. Obviously dirt weakly stuck to a strong object is going to be easyto clean off without damaging the object (unless the ‘Object is porous and dirt is trapped in pores and crevices), while dirt firmly stuck to a weak object presents difficult problems. In other ‘words, as you will know from practical experience, when cleaning an abject you have to consider not only the dirt you want to remove but also the material you want to take It from, Where the bondings are similar the task is awkward, and where the forces of adhesion are stronger than those of cohesion the problem is dificult. D Cleaning techniques Tei because theres so much variety inthe combinations of adhesion tnd cohesion oft objects and cleaning solutions that its necess- ary for you tows widely vared techniques. A method has to be hsen 3p that you can stack the dirt without tacking the object. Sometnesmectanical methods canbe used, mechanical force bing toed to break the bond between the drt and the objec, In & he natn of van der Waals forces adhesion and cohesion »leaning mechanical cleaning. techniques shipyard, for example, a pneumatic hammer might be used to removerust. This quite obviously constitutes a brutal attack (though ln this case, justified by the scale of the job), However all the other, far more geatle approaches to breaking the bonds between dirt and ‘object can also be looked upon as some kind of hammering, and doing so brings out some common features of cleaning techniques and especially highlights the inevitability of damage during clean- ing. A dirty object is one on to which extra material has moved; cleaning is the business of re-moving that extra material, One class of cleaning techniques, those called mechanical, have in common the method of getting the dirt to move. All involve arranging @ collision between the dirt and some material abject. As an analogy think of sculptor who uses a variety of tools to remove the superfluous stone (dirt) to reveal the desired form (object), Points and chisels of increasing fineness are made to collide withthe surface and itis hoped that, with each blow, nothing more than the unwan- ted material will be struck aff. When cleaning an abject consider the following questions. Can you arrange only to hit the dirt? Answer ~ no. Will hitting the object damage it? Answer yes. Will the dirt part from the object cleanly? Answer ~ maybe, Where will the dirt {0 to? Answer ~ back on to the object unless you collect it Chemical cleaning is not exempt from the hammering analogy. ta Book I you learnt how chemical bonds are broken by impacts from adjacent molecules. At ordinary temperatures the velocities of ‘molecules are of the order of several thousands of kilometres per hour. Any solventor reactant you puton an object and its dirt causes chemical collisions with both, and although the dirt may come off {you can guarantee that some traces of the chemical you have used will have worked their way into the object. Again, minute damage ~ butt is there. The useful thing about using chemical collisions is that they can be chosen to be highly selective; you can arrange todo far greater damage to the dirt than to the object, provided you know enough chemistry to make a wise choise of cleaning substance. It should be obvious that gentleness does not so much prevent damage as render it invisible. Damage, to some degree, occurs what ever method is used,Mechanical cleaning A Review of mechanical cleaning techniques Al Dusting and polishing A2__ Picking methods for removing solid layers 3 Abrasive methods Ad Vibrations Energy: familiar word ~ new conceptMechanical cleaning Inthe last chapter we looked atthe nature of dirt and the ways itcan auhere toan object. This chapter eoncentiates on the science affect- ing the various forms of mechanical cleaning which conservators lise. The concept of energy as it relates to mechanical cleaning processes is introduced, A Review of mechanical cleaning techniques ‘All the cleaning techniques termed "mechanical" involve arranging ‘collision between the dirt and some material object. The purpose Of the collision isto produce a force which will (a) break the contact between dire and object and (b) move the dirt away from the object. ‘You have to try and ensure that the break occurs at the interface betwreen object ind dirt and thatthe method you use to produce this break actually its the dirt and not the object. Both these problems are essentially ones of contro. ‘Mechanical deaning, merely breaking the adhesion of the diet and moving itaway, contrasts with chemical cleaning, accomplished cither by dissolving the dirt (see Chapters 4 and 5) or by causing Something to react with it (Chapter 7). Mechanical cleaning methods have certain advantages forthe object since nothing isadded during them that might cause further deterioration, such as solvents carry ing the dirt furtner into porous materials, or water causing swelling in hygroscopic jwater-attracting) materials or starting corrosion inleaning Py safety energy ‘cals, Similarly, for the conservator there Isao Involvement with toxic chemicals. You must note, however, that virtually all mechan- ical cleaning processes require protection for the eyes, skin and lungs of the operator. You should take care to consult safety manuals and the instructions for the use of equipment before undertaking ‘work of this kind, ‘Questions that must be answered when choosing a mechanical cleaning method are *+ How firm is the adhesion between diet and object? + Isthe dirt brittle (easly fractured) or tough (resistant to fracture)? + What are the mechanical properties ofthe object? So complex are the interrelations of these factors, even within a single object, that specific guidance is dificult and would be out of| place ina book like this. What can be done is to show the influence ‘of general scientific factors upon each treatment as it is reviewed. Another scientific idea needs to be introduced. This is the concept of energy which is sometimes defined as the ability to do work; the “work’” of interest here being mechanical cleaning. AL Dusting and polishing Dustis dire which has notcohered toftselfnor adhered very strongly to the object. Itcan therefore easily be moved with cloth ora brush ‘ora feather duster, Delicate and gentle the process may be, but you ‘cannot ensure that only the dust is moved, Threads or feathers pulling at flakes on the surface of an object can move these too and YYou may have seen fragments of cloth or feathers caught in cracks 'n objects. Those fragments of torn off duster represent a gamble ‘being taken ~ that the feathers will break before the object docs Also, once you have moved the dust, where does it go to? A vacuum cleaner is another kind of duster. At least it has the advantage that most of the dust shifted off the objects is contained in the bag. Vacuum cleaners move dust by causing a rush of air through and past the object being cleaned. A stream of air molecules strikes the dust and makes it move ~ together perhaps with loose parts ofthe object. One snag is that the amount of suction provided by a machine is largely pre-determined by the manufacturer, You ‘an exert some control on how much air goes through or past the object by using different attachments or by holding the nozzle closet to or more distant from the object. The wind speed can also be controlled by the size ofthe nozale, narrow ones producing a higher speed flow. When dirt has been put in motion, damage may be caused for cother reasons. Ifthe dust is harder than the material of the object itself, it may, once moving, scratch or cut into the object's surface Grit causes damage when it s moving. This is why the sharp sandy rr : en with Jon from peopl s shoes must be removed from carpets B tagger olber protective material on top, the grinding ston of {.tkig can case damage which can be measired by stable est Wiipmeat Te cleaning proces also docs damage, bot os lesser ent . Polishing is another common treatnent for certain objets. ugh sparing glass and glossy furniture may be pleasing to ook saoet ing ea rue hare toe object: Thee ae tes Pose fessons for ths 1 Abrasion The frst problem with polishing s abrasion scratching). The cause isthe same as itis whem dusting hard particles onthe move will ot int soft surfces, Some polishes for example those for glas snd ‘petal deliberately contain abrasive particles, the intention beng 0 fut away thin fms of wel-bonded Girt or tarnish, Inevitably sich f deaning compound will produce microscope scratches on the Surface ofthe oject too If such compounds are used with ere and Enowiedge, a minimal level of abrasion may be considered accept tole in some caes, Much worse, howeves, is damage eased by foreign particles of larger siz which may find their way om o your polishing cloth, There ls only one way to avoid thls scrupulous Steanliness ofthe objec, the cloth and the polish 2 stati electri Fricton asa cus of sat etic wae dterbed the previous Chapter (Section BY, Bren the ton of dusting may be cng fo trea surface trac st again but pling ave sient, fan ccctrcaly charged sufae wil aac dst, which canon be teped avy. Hess the additonal icon reinforce the static “hurge;sctod, he dase wl ump straight back fom your duster tout charged sje The cut mus be Sought in geting ed of the Charge or ever generating tn the Sit pace. here re several vray of doing ae remember, + Conducting the charge away directly. As you will r this is difficult to do on an insulator since every point on the surface needsto be connected to the earth and this isnot possible, In practice, with wood, glass or plastic ‘Conducting the charge away indirectly by providing charged fons over the whole srfae, Watet molecules wild this i the ‘humidity of te room is raised, dspersing the charge aay from the surface. he fons left behind by anttatie polishes may also help by atrasting water molecles to the surace ofthe objet. The cnge or ans can enero condutedsay by charged lone in thes. These cn be generated in sever ways. ‘ite violet igh wil nize the ara the one wl be ataced tov surface with the opposite charge, but ofcourse even sal Gants of ultra-violet ght are not wanted where organic Mechanica ening abrasion static chargeeoning materials are on display, because of the deterioration Ht uses Commercially available electrostatic “guns” produce. charged fons and are sometimes effective at neutralising the state beta, up. *+ Never generating the charge in the first place. This ideal can be partially achieved by using a vacuum cleaner instead cf 5 luster (¢he alr fiction is tess than cloth friction although some satic may sil be created) or by using a polish which ederes te friction ofthe dusting. All polishes, however, have the disadvan tages described below. 3 Wax polishes ‘The many proprietary waxes and polishes for furniture, glas, et. all give their effect of glossiness by leaving avery this ies ata greasy substance on the surface (however subile a “blend at Silicones and natural products the container proclaims) Aull appearance is caused by surface irregularities too fine for the naleed Ye to see, which scatter the light in all directions s0 that no close reflected image is seen, Polishes ill n the minute dents and sesgcnog {2 produce the desired smooth finish, which reflects the light Luiformly. As wellas looking good, a waxed object may be protecced somewhat from moisture, which could be beneficul, Howena, waxing has the disadvantage of making surfaces sticky and stron, {ive to dust. Moreover, unless the polish is specially formulated tor gnitstatic properties, he surface wil be electrically inulating fd leather tends to produce the same qualities and consequences, You may eventually need to use a solvent to remove dirt stuck on by the gris from polishes, soit is worth thinking ereully about the pote and cons of any treatment of this kind which may encourage tore aire to stile A2 Picking methods for removing solid layers This form of mechanical cleaning exploits the diference in physical Bropertcs between the dit, whether corrosion or deposited layer, and the object, Its most often used to breakup a hard, britle cece Piece by piece, and remove it from the surface ofthe object. Spliting Off corrosion layers with scalpels, needles and dental picks aed Pinging and picking pinging or picking off small Aakes is a method otied weed oe Porous corrosion layers. On dense compacted layers the point of the tool should be held vertical and close to the edge of the corrosion layer so that only e small pieceis broken offatatime, Trying tobreah ‘off to0 much at once may break the abject aswell, Figure 2.1 shows what you are trying to achieve, First the blade oF needle has to fracture the layer through the thickness of te Corrosion, then the plane of fracture needs to turn suddenly and proceed along the interface between “int” and object. Mechanica leaning bade it biest in of racture intend Figure 2.1. The desired pracedire for removing hard biti crust fom Snobject a smal piece at tine through the thickness onside fst ihe action of making crack throug thee spel eid gh make onitpresion inte sri f the layer. Figure 22) shoves hs condition. Blox Figure 2.23 cracks J queston ow what wil happen the ot ofthe shed sued tol est ape ifr, The arr depen html propa he mel tino ee Sanne bt nigh sc ll Meth vids wnt the merlace wth eo scalps eke ck the object before the erack runs on, eatsing damage tothe objec sel Tannin mcteiore a ee St reasonable thickness - you cannot “ping” the silver sulphide rah ay tem a an etl er 112 iethin Wow te ech wo un abe fhe Bade What should happen is usrated in Figure 22 (below Boos fracture toughness tk Jape Figure 2.2 amleaning shear How can you divert the crack? Because the Tool ls wedge-shaped ‘twill be pushing on the sides of the crack as you press down: load ‘ace moving soopar sonays thrust Figure 2.26 The force sticking the dit onto the object must be overcome by the sideways thrust from the wedge. Clearly the total force needed to push the chip of dirt sideways (to shear it) depends on the strength of the bonding and on the area ofthe chip. Ths is why you ‘must always go for a small chip, where the total force needed will be small, ‘Taking small chips ensures that dirt shears off before the frst crack gets a chance to run past the interface and into the object: ‘ck may spread Soc ehipoes ots oft Figure 224 Scientific understanding of mechanical processes such as the one just described depends on careful distinction between several ‘mechanical qualities ~ toughness contrasted with brittleness; strength versus weakness; hardness compared with softness. These ‘matters will be taken up in some detail in Book 3. A3 Abrasive methods ‘Abrasion consists of cutting away a deposit as opposed to the previous method (snapping it off}. Very small fragments of material are cut away and the attack is mounted by many cutting edges simultaneously. The tools come in several guses and range from Big and rough to litle and gentle: Eels rane cindng whos ———) dont dil Wie ich ee) sis fre brushes oe coorse grinding pastes mmm wos rouge, polishes enc r “Fhe cating edges, a5 you see, are frequently hard, sharp, gritty es which may be fixed to a rotating disc, glued to paper or Pith, used as ashiry or carried in a blast of air. On impact with dirt sCobject, indiscriminately, the sharp edges hack away a tiny frag- rent of the target. The method involves problems of control ~ itis ‘ery important to decide where to stop, especially when the surface Srthe object is easly abraded. ‘There isa critical difference between scratching and polishing in the mind ofthe conservator, the curator and indeed any other obser- ‘yer, but there sno scientific distinction between them, In the end the difference comes down tothe size ofthe scratches ~on a polished ‘bject they are too fine to be scen. Working with abrasive methods thus requires us to consider the factors which decide whether the tbject i in danger of being “seratched”in the final stages of clean Sng. The relative hardness of the abrasive grit and the object is one factor. Hardness is compared by determining what will scratch ‘whats ifthe grits les hard than the object then it eannot scratch it. But the object may not be uniformly hard and the abrasive may be vatiable, 100, Also, it isthe hardness of the crust that is important ‘until you get through it and contact the surface ofthe object. Ifthe ‘crust is softer than the object, there is no danger, but corrosion layers and deposits can be very hard. Consequently abrasive grits are chosen for thelr hardness; examples are sand, carborundum and. fluminium oxide, Another factor is the size of the particles of abrasive. Often the same abrasive can be obtained in different sizes of particles, the coarser for preliminary cutting work, the finer for finishing and polishing. Heat results from friction between surfaces during abrasive processes. Water, solvents and oils are sometimes Used to remove this heat and to prevent damage. These liquids carry away loose particles of abrasive which would otherwise clog the ‘wheel or paper, or stick in the surface causing scratching. Liquids ‘an also act as lubricants, lessening the effect of the abrasive part lcles, (You can demonstrate this by experimenting on scrap pieces of| ‘metal with the same abrasive used wet and dry.) Remember though ‘that water, solvents or olls will have other effects on the object and. that it may not be safe to leave them behind; they themselves may have to be cleaned off. “Abrasion by rubbers (erasers) or rubber powder in cleaning paper ‘objects is rather different process which is used to remove relative Iy loosely held dirt. The stickiness of the rubber picks up and holds ‘the dislodged particles, preventing them sticking back onto the surface again, Some erasers contain an additional abrasive, to make them more effective in removing ink, but these are usually too rough for conservation use, where original ink and pigment are to be left untouched, Aa Vibrations ‘Another way of dislodging unwanted particles of dirt or corrosion {sto use a vibrating tool to break up a dirt layer. Electrical pulses are ‘used in some commercially available tools to produce vibrations in lubricants Mechanical cloning aleaning ultrasonic cleaning points (needles ete) of different sizes for cleaning and engraving These tools are essentially automatic versions of the hand-held needle used for picking. It is necessary to be careful thatthe object doesnot itself get vibrated so much that damage i caused and to top at cleaning and not start engraving. Ultrasonic cleaning also uses vibration, The vibration is produced electrically in specially made crystals (in the transducer) Andis transmiteed through metal plats to the liquid in the cleaning bath. This is usually water but organic solvents may be used. Sound ‘waves are carried by the alternate compression and expansion ofthe liguid. If this alternation is rapid enough, the intense waves of vibration travelling through the liquid tear hols init. Cavities of ‘vapour appear and collapse at ultrasonic frequency-a phenomenon known as cavitation. These “ultrasonic bubbles” have a brushing Action om the surface ofan object placed in the tank because as the bubbles collapse, the liquid, locally, moves very fast. The process can be thought of as abrasion with molecule-sized grit, uitrascnic leaning fank ‘abject in beaker ‘eareng solution transcucer hgh trequency generator sna BedK — SOME Figure 2.3. Diagram of an utrasome tank Ultrasonic equipment can be used to clean otherwise inaccessible places, for example inside narrow-mouthed vessels, The method has been used by conservators on metal objects and on stained glass but should not be used where there is loose, flaking decoration which aight also become detached with the dirt. 1¢ will not remove dirt ‘which isanchored tothe surface with grease unless solvent or deter- {gentis used in the bath. Ultrasound is not effective for cleaning lead, Decause the metal isso soft and malleable that it “soaks up” the vibrations. This indicates again, as with other mechanical cleaning treatments, that the physical properties of the original object are as important as those of the dirt layer. The equipment used by dentists to descale teeth is also used in conservation, This has an ultrasonic vibrating head immersed ina spray of water which flows round and. ‘through it. The vibration is transmitted into the water layer creating ‘movement, vibration and cavitation, and thus cleaning the surface, B Energy: familiar word ~ new concept concentted mainly on descriptions of what mater. The texaugwchiseen mee al telmindec no oe hinge change, Sclestas communicate tel ess su say te or stablity “which the lk of change ~ by wing the cae ofenergy ou ned ern whet cents mest by ene Ssishoethertnerpngasonpoesboatitae tain to! arnt how they esebe what ching ar in atom terms yorpere isan everyday usage ofthe word energy, asin “an energetic enon’ which sontabe tesence ofthe teetifemesnng for ora person ts things done Slay the hea tha is MGhonp of eng betncen mater which ie change, Incident ST oedy othe relationship between energy ~eapecllly est 2 dimer Walled thermodyoamis You kw tht by buying iN commodities cosh peo, cls you ae efectivly ayig energy tomake use fit However younceds device wich, ty precasing the Tel "gets things done”, And you hnow that Oy neegiced wo cre change’ fo make hinge ove ort mae ‘Tid Wl Aj uch telly wate be mo dutrencwaye~tsing gu cece or wood fire Moving» fan be done by aeopl, horses, steam engines or diese lores The She oprequcthe sme amunt of encgy but thee are erent Saye ofgengt doe, Enryexpteses te possi of what ware done Seen In this ay 4 something which i need, ple convened used n'a acts af eet energy ak tauely al that fila currency money To help yout set ow th vues for using the energy dea ake sense, may belp {rw an angy betwen wonsedons wi ooey and henge in nergy Mone flow in smal busines Imegie you are unnnga sal busines sich a» commer Conterebon wh Ea eens acethta eae Mechanical eoing ‘thermodynamics 3Chaning “he iogram shows the How of goods, services and sills mand out ofthe workshop. The signicae thing heres tha theres no vray of comparing one item with another. To make obserestions prckictions about the sucess of the Busines the afferent factors ust be measured, and measred in unis that canbe compared. A lige of solvent, an hour of work, a cuble foot ef os, ceanot be compared Bt ee cnt the Hows of matey tie snd Services are costed then the consequence of changing te input of neo them can beestinuted. A sect dagram can be dren hich Includes this factor: ferme yey woristoo iin AND MATERIALS. umumes PENT STAFFTRAINING Beer ai (OTHER STAFF Paes lasso tireens Once al the facets ofthe business have been expressed in money terms, a simple rule governs the suctess ofthe enterprise: icone (ineluing profits) mus equal expendi “The diagram shows tht thre sre many more ways for money to flow out ofthe business than fori to come In Since the incoming money comes at intervals rater than as a continous How, the suggested rule doesnt allow any expenditure except immediate after Income has arrived. A ble store of money le needes where Toney can accumulate to be spent. By rranglog for ‘ma businesses to use the same store a bank ~expenitare ca, tem poral cren bellowed enced nee dere om wk one, This effcively maintains the ul of income equals exponditare providing another source of income, a bank loan. 7 ‘Money as an analogy to energy First, notice that money can be used asa measure for many different things ~a worker's time, a quantity of chemicals, an advertisement {a journal or being connected to the water supply. As transactions dreimade, what tie money represents changes its form. Energy too has May forms; some chemical fuels and electricity have been men- oned already; Feat and light ae further examples. Matter in order- Jy motion, such a the wind or a lowing stream is a form of energy iis matter in astate of stress —a compressed spring or a stretched Tubber band, Just as economists see the interdependence of human {etivities as represented by flows of money, o scientists see events {nthe physical world as flows of energy. Consider again the propags- ack a a chip of crusty diet Is pinged away: tion of a ‘Stage 1 Chemical energy in your body is converted into the force you exert oma scalpel blade which moves into the encrusta- Stage 2 As the blade is pushed down, a notch is formed. Material at the root of the noteh is stretched — atomic bonds acting like litte springs have energy put into them. Materialat the sides ofthe blade is compressed ~ springs in another con- dition. Stage 3 The crack runs on, two fresh surfaces are created ~ stretch Ing energy is converted into surface energy (because the atoms atthe surface do not have all their bonding requlre~ ments satisfied), Stage 4 When the crack i complete, the compression energy’ becomes energy of motion as the compressed material makes she chip spring away from the blade. Several kinds of energy are brought into this description. Energy is sald to be “converted” from one form to another rather as cash from the bank is “converted” to2 litre of solvent, which is “converted” intoa completed job. Notice thatat stage 2 above some ofthe material ‘was compressed and some stretched (Figure 2.6}. both being force stretched Figure 26 Conpressing ant stratcning forces caused by 2 biode beWng pushed down inte materal represented as a matter with energy put Into it. The stretching ‘nergy was immediately converted but the compression energy was held until ater, when the crack was complete, when itmade the chip fly off. Here is the energy equivalent of the bank - a way of storing Mechanic leaning forms of energy energy conversioncling Principle of the Conservation of Energy kinetic energy potential energy friction nergy pending ater event. A Fal seven more like the bank, for ‘what sored ean be spent in many waysat chosen ines by anyone tho can get access fo t= for example va a cheque book for money ffom the bank, or vn an engin for energy fom fuel The rule for spending energy i the same at that for money: Income must equa expenditure In other words, I'youaddupall he nergy pt nt an event and ll the energy present atthe end of the ven he sums must be equal, You maybe amused to learn that his ‘ules knownas the Prinelple of the Conservation of Energy and this i the it lw of thermodynamics A dlecgson ofthe units that are sed to measute and compare ciferent types of energy (2 jqantiive weatment) i not necesary Bere but iis uefa the Stage to make qualitative distinedons between various forts of nergy. You saw that when achip of encrusted dit is eemovea, ventally the chip caries away energy because of ts movement. ‘This is known as kinetic energy. The amount of kinetic nergy porscied by » body in motion depends omits ase a well as upon fs speed, The other forms of energy in the example are not cou- taected with motion, The energy hed by stretched or compressed ‘aterialis du instead tothe ative postions of particle of ate, Allsich kinds ofenergy are known as potental energy. Potential (capable of coming int action) implies that motion could reul from this enesgy fa tllable mechanism existed, Thus the potential nergy duet compression of material atthe sides of sealpelsotch cull only he converted nto kate anergy when the rack ad ‘tended sl sound the hip. Simlany a as chemical potential ergy ~only convrible to kinetic energy bya mechanism such as snengine ‘Ancther example you bave met is poten energy due tothe Justposion of two elect charges If the bodies Carying the Charges cin move, the potential energy will be converted into Kinet ie energy~thus dust moves on to showease. Gravity provides the ‘ost falar example of potenal energy. An objet alin under aravity Is gaining Kinetc energy as it acclerates towards the round, Ihas potential energy de tots poston in the gravitational tractive region around Barth Ths decreases as ts kinetic energy increases ‘The examples jst etd all show potential energy turning into netic energy se coon ait ible, It opis fo look aifatendency towards lowe potential energy is what sakes things happen, ln he world of mater on 4 much ager sce than atoms thi tr, but 2 you wil ce in Chapter 3 there ate complications for systems here he nteractions a individal atoms and molecules are impor. tant, for example, in chem reactions. “The begining ofthese complications comes when you think what happens so often to Lneic energy. Moving tings generally slow down, becuse of fiction (resistance tothe movement) and this fection generates het to expres this energy conversion You would say “Lines energy bosoms best energy va the action of tion’ However ax you wil member from Book (Chapter 2) the base ‘Square of what we cal heat must be described at the evel of atoms nd molecules, for heat is the kinetic energy oftheir random move ‘nent. You will remember that atoms and molecules are described as Deing in constant agitation, with collisions among them being the brigin of chemical change. There is thus another tendency, which is forthe orderly motion of larger things to become the random ‘motion of atom ‘Matter may pessess energy either by virtue of motion or position, cach of which may be orderly or random. These distinctions have a {great deal to do with whether the matters energy can be converted ‘fom one form toanother. Observation has shown that there isa limit tw the proportion of random energy (heat) which can be converted {into ally orderly form of energy, The Second Law of Thermo- dynamics expresses this limitation. The money equivalent is {anation, You would generally prefer the whole income of your workshop to be entirely your own wages. The conversion desired is completed work personal income ‘expressed in themedium of money. It would be nice ithe efficiency ‘of the conversion could be 100%, But you know it cannot be. Figure 2.4 showed how many are the drains on money. Income has 10 be Speat to achieve the job and some is even wasted, as far as the business is concerned, on taxes. Indeed, some of these unwanted expenditures (tases, rates, interest) have priority claim on the werk ‘shop's income. 'So with energy; when a machine is arranged to convert heat ‘energy into another form, the conversion cannot be 100% efficient. ‘There is an enormous "tax" on such a conversion. Even conversions where heats notthe source cannot be perfectly efficent. In cleaning the concern is that energy flows from the tool to the dirt and not into the object, Control of energy flows is therefore important. By and large contro is eisier ifthe rat of energy conversion is low, that is, if the process is gentle. The amount of energy that changes form every second Is known as the power of the process and fs measured in watts, This is a famillar measure of power? most clectrical apparafus caries a label indicating its power in watts. For ‘comparison a running man generates about 500 watts. When you see [power ratings on a power tool in the range of several hundreds of ‘watts and compare the delicacy of manual cleaning with the act of running, you should realise that using power-tools requires the ‘control ofa lot of encrgy per second. Where does ital go? Consider airbrasion as an example. The following diagram shows many of the rov'es for energy flow. Some of the observable results are what was intended, some are unimportant losses (wasted, but not Iharmful) but sore must involve damage to the object. The point is ‘that complex energy analysis can provide an assessment ofa method ‘without resort tral and, perhaps, error, once you understand the [Process of conversion and the losses involved, Mecanialcleaning Theat orderly and random Second Law of ‘Thermodynamics power wattsCloning ELECTRICAL POWER INPUT octal eneray losses NG Ssheat and ound LOSSES triton heating, lurbulenee sound SPSS ANBAR | ‘Muci oF THe ae SANDavAgT Misses seboeiect Figure 2.7. A very simplified representation of arévaswe equipment showing possible energy loses. “The main virtue ofthe range of mechanical techniques for clean ing is that the task of separating dirt from object is closely under {your control, as the operator, so that with skill, experience and care, you can make the energy flow where itis needed and make safe judgements about the amount of power to useLiquids and solutions A Properties of liquids AL Viscosity A2_ Capillarity and surface tension A3 Volatility and drying Describing solutions Bl What a solution is B2_ Measuring concentration B3- Solubility The science of solutions C1 Making a solution C2 Energy changes in solutionsLiquids and solutions “This chapter considers the nature of liquids and solutions, deserib- ing how and why they are formed and showing bow this depends upon the seconlary bonds which exist between molecules. From this, you will surt to see which liquids ae likely to dissolve which substances, The concept of energy, introduced in the ast chapter, {s expanded to explain its role in the formation of solutions A Properties of liquids ‘What are the properties of aliquid which are important in determin- {ng whether i issuitable fr a particular cleaning job? Here are some, although you my be able to think of others. + Will the liquid dissolve the dirt? + Will it damage the object by reacting with it? + Is the liquid runny enough to penetrate as required or sticky enough to stay where itis needed? Isthe liquid volatile enough to dry offatareasonable temperature cor is it so volitile that the dir will be redeposited during clean- ing? ‘Are the fumes from the liquid toxic andjor flammable? ‘The first two questions are obviously very important but to answer all these questicas you need to know something about the properties ‘common to liquids. A substance is recognised as being liquid by its ability to flow (this was discussed briefly in Book 1 in Chapters 2and 4), However, a definition of the liquid statealso needs some commentleaning capillarity ‘on the formation ofa surface, since having a recognisable surface is ‘what distinguishes liquids from gases, which als flow. The chemical properties which will tell you which liquid will dissolve which substance, and the physial properties, such as viscosity and volatil- ity, can be qualitatively understood in terms of secondary bonding forces between molecules, Al Viscosity 4 liquid that is relatively immobile (not “runny”) is said to be viscous. Viscosity Is the scientific measure of a liquid’s mobility and is an important property to consider when using liquids for ‘To explain the flow properties of liquids it is necessary to visualise liquids at a molecular level. low implies that molecules are able to move part cach other easily. Molecules wihich are attracted to one another by the stronger secondary bonds will form viscous liquids. The hydrogen bonding between water molecules means that water flows less easly than, say, ether, acetone or hexane which, although their molecules are bigger and heavier, possess only weak Secondary bonds between theie molecules. Concentrated acids (such as glacial acetic aid) are notably viscous because of their hydrogen. bonding. Liquids containing long molecules which get entangled swith one another also have high viscosities. This is why lubricating oils (with chains of 16-20 carbon atoms) are more viscous than their losely related hydrocarbon solvents (such as hexane which is only ‘i carbon atoms long). ‘Sometimes it is necessary to control viscosity. If you want to Increase the viscosity ofa liquid, something must be dissolved in it which may use either, or both, ofthe properties mentioned above. Methoxy cellulose which has long molecules and the potential for hydrogen bonding is a common additive used to make a solvent less mobile. For example, itisadded tothe very mobile active ingredient, dichloromethane, CHCl, to make paint Stripper. “Temperature also affects viscosity. Liquids become less viscous as the temperature rises; animal size is an example where this is quite marked. A great change in viscosity occurs when a solid melts and turns into a liquid. The same forces of attraction which held the smoleciles in place in the solid are stil there in the liquid, because in changing from solid to liquid state there are relatively slight changes in the separation of the molecules. However, if you were to visualise the behaviour of one particular molecule ina liquid, you ‘would see it changing its loosely bonded association from one neigh bour to another and then another. This contrasts with the solid state in which atoms or molecules only rarely change their relative positions (sve for their constant vibration), The effect of increased ‘molecular motion produces lower viscosity. A2 Capillarity and surface tension Liquids are drawn spontaneously into very fine tubes or pores. This blotting paper” effect is known as capillarity and is important in Gomvervation in many ways. For example, itis used in Blotting up Iiquids such as water or molten wax. In cleaning it transports sol- tents to inaccessible dirt in fine erevices or pores and carries dirty ‘Solvent off surfaces to which poultices have been applied It can also det destructively; ifit carres water into cracks in objectsitmay help to cause corrosion or, if it freezes, the water will expand and cause stresses which break the object "To explain capllarity you have to think ofthe forces between the ‘wo different kinds of molecules ~ those in the liquid and those in the material ofthe tube or pore. There are attractive forces between {ll molecules; theimportant question is, which onesare the stronger phe cohesive forces between the molecules of liquid or the adhesive forces between the molecules in the liquid and those in the solid? ‘The balance between these forces determines whether the liquids twill be drawn up a fine tube and what the shape of the curved Surface (called a meniscus) will be where the liquid touches a solid. ‘There are two cases a b gud Suid Where there 's a strong attraction between the liquid and the soli, the liquid climbs up the sold’s surface as in (a). Where the balance lies the other way, and the cohesive forces are strong but the adhesive forces weak, the liquid pulls in towards itself asin (b). Strong capillaity is to be expected with polar liquids which, although they cohere strongly, may offer a mechanism for strong intermolecular forces from solid to liquid. If the solid can offer hydrogen bonds to a polar liquid (for example water) there will be absorption, Suca materials (for example, cotton, wood and proteinaceous materials) are hydrophilic which means water loving, Greasy surfaces repel water and are termed hydrophobic or ‘water-hating, Asthey cannot make hydrogen bonds with grease the Water molecules cohere together. Most natural waterproofing mnethods (such as those of furs and feathers) depend on coatings of [grease; coatings of non-polar molecules like paints and varnishes hhave a similar waterproofing effect. ‘You will often have noticed droplets sitting on fibres failing to wet them or pexetrate. This condition, which obviously prevents cleaning, comes about because the forces of cohesion between the ‘water molecules are stronger than the forces of adhesion between ‘water molecules and fibre molecules. The role of soaps and deter- ents as additives to water isto ensure that the forces at the surfaces ‘where solid and liquld meet are better matched (hence their general name of surfactants, meaning that they act on the surface), igus ad solos bhydrophi and hydrophobic materials surfactantstani ‘surface tension volatility Desens af thse ccs are oe given Tn terms af wurtace tension for soneimes surface ene) Catesve forces in gud have the effet of paling is moles as cls to one snot posible. Fora smal qusnty of lid this tendency wil produce 2 spherical drop, since this shape every molecule Was cle toa {he other aston be. This shape sso has the smallest sate aes fora given volume. Imagine the liga surrounded by 1 seetched skin plling Wt ito shape, rahe ite guid at ns talon There would bea certain stretching force or "tension nthe skin equivalent tothe cohesive forces "A change of shape, sy fom shops nding om surat tp il leo crease in surface area amd hence woul eure work nergy puts) toattetch the skin, ses fora drop to spread and et the surtace ts molecla cohesive orcesare weak oes eon iow. These are two ways of xying the Same thing Although dats forthe sure tension of water (and for other liquids are given in Bandbook, this snot often very ell for your purposes. A surface mast separate tuo materials ut ually Only one other material oem las or the lig’s veut) Specified in such ables for parila lguid, Thus the anabooks A nat ep you to compar te proper othe solvent when they felin contact wither matey that i thee ofthe eer you re daling with. For this eso, i ie probably beter to ink in terms of he phil phobiedstnction deserted above ‘A3 Volatility and drying ‘After any liquid cleaning process itis usually important that the object isdried. A liquid which rapidly evaporates off a surface is said to be volatile. When a liquid evaporates its molecules become separated from one another and the liquid no longer coheres. Thus, tobe volatilea liquid must have weak intermolecular forces. Volatile liquids usually have light molecules, and so the same amount of energy will make them move faster than heavier molecules or long, tangly ones. As with viscosity and surface tension, volatility also relates to the way the molecules hang on to one another. Hence liquids which have low viscosity and surface tension (such a5 acetone) tend also to have high volatility and, vice versa liquids With high viscosity and surface tension each a water and glycerine) have low volatility Im cleaning, if a solvent evaporates too quickly the dirt it has taken up will be redeposited on the object (perhaps making matters ‘worse in the process ifthe solvent has carried the dirt into erevices), However, ifafter cleaning the drying process i too slovr and heat is needed to speed it up, the object may again be put at risk. One useful ‘way round this problem Is to clean with one solvent, and then t0 wash away that solvent with another one which is more volatile. Using acetone to help dry something wetted with water is an ex- ample. An evaporating solvent such as water willtend to saturate the air around the object: using a fan to create an air flow ean help to speed up the evaporation process. Inacohesen of tesqud iqud 1 soc he ‘pimearant selerminng factor Figure 3.2. Wete trapped tthe bottam af corrosion pit ‘Water, asa relatively non-volatile cleaning fluid and as 2 polar solvent which dissolves ionicsubstances, presents its own problems. ‘The least bit of water remaining in a corrosion layer on metals, ‘Specially if notall the salts have been removed, may be enough to Start up the corrosion all over again. At the bottom ofa corrosion pit the walls are close together and the layer of water very thin, so that {in addition to the physical difficulties of getting the water out, the chemical bonds extend from the solid to each individual water fnolecule and prevent the water leaving. (This is the same adhesion between solid and liquid that occurs in surface tension.) “To avold leaving salts behind as the water dries off, they must either be totally washed out or deposited elsewhere (for example in {poultice of paper pulp or a mud pack). B Describing solutions BI What a solution is 7 : Uary mitre of substances which is homogenous down 0 a ‘lecture seal quate forthe name of solution though the word ‘Econmonly usd for solid dissolved in iguids. Before concentat- Ingram these remind youret of 4 few examples of noolquld laos es mitt a gs chars oinyatogen ad Shygen) cam lgimotely be regarded as a solution bectse Ile are intimately an andomly mixed, A sare ot ess engerous’you would nt find pockets of pure oxygen and others Srpus niogevevenita very sal sampe(s ee milion molecules) srqanalysed, Sold slutons include several meta alloys. lectrum [Giver and gids one example, cupronickel (copper sed nickel) cooher, Gabe an dislve in liquids the amount of gus dsolved San be inrease! by increasing the pressure. The ze when abot sf champepne i opened is carbon doxid coming out of solution as the mreige i eased Ligulds can also dissolve i guid. If to bguids combine to fora a soliton they are miselble. Ethyl ‘Noho and water are miele but toluene and water are nt “The more fimilor solutions of saids In liquids need to be ented in more deta and tl be belpl'o define some words ‘fore cxplaning what happen whe solutions are formed. When I iigald dissolves sold the soi Se aown asthe solute and the igus and slats miscibility solutelong wolvent concentration guid ss the wolvent Vou wl be lar wits what Papp The sold "Snappears nt the gl. Tat stil heen one fora ie often selevdent (for example bythe changed taste of water whem sogr or st solved in ior fom » change of solu) [Although the sold substance sno longer fo be see, sil thers So finely vided tat tno lager has sold orm The sold can Be recovered, however by evaporating the gui Io sg ston nate th ton of ston a intimate more of moleele adequate, However, ou know from Book 1, Chaper ) tonic compounds do. bot ave We solecules thei sold crystals sre ogee arrays of potve snd fopeive fons. When sich 2 substance disolve, the ions are Insulated fom one another by the water nd so the mixture exis 2a sa-merolar level The evidence forthe independene of os in solution has aendy been mentioned in Chapter 2 where It was txpuined that one slutons ae capable of conducting esr Ofcourse, when the solvents craorate roan one solton the tons come together agin and Decase of het letra neraction they oem cst B2 Measuring concentration ‘There are two things needed to describe a mixture; what its ‘constituents are and what the proportions of each constituent ae. Unfortunately no single convention has been chosen to describe the concentration ~ the proportions of each constituent in solutions ‘One way would be to State the relative proportions of molecules af ‘cach type inthe mixture. However, chemists measure the concentra- tion of the solution, by working out the number of moles of solute In one litre of solution. ‘The practical good sense of using molar concentrations (see Book 1) rather than molecular proportions lies inthe way solutions are used. For liquid solutions, the obvious measure of quantity is volume. This ‘ould be measured roughly in spoonfuls, more accurately with a graduated cylinder and most accurately, when necessary, with a pipette or a burette. ‘When solutions are used as chemical reagents (chemically reactive substances), itis the solute which is doing the reacting: the solvent ismerely a vehicle to carry the solid into the reaction in its ultimately finely divided form. Thus what you need to know is the number of ‘moles (see Book 1, Chapter 3) af soluze you ate providing for the reaction. You will remember that given 3 chemical equation for the intended reaction, you can use one piece of information (how many mmoles of one reactant you have) to calculate another (the maximum amount of the other reactant which will be consumed or the amount of product formed) ‘Specifying solutions In practice, however, the exact quantity of one of the reactants, the dirt, will not be known, nor will Its exact chemical nature. It 1s pointless to measure the number of moles of solute fora cleaning Zaction so you reed not bother with the calculation of molecular ‘feiss and s0 forth But you do have to make up solutions exactly and Rprodetbly, 30 there must be some convention for desribing the eecentration of solute. Clear instructions can be given by speci- fying the weigh f solid to be present in a given volume of solution. ‘his is the simplest and most easily understood measure. A con- ‘Jenientand universally accepted description is the number of grams reolute ina litre of solution, written asso many g/l (grams/litre}. ‘You must remember, however, that by convention concentrations are always described asso much solid per unit volume of solution and or per nit of solvent, This means that to make up a solution to an ‘Thaee concentration you have first to dissolve the weighed amount Stool in small amount of solvent and then dilute this solution to the prescribed velume. “rhe descriptive form, grams/lite, just explained, is unambiguous and therefore unlikely to cause mistakes. There are other less Straightforward ways of describing solutions. Loosely to talk of a Solution of “so many per cent” is particularly confusing, A “ten pper-cent solution” might refer to a weight per volume per cent olution or a valume per volume percentage, depending on the Solute. A 10% solution of sodium hydroxide means that 10g of solid has been dissolved to make 100ml of solution (w/v%,). A 10% solution of etharol could contain 10m of liquid alcohol diluted t0 100ml of solution (v/v%4). The w/v% convention can cause con- fasion as the units of measurement are not stated. A 10% solution ff salt in water cnuld be LOIbs of solid in 100 gallons, which gives a Solution only one tenth as concentrated as 10g in 100ml. So for Consistency the units should be stated, in which case you might just {8 well have stated the concentration in gl. B3 Solubility "There isa limit t the amount of solute which can be dissolved in a given amount of solvent. This maximum amount of solute is termed {the solubility othe solute. It varies from solute to solute and fom solvent to solvent. The solubility of solids increases with rising Temperature. (For gases dissolved in liquids solubility is ess at higher temperarares.) A solution which contains as much solute as possible is called a saturated solution. (The same word is used t0 {describe air that can hold no more water vapour, because the water ‘vapour is a solute in air) Tn cleaning applications, provided the dirt can dissolve in the solvent to some reasonable extent, the actual solubility does not ‘much matter; extra solvent can always be made available. If you ‘choose to use a warm solvent, if is more likely that you intend to increase the speed at which the drt is dissolved rather than the total, amount the solvent can hold. What is innportant, on the other hand, fs the solubility of the abject in the solvent, Strictly speaking there is no such thingas an insoluble substance. Every slid will dissolve in every liquid to some extent. Its vital that the solubility of any ‘part of the object in the uid chosen for solvent cleaning should be iui ond slot gramslitre solubility saturated solution Insolubilityleaning ‘very, very small. Only then can you afford to immerse the object in large quantities of solvent. There are obvious examples where an ‘object's solubility is too high, such as alabaster in water, limestone and bronze in acids. There are many other examples of solvents that attack both dirt and object. Many stains and dyes are both affected by the washing of textiles. Published recommendations to use ‘unusual solvents, such as N-methyl-2-pyrrolidone for dissolving starch away from cellulose, usually stress the problems of safeguard- ing the object rather than those of atacking the unwanted material, Starch and cellulose are very similar chemically and this solvent has been chosen because itis more selective than any other. It may not bbe the worst solvent for cellulose nor the bes for starch but itis one ‘of Few compounds which distinguishes between them, Hct NCH, che if Figure 8.3. The soucture ofN-methyl.2-nyroidone, The pyrolid part of {tha name retors tothe five-membered ring containing @hivogan atm The 2 and the -one ay that the second atom counting round the rng fom re ritrogen has» double banded oxygen attached. The N-methy tos you Choe is « CH rou joe 0 the magan ata. For cleaning, therefore, you must find a solvent which: + does not dissolve to a significant extent any part of the object. + dissolves the dit or whatever is holding the dirt in place + dries out, but not so quickly that it eaves dirt infiltrated into the object. C The science of solutions Cl Making a solution ‘When a solid is put into a liquid the significant events occur a the {interface between the two substances. You can think of what goes on using Figure 3.4 The kinetic energy of the molecules of both liquid and solid results in some of the liquid molecules worming their way into the solid (stage 2), As this effect increases the solid swells because the ‘molecules of the solid move apart. As the solvent penetrates further, ‘molecules of the solid lose contact with their neighbours and join in the random wriggling motion ofthe liquid. In going from stage 1 to stage 2a molecule of the liquid, which happens to be moving fast {enough in the right direction to penetrate the sold’s surface, has broken the strong bond between two “solid” molecules and ene oeges eo & o~ sole laud smoecules molecules ‘Stage 3 > oo oO. O 3% oe % casing sven random ésperson thesis Shion Figure 3.4 repaed by bonds between “sll” molecules and “gud” seals "rear however two fciors which ae Hkly tfc this proc: Te fer te “qu lcs ove the more ikl SST owl be broken and th tearm of negy inated “ul chenge fom kei to porn The now bond ore Set “ero aalindecls nd gud” nolcls nto Bes stong SRE tnd a prvi Sass bess cme SSA ih hry Sow replce) sot the penetnting “gu Seacelicdo neha the nary to spite ot ous Bering iad ce omerans you il ht the os more thelyo dle + The temperature is high since this means more molecules are moving fst. + The forces between the molecules of the liquid and the molecules ofthe solid are of similar strength, This then means ‘that the solid will be more likely o accept “liquid!” molecules into ft and that the “liquid” molecules are not strongly pulled back. themselves to remain as a separate liquid. igus ond soltonscleaning Ligue and slions ‘Thus, in terms of the secondary bonding forces between molecules (described in Chapter 1), liquids and solids showing similar strengths and types of bonding between their molecules ae likely to dissolve together Take a specific example, that of water tying to dissolve grease, which, as you know, it does not manage very well. Grease molecules are only held together by weak dipolar forces, as was described i Chapter 1, and so there should be no problem for water molecules to penetrate between the grease molecules, However, itis dificult for Individual water molecules to break fre from the bulk ofthe water ‘where the much stronger hydrogen bonding is inaction. Tt is this ‘which accounts for water's failure to dissolve grease. In contrast, hydrocarbon solvents (eg hexane) dissolve grease readily. The sol. vent molecules are subjected to much the same forces when they. have penetrated the grease as when they ate par ofthe bull of the solvent. Thus, as there is nothing to prevent the mixing, the random ‘motions ofthe molecules soon produce a solution. The question you need toask is; what restricts solubility? When nothing does, solution automatically occurs through the random motions ofthe molecules, ‘The example just cited shows a solution forming when there ae similar secondary bonds between molecules of solvent and between solute molecules. Hence the famillar adage “like dissolves like”, How can you tell what is like what when you are trying to choose 4 solvent? You can get a better idea of this when you understand ‘more about how electrons are distributed in particular molecular structures. The electric charge distribution Is what dictates the strength of the secondary bonding forces, We shall earn more of that in Chapter 4 C2 Energy changes in solutions You may have seen an article on choosing solvents inthe journal The Conservator. i discusses the changes in energy that occur when something is dissolved. The key idea is expressed by an equation: AG rin AH nie TASmoe Like a chemical equation, this is merely a shorthand notation for something that could be expressed in words as a fairly lengthy sentence, Once the meanings of the symbols are known the equation fan be used to predict behaviour or, more usually, to support descriptions of observed behaviour, ‘The triangle is a capital delta from the Greek alphabet. It means “The change in ‘The subscript “mix” means “on mixing’. This distinguishes the {quantities in the equation from other similar ones relating to other ‘changes such as chemical reaction or going from liquid to vapour "Solubility Parameters and Varnish Removal A Survey. 6 Helly, The Gomsarvaton a4 1980, p12 @ isthe symbol for something called ve nergy.) Thee His the symbol for something called enthalpy. wie § is the symbol for something called entropy. om ‘Tis the tempersture. “TAS means T multiplied by AS. {$0 AGmux is the symbol for “The change in free energy on free energy Se eh tip nde amount I needed to pay. Indeed I may be asked for more. after the subtracton. AGnix Will be zero. But if TAS qi is smaller I ae ae east pt BH mie TAS mix 1c renon fr these alewations willbe a negativevale for AG Th = iShwsifhlor Syn tobe nea aston shld Beton te uti or pst umber he hem Substances wil nse form sation " “Fs rent vey tle tothe changes of energy fn the mechanical syste we disused in Chapter 2. As compresed ‘pring is tease or ab a rick falls potential energy” PE) {Recto The lange in potential energy, APE. on going fom an inti satetoascond state gate, APE epithe event esrb isonet happens spontaneously. Event for which APE t pontve (pring compressing themselves, fics ling upwards) not occu el 10 Ssse of te grat thermal agitation of molecules itis possible shania pics may be bnocked fom sate ofp at eurgyt oe high potatoe, the eer ed energy change the Bll material wl bein he revere cree on Hee guantlies AG, AH and AS reer tthe ove ste of Tillons of aries and oto nv change, At he maleclar Tove there are to conetng tendencies + those preventing solution ~ the tendency of the atactive forces hold together the molecules ofthe substance tobe d+ solved ‘changes of energyeoing enthalpy entropy. + those encouraging solution— the tendency of molecular motion tomix things up. Ifthe equation isto predict that solution will take place when the ‘answer is negative, then the mixing up tendency must have a negative sign in front of it and the holding together tendency 2 positive sige, so chat the mixing tendency athe greater the ane Wil be negative Tritt 11 The enthalpy “The enthalpy (H in the equation) isthe coal energy of all the Particles in the system. When two substances are mise and hes focm a solution there i no increase inthe total numberof particles, the temperature remains the sme the total kine energy ofthe particles not altered. So the only change isi the inter parte Potential energy. If the molecules or ions in a sold are wrongly Bonded then energy is required to break them apart. There increase in potent energy Since the breaking of bonds inhibits formation ofa solution the change in enthalpy is pven a postive sgn inthe equation. Changes in ataey ae sntmes dei eat sored credo forming a volution. A positive enthalpy change is shown by the solution getting colder. . 7 5: The entropy Tes more dificult to express in terms of energy th energy the tendency of mmlecular motion to mix the molecules, That hs endeny depends upon temperature through the agency of molecular kine energy Slnnot be doubted. But temperature iso energy and docs ot measure the amount of mixing produced by diseleing Entropy {Sin the equation) isthe quantity which falls the connecting eee Suppose. fr istance, supe is dsoved in water crystals water suger {L rmlecules unaligned signed wralones Figure 3.5. The rearangament of molecules ina solid to form arandem Soreod afer dissolution ina gui. The insets show dlagrammatcaly ‘magnified partons of the vo sates. afore the sugpr dissolves, its molecules are in regular erystal iter and quite separate from the water. After dissolving the pavfecules are randomly spread through the water. Many ways could moltwented for describing the order of "before" and the disorder of "efter" For example the length and angles between lines joining ame number of nolecules could be averaged (Figure 3.6) costal solton aa lengths and anges eq lengths and angles diferent Figure 3.8 Hypctheticl means of deseribng the order anc asorder of foil and dissolved crstas. Entropy is one possible description of the extent of disorder ina system. The mathematics that relates the number of possible states EFA System such asa solution and compares the order im a crystal vith the disorder in solution is very complex. What you need to remember is: + Entropy measures disorder. «Entropy is greater for disordered conditions than for orderly ones. ‘The usual teadency for mixing by molecular motions makes ‘entropy increase, Another way of stating the Second Law of ‘hermodynanics (Chapter 2) is to say that there is a general tendency for entropy to increase. ‘With this information the free energy equation can, at last, make Gwe = Aix ~ TAS ic will come out negative ifa big changein entropy, ASai, cam coincide \with a small chenge in molecular potential energy, AFiq:,. Mixing jiven number of molecules in a given volume will produce more or ffs the same AS... whatever the molecules may be. So if they happen to be ores which cobere tightly (AF, large) you may have to crease the temperature T to make the negative part of the equa~ tion swamp the postive part ~ of, in reality as opposed to in the ‘model of reality, you may have to increase the temperature to make a solution, “All these general ideas about liquids and solutions eventually come together when a choice is made of a particular solvent for a ob. The following chapters look at some of the options ‘which are available to you. gue ad slations aOrganic solvents > General observations Classes of organic solvents BI Nor-polar hydrocarbon solvents B2 Halogen-substituted hydrocarbons B3- Polar solvents containing oxygenOrganic solvents “This short chapter reviews the structures and properties of some “rganie substances which ae liquid at ordinary temperatures and re used as solvents for cleaning. The division into polar and non ‘polar categories cllows you to apply the idea that ike substance will Uissolve like (introduced in the previous chapter) with a litle more precision. It also enables you to explore further the characteristics Of groups in organic molecules. A General observations like substances dissolve like, then you will expect to use organic solvents on orginic dirt (uch as grease, old varnish, paints and flues, ar and mildevr stains) Since this type of dirt soften found ‘on objects made of organic materials, it may be a tricky matter to Choose a solvent which is both effective and safe. However, sub- Stances ffom which such artefacts are made tend to have giant ‘molecules with either primary or strong secondary bonds linking them, These are more difficult to dissolve than the small dirt molecules, The consequence for cleaning is that organic solvents, in ‘general, are likely to be innocuous as far as any risk of dissolving the in structural materials, such as proteins or cellulose, are con~ ‘cemed, Nature's solution is to use enzymes (see Chapter 7). You can be rather less sure, however, about the supplementary materials of anobject. dyestuffs, varnishes, essential ols, and soon. The solventssong orgies ‘can be categorised by the type of secondary bonds they can make you know solvent A is unsafe in such and sucha circumstance you ‘won't ignorantly try solvent B which ie similar. Or, if you know A ‘works but isa bit too volatile, you will know which substances are similar in solvent action but are less volatile "You will xemember {tom Chapter I that the main subdivision of secondary bond types is between non-polar molecules which shove only the weak Van der Waals attraction, and polar molecules which have additional stronger electrostatic attractions dueto their uneven electric charge distributions. Since we have seen that physical Properties as well 5 chemical ones are under the control of these bonds it willbe valuable frst to see the effects at work on a simply measured property ~ the boiling point (which at east partly 1s & comment on volatility). Weak bonds and light weight should make for low boiling points: opposite tendencies give high-boiling liquids So if you look at families of compounds with similar bonds the boiling point should go up with molecular mass. Here are two sets of examples: Hydrocarbons (paraffins) -non-polar molecules Nome Formula ‘Mol. mass" Bolling point “C methane CH ie et ethane Calls 30 a9 propane CH,CH,CH, 48 =a n-butane CH,CH.CH,CHy 58 ° Fepentane CHICHCHCHCH, 72 +38 Penexane —CHA(CH)CHs 88 +88 1m fact all these are too volatile to be considered as solvents but the last ofthese isthe lightest fo stay liquid long enough to dissolve anything. Compare those boiling points with those of a family of polar molecules, noting the similarities in molecular mass, Alcohols - polar molecules with H-bonding Name Formul Mol. mass.” Bolling point “C rmathanol chy) 2 co thane! GoHi-OH a 78 -propanol —GyHs-O8 6 97 ‘-butenot CaH-OH 7 ne {tis clear that, weight for weight, the alcohols are far less volatile than the paraffins. We can ascribe this to the stronger cohesion between their molecules. Water (mol, mass 18) which also bas an OH group has an amazingly high boiling point (100°C) but of ‘course both ends of its molecules can make secondary bonds to other ‘molecules. Its also instructive to compare boiling points of substances with similar molecular masses but different polar groups, Here are some ‘examples, all with a molecular mass around 60. a Name Formula ‘Mol, mass Boiling point C urane CHACHCH.CH, 3 5 muthy thy ether CHCH,OCH, 50 1 testone cHicch, 58 6 i ° propanol CH,CH,CH,OH 80 9 fesueecis —— CH.C~OH 0 6 1 ° ‘These five substances have nearly the same molecular mass yet there isa range of boiling points of more than 100°C, This demon- States the polarry associated with the electronegative oxygen atom bond in ethers and more especially when itis double onded to carbon as in the ketones, The ability to hydrogen bond, provided by the ** OH group, gives a higher boiling point, while the acid with both < oft and a strongly polar C~O double bond has the highest boiling point ofall. Since volatility can be controlled both by melecular ‘weight and strength of secondary bonding, subtle choices can be ‘made within each class of solvent. B Classes of organic solvents ‘BI Non-potar hydrocarbon solvents Because nparosrbons interact only by Van der Wals forces shey non-polar hydrocarbons re ligud aly when thts molesles ae gute heavy. Hexanes the ight of te ghtcarn hy rosarbons whichis suenty nom wine tobe ote in leaning Cyclohexane, Chas molecules Inthe frm ofa ring (eel fom Greek gh i 4» Ae Aaah 7 / iF nl \, 4 4 Z q Because the bonds from the carbon atoms point tothe corners of an imaginary tetrahedron (see Book I, Chapter 3) the ring isnot lat. ‘This is in contrast to the aromatic hydrocarbons (such as benzene, ,H,) where thes} carbon atoms in the ringare allin thesame plane, ‘The molecular arbitals which connect all six carbons at once in aromatic compounds can only be formed if the molecule is fatleaning and aromatic hydrocarbons halogens Figure 4.2 Structure of benzene. Molecular orbitals are seen at clouds Of elecrons above and below te plane of te carbon and hydrogen aroms ‘The principal disadvantage of hydrocarbon solvents is that they. are flammable, although they do find some uses in cleaning. They are "useful for softening or dissolving greasy deposits which are, largely, hhydrocarbons themselves (ike dissolves like), ure hydrocarbon compounds may be too expensive for all but special applications but many cheaper mixtures are available. White spirit, solvent naptha, Stoddard solvent, etc., are mixtures of aliphatic (alkyl) and aromatic (aryl) hydrocarbons distilled from petroleum. The standard trade descriptions of these define only the flash point (the lowest temperature required to form a vapour/air mixture which will explode) and a range of boiling points. Within this range fall many different hydrocarbons so that the solvent strength may vary from batch to batch. Mixtures with more closely controlled composition, and hence more consistent solvent strength (such as Shellsol T), are made and sold by the oil companies. Of the aromatic hydrocarbons, benzene must be avoided in work- shops because its vapour is very poisonous. Toluene (which i less ‘oxic) is the solvent used in some impact adhesives, and so it may be used to loosen joints made with these. It is also particularly effective for removing tar because tar contains many aromatic compounds (another like dissolves like). Xylene (dimethyl benzene) is sold com- ‘mercially as mixture ofits three isomers (see Book I, Chapter 5) and Js a useful solvent for many rubbery materials. Commercial diethyl benzene is, similarly, a mixture of three molecular species and is used as the solvent for certain methacrylate polymers. 1B2 Halogen-substituted hydrocarbons ‘The group of elements fluorine, chlorine, bromine and iodine are known as the halogens. If a hydrogen atom in a hydrocarbon is replaced by a halogen atom the compound is considerably less flam- ‘able (but these compounds are toxic), The series based on methane, Hy Is: CHCl chloromethane methy! chloride), a gas at room temperature, CH,Cl, dichloromethane (methylene chloride) used in commercial pn strippers (eg Nitromors) CHICI, trichloronethane (chloroform) which you will recognise asan anaesthetic, as are most of these compounds. CCl, tetrachloromethane (carbon tetrachloride), ‘There are many examples of halogen-substituted hydrocarbons based on ethane, containing two carbon atoms. Figure 43a) shows 1, 1, 1 trichloreethane; the numbers 1, 1, 1 indicate that three chlorine atoms are on one carbon atom. This compound is used asa ‘metal degreasing agent, Figure 4.3(6) shows trichloroethylene, one fof the dry cleaning fuids aa ak 81.1.1 tchlorcethane “Genklene 44 cl bo rT ar {© 1,1 diluoroterachioroethane 1,1, 2 Wluor tichloroethane "Vactone’ "arton Figure 4.3 Some examples of halogenated solvants derived tom ethane (io carbon ators) Hydrocarbons containing chlorine and fluorine are much more volatile than unsubstituted hydrocarbons of similar molecular mass. Compare Arklon, C,CI,, (mol. mass = 188) shown in Figure 4.3 (4) ‘which boils at 47°C with tridecane, C,H, (mol. mass = 184), which foes not boil all 243°C, The forces of attraction between the ‘molecules in chlorinated and fluorinated hydrocarbons must be very ‘weak. This may be because the carbon atoms are more or less com pletely surrounied by electron-grabbing halogen atoms, so the outer surfaces ofthe molecules are negatively charged and the attra tive forces between the molecules are to some extent cancelled by repulsive electrstatic Forces, ‘Chlorinated hydrocarbons are good grease solvents. This suggests that the Van der Waals bonds that they can form with ocher molecules, whic do nor contain a lot of halogen atoms, are of much the same strength as those of hydrocarbons. Halogen-substituted hydrocarbons are to be preferred to dnydrocarbons of similar volatility (such as petrol) for a very impor- ‘ant practical reason~they are not flammable and so are safer to have around in large tanks. However, most chlorinated hydrocarbons ‘decompose to phosgene, COCl,, a poisonous gas, if they are heated ina flame. Evena cigarette is hot enough longo solventslong molecular polarity ‘The high volatility of the chlorinated hydrocarbons used as dry ‘leaning solvents is useful in that the cleaned textiles can be dried ‘easily by passing warm air through them, (White spirit, for example, {is much less volatile and it takes much longer to dry off after teat. ‘ment.) But a major problem about volatile solvents is that because they evaporate rapidly a high concentration builds up quickly in the air around the table, ‘The density of a vapour is related to the molecular mass of the compound. The higher the mass the greater the density. If the ‘molecular mass is much greater than 30 the vapour will tend to sink tothe floorasitisheavier than air(N, mol. mass = 28;0,, mol. mass = 32), The vapour ofl, 1, 1 trichloroethane (Genklene, mol. mass = 133)is three times as dense as that of ethanol (“meths”, mol. mass = 44) although thei boiling points (volatilities) are nearly the same. ‘This means that although ethanol vapour may be sucked up into an ‘overhead fume hood, the heavier vapour probably will not. Ideally chlorinated hydrocarbons should be used in a completely enclosed apparatus lke those used in dry-cleaning shops, fume hood light solvent goas uP conservator object haw solvent goes down Figure 44_ The pats of eaporaun fr solvents. v0 use on a conservators workbench B3 Polar solvents containing oxygen Polarity in molecules is caused by uneven distribution of electric charge. The origin of this imbalance isthe great need displayed by elements to achieve an outer shell containing eight electrons when they form covalent bonds (see Book 1). Oxygen is notable for this behaviour and several commonly used polar solvents contain ‘oxygen combined in diferent ways, Figure 4.5 summarises these: Name General Formula Bample Alcohols R-O-H cath OH thane! ethers R-o-F Hy O=Cy dlethy ther Aldahydes R-G=0 Ketones a—Gmo R CMe scetie acid core che gm0 Onc, ethyl acetate Figure 4.5 Cassa afonygon-contaning organic substances (The symbol [Re stands fora hyeroca’bon group such asimethy ety. andsoon) opertcn ofthe polar orgie solvents sed in conservation fal tte te tegriey showin tls table. The ange of sight ‘aratns of compestion allow a vey proce selection fo be made ‘The panty varies between the dierent class ar wll be ox nied shorty and canbe adjusted thi these clases by changing fhe vadcals (dented R~). Acts, however, wil ot be cused er unl Chapter 6 “en mre vrtong ar vale you we ness ithe oxygen coualng groups: These groups may fer fom one nother for enepley Ztoxy-ctanol, y=O~ Cy OF, Shih s bh an alaol and an ether. Tall hese molecules, the oxygen atom acqulres the major share of electrons inte covalent onde wih forms and the oxygen Som therefore Fecomesantively charged rion ofthe moerue ‘he astinction between te clase drive fom the sources of he ‘lcs whieh hc nygen atm sseqirng inorder tilts outer he oxygen atoms in water molecules can only take estrone foam hyaoyen which Is the ony ether specin of stom Presentleaning alcohols “Hydrogen atoms possess only one electron but if hydrocarbon ‘groups replace hydrogen a more prolific source of electrons becomes available and the resultant positive charge, in regions that are deficient in electrons, ean then be spread out over several atoms y @ 20 7 @ water methanol ® @@ @°@ 0° @ ballon @:@ era @ 'soproprlatcahol Figure 4.6. Charge cisoxbuions in some polar molecules The consequence of spreading out the positive charge over several atoms is thatthe polar effects are less pronounced in molecules with longer hydrocarbon chains. Notice in particular that hydrogen atoms not directly attached to the oxygen are unaffected. Since these Inydrogens are not starved of electrons, they are unable to form the Inydrogen bond bridges to other molecules. Alcohols ‘Hydrogen atoms that are joined directly to the oxygen, however, do suffer some loss of electrons and in alcohols, therefore, there is some degree of hydragen bonding. Because of these hydrogen bonds, alcohols can be expected to mix well with water. Inmolecules with large hydrocarbon chains the ‘non-polar part ofthe molecule is not compatible with water and so ‘miscibility (the ability to mix) with water is less for higher alcohols. ‘The higher alcohols (those with higher molecular mass) have longer and heavier molecules which are more likely to become entangled ‘with each other. Ti follows that these liquids are more viscous than the familiar aleohols like ethanol (IMS, meths) and propan-2-ol (IPA). More nergy is needed to separate the molecules and disperse them into the air and so they have higher boiling points, low volatility and are slow to evaporat Ketones and aldehydes ‘The characteristic group isthe carbonyl group, C=O. The double bond shows that there is a high density of electrons between the atoms and of course the oxygen gets the greater share of them. The ‘Oatom is therefore charged negativeand the C, positive, Compounds ‘containing carbonyl groups are very polar. The polarity Is higher or Tower depending upon what groups are attached to the carbon. If ‘one of the spare carbon bonds is occupied by hydrogen the sub: Stance is called an aldehyde. Formaldehyde is the most polar of this, clas: 4 \ fon} ‘The attraction between molecules is so great that formaldehyde is ately found as monomer (single molecule) but as polymers made from groups of molecules ‘Acetaldebyde and acetone are slightly less polar: ce ct X Neco “ chy scotalderyde soetane [As bigger hydrocarbon groups are used, the postive charge becomes diffused over many atoms and the polar effects decrease slightly. "There is n0 possibility of hydrogen bonding between these molecules because their hydrogen atoms are not joined directly to oxygen and are not starved of electrons. The negatively charged ‘oxygen atom is, however, an ideal site for hydrogen bonding from other types of molecules. Thus acetone mixes with water, and may be regarded as @ reasonable solvent to use on a hydrogen-bonded solute, such a6 nitrocellulose glue. ‘Because acetone is miscible with water, it can be used to speed up the drying of weter from wet objects. It evaporates very fast, ow- ‘ever, which cool the surface, and this can make water vapour from the air condense, causing bloom. Bloom effects may also be due to ‘varnish redepostting in 2 finely divided form from solution in the ‘acetone. If this cecurs, a ketone witha higher molecular mass, and hence slower evaporation rate, would probably be more successful Orgone savers carbonyl group aldehyde ketoneCanine ethers ‘Another useful solvent is diacetone alcohol (-hydrony-4-methy] pentan-2-one}: oH CHE CHE =o oon Its slow to evaporate and can form hydrogen bonds through is = OH group. The combined alcohol and ketone groups make this compound a good solvent for a wide variety of resins. Ethers ‘The general formula for ethersis: ROR, where R~ stands foran hhydrocarbon group and the two Rs may be different from each other. ‘The oxygen atom, again, becomes negative but the positive charge is distributed thinly over both R— groups, which means that the polar effects are weak. For thisreason, ethers are volatile and are not ‘very miscible with water, though they will dissolve ifa small amount of alcohol is present. Ethers are good solvents but evaporate too quickly tobe useful in removing varnishes, They are sometimes used for @ quick surface clean an a solvent sensitive surface, where their {quick evaporation prevents them penetrating, swelling or dissolving the surface finish. They must always be used with care because of their extreme flammability and, as all ethers have anaesthetic properties, fame extraction should be used, Esters ‘The general formula for esters is: R—C—0—A i o Although they do not form hydrogen bonds with their own molecules, they do hydrogen bond with water. They are polar and miscible with water. Examples in conservation use include: “These ae the bet solvents avallable for loco; the ners wth higher molecular mass ar lo god for polyvlayl acetate and hylmethacryate (Perspex) rth najer dios of erganke solvents dsrbed inthis section have been chosen to exemplify the general pizelpesout- fed a the start of the chapters Quite Incidentally they probably Cover alma argante solvents wed commonly In conservation. here are afew exceptions ~ the select of Nemethy Zpyrolldone in disolving starch, but not cellos, has already ‘ch mentioned similarly, ile is known about why morpboline elec solver for shill casein and oxldsed nse ol ch ch x o NH None Figure 4.7. The srvewro ofmohetine. ‘Some of the more powerful solvents (powerful inthe sense that they ‘move dirt that other solvents will not touch) may not be forming true solutions. They may bereacting chemically with the dirt. This means that what could ke recovered from the solvent would not be chemic- ally identical to what was dissolved. orgie sues 7Cleaning with water A. The special properties of water B Tonic solutions in water C Purifying water CI Deionisation C2 Water softeners D_ Soaps and detergentsCleaning with water ‘Water is the most important liquid cleaning agent, with the triple advantages of being very cheap, easily available and without hazard to the conservator. It isa remarkable substance, different in almost every scientifically measurable respect from other solvents, which {is why it bas a chapter to itself. This chapter describes some of ‘water's special properties in terms of molecular structure. Its surface tension propertivs and its ability to dissolve ionic compounds are explained, The sonservation implications of its ability to act 25 2 solvent for ionicdirt, and of the need to purify water by removing ions, are also considered ‘in practice, water is rarely used alone as 2 solvent, and all kinds ‘of additives are used to modify its properties, Soaps, detergents, and miscible organic solvents are added for various practical reasons. ‘This chapter explains how these additives work. A The special properties of water “The special properties of water can be related to its molecular strue- ture, which governs the way its molecules interact with each other and with other substances. You have already learnt that when ‘covalent bonds are formed between two hydrogen atoms and an ‘oxygen atom the electrons are not shared equally. The strong need for electrons shown by oxygen atoms leads to the electrons in the bond being draven away from the hydrogen atoms onto the oxygen atom. The oxygen atom thus becomes negatively charged, leaving the hhydrogen atome positively charged. The distribution of electrons 3leaning around the oxygen atom is such that both the hydrogen atoms are ‘on one side of the oxygen, making the molecule a dipole (see Chapter 1). the molecule were linear, although the actual bonds would be polar, the whole molecule would be non-polar as the effects would be equal and opposite © y 4 Figure 5.1. The water molecule "The negatively charged oxygen atom provides a site for hydrogen bonding between the water molecules. The polarity of the water ‘molecule and its ability to form hydrogen bonds allow water to dissolve, soften or swell organic substances whose molecules contain enough polar groups (often — OH), for example, polyvinyl alcohol, polyethylene glycol and starch, to say nothing of wood, leather and ‘many organic structural materials. ‘The strong polarity of water molecules is one of the reasons why water is also able to dissolve Jonie compounds (salts) which mest organic solvents do not touch, ‘The sttong secondary bonding between water molecules is ‘manifest in its physical properties too. Extra energy is needed to break the hydrogen bonds and cause the molecules to move fast {enough to escape from the surface and disperse into the atmosphere as a gas. This is why water has a boiling point well above that to be expected ofa compound with so low a molecular mass (18) Similar compounds which have higher molecular masses ~ eg hydrogen sulphide, H, (34), and carbon dioxide, CO, (44)~ are gases at ordin- ary temperatures. Clearly it is useful that water is liquid bue other properties of water are not so convenient for cleaning, especially its high surface tension, "The tendency of water molecules to cling to one another, and s0 to require alot of energy to move them apart means that water does not flow as easily a8 other liquids composed of molecules which do not form such strong secondary bonds. Water is viscous compared with ether, acetone and hexane which, although made of heavier molecules, are not hydrogen-bonded, so flow more easily. B Ionic solutions in water ‘The most common compounds of metals are their salts, which have onic bonds. As explained in Book I (Chapter 4), these result fom the ‘complete transfer of electrons from metal atoms to non-metallic atoms or groups. The metal atoms become electrically charged positive ions and the non-metallic parts become negative ions. The Conventional symbols for ions are, you willremember, the usual sym- bole for the atoms or groups of atoms with as many + signs or — signs as electrons lost or gained. Thus Na* is 2 sodium atom which hhas lost one electron to become a sodium ion. Fe*" is two electrons short ofan iron atom, CI- has one more electron than a chlorine atom Sand SO_~, the sulphate ion, is an assembly of atoms carrying two more electrons than all the individual atoms would separately. These arrangements satisfy the rule of eight electrons to give a complete and Stable outer shell of electrons forall the atoms. They also lead to ‘very strong electrostatic attractive forces which make up the pri ‘mary fonic bond between the positive ions and the negative ions. As these forces act in all directions it is inaccurate to think of “molecules” of silts, Instead, there are regular arrays of vast num- bers of ions arranged so that positive tons are surrounded by negative ions, These arrays are recognised as crystals (see Book 1, Chapter 4), ‘Consider how erystals might dissolve in water. It takes a lot of energy to disrupt the crystal structure ofan ionic compound and so ‘only the fastest water molecules will succeed in dislodging ions from the crystal. These extra fast moving molecules would soon be used Lp if there was no way of recovering the energy they spent in knocking fons ott of the crystal, Belng polar, water molecules can form electrostatic bonds with ions of either sign: IEG WAH Figure 5.2 The way watermolacules can form electrostatic bonds with ‘both postive and aegativeians to bacome hydrated ins of either sign ‘The ions are then said to be hydrated (combined with water). Two consequences follow: + There isa drop in the potential energy ofthe water molecules. The potential energy lost by the water molecules as they cluster round the fons is converted to kinetic energy which, after trans- fer by collisins to unattached water molecules, maintains the supply of molecules moving fast enough to knock more ons out of the crystal ‘The ions coated with water molecules are less likely to recombine with the crystal because they are now the wrong shape, and, because the electrostatic forces in the crystal have to act over a longer distance, and are consequently weakened. leaning with water hydrated ions‘leaning hhard and soft water vapour pressure C Purifying water ecause water i such an effective solvent for ionle compounds you would expect water taken straight from the ap to tones ban dissolved from the rocks‘thas percolated through aad flowed oes Water rom limestone areas wl have sigalieatt quant ote (C85, Mg, $0", cl, CO,2", and HEO,”)disaived it Sack wate i said to'be hard, and’ you will know that i rae sn soso scum with soap and dées not lather easily. ‘The contre ‘ith soft water well Kowa, For conservation use, waiter needs to be putified, The two Alisllaion and methods most often used ae distillation and detonation, racer Alelonisation lation the waters boiled and the steam that comes ot olecea and condensed (cooled to form a liqud from a gat) eng spparten ‘which iin pencil ike tht in Figure 3) “MB APP ‘round-bottomed. d fe | seteerer dirty water chips of china * foprevent bg So abies forming) 'somantle— thermostaicaly contaled electric heater (ne naked flames with fammabla sovents) ean water Figure 6.3. The basic apparatus for he alstiltin of water condensate The condensate (that which is condensed) is called distilled water and consists of water molecules only. When a solution i boiled, the light solvent molecules leave the surface of the liquid more readily snd evaporate off into the atmosphere, the heavier solute molecules ‘remaining behind. This same process of evaporation also occurs at ‘oom temperature, although much more slowly, as there is always 2 small proportion of molecules with enough energy to leave the liquid, As energy in the form of heat is supplied to the water the hydrogen bonds between the molecules break, and the molecules ‘move about rapidly until they are leaving the surface in considerable ‘numbers. The amount of water vapour inthe air above the liquid is ‘measured as the vapour pressure. The vapour pressure increases ts the temperature of the liquid rises. When the vapour pressure of ‘molecules trying to get out ofthe water equals the pressure ofthe alr ‘keeping them in, the water boils. (This relationship between boling and alr pressure is why water boils ata lower temperature on the top of a high mountain, where the alr pressure is lower) 2 Detonisation 7 ; ; 3c deionlsing columns wed in purlying water for conservation Touip' mina of two deca eles one to reneve paive ‘ono th other nptive fos, The esie ae invlubleand the iso ed lons in water become firmly attached to what aren effect gant Sitions and apis: Let call the two resins Resin — ad Resi MOH and look athe removal of calcium sulphate as an example Cn the at ein Ca +50 +Aesn—H+H' +80: + Resin—ca ad soent (0n the second He +SO!+ Resn—-OH+ HO+ ——Resin-S0, bose pure spent ream ater res (You should not that no attempt has been made to balance these {Gjations) Wherallthe set which reaction cn take pace om the Tehinare wed up he resn hast beregenerated otha ean be wed Sauipe cn hae tly tee we thanufactare or suppl for regenerating Delonisation fay economical in sof water areas where there is not much lnk material to take ot and one charge of rex laste ‘ong ine tnaravofard water the resins gt used up qucky snd frequent replacenet is necesary, To determine when the Fes Cevtldges need replacement, the equipment i fied with aconduc- tivity meter working either rom a ater of from the as. This pases lect through a sample of the waters runs trough {system and measure the ablity ofthe sample to conduct lecnc- ity Pure water hea low conductivity becaure conduction depends ton lone to cary the electric. When even a soall quantity of Ss dasolvedasionsis present the conductivity shoots up and the indicator shows this, uetally ona meter dal, indicting that anew tenn charge receosry. Iti sometimes thought that when the ‘lectrctyo switched off the resine will ot lean the water. Thies fot so. The confision is cased, perhaps by the explanations in Calving ine and charges inte water. The electicly soppy irony Sed tovear the water quality and so withthe eletricy switched of You cannot tel whether the resins are working oro. C2 Water softeners ‘Water which hasbeen through a water softener (such asthe Permutit type) isnot deiorised; it still contains dissolved salts. This could be shown by measuring its conductivity. The water has been made “soft” by exchanging the calcium ions, Ca**, and magnesium ions, leaning with water conductivityleaning fatty acids ‘Mg, for sodium ions, Na*. "Softened’” water wil not produce scum when used with soap as the scum is insoluble calcum and ‘magnesium salts. (The equivalent sodium salts are soluble.) While ‘his treatment i satisfactory for domestic purposes, for conservation Uses it isnot, because salts will still be deposited when this water dies out. The jon exchange materials in water-softeners are either natural clay minerals (such as sodium aluminium silicate) or beads of synthetic polymer, carrying resins of the structure Resin ~ Na on thelr surfaces. The reaction (which isnot shown asa balanced equa tion) is Resin~Na+ Ca!" Rasin—Cat Ne i ditferent ietin ‘onsin apparatus water ‘When all the active reagent has been used up the reaction can be reversed, by passing a very concentrated solution of sodium chloride through the apparatis. This regenerates the activity of the ‘water-softener. ‘Treatment of water by the batch using “Calgon” (sodium hhexametaphosphate) also softens without deionising, The calcium fons are removed from solution and replaced by sodium ions. D Soaps and detergents The advantages of water asa solvent do not include an ability to dissolve grease. Soaps and detergents are additives which ensble Water to be used as a grease solvent. As you have seen, organic solvents offer an alternative treatment for greasy dirt. Consequently you have to decide when to use “dry cleaning” methods using ‘rganic solvents and when to "wash" using water plus an additive Tobe able to make this sort of decision, you need to know something. about the chemical composition of soaps and detergents and how they work Chemically, soaps are salts of organic acids, part of whose ‘molecule is along hydrocarbon chain, These acids in other combina. ‘ons are constituents of animal fats and vegetable oils and are collec. tively known as fatty acids. Oleic acid, C,HjCOOH, will serve as an example. If you compare this molecule with acetic seid, CH,COOH, you will see thatthe diference Is that the acid-making part of the molecule gp, OF Tm Cac abo) oa ghyorarbon one CB cared butt sre one, C= nace When se Sec up wi al sat ofthe aids ae formed. Typ Petts Slate common 4p Cate e—O-K — j § + ont and negative vee doles in water forming poste 1 e Tee deetGy coo" Ws thse negative los which make the ie hyocarbon cai instuated thas double bond ea re sodom easof e sn le Ordony ssp 2 mit he sed ny ae whch havea of umber of carbon e"hyaacron chain fom coi COOH, fee The soins ar der sds sb tan he ce etiig psu el, Pout mals derived fom Soaps gael i igo yrorarbon chains the onetaion ofthe arin cath taon som i tetabetal ee Book 1 Chapter 4) \ At ANA 7 / "INF SY Ne eo i # AN, rin Asnclmonantoa!s hein coh Tate cf ei ia oem anata Be See i sw mp ete ye eet Temp i re Speen aiegtace a eae snipe cogent Tamerica sro and hydrophilic head: ant Cleaning with werleaning detergents anionic and cationic detergents non-ionic detergents ‘One end ofthe ion would prefer to dissolvein water the other end 4s more compatible with grease, Detergents generally have molecules with the same type ofstruc- ture but are derived from a mineral acid, such as sulphuric acid, H,S0,, or phosphoric acid, H,PO,. The sulphonate detergents have the structure: 9 Oye new 0-8-0" Ns 8 ‘There is a variant which has SO, rather than $0, in the chain and includes a benzene ring: ° moe Q)=feor mt 6 (Chemical variations, as you can imagine, are endless, with shorter ‘or longer chains, branched or straight ones, with or without rings or double bonds; but on the whole, ifthe hydrocarbon part contains ‘more than a dozen carbons, the compounds will act as detergents. Domestic detergents are mixtures and may include many other {ingredients (such as colouring and scent to help them sel) mall the soaps and detergents mentioned so far, the active part isan anion (negatively charged). They are therefore called anionic detergents. Although there are cationic detergents where the active portion of the molecule is a positive ion, they are not used in Conservation to any extent and so will not be discussed here. There {sa third type, non-ionic detergents, where the polar end of the molecule is not completely ionic but is sufficiently polar to give solubility in water. These are extensively used. One ofthese occurs naturally in the plant soapwort and has been successully used in conservation for washing textiles. Just as safe, cheaper and more consistent in properties are the industrially made ones, known (Grom their mode of manufacture) as ethylene oxide condensates ‘The general pattern of their molecules is shown below. ner OCH, CH, OCH, CH, OH tong hyarocarbon chain non-polar end ther links and sleohol and confer Some polarity to his ond Variations in the hydrocarbon chain, in the spacing of the oxygen atoms and in what spaces them out (sometimes benzene rings) form ‘the many different members ofthis clas of detergents. Like substances dissolve like. The polar end ofthe molecule gives it solubility in water and the non-polar end gives solubility in grease. Grease molecules become attached tothe tals (the hydrocar- bon chains) by Van der Waals forces and are carried into solution. Let us look at this process in more detail, ‘The action of soaps and detergents at the interface between water leaning wit water Gad-a greasy sarace explains why these sddives ae Known & SGrtactamts Certainly the sure a the water should be expected surfactants tobe covered wit theacive ions the hydrophobic allsstckngout ffom the water and able to gta the presse gure 5.5) ene Figure 5.5 The hydrophobic tals ofa surfactant sticking out ham the tater surface: the hydrophilic heads emin in close contact ‘Within the body of the liquid the polar anions form miscelles, miscelles small casters with the hydrophobic tails all together inside a rough Sphere and the hydrophilic ends on the outer surface in contact with the water. "Like with lke" yet again. wy. “ays Figure 8.6. A crase-section through a miele whichis roughly spherical shape The centreof tis mise ts non-polar solvent. Greatemlecules canbe sborbed end eld in sltion in these conte, ths removing them from theelet or surface. In addition the diay beremoved In larger imps coshting of any greae molec. ‘The flowing diagram shows how a washing solution containing a surfactant gett nt, its away and suspends the die 3‘Cleaning leaning th water — fi, .. a4 | lip yy laud | drtdetacnes SS, it k sy wi: m eee hon unuatey it ene Figure 8.7 A series ofilustrations to show the process by which @ Surfactant contained in a ashing solution acts on Ot In addition to surfactants, water washing solutions may contain compounds to keep the solution mildly alkaline. Sodium carbonate Js used with sodium siliate (also called sodium metaslicate) to stabilise the pH (see Chapter 6). Alkaline solutions clean more effec- tively, and help the surfactants to attack grease. They prevent the formation of insoluble metal salts or soaps which would be precipitated. Alkaline solutions should only be used on cotton, not ‘0n wool oF silk because alkalies damage protein molecules. ‘Another additive used is sodium carboxymethyl-cellulose, which suspends dirt and prevents resoling. Re-soling or greying is due to re-deposition of the dir. Re-deposited dirt can be more difficult to remove than the original dirt was, Sodium hexametaphosphate is added to form complexes (see Chapter 7, Section C) with calcium salts in order to prevent any deposit of these and other metals. It can hhowever, increase the risk of dyes running Hard water, as you know, forms scum with soap. This is because ‘of an ion exchange reaction between calelum ions in the bard water and potassium ions in the soap: 2CpHaCOOK + Ca" + (CyHyCOO),Ca + 2K7 calcium oleate CCalelum soaps ae insoluble and these form the scum. When soap is ‘chosen for washing delicate textiles, deionised water should always be used, Even where deionised water is used to make up the washing solution there may be calcium salts in the object which would react; s0 that an insoluble scum isleft behind on the object, For this reason, soaps of this type are hardly ever used in conservation work. The use of soft soap on marble or other calcareous stones should also be avoided because it forms a yellowish-grey, insoluble film that alifficule to remove, The immediate advantage of the synthetic deter- gents is that their calcium sats are soluble and da not form scum, Tis important o wash away all he detergent and other additives with clean fresh water so that no residues are left behind. Tis AMcul o predict exactly how any resides might react wit the mmteral ot which the objects are made over long period of ne, nd it ha been observed in the laundry industry that detergent, tosis increase he rate ofesling. Te object wil gt dry aga tnove quickly ia residue i le 7 ‘The strong pouty of detergents has two dsadvanages whic cannotalvaysbeavolded: swelling of the material being washed (eg ‘wood, ory, paper leather, textile bres, ete) which may be are Thi in iwel or ay encourage dyes to bleed, pigment to Lit for fxample; and the dificulty of removing the detergent fom the bjt ater cleaning. 5Water, acidity and alkalinity A Hydrogen ions in water Al Molecular conditions in pure water A2__ The pH scale for hydrogen ion concentrations B Acids, bases and alkalies BI How water becomes acidic B2 Uses of acids in conservation B3_ pH greater than 7 Bs Weaker bases BS Uses of alkalies in conservation C The measurement and control of pH C1 The measurement of pH C2 Buffer solutionsWater, acidity and alkalinity ‘There are many conditions of objects, and treatments for them, where acidity and alkalinity are important factors. This chapter explains what makes some solutions in water acidic and others al- kaline. The chapter also discusses what the pH scale of measurement means as well ss looking at ways of measuring and controlling pH. A Hydrogen ions in water Al Molecular conditions in pure water ‘A further consequence of hydrogen bonding between water molecules has to be considered in order to understand acids and alkalies. Figure 6.1 shows two molecules of pure water joined together by a hydrogen bond: Figures. ‘The hydrogen atom forming the bridge is involved in two bonds, 1 covalent bond tits own oxygen atom and a hydrogen bond to the ‘oxygen of the nearby molecule. However, the electron arrangements are exactly the same in both bonds. The only distinction between ‘them is thei length. As the molecules jostle around, firs one bond isthe longer, thea the other. In collisions which are hard enough toclsning chemical equilibrium acidity and alkalinity ‘break a bond, the longer, weaker one is the more likely to break Sometimes the pair will break to form two separate H,0 molecules; at other times i wil break to H,O and OH. In the second case the H,0 has gained the extra positive charge ofthe hydrogen nucleus and so 1,0 isa positive ion, H,0*. The molecule which has lst a hydrogen nucleus stil holds its electron and so the ion OH~ is formed. In summary, what has been described is the reaction: 2H/0-+ 4,0" +H" It is, of course, quite possible that each of these jons will bump Into others of the opposite sign as they wander around inthe liquid. Then the reverse reaction may occur: H,0° + OH" +2440 ‘The chances ofthis reverse reaction occurring depend upon the population of ions of each sort. A steady state wil be reached where the chances of new ions being formed are equal tothe chances ofthe ‘existing ones recombining. The balanced situation where ions are ‘made and destroyed at the same rate is known as a condition of ‘chemical equilibrium. The chances of ions forming depend upon temperature since this controls the probability of bond-breaking collisions. The chances of them recombining depend upon concentra- tion, since this controls the probability of positive and negative ions finding each other. The concentration of the two sorts of ion must be exactly the same because an H,0" ion can only be made simul ‘taneously with an OH fon In pure water at 25°C equilibrium exists with a concentration of fone ten-milionth ofa mole per litre ofeach sor of ian. Although this is 2 tiny concentration it does mean that even the purest of pure water is not, chemically, 2 single molecular species. Moreover, because the ions are chemically more reactive than their parent molecules, their presence strongly influences the chemical interac- tion of water with other substances. ‘A chemical equilibrium, lke other forms of equilibrium or stabil- ity, can be upset by suitable external influences. The conditions of acidity and alkalinity are just ths. The equilibrium is disturbed so that the concentrations of H,O" ions or OF” ions are no longer one ten-millionth ofa mole per litre. n acidic solutions the concentration of H,O" is increased by hundreds, thousands or millions of tes. Alkaline solutions, conversely, have the concentrations of OH” fons dramatically increased. Thus, the chemical behaviour ofthe solution becomes controlled by the behaviour ofthese ions. The compounds called acids and alkalies can bring about these remarkable changes Jn water when they go into solution. [A2 The pH scale for hydrogen fon concentrations The concentration of H,0* and OH ions in pure water is one ten- nuillioth of a mole perlite. Written asa ffacuon this Is mais ‘which cam be written more compactly as 10°, t0 be read a5 “ten to the minus seve Water eid and alktinty “The convention for describing numbers like this Is simply to count how many noughts there are in the number. Numbers bigger than 1 are given plus index; thus 1000 is 10°?, ie “ten to the plus tHhree” (normally ust 10° or "ten to the power of three"), Fractions are indicated with a minus index. The fraction yy is 10-2, “ten to ‘the minus three” tis long-winded torefer toconcentrations in moles per litre when the numbers beesme awkward mouthfuls like “one ten-millionth” s0 a shorthand convention based on the “ten-to-the-something’” system has beer adopted. When used for describing acids and alkalis this is known as the pH seale and describes the concentration ‘of hydrogen ions (more strictly, of H,0" ions) The pH ofa solution of concentration 10°’ molesfite i 7, so you can see the origin of the pH number. Its the power of ten which ‘describes the coxcentration, but with the siga changed. You will hhave come across the pH scale before and probably know that acid solutions are described by pH numbers less than 7. Thus pH is acidic, Working aackwards you willsee that this means concentra- tion of 10-* moleliee for #H,0* ions. 10-* means ;-x, or one millionth. [Now notice ths carefully! A concentration of one millionth of a mole per litre is tn mes more than that ofa ten-millionth mole/litre, 50 2 pH solution is ten times more concentrated in H,0" ions than isa pH? solution Similarly you can show that pH i ten times more concentrated than pH6, 100 times more than pH, and so on. Acids fre thus solutions in which the concentration of H,0* Is much higher than 10 moleliee. "The most immediate consequence of getting more H,O" jons into, solution (you will see how this is done, so0n) son the population of| (OW fons. Formation of these ions, by the break-up of H,0 molecules in collisions, stil occurs at the same rate as in pure water but now the chances of meeting an H,O" ion and recombining with it are ‘vastly increased so the population of OH ions collapses. So when water is made acidic not only are there more hydrogen ions (hydrated to H,0") but also many fewer hydroxide ions. So the ratio ‘of H,O° to OH”, whichis :1 at pH, changes dramatically. Figure 6.2 shows the rao of populations for various pH values. PH Ratio of H,0" ions t00H ions 7 1 oe ten-miionth a5 2 6655 6510. 6 100 cone miliorth 55 1000 4 1 milion ‘one tan-thousaneth 28 1 thousand milion 1 4 million milion” one tech Figure 6.2 pH far 1107 PH scale ion ratios aclang oxyaclds Figure 6.2 concentrates upon weakly acid solutions. Very small ‘changes in pH mean larger changes inthe ratio of H,0* to OH”. pH6 ‘may not sound very different from pH, but you can see that already the H,0* ions are the dominant species in the solution, The pH description of alkaline solutions uses numbers greater than 7. This ‘will be dealt with later, but let us see what sort of substances cause these remarkable changes in water when they go into solution, B Acids, bases and alkalies BI How water becomes acidic ‘You have seen how lonie crystals made up of separate ions go into solution in water Because the polar water molecules offer electrostat- ically “comfortable” places for the fons to go. The pre-formed ions, such as Na* and Cl~, exist by the exchange of an electron between metal atom which is happy to lose it and a non-metal anxious to grab it Similar compounds with hydrogen in pace ofthe meta are | covalent but strongly polar, with the hydrogen almost fonised, eg H — Gl. Put this in water and the hydrogen finds a better share of electrons if it goes on to 2 water molecule. Thus: | HL+HO hydrogen chide ‘and water Hot + cr > nyorocnione se or, showing the electrons: Figure 6.3 Now, different kinds of molecules may lonise to. greater or lesser extent as they dissolve in water. At the extremes, common salt, an ‘onic compound, dissolves entirely to become separate ions; sugar, 2 covalent compound with ~OH groups available for hydrogen bonding, does not ionise at all in solution. These two statements could be checked by electrical conductivity tests on solutions. The amount of ionisation in solution is closely linked with the polarity inthe undissolved molecules. Acids, like water, have strongly polar molecules with hydrogen atoms as the positive part and oxygen atomsare very often the source of the polarity as they draw electrons to themselves, Apart from hydrochloric acid and hydrofluoric acid, LE, all the common acids contaln oxygen and are knowin collectively as oxyacids. Here are some of their molecular structures, Water, acy ond tainty ° Ho. é \ oon pon’ + Sooo No Hao ar cotbonic acid no 0 Ve f - + AS no” So iphurcacs oe “wo ooh A he +s no So phosphoricacid Figure 6.4 Some oxyscd structures (* sheded) ‘The scan srctrl common ets thee ole ae the OH groups covalently coupled through another atom double bonded oxygen som. The electrons are pulled towards the double Bonded oxygen alom() leaving the hydrogen precariously bonded The moleces ae polarised as sows “Theres strong ujirogen bonding between the molecules ofthese sc im pre frm ou may fave et act siphon esphoriacdsin pure or nearly preform, and Know them to Fieky viscous lculde Phe argusnent for thelr high isos isthe fame a for wate ‘Mining these substances with water gives the loose hydrogen atoms the optonof being attached to water molecules as #30" los insted of fo thei orginal molecule. The option is taken up. sometimes competely, sometimes less than completely, depending Spon how losay the hydrogen atoms are eld othe acid moleule ‘has hydrogen chloride sod ntl aid fonise completely in water Whereas among organic ackls only 2 small proportion of the Ioleculs break up. for acetic aid the igure about 1a 100, but iis millons of times more than the numberof broken water Imoleculs tht exist n pure water, so ace acid succsstully ods the solution wit H,O™ fons “the fact tat sme aids onsen soltion moe than others leads to some confusion in conversation, Speaking scienteally, acids * Carboni cdc be prepared pare becuse composts to H,0 and CO,leaning Strong and weak acids dilute and concentrated acids organic acids ‘which ionise completely are strong acids while those which tonise Partially are called weak acids. Although it may seem allright to call 41 pH solution “weak” and a pHI solution “strong”, it Is much better, because its more accurate, to refer instead toa weakly acidic solution or a strongly acide solution Further confusion often arises when deseribing acids between the terms “weak” and “strong” and the words dilute and cone centrated. Suppose you want a solution ofa certain pH. To make solutions of the same acidity you can use a dilvte solution of a completely ionising trong acid or a more concentrated solution of a ‘weak acid. A solution of pH3 could be 0.1 mole/litre of acetic acid or 0.001 molejlitre of hydrochloric acid. Consequently, you need to ‘think clearly about the precise meaning of these words if you wish to be clearly understood B2 Uses of acids in conservation Hydrochloric acid has been used to remove calcereous deposits, ‘mainly calcium carbonate, from ceramics and stained glass, The 2HCI+ CaCO4-+ CaCh + CO, + HyO The insoluble carbonate is converted into a soluble chloride which can be easily washed away and, provided the acid is also thoroughly rinsed out there should belittle, any, damage. It has also been recommended for removing lead carbonate from lead ob- Jeets. This would have to be done very carefully indeed because metalic lead is attacked by hydrochloric acid, Hydrofluoric acid has been used to remove iron stains, Unlike hydrochloric acid, ie does not react with carbonate to liberate CO, 50 has been used on marble and limestone. Also since it Is not at oxidising acid, a is for instance sulphuric acid, it does not readily attack the cellulose of cotton textiles or paper socan be used on these (provided it does not affect any colouring matter which should be on the object). Nitric acid, however, is a powerful oxidising agent. Orthophosphoric acd H,PO, is used both to remove iron oxides and to protect ion from corrosion. It probably does both these things by forming complew compounds, soluble in the first case, but insoluble in the second. Some comments about complex metal com- pounds will appear in Chapter 7, Organicacids also find uses. Formic acid, HCOOH, has been used to remove silver chloride from silver and also to dissolve copper corrosion products. Acetic acid CH,COOH, Is sometimes used 10 prevent dyes running and is often chosen to neutralise excess alkali, after bleaching process for example, but although it may not itself be harmful, residues of the products of reaction in some circum- stances can be damaging. Formation of magnesium acetate For exam- pile, will tenderise cellulose, promoting oxidative degradation of cellulose as it ages. So the acid and reaction products should be thoroughly rinsed out of the object after use. It attacks lead, and should not be used on this metal Water act ad alainty Gitric acid is sometimes used to dissolve cupric oxide, which it does by forming a soluble complex (see later). Other organic acids also form complexes and are useful for metal cleaning. Examples are tartaric acid and thioglycollie acid 1 : i 4 H=¢-cooH < i \ Hoon oH be Figure 6.5 BS pH greater than 7 [Now let us furn attention to the other end of the pH scale, 7 to 13. Remember that neutral water, pHT, has the same concentration of HO" and OH” lons, and that these concentrations are amheam mole/iitie = 10? moleslive, Also, we said that pH measures the concentration of H,0", so a pH solution, say, has a concentration of H,0° ions of rar mole/lte ~ 10°* molylve "This means theres only one hundredth the concentration of H,0* ions as there is ir neutral water, so the question is where have all the H,0” fons gone? The answer is that they have been mopped up by recombination with OH lons. To arrange for this to happen the solution has to be swamped with OH™ ions to increase the chances of 1,0" lons meeting them and recombining. An obvious Source of OH” ions is a metal hydroxide, caustic soda, NaOH, or slaked lime Ca{OH),, These are crystalline solids which contain pre-formed OH ions, Dissolving such ionic compounds in water therefore raises the OH™ concentration and forces the H,O* con- centration down. The rato of OH” ions to H,0* ions, which was 1:1 at pH, shifts rapdly. Compare the following table with Figure 6.2. hydroxides pH Ratio of OH" ions Mol 10 H,0" ions. of OH 7 1 10 715 2 736 5 75 io 8 00 ro Bs +1000 10 milion 10 | ns 1 thousand milion . 13 1 muon milion 10 Figure 6.6 Ponulstion ratios for OH” ins 10H," ions in solutions with pH greater than 7leaning oe base strong bases or alkalies “Any substance which produces OH ions in solution, whether by ‘virtue of containing them pre-formed or by reactions with water, i ‘known as a base, Substances which contain pre-formed OH” ions {in the anhydrous (water-free) condition and which merely release them into solution are strong bases or alkalies. The word “strong is used here in the same sense as for “strong” acids strong. ‘bases are completely ionised when dissolved. ‘The method of producing an alkaline solution is typified by the dissolving of caustic soda (sodium hydroxide) NaOH in watar-e Nat + OH” followed by: OH + HOt +20 + On large eumbers sparse surplus population ‘The H,0* ions are mopped up leaving a surplus of OH ions Both alkalies and acids cam legitimately be regarded as the result, of reactions between oxides and water; metal oxides produce alkalies, non-metal oxides generate acids. Example are the saking of {quicklime to make an alkali and dissolving sulphur trioxide to form sulphuric acid C20 + H,0-> Ca(OH) alka 80, + H.O->H.S0, acid ‘The difference in the behaviour ofthese substances when dissol- vved in more water is an immediate consequence of the metal oxide ‘being ionicand the non-metal oxide being covalent. Metal atoms give up their outer electrons completely, satisfying the oxygen atoms, So the oxygens make less demands for electrons from the hydrogen ‘atoms. In solution, therefore, Ca(OH), breaks into Ca?” jons and OH fons. In contrast, sulphur does not shed its electrons to oxygen, so the tendency of oxygen to collect electrons is satisfied at the expense of hydrogen atoms. The molecule H,S0, ow 0. Vf s an, 0” oH therefore, has its weakest covalent bonds at the O—H positions. ‘The ions formed in solution are SO,2~ and 1°, the later hydrating tH,0". B4 Weaker bases Strong bases, (alkalies), find occasional use in conservation, but itis also important to understand how weak bases are effective. We shall ‘now concentrate upon ammonia and its derivatives, and the car~ Donates of alkali metals (sodium and potassium). ‘Ammonia and tis derivatives When ammonia gas, NH, dissolves in water three possible molecular states are found which interchange with one another: NH, +HO- NHOH -+NH, o# hydro on fends rection) sends reaction “1 fecwonss ‘omens “The key to understanding what goes on is the hydrogen bonded, compound, NH,OH (ammonium hydroxide). This forms because both ammonia ard water are polar molecules. The case is analagous to the two water molecules shown at the beginning of the chapter ‘which were joined by a hydrogen bond bridge. They could break to form either two separate water molecules or H,0* and OH ions. ‘in ammonium hydroxide the nitrogen and oxygen atoms are joined by a hydrogen bond bridge 4 4 Figure 6.7. The aycrogen bond bridge bonwsen the nirapen ond oxygen atens Jinan ammonium byarence molecule 4 Either ofthe arrowed bonds can be broken by collisions and bot’ kinds of break cecur. Not only do the two reactions involving the INH, grouping have to find equilibrium, but the reaction in which ‘water ionises is involved too, because H,0* ions may be lost as a result of the increase in OH” concentration caused by the lonisation fof ammonium hydroxide. In other words there are three reversible reactions finding mutually stable balance points: NH*H,O=NH,OH NHOH=NH,'+08 2H,0=2H,0" +08" “The sign = indicates a reaction that is rversibe “The results, of course, an alkaline solution, rich in OH~ ions and poor in H,O* jens, The strength of ammonia as a base is such that 10.1 mole/litre solution of ammonia is about pHI1. This indicates that about 1% af the ammonia molecules dissolved in the solution are ionised at equilibrium. Notice thatthe pH value tells us nothing about the state of the other 99% of ammonia molecules how many fare present as NH,OH for instance. ‘Organic derivatives of ammonia also behave as bases. Some exam- ples are given in Figure 6.8. You can see that their structures are Similar to that of ammonia, Wter acy and aalnty organic basesleaning carbonates y cH ¥ i i 4 \ 4 Rock, noo! NACH, I i Ls, i 4 cH, So ce cH, N ‘cHi—6 smmonia methylamine dimethyl formamide morpholine Figure 6.8 Swuctures of some orgonic bases. compare to ammonia Imevery one ofthese compounds the nitrogen atom has a par of electrons (own by dts which can be ses ors yogen atom Which has lst ts electron. In wate, these compound wil fale (OH ion concentations inthe sme way that ammonia does. The ammonia molecule isnot Bat. The electronegative nitrogen atom Gareying its extea pair of lectons isnot in the sme plate 06 three hydrogen alms (ce Figure 69) This is why the molecules 2 dipole ammonia splat. <= | Figure 8.9. The cage csviouien ina amon nlc ‘The other nitrogen-containing bases have similar hent structures. Carbonates ‘A chain of reversible reactions similar to that just described for ‘ammonia occurs when carbon dioxide dissolves ia water. CO, being the oxide of a non-metallic element, produces an acidic solution, Rainwater normally hasa pH of about 5 because ofthe dissolved CO, ‘This accounts for much long term deterioration of limestone and marble, (hs eects are more date in an indusealy plated atmosphere because $0, dissolves to reach a much lower reactions of CO, are » 60,7 4,0 === ,c0, HHLs He0,-+H,0° Seco +2H,0° nesetes cxboie _benante carbonate (unstabiey ‘These three reactions and the ionisation of water reaction have to come to equllirium simultaneously. Measurement show thatthe concentrations of CO, and HCO,~ are much greater than of and CO, ee It's interesting to consider what happens if'a soluble carbonate, for example, washing soda, Na,C0,,10410, is dissolved in water. ‘The equilibrium concentration for the carbonate ion i low while for the bicarbonate ion itis high, causing: CO" +H, HCO," + OF {p occur which means that sodium carbonate is a base. Sodium bicarbonate is also. base because ifthe solution is overloaded with HCO,” jons: HCO,” > COx(q) + OF ‘occurs, with the CO, becoming a gas (shown by the “g")and fizzing ‘out of solution, ‘Soluble carbonates and bicarbonates, therefore, offer you source of weak bases which are safer to handle and more gentle to use for Conservation purposes than the caustic hydroxides. B5 Uses of alkalies in conservation One use of alkaliesin conservation isto neutralise acs, The action {S encapsulated in the adage you may have heard at school ~ “acid plus base gives sak plus water”. Tis tells you the overall effect of Frid mecting base and warns that when you have neutralised an acid there is a salt of seme kind to be removed from an object treated in this way. Iris worth realising what is happening in the solution. If, for example, sulphuric acid is being neutralised by a solution of sodium hydroxide, the solution contains H,0" and $0,* ions from the acid and Na” and OH” jons from the alkali, The only reaction ‘occurring is: Huo" + ON > 2440 caused by the high population of both ions. which increases thelr Chances of meeting and recombining. As the solution dries out, #0 tmolecules evaporite raising the concentration of all the ions and. Causing more recombination of H,O* and OH” ions, Eventually, if ‘actly the right amount of alkalis present, only Na* and SO’ will ‘remain and will combine to form solid crystals. Iti imperative, even {f the neutralisation is exactly done, to wash away the saline residues before the object s dried. In fact you would not choose strong bases. ‘The alkaline hydroxides are rarely used for deacidification because they might cause further damage to the object by overcompensating for acidity and because unduly rapid reactions could cause damage by releasing a lot of heat. ‘The favoured base for many deacidifying tasks is ammonia solution, partly because ammonia is a weak base, but also because ‘most ammonium salts are very soluble. “Ammonia has been used to deal with the particular problem of “vzed rot” in leather which is caused by attack from sulphur dioxide pollution in the atmosphere, The treatment is carried out dry, the Teather being suspended in the fumes above concentrated ammonia solution, Then: INHy + H,SO4-> (NHS. ‘You can regard this reaction asthe formation of hydrogen bonds through the weakly bound hydrogen atoms on the sulphuric aid ‘molecules tothe aegative end ofthe ammonia molecules, hough the transfer of H atoms is probably more definite than this suggests Water, acy od alainty neutralisation deacidificationleaning Water aly ond alkalinity Indicators pH meter en x eon because ammonium sulphate forms ionic crystals (NH,*),502~ Because no water is involved, the ammonium sulphate stays on the leather. Any moisture absorbed from the atmorphere cannot release ‘cid H,0° ions from the sulphuric acid because the hydrogen atoms are already bonded into NH,* Jons. This deacidification treatment has seemed to work and has caused no damage over a period of time after treatment, However, there are doubts as to whether ammonium sulphate s going tobe stable on leather; under some conditions some ammonia will be lost, reforming sulphuric acid to continue its attack ‘on the collagen (protein) flbres ofthe leather, C The measurement and control of pH C1 The measurement of pH ‘The colour of many organic substances depends upon hydrogen ion concentration. These can be used as indicators, the most common being litmus which ie red in acid, and blue in alkaline colution. “Universal Indicator” undergoes subtle changes of colour which cat bbe compared with those on a chart over a wide range of pH and can ‘thus be used to estimate the pH of a water solution, ‘A pH meter is an instrument for measuring the hydrogen ion concentration, and shows whether a solution in water is acid ot alkaline. The probe of the pH meter is designed to be immersed in ‘8 water solution. There isa special membrane in the probe through ‘which only H,0° ions can diffuse and the flow of electricity behind this membrane is measured. The electricity can only flow by being ‘transported by the H,0" ions, and the instrument is calibrated to isplay the flow of current asa measurement of the concentration of these fons in the original solution, that is ite pH. Proper measurements for pH require the temperature to be taken into account. Readings intended for comparison should be carried ‘outat the same temperature, or compensation should be made ifthey are taken at different temperatures, Standard measurements are taken at 25°C. Your pH meter will have a control which can be adjusted for different temperatures and may also have its own ther- ‘mometer builtin. (Ifnot, a separate thermometer Is necessary toread the temperature of the liquid.) Readings taken at different tem- peratures without measurement of temperature and compensation for that difference are not comparable one with another, and are consequently virtually useless. The simple explanation for the effect ‘of temperature is that, a5 you will remember, the ionisation (break ing up) reactions in water are accelerated at higher temperatures “while the recombination reaction is slowed as ions are les likely to catch each other. Figure 6.11 A pHmoter meters are sed to measure the pit of washing solutions before anil ater rinsing an object, and to indicate the amount of aid present in enolic in tutions where a sample canbe ssrfied {oie maceted soaked snd broken up in dsl or deionised ‘fate. Thishas tae done becasyalltheacd must be extracted and “lssolved inte water forthe pi to be epntered accurately on the tncer. tis inpotant to have the solution thoroughly mixed before {aking sample for pil measurement, Because differences ay Ou tivoughout the bulk. For example a washing tanks there may be temperature afrencs te cold solution sink and vam rac letor papers ares senlive than pi eters but both bave thee tes Ifa indication of whether the slutlon i ci or alkall sal thats neded tc use pt paper only may well Be adequate Problems with pH readings It is important toremember that when we talk about the distinction between acids and alkalies, we are talking about what happens to ‘water when thesesubstances are added tot. Thus, the measurement of pH only has validity when water is present. A pH{ value for the soliton left after washing an object in an organic solvent, contain- ing no water, has no meaning. Similarly, itis impossible to measure the pif ofa dry cbject, such asa piece of paper. The dry solid may be loaded with an acid salt such 2s sodium bisulphate which will become actively acid when wetted but the pH of that solution will depend upon its concentration. Thus, even if you “moisten” the sold, the meter can do no more thaz tell you of the presence of acid the particular rumber indicated will have far more to do with the ‘amount of water you have used than with any other features of the Object. That s why there are conventional procedures for preparing, ‘water extracts from solid samples which will give consistent pH